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- This book is sold for informational purposes only. Neither the author nor the publisher intend s fiJ,. any of the information in this book to be usedfor criminal pwposes.
- Secrets of Methamphetamine Manufacture
- Including Recipes for MDA, Ecstacy, and Other Psychedelic Amphetamines
- Revised and Expanded, Eighth Edition
- © 2009 by Uncle Fester
- All rights reserved. No part of this book may be reproduced or stored in any form whatsoever without the prior written consent of the publisher. Reviews may quote brief passages without the written consent of the publisher as long as proper credit is given.
- Published by:
- Festering Publications 826 S. Baird SI.
- Green Bay, WI. 54301
- Drawings by Donald B. Parker and Ray Bosworth
- ISBN: 978-0-9701485-9-9
- Library of Congress Catalog Number 205900622
- CONTENTS
- INTRODUCTION.................................................................................................................. i
- Chapter One
- Chemical. and Equipment ................................................................................................... 1
- Chapter Two
- The Leuckardt-Wallach Reaction: An Overview ............... ............ ........................ ... ..................9
- Chapter Three
- Prepar.tion of Phenylacetone ............................................................................................. 10
- Chapter Four
- Prepar.tion of N-Methylformamide ...................................................................................... 2 1
- Chapter Five
- M.king Methamphetamine ................................................................................................ 25
- Chapter Six
- Industrial Sc.le Production ..... ...........................................................................................37
- Chapter Seven
- Phenyl.cetone from B -Keto Esters ............................................................... ..... ............... . 40
- Chapter Eight
- Phenylaeetone via theTuhe Furn.ce ..................................................................................... 45
- Chapter Nine
- Other Methods of Making Phenylacetone .............................................................................. 52
- Chapter Ten
- Psychedelic Phenyl.cetones from Essenti.1 Oil ........................................................................ 75
- Chapter Eleven
- The Way of the Bomb ............................................. ................. .........................................87
- Chapter Twelve
- Reductive Alkylation with out the Bomb .............................................................................. 100
- Chapter Thirteen
- Methylamine ................................................................................................................ 112
- Chaptfr Fourteen
- The Ritter Reaction: Amphet.mines Directly from Allylbcnzene .............................................. 115
- Chapter Fifteen
- Methamphetamine from Ephedrine or P.eudephedrine, Amphetamine from PPA ......................... 1 19
- Chapter Sixteen
- Methcatbinone: Kitchen improvised Crank .......................................................................... 177
- Chapter Seventeen
- Brewing Your Own Ephedrine .......................................................................................... 180
- Chapter Eighteen
- Cooking Your Own Ephedrine .............. ............... .. ........................................................... 184
- Chapter Nineteen
- MDA. Ecst.cy (XTC). and other Psychedelic Amphet.mines ............................................. ........ 188
- Chapter Twenty
- Ice.......................................... ......................................................... ..................... ...... 195
- Chapter Twenty One
- Calibrating the Vacuum .............................................................................. ..................... 196
- Chapter Twenty Two
- Production from AJlylchloride and Benzene .......................................................................... 197
- Chapter Twenty Three
- Phenyl.cetone from Benzene and Acetone ................................................................ .......... .. 206
- Chapter Twenty Four
- Last Resort: Extracting 1-Methamphetamine from Vicks Inhalers ............................................... 209
- Chapter Twenty FIve
- Keeping out of Trouble ..................................................................................................... 210
- Chapter Twenty Six
- Legitim.te Uses of some Chemicals ...................................... ....................................... 216
- Chapter Twenty Seven
- Web Sites ........ ...................... ................... ...................................................... .... 217
- Chapter One Chemicals and Equipment
- Chapter One Chemicals and Equipment
- The heart of the chemical laboratory is the set of glassware collectively called "the kit." It consists of several round bottom flasks, a claisen adapter, a still head with thermometer holder, a thermometer, a condenser, a vacuum adapter and a separatory funnel (sep funnel, for short). These pieces each have ground glass joints of the same size, so that the set can be put together in a variety of ways, depending on the process being done. For the production of a quarter to a third of a pound batches, 24/40 size ground glass joints are used. Also necessary are one each of the following sizes of round bottom flasks: 3000 ml, 2000 011 and 500 011; and two each of 1000 011 and 250 011. Two condensers are also required, both of the straight central tube variety, one about 35 cm in length, the other about 50 cm in length.
- The standard taper glassware kit suitable for use in doing distillations and reactions has become very risky and difficult to obtain by any method other than theft or diversion from a friendly source. We can take this as further evidence of the creeping police state we are caught in. The aim of the system is to produce a disarmed and dumbed-down populace, a goal which is being achieved to an alarming degree. The very thought that home chemical experimentation might have some purpose other than drug manufacture has been banished from the general consciousness. In keeping with this, the suppliers of glassware keep their purchase records open for regular inspection by agents of the police state. Further, most of the suppliers will not do business on a "cash-and-carry" basis. Rather, they insist upon setting up an account, whereby they compile a dossier on their customer before doing business.
- Fortunately, this is not a real obstacle to production. The chemical manufacturing industry gets along just tine without using standard taper glassware in which to cook their chemicals. They rightly view it as expensive, and very prone to breakage. Instead, they construct their reaction vessels and distillation apparatus from materials like stainless steel and Teflon. The only thing lost from the use of these materials versus glass is that you can't watch the batch cook or distill, and magnetic stirring is prevented.
- The inability to stir magnetically is quite easily circumvented by use of a mechanical stirrer. These are available commercially, or may be constructed at home. The preferred construction materials are a stainless-steel shatt, and a Teflon paddle. Teflon-coated steel is also acceptable. A typical stirrer is shown in Figure 1.
- Figure I
- Construction of stainless-steel cooking apparatus is simplified if the necks of cooking vessels and condensers are made wide enough for the shaft of the stirrer to fit down into them, and yet have enough tree space for the condensation of vapors and their easy return to the cooking pot.
- The inability to see what is going on inside the apparatus is more troublesome. An oil bath must be used to heat the vessel, so that by tracking the bath temperature, one can guard against overheating the contents
- Chapter One Chemicals and Equipment
- can be threaded into the water source. Alternatively, the threaded head can be pushed inside a section of garden hose and secured by a pipe clamp. The hose can then be attached to a cold water faucet. The bottom end of the aspirator, where the water comes out, is rippled and can also be pushed and clamped inside a section of garden hose leading to the drain. The aspirator is kept in an upright position and at a lower level than the glassware it serves. This is because water has a habit of finding its way into the vacuum hose and running into the batch. Keeping the aspirator lower forces the water to run uphill to get into the glassware. The aspirator has the disadvantage that it requires constant water pressure flowing through it, or the vacuum inside the glassware draws water from it inside to make a mess of the batch. For this reason, only city water is used. And, unless the vacuum line is disconnected from the glassware before the water flow through the aspirator is turned off, the same thing will happen. The aspirator has these advantages: it flushes fumes from the chemicals down with the water flow, costs only about $10, and produces no sparks. A well-working aspirator produces a vacuum of IOta 20 torr (2 to 3% of nornml air pressure). (The unit '"torr" means one millimeter of Mercury pressure. Nonnal air pressure is 760 torr.) A good aspirator is getting hard to find these days.
- The other choice for a source of vacuum is an electric vacuum pump, which costs about $200, not including the electric motor, purchased separately. To avoid the danger of sparks, the motor must be properly grounded. The pump has the advantage that it can be used in the country, where steady water pressure is not available. It also produces a better vacuum than the aspirator, about 5 torr, for faster and lower temperature distillation. It has the disadvantage of exhausting the chemical fumes it pumps into the room air, unless provision is made to pump them outside. The oil inside the pump also tends to absorb the vapors of ether or toluene it is pumping, thereby ruining the vacuum it can produce and making it necessary to change the oil.
- Another necessary piece of equipment is a single-burner element buffet range with inlinite temperature control. It is perfect for every heating operation and only costs about $20 at a department store. Finally, a couple of ring stands with a few Fisher clamps are used to hold the glassware in position.
- Since I wrote the first edition of this book 25 years ago, a whole slew of new restrictive laws have been enacted in a futile attempt to prevent clandestine cookers from practicing their craft. Restrictions on the sale and possession of glassware have already been mentioned. Many chemicals are also subject to the reporting of their sale as a result of the Chemical Diversion Act. The chemicals subject to reporting are given later in this chapter. All of this is just a waste of time on the part of those posing, pandering politicians. It is the purpose of this book to expose them, and hold them up to the ridicule they deserve. If there is one thing a politician can'l stand, it is ridicule and a practical demonstration of their impotence.
- An even more noxious, yet similarly futile law has been enacted in California. Since this is bound to be
- the model for similar laws enacted throughout the country, let's examine it more closely.
- The most easily defeated part of the law concerns the sale of chem lab equipment and chemicals. The law states that purchasers of equipment andlor chemicals in excess of $100 must present proper ID, and that the seller must save the bill of sale for inspection by officers of the law. Since most individual pieces of chern lab equipment go for less than $100, this law is gotten around by keeping one's equipment purchases under $100, and splitting up one's business between various suppliers. The five finger discount method while attending college chern lab courses is another option. Similarly, transfers between friends, and the old-fashioned heist from well-stocked labs are other ways around this law.
- The most stringent section of the law is aimed primarily at production of meth, LSD, MDA and MDMA, PCP, and the barbiturates. Of those chemicals relevant to this book, it lists: phenyl acetone, methylamine, phenylacetic acid, ephedrine, pseudoephedrine, norpseudoephedrine, phenylpropanolamine, isosafrole, safrole, piperonal, benzyl cyanide, chlorephedrine, thionyl chloride, and N-methyl derivatives of ephedrine.
- Secrets of Methamphetamine Manufacture Eighth Edition
- This section of the law states that anyone wishing to purchase these chemicals must obtain a permit.
- Anyone wishing to obtain such a permit must submit two sets of his ten fingerprints to the authorities.
- A third, and less restricted, class of chemicals deals mainly with meth and PCP. The chemicals of interest here are: sodium and potassium cyanide, bromobenzene, magnesium turnings (the last two also have PCP implications), mercuric chloride, sodium metal, palladium black, and acetic anhydride. For this class of chemicals. the law requires presentation of proper !D (i.e., state-issued photo !D) and calls for the seller to record said !D. The obvious ways around this section of the law are to do business in less nosy states, or to obtain false identification.
- Clandestine operators also keep in mind that the law allows the central scrutinizers to add chemicals to the lists without warning or approval. So the new precursors mentioned in this book could go on the lists of restricted chemicals at any time.
- Waste Exchanges
- A really great source of chemicals which has appeared in recent years is the surplus market. This market has arisen because of increasingly stringent environmental laws which prohibit the haphazard dumping of surplus chemicals. To avoid having to pay exorbitant fees to hazardous waste disposal companies. universities and firms list their surpluses with waste exchanges who act as matchmakers to pair one firm's waste with another firm's need. This second-hand market seems to be, at the time of this writing, completely un policed and full of eager sellers. It looks like all one needs to do is get some fake company letterhead printed up, send it to the waste exchanges and ask to get on their mailing list. The desired chemicals listed can then be obtained, usually at no charge other than shipping.
- The United States Environmental Protection Agency has released a new publication entitled. Review of Industrial Waste Exchanges. Copies are available, free of charge, from the RCRA Hotline. Call 800-424¬9346 or TDD (hearing impaired) 800-412-7672 and request publication number EPA-53-K-94-003.
- There is some information which is contained in the Chemical Diversion and Trafficking Act (21 CFR part 1300 onward) that is essential for those who are interested in the chemicals which are required for many of the processes outlined in this book. The government has listed many precursor and essential chemicals, and provided threshold amounts for them. Any transactions which equal or exceed these threshold amounts must, by law, be reported. This list was established 411/98, and will never get smaller. It can only grow larger, as the feds become aware of additional chemicals that can be used for drug syntheses. A careful reading of the Chemical Diversion and Trafficking Act would be a wise course of action for those who wish to acquaint themselves with the subject matter at hand.
- Listed Precursor Chemicals:
- Anthranilic acid and its salts (30 kg)
- Benzyl cyanide (I kg)
- 1. Ergonovine and its salts (10 gr)
- 2. Ergotamine and its salts (20 gr)
- 3. N-Acetylanthranilic acid and its salts (40 kg)
- Norpseudoephedrine, its salts, optical isomers, and salts of optical isomers (2.5 kg)
- 1. Phenylacetic acid, its esters (like ethylphenylacetate!) and its salts (1 kilo)
- 2. Phenylpropanolamine, its salts, optical isomers, and salts of optical isomers (2.5 kg)
- 3. Piperidine and its salts (500 gr)
- 4. Pseudoephedrine, its salts, optical isomers, and salts of optical isomers (all sales!)
- II. 3, 4-Methylenedioxyphenyl-2-propanone (4 kg)
- Secrets ofMethamphetamine Manufacture
- Eighth Edition
- The most low-profile method of obtaining chemicals is to make a run to the hardware store or grocery store, and subvert the common place items found there to our needs. Solvents such as tol uene, xylene, acetone or naptha, or even Coleman camper fuel are easily obtained and work very well for making meth. Toluene is getting harder to find on hardware store shelves because it is so useful, but xylene is still universally available and it substitutes well for toluene. Similarly, Liquid Fire drain opener substitutes well for concentrated sulfuric acid, and hardware store muriatic acid is almost as good as lab grade hydrochloric acid. Lithium batteries are a good source of lithium metal. The ephedrine or pseudoephedrine so widely used for making meth is easy to get in the form of Sudafed pills or the ephedrine "bronchodilator" pills sold in gas stations.
- Internet sites catering to hobbyists are another wonderful source of useful chemicals. I'm not talking about lab supply companies here, as even the smallest of them may have been bludgeoned into "cooperation". Rather, I'm referring to sites such as soap making hobby shops which can be a good source of potassium hydroxide. This cousin of lye is used to make soft soaps, and is VERY useful in breaking up the polymers which infest the present day sudafed and ephedrine pills.
- The more one can stock and operate a meth lab with ordinary materials, the more clandestine it will be. Care, however, should be taken in disposing the empty containers of these household items. Search warrants can be obtained if the heat examines the trash ofa suspect and finds empty
- Sudafed boxes, the remains of disassembled lithium batteries, or solvent cans. Materials discreetly tossed into a dumpster are not traceable to clandestine chemists.
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- Now tum the heat back on a little hotter than when ret1uxing the reaction mixture. Water t10w to the condenser is resumed. The mixture soon begins boiling again and the vapors condense in the condenser and t10w to the collecting round bottom t1ask. What is being boiled off is a mixture of pyridine and acetic anhydride. The phenylacetone remains behind in the distilling round bottom flask, because its boiling point is about 100 degrees Celsius higher than the pyridine and acetic anhydride. This process is called simple distillation. Distillation continues until 1300 ml has been collected in the collecting round bottom flask, then the heat is turned off. The 1300 ml is poured into a clean dry glass jug about one gallon in size which is then stoppered with a cork. Later in this chapter, I will describe a process by which this pyridine is recycled for future use. Since pyridine is so expensive, this cuts production costs considerably.
- What is left in the distilling round bottom tlask is a mixture of phenylacetone, some acetic anhydride
- and pyridine, and a high-molecular-weight tarry polymer which is reddish-brown in color. The next step
- is to isolate and purify the phenylacetone.
- The flask is taken out of the hot oil and allowed to cool down. Three-quarters of a gallon of 10% sodium hydroxide solution (NaOH) is needed. So a gallon-size glass jug is filled three-quarters full of cold water and about 10 ounces of sodium hydroxide pellets are added to it. A good quality lye, such as Red Devil or Hi-Test. is a substitute that saves a good deal of money and works tine. Eye protection is always worn when mixing this up. It is mixed thoroughly by swirling, or by stirring with a clean, wooden stick. The dissolution of NaOH in water produces a great deal of heat. It is allowed to cool off before the chemist proceeds.
- About 500 ml of the 10% NaOH is put in a 1000 ml sep funnel, then the crude phenylacetone mixture from the round bottom flask is poured in the sep funnel also. The top of the sep funnel is stoppered and mixed by swirling. When the funnel gets hot, it is allowed to set for a while. Then the mixing is continued, with the underground chemist working his way up to shaking the sep funnel, with his linger holding in the stopper. What he is doing is removing and destroying the acetic anhydride. Acetic anhydride reacts with the sodium hydroxide solution to produce sodium acetate, which stays dissolved in the water, never to be seen again. Some of the pyridine and red-colored tar also goes into the water. The destruction of the acetic anhydride is what produces the heat.
- Arter it has cooled down, about 100 ml of toluene is added to the sep funnel and shaken vigorously for about 15 seconds. The sep funnel is unstoppered and allowed to sit in an upright position for about one minute. The liquid in the funnel will now have separated into two layers. On top is a mixture of toluene, phenyl acetone, and red tar. On the bottom is the water layer, which has some phenyl acetone in it. Pyridine is in both layers.
- Two 500 ml Erlenmeyer flasks are placed on the table, one marked "A," the other marked "B." The stop cock on the sep funnel is opened, and the water layer is drained into B. The top layer is poured into
- A. B is poured back into the sep funnel, and 50 ml of benzene is added. The funnel is shaken for 15 seconds, then the water layer is drained back into B. The top layer is poured into A. The purpose of this is to get the phenylacetone out of the water. Once again the water in B is put in the sep funnel. Fitiy ml of toluene is added. and shaken. Xylene is for almost all purposes substitutable for touene, and is at present easier to get at the hardware store. The water is drained into B and the toluene layer poured into A. The water in B is poured down the drain and the contents of A put into the sep funnel along with 400 ml of
- 10'10 NaOH solution trom the jug. After shaking, the water layer is drained into B and the toluene layer poured into A. The contents of B are put back in the sep funnel and 50 ml of toluene added. After shaking, the chemist drains the water layer into B and pours it down the drain. The contents of A are added to the funnel again. along with 400 ml of 10% NaOH solution; the funnel is shaken again. The water layer is drained into B and the toluene layer poured into A. The contents of B are returned to the sop funnel, along with 50 ml
- Chapter Three Preparation of Phenylacetone
- distillation is continued until 750 ml of pyridine has been collected. Sometimes it does not keep well, but so long as it is used to make another batch of phenylacetone within a few hours after it is made, this pyridine works just as well as new pyridine.
- Now let's talk about the Russian recipe, and how [ messed it up when [ was a neophyte cooker 20 years ago, and the right way to do it. The Russian recipe, which dates to about 1940 during the height of Stalin's wackiness when all sorts of politically motivated "science" was turned out by people fearing losing their lives if they didn't get the "politically correct" results, calls for mixing 420 grams of phenylacetic acid with 700 ml of acetic anhydride and 210 grams of sodium acetate in a 2000 ml flask. Two advantages are obvious here. The expensive reagent pyridine has been replaced with the cheap chemical sodium acetate. Also, the reaction is being done considerably more concentrated than with the pyridine recipe, i.e., more phenylacetic acid is getting poured into the 2000 ml flask, so more phenylacetone will be produced at a single cooking session.
- Back in, J think it was 1979, J tried this recipe using a standard round bottom flask, which I just set upon a magnetic stirrer hot plate, and began to cook. Just setting a round bottom flask on a hot plate surface is a poor way to heat this flask. J had to tum the heat up to maximum just to get it to start to boil. Shortly thereatter, the magnetic stirrer motor burned out from all the heat from the hot plate, and the sodium acetate just sat at the bottom of the flask with the weak boiling I was making. At the end of the 18 hours of prescribed cooking, I got maybe a 20% yield of product, and was soured on this method for 20 years.
- Now for the right way to do this reaction, first of all an oilbath or heating mantle should be used to heat the reaction flask, because a weak and puny boil isn't sufficient. The reaction mixture must reach 145-1500 C. Acetic anhydride boils at 1390 C, but with the higher boiling phenylacetic acid mixed into the solution, and similarly high boiling point phenyl acetone being produced, it's not too hard to make the solution reach this temperature if it is being boiled good and hard. With a good hard boil like that, just one condenser isn't enough. One must use a three-necked flask, and attach a condenser on two of the necks, and plug the third neck with a glass stopper, as shown in Figure 16:
- Figure 16
- No stirrer is really necessary with this reaction, as the strong boil will lift sodium acetate off the bottom of the flask, and mix it with the solution. Three-necked flasks are a bitch to get these days, but stainless steel is fine for this reaction, as is a Teflon-coated metal replica. As an added bonus, using metal replicas makes it impossible to bust one for having glassware for the purpose of making meth, a 10 year felony under the Meth Act of 1996. Drying tubes should be attached to the tops of the condensers, as in the example using pyridine.
- Heat the oil to about 1600 C or so to get a good boiling inside the flask, and let cook for 18 hours. At the end of the cook, allow the flask to cool, then pour the reaction mixture into a gallon of cold water.
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- Phenylacetone will float on top of the water, and the acetic anhydride and sodium acetate will stay in the water.
- Using a sep funnel, separate off the phenyl acetone from the water, and pour it into a convenient container. Now extract the water layer with two 200 ml portions of toluene, and add these extracts to the phenylacetone. The water can now be thrown away. The combined phenyl acetone and toluene extracts should next be poured into a large sep funnel, and washed two times with 500 ml portions of 5% sodium hydroxide or lye solution in water. This will destroy any acetic anhydride left floating around.
- The toluene solution containing the phenyl acetone is poured into a beaker, and allowed to sit for a few hours. Some water will fall out of the solution, and sit on the bottom of the beaker.
- Next, the toluene solution containing the phenylacetone is poured into a distilling flask, and a distillation is done, just like in the recipe using pyridine. First the toluene-water azeotrope distills; drying the mixture, then pure toluene distills. The toluene can be reused. When the toluene has distilled, the mixture is allowed to cool some before commencing vacuum distillation of the phenylacetone. The Russians would have you believe that about 400 ml of phenyl acetone will result from the cook. I have been told by people in a position to know that 300-350 ml is more likely. Not a bad day's work, by any means.
- An alternative procedure for making phenyl acetone from phenylacetic acid can be found in The Journal of the Society o/,Chemical Industry, Volume 44, pages 109-112 (1925) and in the Journal oj'the Chemical Society, Volume 59, pages 621 -629 (1891). In this method, the calcium salts of phenylacetic acid and acetic acid are mixed together and then heated. The product we want, phenylacetone, distills out of the reaction mixture. The advantage to this method is that acetic anhydride and pyridine don't need to be obtained. They are replaced with the very cheap and easily available chemical calcium hydroxide. Phenylacetic acid still is required in this method, and as a List One chemical, it should never be purchased. See Advanced Techniques of Clandestine Psychedelic & Amphetamine Manufacture
- To do the reaction, first one must make the calcium salt of phenylacetic acid. To do this, put 500 grams of phenylacetic acid into a glass container. Add about two quarts of a 50-50 mixture of denatured alcohol and water. This is the reaction solvent. Stir and warm the mixture using a hot water batch until all the phenylacetic acid has dissolved producing a clear water-like solution. Now to this solution, add 135 grams of finely powdered calcium hydroxide. It should be added slowly with strong stirring of the solution. Heat will be produced by the reaction to make calcium phenylacetate, so take care that the mixture doesn't boil during the addition.
- Once all the calcium hydroxide has been added, continue stirring for an additional hour, and allow the mixture to cool. A white-colored precipitate of calcium phenylacetate will have been formed. This product should be filtered out, rinsed with some water, then spread out to dry on wax paper or clean dishes.
- The next thing one needs is a reaction vessel to produce phenyl acetone from the calcium phenylacetate. Luck is on our side here. It has been found that iron and steel reaction vessels are superior to glass when doing this reaction. They don't need to be coated on the inside with any protective paint. I would avoid the use of galvanized steel because the zinc metal coating may interfere with the reaction. The reason why an iron reaction pot is superior is because it conducts heat so well. The top of the reaction vessel gets almost as hot as the bottom. [n this way, the phenylacetone formed and boiled out of the reaction mixture doesn't condense on a cold top of the pot and drip back into the reaction mixture. At that point a lot of it would be destroyed. Now go to your metal workshop and construct a reaction pot that looks pretty much like the one shown in Figure 17.
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- The glassware is set up as shown in Figure 18. The 40% methylamine is in a 1000 ml round bottom tlask attached to a long condenser. [n the top of this condenser is a one-hole stopper. A bent piece of glass tubing is pushed all the way through this stopper so that the end of the piece of tubing extends about one or two millimeters below the bottom of the stopper. This bent piece of tubing then extends down through the center of the other condenser into the flask containing the formic acid. It should extend below the surface of the formic acid and end about one centimeter above the bottom of the flask containing the formic acid. The idea here is simple. The 40% methylamine is heated causing methylamine gas to be boiled out along with some water vapor. These gases then travel up the condenser where the water is condensed out, allowing nearly pure methylamine gas to be forced by pressure through the glass tubing into the formic acid.
- The bent tubing has to be bent by the chemist himself from a 3-foot-long piece of glass tubing. Its outer diameter should be about V. inch. The glassware is set up as shown in Figure 18 and he decides about where the tubing should be bent. If necessary, he will consult the chapter on bending glass in an Organic Chemistry lab manual. With a little practice, it is easy. A good source of flame to sollen up the glass is a propane torch with the tlame spreader attachment. After it is bent, he will blow through the tubing to make sure he did not melt it shut.
- He is now ready to proceed. All pieces of glassware are clean and dry. Into the round bottom 1000 ml Ilask sitting on the heat source is placed 500 grams (about 500 ml) of 40% methylamine in water, along with 3 or 4 boiling chips. Into the other 1000 ml round bottom tlask is placed 250 ml of 88% formic acid. Water flow is begun through the longer condenser. It is advantageous to use ice cold water in this condenser, because it will then do a better job of removing water vapor from the methylamine. A good way to get ice cold water for the condenser is to get a couple of 5-gallon pails. One of them is filled with ice cubes no bigger than a fist and topped off with water.
- Then the section of plastic tubing that runs to the lower water inlet of the condenser is placed in the pail. Its end is weighted to keep it on the hottom of the pail. This pail is placed on the table along with the glassware. The other pail is placed on the floor and the plastic tubing from the upper water exit of the condenser is run to this pail. By sucking on the end of the water exit tubing, the ice cold water can be siphoned from the pail on the table, through the condenser, to the pail on the floor. The rate of water flow can be regulated to about one gaJlon per minute by putting a clamp on the tubing to slow its flow. When the pail on the table is about empty, the water that has flowed to the pail on the floor is returned to the table.
- The heat on the methylamine is turned on to about V. maximum. Soon the methylamine begins boiling out and moving through the tubing into the formic acid. The underground chemist checks for gas leaks in the system by sniffing for the smeJl of escaping methylamine. If such a leak is detected, the joint it is escaping from is tightened up.
- The methylamine bubbling into the formic acid produces a cloud of white gas inside the flask containing the formic acid. It makes its way up to the condenser, and then returns to the flask as a liquid. For this condenser, tap water flow is fine. The rate of methylamine boiling is adj usted so that the white gas does not escape out the top of the condenser. As more methylamine is boiled out, a higher heat setting is required to maintain the same rate of methylamine flow.
- In this process, the formic acid gets very hot. [t must get hot to produce good yields of N¬methylformamide. It sometimes gets hot enough to boil a little bit (105° C), but this is no problem. As the chemist continues bubbling methylamine into the formic acid, its volume increases until it is double its starting volume, about 500 ml. At about this time, the cloud of white gas thins and then disappears. This white gas is formed by the fumes of formic acid reacting with methylamine above the surface of the liquid formic acid. It disappears because there is no longer much fornlic acid left. The chemist now begins checking to see if the reaction is complete. He puJls out one of the stoppers from the 3-necked
- Chapter Four Preparation of N-Methylformamide
- flask that contains the N-methylformamide and sniffs the escaping fumes for the odor of methylamine. He does this periodically until he smells methylamine. Once he smells it, he turns off the heat on the methylamine. When the methylamine stops bubbling into the N-methylformamide, he immediately lowers the level of the 3-necked flask so that the bent glass tubing is above the surface of the N¬methylformamide. This is done because, as the methylamine cools, it will contract and create a vacuum which would suck the N-methylformamide over into the other flask in a flash, ruining his work.
- Both flasks are allowed to cool down. The methylamine is almost gone, so it can be poured down the drain. The next step is to fractionally distill the N-methylformamide. The glass-packed c1aisen adapter is used as the fractionating column. The glassware is set up as shown in Figure 13, back in Chapter Three. The distilling flask is a 1000 ml round bottom flask with 5 boiling chips in it. The collecting flask is a 250 011 round bottom flask. Unlike the distillation of phenyl acetone, in this case the distillation is done under a vacuum from the beginning. The ice water siphoning system is used for the condenser, because N-methylformamide has a very high latent heat of vaporization, and, without this precaution, it may collect very hot in the collecting flask.
- The underground chemist is now ready to distill the N-methylformamide. All of the crude product is put in the 1000 ml round bottom flask filling it about half ful!. The vacuum is applied at full strength, and the heat source is turned on to 113 to Y, maximum. The water in the mixture begins distilling. The temperature shown on the thermometer will show a steady climb during the process.
- In a while, the temperature rises high enough that the chemist can begin collecting the distilled liquid as suspected N-methylformamide. If he is using an aspirator, he begins collecting in a clean, dry 250 ml round bottom flask when the temperature reaches 95-100° C. If he is using a good vacuum pump, he begins saving the distilled material at about 85° C. As the N-methylformamide distills, the temperature rises a little bit above the temperature at which he first began collecting the N-methylformamide, then holds steady. This temperature is noted. Distilling is continued until he has collected 100 m!. Then the heat is turned off. When the boiling stops, the vacuum hose is disconnected from the glassware.
- During the distillation process, a fair amount of methylamine was lost, leaving the N-methylformamide with too much formic acid. The next step is to correct this problem.
- The 100 ml of N-methylformamide that has been distilled is poured back in the distilling flask with the undistilled materia!' The distilled material is clear, while the undistilled material has turned yellow from the heat of distilling. The glassware is set up again as shown in Figure 18. This time, the round bottom llask holding the methylamine is a 500 ml flask. It has 100 ml of fresh 40% methylamine in water in it. The bent glass tubing leads into the flask containing the N-methylformamide. This flask does not need to have a condenser on it.
- The heat is turned on the methylamine and the Ilow of ice water through its condenser is begun. Soon the methylamine gas is bubbling into the N-methylformamide, reacting with the excess formic acid in it. Within about 10 seconds, the odor of methylamine can be detected above the N-methylformamide. The heat is turned oft and when the bubbling stops, the level of the N-methylformamide is lowered so that it is not sucked into the other flask. Once the methylamine has cooled off, it can be poured back in with the good methylamine, because it is not exhausted. Once a bottle of methylamine has been opened, it should be reclosed tightly and the cap sealed with vinyl electrical tape in order to hold in the methylamine gas.
- Now the N-methylformamide is to be distilled again. The glassware is set up again for fractional distillation as shown in Figure 13. The distilling flask is a 500 ml round bottom flask, while the collecting flask is 250 m!. All pieces are clean and dry.
- The N-methylformamide is placed inside the distilling Ilask with 5 boiling chips. (Fresh chips are used every time.) The vacuum is reapplied and the heat is turned on again to 1/3 to y, maximum. A little bit of water is again distilled. The temperature shown on the thermometer climbs as before. When it reaches a temperature r C below the temperature at which it leveled off the first time around, the chemist begins
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- collecting in a clean dry 250 ml flask. The distilling continues until it has almost all distilled over. About 10 or 15 ml is left in the distilling flask. If he is using an aspirator, the chemist makes sure that no water is backing into the product from the vacuum line. The yield is about 250 ml N-methylformamide. Ifhe gets a little more, it won't all fit in the 250 ml collecting flask. If that happens, he pours what has collected into a clean dry Erlenmeyer flask and continues distilling. N-methylformamide is a clear liquid with no odor.
- The N-methylformamide the underground chemist has just made is perfect for the Leuckardt-Wallach reaction. Because he began collecting it 7 degrees below the leveling off temperature, it contains a mixture of N-methylformamide, formic acid and methylamine. To get good results, he uses it within a few hours after distilling it.
- There are other variations on this procedure. A lot of methylamine was lost during the distillation of the mixture. Much of this could be prevented if the reaction mixture between the formic acid and the methylamine was forced to completion. If one has a large stainless steel pipe, the initial reaction mixture could be heated under pressure at about 140 C for an hour or so to make the reaction to N¬methylformamide go further before distilling the mixture.
- References
- Journal of the American Chemical Society, Volume 53, page 1879 (1931).
- I explained the general theory behind this reaction in Chapter Two. Now, after doing the reactions described in the previous two chapters, the underground chemist has phenylacetone and N¬methylformamide suitable for making methamphetamine. He will want to get going before the chemicals get stale.
- The tirst thing he does is test the chemicals. He puts 5 ml of phenyl acetone and 10 ml of N¬methylformamide in a clean dry test tube or similar small glass container. Within a few seconds they should mix together entirely. At this point, he may offer a prayer to the chemical god, praising his limitless chemical power and asking that some of this power be allowed to flow through him, the god's High Priest. He may also ask to be delivered from the red tar that can be the result of this reaction. If they do not mix, there is water in the N-methylformamide. In this case, he must distill it again, being more careful this time.
- Having tested the chemicals, he is ready to proceed with the batch. (However, if the underground chemist was reckless enough to obtain N-methylformamide ready made, he will have to distill it under a vacuum before it can be used in this reaction.) The phenyl acetone he made (about 100 ml) is mixed with the N-methyIformamide. The best amount of N-methylformamide to use is about 250 ml, but any amount from 200 to 300 ml will work tine. With 200 ml of N-methylformamide, there are about four molecules of N-methylformamide to one of phenyl acetone. This is the bare minimum. With 300 m!. the ratio is nearly six to one. Any more than this is a waste ofN-methylformamide. The best flask for mixing them is a 500 ml round bottom flask. Alier they are mixed, this flask is set up as shown in Figure 19. The tlask is sitting in an oil bath, to supply even heating to the flask. The oil (once again, Wesson is a good choice) should extend about 2/3 of the way up the side of the flask. A metal bowl makes a good container for this oil bath. This is better than a pan, because it will be important to see into the flask. The fact that the oil will expand when heated is kept in mind when filling the bowl with oil. A thermometer is also needed in the oil bath to follow its temperature.
- Figure 19
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- The test material is added to the flask. The heat source to the flask is turned on. A low heat setting is used so that the rise in temperature can be closely controlled. The thermometer used in the distillations is placed (clean and dry) inside the flask.
- The rise in temperature of both the oil bath and the flask is monitored. The contents of the Ilask are stirred regularly with the thermometer. The temperature of the oil bath is brought to 100° C over the course of about 45 minutes. Once it reaches this level, the heat is turned back down a little bit to stabilize it in this area. The chemist must closely control every degree of temperature increase from here on. The temperature of the contents of the flask is worked up to 105° C. The contents of the flask are stirred every 15 minutes. At about 105° C, the reaction kicks in, although sometimes the heat must go as high as 1 10° C before it starts. When the reaction starts, the contents of the flask begin to bubble, sort of like beer, except that a head does not develop. A trick to get this reaction going at a nice low temperature is to gently scrape the thermometer along the bottom of the flask. Although I have never had the sophisticated equipment to prove it, it is a pet theory of mine that this is because ultrasonic waves are generated, producing a condition of resonance with the reactants that causes the reaction to start.
- The chemist wants to keep the temperature down at the same level at which the reaction first kicked in for as long as the reaction will continue at that level. Generally, it can go for a couple of hours at this level before the reaction dies down and an increase in temperature is necessary. The reaction mixture has the same color as beer and gently bubbles. The bubbles rise up from the bottom of the flask, come to the surface, and then head for where the thermometer breaks the surface. Here they collect to form bubbles about 1 centimeter in size before they break. This may look like boiling, but it is not. Everything inside the flask has a much higher boiling point than the temperatures being used. These are actually bubbles of carbon dioxide gas being formed as byproducts of the reaction. The chemist can tell how well the reaction is going by the amount of bubbling going on.
- When the rate of bubbling slows down to almost stopping, it is time to raise the temperature. It should only be raised about 3° C. This requires turning up the heat only slightly. The highest yield of product is obtained when the lowest possible temperature is used. For the duration of the reaction, the contents of the flask are stirred with the thermometer every half hour.
- And so the reaction is continued. As the reaction dies down at one temperature setting, the temperature is raised a few degrees to get it going again. It will be able to stay in the 120° to 1300 C range for a long time. The reaction has a lot of staying power in this range. Finally, after 24 to 36 hours, 1400 or 1450 C is reached. The reaction stops. The chemist takes his time working up to this temperature because the amount and quality of the product depends on it.
- Once 140° to 1450 C is reached and the reaction stops, the heat is turned olT and the contents allowed to cool down. It should still look like beer. A reddish tint means that his prayer failed and he was not delivered from the tar. Even so, there's still lots of good product in it.
- While it is cooling down, the underground chemist gets ready for the next step in the process. He is going to recover the unused methylamine for use in the next batch. This cuts his consumption of methylamine to about half of what it would be without this technique. What he is going to do is react the unused N-methylformamide with a strong solution of sodium hydroxide. The N-methylformamide is hydrolyzed to form methylamine gas and the sodium salt of formic acid (sodium formate). In chemical writing, this reaction is as follows:
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- reacting with hydrochloric acid to produce methamphetamine hydrochloride and formic acid. This is a hydrolysis reaction.
- After the two hours have passed, the heat to the flask is turned off. While the flask is cooling down, 80 grams of sodium hydroxide and 250 ml of water are mixed in a 1000 ml round bottom tlask. Once again. n good quality lye is acceptable. If the 35% laboratory grade of hydrochloric acid was used in the last step, then 100 grams of sodium hydroxide is mixed with 300 ml of water.
- When both flasks have cooled down, the black reaction mixture is cautiously added to the sodium hydroxide solution. It is added in small portions. and then swirled around to mix it. They react together quite violently. The reaction here is sodium hydroxide reacting with hydrochloric acid to produce table salt, with formic acid to produce sodium formate, and with methamphetamine hydrochloride to produce methamphetamine tree base. When the sodium hydroxide solution gets very hot, the chemist stops adding the reaction mixture to it until it cools down again.
- After all the black reaction mixture has been added to the sodium hydroxide solution, there is a brown liquid layer floating above the sodium hydroxide solution. This brown layer is methamphetamine free base. It also has a good deal of unreacted methamphetamine hydrochloride dissolved in it. This latter has to be neutralized because it will not distill in its present form. The 1000 ml flask is stoppered and shaken vigorously for 5 minutes. This gets the methamphetamine hydrochloride into contact with the sodium hydroxide so it can react.
- The bottom of the Ilask is full of salt clystals that cannot dissolve in the water because the water is already holding all the salt it can. The chemist adds 100 ml of water to the flask and swirls it around for a few minutes. If that does not dissolve it all, he adds another 100 ml of water.
- After the tlask has cooled down, it is poured into a 1000 ml sep lunnel, and 100 ml of toluene is added.
- The sep funnel is stoppered and shaken for 15 seconds. It is allowed to stand for a couple of minutes, then the lower water layer is drained into a glass container. The brown methamphetamine-toluene layer is poured into a clean. dry 50n ml round bottom flask. The water layer is extracted once more with 100 ml toluene, then thrown away. The toluene layer is poured into the 500 ml flask along with the rest of the methamphetamine.
- The chemist is now ready to distill the methamphetamine. He adds three boiling chips to thc 500 ml round bottom flask and sets up the glassware for fractional distillation as shown in Figure 13. The 500 ml flask sits directly on the heat source. The glass-packed claisen adapter is the proper fractionating column. The collecting flask is a 250 ml round bottom flask. Tap water is used in the condenser.
- The heat source is turned on to V. to 1/3 maximum. Soon the mixture begins boiling. The tirst thing that distills is toluene-water azeotrope at 85° C. Then pure toluene comes over at 110° C. Once again. as in the distillation of phenyl acetone. foaming can sometimes be a problem. In that case, it is dealt with in the same way as described in Chapter Three.
- When the temperature reaches I 15° C. or the rate of toluene collecting slows to a crawl, the heat is
- turned off and the flask allowed to cool down. The collected toluene is poured into a bottle. It can be
- used again the next time this process is done. The same 250 ml flask is put on the collecting side.
- The distilling flask is now cool, so vacuum is applied to the glassware at lull strength. The last remnants of toluene begin to boil, and the heat is turned back on to 1/3 maximum. The temperature begins to climb. Ifan aspirator is being used, when the temperature reaches 80° C, the chemist quickly removes the vacuum hose and replaces the 250 ml flask with a clean dry one. If he is using a good vacuum pump, he makes this change at about 70° C. The flask change is done quickly to avoid overheating in the distilling flask.
- Chapter Five
- Making Methamphetamine
- The methamphetamine distills over. With an aspirator, the chemist collects from 800 C to about 1400 or 1500 C, depending on how strong the vacuum is. With a vacuum pump, he collects to about 1200 or 1300 C. Once it has distilled, the heat is turned off and the vacuum hose disconnected.
- The product is about 90 ml of clear to pale yellow methamphetamine. If the chemist is feeling tired now, he may take out a drop on a glass rod and lick it off. It tastes truly awful and has a distinctive odor, somewhat biting to the nostrils.
- He is now ready to make his liquid methamphetamine free base into crystalline methamphetamine hydrochloride. Half of the product is put into each of two clean, dry 500 ml Erlenmeyer flasks.
- The chemist now has a choice to make. He can use either toluene or ethyl ether as the solvent to make the crystals in. Toluene is cheaper, and less of it is needed because it evaporates more slowly during the filtering process. Ether is more expensive, and flammable. But since it evaporates more quickly, the crystals are easier to dry off. If ether is used, it is anhydrous (contains no water).
- A third choice is also possible for use as a crystallization solvent. This is mineral spirits available from hardware stores in the paint department. Mineral spirits are roughly equivalent to the petroleum ether or ligroin commonly seen in chern labs. Those brands which boast of low odor are the best choice, such as Coleman camper fuel. Before using this material it is best to fractionally distill it, and collect the lowest boiling point half of the product. This speeds crystal drying. Since the choice of mineral spirits or naptha eliminates ether from the supply loop, the clandestine operator may well go this route. Toluene is also a very acceptable solvent.
- With the solvent of his choice, the chemist rinses the insides of the condenser, vacuum adapter and 250 ml flask to get out the methamphetamine clinging to the glass. This rinse is poured in with the product. Solvent is added to each of the Erlenmeyer flasks until the volume of liquid is 300 ml. They are mixed by swirling.
- 125 ml .v'Sep funnel
- Glass
- {tubing
- ,*,1 hole stopper
- s.t InC! hydJrxHoricte eel no. Plllle by Iddin; He1 to selt If'Id ming. The ....f.c. mo.Jd be rOl4'l WId • good I'U'I'Iber of holes ahoIJd be poked no the peate for k:IrNo1iumQ generltion of He1 .
- Figure 20
- A source of anhydrous hydrogen chloride gas is now needed. The chemist will generate his own. The glassware is set up as in Figure 20. He will have to bend another piece of glass tubing to the shape shown. It should start out about 18-inches long. One end of it should be pushed through a one-hole stopper. A 125 ml sep funnel is the best size. The stoppers and joints must be tight, since pressure must develop inside this flask to force the hydrogen chloride gas out through the tubing as it is generated.
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- Into the 1000 ml three-necked flask is placed 200 grams of table salt. Then 35% concentrated hydrochloric acid is added to this flask until it reaches the level shown in the figure. The hydrochloric acid must be of laboratory grade.
- Some concentrated sulfuric acid (96-98%) is put into the sep funnel and the spigot turned so that I ml of concentrated sulfuric acid flows into the flask. It dehydrates the hydrochloric acid and produces hydrogen chloride gas, and also goes on to make more HCL from reaction with table salt. This gas is then forced by pressure through the glass tubing.
- One of the Erlenmeyer flasks containing methamphetamine in solvent is placed so that the glass tubing extends into the methamphetamine, almost reaching the bottom of the flask. Driping in more sulfuric acid as needed keeps the flow of gas going to the methamphetamine. If the flow of gas is not maintained, the methamphetamine may solidity inside the glass tubing, plugging it up.
- An even more distressing phenomenon can occur when using hardware store sulfuric acid. This material is not quite as concentrated as lab grade sulfuric acid, and the initial "push" of HCI gas in the flask can turn into a "pull". This vacuum will suck your product up the tubing and into the HCL generating flask. You can imagine how that really sucks! Hah, Hah!
- When using lower grade sulfuric acid, one needs to watch carefully, or use a closely related procedure.
- In this procedure, the HCL generating flask is filled 1/4 full of hardware store sulfuric acid and the sep funnel is filled with muratic acid. By dripping the muriatic acid into the sulfuric acid, the HCI solution (muriatic) is dehydrated to dry HCI gas, and the gas is pushed out the flask and tubing.!t is advisable to do a dry run first without product at risk when using hardware store acids in this procedure to avoid heart breaking losses.
- Another popular clandestine method using lower grade sulfuric acid is to put the salt in a mason jar, and punch two holes in the lid. Plastic tubing is attached to both holes. One line of tubing goes into the solution of free base meth in solvent. The other line of tubing is run to an aquarium pump or other source of aiL The low grade sulfuric acid is then added to the mason jar, and the air blower is started to slowly keep the fumes of dry HCI flowing into the meth free base rather than ever being sucked backwards.
- Within a minute of bubbling, white crystals begin to appear in the solution. More and more of them appear as the process continues. It is an awe-inspiring sight. In a few minutes, the solution becomes as thick as watery oatmeal.
- FIt/Mre l1
- It is now time to filter out the crystals, which is a two-man job. The flask with the crystals in it is removed from the HCl source and temporarily set aside. The three-necked flask is swirled a little to spread around the sulfuric acid and then the other Erlenmeyer flask is subjected to a bubbling with HC!. While this flask is being bubbled, the crystals already in the other flask are filtered out.
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- soaked in ether or toluene and filtered. If this doesn't cure the problem, cutting the material to 50% purity should take care of it. Crystals Are Sticky. Here the crystals seem covered by a thin layer of oily material, causing them to stick to razor blades, etc. The problem is dealt with in the same way as melting crystals.
- Crystals Fail to Form. This problem occurs during the process of bubbling Hel into the methamphetamine. Instead of forming crystals, an oil settles to the bottom of the flask. This is generally caused by incomplete hydrolysis of the formyl amide. Perhaps it didn't mix with the hydrochloric acid. It is put in a flask and the solvent boiled off under a vacuum. Then 200 ml of hydrochloric acid is added and the process is repeated, starting from the hydrolysis of the formyl amide of methamphetamine. The 35% laboratory grade of hydrochloric acid is used.
- In the event of melting or sticky crystals, cutting is first tried on a small sample of the crystals to see if that will solve the problem. If it does not, then a recrystallization must be resorted to. This is done by dissolving the crystals in the smallest amount of warm alcohol that will dissolve them. One hundred ninety proof grain alcohol, 95% denatured alcohol, or absolute alcohol may be used. Then 20 times that volume of ether is added. After vigorous shaking for three minutes, the crystals reappear. If not, more ether is added, followed by more shaking. After being filtered, the crystals should be in good shape.
- A technique which may be used in especially stubborn cases is to dissolve the crystals in dilute hydrochloric acid solution, extract out the oily impurities with toluene, and then isolate the methamphetamine. This is done as follows:
- For every 100 grams of crystal, 200 ml of 10% hydrochloric acid is prepared by mixing 60 ml of35% hydrochloric acid with 140 ml of water. The crystals are dissolved in the acid solution by stirring or shaking in the sep funnel. One hundred ml of toluene is added to the solution in the sep funnel, which is then shaken vigorously for about 2 minutes. The lower layer is drained out into a clean beaker. It contains the methamphetamine. The toluene layer is thrown out. It contains the oil grunge which was polluting the crystals.
- The acid solution is returned to the sep funnel and the acid neutralized by pouring in a solution of 70 grams of sodium hydroxide in 250 ml of water. After it has cooled down, the mixture is shaken for 3 minutes to make sure that all the methamphetamine hydrochloride has been converted to fTee base. Then 100 ml of toluene is added and the mixture shaken again. The lower water layer is drained out and thrown away. The toluene-methamphetamine solution is distilled as described earlier in this chapter. Then, as described earlier in this chapter, dry hydrogen chloride gas is bubbled through it to obtain clean crystals. (Hydrogen chloride gas must be made in a well-ventilated area; otherwise, it will get into the chemist's lungs and do real damage.)
- There is an alternative method for converting amphetamine free base into the crystalline hydrochloride. It is based on the method that South American cocaine manufacturers use to tum coca paste into cocaine hydrochloride. This method does not give the really high-quality crystals that the bubble-through method gives, but its use is justified when really big batches are being handled.
- In this alternative procedure, the free base is dissolved in two or three volumes of acetone. Concentrated hydrochloric acid (37%) is then added to the acetone while stirring until the mixture becomes acid to litmus paper. Indicating pH paper should show a pH of 4 or lower. The hydrochloride is then precipitated from solution by slowly adding ether with stirring. It will take the addition of IO ta 20 volumes of ether to fully precipitate the hydrochloride. Toluene or mineral spirits may be substituted for the ether. Then the crystals are filtered out using a Buchner funnel as described before, and set aside to dry. The filtrate should be tested for completeness of precipitation by adding some more ether to it.
- For really big batches, it would seem that using sulfuric acid to make the crystalline sulfate salt of the amphetamine has its advantages. This is a transcript of a conversation I had with another cooker on the Internet:
- Chapter Five Making Methamphetamine
- That is an interesting recipe, isn't it? I wish I'd have known about it back when I was cooking. Can this European variation using formamide be adapted to use with N-methyl lormamide to make meth instead of benzedrine? Your Uncle would say that the answer is "Yes!"
- Your Uncle suggests this: Go to Chapter Four, describing how to make N-methyl formam ide.
- Methylamine is bubbled into formic acid to make N-methyl formamide. Then it is distilled, and some more methylamine is pumped into the mixture. I would stop right there. Instead of distilling it again, I would just use that mixture. If the mixture smells mildly of methylamine, all the formic acid has been neutralized. I would just mix the phenyl acetone with this mixture, and let it sit for a few days as in the European variation. Then I'd put a hand full of boiling chips in the reaction flask, and heat the mixture just as described in the main body of this chapter, stopping when 1450 C is reached. The NaOH hydrolysis should be used to recover the unused methylamine, then HCI hydrolysis of the formyl amide of meth. just as described in this chapter. Yields should go up, and there should be no upper limit on possible batch sizes.
- The Russian Advance
- A variation upon the standard Leuckardt Reaction method
- IS given in Zhumal Obshchci Khimii Volume 25, pages 1432-7 (1955). This variation claims very high yields and is well wonh checking out by anyone pursuing this reaction method.
- In their method, the general reaction procedure is the same as given earlier in this Chapter. They simply add on two little details. The tirst change they make to the standard reaction method is that they add a little bit of nickel hydrogenation catalyst to the reaction mixture. In their procedure, they add about one per cent by weight of Raney nickel to the N-methylformamide. This form of nickel is discussed in Chapter II , and I'm pretty sure that other forms of nickel catalyst could be substituted for it.
- The simplest nickel catalyst to make is prepared by dissolving a few grams of nickel suitate or nickel chloride in water. Then to that water solution of the nickel one adds sodium borohydride. The sodium borohydride is first dissolved in some water, and slowly, with stirring, the sodium borohydride solution is added to the nickel solution. The nickel solution will tizz during this addition and tum black. The black
- panicles are the nickel catalyst, and when the stirring is stopped they will settle to the bottom of the
- beaker.
- One can check to see if the reaction is complete by stopping the stirring and letting the black panicles settle. If the water solution is still blue (for nickel sulfate) or green (for nickel chloride), then not enough borohydride has yet been added to convert all of the nickel into the active catalyst. The reaction is complete when the black powder settles leaving a clear water solution.
- Next, one cleans this catalyst by decanting off the water from the settled black powder. Then add some alcohol to the beaker and stir. Then let the black powder settle again, and decant off the alcohol. Finally add just enough fresh alcohol to the beaker so that the black powder can be suspended when the mixture is stirred. This is your catalyst, and it contains an amount of nickel which is roughly half the weight of the nickel sulfate or nickel chloride originally used. It should be used immediately, or bottled up and stored in a refrigerator.
- The next point on which these Russians vary from the standard procedure is that they don't just mix the phenyl acetone together with the N-methyl formamide and begin heating. What they like to do is to put the N-methyl formam ide into the flask along with that Iitle bit of nickel catalyst. Then they start to heat this mixture in the oil bath. When it warms up to roughly 90 C, they begin to drip the phenylacetone into the N-methyl formamide. They take about an hour to add all the phenyl acetone to the N-methyl formamide, and while they are adding the phenylaeetone they allow the temperature to slowly rise to about 120C in the reaction mixture.
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- From there on out, the reaction is done exactly the same as the standard method given in this chapter.
- Heating is continued as the reaction bubbles, and the temperature is slowly raised to keep it going. Then the product is obtained from the reaction mixture in exactly the same way as described earlier in this chapter.
- Aluminum salts have been found to be catalytic for this reaction. Adding a bit of aluminum sulfate, or
- just adding a small amount of aluminum foil to the reaction mixture will likely increase the yields.
- References
- Journal o[Organic Chemistry, Volume 14, page 559 (1949).
- Journal of the American Chemical Society, Volume 58, page 1808 (1936):
- Volume 61, page 520 (1939); Volume 63, page 3132 (1941).
- Organic Syntheses, Collective Volume II, page 503.
- Chapter Six Industrial-Scale Production
- Chapter Six Industrial Scale Production
- In the previous five chapters, I described a process by which underground chemists make smaller amounts of methamphetamine, up to about one-half pound of pure methamphetamine. The process takes about three days with two people working in shifts around the clock. Thus, the maximum production level is stuck at one pound per week.
- There is a way to break through this production limit, which is to produce phenylacetone and tum it into methamphetamine by different methods. These methods produce more in less time, and they are cheaper. Two of them, the tube furnace and the hydrogenation bomb, are major engineering proj ects. But they are no problem for those with a Mr. Handyman streak. If constructing a factory for meth production wasn't what you had in mind, you will also find in the next few chapters many methods which use standard labware and which also can potentially produce large amounts of meth fairly quickly.
- However, underground chemists will not move up to industrial-scale production until they are sure that they are going to be able to sell it without having to deal with strangers -unless, of course, they want to get busted.
- One major difference in the logistics of a large-scale operation versus a smaller one is that a different source of chemicals is required. An outlet that specializes in pints and quarts of chemicals is not going to be much help when multi-gallons are needed. Here a factor comes into play which cannot be taken advantage of at lower levels of production. Most chemical suppliers will not deal with individuals, only with corporations and companies.
- Now the underground chemist can tum this situation to his advantage by means of subterfuge. First he develops a false identity. He gets some of the books on false ID and Abracadabra! He's Joe Schmoe. He uses this identity to form several companies. Ifhe wants to be official, he consults the book. How to Form Your Own Corporation/or under 50 Dollars. available in most libraries. Otherwise, he just has some invoice-order forms printed up for his company. He may also open a checking account for his company to pay for chemicals. He uses checks with high numbers on them so that they don't think that he just appeared out of thin air. As an alternative, he may pay with certified checks from the bank.
- The next step is to rent some space as his company headquarters and chemical depot. Indeed, he'll probably rent a couple such depots to house his various companies.
- Now he starts contacting chemical dealers, ordering enough of one or two chemicals to last for a couple of years. Then he contacts another dealer and orders a similar quantity of one or two other chemicals under a different company name. He continues this process until he has everything he needs. He offers to pick them up so that they do not see the dump he's rented as his headquarters. As a precaution, he equips these dumps with a phone and answering machine so that they can call him back. If he doesn't live in a large city, he does business out of town. That way they won't be surprised that they never heard of him. But he does not do business too far away from home base, so they won't wonder why he came so far.
- There is a better strategy to follow in getting the equipment and chemicals needed for clandestine meth production. The best method to use is to first order the equipment and a couple of the most suspicion¬arousing chemicals. Then the underground operator lays low for a while. The narco swine have a habit of going off half-cocked on their search warrants. If the initial purchases caught their eyes, they will likely swoop right in, planning on finding an operating lab, or at least enough to make a conspiracy charge stick. If they move now, the meth meister will not be prosecutable, so long as he does not admit guilt. An alternative narco swine strategy would be for them to initiate intense surveillance upon Joe Schmoe.
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- So long as Joe is not brain dead, this will be pretty obvious after awhile. If surveillance is noticed, il is lime to put Ihe plan into a deep freeze, and consider the inilial purchases a long-Ierm investmenl rather Ihan a quick payoff. If Joe is able to get the most sensitive materials unnoticed, il is Ihen time 10 quickly gel Ihe more mundane items needed and immediately turn to the production end of Ihe operation.
- When it is time for the underground chemist 10 pick up the chemicals, he uses a pickup or van registered in Joe Schmoe's name. As a precaution, he equips his vehicle with a radio scanner. He buys the book, Us. Government Radio Frequencies. and tunes the scanner to pick up the FBI, the DEA, the stale and local police. He picks up the chemicals and returns with them to his headquarters and depot. He lakes a roundabout route 10 make sure he isn't being followed. Two tricks he may use to detect a tail are 10 tum into a dead-end streel and to drive either 100 fast or too slow. He leaves Joe's vehicle at the depot and lakes a roundaboul roule home. He stops at a few bars and leaves by the back exit.
- A very common and quile stale Irick is for the narco swine to place a radio-tracking device in Ihe packing materials surrounding jugs of chemicals purchased by suspecled drug manufacturers. All items purchased should be carefully inspected during Ihe drive away from the point of purchase. If such a device is found, il is cause for clear thinking action, rather than panic. While using such a device, Ihe heat will usually lay quile far back in their pursuil 10 avoid being nOliced. They will rely on the Iransmitter to tell Ihem where you are going. It is best not to smash such a transmitter, but rather keep it in hand, and loss il into the back of another pickup truck at a stoplight. This is then followed by putting the plan into a deep freeze until the heat grows bored with you.
- The next thing the underground chemist needs is a laboratory location. A country location makes any surveillance very obvious and keeps chemical smells out of the way of nosy neighbors. Electricity and running water are absolutely necessary. Now he loads the chemicals onto Joe's wheels and heads for the laboratory in a very roundabout manner, keeping an eye open for any tail and paying close attention to Ihe scanner. He leaves the scanner at the lab for entertainment in the long hours ahead.
- A nice addition to any underground laboratory is a self-destruct device. This consists of a few sticks of dynamite armed with a blasting cap, held inside an easily opened metal can. The purpose of the metal can is 10 prevent small accidental tires from inilialing the self-destruct sequence. If Johnny Law pays an uninvited visit to his lab, the underground chemisl lights the fuse and dives out the window. The resulting blast will shatler all Ihe glass chemical containers and set the chemicals on fire. This fire will destroy all the evidence. He keeps his mouth shut and lets his lying lawyer explain why Ihe blast happened to come al the same time as the raid. He has no reason to fear the state crime lab putting the pieces of his lab back together. These guys learned their chemistry in school and are truly ignorant when it comes to the particulars of a well-designed lab.
- The feds, on the other hand, have a higher grade of chemist working for them, but they are tiny individuals who are haunted by nagging self-doubt, wondering why after obtaining a Ph.D., they are just !aceless cogs in a machine. To compensate for this, they will claim to make great discoveries of the obvious. Case in point is an article published in the Journal a/Forensic Sciences. This is a petty journal published by Johnny Law where the aforementioned tiny individuals can stroke their egos by getting published. In an article covering the lithium in ammonia reduction of ephedrine to meth production melhod featured in Chapter Fifteen of this book, the unnamed tiny, frustrated chemists trumpeted "we found that a nitrogen atmosphere to protect the reaction was unnecessary, contrary 10 the claims of the authors who said it was essential."
- The authors to which they refer here are Gary Small and Arlene Minnella, legitimate scientists who were published in a legitimate scientific journal, the Journal oj OrganiC Chemistry. In their anicle covering the lithium in ammonia reduction of benzyl alcohols, they used really tiny batches that might actually need a nitrogen atmosphere to protect them, and in no place claimed that it was essential. See the
- Journal of¬
- Chapter Six Industrial-Scale Production
- -Organic Chemistry article, cited in Chapter Fifteen of this book. It was obvious that the steady boiling away of liquid ammonia would form its own protective gas blanket when done on a scale corresponding to real meth production.
- They further went on to nitpick the purification procedure used by the real scientists, claiming it was unnecessary. Everyone who reads the journals knows that it is unnecessary. This is just the protocol that has been followed by research scientists for the past god-knows-how-many ages. They just do this so that if they get unexpected results in their research, they will know that it is not due to impurities in the reaction mix. To make a great discovery out of finding that these rigorous purification schemes are not needed for practical production methods just shows how shallow these people are.
- Secrets of Methamphetamine Manufacture Eighth Edition
- Chapter Seven Phenylacetone from B-Keto Esters
- In this chapter, I will cover another method of making phenylacetone. The chemicals must be weighed and measured fairly exactly. This is unlike the method described in Chapter Three, where anything within a ballpark range will work. This method requires a reliable scale.
- This reaction uses sodium metal, which is some nasty stuff. It reacts violently with water to produce sodium hydroxide and hydrogen. It will also react with air. The chemist never touches it intentionally; if he does touch it, he washes it otf with warm water. Sodium metal comes in a can, covered with a bath of petroleum distillate. This is to protect it from water and air. As long as it stays covered, it causes the chemist no problems.
- In this reaction, sodium metal is reacted with absolute alcohol to make sodium ethoxide (NaOCH2CH3). Ethyl acetate and benzyl cyanide are then added to this to produce a beta keto ester. Reaction with acid then produces phenylacetone:
- CH3jJ CH2CH:3
- Ethyl acetate Bonzyl cyanide
- CN
- OCH C CH3
- PnenylacetonitriteSodium attlmcide
- 9
- OCH2"C-CH3
- Pher¥scetone
- Figure 22 shows the glassware used. The glassware must be very dry, so it is dried out in the oven for an hour or so. If the sep funnel has a plastic valve, the valve is taken out before the sep funnel is put in the oven. The magnetic stirring bar does not go in the oven either. It is coated with Tenon, so it does not have any water on it. A magnetic stirrer is necessary to do this reaction, because good stirring is very important. An extra claisen adapter is needed IClf this reaction; one is filled with broken pieces of glass for use as a fractionating column. the other is kept as is for use in the Figure 22 apparatus.
- Chapter Sel'ell Phellylacetollefrom B-Keto Ester .•
- Vacuum 41
- r adapter
- Plugged with bed vacuum ofQrieril&
- nippla
- oul
- Long....-e'ondenser
- Wal8r
- Claisen
- o 0 Mag'."c
- "Wo-sliNet
- hot plate
- Figure 22
- To begin, the underground chemist puts a bed of Drierite in the vacuum adapter as shown in Figure 9, being sure to plug up the vacuum nipple. The water lines arc attached to the condenser and cold water started flowing through it. But if it is humid, the water flow is not started until the glassware is assembled.
- In this case, the main reactant is benzyl cyanide, also called phenyl acetonitrile or alpha-tolunitrile.
- Benzyl cyanide is now a controlled substance precursor. and so must be made.
- Benzyl cyanide is not outrageously poisonous like sodium cyanide, it's an organic cyanide called a nitrile. As long as the chemist doesn't drink the stuff. he's OK. It is a somewhat smelly liquid. clear in color. For a recipe to make it trom benzyl chloride and cyanide. see Organic Syntheses, Collective Volume I.
- The chemist starts with a chunk of clean sodium metal that weighs 128 grams. It is weighed out in a 300 ml beaker haltti lled with petroleum distillate or xylene. Then the sodium metal is transferred to another beaker half-filled with anhydrous ether and chopped into small pieces with a clean knite. Then it is scooped out with a spoon and put in the 3000 ml tlask. The glassware is quickly assembled as shown
- in Figure 22, with the 3000 ml flask sitting in a pan. Water flow through the condenser is begun, and 300 mi DI' absolute ethyl alcohol is put in the sep funnel. As the alcohol is allowed to flow in onto the sodium, the reaction is kept under control by putting cold water in the pan and wrapping the flask in a wet towel.
- When the reaction is under control, more alcohol is added until a total of 1500 ml has been added. The alcohol is gently boiled until the sodium metal is dissolved.
- Now the chemist mixes 500 grams (490 ml) of benzyl cyanide with 575 grams (637 ml) of ethyl acetate and stars the heating of the ethanol solution. Just as it stops boiling, the mixture of ethyl acetate and benzyl cyanide is added with good magnetic stirring. This addition takes about 15 minutes. The stirring is continued for about 1 () minutes after the addition is complete, then the mixture is heated in a stcam bath or in a pan of boiling water for about 2 hours. Then it is taken out of the heat and allowed to sit overnight or at least tor a few hours.
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- Eighth Edition
- The underground chemist has just made the sodium salt of phenylacetacetonitrile. To collect it, he cools the flask in a mixture of salt and ice. With a clean wooden stick, he breaks up the chunks of crystals that have formed, as the flask is cooling down. When it reaches -10° C, he keeps it at this temperature for a couple of hours, then filters out the crystals. They are rinsed a couple of times with ether or another solvent such as hexane, then, while still wet with ether, added to a large flask or beaker containing 2000 ml of water. They are dissolved by stirring, then the flask or beaker is cooled down to 0° C by packing it in ice mixed with salt. When it reaches this temperature, 200 ml of glacial acetic acid is added to it with vigorous stirring. The chemist must make sure that the temperature does not go up more than a few degrees while he is adding it.
- He has now made phenylacetacetonitrile. He filters the crystals off it and rinses them a few times with water. The crystals must now be kept moist in order for them to be turned into phenylacetone.
- All is now ready for producing phenyl acetone from these crystals. In a 2000 ml flask, he puts 700 ml of concentrated sulfuric acid. It is cooled down to -10° C by packing the flask in a mixture of salt and ice, then magnetic stirring is begun. The crystals are slowly added to the sulfuric acid. They must be moist, or he will get a mess. It takes about an hour to add the crystals to the sulfuric acid. Once they are added, the flask is heated in a pan of boiling water and swirled around to dissolve the crystals. After they have dissolved, the flask is heated for a couple more minutes, then removed from the pan of boiling water. It is cooled down slowly to 0° C by first letting it cool down, then packing it in ice.
- The underground chemist puts 1700 ml of water in a 3000 ml flask. Half of the sulfuric acid solution is added to it. It is heated in a pan of boiling water for a couple of hours. It is given a couple of good shakes every IS minutes. A layer of phenyl acetone fornls in the mixture.
- After 2 hours of heating, the mixture is poured into a gallon-size glass jug to cool off. Another 1700 ml of water is put in the flask and the rest of the chilled sulfuric acid solution is poured into it. It is also heated for 2 hours in a pan of boiling water, then poured into another glass jug.
- The chemist is ready to separate the phenyl acetone from the water and distill it. The liquid in the first jug is slowly poured into a 1000 ml sep funnel until the sep funnel is full. Most of the phenyl acetone layer will be in the sep funnel, because it is floating on top of the water. The water layer is drained back into the jug, and the phenylacetone layer is poured into a large beaker. He adds 300 ml of toluene to the jug, stoppers it and shakes it for IS seconds. Then he stops and lets the layer of toluene containing phenylacetone float up to the surface. It is slowly poured into the sep funnel, and the water layer is drained back into the jug. The water is thrown away. This process is repeated with the other jug.
- This phenylacetone has some sulfuric acid in it. The chemist puts ISO ml of a 5% solution of lye in water in the 1000 ml sep funnel. He also pours half of the phenyl acetone and toluene mixture he got Irom the two jugs into the sep funnel. He shakes it with the water to remove the sulfuric acid. The water is drained out, and the phenyl acetone-toluene layer is poured into a 1000 ml round bottom flask. Another
- 150 ml of water is put into the sep funnel and is shaken, then the water layer is drained off He pours as much of this toluene-phenyl acetone mixture into the 1000 ml round bottom flask as he can until it reaches 2/3 full.
- The glassware is set up as shown in Figure 13 in Chapter Three, with a few boiling chips in the 1000 ml flask. The collecting flask is 250 ml. He distills off a couple of hundred ml of toluene to make room for the rest of the product. When there is some room, he turns off the heat and waits for the boiling to stop. Then the rest of the toluene-phenyl acetone mixture in the sep funnel is added to the 1000 ml flask. The distillation is continued until the toluene stops coming over. About 500 to 600 ml of toluene will be collected.
- When the rate of toluene distillation slows down to just about stopping, the heat is turned off and it is
- allowed to cool down. Then the last of the toluene is removed under a vacuum. When the toluene is gone,
- the caHecting flask is changed to a 500 ml flask and the phenylacetone is distiHed under a vacuum at the
- Chapter Seven Phenylacetone from B-Keto Eslers
- Isual temperature range. The yield is about 300 ml of phenyl acetone. Once the toluene is gone, virtually
- <II of the material left in the Oask is phenylacetone. If there is a high boiling residue, it is unchanged
- ,hen y lacetacetonitri Ie.
- A claimed improvement upon this recipe is found in Chern AbsTracts, Volume 36, column 2531 (1942).
- ere once again we come to the question of Russian science, and do we believe them, or are they lying hrough their rotten, stinking teeth? Your Uncle is tending towards believing them, because the variation hey use is a general one that has been found to give improved yields in related reactions. Let the reader mow that I haven't tried this improved procedure, so I'm just passing along the recipe from the literature 'or what it's worth.
- In the above example, absolute alcohol is used both to react with the sodium metal to produce sodium ,thoxide, and as the solvent for the reaction. It has been found in general with other reactions of this type :hat the presence of all that extra unreacted alcohol in the solution tends to cause side reactions which lower the yield of the desired product. In the Russian recipe, the extra alcohol beyond that amount needed to react with the sodium metal is left out, and replaced with anhydrous ether. The yield of phenylacetacetonitrile as a result goes up to 86% from the roughly 50% or so obtained when all the extra alcohol is in the reaction mixture.
- For clandestine purposes, anhydrous ether is a very undesirable material. It's very flammable, and evaporates so quickly that an explosive cloud of vapors can easily fill a room. All it's lacking is a spark to set it off. It also smells to high heaven, and can be detected far downwind. This could easily attract unwanted attention. For strike number three, one just doesn't run down to the hardware store and pick up a jug or pail of anhydrous ether. It is associated strongly with drug manufacture.
- One need not be discouraged on this point. Anhydrous ether isn't the only possible replacement solvent. No doubt it was just lying around the commie lab, so they grabbed it and used it. Alternative solvents would include anhydrous acetone, hexane, toluene, xylene, or even that Coleman camper fuel. The latter three can be picked up at the hardware store. None of them produce the smell or fire hazards thai ether does.
- NolV to go back to the recipe. The 3000 ml flask is set up as in the previous example, and 1000-1200 ml of the alternative solvent is put into the flask. The sodium metal is cut up and added to the flask as in the example given. Then just enough absolute alcohol to react with the sodium metal is added to the solution. For 128 grams of sodium metal, this works out to 325-350 ml of absolute alcohol. Three hundred fifty ml would give a little excess alcohol to speed up the reaction of the last bits of sodium metal. It will take considerably longer for the sodium metal to react using a dilute solution of absolute alcohol as compared to just dissolving it in straight absolute alcohol. A mixture of sodium ethoxide with the solvent will be produced. Methanol can be substituted for the absolute alcohol if this material is easier for you to obtain. In this case, roughly 215 ml of methanol would be used for this example reaction.
- Next, the benzyl cyanide and ethyl acetate mixture is slowly added just as in the standard example given, and the mixture boiled for a couple of hours to produce the sodium salt of phenylacetacetonitrile. It is filtered out and then reacted with acetic acid to produce phenylacetacetronitrile, just as in the standard recipe.
- We next come to another claimed improvement in this process given in the Russian article. To produce phcnylacetone from the phenylacetacetonitrile, they claim that phosphoric acid is superior to sulfuric acid. One would just take the standard procedure given here, which by the way can be found in Organic Syntheses, Collective Volume Two, and substitute phosphoric for the sulfuric in that step. Rather than heat the sulfuric acid and phenylacetacetonitrile mixture on a steam bath, they prefer to heat the mixture to 1500 C. An oil bath heated on a hot plate would work well for this variation. From there the procedure works
- Secrets of Methamphetamine Manufacture Eighth Edition
- exactly the same way as in the standard procedure. The claimed yield should increase to over 400 ml of phenylacetone, as compared to maybe 300 ml with the standard procedure. It's worth checking out.
- References
- Journal of the American Chemical Society, Volume 60, page 914 (1938).
- Chapter Eight Phelly/acetolle via the Tube Furllace
- Chapter Eight Phenylacetone via the Tube Furnace
- The best way to produce phenyl acetone on a large scale and continuous basis is by a catalyst bed inside a tube furnace. This has several advantages over the other methods described in this book. Cheap and very common acetic acid is used to react with phenylacetic acid instead of the expensive and more exotic acetic anhydride and pyridine. Use of the tube furnace frees up the glassware for use in other operations. The furnace requires very little attention while it is in operation, which allows the underground chemist to spend his time turning the phenylacetone into methamphetamine. There is no reason why this process cannot be used in small-scale production. It is just that its advantages really come out when large amounts of phenylacetone must be produced.
- In this process, a mixture of phenylacetic acid and glacial acetic acid is slowly dripped into a Pyrex combustion tube which is tilled with pea-sized pumice stones covcred with a coating of either thorium oxide or manganous oxide catalyst. This bed of catalyst is heated to a high temperature with a tube furnace and the vapors of phenylacetic acid and acetic acid react on the surface of the catalyst to produce ketones. Three reactions result.
- The acid mixture is prepared so that there are three molecules of acetic acid for every molecule of phenylacetic acid. This makes it much morc likely lhat the valuable phenylacetic acid will react with acctic acid to produce phenylacetone rather than with another molecule of phenylacetic to produce the useless dibenzyl ketone.
- CH C' o
- 3 'OH
- Acetic acid
- continued
- o
- OCH2C CH3 + CO2 + H20
- Pheny1acetone
- ,0 9
- + CH3C'OH -CH:3C CH3
- + CO2 + H20
- Acetone
- Acetic acid
- Chapter Eight Phenylacetone via the Tube Furnace
- glass wool (Angel Hair) somewhat larger than a fist. The glass wool will be going into the combustion tube, so it must be cleaned off along with the pebbles. The glass wool is packed down. Then nitric acid is added until both the pumice and glass wool are covered. The beaker is put on an electric hot plate and the nitric acid boiled for half an hour. This converts metal impurities into soluble nitrates, and oxidizes other garbage. The nitric acid is all poured off and down the drain. The pumice and glass wool are then covered with distilled water and soaked for 5 minutes. This water is then drained off and replaced with more water. The water is boiled for 10 minutes, then drained off. This boiling water rinse is repeated two more times using distilled water. Finally, the water is drained out and the beaker placed on its side to drip out the last drops of water.
- The pumice pebbles are now ready to be coated with catalyst. About 450 ml of distilled water is put into a clean 1000 ml beaker. The chemist dissolves 276 grams of thorium nitrate into this water. In another clean beaker, he dissolves 106 grams of anhydrous sodium carbonate into 400 ml of distilled water. (He uses A.R. grade chemicals.)
- Slowly, and with constant stirring, the sodium carbonate solution is added to the thorium nitrate solution. Using a mechanical stirrer to stir the thorium nitrate solution is best, but a glass rod also works.
- Thorium nitrate reacts with sodium carbonate to make thorium carbonate and sodium nitrate. Thorium carbonate does not dissolve in water, so it forms a white precipitate. Sodium nitrate stays dissolved in water. The stirring is continued for a couple of minutes after all the sodium carbonate has been added, and then it is allowed to settle. The thorium carbonate settles into a gooey gunk at the bottom of the beaker. As much of the water as possible is poured off. Then 600 ml of distilled water is added to the thorium carbonate and stirred around with a clean glass rod. The chemist makes sure that all the thorium carbonate gets into contact with the clean water, and that any lumps are broken up. This dissolves any remaining sodium nitrate.
- The thorium carbonate is allowed to settle again, then as much of the water as possible is poured ofT.
- Small amounts of distilled water are added and stirred in until a fairly thick paste is formed. Now the purified pumice pebbles are added and stirred around until they are all evenly coated with thorium
- carbonate.
- A Pyrex glass cake pan is placed on the electric hot plate. The heat is turned on to It, maximum and about 1/8 of the coated pumice pebbles are added to the glass pan. They are heated there with constant stirring with a thick glass rod, so that the pieces dry out evenly. When the coated pumice pebbles no longer stick together, they are dry enough. They are transferred to a clean sheet and an equal amount of wet pumice pebbles is put in the cake pan. They are dried out like the first group of pebbles. This process is repeated until all the coated pumice pebbles are dry. Any white powder that failed to stick to the pumice is collected and saved in a glass jar. If it is later necessary to change the catalyst bed, this material is wetted and used to coat new pumice pebbles.
- A plug of the purified glass wool about 3 em long is put into the combustion tube about 15 em from
- the male end. This will hold the catalyst bed in place. The tube is tilled up with the coated pumice
- pebbles for a length of 70 em or so. A small plug of purified glass wool about I em in length is put every
- 15 COl. This reduces the danger that tar building up on the pumice pebbles will block the tubc.
- The tube is put inside the furnace. If two Hoskins tube furnaces are used end-to-end, the tube is
- insulated in the space between the two furnaces with several laycrs of asbestos paper or cloth. In this
- space, the tube is tilled with loose glass wool. This space is not counted as part of the necessary 70 cm of
- catalyst bed.
- The apparatus is set up as shown in Figure 23. It is tilted at an angle of about 20 degrees, the end with
- the sep funnel being higher than the end with the collecting flask. The sep funnel has a one-hole stopper
- with a piece of glass tubing running through it almost all the way to the valve of the sep funnel. This is a
- Chapter Eight Phellylacetolle via the Tube FUrl/ace
- Now the tube furnace is heated to 425-450° C, while the slow stream of nitrogen continues through the tube. The heat turns the thorium carbonate into thorium oxide. The heating continues for 12 hours, after which the catalyst is ready to produce phenyl acetone.
- The chemist mixes 200 grams of phenylacetic acid with 250 ml of glacial acetic acid. He mixes them thoroughly, the phenylacetic acid dissolving easily in the glacial acetic acid. (Glacial acetic acid is the name for pure acetic acid; it is so called because it freezes at a little below room temperature.) Next add about 10 ml of water to this acid mixture and shake or stir it to get the water evenly dissolved throughout the solution. This small amount of water helps to prevent the formation of tar on the hot catalyst bed while it is working. Tar represents lost product, and a tar covered catalyst can't participate in the reaction we want to perform
- This acid mixture is poured into the sep funnel and the funnel is stoppered with the one-hole stopper with the glass tubing constant pressure device. The temperature of the furnace is 425-450° C, and a one¬bubble-per-second stream of nitrogen has been flowing through the tube for at least 12 hours. The valve on the sep funnel is opened so that about 20 drops of the acid mixture drip into the tube from the sep tunnel every 30 seconds.
- A slow flow of water is put through the condenser to condense the ketones as they leave the furnace.
- The product collects in the 500 ml flask and the nitrogen gas exits through the vacuum nipple of the vacuum adapter connected to the condenser. If there is trouble condensing all the acetone, the 500 ml flask is packed in icc.
- It takes about 5 hours for all the acid to drip into the tube. When all the acid mixture has dripped in, 25 ml of acetic acid is added to the sep funnel and dripped in. This flushes the last of the product out of the catalyst bed.
- The product in the 500 ml flask consists of a lower water layer and a brown-colored organic layer on top. The latter is poured into a 1000 ml sep funnel; the water layer is then drained off into a clean beaker,
- and the organic layer is poured into another beaker. The water layer is put back into the sep funnel along
- with 50 ml of toluene, and the funnel is shaken. It is allowed to sit for a few minutes, then the lower water layer is drained off and thrown away. The toluene layer is poured in with the organic layer in the other beaker.
- The chemist is now ready to clean up the phenylacetone so that it can be distilled. He mixes up a supply of 10% sodium hydroxide solution by adding 10 ounces of lye to % gallon of water in a glass jug. He pours the organic layer into the sep funnel, adds 400 ml of the sodium hydroxide solution and shakes.
- The water layer is drained otl' into a clean beaker and the organic layer is poured into another beaker. The
- watcr layer is returned to the sep funnel and 75 ml of toluene added. The funnel is shaken, then the water layer is drained off and thrown away. The toluene layer is poured in with the organic layer. This is repeated three more times, then the phenyl acetone is distilled as described in Chapter Three. The yield of phenylacetone is about 100 ml.
- The temperature of the furnace is raised to about 525° C, and a slow stream of air is drawn through the tube for two hours. The air is drawn through by turning off the nitrogen flow, opening up the valve of the scp tilllnel and attaching a vacuum hose to the vacuum nipple of the vacuum adapter on the 500 ml flask side of the apparatus. This air flow burns off built up crud and tar on the catalyst and charges it up for another run. It is done atier the first run, and then after every few batches.
- The furnace temperature is set at 425-450° C again and the flow of nitrogen through the tube is resumed. It is flushed out for a couple of hours, then the sep funnel is filled with acid mix for another run. It is dripped in as before to get another batch of phenylacetone. In this way, phenylacetone can be produced on a continuous basis.
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- If the homemade furnace has trouble reaching the necessary temperature, the chemist wraps it with more insulation. If that does not do enough, a lower temperature process can be used by replacing the thorium-oxide-coated pumice pebbles with manganous-oxide-coated pumice pebbles. The process goes as follows:
- The pumice pebbles are made and purified with nitric acid as described earlier. In a 1000 ml beaker, 70 grams of manganous chloride (MnCI2) is dissolved in 300 ml of distilled water. In another beaker, 38 grams of anhydrous sodium carbonate is dissolved in 500 ml of distilled water. The sodium carbonate solution is slowly added to the manganous chloride solution with constant stirring. Manganous chloride reacts to form manganous carbonate, which does not dissolve in water and precipitates out. The manganous carbonate is filtered out in a Buchner funnel as described in Chapter Five. The crystals are rinsed with distilled water.
- The manganous carbonate is returned to a clean beaker and enough distilled water is added to make it into a fairly thick paste. If too much water is added, it does not stick well to the pumice. The pumice pebbles are stirred in until they are evenly coated. The beaker is heated on a hot plate while the pumice stones are vigorously stirred. Local overheating must be avoided or the catalyst will be ruined. When most of the water is evaporated, the catalyst is transferred to a Pyrex cake pan and gently heated on a hot plate. The pumice chips are stirred constantly to get even drying. When they no longer stick together, they are transferred to a clean sheet of paper.
- The chemist tills the combustion tube with the catalyst as before and sets up the apparatus. He heats the furnace to 360-400° C while passing a stream of nitrogen through the tube. This converts the manganous carbonate to manganous oxide (MnO). This heating is continued for 8 hours. Then the heat is reduced to 3500 C, while the stream of nitrogen is continued at a rate of one bubble per second. When 350° C is reached, he drips in the same phenylacetic acid-acetic acid mixture used earlier in this chapter. The correct rate is 20 drops every 30 seconds. When it has all dripped in, he adds 25 ml of acetic acid to the sep funnel and drips it in. He then either adds more acid mix to the sep funnel for another run, or shuts down the furnace. If he shuts down the furnace, he must continue the flow of nitrogen through the tube until it has cooled off. This prevents the MnO catalyst from being oxidized to Mn02, etc. When he turns it back on, he must immediately start the nitrogen flow for the same reason. The product is purified in the same way as described earlier in this chapter,
- Since no air is sucked through the tube at high temperature, gunk builds up on the catalyst and eventually puts it out of commission. When this happens, the catalyst bed is changed, The yield using the manganous oxide catalyst bed is not as good as that using the thorium oxide catalyst bed. Thorium oxide is used, unless the chemist has no choice.
- A somewhat more complicated way to do this reaction is to use what is called a thorium oxide "aerogel" catalyst. A lower temperature and a higher rate of production are possible, For more information about it, see Industrial and Engineering Chemistry, published in 1934, Volume 20, pages 388 and 1014.
- Before leaving this topic, we should address the subject of smells, in particular the smells which can accompany this process, The tube furnace is not something which should be set up in an apartment building or in a rental house that the landlord stops by to visit on more than rare occasions.
- Phenylacetic acid smells just like cat piss, and the smell gets on surfaces and just lingers and lingers.
- The heat knows what this smell is associated with, and neighbors smelling it all the time will just get mad, They will think you have a herd of screaming tom cats pissing on the walls or a bunch of ferrets gone bonkers! There are certain sections of cities where using the living room as a bathroom is nothing unusual, but we'll assume that you don't want to set up shop there,
- One might say, '"Hey, I won't spill any, so I won't stink up the place." Let me assure you, stuff happens, especially with a furnace. All it takes is a loose joint on the glassware to drip phenylacetic acid
- Chapter Eight Phenyiacelone via the Tube Furnace
- solution all over the place. Pouring spills happen and there is the glassware to clean. The stuff gets around.
- The best way to clean up phenylacetic acid is to mix some lye in with rubbing alcohol. While wearing gloves, you can sponge this solution into the spilled phenylacetic acid. It will be converted to the sodium salt of phenylacetic acid, which doesn't stink. The sodium salt is also soluble in water, so further cleanup with soap and water will be successful.
- Another source of smelly emanations from the tube furnace is due to the form in which the product tends to exit from the furnace. There is a strong tendency for the product mixture to form a fog as it exits the furnace and gets cooled down in the condenser. This fog is pretty hard to get condensed completely down to liquid with just a trip through a condenser. Organic Syntheses goes so far as to suggest that the vapors be passed through a bed of marbles to break the fog. Your Uncle suggests that the upper part of the vacuum adapter be packed with glass wool to give a lot of surface for the fog to condense upon before reaching the exit of the apparatus. Fog escaping the apparatus results in a lower yield and lot's of Slink, both are undesirable.
- References
- Journal of the Chemistry Society, page 612 (1948); page 171 (1940).
- OrganiC Syntheses, Collective Volume Two.
- Chapter Nine Other Methods of Making Phenylacetone
- dollars to have it carted away by a hazardous waste disposal company. They won't be looking for incriminating evidence in the waste, and, for a large operation like the one using hundreds of pounds of cyanide, the couple thousand dollars is chicken feed.
- An alternative method for disposal of cyanide waste is to destroy it with bleach. Then the water solution which is left can be safely poured down the sewer. To do this, add an equal weight of sodium hydroxide to the cyanide waste and add water to bring the two ingredients into solution. Then slowly and with constant stirring add about 4 volumes of bleach to the cyanide solution. The bleach best bleach is the highly concentrated 15% hypochlorite solution available from pool suppliers, although 5% household bleach can be used by tripling the amount added. The reaction creates a lot of heat, so when the solution starts steaming just take a break and let it cool down.
- Another way to come at the production of phenylacetone is to start with common materials that will react to produce phenylacetic acid easily and in high yield. There are more than a couple of such materials, and none of them are subject to reporting requirements. I am ashamed that my government could be so sloppy in compiling their List I chemicals! This situation must be corrected, because it is my Ii felong goal to get every chemical under the sun on some type of reporting list.
- Probably the simplest and easiest precursor to phenylacetic acid is its ethyl ester, ethyl phenylacetate. This substance is used in fairly large amounts in perfumes, so by disguising yourself as a perfumer, pails or drums of this very useful chemical could be had by tapping into the perfumer's supply lines. Ethyl phenylacetate is also used in artificial fruit flavorings and to produce an aroma of honey. One would first be well advised to become at least passably informed about perfume formulations. Books such as Common Fragrance and Flavor Materials by Bauer, Perfume and Flavor Chemicals by Arctander and The Perfilme Handhook by Groom are a great place to start one's education on the topic. Then one goes to trade journals such as Soap, Perfumes and Cosmetics to look for advertisements from chemical suppliers to the perfume trade. These suppliers are greatly preferable to doing business with scientific supply houses, who will also stock ethyl phenyl acetate. The rule of thumb is that one should try to avoid any supplier who also sells List I chemicals. To sell List I chemicals, one must be a trusted snitch and lackey. I also must regretfully inform you that ethyl phenylacetate has recently been placed on the List I. In countries other than the US, such as Mexico, it is easily available. Perfumers are still using it though, so one may be able to hide among the trees in the forest. If one orders the chemical in solution with other ingredients, then it isn't subject to reporting. The simplest solution of all would be ethyl phenylacetate in alcohol solution. Then this purchase would certainly appear to be from a perfumer seeking to impart its fragrance to his product.
- The reaction to convert ethyl phenylacetate to phenylacetic acid is just a simple ester hydrolysis. Alkaline hydrolysis, also called saponification, using NaOH or KOH, is superior to acid catalyzed hydrolysis in this case. The following reactions bring about the transformation:
- o
- @-CH2-OC¥H3
- Ethyl Phenylacetone
- Satt o! Phenylacetic aCId
- Y
- @-CHOH
- Phenylacetic acid
- For example, take a 2000 ml round bottom flask, or a copper or stainless steel replica. Into the flask put 200 ml of ethyl phenyl acetate, toOO ml of 190 proof vodka, and 140 grams of KOH.(potassium hydroxide)
- Secrets of Methamphetamine Manufacture Eighth Edition
- These two paths to amphetamines starting with allylbenzene become of extreme importance in making psychedelic amphetamines such as MDA or MDMA from commonly available essential oils which often contain large amounts of appropriately substituted allylbenzenes. For example, sassafras oil contains 80¬90% safrole, which is 3,4-methylenedioxyallylbenzene. One has the choice then of converting the allylbenzene to either the phenylacetone or bromosafrole. Reaction then with methylamine gives MDMA. Substituting ammonia for the methylamine gives instead MDA. The so-called Wacker oxidations of allylbenzenes to phenylacetones are covered in the next chapter. The reductive amination of the phenyl acetone to the amphetamine is covered in Chapters Five, Eleven, and Twelve. The other pathway using HBr is discussed in Chapters Seventeen and Twenty. Both are quite workable, and which one to choose is largely a matter of taste or availability of chemicals. Distilling the products is quite important with the second pathway, to get a pure product.
- Now to get allyl benzene from cinnamaldehyde or cinnamon oil (aka oil of cassia, Chinese cinnamon oil, or cinnamon bark oil; avoid cinnamon leaf oil), put 130 ml of the cinnamaldehyde or cinnamon oil into a 1000 ml flask. Heating will be required for a fairly short period, so a round bottom flask equipped with reflux condenser is best. A volumetric flask could also be used by wrapping a cold rag around the long neck of the flask to act as a reflux condenser. Next add about 260 011 of 95% ethanol (190 proof vodka). The recipe given in Organic Syntheses, Collective Volume 6, page 293, uses 95% ethanol and gets a 90% yield of the tosylhydrazone derivative. Other recipes (given in Journal of Organic Chemistry,
- Volume 40, page 923 (1975) and Volume 43, page 2299 (1978) and Volume 46, page 1217 (1981»
- use absolute alcohol. One hundred ninety proof vodka is available at the liquor store, so this is the way to go. Finally, add about 220 grams of p-toluenesulfonylhydrazide. This material is listed in my Eastman catalog, selling for 30¢ a gram, and is available in bulk at a discount. It can also be made in high yield from p-sulfonyl chloride and hydrazine by the procedure given in Organic Syntheses, Collective Volume 5, page 1055. P-toluenesulfonylhydrazide is covered by no reporting requirements, and hasn't been the focus of suspicion. The list of potentially incriminating chemicals is now getting so long as to be almost useless anyway. I would suggest getting some in bulk, and doing no further business with whomever the chemical is obtained from. This substance is available in the web of commerce as a foaming agent for epoxy and rubber. It is sold under names such as Celogen TSH-C.
- Swirl around the contents of the flask to mix them together and then heat the flask on a steam bath or in some boiling hot water with either magnetic stirring or swirling. Once the mixture starts to get hot, the p-toluenesulfonylhydrazide will react with the cinnamaldehyde, and the mixture will become clear, or at least transparent, if oil is being used. A reaction time of about 15 minutes is needed, once the mixture becomes hot. If a makeshift reaction apparatus like a volumetric flask is being used, take care that vapors of alcohol don't come out of the vessel and into contact with sources of ignition, such as a hardware slore hotplate. Keep the neck of the flask cool, and attach some tubing to the top to lead escaping vapors away.
- Once a clear or transparent reaction mixture has been achieved, stop the heating, and allow the mixture to begin to cool. As it cools, crystals of the tosylhydrazone derivative wil! begin coming out of solution. This is a good point to pour the mixture into a 600 ml beaker or glass measuring cup. The mass of crystals which will form are much more easily poured and scraped into a filter from this container than from a round bottom flask or volumetric flask.
- When the mixture has cooled down to room temperature, the mass of crystals should be fi ltered out using a Buchner funnel and vacuum flask, just as described for filtering out meth crystals in Chapter Five. The filtered out crystals of the tosylhydrazone derivative should next be recrystallized from 190 proof vodka. This is done by putting the crystals back into a clean round bottom flask or volumetric flask, adding about 200 to 250 ml of 190 proof vodka, and heating the mixture with Sleam or hot water to redissolve the crystals. When they have redissolved, the heating is stopped, and the liquid poured once again into a beaker or measuring cup once crystals begin to reappear. When the mixture gets cooled to
- Secreta of Methamphetamine Manufacture Eighth Edition
- sodium borohydride at such a rate that the foaming of the reaction mixture doesn't cause the mixture to froth out of the container. This will take about an hour or so. In this variation, a lot more hydrogen gas gets produced than in the first method, so some ventilation should be provided to avoid explosion hazards.
- After the borohydride is added, continue stirring for about an hour at room temperature, then heat the mixture to about 70° C for about an hour and a hal f. Then allow the mixture to cool down, and pour it onto crushed ice as in the first example, then add sodium hydroxide solution as before to make the solution alkaline, extract the mixture with toluene, hexane or Coleman camper fuel, and distill to get in this case around 60 ml of allylbenzene.
- By using sodium cyanoborohydride as the reducer, the yield of allyl benzene can be increased to nearly 100%. Your Uncle doesn't recommend this variation because sodium cyanoborohydride isn't the common industrial chemical that sodium borohydride is. Sodium cyanoborohydride is available from those snitch-filled scientific supply houses, and the notation by the chemical generally says something along the lines of "selective reducer for Schiff's bases." Yes, it's a really convenient chemical to reduce phcnylacetone-methylamine mixtures to meth in high yield. This chemical would be too scary for me to order from those people if I wanted to cook some crank. My advice is to stay away from buying this chemical.
- This recipe also uses some fairly uncommon solvents, as opposed to the glacial acctic acid used in the previous two methods. This method is provided for educational purposes.
- Into a container of around 10,000 ml capacity put 2500 ml of dimethyl formam ide (DMF) and 2500 ml of sulfolane. Mix them together, then add 300 grams of the tosylhydrazone derivative of cinnamaldehyde and 250 grams of sodium cyanoborohydride. Stir them into solution and then add a few tenths of a gram of the acid-base indicator bromocresol green. When the indicator dissolves, it will color the solution blue.
- Next heat the solution to 105° C, then dropwise add concentrated hydrochloric acid until the pH drops
- below 3.8 as indicated by the color change of the solution from blue to tan. Then add 2000 ml of
- cyclohexane to the solution, and continue the heating with stirring for about an hour. I would think that toluene could be substituted for the cyclohexane. A little more bromocresol green is added during the heating period, and after one hour of heating, a little more hydrochloric acid is added dropwise to keep the pH below 3.8 as indicated by the tan color. Continue heating for an additional I y, hours, for a total of around 2Y, hours of heating.
- After the solution has cooled, pour it into about 7000 ml of water, and shake the mixture around for a hit. Then separate ofT the organic layer floating on top of the water layer. Take the water layer, and extract it a couple of times with 200 ml portions of cyclohexane or toluene. Add these extracts to the organic layer which had been separated off. Your product is in there, heavily diluted with solvent.
- Take the combined organic layer and solvent extracts, and wash this with about 1000 ml of water.
- Drain off the water layer, and repeat the water wash a couple more times.
- The solvent-allylbenzene solution is next put into a large distilling tlask, and the solvent is distilled off. Then the allyl benzene can be distilled as in the previous examples. The yield will be over 100 ml of allyl benzene.
- Another good method of making phenylacelOne is to use a method called the Knoevenagel reaction. In this method, the starting material is benzaldehyde. The advantages to being able to use a wide variety of starting materials to produce phenylacetone are obvious.
- There's just so much stuff to "watch" that the "watchers" can't do a proper job of policing transactions. In this case, we can all sleep better at night knowing that benzaldehyde, and the other chemical uscd in this synthetic route, nitroethane, are both on the List I of reportable chemicals. However, don't let that warm fuzzy feeling of comfort and safety grip you too deeply. Technical grades of benzaldehyde used for flavorings in food are exempt from reporting. 0il of biller almonds contains
- Secrets of Methamphetamine Manufacture Eighth Edition
- We'll go into some of these direct reductions to amphetamine in some more detail at the end of this upcoming recipe. The main point to get now is that racemic amphetamine, aka benzedrine, isn't a bad buzz.
- Direct reduction to amphetamine rather than proceeding through phenyl acetone to get meth eliminates the need to get or make methylamine because the nitrogen atom is already there in place. Amphetamine also carries a great deal lesser federal penally if one should happen to get busted. The direct reduction techniques are just as applicable to the substituted nitroalkenes one so often comes across in making psychedelic amphetamines as they are to nitroalkene proper.
- This reaction is done as follows: Into a clean, dry 3000 ml round bottom flask is placed 400 ml of absolute alcohol, 20 ml of n-butylamine, 428 grams (407 ml) of benzaldehyde, and 300 grams (286 ml) of nitroethene. The underground chemist sets up the glassware for refluxing as shown in Figure lO in Chapter Three. He includes the drying tube with Drierite as shown in Figure 9. He swirls around the flask to mix the contents, then sets the flask on a hot plate and begins heating it. The water flowing through the condenser should be fairly cool, to be sure of condensing the alcohol vapors. A good, gentle rate of boiling is what he aims for. He continues the boiling for 8 hours. The solution will tum yellow.
- He makes sure that his chemicals, especially the nitroethane, are of a good grade. Nitroethane is widely used in the paint and varnish industry as a solvent for cellulose acetate lacquers, vinyl resins, nitrocellulose, waxes and dyes. Ifhe has the industrial grade, he first distills it before use. Benzaldehyde smells like bitter oil of almonds and should be clear. Benzaldehyde is used in flavorings and perfumes. The benzaldehyde must be reasonably pure as well. Old bottles of benzaldehyde could contain a lot of benzoic acid formed by reaction with air upon exposure to light. Home brewed benzaldehyde could be especially prone to oxidation to benzoic acid because traces of metal impurities greatly speed this reaction. Benzoic acid will neutralize the amine used as the catalyst in this reaction. and prevent it from occurring. One can remove the benzoic acid by shaking the benzaldehyde with some bicarb solution in water.
- When the eight hours of boiling is done, he turns off the heat and lets the flask cool down. Once crystals begin to appear, he takes off the condenser and begins stirring the solution with a glass rod. He continues the stirring, and transfers the flask to a sink of cool water to help speed the cooling. He continues the stirring until the mass of crystals becomes too thick to stir, or the flask is cooled off. The idea of the stirring is to prevent the batch from selting into one solid mass of crystals. The crystals should be yellow in color. Be aware that these crystals may foml slowly or with great difficulty. Just because the whole mass doesn't immediately tum to slush doesn't mean the batch is a bust. Addition ofa seed crystal greatly speeds crystallization. Alternatively, cooling the mixture and allowing it to stand for a couple of days in the cold will generally do the trick. For stubborn cases, adding some water to the reaction mixture will force crystallization.
- He now proceeds to purify this l-phenyl-2-nitropropene. The simplest way to do this is to add ice cold alcohol to the crystals until a slurry is formed (about 200 ml) and then break up any lumps of crystals with a glass rod. He then filters the slurry through a large coffee filter and squeezes the mass to force out as much of the alcohol as possible. Along with the alcohol, he will be removing most of the unreacted benzaldehyde and nitroethene. The crystals will still be yellow, but they will no longer be sticky and gooey. If he still smells n-butylamine on them, he may rinse them with alcohol again.
- A better way to clean up these crystals is to recrystallize them. In large batches like this one, it is a lot of work and he must make provisions for exhausting the fumes to the outside to prevent the danger of explosion, but he will get a cleaner product.
- It is done as follows: To the crystals which have been rinsed off with alcohol and returned to a cleaned, dry 2000 ml round bottom flask, he adds just enough alcohol to dissolve the crystals. This takes in the neighborhood of 400 ml of alcohol. Any type of alcohol will do. If he has access to methanol or
- Chapter Nine Other Methods of Making Phenylacetone
- 67
- mixing two parts ethanol with one part acetic acid and one part sultiICic acid. This is your catholyte. Enough should be made to make the catholyte reach nearly to the top of the cathode. The nitropropene (l -phenyl-2-nitropropene) should then be added to this catholyte. It is added such that one mole (164 grams of the nitropropene) is dissolved in two liters of the catholyte. Do not premix the nitropropene into the catholyte until the reduction is ready to be done.
- Anolyte is made by diluting concentrated sulfuric acid to 5% by volume with water. For example, 5 ml of concentrated sulfuric is diluted to 100 ml volume with water. The anolyte is poured into the cell divider until its liquid level roughly matches the catholyte.
- Then stirring is begun and current (DC current, of high quality) pushed through the solution. How much current? The surface area of the cathode is measured. Only the area on the side facing the anode is counted. For each square centimeter of surface, .2 amp (200 milliamps) is caused to flow through the solution. If one has a DC recti tier, the voltage is simply increased until the desired amount of amps flows through the cell. If using a battery, choose a battery or batteries hooked in a series to give a voltage sufficient to move the current needed. Increasing voltage increases current flow through the cell. E=IR.
- Heat will be produced by pushing current through the cell divider and by reaction at the cathode. The temperature of the solution should be watched, and not allowed to go over 40° C. External cooling is good enough for beakers and pails. For a plastic drum, copper pipe run through the solution as a heat exchanger might be needed as well.
- Let's take the example of a one mole batch done in a 2500-3000 ml beaker. A reasonable size cathode in this case would measure at least 12 em by 6 cm, for a face area of 72 square centimeters. 200 milliamps (.2 amp) per square centimeter of face gives a required current flow of 14.4 amps, shown on the current meter. The current meter is wired in on the line serving the anode. Fairly heavy wiring, well beyond that in a set of alligator clips, would be needed in this case to carry that much current without overheating the wiring. For still larger batches, jumper cables would be needed to carry the current.
- The reduction of l-phenyl-2-nitropropene to amphetamine is an 8 electron reduction. So the theoretical amount of current needed to do the reduction is 8 faradays per mole of the nitroalkene in solution in the catholyte. One faraday is 96,500 coulombs, and a coulomb equals an amp-second. At 14.4 amps, one faraday passes into solution in 6700 seconds. This is 1.86 hours. Eight faradays flow in just under 15 hours. The process isn't 100% efficient, however, so at least 12, and up to 16 faradays will be needed to do the reduction to completion. This will take 24-30 hours. Increasing the electrode area will allow for greater currents to be passed, with a proportional decrease in the amount of time needed to do the reduction. The anolyte may decrease in volume during the course of the reduction, as the water in the anolyte gets convened to oxygen electrically. Water should be added to that companment of the cell occasionally to make up for such losses.
- When the required amount of current has flowed through the solution, the electrodes can be removed from the beaker, pail or whatever, and the catholyte, which now contains amphetamine, can be poured into a distilling flask. The ethanol is then distilled out of the solution. Ethyl acetate is also formed during the distillation by reaction between the acetic acid and ethanol. This distills off easily as well. A vacuum assist during the distillation makes the process go faster, and at a lower temperature.
- Thc residue left in the flask after the alcohol and ethylacetate have distilled off consists of a solution of amphetamine in sulfuric acid and acetic acid. This should be allowed to cool down, then chilled in some ice. Add to this acid solution sodium hydroxide solution to neutralize the acid. 10-20% NaOH or lye in water is about the proper strength for this sodium hydroxide solution. Adding this to the acid produces a violent reaction, generating a lot of heat. It should be added slowly with stirring or swirling, taking breaks to allow the acid solution to cool down during the course of this neutralization. It's going to take in the neighborhood of a couple of pounds ofNaOH or lye added to neutralize all the sulfuric and acetic acid in the flask, and make the solution strongly alkaline (pH 13+ to pH papers). As the neutralization
- Chapter Nine Other Methods of Making Phenyia£'e/one
- should be noted that the nitroalkene has a slight tear gassing effect upon the eyes, and also irritates the skin. Do not use the stuff as a body balm.
- If phenylacetone is desired from the nitroalkene, the toluene solution produced in the reaction is used directly in the next step. Once it has cooled down, it is poured into a 2000 ml 3-necked flask. Then into the 3-necked flask is added 500 ml of water, 200 grams of iron powder (40 to 100 mesh), and 4 grams of ferric chloride (FeCI3). Into the center neck of the flask is put a mechanical stirrer reaching almost to the bottom of the flask. There should be a tight seal so that the ensuing vapors of toluene when the flask is heated do not escape by this route. A good condenser is attached to one of the other necks. and a sep funnel, or dropping funnel with matching ground glass joint is put into the remaining neck. With vigorous stirring, the contents of the flask are heated to about 750 C, and 360 ml of concentrated hydrochloric acid is added to the flask by means of dripping it into the mix through the sep funnel over a two hour period. The reaction mixture will boil vigorously. The heating and stirring are continued for an additional half hour after the last of the hydrochloric acid has been added.
- Next it is time to get the phenyl acetone out of the reaction mixture. Once the t1ask has cooled down, the iron is filtered out by pouring it through the plug of angel hair described earlier in this chapter. It is a good idea to rinse down the trapped iron powder with a dash of toluene to get any clinging phenyl acetone off of it. Then the toluene layer is separated using a sep funnel. It is poured into a round bottom flask. The water layer has about 100 ml of toluene added to it, and this is shaken to draw suspended phenylacetone into the toluene. The toluene layer is then separated and added to the aforementioned round bottom flask. It is then rigged for fractional distillation as shown in Figure 13. The toluene distills off first as the toluene-water azeotrope at 850 C, and then as pure toluene at 1100 C. Once the toluene is mostly gone, vacuum is applied, and phenyl acetone is collected at the usual temperature range. The yield is about 120 ml of phenyl acetone.
- This recipe was taken from OrganiC Syntheses, Collective Volume 4. Look in the table of contents for o-methoxyphenylacetone.
- Making Shitloads of Your Own Benzaldehyde
- As was mentioned earlier in this chapter, small to moderate amounts of that List I controlled chemical benzaldehyde are most conveniently obtained by vacuum distilling oil of bitter almonds, which contains about 95% benzaldehyde, or by similarly distilling technical grade mixtures containing benzaldehyde used lor flavorings and fragrances. When larger amounts are wanted, such as a gallon or more, then the recipe which J will give here is the way to go. It is an old industrial process for making benzaldehyde that gives high yields of product, and produces next to no waste to be disposed of. This process uses the electrode-generated reagent, Mn+3, to oxidize toluene to benzaldehyde in very high yield with very few byproducts. The Mn+ 3 is electrically made from the easily available Mn+ 2 salts. During the reaction, the Mn+3 is reduced to Mn+2, which can be returned to the process and used over and over again just by electrically oxidizing it again to Mn+3. I suspect from my correspondence with various sources that this method is being used with great success by clandestine cookers out there to make loads of benzaldehyde easily and quickly. This same process can be scaled down to run in a one gallon plastic pitcher using a car battery charger as the power source.
- This method is taken from US Patent 808,095, which dates to 1905. This process is no longer used industrially to make benzaldehyde because it has been replaced by the air oxidation of toluene using various catalysts. That's cheaper for those big manufacturers, but for our purposes here, this method is better.
- Secrets of Methamphetamine Manufacture Eighth Edition
- The first thing which must be done is to make mangano-ammonium sulfate. This is the substance that the patent prefers to use as the Mn+2 compound. Other, later work published simply used MnS04 as the Mn+2 compound, but they talk about using divided cells whereas this procedure can be done in a simple, undivided cell.
- Take a 55 gallon plastic drum, well cleaned with the top cut off. Add 45 liters of water. That's roughly 12 gallons of water. Next add around 44 liters of concentrated sulfuric acid, slowly and with stirring. It will make a lot of heat and the steam coming off the addition will be quite irritating. Stay upwind, and wear protective gear while taking one's time doing this addition. The standard commercial technical grade of sulfuric acid will work fine. If one is using a higher strength lab grade sulfuric acid, then the amount of sulfuric acid added can be cut by a few liters.
- Next, while the water is still hot, take 85 pounds of manganese sulfate, and add it to the drum. Stir until dissolved. Then take about 40 pounds of ammonium sulfate, and add it to the drum. Roughly 100 kilos of the mangano-ammonium sulfate will form in the hot acid solution as the ammonium sulfate is added and goes into solution. Continue stirring.
- Both manganese sulfate and ammonium sulfate are easily available at industrial chemical outlets, and the technical grade of each chemical is good enough for this purpose. Manganese sulfate generally comes as the tetra and pentahydrate mixture, and the amount used in this example assumes that this is the material used. It will come in 50 pound bags for use as a fertilizer ingredient. Ammonium sulfate also comes in 50 pound bags, and it too is used as a fertilizer ingredient.
- One could just usc ammonia if that is more convenient. In that variation, add about 12 liters of strong
- ammonia to the initial water added to the drum, then increase the sulfuric acid addition by about 12 liters. In that way obtaining ammonium sulfate could be entirely skipped.
- Now an electric cell should be constructed. The most suitable container would once again be the plastic 55 gallon drum, in which the reaction solution was made .. The inner vertical wall of the drum should be lined with a sheet of lead. It's pretty easy to get lead sheets about Y.i inch thick. It is sold by suppliers to electroplaters of chrome. See the Metal Finishing Guidebook and Directory for a large selection of such suppliers. Look under "Anodes -Lead" in the back of the book. Your library should be able to get this guidebook for you through inter-library loan. One could also page through the trade magazines Plating and Sur/ilce Finishing or Metal Finishing for ads featuring lead anodes. Typical sheets will measure 4 fect by 8 fect. One sheet will be plenty, and weigh plenty as well.
- The standard 55 gallon drum stands 3 feet tall, and has a diameter of about 22 inches. The inner circumference is then about 69 inches. Cut a section from the lead sheet measuring a little under 3 feet by 69 inches, put it in the drum, and make this sheet of soft metal line the inside surface of the drum. This will be your anode, the place at which the Mn+2 gets oxidized to Mn+3.
- To get current to flow through this cell, we need a cathode. Start with a copper ring about one foot in diameter. It should be heavily constructed enough to support the cathode, which in this case is also made of lead. Cut strips of lead roughly an inch wide and long enough to almost make it down to the bottom of the drum, or a little under three feet long. You will need ten or twelve of them. These are your cathodes. Clamp the top of each of them to the copper ring with even spacing. Next take two sections of steel rod. Each one is two feet long. Wrap them in some heavy plastic, using rubber bands to keep the plastic tightly wrapped around the rods. These are the supports for your cathode ring. Lay them on top of the drum, then rest the rings of cathodes on top of these rods. Finally, stick a mechanical stirrer down the center of the drum, almost reaching the bottom. When done it should look like Figure 28.
- Secrets of Methamphetamine Manufacture Eighth Edition
- That will eliminate this danger. Contact between the cathodes and the anode must similarly be prevented. Don't stir too rapidly and cause the easily bent lead cathodes to touch the anode.
- Once the required amount of current has flowed through the cell. tum off the current. then pull the cathode ring out of the drum. Then add 4 kilos (4.6 liters) of toluene. The toluene available at the hardware store in the paint section is good enough for this reaction. Turn up the speed of agitation to get the toluene, which would naturally like to float on top of the mixture, down into contact with the Mn+ 3 oxidizer.
- The preferred temperature for the oxidation is 50° C. The reaction mixture is likely to be nearly that warnl at the end of the electrolysis, but it will cool down once the current is turned off. The directions call for the addition of about 8 liters of additional water during the early stages of the oxidation, so adding boiling hot water will help to maintain warm reaction conditions. Additional heating may have to be supplied. Both the temperature of the reaction and the concentration of the sulfuric acid are crucial to getting good results. Sulfuric acid which is too dilute will give benzoic acid rather than benzaldehyde. Too concentrated sulfuric acid gives condensation products, or tar.
- At the end of two to three hours of stirring, the oxidation of the toluene is complete. The red Mn+ 3 salt will have redissolved, and a clear solution will be produced once again. One's eye can be the guide to when the reaction is complete.
- The droplets of benzaldehyde churning through the reaction mixture can be extracted by adding about 3 gallons of toluene. and continuing the strong stirring. Then turn off the stirrer, and allow the toluene¬benzaldehyde droplets to rise to the top of the reaction mixture. This top layer can then be separated off, and distilled in the same manner as all those previous examples. Benzaldehyde boils at 178° C at atmospheric pressure, and at roughly 80° C under a typical good aspirator vacuum of 25 torr or so. The yield will be around a gallon and a half. The toluene which distills can be reused, of course, in the next batch. One could also do a simple distillation to remove most of the toluene, then save the residue in a treezer. Benzaldehyde is very prone to self destruct in storage. Contact with air and light causes it to oxidize to benzoic acid. Check out US patent 2,280,311 for a full description of this unfortunate circumstance. Distillation without a vacuum will give a fair amount of benzoic acid. Steam distillation of the product will largely avoid this. It is air, light and the presence of metallic impurities which drive the reaction to make benzoic acid.
- To do the next batch, one simply reinserts the cathode ring, checks to make sure that the liquid level in the drum is about what it was originally, and repeats the electrolysis of the mixture to reoxidize the Mn+2 back up to Mn+3. In this way, batch after batch can be run with the only feed material needed being toluene. This is a good way to make lots of benzaldehyde.
- To do this reaction in a plastic one gallon pitcher with a car battery charger instead, simply divide all the additions by 50. Then on one side of the plastic pitcher, place a piece of lead sheet (tishing lure sinkers pounded by hammer into a sheet) measuring 5 inches by 8 inches as the anode. This connects to the red pole of a car battery charger, and offers a face of about 40 square inches. On the other side of the pitcher, put a considerably smaller lead rod or sheet. On this scale, if most of the lead anode is in contact with the solution, the current draw should be about \0 amps. One must measure the area of the anode face in solution! Roughly one quarter amp per square inch facing the anode is correct.
- A more current efficient and rapid method was worked out by the Japanese. It is to be found in Chemical Abstracts Vol. 20, page 339 (1926). This makes use of a divided cell because both stages of the
- reaction are going to be done simultaneously.
- An old and simple way to shield off the lead cathode plus pole is to wrap it in canvas as far as it inserts
- in the solution. Rubber bands would be most effective to keep the canvas clinging tightly to the black
- pole. Then into a one gallon container they put 100 grams of MnS04 in 1000 ml of 55% sulfuric acid. I
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- Eighth Edition
- Phenylacetone from Hydratropic Aldehyde
- There is another phenyl acetone recipe that looks pretty good. I haven't heard of a lot of usc of this method in clandestine chemistry, but it is simple and creates phenyl acetone in one step from commercially available materials. The biggest problem with this procedure is that the starting material from which the phenyl acetone is made, hydratropic aldehyde, isn't very widely used commercially. It tinds some use in perfumery, but massive amounts of it aren't used. A jive gallon pail might be the largest quantity that one could reasonably obtain through normal commercial channels. To obtain this chemical, one wou Id probably be best advised to go to one of the perfumery trade publ ications mentioned throughout this book and in Advanced Techniques 0/ Clandestine Psychedelic & Amphetamine Manufacture and look through the trade journals for ads from chemical suppliers. Then disguise yourself as a perfumer, and order some.
- To do this reaction, one only needs a beaker, or some other glass container. Into the beaker put 400 ml of concentrated sulfuric acid. Then measure out 90 grams of hydratropic aldehyde, also known as 2¬phenyl propanol, or as methyl-phenyl-acetaldehyde. Cool the sulfuric acid down to _160 C using an ice bath to which either salt or alcohol has been added to further chill down the ice. When the sulfuric acid has cooled down to _160 C, slowly with stirring add the hydra tropic aldehyde over a period of about one hour. Maintain the cold temperature of the mixture throughout the addition of the aldehyde, then let the mixture react for an additional 15 minutes after all the aldehyde has been added. Don't let the temperature fall much below -16 C, or the hydratropaldehyde will freeze in the reaction mixture and will fail to convert to phenylacetone. The following reaction, which is just a rearrangement of the aldehyde molecule, takes place:
- o
- "
- C-H
- CH3
- HydrotropIc aldehyde
- H04 o
- @"
- o -CHZC CH3
- Phenylacetone
- After the additional 15 minutes of reaction, the sulfuric acid solution is then poured onto about 5 pounds of cracked ice. The whole mixture is then allowed to come to room temperature. As the ice melts, an oily liquid and some gummy goo are formed. Extract the water with about 300 ml of toluene. This will pull the phenyl acetone into the toluene. Separate the toluene layer from the diluted sulfuric acid. A large sep funnel would be the best tool for this job. The toluene will be floating on top of the water. Wash the toluene/phenylacetone solution with some water. and then with some bicarbonate dissolved in water. This will remove any sulfuric acid which has been carried over. Finally distill off the toluene, and vacuum distill the phenyl acetone. The yield will be around 60 ml of phenyl acetone. Not a bad procedure iI' you can get the hydratropic aldehyde.
- Should hydratropic aldehyde become a "listed chemical", it would still be pretty easy to set up large scale production or this substance using commonly available chemicals. Hydratropaldehyde
- can be made in fairly good yield from cumene, which is a cheap and readily available commercial solvent and chromyl chloride. The procedure is called the Etard Reaction, and can be done in a variety of solvents such as carbon tetrachloride or chloroform. For a review of this reaction, see Chemistry Reviews Volume 58, pages 1-60 (1958). Chromyl chloride is pretty easily made from chromium trioxide and hydrochloric acid. For details on this method, see Inorganic Syntheses, Volume 2 page 205 (1946). I must forewarn you that chromyl chloride is a nasty and fuming chemical which must be handled with respect. In spite of that, putting together a large scale phenyl acetone factory by this method wouldn't be very hard to do. Expect to read in depth details in an upcoming second edition of Advanced Techniques ....
- Secrets of Methamphetamine Manufacture
- Eigbth Edition
- u'F o
- ..
- O-<Q7CH-CHoCH3
- Isosafrokl
- LII
- To read more about this reaction method, see Journal o(Organic ChemisTry, Volume 46, pages 3312¬15 (1981) and Volume 49, pages 1830-32 (1 984). Note that in these papers, they used a platinum cathode instead of stainless steel, and so got partial reduction of the epoxide. Lithium iodide isn't the only substance that will bring about the rearrangement of the epoxide to the phenylacetone.
- 0
- O-@-CH-CH-CHa
- Epoxide
- d'f
- O-@-CH2 C CIi:!
- M-D-Phenylacetone
- Another way of doing the electric cell method of turning the propenyl benzene into phenylacetone is given in the Journal o( Organic Chemistry article, Volume 49. If, at the conclusion of passing current through the reaction mixture, a little I % solution of sulfuric acid is added and stirred for an hour, the product of the cell is 98% yield of the same glycol by the formic acid and peroxide method. A much quicker, easier, and higher yielding reaction. The glycol is then made into phenyl acetone by the usual method given by Shulgin in PIHKAL, page 734. Heating with a sulfuric acid solution turns the glycol into the phenyl acetone.
- We digress. We still have the toluene extract of the reaction mixture. It contains the phenyl acetone and (he propenylbenzene. Both are valuable and must be recovered. How to do it, depends upon batch sizes and how much equipment the clandestine cooker has available.
- For reasonable size batches, such as the one given in this example, the simplest way to separate the two substances is by distillation under a vacuum. A c1aisen adapter packed with broken pieces of glass, and insulated on the outside by wrapping with aluminum foil provides good separation. The toluene-water azeotrope will distill tirst, thereby drying the solution. Then pure toluene will distill. The toluene can be recycled to extract the next batch. When the toluene is almost all distilled off (there will be a little over 150 ml of high boiling liquid left in the distilling t1ask, and the rate of toluene distillation will slow and
- Chapler Ten P,ychedelic Phenylacelones from E.sunlial Oils
- the temperature shown on the thermometer will rise above the 1100 C boiling point of toluene), then the heat should be turned off the mixture, and once cooled down a bit, vacuum can be applied. The vacuum should be applied cautiously at first, in spurts, to allow the vacuum induced boiling to cool the contents of the flask further. Then full force vacuum can be applied, and a vacuum distillation commenced. Boiling chips made from a pumice footstone will work on sassafras family compounds, but an oil bath must be used to heat the flask. Direct heating on a hot plate surface will cause bumping during distillation. With meth and regular phenyl acetone, even direct heating like that doesn't cause bumping during distillation.
- Once the toluene has been removed under a vacuum, the receiving flask should be changed to catch the propenylbenzene, such as isosafrole in this example. A good aspirator using cold water will distill it at about 12()0 C. The yield of it will be somewhere around 75 mi. After changing receiving flasks, the phenylacetone will then distill around 155-16()O C under that same good vacuum. If the water where you live has a temperature akin to urine, then these boiling points will be correspondingly higher. The yield of phenyl acetone will also be around 75 ml.
- The phenyl acetone is then of course used to make the amphetamine. To make meth from phenyl acetone, just pick out any of the methods given in this book. Ditto for MDMA. To make MDA from the phenylacetone, the best method is hydrogenation using Raney nickel catalyst as described in US Patent 3,1 87,047.
- If you would like to check out this whole topic being discussed at incredible length, go to www.lycaeum.orgJ-strike. I hosted the web site there for a month or two in the most foolhardy act anyone has talked me into for ages. While you're there, you might as well pick up Strike's book on this same topic. It's well worth the $25. Just promise your Uncle that you won't even consider using the methods in his book using mercury.
- Another way of doing this same reaction dispenses with the need for the special dropping funnel, the chemical glassware, and all the dancing around required to use oxygen under pressure. One can do this reaction in a beaker, or any other glass or Teflon-lined container, if the oxygen for the reaction is supplied by hydrogen peroxide. Hydrogen peroxide is a fairly common industrial chemical. It comes in 55 gallon drums at a price ranging from 40 to 80 cents a pound for 30-35% hydrogen peroxide. A guy named Peter Card used to sell quarts and gallons mail order at a jacked up price for alternative health uses. Check alternative health publications to see if he or somebody else is still in business. In any case, 30-35% hydrogen peroxide is a commonly used substance not requiring one to do business with chemical supply houses such as Aldrich.
- To do this variation, let's consider the same one mole size batch. 700 ml of dimethylformamide is placed in the beaker, followed by 100 ml of 30-35% hydrogen peroxide. The catalyst is next added with strong stirring, and a drip of the allyl benzene such as safrole is commenced into the solution. 150 ml of sa Ii-ole is added over one half to one hour as in the previous example, and the stirring continued for 24 hours as in the previous example. Then, just as before, the reaction mixture is poured into 3N hydrochloric acid solution, and the product extracted out using toluene. I like to use toluene as extractant whenever possible because it is available at the hardware store in the paint thinner section, and it doesn't smell much.
- So here once again we have the toluene extract containing the phenylacetone and propenyl benzene.
- Let's use this opportunity to check out another way to separate the propenylbenzene from the phenylacetone. This way is preferable if really big batches are being done, or if access to chemical glassware for vacuum distilling is denied you. The first thing which should be done is to distill off the toluene as in the previous example. A homemade still could do this job quite well. Be careful of fire
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- hazards when constructing it. Use electric heating to warm the pot. Make sure the toluene vapors get condensed and cooled well. Supply ventilation to keep flammable fumes from binding up. When the toluene has distilled, the propenyl benzene and phenylacetone mixture can be drained from the still by opening a drain or spigot on the bottom of the distilling pot.
- Now this mixture can be separated by fanning the bisulfite addition product of the phenylacetone.
- Sodium bisulfite or sodium metabisulfite is widely used in brewing to disinfect the brew vessels. and in vinting to keep the wine from spoiling. A few pounds on up is easily gotten at brew supply shops. It is cheap. One hundred to 150 grams will be plenty for this size batch. Add water to the 150 grams of bisultite with stirring to make a saturated solution. This requires 500 ml of water.
- Add the phenylacetone and propenyl benzene mixture to the saturated bisulfite solution, and shake or strongly stir for a few hours. Heavy masses of the bisulfite addition product with phenylacetone form in solution as crystals. Aller the reaction time is finished, they can be filtered out and rinsed down with some toluene. The filtrate will consist of a layer of the propenyl benzene in toluene from the rinse floating on top of the bisulfite solution. This top layer should be separated off, washed with some water and the toluene evaporated away to give the propenyl benzene in about 75 ml yield. If safrole was used in the reaction, then the isosafrole thereby obtained will smell like licorice.
- The crystals of bisultite addition product should be placed in a boiling flask rigged for retlux along with about a quart of a saturated solution of sodium carbonate or bicarbonate. Ann and Hammer baking soda or baking powder will work just fine. Reflux for a couple of hours to regenerate the phenylacetone tram the bisulfite addition product. Cool, and separate off the phenylacetone. Extracting the bicarb solution with toluene will prevent any loss of product. Mix the toluene extract with the phenyl acetone, distill off the toluene, and the residue is pure phenylacetone. If you are familiar with the smell of phenylacetone, you will instantly recognize it as product. Methylenedioxyphenylacetone smells almost exactly like regular phenylacetone in its pure state. Sometimes scams are run, selling people the MD¬phenyl acetone, telling them it's regular phenylacetone. In this case, the phenylacetone is likely to smell a little like the candy shop stuff it was made from. The yield in this case of phenylacetone will be around 75 m!.
- Obtaining dimethylfonnamide can be an obstical to people contemplating this route of production. If that is the case, it is easily replaced with alcohol. The preferred alcohols to use in place of the formamide are 190 proof vodka and 9 I % isopropyl alcohol. The latter material can be picked up off the shelf at the drug store. There needs to be some water in the mixture for the reaction to go, and these two alcohols are the most easily available and non-toxic choices.
- To do a run using thc alcohol solvent instead of formamide, the same equipment and procedures as used in the last two examples are followed, except that the formamide is replaced with the alcohol solvent, and only cupric chloride can be used as co-catalyst. From there, it works exactly the same, except that the yield of product is closer to 70%. The reaction also seems to go faster in alcohol.
- What would seem to be a much better method of doing this conversion of the allyl benzene to the phenyl acetone is to be found in Journal of Organic Chemistry, Volume 45, pages 5390-92 (1980). In this paper they found that t-butyl alcohol is a much better solvent for doing the palladium catalyzed oxidation of the terminal olefin to methyl ketone. This is good, as t-butyl alcohol is a common and cheap industrial chemical. Fifty-five gallon drums of it are no problem to obtain at all.
- In this solvent, palladium chloride can't be used; rather palladium diacetate is the preferred catalyst, and just a tiny amount of it does wonders. Later, I'll tell you how to make your own palladium diacetate from an ingot of palladium metal.
- In their procedure, they mix a liter or so of t-butyl alcohol with the tenninal alkene, such as, for instance, safrole. About one mole of sa fro Ie (150 ml) in the liter oft-butyl alcohol would be a good mix. This mixture is heated to about 800 C in any glass or Teflon-coated reaction vessel. Then a gram and a
- Chapler Tell P.<ychedelic Phenylacelolle.< from Essential Oils
- half of pal1adium diacetate is added to the reaction mixture. After adding that, about 500 ml of 30-35% hydrogen peroxide is added dropwise over a 30 minute period with good stirring. The temperature of the reaction mixture is maintained at around 80° C for about 6 hours, and an orange-colored solution should result. If during the addition of the peroxide, it looks like the safrole or product phenylacetone is coming out of solution, then just add some more t-butyl alcohol solvent.
- After the six hour reaction time, cool the mixture and pour it into 5000 or so ml of water. The product phenylacetone should float to the top as a yel10w layer. Separate it off, and extract the t-butyl alcohol and water solution with a few portions of toluene. Add the toluene extracts to the main body of the phenylacetone, and wash a few times with 5% NaOH solution to remove t-butyl alcohol. Distilling should give over 80% to near 90% yield of phenylacetone. I know the first three methods given here in this chapter work. This one should too.
- Making Palladium Diacetate
- The best ways to make pal1adium diacetate involve dissolving some of a palladium ingot in nitric acid to make a solution of palladium nitrate in nitric acid or anodical1y dissolving some of a palladium ingot in hydrochloric acid, as described in Advanced Techniques of Clandestine Psychedelic & Amphetamine Manufacture, to make palladium chloride in hydrochloric acid. The acid is neutralized by slowly adding sodium hydroxide solution with good stirring, then the addition of some more sodium hydroxide solution precipitates the palladium as hydroxide. The hydroxide sludge is separated from the liquid and then reacted with acetic acid to make palladium diacetate. See Chemistry and industry (London) 1964, page 544 and US Patent 3,3 1 8,891.
- For example, let's take that convenient and productive one mole size batch which uses about I y, grams of palladium acetate as catalyst. To prepare the catalyst for this batch, one would take an ingot of palladium (obtained from the neighborhood coin and precious metal dealer), and dissolve away about .75 grams of the ingot either by immersing the ingot in nitric acid, or anodically dissolving it in hydrochloric acid.
- One then takes the acid solution containing the dissolved palladium, and slowly with strong stirring adds a 5-10% solution of sodium hydroxide to the acid. One must keep the temperature of the solution below 60° C during the addition of the hydroxide, as higher temperatures will produce a polymeric metal¬hydroxide sludge which is useless for producing catalyst. Nestle the acid beaker in ice or cold water to keep the temperature of the solution down while the acid is being neutralized.
- Using a pH meter, keep track of the pH of the acid solution during the addition of sodium hydroxide solution. Once the pH of the solution nears 7, a sludge of palladium hydroxide will start to form. Continue adding sodium hydroxide solution with stirring until a pH of lO is reached. It does no harm to overshoot this pH, within reason. For example if a pH of II is produced, no harm will be done. No more than 15 minutes should be taken to move the pH of the solution from about 3 or 4 up to 10 or II. Most of the sodium hydroxide solution will be used in neutralizing the initially strong acid with a starting pH below I, to get the pH up around 3 or 4. Comparatively little sodium hydroxide will be needed to move the pH tram 3 or 4 up to 10. The movement of the pH reading from 3 or 4 up to about 10 must be done quickly to prevent the formation of a polymeric hydroxide sludge.
- When a pH of 10 or so is reached, a precipitate of palladium hydroxide will form in the solution. These
- tiny particles will settle to the bottom of the beaker with time. Decant off the clear water solution, and wash the sludge with four 25 ml portions of distilled water. The sludge is suspended in the clean water, then allowed to settle out. and the water rinse is decanted off. Finally, using a Buchner funnel and source or vacuum, the palladium hydroxide sludge is filtered out of the last water rinse, and sucked to a semi-dry
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- filter cake. A reasonably fine grade of laboratory filter paper will catch all the palladium hydroxide. The water filtrate should be clear.
- Next, add the semi-dry palladium hydroxide filter cake to about 20 ml of glacial acetic acid, and stir for about 2 hours at 800 C. This will form a solution of palladium acetate in acetic acid. This solution can be added to the batch as catalyst. If the solution stands around for a while in the cold, yellow needle-like crystals of palladium acetate will form. This too can be used as catalyst, so long as all the crystals get rinsed into the reaction solution.
- Electric Oxidation of Propenylbenzenes to Phenylacetones
- Question: "I've tried the electric cell procedure you gave in Practical LSD Manufacture a number of times. My yield of phenyl acetone is OK, but no better than what I can get by the old formic acid and peroxide in acetone method. I took a look at the European patent you cited in the book, and it seems I'm following the directions. Why am I not getting the near 100% yields claimed in the patent?" -Puzzled in Holland
- Answer: This isn't a case of a bogus patent. This procedure is the real McCoy. See also Journal of Organic Chemistry, Volume 46, pages 3312-3315 (1981) and Volume 49, pages 1830-32 (1984) for confirmation of the excellent results. Sigeru Torii, the author of the Journal of Organic Chemistry articles is no lightweight either. He is highly respected in the field of electrochemistry.
- Let's start by getting you some good quality graphite rods or bar stock to use as anodes for this reaction. Those welding supply shop carbon rods aren't the best for doing electrochemistry with. The following list of suppliers taken from the Metal Finishing Guidebook is only a partial listing of all the suppliers of these good quality graphite anodes. If they should happen to ask, say you use these graphite anodes in a Wood's nickel strike, which you use to electroplate on top of stainless steel. Plating suppliers aren't a suspicious lot, so no problems should result from buying graphite anodes.
- Atotech I -800-752-464
- MGP 2 I 6-459-08 I 7
- Plating Supplies 4 I 3-786-2020
- Sifco 216-524-0099
- Technic 401-728-7081
- Unique Industries 203-735-875 1
- Univertical 313-491-3000
- The next thing to line you up with is a good source of DC current. A toy train transformer or other cheap transformer just doesn't tum out a "clean" enough DC output. These cheapie DC sources have what is called "AC ripple." This is AC current superimposed upon the DC output. If you hook such a cheap DC source to an oscilloscope, you will see on the screen the so-called "picket fence" output. This won't do.
- A good source of DC current for electric reactions is a Hull Cell rectifier. These are very commonly used by electroplaters to do test plating runs in the lab, and to troubleshoot their plating baths. The output is easily varied from zero to over 20 volts DC, and will commonly put out up to around 15 amps. They generally have pretty accurate gauges on them which measure the voltage and amperage flowing at any given time. New, they go for around $500 to $600. Some major suppliers of these rectifiers are:
- Chapter Ten Psychedelic Phenylacetone.' from Essential Oils
- AIter the solvent is evaporated under a vacuum, the residue in the flask, which consists of close to a 100% yield of the glycol mixed in with crystals of sodium carbonate, is extracted with some ethyl acetate. The ethyl acetate solution of the glycol is next washed with some saturated salt solution. Finally, the ethyl acetate solution is dried with some anhydrous sodium sulfate, then the ethyl acetate is evaporated away under a vacuum to leave a residue of nearly pure glycol. It will be an oil that may crystallize over time. One should not wait around for that to happen. Rather, moving right on to making the phenyl acetone should be done.
- The procedure for doing this is found on page 734 of PIHKAL. For a batch of the size given in this example, the residue of nearly pure glycol is mixed with about 40 ml of methanol (Heet gas line de-icer). Then about 250 ml of a 15% solution of sulfuric acid in water is added, and after thorough mixing, the solution is heated for about 3 hours on a steam bath or in a pan of boiling hot water. After cooling this reaction mixture down, extract three times with 50 ml portions of toluene. The combined extracts are washed lirst with water, then with a 5% solution of sodium hydroxide or lye in water.
- The toluene solution containing the phenylacetone should then be fractionally distilled. The toluene¬water azeotrope will distill first as a milky-looking mixture, then pure toluene will distill, looking clear. When the toluene is mostly all gone, the heat should be removed from the distilling flask, and vacuum applied cautiously at first, as the hot mixture will boil furiously at first when vacuum is applied. Then full strength vacuum can be used, and the pure substituted phenyl acetone will distill as a clear liquid. If cold water is used with a good aspirator, methylenedioxyphenylacetone will distill around 1500 C to 1600
- C. This is the product from isosatrole, and is used to make MDA or MDMA (X or Ecstasy). If asarone (or B-asarone) was used as the starting material, the boiling point is considerably higher. It's probably better in this case just to remove the toluene under a vacuum rather than try to distill the 2,4,5¬trimethoxyphenylacetone. Further purification can be done by the bisulfite addition method given in I'radical LSD Manufacilire. This phenyl acetone is used to make TMA-2.
- H3C-O CH2-C-CH3
- '@/ II
- / "-0
- o
- H3C-O O-CH3
- 24,5-Trimethoxyphenytacetone
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- Eighth Edition
- That should take care of your problems, Puzzled. The most important points are to use good grade graphite anode material, and use an AC-ripple-free DC power source. The electrodes, of course, can be used over and over. A good cleaning after each batch run should be all they need to keep them in working order.
- Figure 31
- Chapter Eleven The Way of the Bomb
- Chapter Eleven The Way of the Bomb
- "Blessed be the bomb ... and all its work." -The mutants of, "Beneath the Planet a/the Apes "
- When underground chemists move up to industrial-scale manufacture of methamphetamine, it soon becomes obvious that the Leuckart-Wallach reaction is not suitable for making large amounts. There are two reasons for this. N-methylformamide distills slowly, because of its high latent heat of vaporization. This makes the production of large amounts of N-methylformamide a very time-consuming process. Secondly, the Leuckart-Wallach reaction can take up to 48 hours to complete.
- It's also a rather finicky and kind of unpredictable reaction, as was noted earlier in Chapter Five. I still prefer it, however, because of the warm memories it brings back to me.
- To increase production, a faster method of turning phenylacetone into methamphetamine is necessary. Reacting phenylacetone with methylamine and hydrogen in an apparatus called a "bomb" is such a method. A bomb is a chemical pressure cooker where hydrogen gas is piped under pressure to react with the phenylacetone and methylamine. It is called a bomb because sometimes reactions like this are done under thousands of pounds of pressure, and occasionally the bomb will blow up. This reaction is done under a pressure of only 3 atmospheres, 30 pounds per square inch greater than normal air pressure, so there's no danger of the hydrogenation bomb going off. This reaction is called reductive ami nation. It is not especially difficult to do, but it is necessary to have the hardware in proper working condition and to keep out materials that would poison the catalyst. Reductive amination is a quick, very clean and high¬yield process.
- Methylami ne
- H
- + CN:
- H
- . Methamphetamine
- Intermediate Schltf's base
- H CH
- -CH:5 'N' :5
- o CHC-CH3 0 CHZC .... C
- + O
- Phenylacetone reacts with methylamine to produce a Schiffs base and a molecule of water. This Sehift's base then reacts with hydrogen and platinum catalyst and gets reduced to methamphetamine. To encourage the formation of this Schiffs base, the amount of water in the reaction mixture is held to less than 10%; 5% is even better. If the underground chemist is able to get methylamine gas in a cylinder, it is easy to control the amount of water in the reaction mixture, but 40% methylamine in water can be made to work with little effort.
- Two main side reactions interfere with the production of methamphetamine in the hydrogenation bomb. They are both controlled by properly adjusting the conditions inside the bomb. The first side reaction is the reduction or the phenylacetone.
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- Eighth Edition
- Pt
- Hydrogen
- Phenytac8tone
- OH ®-CHtCH-CH3
- Methyl ben carbinol (1-phenyl-2-propanolJ
- The phenylacetone can react with hydrogen and platinum instead of with methylamine, This side reaction is held to a minimum by not letting the hydrogen gas pressure get much above 30 psi, It is also controlled by encouraging the phenylacetone to react with methylamine instead, This is done by keeping the amount of water in the reaction mixture small, having enough methylamine around for it to react with, and running the reaction at the right temperature,
- The other side reaction that can be a problem is phenyl acetone reacting with methamphetamine to produce a tertiary amine,
- This reaction is held to a minimum by having enough methylamine in the reaction mixture to tie up the phenyl acetone, and by keeping the solution fairly diluted, so that they are less likely to bump into one another.
- The psychedelic amphetamine MDMA can similarly be made cleanly and on a large scale by the same method, One simply uses methylenedioxyphenylacetone, made according to the directions in the previous chapter, in place of phenylacetone, It reacts in exactly the same way to give around 90% yields of MDMA from the m-d-phenylacetone,
- When it is desired to make benzedrine Irom the phenyl acetone, or a psychedelic amphetamine such as MDA or TMA-2 from the appropriately substituted phenylacetone, then the preferred catalyst for the reduction is Raney nickel rather than platinum, In this case, ammonia is used to form the Schiffs base with the phenyl acetone, which then reduces to the desired amphetamine through the absorption of hydrogen Irom the catalyst. Even better results are obtained when the ammonia is used in the form of ammonium acetate, because ammonia in this form is much more efficient at forming the Schiffs base with the phenylacetone than straight ammonia,
- Raney nickel is a much less convenient catalyst to use than platinum, It is attracted towards magnets, just like iron filings, so magnetic stirring inside a hydrogenation bomb isn't possible with Raney nickel. Hydrogenations done with this catalyst also generally require much higher hydrogen pressures be applied inside the bomb, and that heating of the mixture be done, Platinum, on the other hand, works just tine at relatively low hydrogen pressures and at room temperature, Magnetic fields don't affect it, so magnetic stirring can be used with this catalyst. It is much more convenient to use,
- Reductive alkylation using platinum catalyst can be done inside a very easily constructed apparatus, For example, a champagne bottle of about 1.5 liter capacity can be used, Champagne bottles are built to withstand pressure, and have no problem holding up to the approximately 30 pounds of pressure used in the reduction, The glass is quite inert to chemicals, so it is desirable from that point of view as well. On the downside tor this reaction vessel, there is no obviously easy way to attach pressurized lines to the bottle other than using hose clamps, or inserting a stopper into the neck and wiring it into place, Glass is brittle, and may break i I' the clamps are tightened down too much, Heating isn't possible using this glass container, as this will likely cause it to crack, and then burst under the 30 pounds of pressure, Coating the bottle with fiberglass resin helps avert this danger.
- An alternative is "The Poor Man's Hydrogenation Device," It is an aluminum fire extinguisher which has been emptied of contents, washed, and then coated on the inside with either Teflon or Tenon paint such
- Secrets of Methamphetamine Manufacture Eighth Edition
- A magnetic stir bar is slid down into the bottle, and regardless of the variation used, about 5 grams of platinum black or platinum oxide (Adam'S Catalyst) will be enough for the purpose.
- The apparatus shown in Figure 32 can be constructed by anyone with access to machinist's tools. Alternatively, the clandestine operator can have it made for him with little or no chance of anyone suspecting its real purpose. The threads are fine, and coated with Fonn A Gasket immediately before assembly. The valves are of the swage-lock type.
- Before beginning production using this device, the joints are checked for leakage by brushing soapy water on them and looking for the tell-tale bubbles.
- The chief danger in using the hydrogenation apparatus is from fire due to leaking hydrogen coming into contact with a spark or flame. The magnetic stirrer is a possible source of static-induced sparks. To eliminate this danger, it is wrapped in a sturdy bread or garbage bag. This prevents hydrogen from coming into contact with it. Good ventilation in the production area likewise prevents hydrogen from building up in the room.
- To begin production using this device, the champagne bottle is attached to the rig immediately atler ti lling with the reactants. The air is sucked out of the bottle by attaching the exit valve, a vacuum line leading to an aspirator. After sucking out the air for 30 seconds, this valve is closed, and hydrogen is fed into the bottle from the cylinder until it has pressurized to a few pounds above nonnal air pressure (i.e., a few pounds show on the gauge). Then the input valve is closed, and the bottle is vacuumed out once more. Now the bottle is practically free of air. The exit valve is closed once again, and hydrogen is let into the bottle until the gauge shows 30 pounds of pressure. This is 3 atmospheres of pressure, counting the 15 pounds needed to equal air pressure. Magnetic stirring is now started, and set at such a rate that a nice whirlpool fonns in the liquid inside the bottle.
- The hydrogen used in this reaction is of the purest grade available. Cylinders of hydrogen are obtained at welding supply shops. which generally have or can easily get electrolytically produced hydrogen. This is the purest grade. The cylinder must have a regulator on it to control the pressure of hydrogen being delivered to the bomb. The regulator must have two gauges on it, one showing the pressure in the cylinder, the other showing the pressure being fed into the line to the bomb.
- With "The Poor Man's Hydrogenation Device," all the construction is omitted. After filling the extinguisher about half full of reaction mixture, the top is screwed back on. A vacuum line is attached to thc spray nozzle of the fire extinguisher, the valve is opened by squeezing the spray lever, and the air suckcd out. Then the hydrogen line is attached, and about 30 pounds of hydrogen gas pressure put into the extinguisher tank.
- After beginning stirring the contents of the bomb, an induction period of about an hour or so usually follows during which nothing happens. No hydrogen is absorbed by the solution during this period. It is not known just why this is the case, but nothing can be done about it. Use of pre-reduced platinum catalyst does not eliminate this delay. (Pre-reducing is a procedure whereby the platinum catalyst is added first, and then contacted with hydrogen to convert the oxide of platinum to the active metaL)
- In an hour or so, hydrogen begins to be absorbed by the solution, indicating production of methamphetamine. The pressure goes down on the gauge. More hydrogen is let in to maintain the pressure in the 30 pound range. Within 2 to 4 hours after uptake of hydrogen begins, the absorption stops. This indicates the end of the reaction.
- The valve on the cylinder is now closed, and the exit valve slowly opened to vent the hydrogen gas olllside. Now the bottle is removed from the apparatus, and the platinum is recovered for reuse by filtering the solution. The platinum is stored in absolute alcohol until the next batch. Many batches can be run on the same load of platinum catalyst, but it eventually loses its punch. It is then reworked in the manner described later.
- Chapter Eleven The Way of the Bomb
- The filtered reaction mixture is then poured into a 2000 ml round bottom flask, along with 3 or 4 boiling chips. The glassware is set up as shown in Figure II in Chapter Three. The chemist heats the oil no hotter than 1100 C, and distills off the alcohol and water. When the volume of the mixture gets down to near 500 ml, he turns off the heat and transfers the reaction mixture to a 1000 ml round bottom flask with 4 boiling chips. He sets up the glassware for fractional distillation as shown in Figure 13 in Chapter Three. and continues distilling off the alcohol. The temperature shown on the thennometer should be about 800 C. When the volume of the reaction mixture gets down to about 300 ml, he turns off the heat and lets it cool off. He attaches a 250 ml round bottom flask as the collecting flask and begins a vacuum distillation. The last remnants of alcohol are soon gone, and the temperature shown on the thennometer climbs. If he is using an aspirator, when the temperature reaches 80° C, he changes the collecting flask to a 500 ml round bottom tlask and distills the methamphetamine under a vacuum. If he is using a vacuum pump. he begins collecting methamphetamine at 70° C. He does not tum the heat setting on the buffet range above 1/3 of the maximum. Virtually all of the material distilled is methamphetamine. He will get between 200-250 ml of clear to pale yellow methamphetamine, leaving about 20 ml of residue in the flask. A milky color to the distillate is caused by water being mixed with it. This is ignored, or removed by gentle heating under a vacuum.
- The distilled methamphetamine is made into crystals of methamphetamine hydrochloride in the same way as described in Chapter Five. He puts about 75 ml of methamphetamine in each Erlenmeyer flask and adds ether or toluene until its volume reaches 300 ml. Then he bubbles dry hydrogen chloride gas through it and filters out the crystals fonned. The yield will be close to Y2 pound of pure methamphetamine.
- Making and Reworking Worn Out Platinum Catalyst
- Ready-made platinum oxide (Adam's Catalyst) is available tram scientific supply houses at the steep price one would expect for platinum compounds. It's not on any reporting lists, and I don't think it's a particularly "hot" item at the time I am writing this. However, being able to bypass these snitch dens is always of value. Platinum catalyst can be made either from platinum metal, or from the chloride salts of platinum. The metal is easily picked up at dealers of precious metals and coins in the fonn of ingots and coins. The chloride salts of platinum can be easily obtained from suppliers of precious metal salts to electroplaters. Go to the Metal Finishing Handbook and Directory and look in the index under platinum plating baths for a list of suppliers. For a really thorough discussion on making platinum catalyst, see Organic Syntheses, Collective Volume I. Look in the table of contents under Platinum Catalyst for Hydrogenation.
- The process used to tum platinum metal into active catalyst is identical to the method used to recycle worn out platinum catalyst into reborn material. The first step is to dissolve the metal in aqua regia. Aqua regia is a mixture of three parts hydrochloric acid, and one part nitric acid. Only laboratory grade acids in their concentrated forms are used for this process. Lower grades may well introduce catalytic poisons into the precious metal. The nitric acid is the 70% material. The hydrochloric acid is the 37% laboratory material. About a pint of mixed acid serves well to dissolve the few grams of platinum needed to run man-sized batches of methamphetamine. The acids are simply mixed, and then the platinum metal is added. A few fumes of N02 are given off in the dissolution process. Occasional swirling and some heating speeds the process of dissolving the platinum. The dissolution converts the platinum to chloroplatinic acid H2PtCI6. This substance is the starting point for both of the alternative pathways to active platinum catalyst.
- When all of the platinum metal has disappeared into solution, heat is applied to boil away the acid
- mixture. Then some concentrated hydrochloric acid is added. and this too is evaporated away to dryness.
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- The top of the tank has 2 holes drilled in it. One small one in the center of the tank is an entrance for the hydrogen gas. This has a section of stainless-steel pipe about 5 inches long welded around it. It is usually necessary to melt in some stainless-steel welding rod while making this Tig weld, to get it strong enough. This top section is then welded onto the top to create the reaction vessel shown in Figure 33.
- A steel rocking frame is then welded onto the outside of the reaction vessel as shown in Figures 33 and
- 34. The area where it is welded should be reinforced. All welds are done with a Tig welder.
- The chemist can now assemble the bomb. He starts out with heavy wooden planks as the base. This will keep vibration to a minimum. He sets up and bolts down the frame. He attaches some clamps to this frame, then puts sheaths and bearings on the arms of the steel rocking frame, and suspends the reaction vessel about 6 inches off the ground. It should swing back and forth easily.
- Figure 35
- He attaches a band around the reaction vessel, just below where the steel rocking frame is attached to the reaction vessel. The band is attached to the rocking arm, which is attached to a spindle on the driving pulley, as shown in Figures 34 and 35. Both these joints should swivel easily. The driving pulley is about 10 cm in radius. The pulley on the motor has a radius of about 2 cm. The spindle, which extends from the driving pulley to the rocking arm, is about 3 cm from the center of the driving pulley.
- The motor is the usual 1760 rpm type of motor, with a power of at least 1/30 hp. When the motor is turned on, it spins the driving pulley, which moves the rocking arm back and forth, which in turn shakes the reaction vessel.
- The chemist is now ready to test the system. He opens up the valve and puts 2000 ml of distilled water in the reaction vessel. He closes the valve and turns on the motor to begin shaking. If any water comes out the top of the stainless-steel pipe, he secures the wooden base 10 minimize vibration. He shuts it off and opens the valve, then siphons out all the water.
- He now runs a line of heavy rubber tubing from the hydrogen cylinder to the stainless-steel pipe. He crimps in the end of the pipe, then pushes the rubber hose down over the pipe, at least halfway to the tank. He superglues it to help hold it in place. Then he covers the entire length of the hose with a series of pipe clamps so that it does not blow out or slip off the pipe. This hose is slung over a sling in the frame so that it leads straight down to the reaction vessel. There must be enough slack to allow for the rocking mOlion.
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- Using a funnel, the reactants are added to the hydrogenation bottle. Raney nickel generally comes commercially as a suspension in alcohol. It should be thoroughly shaken before measuring out the amount of Raney nickel added, so that a homogenous mixture is being measured out.
- When the reactants have been added to the bomb, the cap is screwed onto the addition portal. making sure the threads are clean, and that the cap has been tightened enough to prevent leakage. A pressure of at least a couple hundred pounds per square inch of hydrogen is then let into the bomb; heating is begun along with the shaking of the hydrogenation bottle. Hydrogen absorption by the solution starts almost immediately, and speeds up as the mixture warms. The hydrogen pressure is maintained by periodically opening the valve to the hydrogen cylinder.
- A few hours after the mixture gets warmed up, the absorption of hydrogen by the solution stops. It is now time to get the product: Heating is stopped, and once the solution has cooled down close to room temperature, the shaking is stopped. All valves from the hydrogen cylinder are checked to make sure they arc tightly closed. Then with good ventilation, the cap is first loosened on the hydrogenation bottle to vent off hydrogen pressure. Then the cap is removed, and the contents of the bomb poured or pumped into a one gallon beaker or jug.
- The Raney nickel catalyst must tirst be removed from the product mixture. This can be done by letting the mixture sit and letting the catalyst settle to the bottom of the container. Then the product mixture can be decanted off of the settled catalyst. Another way to remove the catalyst is to filter it out. This is much laster. One must be careful filtering out Raney nickel catalyst because it is pyrophoric. That means that when it dries out and is exposed to air it first starts to smoke, then bursts into flames. This is quite dangerous because the methanol solvent is flammable as hell. When filtering the catalyst, keep it wet by rinsing it with more alcohol solvent. Whichever method of removing the catalyst is used, it should be saved because it should be reusable several times. The catalyst is kept submerged under alcohol in a bottle or jar until its next usc.
- The product mixture should next be poured into a distilling flask. The apparatus is set up for distillation, then the methanol is distilled off. The residue left inside the distilling flask is allowed to cool down. When it has cooled, a 10-20% solution of sodium hydroxide should be added slowly with occasional shaking of the contents of the flask. When enough sodium hydroxide solution has been added to leave the water layer inside the flask strongly alkaline (pH 13+) then a product layer of amphetamine wi II Iloat on top of the water. It should be no more than yellow colored. A strong smell of ammonia should also be noted from the free basing of the ammonium acetate. Add about four or live volumes of toluene for each volume of phenyl acetone used in the batch, and shake the mixture in the flask to extract all the amphetamine into the toluene. This layer will float on top of the water when shaking is stopped. This layer should be separated off using a sep funnel. This amphetamine-toluene solution can be allowed to sit lor a couple hours to settle out entrained water, then after pouring the toluene-amphetamine solution otIthe settled water, the solution can be poured into a large filtering flask, and a vacuum applied to it. This will cause the ammonia in the solution to be sucked out. Some shaking while under vacuum will help speed along the removal of ammonia. Your nose can be the guide as to when all the ammonia has been removed li'om the solution. Then bubbling with dry HCI through the solution can be done just as described in Chapter Five to get crystals of amphetamine hydrochloride. These are filtered out as described in Chapter Five.
- Alternatively, one can distill the toluene-amphetamine solution, and then dilute the distilled amphetamine with some Iresh toluene, and bubble it with HCI as described in Chapter Five. The yield in either case will be around a pound from the roughly 450 ml of phenylacetone used in this example.
- Chapter Eleven The Way of the Bomb
- Raney Nickel Catalyst
- Ready-made Raney nickel catalyst, sold as a suspension in alcohol or water, is available from scientific supply houses at a fairly steep price. I'm not sure just how "hot" this material is to purchase through regular channels. Buying the material ready-made will assure one of having a good and active catalyst.
- Scientific supply houses also sell Raney alloy, or aluminum nickel-alloy -the material from which Raney nickel catalyst is made. This sells at a more reasonable price, but I'm also unsure of just how "hot" it is.
- In Advanced Techniques of Clandestine Psychedelic & Amphetamine Manufacture, I describe melting your own Raney alloy in a high temperature crucible. This isn't very hard to do, and is very low profile indeed! Let me improve the procedure given in that book. If one takes a clean file and tiles off the required amount of nickel metal from the nickel anode, these small particles of nickel metal melt into the molten aluminum much easier than larger chunks of nickel metal. The result is a more homogenous and more easily made alloy. Nickel is about as hard as iron, so filing chunks of nickel metal down to grit is not very difficult to do.
- Making Raney nickel catalyst from the Raney alloy, either purchased as such or homemade isn't vcry hard to do either. The alloy is a 50-50 mixture of nickel and aluminum. By reacting the finely ground alloy with sodium hydroxide solution, most of the aluminum dissolves out, leaving the Raney nickel catalyst. The catalyst retains a few percent of aluminum mixed in with the nickel, and this few percent of aluminum is very important in its activity. Otherwise one could just use nickel metal and expect to see catalytic activity. Let's make a batch of Raney nickel catalyst from Raney alloy.
- Here's how it's done. In a 2000 ml beaker, the chemist dissolves 190 grams of sodium hydroxide pellets in 750 ml distilled water. The solution is cooled down to 10° C by packing the beaker in ice. He adds 150 grams of the nickel aluminum alloy to the sodium hydroxide solution. It is added slowly and with vigorous stirring. The temperature of the solution must not get above 25° C. The sodium hydroxide reacts with the aluminum in the alloy and dissolves it, producing aluminum hydroxide and hydrogen gas. The nickel is left as tiny black crystals. The hydrogen which bubbles out of the solution causes foaming, so the alloy is added slowly enough that the foaming doesn't get out of control. If that fails, I ml of n¬oetyl alcohol helps to break up the foam. It takes about two hours to add all of the alloy to the sodium hydroxide. When all of the alloy has been added, the stirring is stopped and the beaker is removed from the ice bath. The bubbling of hydrogen gas from the solution continues as the beaker warms up to room temperature. Hydrogen gas is not poisonous, but it is very flammable. Smoking around it can cause an explosion.
- When the bubbling of hydrogen from the solution slows down, the beaker is set in a large pan of hot water. Then the water in the pan is slowly heated to boiling. This will get the hydrogen bubbling again, so it is heated on an electric heater in a well-ventilated area. This heating is continued for 12 hours. Distilled water is added to the beaker to maintain its original volume.
- Alier the 12 hours are up, the chemist removes the beaker from the boiling water bath and stirs it up.
- Then he allows the black Raney nickel catalyst to settle to the bottom of the beaker, and pours otf as
- much of the sodium hydroxide solution as possible. The nickel is transferred to a 1000 ml graduated
- cylinder with the help of a little distilled water. If the nickel catalyst is allowed to dry out, it may burst
- into !lames. It must be kept covered with water. Again the chemist pours off as much of the water as
- possible. Then he adds a solution of 25 grams of sodium hydroxide in 250 ml of distilled water to the
- nickel in the graduated cylinder. The cylinder is stoppered with a cork or glass stopper (not rubber) and
- shaken for 15 seconds. Then it is allowed to settle again and as much of the sodium hydroxide solution as
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- possible is poured off. The catalyst is now ready to have the sodium hydroxide removed from it. All traces must be removed, or it will not work. The chemist adds as much distilled water to the cylinder as it will hold, then shakes it to get the nickel in contact with the clean water. He lets it settle, then shakes it again. When the nickel has settled, he pours off the water and replaces it with fresh distilled water. This washing process is repeated 25 times. It takes that much to remove all the sodium hydroxide from the catalyst.
- After the water has been poured off from the last rinse with distilled water, 100 ml of rectified spirit (95% ethyl alcohol) is added to the nickel and shaken. After the nickel has settled, the alcohol is poured off and the washing is repeated two more times with absolute (1 00%) alcohol. The result is 75 grams of Raney nickel in alcohol. It is transferred to a bottle that it will completely fill up. If necessary, more alcohol (100%) is added to fill up the bottle. Then the bottle is tightly stoppered. When the chemist is ready to use it, he shakes it to suspend the nickel and measures out the catalyst. One ml contains about .6 grams of Raney nickel catalyst.
- It has been claimed that a more active catalyst can be made by adding the sodium hydroxide solution to the nickel-aluminum alloy instead of vice versa. But when this is done, care must be taken that the foam doesn't get out of control. Also, the alloy must be stirred into the solution so it can react. Other than that, the catalyst is prepared in exactly the same way.
- Raney nickel is a pain in the ass to use, largely because its magnetic properties prevent the use of magnetic stirring during reduction. There are other nickel catalysts that are said to resemble Raney nickel in activity. Even better, they aren't pyrophoric, so that danger is eliminated. They are also said to work at fairly low hydrogen pressures and without the need for heating to be applied. "The "Poor Man's Hydrogenation Device" could be used instead of that shaker bottle monstrosity!
- These catalysts are made by the reduction of the common nickel salts such as nickel chloride or sulfate by borohydride or by zinc dust. These common nickel salts are widely used in electroplating. For some directions, see Journal 01 Organic Chemistry, Volume 35, page 1900 (1970) and Chem. Commun., 1973, page 553 and Bull. Chern. Soc. Japan, Volume 33, page 232 (1960). It's worth checking out!
- One tinal topic must be addressed while on the subject of hydrogenations. That subject is the use of catalytic converters from cars as hydrogenation catalysts. I've been hearing these stories for about a decade now. I don't know how well it would work. It may well be the equivalent of an urban legend. We dope cookers have our own lore and mythology, you know?
- The converter contains a mixture of platinum and palladium thinly spread over the surface of a supporting medium. Palladium behaves quite similarly to platinum as an hydrogenation catalyst, except that it remains active in acid solutions.
- To use this material as an hydrogenation catalyst, a new catalytic converter should be obtained. An old used one from the junk yard will not do, because the catalyst may have been poisoned from the use of bad fuel, and it will also likely be covered with a sooty film. Cut open this new catalytic converter to get the converter element inside. The catalyst itself is a mass of BB-sized pellets packed inside the converter. These should be removed and washed clean in soapy hot water, followed by a rinse with rubbing alcohol.
- There are problems associated with the use of this makeshift hydrogenation catalyst. The amount of catalyst used must be greatly increased because these pellets don't possess the enormous surface area that a finely divided material has. Catalytic hydrogenation takes place at the surface of the metal, so this is an important point. Further. these pellets aren't easily stirred up in the solution to catch a breath of fresh hydrogen. so they can quickly go dead. They are better used in a bomb which is agitated by shaking. Also. their mass makes them likely to break a hydrogenation bomb made of glass, so a bomb constructed of metal is more compatible with their use.
- Chapter Eleven The Way of the Bomb
- References
- Organic Reactions, Volume 4, page 174.
- Journal of the American Chemical Society, Volume 61, pages 3499 and 3566 (1939):
- Volume 66, page 1516 (1944): Volume 70, pages 1315 and 2811 (1948).
- Reductions in Organic Chemist/y, by Milos Hudlicky.
- Practical Catalytic Hydrogenation, by Freifelder.
- Chapter Tweil'e Reductive Alkylation without the Bomb
- Method One
- In this method, the activated aluminum reacts with alcohol and water to produce hydrogen gas. This hydrogen then reduces the Schiffs base fonned from methylamine and phenyl acetone to give methamphetamine.
- The chemist needs a magnetic stirrer-hotplate to do this reaction. On top of the stirrer-hotplate. he places a Pyrex bowl or cake dish large enough to hold a 3000 ml flask. The bowl or dish cannot be made of metal. because the magnetic stirrer will not work through it. He places the 3000 ml flask in the dish and fills it with cooking oil until the oil reaches about halfway up the sides of the flask. He must be sure to leave enough room for the oil to expand as it heats up. He puts the magnetic stirring bar in the flask along with 1600 ml of absolute alcohol or 190 proof grain alcohol. Then he adds 340 ml of phenylacetone and 450 ml of 40% methylamine in water. Now he turns on the magnetic stirrer and begins heating the oil in the dish. He keeps track of the temperature of the oil with a thermometer, and does not allow it to go above 100° C. While the oil is heating up, he adds ISO grams of activated aluminum to the flask. He makes sure that the stirring is fast enough that the turnings do not settle to the bottom of the flask. The reaction mixture will quickly begin to turn grey and foamy. The aluminum is added at such a rate that the bubbling and foaminess it produces does not overflow the flask. When all of it has been added, a condenser is fitted to the flask, and water flow is begun through it.
- The chemist now lets them react for 8 hours. He keeps the temperature of the oil bath at 100° e, and the stirring strong. The activated aluminum slowly dissolves and produces hydrogen gas. The explosive danger from this gas is eliminated by running a length of tubing from the top of the condenser out the window. The fumes from the reaction are noxious, so this is far better than just staying upwind.
- When the 8 hours are up, he removes the flask from the oil bath and wipes the oil off the outside of the flask. He decants the solution to remove the aluminum sludge, then rinses the sludge with some more alcohol to remove the last traces of product from it. The rinse alcohol is added to the rest of the filtered product.
- The underground chemist can now distill the product. He pOllrs it in a 3000 ml round bottom flask that is clean and reasonably dry. and adds a few small pieces of pumice. He places the flask on the electric buffet range, then sets up the glassware for fractional distillation, as shown in Chapter 3. He begins heating it. The first thing that distills is a mixture of alcohol, water, and methylamine. This occurs when the temperature shown on the thermometer is about 7S-S0° C. He collects about 1600 ml of this mixture, then removes the flask from the heat. He lets it cool down, then pours the contents of the 3000 ml flask into a 1000 ml flask, along with a few fresh boiling chips. He puts about 15 ml of alcohol in the 3000 ml flask. swirls it around to dissolve the product left clinging to the insides, then pours it into the 1000 ml flask.
- The chemist again sets up the glassware for fractional distillation, with a 250 ml flask as his receiver.
- He applies a vacuum, preferably from an aspirator, and begins vacuum distillation. When the boiling gets under control, he begins heating the flask. The last remnants of alcohol and water will soon be gone, and the temperature shown on the thennometer will climb. When it reaches about 80° e with an aspirator. or about 70° C with a vacuum pump, he quickly changes the receiving flask to a clean, dry 500 ml flask, and reapplies the vacuum. He will get about 350 ml of clear to pale yellow methamphetamine free base. A lew milliliters of tar will be left in the distilling flask. The liquid free base is converted to crystals by dissolving it in ether or toluene and bubbling dry Hel through it, as described in Chapter Five.
- The underground chemist gets an even purer product hy varying this procedure slightly. Once the 1600
- ml of alcohol, water, and methylamine is distilled off, he pours a mixture of 650 ml of 28% hardware
- store variety hydrochloric acid and 650 ml ofwater into what remains in the 3000 ml flask, after it has
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- cooled down. A lot of heat is produced in the mixing because the methamphetamine free base is reacting to make the hydrochloride, so he adds it slowly, then swirls it. When it has cooled down, he stoppers the 3000 ml flask with a cork or glass stopper and shakes it vigorously for 3 to 5 minutes. It should pretty much all dissolve in the hydrochloric acid solution. Now he adds 200 ml of ether or toluene to the flask and shakes it up well. The ether or toluene dissolves any unreacted phenyl acetone and tar. He lets it sit for a few minutes. The ether or toluene layer floats to the top. He pours it slowly into a 1000 ml sep funnel, so that the top layer all gets into the sep funnel. Now he lets it set, then drains the lower acid layer back into the 3000 ml flask.
- The acid must now be neutralized to give back amphetamine tree base, so it can be distilled. The chemist mixes up a solution of 350 grams oflye in 400 ml of water. When it has cooled down, he pours it slowly into the acid solution in the 3000 ml flask. A lot of heat is generated from the reaction. When it has cooled down, he stoppers the flask and shakes it strongly for about 5 minutes. Upon standing, the amphetamine forms a layer on top. He slowly pours it into a 1000 ml sep funnel. He drains the water layer back into the 3000 ml flask. The methamphetamine layer in the sep funnel may have some salt crystals floating around in it. He adds 100 ml of toluene to it plus a couple hundred ml of a dilute lye solution. He stoppers and shakes the mixture. The salt will now be dissolved in the water. He drains the water layer into the 3000 ml flask and pours the methamphetamine-toluene solution into a clean 1000 ml tlask. There is still some methamphetamine left in the 3000 ml flask, so he adds a couple hundred ml of toluene to it. [I' there is a lot of undissolved salt in the flask, he adds some more water to it. Now he shakes the flask to dissolve the meth in the toluene, then lets it set. The toluene comes up to the top. He pours it off into the sep funnel, and drains off the water layer. He pours the toluene layer into the 1000 ml flask with the rest of the product.
- He can now begin distilling it. He adds a few boiling chips, sets up for fractional distillation, and proceeds as described in Chapter Five. The yield once again is about 350 ml of free base, which makes close to 400 grams of pure crystal.
- Method Two
- This method is not as good as the first one. It takes longer, it uses up more chemicals to make a given amounl of product, and less can be produced at a time.
- The equipment is set up as in Method One. Into the 3000 ml flask is placed 1575 ml of 190 proof alcohol and 150 ml of distilled water. Then the chemist adds 150 ml of phenylacetone and 220 ml of 40% methylamine in water. He begins magnetic stirring and adds 160 grams of activated aluminum. He heats the oi I bath to 100° C or so and attaches a condenser to the 3000 ml flask. He begins water flow through the condenser and genlly boils the contents of the flask for 16 hours. At the end of this time, he removes the flask from the heat and lets the aluminum sludge settle. He filters the alcohol solution, rinses the sludge with alcohol and adds the filtered alcohol to the rest of the product. Then he proceeds as described in Method One. The yield is about 150 ml of methamphetamine.
- Method Three
- This method is not as good as Method One either. Ether is used as the reaction solvenl, which adds danger and expense. The ether is a chemical which should be rarely used by clandestine chemists. Another problem with this reaction is that it is done so dilute that large amounts can't be made at one time.
- In the same set-up used in Methods One and Two, the underground chemist places 1000 ml of absolute ether in a 3000 ml flask. Then he adds 100 ml of phenylacetone and 160 ml of 40% methylamine. He
- Clrapter Twelve Reductive Alkylation witlrout tire Bomb
- begins stirring and adds 65 grams of activated aluminum. He attaches an efficient condenser, runs cold water through it, and heats the oil bath to 45-50° C. He gently boils the solution for 6 hours. The activated aluminum reacts with the water in the methylamine to produce hydrogen.
- When the six hours have passed, he distills off the ether and treats the residue as described in Method One, i.e., distills it under a vacuum, etc. The yield is about 90 ml ofmeth.
- For more information on this method, see U.S. Patent Nos. 2,146,474 and 2,344,356.
- Method Four
- This variation on the activated aluminum method of reductive alkylation has the advantage of using methylamine hydrochloride directly in the reaction soup. Since methylamine is now very dangerous or impossible to obtain commercially, and also since the best method for making methylamine yields methylamine hydrochloride, the usefulness of this variation is obvious.
- This method involves the addition of an alcohol solution containing the Schiff's base formed between methylamine and phenylacetone onto the activated aluminum. In the other methods, the opposite order of addition was employed. To maximize yields of product, the competing side reactions are suppressed. In the case of activated aluminum methamphetamine production, the main side reaction is the reduction of phenyl acetone into an interesting, but quite useless pinacol. It has the structure shown below:
- Pinacol
- OCHz-t-OHCI+J OCHz--I CI+J
- OH
- This side reaction is minimized by keeping the amount of water in the reaction mixture to a minimum, and also by using a healthy excess of methylamine. This scheme of things encourages the phenyl acetone to tie itself up with methylamine to form the Schiff's base, rather than float around freely in solution where it could be reduced by the aluminum.
- To do this reaction, two 2000 ml volumetric flasks are obtained. Volumetric flasks work well for this reaction because the chemist can swirl around their contents quite forcefully without danger of spillage. They also pour pretty well. One volumetric flask is for preparing the activated aluminum, and is also the ultimate reaction vessel. The other volumetric flask is for the preparation of the Schiffs base. The lab work is organized so that both products are ready to react at about the same time.
- Into the volumetric flask destined to be the ultimate reaction vessel, the chemist places 108 grams of aluminum foil. It is cut into one inch squares. The best brand of aluminum foil for this purpose is Heavy Duty Reynolds Wrap. It is then treated with sodium hydroxide solution as described in Method I. After a rew good rinses to remove the sodium hydroxide, it is ready to become activated aluminum. To do this, the volumetric flask is filled almost to the neck with distilled water, containing about 2V, grams of HgCI2. The flask is swirled every few minutes for the next 30 minutes. During this time, the water becomes a cloudy grey color, and the aluminum loses its shine. The water is then decanted off the aluminum, and the flask is filled up with fresh distilled water to carry away unreacted mercury. After a period of swirling, the rinse water is poured off, and the rinse repeated with a fresh portion of distilled
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- water. On the last rinse, the chemist makes sure that the water drains off well. This leaves activated aluminum ready to go.
- In the second volumetric flask, Schiffs base is made. To do this, 163.5 grams of sodium hydroxide is dissolved in one liter of 190 proof vodka. To this is added 270 grams of methylamine hydrochloride. This methylamine is dry so that the chemist is not weighing water contamination. If this is home brew methylamine hydrochloride. the first crop of crystals is acceptable material, but the second and third batches of crystals are recrystallized as described in Organic Syntheses, Collective Volume I. Look in the table of contents for methylamine hydrochloride. The mixture is kept cool during the addition to prevent methylamine gas from escaping. Good stirring is also essential. The result of this operation is an alcohol solution of methylamine. Some salt and water are formed.
- To make the Schiffs base, 200 ml of phenyl acetone is then added to this solution. The addition produces a fair amount of heat, and some methylamine fumes are driven off as a result. Active swirling of the flask keeps this to a minimum. The chemist also tips the flask during swirling to dissolve any phenylacetone which may be stuck up in the neck of the flask. This is the Schiffs base solution.
- To do the reaction. the Schiffs base solution is poured onto the activated aluminum. Once the pouring is complete, they are swirled together energetically for a few seconds, then a thermometer is carefully lowered into the flask. Following this, a section of plastic tubing is stuffed into or over the top of the volumetric flask, and led outside. This is for fume control. The reaction mixture is swirled continuously for the tirst few minutes. The temperature rises quite rapidly because the reaction is really vigorous. It is necessary to have a bucket of ice water close by to dunk the reaction vessel into to keep it under control. The experimenter strives to keep the reaction mixture in the 50 to 60° C range. After the initial rush, occasional swirling is acceptable, so long as the temperature guidelines are followed. After 90 minutes, the reaction is complete.
- At least in the case of MDMA, for meth, one should cook more aggressively. Once the initial rush of the reaction is over, heat should be applied to bring the mixture to reflux as soon as it is safe to do so. Serious experimenters should also note that Dr. Shulgin likes to have some free NaOH floating around the reaction media, along with salt. Even more serious experimenters should note that the original patents for this process stated that best yields were obtained when the hydrogen gas generated was held in by means of a pressure vessel. An emptied fire extinguisher may well be the best reaction vessel.
- To process the product, the alcohol solution containing the product is poured off into the distilling flask. The mud-like gunk at the bottom of the flask contains a fair amount of trapped product. This gunk is untreatable as is, but with some lightening up, it can be filtered. A lab product called Celite is added to the gunk until it appears more amenable to filtration. As an altemative, washed white sand. found in the cement section of your friendly neighborhood store, is a good substitute. This is mixed in witb the gunk until it lightens up a bit. Then two portions of 200 ml of warm vodka (190 proof) are mixed in and the trapped product is filtered out of the gunk. These gunk filtrates are added to the main product, and the whole mother lode readied for processing.
- The first step is to place all the liquid into the distilling flask along with a few boiling chips, and
- remove the alcohol with a vacuum. A fractional distillation then gives pure methamphetamine free base
- ready for crystallizing into tbe hydrochloride.
- The same method can be used to give MDMA just by substituting MDA phenylacetone for regular phenyl acetone.
- Method Five
- This is the so called Laboratories Amidos recipe. If you don't feel like reading a French patent, the
- description of the recipe can be found in Chemical Abstracts, Volume 62, column 5228 (1965). This
- procedure mainly varies from the other processes given in this chapter in that a smaller amount of
- Clrapter Twelve Reductive Alkylation witlrol/l lhe Bomb
- mercuric chloride is used, but this smaller amount of mercuric chloride isn't rinsed off of the aluminum foil and removed from the reaction mixture, Rather, this smaller amount of mercuric chloride is allowed to remain in the reaction mixture, where presumably it just keeps on working forming freshly amalgamated aluminum during the course of the reductive alkylation. The word out there is that this variation is a good recipe to use for this method of making meth or M DMA from the phenylacetone.
- To do the reaction, start with a 1000 ml flask, and place inside that flask 40 ml of phenylacetone or m¬d-phenylacetone, followed by 200 ml of 190 proof vodka, and 200 ml of a 25% solution of methylamine in water. This solution can be made from methylamine hydrochloride just by dissolving the required amount of methylamine hydrochloride in water (roughly 100 grams of methylamine hydrochloride diluted to 200 ml with water) and then adding the calculated amount or slightly more NaOH to the water solution of the methylamine hydrochloride with cooling and stirring. In this case that would require about 60 grams of NaOH. The salt formed by this neutralization isn't harmful, and may even be beneficial, so this neutralized methylamine solution can be just poured into the mix as is without any filtering.
- Next add 40 grams of aluminum to the flask. The patent srecifies aluminum turnings, but I would think that aluminum foil fresh off the roll and cut up into one inch squares would work just as well. Then tinally add .3 gram of mercuric chloride. Swirl or stir this mixture to get the mercuric chloride dissolved, and aluminum amalgam formed on the surface of the aluminum. Mercuric chloride dissolves very slowly even with stirring, so let one's eyes be the guide to when the mercury has formed an amalgam on the surface of the aluminum.
- Once the amalgam has formed, rig the flask for retlux, and heat the mixture to boiling for a couple of hours. At the end of the heating period, allow the mixture to cool down, then rig the tlask for distillation. Apply a vacuum from an aspirator to boil off the alcohol and the methylamine. Some heat will have to be applied to the flask to make this distillation proceed at a reasonable rate.
- When the alcohol and methylamine have distilled off, the residue inside the flask should be poured into about a liter or so of ice water. Rinse the inside of the flask with water and add it also to the ice water.
- Then to the ice water mixture. add about 120 grams of potassium hydroxide (KOH) pellets. Stir the mixture until the pellets have dissolved. The KOH will react with the residue of aluminum in the mixture to form aluminum hydroxide. Hydrogen gas will fizz out of the solution during this process and produce some foul mist. One is advised to stay upwind, and add the KOH at such a rate that the mixture doesn't foam over. The KOH will also react with the mercury in solution to form the hydroxide or oxide of mercury. This too will fom] a sludge in the water solution.
- When the fizzing of the aluminum has subsided, the mixture should be strongly shaken for a few minutes. Any gas given off should be vented occasionally. Then extract out the meth or MDMA with two 200 ml portions of toluene. After these extracts have been separated off the water layer, they should be filtered if any sludge is seen floating around the extracts. This should completely remove traces of mercury_
- Next mix up about a pint of 10% HCI solution. This is made by starting with 30% hardware store
- hydrochloric (muriatic) acid. and diluting it with two volumes of water. Place the toluene extracts into a
- large sep funnel, then add the pint of 10% HCI to the sep funnel. Shake strongly for a few minutes. The meth or MDMA will form the hydrochloride salt, and dissolve in the dilute acid. What remains in the toluene solution will be bunk that can be thrown away. One can check the toluene for the presence of phcnylacetone, but I doubt that a significant amount will be found.
- After the shaking, allow the mixture to sit in the sep funnel for a while. The toluene solution will rise to the top, and the acid solution of the product will be on the bottom. Separate the two, then return the acid solution to the sep funnel. Now to this acid solution, add a 20% solution of lye in water until the mixture is strongly alkaline (pH 13+ to pH papers). This addition should be done slowly with shaking
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- between adds of lye solution. As the mixture gets hot, take time to allow it to cool. Roughly 100 grams of lye should be enough to make this solution strongly alkaline, but let pH papers confirm the situation. As the acid gets neutralized, the free base of meth or MOMA will form and float on top of the water solution.
- When the solution has been made strongly alkaline, shake some more, and allow the mixture to cool.
- When cooled down, extract out the product with two ISO ml portions of toluene. The pooled extracts can be allowed to sit for a while to settle out any entrained water, then poured into a fresh container and bubbled with HCI to get crystals of meth or MOMA. Alternatively, the toluene extracts can be placed into a distilling flask, and fractionally distilled. This is done just as described in Chapter S. Then the distilled meth or MOMA can be diluted with a couple hundred ml of toluene and bubbled with dry HCI to get crystals of meth or MOMA. In either case, the yield would be around 30 grams of product. Distilling would of course give a purer product.
- Method Six
- "The Racer's Edge"
- Methylamine is the crucial ingredient required in all methods of producing meth or MOM A from their respective phenylacetones. There are several recipes for cooking one's own methylamine in the next chapter. but if one has chosen the activated aluminum reduction as the meth production route, then it is more than just convenient to also use activated aluminum to make the methylamine. How the gods have smiled upon us to order the laws of chemistry in such a way that activated aluminum is also the most effective way to convert nitromethane to methylamine!
- Nitromethane is pretty easily available at hobby shops where it is sold as fuel for model airplanes and race cars. Gallon jugs full of the fuel are likely to be lining the wall in one comer of any store catering to the needs of the model enthusiast at a price of roughly $25 each. This fuel is sold in concentrations of 10% to SO% nitromethane dissolved in methanol solvent. For the purposes of this reaction, any fuel 10% concentration and above will work just fine.
- Now to convert the nitromethane model airplane filel to methylamine, one needs a 2 or 3 necked flask, a good condenser, and a sep funnel. The flask should be at least 2000 ml in capacity. Into the flask put about ISO grams of heavy duty aluminum foil cut up into one inch squares. Next, measure out enough model fuel so that one has roughly 160 ml of nitromethane. If it is 10% nitromethane, that would mean using roughly 1600 ml of fuel. 20% nitromethane fuel would require the use of half that amount, and stronger fuels would require that even less be used, but they would have to be diluted with methanol to be used. To the fuel mixture, now add SS ml of water. This is very important to getting the reaction to turn out correctly, as some water is needed to get the activated aluminum to work. Stir or shake the fuel mixture to get the water evenly dissolved in.
- Now add just enough of the model fuel mixture to the Ilask to just barely cover up the aluminum foil.
- Finally add 112 gram of mercuric chloride to the flask and swirl to get it spread around.
- The aluminum foil will begin to amalgamate pretty soon, so quickly attach the condenser to one neck of the flask and the sep funnel or dropping funnel to the other. If there is a third neck on the flask. stopper
- it. Swirl the flask every couple of minutes to mix the ingredients, and begin a flow of cold water through
- the condenser. It should be as cold as possible and siphoned ice water from a pail as described in the N¬methyl formamide chapter would be best.
- The contents of the Ilask will begin to get hot as the reaction kicks in. One should be noting significant
- heating within IS minutes. It is likely to boil on its own due to the heat of reaction. If a significant
- heating of the solution isn't noticed within 20 minutes. immerse the flask in boiling hot water to kick start
- Chapter Twelve Reductive Alkylatioll without the Bomb
- hings. It is more likely that the solution will get hot enough that the flask should be wrapped in cold wet
- owels to calm things down.
- Another thing which will be noted as the initial reaction kicks in is that some methylamine gas is :scaping out the top of the condenser. You neither want to breathe in this stuff, nor lose it to the air. ,imply attach some tubing to the top of the condenser and lead it into some dilute hydrochloric acid ,olution. There the bubbles of methylamine gas will be caught as methylamine hydrochloride. You can ater evaporate that solution down and obtain some extra methylamine. It is cleaned up as described in he next chapter.
- .vhen the initial rush of the reaction has subsided, take some of the remaining model fuel-water mixture lnd pour it into the sep funnel attached to the flask. Drip in this solution at such a rate that the boiling of he solution stays managable. Continue adding this solution until all of the original solution you have neaslired out has been added. This will take at least half an hour. During the course of the reaction, :ontinue to swirl the flask every couple of minutes to keep the aluminum from getting stuck on the )ottom of the flask and covered with goo.
- In about an hour, the reaction will begin to slow. When it has stopped boiling, take a pipette and .vithdraw about \0 ml of the reaction mixture. Squirt it into a beaker half filled with water. Next, take ;ome hardware store 30% hydrochloric acid, and dilute it with two volumes of water. Mix well, then lsing a pipette, measure out again about 10 ml of the acid solution and with stirring slowly add the acid to the methylamine reaction mixture until a pH of about 7 is reached. A pH meter is very handy for tracking this reaction. Note how much acid was needed to react with the methylamine. If 10% nitromethane fuel was used, the amount of acid required should be 5 to 7 ml. If 20% nitromethane was used, the amount of acid required would be double that. If the amount of acid required is significantly less. then the reaction isn't complete, and the mixture should be boiled for another hour or so. I f this still doesn't bring the reaction to completion add about 200 ml of 50% sodium hydroxide to the reaction mixture, and let it boil some more. This last resort shouldn't be done routinely because it makes your product less suitable for direct use in the next stage of the reaction, which is cooking meth or X from the methylamine just made. One might well have to distill a mixture to which sodium hydroxide has been added.
- This reaction has just made roughly 3 moles of methylamine dissolved in methanol. That is about the right amount to use to convert one mole of the phenylactone to meth or X. One mole of phenyl acetone is roughly 135 ml, and one mole of m-d-phenylacetone is around 160 ml. We now proceed to the next stage, which is using this methylamine to make the product.
- If NaOH did not need to be added to complete the reaction, just let the reaction mix cool and settle. Then decant off the product methylamine solution through a filter to remove aluminum debris and keep it in a stoppered bottle while preparing the next stage of the reaction. How to dispose of the mercury amalgamated sludge left over is covered later in this chapter.
- Making Product
- Into the same three necked flask used to make the methylamine (once it has been cleaned out and dried) put roughly 40 grams of heavy duty aluminum foil cut up into one inch squares. Then add around 100 ml of clean methanol to cover up the aluminum foil. Add more methanol if they aren't submerged. Finally, add 114 gram of mercuric chloride, and swirl it a bit to mix.
- As it is dissolving, get the methylamine solution in methanol just made and add it to the flask, and swirl some more. Attach a condenser to the flask. Finally, add one mole of the phenyl acetone of your choice and 30 ml of water. Mix some more, then add a magnetic stir bar for stirring action. Allow the reaction to kick in, then supply heat as needed to keep it boiling for a few hours. Your reaction is complete.
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- Let the debris settle for a bit as it cools, then decant the reaction mixture through a filter. The larger particles can be caught first with a stainless steel screen before going through the finer fi lter. To the debris left in the flask, add 100 ml of methanol and heat to boiling to get trapped product out. Filter that solution and add it to your main load of product.
- Now one has to distill off the methanol from the reaction mixture. Simply pour the filtered reaction mix into the original reaction flask after it has been cleaned out, and rig for simple distillation. Boil off most of the methanol from the product until it seems that there are two layers forming in the distilling flask, or until one is down to roughly 200 ml left in it, whichever comes first. Then let it cool.
- It's now time to get the product. When the solution has cooled down, add about 200 ml of 10% sodium hydroxide solution in water to the flask, and shake it for a couple of minutes. Then add about 400 ml of toluene or xylene to the flask and shake some more. When the layers separate upon standing, the product will be in the toluene layer, which will float above the sodium hydroxide and water layer.
- Pour the mixture into a separatory funnel, and then drain off the water layer. The toluene layer should then be poured into a distilling flask. One then distills off the toluene or xylene as in the previous examples, and then the product is distilled under a vacuum as in the other examples. One will get roughly an 80% yield of Iree base meth or MDMA, which is then dissolved in several volumes of toluene and the crystals of product are obtained by bubbling dry Hel gas through this solution of product in toluene. just as in the other examples.
- Aluminum Amalgam
- Question: "Why won't my aluminum amalgamate?" -Someone on the Internet
- Answer: The questioner here refers to the methods given earlier in this chapter wherein aluminum metal amalgamated with mercuric chloride solution produces aluminum amalgam, which can be used as a reducer for the Schiffs base produced by mixing methylamine and phenyl acetone or methylamine and M D-phenylacetone to yield methamphetamine or "X" respectively.
- If we look in Reagents fbI" Organic Synthesis, Vol. I. by Fieser, under aluminum amalgam, we find two procedures for making aluminum amalgam. In the first procedure, the oil and grease free aluminum is first etched with dilute sodium hydroxide to the point of strong hydrogen evolution. Using really dilute sodium hydroxide solution, like the one-hall% solution recommended in the book you are now reading, the solution is going to have to be heated to get a strong hydrogen evolution.
- Once the aluminum starts to fizz well, the sodium hydroxide solution is decanted off, and the metal is washed once with water so that the surface still retains some sodium hydroxide solution. Sodium hydroxide clings to surfaces, so this isn't a difficult requirement to meet.
- A one-half % solution of mercuric chloride in water is then poured on top of the aluminum until it is submerged. After about a two minute reaction time, the mercuric chloride solution is decanted oft and the process repeated with some fresh mercuric chloride solution. The light brown smut which formed on the aluminum metal surface trom the sodium hydroxide etch should now all be gone, and replaced with a shiny surface layer of aluminum amalgam. It is now ready to use, once rinsed free of the mercuric chloride solution.
- In variation number two given in Reagents for Organic Synthesis, the surface of the aluminum foil is ilrst sandpapered, then it is immersed in mercuric chloride solution to form the aluminum amalgam.
- Experience has shown that when using clean aluminum foil fresh off the roll, the preliminary sodium hydroxide etch or sanding of the surface can be dispensed with. It just takes considerably longer for the amalgam to form because the surface oxide layer on the aluminum has to be broken before amalgamation can proceed. Let your eyes be your guide to the completion of the process. According to PIHKAL. the amalgamation is allowed to proceed until the surface of the aluminum looks grey with occasional silver
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- The main drawback to this method is the fact that cyanoborohydride is pretty much only available from scientitic supply houses such as Aldrich. Those folks were born to be inveterate snitches. Any business that sells List I chemicals has to have an approved snitch plan in place. Of course, mercuric chloride is also mainly available from these same supply houses, but it has many more uses than cyanoborohydride. Cyanoborohydride is almost exclusively used as a reducer for Schiffs bases.
- Clandestine chemists have recently found that when making MDMA, the much more common chemical, sodium borohydride, can be used. In Advanced Techniques I gave a lot of coverage to this chemical, and how it can be obtained so I won't waste space here to repeat. What they found was that using almost water free reaction conditions, the methylenedioxyphenylactone could be reduced to MDMA in almost 100% yields using methylamine free of water and sodium borohydride as the dry powder. They put their m-d-phenylacetone into a flask, and then added three moles of methylamine in methanol. The most convenient way of doing this is to put three moles of methylamine hydrochloride into 1000 or so ml of methanol, and then adding three moles of KOH to free base it, and after a good mix and reaction of half an hour, filtering out the salt which forms. One could also use the fairly dry methanol solution of methylamine which is made in Method 6 of this chapter. Once the two of them are mixed, slowly add about one-tenth the weight of sodium borohydride as compared to the phenylacetone. The addition should take at least half an hour, and the schiffs base will be turned into MDMA. Then the MDMA can be recovered just as in the sodium cyanoborohydride method just mentioned. The bad thing about this method is that it doesn't work for making meth from phenyl acetone, as even small amounts of water ruin the yield. Check out Journal of Organic Chemistry Volume 28, pages 3259-61 (1963) for some background on this reaction route. The free wheeling experimenter looking to break new ground may wish to try dimethylaminoborane instead as the reducing agent. This substance is easily obtained in large amounts from the reducer component of many electroless nickel plating baths which produce a nickel¬boron alloy. Check the MSDS sheet of the electroless nickel product before buying some, and keep in mind that most electro less nickel baths produce a nickel-phosphorus alloy instead by using sodium hypophosphite as the reducing agent.
- This leaves catalytic hydrogenation of the methylamine/phenylacetone mixture using platinum catalyst as the non-toxic and non-polluting method of choice. Catalytic hydrogenations using platinum catalyst have been done for over a century. This speaks to the simplicity and effectiveness of the procedure. The yields from catalytic hydrogenation are about the same as using cyanoborohydride.
- The best hydrogenation vessel for clandestine cooking is an aluminum tire extinguisher, emptied and cleaned out (see 'The Poor Man's Hydrogenation Device" in Advanced Techniques of" Clandestine Psychedelic & Amphetamine Manufacture). Then a magnetic stir bar is put in the fire extinguisher bottle followed by 150 ml of phenylacetone followed by 300 ml of 190 proof vodka. Then 150 ml of 40% methylamine in water is added. As an alternative, an equivalent amount of methylamine hydrochloride can be put in a beaker with the alcohol, and an equimolar amount of sodium hydroxide added to free base the methylamine. Then this mixture is poured into the extinguisher. Finally, about 3 grams of platinum catalyst is added. The top is screwed on the extinguisher, and most of the air pulled out with an aspirator. Then 30 pounds per square inch pressure of hydrogen is added and stirring begun. After an induction period of about half an hour or so, uptake of hydrogen begins. The pressure is maintained at 30 psi for the few hours it takes to complete the reaction.
- Then the catalyst is tiltered out for reuse. The unused methylamine is boiled out and piped into hydrochloric acid for reuse. Then the alcohol is evaporated away, and the residue is then either distilled under a vacuum, or simply dissolved in about 700 ml of toluene. Bubbling dry HCI through this toluene solution will give crystals of the amphetamine hydrochloride as in the last example.
- Chapter Twelve Reductive Alkylation without the Bomb
- Question: "What do I do with my mercury waste?" -Somebody else on the Internet
- Answer: You take the same approach that we industrial chemists have been using for decades now. First of all, you choose to use a process that doesn't make such intractable waste. If you just are cooking a little bit, one can pour the remains of amalgamated aluminum down the toilet and let the metropolitan sewage plant deal with it.
- If one is making greater amounts of mercury waste than that, the only responsible thing to do with it is to mix up some concrete, and while it is still wet, stir the mercury waste into it. After it has set up, the rock can be tossed anywhere. The mercury will be trapped for as long as the cement lasts. We should be talking thousands of years there.
- The use of mercury in certain reactions needs to be condemned. For example, phenyl acetones can be made from allylbenzenes by reaction with mercury acetate followed by oxidation with chromic acid. The waste potential in this route is enormous, without discussing the use of mercury in drug synthesis. Such
- methods are best left alone.
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- Chapter Thirteen Methylamine
- Methylamine is very high on the do-not-ever-purchase-through-regular-commercial-channels list. As stich, any meth production scheme that uses the phenyl acetone route will also have to produce its own methylamine. This is no great challenge. In the days before methylamine became commercially avai lab Ie, researchers and practical cookers in industry always had to make their own. To our benefit, they left good directions for us to follow. See Organic Syntheses, Collective Volume I, pages 347-9.
- 9 N'HCH I
- 2H-C-H +
- ,
- H ,H
- Formaldehyde MethylamineAmmonium hydrochlori de chlande
- o
- + H-C''OH
- FormiC acid
- The reaction to produce methylamine is cheap, but requires a lot of labor. Two molecules of formaldehyde react with ammonium chloride to produce a molecule of methylamine hydrochloride and formic acid. Both starting materials are easily obtained in 5-gallon-pail or 50#-bag sizes from commercial chemical outlets serving industry.
- The glassware is set up as shown in Figure II in Chapter Three. The chemist places 1000 grams of ammonium chloride and 2000 ml of 35-40% formaldehyde in the 5000 ml flask sitting in the pan of oil. (These chemicals need not be a very high grade; technical grade is good enough.) He puts a thermometer in the oil next to the flask and heats the oil to 105° C or so, with the aim of heating the contents of the tlask to about 100° C or so. A thermometer inserted into the flask is used to monitor its temperature. A bubbling reaction kicks in, and a condensate made up of formic acid and methyl collects in the receiving flask. When this distillation slows in a couple of hours, raise the temperature inside the flask to 104° C, but no higher. Continue heating at this temp until no more distillate comes over (4 to 6 hours). Periodic applications of aspirator vacuum to the batch will increase yield of methylamine because it pulls the C02 out of the .reaction mixture.
- Then he turns off the heat and removes the flask from the pan of oil. Some liquid will have collected in the 2000 ml flask; he throws it out and rinses the llask with water. The 5000 ml flask is set in a pan of room temperature water to cool it off. A good amount of ammonium chloride crystals precipitate from the solution. He does not want these chemicals, so he filters them out. He returns the fIltered reaction mixture to the 5000 ml flask and again sets up the glassware as shown in Figure II . A 250 ml flask is used as the collecting flask. The reaction mixture should be clear to pale yellow.
- He turns on the vacuum source and attaches it to the vacuum nipple of the vacuum adapter. He boi Is off the water and formic acid in the reaction mixture under a vacuum. Heating the flask in
- the oil pan speeds up the process, but the oil is not heated above 100° C. When the volume of the contents of the flask is reduced to about 1200-1300 ml, he turns off the vacuum and removes the flask from the oil pan. The flask is put in a pan of room temperature water to cool it off Some more crystals of ammonium chloride come out of solution. He filters out these crystals and pours the filtered reaction mixture into a 2000 mf flask. He sets up the glassware as before, and again boils off the water and formic acid under a vacuum. He does not heat the oil above 100° C.
- Chapter Thirteen Methylamine
- When the volume of the reaction mixture has been reduced to about 700 ml, crystals of methylamine hydrochloride begin to form on the surface of the liquid. It looks a lot like a scummy film. When this happens, the vacuum is disconnected and the flask is removed from the oil bath. The flask is placed in a pan of room temperature water to cool it off. As the flask cools down, a lot of methylamine hydrochloride crystals come out of the solution. When the flask nears room temperature, it is cooled off some more with some cold water. This will cause even more methylamine hydrochloride to come out of the solution.
- The chemist filters out the crystals and puts them in a Mason jar. The crystals look different from the crystals of ammonium chloride, so he should have no trouble telling the two apart. These crystals soak up water from the air and melt, so he does not waste time getting them in the Mason jar after they are filtered.
- He pours the filtered reaction mixture into a 1000 ml round bottom flask and again sets up the glassware as shown in Figure I I. He reattaches the vacuum and continues boiling off the water and formic acid under a vacuum. When the volume of the mixture reaches 500 ml, he removes the flask from the hot oil and places it in cool water. As it cools off, more crystals of methylamine hydrochloride appear. He filters the cold reaction mixture to obtain these crystals. He transfers them to a beaker and adds 200 ml of cold chloroform to the beaker. He stirs the crystals around in the chloroform for a few minutes, breaking up any chunks. This dissolves any dimethylamine hydrochloride in the product. He filters the crystals in the beaker, then puts them in the Mason jar along with his first crop of methylamine hydrochloride crystals. He throws away the chloroform and returns the reaction mixture to the 1000 ml tlask.
- He boils the reaction mixture under a vacuum again. When its volume reaches about 150-170 ml, he turns off the vacuum and removes the flask from the hot oil. He pours the reaction into a beaker and stirs it as it cools down, to prevent it from turning into a solid block. Once it has cooled down, he adds 200 ml of cold chloroform to the slush. He stirs it around with a glass rod for a couple of minutes, being sure to break up any chunks. The mixture is then filtered. The crystals of crude methylamine hydrochloride are kind of gooey, so it may not be possible to filter out all the chloroform.
- This batch of crystals is added to the Mason jar along with the rest of the crude product. The yield of crude product is around 425 grams. It absorbs water easily from the air, and melts. Its smell has been described as "like old woman's pussy." The main contaminant of the crude product is ammonium chloride, along with some dimethylamine hydrochloride, and some of the reaction mixture. The 425 gram yield of crude product is therefore deceivingly high.
- Purification would best start with drying under a vacuum. This could be conveniently done by placing
- the crude crystals into a large vacuum flask, stoppering the top of the flask, and applying aspirator
- vacuum for about half an hour. Gentle heating of the flask with warm water during the vacuum drying
- helps speed along the process, as does some shaking around of the contents of the vacuum flask. If one
- has an aspirator that likes to spit back water into flasks under vacuum, then one should use a vacuum
- pump.
- Now to get nice and pure crystals of methylamine hydrochloride, we leave those crude crystals in the
- filtering flask, and add around % of a quart of 190 proof vodka to the crystals. One hundred ninety proof
- vodka won't dissolve ammonium chloride, but it will dissolve methylamine hydrochloride when it is hot.
- Leave the top of the filtering flask stoppered to prevent steam from getting into the flask, then warm up
- the flask using hot water. Water fresh off the stove, almost boiling hot, would be best. Swirl around the
- flask as it warms to get the methylamine hydrochloride dissolved.
- Once the alcohol solution gets hot, stop the swirling to let suspended crystals settle out. Then decant
- off the alcohol solution, taking care to keep the crystals inside the flask. Filtering is necessary. Then put
- the alcohol which has been decanted from the flask in the freezer. As it gets cold, methylamine
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- hydrochloride crystals will come out of solution. When the alcohol is good and cold, filter to collect these pure crystals of methylamine hydrochloride. Store them in a Mason jar with a lid.
- Return the filtered cold alcohol to the filtering flask containing the crude product. Once again heat the alcohol with swirling to dissolve some more methylamine hydrochloride. Then let the suspended crystals settle once again. and decant the alcohol as before, and cool that down in the freezer to get another crop of pure methylamine hydrochloride. A few cycles through this process will get all the methylamine hydrochloride soaked out of the crude product and recovered as pure recrystallized methylamine hydrochloride. The yield of pure methylamine hydrochloride will be around 350 grams or so.
- Sometimes, the methylamine hydrochloride is used directly as such in the reaction, such as, for example, in reductive alkylation using aluminum foil as the reducer. More generally, the free base is used. To obtain a strong solution of methylamine in water, 100 grams of methylamine hydrochloride is placed in a flask with 50 ml water. This is chilled in an ice-salt bath to a temperature nearing 0° F. Then a cold solution of 60 grams of NaOH in 100 ml water is slowly added with stirring. The addition must be slow enough, and the cooling strong enough, to avoid losing the free base as a gas. Methylamine solution produced in this way is roughly comparable to the commercial 40% methylamine, except that it also contains salt and maybe a little NaOH if too much was added.
- This solution should either be used immediately, or stored in a tightly stoppered bottle. Refrigeration of the solution is optional, but desirable.
- Other methods of making methylamine exist, but they are not well-liked by the pioneers mentioned at the beginning of the chapter. Presented here is their preferred method. For example, it can be made in 71 % yield by reacting methyl iodide with hexamine, also known as hexamethylene tetramine. Good directions for making this substance from ammonia and formaldehyde can be found in Home Workshop Explosives by yours truly. The production details for methylamine are found in the Journal a/ the American Chemical Society. Volume 61, page 3585 (1939). The authors are Galat and Elion.
- It can also be made by degrading acetamide with Clorox. See Journal 0/ the American Chemical Society. Volume 63. page 111 8 (1939). The authors are Whitmore and Thorpe, and the yield is 78%.
- It can also be made via the CuTtius reaction in a yield of 60%. See Helvetica Chimica Acta, Volume
- 12, page 227 (1929). The authors are Naegeli, Gruntuch and Lendnrff.
- If one has easy access to mercuric chloride, methylamine can be made from nitromethane fuel by using amalgamated aluminum. This is covered in the "Reduction without the Bomb" chapter.
- References
- Journal a/the American Chemical Society, Volume 40. page 1411 (1918).
- Secrets of Methamphetamine Manufacture
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- the tar left over at the end of the process once more with fresh hydrochloric acid. This will likely yield an additional measure of amphetamine from the stuhbornly unreactive amide.
- This small hassle with the hydrolysis process could be avoided if HCN were used as the nitrile in sulfuric acid solution. However, the extreme danger of dealing with hydrogen cyanide more than outweighs the additional work needed when using acetonitrile.
- To do the reaction, a solution of 450 grams (243 ml) of concentrated sulfuric acid in 400 grams (530 ml) acetonitrile is made by slowly adding the acid to the acetonitrile. Both ingredients are cold when they are mixed together. and the temperature of the mixture is kept in the 5-10° C range during the mixing by setting the reaction container in ice. An admirable reaction vessel is a glass beer pitcher.
- When the addition of the acid to the nitrile is complete, the pitcher is taken out of the ice, and 236 grams (262 ml) of allyl benzene is slowly added to it with stirring. The mixture quickly turns an orange color, and begins to warm up.
- Stirring is continued and the temperature of the mixture followed. It slowly climbs to 50° C. and then more rapidly to 80° C, as the color of the mixture darkens.
- This is a tenfold scale up of the original recipe, so be watchful and protected in case the reaction gets out of control. One wouldn't want this mixture to go postal on you. Once the 80° C temperature is reached, pour the mixture out of the pitcher, and onto a few pounds of ice cubes. Smaller batches can be cooled just by immersing the reaction vessel in ice, but on this scale, go right onto ice.
- Once the reaction mixture has cooled down, the acid should be neutralized by slowly pouring it into a 15% solution of lye dissolved in water. About a pound of lye will be required to neutralize all the sulfuric acid and produce an alkaline solution. Most of the unreacted acetonitrile will end up in the water layer. but some will evaporate during the neutralization. Stay upwind!
- The neutralization of the acid by the lye solution produces a great deal of heat. The lye solution is gently stirred during the addition, and then stirred more vigorously during the following minutes. After a few minutes of stirring, the mixture is allowed to sit for a few minutes. A yellow oily layer floats on the top of the solution. This yellow oil is the crude amide. If the oil were to be allowed to sit for a while longer, it would begin to form crystals of crude amide. There is no need for this. however. so the processing continues immediately.
- The top yellow layer is poured off into a sep funnel, and any water carried along is drained otT. Then the yellow oil is poured into a 2000 ml round bottom flask. It is now ready for hydrolysis with hydrochloric acid solution to make amphetamine. The approximate volume of the crude amide is determined, and five times that volume of 15% hydrochloric acid solution is added to it. Fifteen percent hydrochloric acid solution is easily made by starting with the 28% hardware store hydrochloric acid, and adding just about an equal volume of water to it. A wise move here is to rinse the inside of the sep funnel with acid. This rinses off the amide clinging to the glass insides of the sep funnel.
- When the acid has been added to the amide, the mixture is swirled. They usually mix together well. If they don't, stronger acid is used. Adding some full strength acid to the mix should do the job. Then a few boiling chips are added to the flask, a condenser attached to the flask, and heat applied to boil the mixture at reflux.
- The reflux boiling is continued for 10 hours. During this time the mixture will turn black. At the end of the boiling period. the mixture is allowed to cool down. When it is cool, 200 ml of toluene is added to the flask. The mixture is shaken well for a couple of minutes, then allowed to sit. The toluene floats up to the top. and has dissolved in it most of the unreacted amide, and other unwanted garbage.
- The toluene layer is then poured off into a sep funnel. and any water layer carried along drained back into the flask. The toluene layer is poured off into another container for future processing. It may be difficult to tell exactly where the toluene layer ends and the water starts because of their similar color. A sharp eye and good lighting help to spot the interface of the two fluids.
- Chapter Fourteen The Ritter Reaction: Amphetamines Directly From Allylbenzelle
- The acid solution of the amphetamine is now made alkaline to liberate the free base for distilling. To do this. lye is added to the acid solution in the 2000 ml flask. Assuming the use of about 1200 ml of 15% hydrochloric acid solution, one 12 oz. can of lye does the job. The mixture is first swirled to release heat, then shaken vigorously for live minutes. I cannot emphasize enough the importance of vigorous and prolonged shaking here because the amphetamine base initially formed tends to dissolve unneutralized amphetamine hydrochloride. The oily droplets protect the hydrochloride from contact with the lye solution unless the shaking is strong and prolonged.
- When the shaking is completed, the mixture is allowed to cool down. Then 300 ml of toluene is added
- to the flask, and shaking continued lor a minute or two. After sitting for a couple of minutes, a toluene¬
- amphetamine layer noats above the water layer. This is poured off into a sep funnel, and the toluene¬amphetamine layer poured into a 1000 ml round bottom flask.
- The amphetamine-toluene mixture is distilled in exactly the same manner as described in Chapter Five. The boiling point of benzedrine is 10° to 20° C lower than meth. The yield of benzedrine is in the range of 100 to 150 m!.
- The benzedrine produced by this reaction is either used and removed as is, or it is converted to methamphetamine. A very good and simple process for doing this can be found in the Journal o/ the American Chemical Society, Volume 62, pages 922-4. The author is Woodruff. The yield for this process is over 90%, so a greater volume of methamphetamine comes out of the reaction than the benzedrine input. This is because the gain in molecular weight achieved by adding the methyl group outweighs the small shortfall from 100%. yield. For those who have difficulty reading the Woodruff article, meth is described as B-phenylisopropylmethylamine. The amine is benzedrine.
- A more recent and much more convenient procedure can be found in Tetrahedron Letters Volume 48. pages 7680-82 (2007). This simple methylation procedure uses formaldehyde plus zinc dust to convert Benzedrine to meth in almost 100% yield. Let's take an example starting with two grams of ordinary amphetamine or Dexedrine. It could even have been extracted from Adderall pills, but let's start with the ordinary amphetamine hydrochloride.
- Two grams of amphetamine hydrochloride are dissolved in 20 ml water. Now the buffer solution is made that controls the pH of the reduction. Add 1.6 ml of 85% phosphoric acid to the water solution. Next add .95 grams of sodium hydroxide to the water solution, and mix to get the sodium hydroxide dissolved. Finally add .9 ml of 37% formaldehyde solution and 1.6 grams of zinc dust. Stir lor half an hour at about 30 C.
- The zinc dust will lizz as it dissolves in contact with the acid buffer solution. It is pumping hydrogen to the Schiff base formed between the amphetamine and the formaldehyde, and reducing it to meth. One
- must be careful not to use more than the 1.5 moles of formaldehyde to one mole of amphetamine ratio
- used here, as that would produce dimethylamphetamine. Longer reaction times also contribute to dimethylamphetamine production.
- At the end of the reaction period, Illter out the zinc metal dust with coffee filters. Rinse the filter with clean water, and let this add to the main reaction solution. Now add lye to the reaction mixture until the pH is above pH 13. On this scale. a sep funnel is the best place to do this neutralization. Strong shaking should be used to make oily droplets get into contact with the lye water. Once the solution has cooled down, extract the water solution with about 50 ml of toluene. Separate off the toluene, wash it with some water to remove any formaldehyde, then after the entrained water has been shed, bubble dry Hel gas in a clean dry beaker to get the crystals of meth hydrochloride.
- I r the benzedrine product is used as is, the producer makes it as the hydrochloride salt. This is made the same way as methamphetamine hydrochloride. An alternative to the hydrochloride salt is the sulfate salt. This more hasslesome procedure calls for the use of cooled solutions of amphetamine base to alcohol and cooled solutions of sulfuric acid in alcohol. Furthermore, a recrystallization from alcohol¬
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- ether is required because trapped excess sulfuric acid in the crystals causes them to tum to mush or worse. By using HCI gas, the excess acid floats off as gas.
- An excellent review of this reaction can be found in Organic Reactions, Volume 17. Nearly double these yields should be obtained if the underground chemist is willing to risk using hydrogen cyanide instead of acetonitrile. The hydrogen cyanide is made inside the reaction flask from sodium cyanide and sulfuric acid. For complete directions, see Organic Syntheses, Collective Volume 5, pages 47 1 to 473. The name of the compound is alpha, alpha, Dimethyl beta phenethylamine.
- My opinion is that anyone attempting this variation with hydrogen cyanide in any place other than a well ventilated shed, well upwind from the batch, is just nuts. This variation isn't recommended, nor do I know if it has been specifically tested for efficacy with allylbenzene. It sure as hell is worth checking out, if the required precautions are taken for dealing with hydrogen cyanide solution. This is not for beginners!
- Chapter Fifieen Methamphetamine from Ephedrine or Pseudoephedrine Amphetamine/rom PPA
- I think this emulsion-forming ingredient is some type of fatty acid which forms a soap when sodium hydroxide is added later on to free base the ephedrine, or whatever. Toluene is also quite good at removing guaifenesin from pills. Colored pills should be tested with solvent. If toluene is going to be used as the extractant at the end of this procedure, check to see if toluene dissolves the coloring matter. If it does, then soak the ground up pills in toluene and filter to remove the color. Ditto if Coleman camper fuel is going to be used as the final extractant. Allow the ground up pills to dry after desplooging so that the solvent is removed from them.
- Then water extraction is done. Mix 1,000 ground up pills with 350 ml of water, and stir for about an hour. Another variation is to just mix 1,000 pills with 350 ml water, and after the pills have softened, mush them up and stir for an additional hour.
- Now the pill mush should be filtered. Vacuum filtration through a Buchner funnel is greatly preferred. because it will suck the filter cake dry, giving better extraction with less use of water. The need to keep the amount of water used to a minimum arises from the fact that the "pill extraction deterrents" are less soluble in water than the desired ingredient, so the more water used, the more effective they are. It may be difficult to get the mush to filter easily through filter paper, so a preliminary filtering through clean white cotton cloth cut like a filter paper will be helpful in these cases.
- The filtrate should be clear, and very bitter tasting, as it contains the active ingredient. Hopefully, most of the pill fillers didn't dissolve, and they are sitting in a filter cake in the Buchner funnel.
- Now take this filter cake of pill sludge, remove it from the filter, and mix it with an additional 300 011 of water. Stir this around for an hour, then filter this. If a Buchner funnel was used, this is enough water to extract the pills. If only gravity was used to aid filtration, then the pill sludge should be soaked with a final 100 011 portion of water, and filtered.
- To the combined tiltrates, add a dash of hydrochloric acid to suppress steam distillation, and boil its volume down to about 200 ml. With pseudoephedrine, this isn't so important because it isn't as water¬soluble as ephedrine or PPA free bases, but the volume should be reduced some for it, too.
- Now let the solution cool, and then add 20% NaOH or lye solution with stirring or shaking until the solution is strongly alkaline to litmus paper. Indicating pH paper should say 12+. A pH meter may not be as useful as paper for this reading. The solution at this point should smell strongly of the kind of fishy free bases.
- Extract the water solution with about 100 011 of toluene. This solvent can be found in the paint-thinner
- section of the hardware store or paint-supply outlet. If you can't find this solvent, Coleman camper fuel
- will work almost as well. The water layer should remain a liquid, and the toluene layer should be clear and transparent. If the particular "deterrent" formulation results in a milkshake consistency, just estimate how much is that top 100 011 of solvent, separate it off, and tilter it. Rinse the filtered out gunk with solvent. Repeat this extraction with two additional portions of toluene. With the ephedrine-guaifenesin pills, extract with petroleum ether, hexane or Coleman camper fuel.
- The combined toluene extracts should be placed in a 400 ml beaker and allowed to sit for a few hours.
- This serves two purposes: first, entrained water will settle 10 the bottom of the beaker and stick to the glass. When it is poured into a fresh beaker, the water will be removed. The second reason involves an observation I made some time ago with one particular "deterrent" formulation. In that case the water layer became almost solid after the second toluene extraction, because the solvating action of ephedrine free base was lost for these tillers. The toluene extract in this case, upon standing, grew a mat of white solid about v.-to Y,-inch thick on the bottom of the beaker. After letting this mat grow, and pouring the solution off of it, all proceeded well from that point. Once the toluene has been poured into a fresh beaker, dry Hel gas should be bubbled through it to
- precipitate pure ephedrine, pseudoephedrine or PPA hydrochloride. This is done just like the bubbling to
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- get meth hydrochloride in Chapter Five. The yield from 1,000 25 mg ephedrine pills is about 20 grams, from 1,000 60 mg pseudoephedrine pills about 50 grams, and from 1,000 75 mg PPA pills is about 65 grams.
- Then after extracting the acid concentrate, this concentrate should be made strongly alkaline by adding lye solution and shaking. We now have free base as in the pill example. It can be extracted out with toluene, just as with pills. and the hydrochloride collected by bubbling with HCI, just as with pills.
- Another pill extraction procedure which was briefly touched upon in the fourth edition of this book has proven quite useful when extracting those 200 milligram guaifenesin pills. Through the fifth edition of this book and partway through the life of the sixth ed until roughly the beginning of 2004, this method also was very effective in extracting the various brands of pseudoephedrine pills.
- First the pills are finely ground in a blender. Shaking the blender some while it is running will help to get large pill chunks off the bottom of the blender and into the blades. Next one can pour the powdered rills into a beaker, and desplooge with roughly one ml of toluene for each pill used. Stir it around for about half an hour, then filter. Spread the pill mass out to air dry. I'm not really certain if this step is ahsolutely necessary. Feel free to skip the toluene desplooge step, and see if it makes any difference.
- Return the dried pill mass to the beaker, and add about 4 grams of lye for each 100 of the 25 mg ephedrine pills used. Stir this in. Then slowly add 91% isopropyl rubbing alcohol, or hardware store denatured alcohol, or 190 proof vodka with stirring until a moderately runny paste is achieved. Too much alcohol could make it difficult to precipitate the hydrochloride crystals at the end of this process. Using water instead of alcohol can result in a regrettable mess, especially if too much water is used. That extraction deterrent formulation really kicks in with water, and a horrendous milkshake emulsion easily forms. Stick to alcohol. and use the minimum amount required to get a light paste.
- Stir this fairly light paste for about half an hour. The lye dissolves, and produces the free base of the ephedrine. We now extract out the ephedrine free base.
- Add 50-75 ml of Coleman camper fuel for each 100 pills used, and stir this mixture for about half an hour. Then filter the mixture. Doubled up coffee filters or lab filter paper will be fine enough to catch the pill particles. A clear blue filtrate should result. The blue color is from the camper fuel; it causes no
- problems.
- Rerum the pill mass to the beaker, and add another 50-75 ml of Coleman camper fuel for each 100 pills used. Stir this for about half an hour, then filter.
- The combined clear blue filtrate is now ready for bubbling with dry HCI. This is done just like in all the other examples where we bubble dry HCI to get the crystalline hydrochloride product. The blue color of the camper fuel doesn't color the crystals at all, so long as it is sucked away using a Buchner funnel and vacuum flask. If you don't have such equipment, a final rinse of the crystals with toluene will wash off the camper fuel.
- Camper fuel evaporates quickly, and doesn't leave a lingering smell on the crystals of ephedrine hydrochloride. One can expect to get close to 100% extraction of the pills by this method. so long as the pills were finely ground in the first place. Your Uncle has tried and likes this method!
- Others have also used this method, and offered their variations on the techniques. Suggested retinement number one is to replace the Coleman camper fuel with the naphtha, a common solvent which one can pick up at the hardware store. People have found that naphtha evaporates away faster than Coleman camper fuel, and that it is also a considerably cleaner solvent than camper fuel.
- All of these methods use a lot of solvent, and so produce a lot of waste solvent. The question naturally arises, "What do I do with my waste solvent after it has been used?" There is an easy answer to this. One should never pour waste solvent down the drain, or dump it into the ground, or otherwise dispose of it haphazardly. What one should do is store the used solvent in champagne bottles or other containers that can be sealed up. Then at the earliest convenient moment, pay a visit to the waste oil recycling drop off
- Chapter Fifteen Methamphetamine from Ephedrine or Pseudoephedrine Amphetaminefrom PPA
- point. These can be found in most any town. Just pour your waste solvent into the waste oil container. The waste oil will be recycled as a fuel, and your solvent will do no hann there.
- The years 1999 through 2008 brought with them a series of unfortunate events for meth cookers. Bad news item number one was the pulling from the shelves of products containing phenylpropanolamine. This unfortunate occurrence was due to a number of strokes traced back to taking too much Dexatrim and related products. The resulting lawsuits and FDA restrictions meant the end for OTC (Over-the-Counter) phenylpropanolamine.
- Of even greater signifIcance for meth cookers has been the gradual appearance of and now market domination by a series of "doctored" OTC pseudoephedrine pills. These pills fIrst showed up in Australia in late 1999. The parent company distributing these "gak" pills chose Australia as their test ground because if people keeled over from ingesting the mile long list of "inert ingredients" the publicity in the US would be much easier to kill. One must also consider that the price that a lawyer can extract for a dead Aussie is much less than an American lawyer could get for dead Americans. Add to that the fact that the Aussies had a nice and growing clandestine meth "problem" based upon pseudoephedrine pills. The Aussies were the perfect test market for these new pills.
- Once Warner Lambert demonstrated that their new pill formulations didn't seem to kill people, and also showed that the new pill formulations confused the hell out of clandestine chemists trying to extract them to use as raw material for meth cooking, the pills moved to the US. Then, as of spring 2001, was very hard, regardless of brand, to lind a pseudoephedrine pill which one could extract by the old method of grinding the pill, and extracting with water or alcohol. These "simple extractions" should now be considered to be completely worthless for the pills now on the market.
- The new pseudoephedrine pills can be recognized by looking at the list of inert ingredients on the pill package. The list of ingredients will be a mile long, and will include such things as povidone, eros povidone, lactose, carnauba wax, acacia gum, Xanthane gum, soaps like stearic acid or magnesium strearate, polymers with many names like Polyox or Pluronic. They may also choose to say "may contain one or more of the following" or they may just say, for ingredients, see US Patent 6,136,864 or World Patent 00/15261 and US patent application 2005025619. These patents make for great reading. I'm mentioned over and over. Check them out. The reader is well advised not to pay too much attention to the listed ingredients on a pill package. The fonnulators are not required to list them all.
- The new pseudoephedrine pills were roughly modeled after the gas station ephedrine pills. This should come as no surprise, since the same crew was responsible for them. It is also possible to extract them by a roughly similar method to that used with the gas station ephedrine pills. The difference at present is that the new pseudoephedrine (Sudafed) pills are much more heavily loaded with waxes like carnauba and gums like acacia. Dragging these waxes and gums into a meth production batch will kill the yield, and make isolating any product very hard. The whole idea behind these patents, which claim to make "illicit drug product impossible," is that they are formulated so that the "gak" which has heen added gets brought over through the extraction process into the batch, thereby ruining any batch.
- A method which worked on these new pseudoephedrine pills is to lirst grind them in a blender. It is hard to get a line grind because they are so gummy. Then soak the ground-up pill mass in at least 3 ml of toluene for each pill used. Stir the mixture tram time to time, and after a couple hours of soaking, lilter off the toluene, and allow the pill mass to dry. Then free basing using isopropyl alcohol/lye or lye solution in water can be done just as given previously. This is fooled by extraction of the free base using toluene rather than naphtha or camper fuel. There is no need to use the naphtha to extract these pills since they don't contain guaifenesin. After a couple extractions with toluene, the pooled toluene extracts can be with dry HC I to gel nice looking crystals of fairly pure pseudoephedrine. With the present formulations on the market, this procedure will give a clean enough pseudoephedrine to make meth.
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- Further cleaning of the pseudoephedrine crystals could be done by taking the crystals, and for each gram of crystals, dissolving it in 10 ml of water. Add lye with strong shaking until the pH of the water is 12+ to pH paper. Now extract the water with some toluene, and bubble the toluene extract with dry HC I to get really pure pseudoephedrine.
- This procedure worked well until late 2003, although towards the end of that period, new pill ingredients were added that required the product pseudoephedrine to be soaked in a little cold methyl ethyl ketone (MEK) and then filtered to get a clean product. Then a new generation of gas station ephedrine pills appeared which were completely unextractable by the old method. Within 6 months, the same formulation had spread to the pseudoephedrine pills as well, and clandestine chemists everywhere were stumped as to how to defeat this new menace.
- The culprit behind this plague for meth cooks was US Patent 6,359,01 1, again by those jackasses at Warner Lambert. This Patent relied heavily upon polymers to mess up the extraction and isolation of ephedrine or pseudoephedrine tram pills, and included polymers which mimic the solubility of ephedrine and pseudoephedrine so that chemical methods of isolation of the product were next to impossible. The polymers would be pulled into whatever product could be isolated from the pills, and they would proceed to kill any reaction used to convert the ephedrine or pseudophedrine into meth.
- I love a good challenge like this from "the man". It's always been my belief that playing offense is much easier than playing defense, so I knew the Patent holders were in a losing game. The question was just how to crack this new and heavily polymer dependent formulation.
- Aticr about a month of thinking about the subject in my spare time (oh, there is so little of that!) and a couple of weeks of experimentation again in that very rare spare time, I hit upon the Achille's Heel of all formulations dependent upon polymers.
- Polymers are built up of smaller subunits linked together into long chains. The most common linkage used in the pill additives is the ester link. When I was a kid, I used to watch Granny Clampett cook lye soap by the Cement Pond. She was cleaving ester links in fat to make soap. If Granny can cleave esters, so can I to get something more interesting than lye soap. I knew that once the links were broken in the polymers, they would no longer have the solubility characteristics which make them such a problem.
- There are two general methods for cleaving esters, be they in polymers or anywhere else. They are alkaline hydrolysis and acid hydrolysis. Granny was doing an alkaline hydrolysis of the ester links in fat by the Cement Pond using lye. which is NaOH. For the cleavage of the pill polymers, the morc general chemical method is called for. That method is hydrolysis using potassium hydroxide (KOHl in alcohol solvent.
- To put this method into use, I revived the old alcohol extraction method. To hydrolyse, the alcohol should be the azeotropic mixture. This gives maximum yields, as less or more added water cuts the yield of the desired product. There are two commonly available azeotropic alcohols. They are 95% ethyl alcohol. exemplified by 190 proof vodka and hardware store denatured alcohol, and 91°;;, isopropyl alcohol found in the bandage section of your local drug store. I chose the latter for my work because it doesn't have as great a smell as the denatured alcohol found in the hardware store.
- The extraction method I discovered didn't require the pills to be pre-soaked in solvent to remove their copious supply of gums and waxes prior to extraction. The KOH hydrolysis removed them as well as the new breed of polymer additives. Simply add the sudafed pills to a blender, and grind them up. When the dust settles inside the blender. empty it onto a plate and then use a spoon to chrush any pill bits and pieces which escaped grinding in the blender. When finished with that job, just put the ground up pill mass into a beaker or measuring cup with a pour spout.
- An example batch size of 100 sudafed pills containing 30 mg each of pseudoephedrine will require about 250 to 300 ml of alcohol to extract completely. Measure out about 100 ml of alcohol and add it to
- Chapter Fifteen Methamphetamille from Ephedrine or Pseudoephedrine Amphetaminefrom PPA
- the pill mass, then stir. An orange red solution will start to form immediately as the pills extract. Swirl or stir around this mixture from time to time for about an hour, then it is time to collect the fi rst extract.
- Generic sudafed pills obtained from Walgreens are very closely formulated according to the previously mentioned Patent. Obtaining the first extract from them is very simple. Just pour the mix through a coffee filter and collect the filtrate. Brand name Sudafed pills and Walmart store brand pills are of a bit more advanced formulation which plugs filters. For them, just let the pill sludge in the beaker settle for about an hour, then pour off the alcohol solution Irom the pill sludge. Try to keep as much of the pill mass in the original container as possible.
- If filtering was done, then return the fi ltered pill mass to the original beaker or cup. Then add another roughly 100 ml portion of alcohol to the pill mass for another extraction. If pouring offofthe first soak was done, then just add another 100 ml portion of alcohol to the pill mass. Let the next pill soak proceed lor an hour or so like the first one with some swirling or stirring. Then lilter or decant off the second alcohol soak just like the first one.
- Finally, do a third alcohol soak of the pill mass with another roughly 100 ml of alcohol just as before.
- By now, the alcohol extracts are becoming pale in color, indicating that the pills are nearing complete extraction. Filter or decant this soak just like the previous ones.
- If the pills being used allowed one to fiiter, then the next step can be done immediately. That step is hydrolysis with KOH. If filtering was skipped due to Ii Iter plugging pi lis, then let the extracts settle overnight to shed t10ating crap. I am told that putting some sand into the Illter one is using defeats the filter plugging qualities of these new pills, so do give this a try. It is far preferable to filter the pill extracts, as this allows more complete extraction.
- Now for the big part of the show the KOH hydrolysis. The combined alcohol extracts are now poured into a Pyrex beaker. A Mr. Coffee pot will do fine if you don't have a beaker. Put it on a stove top at medium heat, and then add 20 grams of KOH pellets lor each 100 of the 30 mg sudafed pills extracted. If one has picked up the new 60 mg sudafed pills, then one would use 40 grams of KOH per one hundred pills, and of course the amount of alcohol required to extract them would be double as well. Do avoid the new 120 mg sudafed time release pills, as they are of a gooey formulation you don't want to mess with. The goo is their time release mechanism, and is unlikely to spread to the lower dose pills. Multi ingredient pills like Sudated with Tylenol or guifenesin can't be successfully cleaned up using this method.
- The question which is likely to pop into one's head at this point is "Where do I get KOH?". This close chemical cousin of lye, NaOH, is pretty easy and safe to get from those mail order chemical outlets who advertise in the classilieds sections of some magazine. Keep the order to KOH, and there will be little chance of bad things happening as a result. An alternative source can be found at everybody's favorite department store which is open 2417. Head to the plumbing section, and you will lind a product which is roughly 50% KOH and 50% NaOH. This can be used in a pinch, just by upping the amount used to about
- 15 grams per hundred pills. One can also do some internet shopping. Search under "soap making". KOH is used to make soft soap. One can also search under "hide tanning". KOH is used in that craft as well. Avoid solutions of KOH in water, as the alcohol already has the best amount of water for the reaction in it. If you can only get a KOH solution in water, boil it down. In no case just use NaOH, as it doesn't work. Also avoid getting hardware store drain openers which contain KOH plus bleach. The bleach will simply destroy the pseudoephedrine or ephedrine in the extract and leave you with nothing. As the KOH pellets dissolve into the alcohol extracts, they begin to chew up the polymers, gum and waxes in the pills. This only happens when the alcohol solution is at or near boiling, so a gentle boiling of the alcohol is needed. Adjust the heat setting on the stove top accordingly. Within a few minutes of boiling with the KOH, you will note that the original red orange color of the alcohol extract is fading rapidly, and that an
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- oily layer is forming at the bottom of the beaker, or Mr. Coffee pot, whichever you are using, Continue to gently boil for half an hour and then set aside to cool. With the variety of pills exemplitied by the Walgreens store brand which closely follows the Patent fomlUlation, you will have a coffee colored oil layer at the bOllom of the beaker, and a weakly colored alcohol solution containing the pseudoephedrine you want floating above it. Just pour this mix into a sep funnel and let the oil settle to the bottom and drain it off to get rid of the crap you just destroyed. We can now move on to the evaporation and getting product portion of the process.
- With the brand name Sudafed pills and the Walmart store brand pills, the ones which plugged up the filters, the KOH boil takes a bit of a different course. With these pills, as the KOH dissolves in and the alcohol gets boiling, the red orange color fades, and the solution turns milky. Don't be alarmed by this, as the milky appearence is caused by little white flakes of crap which you have destroyed. Boil in this case for half an hour just as with the previous example. The only difference is after it is done boiling. In this instance, let the solution cool and settle overnight or at least for several hours. The white flakes will settle out leaving a clear alcohol solution containing the pseudoephedrine, and a mat of gooey white tlakes overlaying a layer of gak oil on the bottom of the beaker. When fresh, this oil will most times be yellow colored, but in a few hours it too will tum coffee colored. The white tlake mat is gooey, and given a few hours it sticks to itself. Then in this case, one can just pour off the alcohol solution from the white tlake mat and oil layer to get a clean alcohol extract.
- Now to get the product! Pour the cleaned alcohol extract into a clean beaker, or a tetlon coated pan.
- Then simmer down the alcohol extract. There are two points here to be wary of. Point number one is that alcohol is flammable, and mildly toxic. Be sure to use a good draft of air to clear the vapors away from the boiling spot. Alcohol isn't nearly as flammable as naptha or other solvents,but fire precautions need to be observed.
- Point number two concerns the last phases of the evaporation. It is YER Y important that one not boil
- down the solution to dryness. This will result in a yellow colored product that is crap. As the solution
- gets to nearly all evaporated down, switch to boiling water heat, or just lettinf it evaporate with some aid of heat and blowing off the alcohol vapors. It is far better to let a bit of alcohol remain than bum the product!
- Now the remaining product in the bottom of the flask will consist of left over KOH, pseudoephedine tree base, and assorted crap. Start by adding about 50 ml of water for the 100 pill batch example to the beaker. Swirl it around, and let it work for a few minutes. Then pour it into a sep funnel. Homemade substitutes for sep funnels are easily constructed. Check out Jack B. Nimbles' book for starters to get some ideas. Then add 50 ml of toluene or xylene to the beaker to dissolve your product. Swirl and let it work for a few minutes, then pour that 100 into the sep funnel. Chase the residue in the beaker with a little bit (about 15 ml) more toluene (that means add a bit more!) and pour it too into the sep funnel.
- Now we are on our way home. Shake that sep funnel for about half a minute, and let it set to settle the layers. In the case of the close Patent formulation pills, the water layer will look like Pepto-Bismol. Using the pills which give a milky look upon boiling, this color will nol be seen in the water layer. Drain air the water layer, and add about 50 ml ofwaler for this 100 pill example. Shake the toluene or xylene layer again with this fresh water. Now let things settle in the sep funnel. You should have a clear toluene solution floating above a reasonably clear water layer.
- Drain off the water. Now check the toluene layer. [t should be just clear solution. If there is tloating crap in it, pour it through a coffee filter. This will give you a clear toluene or xylene solution containing the pseudoephedrine Iree base. Let is set in this beaker for a couple of hours to settle any water you dragged in.
- Then pour it into a clean beaker, and bubble the solution with dry HCI gas. You will get roughly 70% yield of the possible pseudoephedrine available from the pills after you filter out the pseudephedrine
- Chapter Fifteen Methamphetamine from Ephedrine or Pseudoephedrine Amphetaminefrom PPA
- hydrochloride, and rinse the product with fresh touene or xylene. This is the same HCl bubbling procedure which has been used throught this book, and for the last 20 years. Become familiar with it!
- Gas station ephedrine pills are almost entirely soluble in alcohol. The complication with them is that they contain guifenesin. This material ruins the results! This method is only applicable to single active ingredient pills.
- 1 know what you are going to say at this point.."That seems like a complicated procedure". Actually, it's really simple. It's just that 1 put in all the possible details for you. It's just an extension of a method which was used to extract the pills from the mid 90's.One could even add the old method of blowing into the bottom of the beaker to get rid of the last of the alcohol to reveal big crystals of pseudoephedrine. Now add to that KOH boil, and destroyed crap removal, and you have the exact same method which was used roughly 10 years ago with the pills that 1 prescribed a solvent pre-soak and water extraction for. Extraction methods do turn a circle. If this method seems complicated to you, check out my website www.unclefesterbooks.com. The Cookin' Crank with Uncle Fester video will make it all just as plain as it really is.
- The next reasonable question is ... "l just can't get KOH!". 1 worked out a method just for poeple like you, but the yield is closer to 50% rather than the 70% gotten from my original method. Dig harder for KOH, but here it is:
- The pill extraction is done exactly like before, except when it is time to boil the pills add instead 20 grams of KCI. This is salt substitute found at your grocery store. Read the label, and get the brand that just says KCl with a couple of other minor ingredients. Then as the pot is warming up to a boil, slowly, with stirring add 10 grams of NaOH ( lye) per one hundred pills used. The best stirring tool is a rubber spatula, and stir well because the alcohol can only dissolve around one gram per 250 ml alcohol, and you want that bit of KCl to react to make KOH plus NaC!. This is making KOH on the sly. The adding of NaOH should take about 20 minutes, with lots of stirring. A big snow fest ofNaCI crystals in the solution will be seen during this process.
- About the time that the last of the NaOH has gone into solution, it's time to boil this mix. During the course of a half hour boil, the initial red orange color of the alcohol will fade to a shade which is best described as melon. Then set aside the beaker, and allow the mixture to cool and settle.
- The next thing to do is to pour the alcohol solution off of the settled layer of salt on the bottom of the beaker. Using a coHee filter makes this separation much more efficient. Then the alcohol solution is carefully boiled down, just as in the previous example. When it gets close to being evaporated down to the bottom of the beaker its best to let the evaporation finish by itself at room temperature. or with mild heating.
- Now add about 50 ml of water to dissolve the salt, KOH and NaOH in the bottom of the beaker. Let it work for about 10 minutes, and pour the water solution into a sep tunnel. Then put about 50 ml of toluene or xylene into the beaker to dissolve the residues of pseudoephedrine in the bottom of the beaker. Let that soak work for about 10 minutes, then add this also to the sep funnel. Finally, chase the last bits of product out of the beaker with a rinse using about 10 or 15 ml of toluene or xylene. Pour this into the sep funnel as well.
- The sep funnel is then shaken hard for about 20 seconds, and set aside to settle. What is left of the orange color will go into the water layer at the bottom of the sep tunnel. A lot of floating crap will be seen. as well as a fairly clear toluene layer at the top.
- Now drain off the water layer. You will note that the floating crap is in both the water layer and the toluene layer. You don't want to be draining off and throwing away the toluene, because that is where your product is. It's better to be leaving some of the water rinse in the sep funnel at this stage than throwing away your toluene product layer.
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- When the water layer has been drained away, add 50 ml of clean water to the sep funnel, and shake again. When the mix inside the sep funnel settles in a few minutes, you will see a nicely clear toluene layer at the top mixed with 110ating l1akes of crap, and a lightly colored water layer at the bottom mixed with floating flakes of crap. Drain off the water layer, and pour the toluene layer through a cotfee lilter to remove the floating crap.
- Rinse out the sep funnel with water to remove clinging flakes of crap from the glassware, then pour the filtered toluene back into the sep funnel and drain off any water whieh carried through the filtration. Then pour the toluene layer into a clean beaker and let it set for an hour or so to shed any water still entrained in the toluene. Finally. pour the toluene into a clean beaker and bubble dry HCI gas through it to get crystals of pseudoephedrine hydrochloride. Filter them out with a coffee IiIter, rinse them with a fresh portion of toluene, and spread them out on a plate to dry. The yield in this case will be around 50% of the maximum possible. In the case of 100 of the 30 mg pseudoephedrine pills, that will be around a gram and a half of product.
- This variation isn't as good as the one using only KOH pellets, but it does avoid any problems associated with getting them as it uses instead KCI salt substitute and lye. I tried one more variation on this procedure. That variation was to use water to extract the pills, and then to the filtered water extract I added 3-5% by weight of sulfuric acid and boiled for about 45 minutes. I obtained the product by making the solution basic by adding lye to the solution when it was cool, and then extracted the product with toluene. washed it a couple of times with water, filtered the toluene extract, and then bubbled dry HCI gas through it. In that instance I got less than 50% yield of a product which was still dirty and would need to be recrystallized to be used successlully in making meth.
- This procedure worked well for a couple of years. Then they countered it. First a filter plugging ingredient was put into the Sudafed pills. This required an acetone pre-soak of the ground up pills to remove this plugging ingredient. Then the amount of KOH required to get a good hydrolysis of the pill polymers rose from 10 grams per 100 pills to 20 grams and then beyond that. Then the boiling time with the KOH rose into the range of roughly 45 minutes to get reasonably complete hydrolysis. Then something in the pills began to come through into the product and wreck the reaction to make meth using hydroiodic acid. I don't know what that ingredient is because the pills are now locked behind a counter and require showing ID to obtain. I am told European versions of the Sudafed pills still respond well to the boiling KOH treatment as 01'2008.
- The "grow your own" option with ephedra is still wide open if one lives in hot and dry places such as the American Southwest or Australia. The seeds can easily be found on search engines under "ephedra seeds" and they are completely legal in the US. One would simply start them out indoors in small peat planters late in winter using very light sandy soil, and then transplant them outside in the spring to grow wild. In a couple of years they will have grown enough for yearly harvests in the fall. The leaves, which look like pine needles, are simply clipped off with a shears. They are then dried in the sun before they become mildewed. Such rot would destroy its content of the desired ingredients. Another way to destroy the alkaloid content of the ephedra is to put them in an oven and bake to dry. The maximum heat allowed
- for drying is 120 F.
- The ephedra plant is a perennial with a reasonably long life. It is considered to have hit the prime of life with year four, but harvests can begin on it in the fall starting with year two. A particularly good plant may have as much as 4% active ingredients in the dried leaves, but I or 2% is more typical. Only plants grown in hot and dry areas will produce much ephedrine and pseudoephedrine in the leaves.
- Regardless of whether one has ephedrine pills, pseudoephedrine pills or ephedra, a big challenge is to extract the active ingredients in an efficient manner. The pill formulations have been continually evolving over the years to make them more difficult to extract by chemical means. I have come up with a way to once again defeat the latest pill formulations. This method is taken from a Chinese procedure for
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- extracting both the ephedrine and pseudoephedrine from ephedra and I have found that it works equally well on both ephedrine pills and pseudoephedrine pills. Time release pseudo pills may not respond so well to this method, but all other types of pills are extracted quite easily and efficiently. The original reference can be found in Chemical Abstracts Volume 54, column 7979.
- First one starts with grinding up the pills or dried ephedra in a blender. The ground up material is then put into an erlenmeyer flask. About 2/3 ml of water is added for each 25 mg ephedrine pill or 30 mg pseudoephedrine pill. Ephedrine pills sold at gas stations commonly have 200 mg guaifenesin in addition to the ephedrine. Pseudoephedrine pills may contain this or Tylenol, or they may be simply pseudo pills. The method works regardless of these additives. Time release 120 and 240 mg pills should be avoided. If one has 60 mg pseudoephedrine pills, the amount of water added may be correspondingly increased. For ephedra, one should add 100 ml water for each 10 grams of ephedra. The pills are just allowed to soak out their active ingredient into the water over the course of an hour or so with the help of some swirling. The Ilask should be no more than one quarter full. With ephedra one should heat the mixture to just below boiling for half an hour to simmer out a tea from the herb. Be sure steam does not escape from the simmering tea.
- The next thing to do is to base the alkaloids so they can be steamed out. To do this, add roughly one quarter volume of washing soda (sodium carbonate found in the laundry section of the grocery store) relative to the original volume of the ground up pills or ephedra. Once that is mixed in, add 50 grams of Lite Salt (50-50 salt and KCl blend found in the grocery store) for each 100 ml of water added to the pills. The salt mixture will raise the boiling point of the water and make it possible to steam out the pseudoephedrine. Then rig up the steaming apparatus shown below:
- A pressure cooker is the source for the steam which heads to the Erlenmeyer flask through some plastic tubing. A two holed stopper is placed in the neck of the flask and two sections of glass tubing are put in the stopper. A longer section of glass tubing which extends almost down to the bottom of the flask is the steam inlet. It is best if this piece of glass is constricted a bit at the tip so that the steam comes gushing out in a jet. This is done simply by heating a section of glass tubing with a flame spreader attachment on a propane torch until the glass glows red. Then just pull and the melted glass area will stretch and finally pull apart. Take a triangle shaped file and saw into this stretched glass area at the point where the internal diameter of the glass tubing is about the thickness of the lead in a pencil. That is roughly the size of the portal one wants the steam erupting from. Blow through the tubing to make sure it is not plugged!
- The shorter section of glass tubing in the two holed stopper is the steam outlet. It should not extend much beyond the stopper so that splashing in the flask is not likely to be sent up the outlet and into the
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- kicker of lye will generally get one past detergents. If all else fails with experimentation, then simmering down the now acidic steam distillate will give one plenty of room to experiment. Neither ephedrine nor pseudoephedrine will simmer ofT once the solution is made acidic. One must be careful not to burn the product near the end of the simmering down process. Once simmered down, the residue could be cleaned up by soaking it in a solvent like ethyl acetate. This material will not dissolve ephedrine or pseudoephedrine hydrochloride, but will dissolve many unwanted materials. One could also try recrystallizing the crude and polluted product from boiling hot acetone or MEK. Other things to try are rinsing the crystals with a bit of ice cold acetone, or rinsing them with some ethyl acetate.
- Another tactic to pursue is to use a bit of sulfuric acid rather than hydrochloric acid to acidify the steam distillate. If one would acidify the steam distillate collected in the beer bottle to roughly pH one or two. then the sulfate salt will be fonmed of the ephedrine or pseudoephedrine. The sulfate salt does not dissolve well in alcohol. That opens up the possibility of simmering down the steam distillate very carefully so as not to burn it at the end, and then extracting the residue with toluene and next alcohol to remove garbage carried over with the desired product. Then basing the product could be done followed by extraction and crystallization as the hydrochloride salt.
- The pill fonmulators have one more card to play, and we may see it sometime soon. That card is to replace the natural "d" isomer of pseudoephedrine with the synthetic "I" isomer. Reduction of this "I" isomer would then give only the very weak "I" isomer of meth. A Patent has already been published claiming tbat the "I" isomer of pseudoephedrine works just as well as the real McCoy for cold relief. If this new product should come to replace the pseudoephedrine presently on sale, the following procedures will prove very helpful. One can racemize "I" pseudoephedrine to "d,I" pseudoephedrine. Reduction of this product would then give "d,I" meth, which is a very nice buzz indeed. In fact it is much better than the strictly "d" isomer meth one generally gets from ephedrine or pseudoephedrine as the starting
- material.
- Racemization of Pseudoephedrine
- This procedure is taken from Chemical Abstracts, Volume 23, pages 3452-4 (1929). It yields racemic ephedrine or racephedrine from pseudoephedrine, thereby allowing the use of pseudoephedrine to get d,l¬meth.
- Pseudoephedrine hydrochloride prepared as described above is dissolved in 25% hydrochloric acid solution. Stronger acid must be avoided, as the use of this stronger acid would produce a significant amount of chloroephedrine. One hundred ml of 35% lab-grade Hel can be diluted to 25% by adding 40 ml of water. In the example given in the Chemical Abstracts, a fairly dilute solution of pseudoephedrine was used, but I can't think of any reason why one can't mix this solution much stronger. Adding more pseudoephedrine to a given volume of Hel solution allows much more material to be processed at once, and also makes recovery by extraction at the end of the process much easier.
- This solution of pseudoephedrine in Hel is then heated at 1000 C for at least one day, preferably two.
- Heating the solution to reflux is to be avoided, as correspondents have infonmed me that reflux temperatures lead to the burning of the product. Simply heat the flask in an oil bath whose temperature is kept at about 1000 C. A reflux condenser must be attached to the flask to keep the acid from evaporating away. In the example Irom Chemical Abstracts, the acid was heated inside a sealed tube, but I can't see why this simpler procedure won't work just as well.
- At the end of the heating period the solution is cooled, and then sodium carbonate is added to the acid solution a bit at a time until all of the acid is neutralized. This point can be spotted because the carbonate will stop fizzing once all the acid is gone. Now shake the solution strongly for a few minutes to ensure
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- that all of the racephedrine hydrochloride has been converted to the free base. Then extract a couple of times with toluene. The pooled toluene extracts can then be bubbled with HCI gas to precipitate the
- product as the hydrochloride.
- METHOD #2
- The hot hydrochloric acid isomerization has the advantage of using easily available hardware store muriatic acid to do the job. The drawback is the tendency this method has of burning the product. A much more refined procedure can be found in US Patent 2,2 1 4,034. To use this isomerization method, one will have to get a chemical named sodamide, aka sodium amide (NaNH2). This material is reasonably cheap and isn't on anyone's "watch list" at the present time. It's also a dangerous chemical which can suck up water and C02 from the air and become explosive. Keep bottles of this powder tightly sealed. Weigh and use portions of this substance quickly, and on dry days. Don't leave it laying around in the open air! Wipe residue of the powder off the threads of the bottle before resealing it. This white to greenish substance turns yellow or brown when it has reached a dangerous state. Small amounts of contaminated soadamide can be just flushed down a toilet, but if you have more than a gram or so of dangerous material. the way to neutralize it is to pour in enough xylene or kerosene to easily cover all of it. then add a 10% solution of alcohol in toluene or kerosene slowly with agitiation to the contaminated sodamide until most of it has reacted. Then it can be flushed.
- To use sodamide to isomerize "I" pseudoephedrine, one starts with a solution of pseudoephedrine free base in solvent. This is pretty convenient, as all the pill extraction methods given here at one point end up with a solution of the free base in solvent just before bubbling dry HCI to get the hydrochloride crystals. The best solvents for this isomerization procedure are high boiling point liquids such as xylene or kerosene. Both of these materials can be picked up at the hardware store.
- The examples given in the Patent are for 50 gram batches of pseudoephedrine, but the method can of course be scaled up or down as desired. 50 grams of pseudoephedrine free base dissolved in roughly 500 ml of xylene or kerosene is placed into a !ODD ml flask. The glassware is then rigged for simple distillation as shown in Fig. II, and roughly 10% of the solution is distilled off to make sure that all water is gone from the mixture. If kerosene is being used as the solvent, the oil bath will smoke a lot and may burn before it gets hot enough to boil the kerosene, so in that case heat the flask directly on the bu ffet range.
- Once about 10% of the solvent has been distilled oft let the solution cool down to about 100 C. Then add roughly 7.5 grams of powdered sodamide in small portions to the flask with some swirling between adds. Ammonia will be fumed off of the mixture as the sodamide goes in.
- When the sodamide has been added, rig the glassware for reflux as shown in Fig. 10. It is important that the mixture be protected from atmospheric moisture, so don't skip the drying tube, or at least use a balloon over the top of the condenser.
- Now gently boil the the solution at reflux for at least a couple of hours. Two hours is about right using kerosene. Xylene boils at a lower temperature, so stretching the reflux out to three hours or so is probably a good idea using that solvent.
- When the retlux boil is finished, let the solution cool down. Then add around 200 ml of 5% hydrochloric acid solution to the t1ask and shake. This will pull the isomerized pseudoephedrine into the acid solution and out of the solvent.
- Pour the liquid into a sep funnel, and drip out a little bit of the lower layer, which is the acid layer onto a pH paper. The paper should tell you that this water is still acidic. If not, add a bit more acid until the pH paper says that the water is acid. This is important, as the pseudoephedrine will not be extracted from the solvent unless the water layer is acid.
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- When two hours of reaction time has passed, let the contents settle in the flask. After about 45 minutes, when all has settled inside the flask, the mixture is carefully decanted off into a one-gallon glass jug. Great care is taken during this decanting to make sure that all of the settled PCI5 remains behind. If any of it were mixed in with the product chloroephedrine it would be reduced in the succeeding hydrogenation to phosphine, PH3, an exceedingly deadly gas. If it appears any is being carried along, the mixture is filtered.
- The PCIS left in the flask should be rinsed with 150 ml of chloroform to get the trapped product out of it. This is done by adding the chloroform, shaking the sludge to mix, allowing it to settle, then decanting otT the chloroform as before into the glass jug.
- There will be a lot of unused PCIS in the flask, and it would be a shame to just trash it. The obvious thing to do is to save it by stoppering the flask, and try using this material to run another batch.
- Next, the product is precipitated from the chloroform solution in the gallon jug. This is done by slowly adding ether or, better still, mineral spirits (cheap and easily available in large amounts) to the gallon jug until it is nearly full. For best results, the mixture in the gallon jug is continuously stirred during the addition of the ether or mineral spirits. Chloroephedrine does not dissolve in ether or mineral spirits, so as the solution changes from chloroform to predominantly ether, the product is thrown out of solution in the I()fm of crystals. If an oily layer forms at the bottom of the jug, this means a dirty batch. The oil may eventually crystallize, but more likely it must be separated, dissolved in an equal volume of chloroform, and precipitated once again by adding ether or mineral spirits.
- After the addition of the ether or mineral spirits, a large mass of crystals fills the jug. This is the product. The jug is stoppered, and put into the freezer overnight to let the crystals fully grow. The crystals are then filtered out and rinsed down with a little bit of cold acetone. Then the crystals are spread out to dry on china plates or glass baking dishes. The yield of chloroephedrine hydrochloride is in the neighborhood of 250 grams.
- A similar recipe can be found in US Patent 6,399,828. In this example they use thionyl chloride to make chloroephedrine, and they did it as follows:
- Into a 500 ml round bottom t1ask they placed 150 ml of thionyl chloride and 55 grams of ephedrine hydrochloride. Pseudoephedrine hydrochloride would probably work just as well in this reaction. One should also be forewarned of the noxious fuming properties of thionyl chloride, and if it gets on your skin it will eat holes through it unless promply rinsed otf.
- They next rigged the t1ask for reflux, and boiled the solution for about an hour. Once the reaction mixture had cooled down, they then evaporated away the remaining thoinyl chloride under a vacuum to get a crystalline mass of crude chloroephedrine in the bottom of their flask.
- They next added a few hundred ml of ether to the flask, and stirred up the crystals to allow the ether to wash off unwanted residues from their surfaces. They then filtered out these washed crystals, and once they had collected and dried them, they recrystallized them. In this instance, they used methanol to dissolve the chloroephedrine, and then precipitated the pure chloroephedrine by slowly adding ether with stirring until no more crystals came out of solution. They are then spead them out to dry as in the previous example.
- The discerning reader will note that in the Patent example, they used no chloroform as the solvent for their reaction. One must understand that patents are also sales pitches, and they were less than artful in their demonstrations of "Prior An", to try to show the superiority of their new method. By using no chloroform solvent in this recipe for chloroephedrine, they got 50-60% yield of chloroephedrine. If one had used a hundred ml or so of chloroform along with the 55 grams of ephedrine and 150 ml of thionyl chloride, the expected yield would be around 90%. Making the "Prior Art" look bad is just one of the things you have to be aware of when reading a Patent.
- Secrets of Methamphetamine Manufacture
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- can't be removed by crystallization or rinsing the crystals. When doing the distillation, the melh distills al the usual temperature range. The next fraction whieh distills is chloroephedrine. Since this chloroephedrine can then be cycled back into the hydrogenation step, it makes both economic and ethical sense 10 remove it from the product. By skipping the fractional distillation, lazy operators cost themselves an added measure of meth yield from their raw material inputs.
- The chloroephedrine tree base thusly obtained is too unstable to keep as such. It must immediately be reacted with HCI to form the hydrochloride.
- It has become kind of obvious that you wonderful readers out there have been having trouble using the table presented earlier in this chapter so some examples of the use of other chlorinating agents other than PCI5 are called for. See Chemical Abstracts, Volume 23, page 3453. For example, with thionyl chloride (SOCI2), one puts into a flask 100 ml of chloroform, 100 ml of thionyl chloride and a magnetic stirring bar. The contents are chilled in an ice bath, then 50 grams of ephedrine or racephedrine is slowly added. Stirring in the ice bath is then continued for a few hours, as the reaction of SOCI2 is slower than that of PCI5. After the reaction time is up, about 500 ml of ether or mineral spirits is slowly added with stirring to precipitate the chloroephedrine hydrochloride. This is filtered out, rinsed with a liltle cold ether, and spread out to dry as in the previous example.
- In the above example, the 100 ml of SOCl2 could have been replaced with 60 ml of PCI3, or 65 ml of PBr3.
- Along a similar line, a correspondent named Yehuda has wrinen to tell of his experience with Ihe use oftrichlorethane as a chloroform substitute. He was nol pleased with the results, and wrote with his homebrew method for making your own chloroform. It's interesting and I'll pass it along. In a sep funnel, he puts 35 ml of acetone (hardware store) and either 500 ml ofClorox bleach or 170 ml of 15% sodium hypochlorite solution. This l5%-strength bleach is easily available from swimming-pool suppliers. The sep funnel is shaken vigorously with frequent breaks to vent the gas from the sep funnel. The solution gets pretty warm. The shaking is continued until it stops producing gas. Then let the solution sil for a few minutes for the chloroform produced to settle to the bottom. Drain it off. Then shake the sep funnel again to get a little more chloroform. Total yield: about 15 ml of chloroform. The crude produci should be distilled. Then preserve the distilled chloroform by adding .75 ml of ethyl alcohol to each 100 ml of chloroform. The boiling point of chloroform is 610 C. Yehuda also writes to remind the readers that all of the chlorinating agents in this section produce noxious fumes, and should be handled with exlreme care. Good ventilation, gloves, protective clothing and eye protection are highly recommended.
- Palladium Black on Carbon Catalyst
- Since palladium black on carbon catalyst is on the narcoswine's watch list of chemicals, il is wise for the operator to make his own supply. Luckily, this is not too difticult, and gives a catalysl that is fresher and more active than oftthe-shel f catalysts.
- To make the catalyst. the chemist first obtains Norit or Darco brand activated charcoal, and washes it with nitric acid. This is done by measuring out about 100 grams of the charcoal, and then putting it into a beaker along with 10% nitric acid. They are mixed together inlo a watery slurry, and healed on a steam bath or in a boiling water bath for 2 or 3 hours. After the heating, the carbon is filtered and rinsed liberally with distilled water until the last traces of acid are rinsed trom it. This requires about a gallon of
- waler.
- The acid washed carbon is then transferred to a 4000 ml beaker. A few grams of the carbon sticks to the filler paper and is otherwise lost, but this is OK since the idea is to get about 93-95 grams of carbon into the beaker. 1200 ml of distilled water is added to the beaker, and it is heated with stirring to 800 C. When this temperature is reached, a solution of 8.2 grams of palladium chloride in 20 ml of concentrated
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- hydrochloric acid and 50 ml of water is added. This acid solution of palladium chloride is heated for a couple of hours before it is added, because PdCI2 dissolves slowly in the acid solution. It is not added until all the PdCI2 is dissolved. If PdCI2 dihydrate is used, the amount used is increased to \0 grams.
- When the PdCI2 solution has been added and stirred in, 8 ml of 37% formaldehyde solution is added and mixed in. Next, the solution is made slightly alkaline to litmus by adding 30% sodium hydroxide solution to the beaker dropwise with constant stirring. Once the solution has become slightly alkaline to litmus paper, the stirring is continued for another five minutes.
- Next. the solution is filtered to collect the palladium black on charcoal catalyst. It is rinsed ten times with 250 ml portions of distilled water. Then after removing as much water as possible by filtration, the catalyst is spread out to dry in a glass baking dish. It is not heated during the drying process since it could burst into flames. When it has dried it is stored in a tightly stoppered bottle and used as soon as possible. This process gives about 95 grams of 5% palladium black on charcoal catalyst.
- An alternative to the filtration and rinse is the settle, rinse, and decant procedure used in the Pd/BaS04 procedure which follows.
- Palladium on Barium Sulfate Catalyst
- As mentioned earlier, Pd/BaS04 catalyst will reduce the chloroephedrine to meth a good deal faster than Pd/C. It is useful in other reduction methods in this chapter, so its preparation will be covered here.
- PdCI2 is used to make this catalyst, just like the Pd/C catalyst, so some more mention should be given to sources of supply for this very useful material. As 1 mentioned before, PdCI2 and H2PtCI6 are both llsed in the plating industry. PdCI2 is used to activate plastics so that they can be electrolessly plated. It is also used to electroplate palladium. The typical bath formulation is 50 grll PdCI2, 30 grll NH4CI and HCI to adjust the pH to 0.1 to 0.5. Similarly, a platinum plating bath is mixed up with 10 grll chloroplatinic acid and 300 mill HCl. Companies which supply platers carry these materials. See the Metal Finishing Guidehook and Directory. Your library can get it by interlibrary loan if they don't carry it. Turn to the back of the book to the "product, process, and service directory" and look under palladium and platinum to get a list of suppliers. This is far better than dealing with a scientific supply house loaded with snitches, and their prices are much better. For example, \0 grams of PdCl2 was going for just under $60 in 1995. By naming yourself XYZ Plating instead of Joe Blow, easy access to these materials is assured.
- To make about 45 grams of 5% Pd/BaS04, a solution of about 5 grams of PdCI2 dihydrate (the usual form) in 10 ml concentrated hydrochloric acid and 25 ml water is made. The PdCl2 will take a while dissolve. and heating the solution to about 800 C speeds the process. It can take about 2 hours. Once it is dissolved, set this solution aside.
- Then in a 2000 ml beaker, a solution of 600 ml distilled water and 63 grams barium hydroxide octahydrate is made and then heated with stirring to 80° C. When this temperature is reached, 60 ml of 6N sulfuric acid (3M; 160 ml concentrated H2S04 diluted to one liter with distilled water is 3M or 6N) is added all at once to the barium hydroxide solution with rapid stirring. Then some more 6N sulfuric acid solution is slowly added to the barium suspension until it is just acid to litmus.
- Now add to this suspension of barium sulfate the PdCI2 solution prepared earlier. Stir it in. then follow
- it with 4 ml of37% formaldehyde.
- Aller the formaldehyde has been stirred into solution, make the barium sulfate suspension slightly alkaline to litmus by cautiously adding 30% NaOH solution with constant stirring. Stir for an additional 5 minutes. then let the Pd/BaS04 catalyst settle to the bottom of the beaker. Decant off the water (it should be clear) and pour fresh distilled water into the beaker. Stir up the settled catalyst to rinse it off. Then let
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- The need for free base in this reaction is no real problem. The naptha or mineral-spirits extract of the pills contains the free base in solution. This can just be added directly to the reaction mixture. This in fact saves the added work of bubbling HCl through the naptha or mineral spirits solution to precipitate the hydrochloride. Correspondents also indicate that the ether or THF used as co-solvent in the reaction mixture with ammonia can be entirely replaced with naptha or mineral spirits. Of these two, mineral spirits is preferred, such as, for instance, Coleman camper fuel or naphtha. One could also consider using ether starting fluid as the extractant for the free base ephedrine or pseudoephedrine obtained from the pill extraction methods given in this book. Then by drying any traces of water out of the ether extract with sodium sulfate or other drying agents, one would have a water free ether extract containing ephedrine or pseudoephedrine free base ready for conversion to meth.
- With a supply of free base in hand, it is now time to consider the lithium metal in ammonia reduction method. A very good review of this procedure can be found in the book Reduction: Techniques and Applications in Organic Syntheses, by Augustine, pages 98 to 105. At the heart of this method is the fact that lithium metal, or sodium metal, or even potassium metal can dissolve in liquid ammonia to lornl blue-colored solutions that have powerful reducing properties. Such solutions are often referred to as "dissolved electrons." These solutions are stable unless water gets in them, or unless they are contaminated with iron from the ammonia tank. When the free bases of ephedrine or PPA are added to these "dissolved electrons," they are quickly and easily reduced to meth or dexedrine respectively. To do the reaction, a 3000 ml round bottom 3-necked flask is set inside a Styrofoam tub. The purpose of the tub is to provide insulation, because once liquid ammonia gets out of the cylinder it starts to rapidly boil away until the liquid is lowered to its boiling point of -330 C. This boiling can be kept under control by adding dry ice to the tub. If a cylinder of ammonia is being used, it is a good idea to cool it down before use by putting it in a freezer. With a tank from the co-op, this is not practical. To get the liquid ammonia out of the tank or cylinder, either clear plastic tubing or rubber tubing is placed over the exit valve of the tank or cylinder, and run into the 3-necked flask. Use of metal, and especially copper, is to be avoided. Then the cylinder is tipped upside down, so that the valve is at the bottom of the cylinder. This assures that liquid comes out rather than gas. Next the valve is cautiously cracked open. and liquid ammonia is run into the flask until it is about Y, full. It will quickly boil away until the volume of the ammonia is down to about 1000 mi. and then more slowly because the ammonia has cooled to its boiling point. Then. wearing rubber gloves and eye protection to keep the fumes out of the eyes, a magnetic stirring bar is placed in the flask, and the tub is put on a magnetic stirrer, and stirring is begun. Now 7 grams of lithium metal is put into the flask. Lithium usually comes in the form of turnings inside a sealed glass ampule under inert atmosphere. It can be used directly as such. If lithium wire is being used, it should be cut into short lengths. and rinsed off with petroleum ether prior to use. Lithium battery anodes should be rinse with a soak in ether or naptha as well. The lithium metal quickly dissolves, forming a blue solution. Next. 500 ml of tetrahydrofuran is added to this solution.
- The purpose of the THF is to aid in the dissolution of the ephedrine or PPA which is to be added next.
- I can see no reason why anhydrous ether can't be used instead of THF, if it is easier to obtain. Many Backwoods Cookers get by with just using Colemans Camper fuel or naptha or ether starting fluid as the co-solvent. Next 55 grams of ephedrine (or 50 grams of PPA) is dissolved in 500 ml of THF or ether or naphtha or toluene, and this solution is added to the lithium in ammonia solution over a period of 10 minutes.
- Some care should be taken to make sure that this solution of the free base of ephedrine in solvent is pretty much free of water. which would quench the dissolved electrons. If one has, for example. pill extract dissolved in camper fuel, the simplest way to assure dryness of this solution would be to add a couple of grams of drying agent such as magnesium sulfate to the extracted solution, stirring it around lor a few minutes, then decanting the extract solution off the settled drying agent. Magnesium sulfate drying
- Chapter Fifteen Methamphetamine from Ephedrine or Pseudoephedrine Amphetaminefrom PPA
- the reaction mixture. This low level of water contamination can probably be overcome by using more lithium metal.
- At higher levels of water contamination, the lithium metal just seems to fizz away in the liquid ammonia, forming hydrogen gas and lithium hydroxide from the water contaminant. At this level of water contamination the batch is guaranteed to be a failure.
- Where is this water coming from? Assuming that the pill extract has been dried of water, either by use of a drying agent or distilling the water off the extract as the water-solvent azeotrope, then the water can only be coming from the "anhydrous ammonia" used. It must not be so anhydrous, so get another source of anhydrous. Low levels of water contamination can also come from absorption of water from the air. Liquid ammonia will pull water out of the air. This method shouldn't be done on very humid days.
- Issue number two is the smell produced by this reaction. If this is going to be tried in any place other than a remote country location, the ammonia fumes will alert anyone nearby to the goings on. They'll also knock you over without really good ventilation. The fumes can be held down during the course of the reaction by cooling in a dry ice bath, but after the reaction, the liquid ammonia must be allowed to evaporate away. There comes a cloud of ammonia fumes! On a small scale, these can be sucked up with an aspirator, and flushed down the drain. Simply run some clear plastic tubing from the aspirator to the top of the reaction vessel, and tum on water flow to the aspirator. This will control the smell from small¬scale batches.
- Another way to address the strong smell and actual physical assaultiveness of liquid ammonia is to replace it as the material in which the dissolved electrons are generated. The most clandestine-suitable substitute for liquid ammonia is ethylenediamine. This substance was mentioned earlier in the Knoevenagel reaction section. It can be obtained from laboratory chemical suppliers for around $20 per liter. It is also used in the electroplating industry as a complexor in nickel stripping solutions. Component A of these strips is m-nitrobenzene-sulfonic acid, component B is ethylenediamine. This industrial grade of ethylenediamine will cost about $20 per gallon. See the Metal Finishing Guidebook and Directory under "stripping solutions," for suppliers.
- The industrial grade of ethylenediamine should first be fractionally distilled (boiling point 1 160 C) to see if there is a significant amount of water in the material. We do this by looking for the toluene-water azeotrope, which boils at 85° C. Mix two parts ethylenediamine with one part toluene, and fractionally distill at atmospheric pressure through a good fractionating column, such as a claisen adapter packed with hroken glass. Ifan insignificant amount distills at the azeotrope temperature, there isn't much water. If a fair amount does distill, the solution can be dried by distilling off the azeotrope. The toluene left in the mixture can just be left there as co-solvent for the reduction. If only a small amount of water was found in the industrial grade ethylenediamine, then in the next run drying can be done by letting the ethylenediamine sit in contact with KOH pellets for about half a day, then distilling the dried ethylenediamine. The amine has to be dry, because water really fucks with this reaction! Once distilled, the ethylenediamine should be stored in a tightly stoppered bottle to prevent absorption of water from the air. To do a reduction using ethylenediamine in place of ammonia, I would follow the method given in the Journal of Organic Chemistry, Volume 22, pages 89 1-4. To get the solid lithium metal, such as would be found by taking apart a lithium battery, to dissolve into the ethylenediamine and form the blue¬colored dissolved electron solution, the solution must be free of traces of water and carbonate formed by absorption of C02 from the air Into a 2000 ml flask, I would put about one quart of ethylenediamine. I would then flush out all the air using argon or nitrogen gas from a cylinder. Argon is commonly used for TIG welding. I would then stopper that flask to keep air from getting back in. I would add about 3\1, grams of lithium metal to the flask (roughly 10 battery anodes). Once the lithium metal has dissolved to produce the blue solution we need, the batch can be run.
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- I would then add, with stirring, pseudoephedrine or ephedrine to the mixture until enough has been added to make the blue color disappear. That should be around 25 grams of pseudoephedrine or ephedrine. Care should be taken to maintain the atmosphere of argon or nitrogen during the adding of the ephedrine because air reacts with the dissolved electrons.
- In what form would one add the ephedrine? The best way to my knowledge of the matter would be to add the ephedrine or pseudoephedrine as a free base in solution with naptha. Naptha doesn't dissolve into anhydrous ethylenediamine. Ether will not, nor will naphtha/camper fuel. Ifone doesn't get mixing of the two solutions, one may not get the reaction we want. One could also add the ephedrine in the form of the hydrochloride crystals without any solvent added to the mixture. Pseudoephedrine free base is a solid and it could be added directly
- Once the blue color has been consumed, one would be left with the problem of how to recover the meth from the mixture. The best way to my thinking would be to pour the mixture into about 5 quarts of water. Then after some stirring, add some toluene to the mixture and extract out the meth. If the ephedrine was added in toluene solvent, one wouldn't have to add so much. Ethylenediamine doesn't dissolve in toluene when water has been added. I would then wash the toluene extract with some fresh water, and finally bubble the toluene extract with dry HC 1 to get the meth hydrochloride product. Others have suggested the possibility of distilling off the ethylenediamine, preferably under a vacuum, and then taking up the residue with toluene, washing the extract with water, and then bubbling dry HC 1 through it. This method should work, and not stink to high heaven.
- If the clandestine cooker wants to substitute sodium metal for lithium, he may tind it difficult or risky to buy sodium metal through standard channels, so a procedure to manufacture sodium metal from household items is of definite value. A process called the Downs cell has been in use since the early days of this century to make sodium on an industrial scale. In its early versions, sodium hydroxide (lye) was the raw material used, but in later versions this was replaced with salt. By using salt instead of lye, another valuable material -chlorine gas -was also obtained. In this procedure the earlier version will be used because we don't want the poisonous chlorine, and because lye has a much lower melting point.
- Some basic precautions must be followed with this cell. The last thing someone wants on their skin or in their eyes is molten lye or sodium metal, so gloves, protective clothing, and a face shield must be worn. Also, molten lye gives off fumes, especially when a current is being passed through it. so good ventilation is mandatory.
- To make sodium metal, a steel or copper pan about I pint in capacity is placed on a stove burner. A gas stove shouldn't be used here because of its open flame. Also, we want to take advantage of the insulation on the electric heating element. An aluminum pan can't be used, nor is Teflon-coating acceptable.
- Now, into this pan put lye until it's % full. Begin heating this lye at medium to medium-high heat, and melt it. More lye can then be added to get the volume oflye back to about % tiIlI.
- When the lye has melted, the standard DC electrochemical cell wiring is done. A graphite anode is inserted into the molten lye. It should be about I inch away from the side of the pan, and it must not touch bottom, or a short will occur. Clamp it in place with a ringstand and insulated clamp. Make an electric contact with the graphite anode by wrapping some bare copper wire around the top of the graphite anode, and twisting it down tight. Run a wire from the positive pole of the DC source, through an amp meter, and to the graphite anode. Then run wiring from the negative pole of the DC source to the pan near where the graphite anode is located.
- Now turn on the DC power source. The best source would be a 0-1 10 volt transformer. Also workable would be a DC arc welder with variable voltage control. One could also hook a couple of car batteries in series to raise the applied voltage to 24 V. I have heard from reliable sources that 12 volts isn't enough to push current through the molten lye.
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- evaporated away from the decanted liquid product, it will leave crystals of chloroephedrine hydrochloride. Scrape them up and save them.
- In method two, he used thionyl chloride instead. In this one he mixed 20 ml of thionyl chloride and 20 ml of chlorofonn. He then added \0 grams of ephedrine hydrochloride or pseudoephedrine hydrochloride. This reaction is slower and after half an hour at room temp, one might wish to heat it a bit. To get his product, he added ether to the reaction mixture to toss out the crystals of chloroephedrine hydrochloride. Staning fluid would work fine for this purpose, and after adding about 10 volumes of ether and cooling in a freezer for a few hours, the crystals could be filtered out.
- Method three comes from the Patent literature. In Chemical Abstracts Volume 54, column 7654 and German Patent 968,545 we learn that heating a mixture of ephedrine or pseudoephedrine hydrochloride in acctic acid loaded with dry HCI gas we get chloroephedrine. The acetic acid has to be glacial acetic acid. This is the pure stuft not vinegar. It is pretty easily available on line with a Google search from small outlets and it has many uses. Simply heating a watery mixture of hydrochloric acid and ephedrine will just give interconversion between its isomers, not chloroephedrine.
- To do this on a small scale, just take 10 ml of glacial acetic acid and put it in a test tube. Then one would rig up a dry HCI generator such as seen in figure 20 of Secrets of Methamphetamine Manufacture and bubble dry HCI gas into the acetic acid for \0 or 15 minutes. This will saturate it quite weI!. Folks have been using this dry HCI generator for 20 plus years, so this should be nothing new. Next add a gram of ephedrine or pseudoephedrine hydrochloride to the HCI saturated acetic acid. Then heat it with boiling water for half an hour to an hour while keeping the top of the test tube stopped with a cork to keep out steam. This is a solution of chloroephedrine in acetic acid, plus a bunch of left over HC!. How to use this depends upon the method chosen in the next section.
- The last conversion method to chloroephedrine is by use of Lucas Reagent. This one is entirely hardware store supplied. The materials used are hardware store muriatic acid (hydrochloric acid 30%) and pennies. I would feel more confident using the previous example with the glacial acetic acid and dry Hel, but this one is all off the shelf.
- To use it, one first needs zinc chloride (ZnCI2). This could be found online with a search, as could stronger 35% hydrochloric acid, but this is the hardware store alternative section. To make zinc chloride, simply get a bunch of pennies. They should all be dated to the late 1980's or beyond. That is because in the XO's, they changed the composition of pennies. They used to be pure copper, but then copper got too expensive to put into pennies. They were worth more than one cent melted down. That was when they switched to a core of zinc in pennies overlaid with a thin coat of copper to keep them looking the same. Just take a file and cut through the copper surface on these pennies to expose the zinc underneath. One doesn't have to remove all the copper coating. Just exposing some of the zinc underneath will be fine.
- The tirst thing to do is to judge how much zinc chloride one would need. Zinc chloride is a little under half zinc metal, so by taking the desired amount of zinc chloride and dividing it by 1.2 or so, you will be in the ball park as to the weight of pennies to use. Take these pennies with the surface copper broken, and immerse them in enough hydrochloric acid to completely cover them. They will fizz wildly as the zinc metal dissolves to make zinc chloride. The copper coating will be untouched. The insides of the pennies should completely dissolve. If they don't, try a bit of heat, or adding more hydrochloric acid.
- When all of the pennies have dissolved, filter off the zinc chloride solution from the copper coats. Now it is time to get zinc chloride from the zinc chloride solution. This is done by pouring the filtered solution into a glass baking dish. It should be a clear colored solution. Then simmer it down. Add some water halfway through the simmer down to help the hydrochloric acid get air borne rather than stuck in your product. As the simmer down gets close to the bottom, switch to oven heating. Gently bake it down to dryness at 250 F. A layer of clear colored crystals should result. Scrape and scoop them out and put them into a sealed container pronto, as they pull water from the air. The product should be white colored and
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- OCH21HCH3
- NHCH3
- Chloroephedrine MethamphetamIne
- The simplest general method of reducing an alkyl halide like chloroephedrine to an alkane like meth is by use of zinc melal in boiling hydrochloric acid. This reaction was tried in the article cited above and the results were jusl miserable. Almost all of the chloroephedrine was converted to propenylbenzene. and only 10% was converted to meth. The authors next tried adding a little palladium chloride into the mixlure with the zinc and boiling hydrochloric acid. That helped. but still most of the chloroephedrine was wasted. It seems that there is just something about zinc metal in the mixture which is just disaslrous for chloroephedrine.
- The next thing he tried was to replace the zinc metal with aluminum. That was when his results became respectable with roughly 50% yield of meth from the chloroephedrine. For a batch starting with 20 grams of ephedrine or pseudoephedrine converted to the chloroephedrine derivative. he began with 9 grams of aluminum powder. This material can be obtained from suppliers for silk screeners of T-shirts, but one may come under scruliny because aluminum powder is often added to explosives to increase their punch. The material sold as A luma-Seal for radiator leaks doesn'l contain aluminum powder as best I can lell because it doesn't fizz upon contact with hydrochloric acid. The simplest and most low key way to gel aluminum powder or grit is 10 simply take a piece of aluminum metal and reduce il 10 grit and powder with a grindstone. One could lay Oul a newspaper to calch the gril as it is produced off the wheel, and Ihen pour it inlo a container for slorage under a layer of alcohol. This is importanl because il will slow Ihe oxidation of Ihe aluminum surface. A can of silk screen aluminum powder comes wetted wilh alcohol. Any hardware store alcohol or drug Slore rubbing alcohol will do.
- When one is ready 10 do the reaction, the alcohol is filtered off the aluminum powder. II is Ihen soaked in .1% lye solulion (sodium hydroxide ... NaOH) at room lemperature for a few minules. This helps to break Ihe oxide layer on the metal grit surfaces . . 1 % would be one tenth gram of NaOH in 100 ml of water. Filter Ihis mixture, and rinse the aluminum powder with several portions of fresh water to remove any traces of lye left on the aluminum. Then while the aluminum is still wei, pul it inlo a beaker along with 200 ml of water and .2 grams palladium chloride. Slir the mixture every once in a while, and let it sit overnight. An amalgam will form belween the palladium chloride in solulion and Ihe aluminum surfaces.
- To do this reduction reaction using the aluminum powder, the chloroephedrine should first be added to the mixture of 200 ml water, 9 grams aluminum powder and .2 grams palladium chloride. If one has made chloroephedrine cryslals by method one or Iwo, just add them. If one has chloroephedrine in acetic acid solution by mel hod three, add Ihis solution. If one had Lucas reagenl mixture, then add Ihal.
- Now quickly add 200 ml of hydrochloric acid and stir it in. This will start to dissolve the aluminum and produce a lot of hydrogen gas in the process. It will be kind of slow at first, but then the fizzing will really kick in. Thai is when the mixture should be cooled down with ice to moderale the reaction. The fumes are nasly as Ihe hydrochloric acid reacts with Ihe aluminum. This should be done in a garage or olher outdoor slruclure. As Ihe aluminum metal dissolves, it will pump hydrogen to the palladium and bring about the reduction of chloroephedrine to meth. Once the reaction has slowed down, add some more hydrochloric acid and lei the mixture warm up again until all the aluminum powder has dissolved. This produces a mixture conlaining roughly a 50% yield of meth from the chloroephedrine.
- To obtain the producl, Ihe aulhors of the article chose Ihe steaming roule. Check the previous chapter
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- for the section detailing steaming ephedrine, ephedra, and pseudoephedrine pills for a simple rig. They left the mixture acid, and blew several hundred ml of steam through the mixture to remove the propenyl benzene by product. They next made the reaction mixture strongly basic with lye after it had cooled from the first steaming. This tosses out of solution a large amount of aluminum hydroxide, but with cnough lye in solution, the aluminum hydroxide redissolves. It will set up into a gel if left for a while. In the paper, they then steamed this mixture and collected their steam distillate as in the pill steaming example. It would take several hundred mls of steam to get the entire product out of the reaction mixture, but it would be very clean. It could then be extracted out of the steam distillate with some tolucnc or other available solvent like xylene, and then gassed with dry HC!. Another alternative would be to simply make the mixture strongly basic with lye until the aluminum hydroxide dissolved. Then exlract the mixture with toluene and get the product in the same manner by bubbling dry HCI through it.
- The author of the article didn't get really impressive results until he removed the dissolving metal hydrogen source from the mixture. Aluminum isn't as destructive towards chloroephedrine as zinc is, but it still bent upon turning half of it to propenylbenzene. He did the well known hydrogenation of chlorocphedrine using palladium catalyst and hydrogen gas under pressure, and got 90% yields. He next embarked upon other hydrogen sources for his palladium chloride. He turned to the hydrides. Note that he published the paper in 1951, so in the late 40's when he was doing the experimenting the selection of hydrides and their availability were limited. He was able to get some calcium hydride, and used it as follows.
- He dissolved II grams of chloroephedrine in 100 ml of methano!. One could also use as chloroephedrine source the Lucas reaction mixture. Another alternative source of chloroephedrine is the acetic acid solution containing dry HCI gas mixed with some ephedrine or pseudoephedrine and then heated lor a period of time. With the latter two mixtures one should add alcohol so as to copy the original procedure once the chloroephedrine has been made, To this solution he added one quarter gram of palladium chloride dissolved in 7.5 ml of hot concentrated hydrochloric acid.
- In another beaker he mixed I I grams of calcium hydride (CaH2) with 100 ml of methanol. The chloroephedrine solution was slowly added to the calcium hydride solution with stirring so that the temperature of the reaction mixture didn't rise out of the 30 to 40 C range. Some cooling of the reaction mixture was provided by means of ice. The reaction mixture will immediately turn black upon addition of th palladium chloride as it converts to palladium black hydrogenation catalyst. A lot of hydrogen fizzing will also come out of the reaction mixture as the hydride breaks down and pumps hydrogen to the palladium. When all the chloroephedrine has been added, the pH of the reaction mixture was adj usted to 3 by means of adding some hydrochloric acid. The reaction was then stirred for another half an hour.
- After stirring for half an hour one could just let the reaction mixture sit for half an hour. The palladium black catalyst will settle out and the reaction mixture decanted off it. Alternatively, one could just filter out the palladium catalyst. In either case a clear solution containing a 90% yield of meth in alcohol solution will be the result.
- Thcre are a couple of ways to obtain the product from this alcohol solution. The way the author of the article did it was to make sure the alcohol solution was nicely acidic with addition of hydrochloric acid. Then by blowing steam through this mixture as in the pill extraction procedure in the previous chapter, hc stripped off the alcohol solvent. Once free of alcohol, the mixture being steamed was cooled and enough lye added to make it strongly alkaline. Recommencing the steaming process then made meth come over with the steam and be collected in ... for example ... a 40 oz beer bottle. Extracting the meth frcc base from the collected steam distillate with toluene and then bubbling dry HCI gas through the toluene solution will give one the 90% yield ofmeth hydrochloride.
- Another approach is to take the clear filtered reaction mixture and simply pour it into a glass baking
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- dish. The take it outside to the garage and apply mild heat to it so as to speed up the evaporation of the methanol. Methanol is a toxic alcohol, so the vapors should not be breathed more than a few sni ffs. One could avoid this danger by replacing the methanol with 190 proof vodka. One could also use denatured alcohol, but that material tends to much smellier than vodka. Alcohols are also flammable, so care must be taken that no sources of ignition are present. Good ventilation must be provided when working with them.
- Once the methanol or vodka have been removed from the reaction mixture by gentle evaporation, a residue will be left that is a mixture of calcium chloride and meth hydrochloride. Add a couple hundred ml of water to this residue and put it into a beaker. Bring it to a boil for a while to drive off any remaining alcohol. Then cool it down and add enough lye to make the mixture strongly alkaline. This should be done in a sep funnel with lots of shaking between the adds of lye until the pH is 13 plus. A lot of calcium hydroxide sludge will be tossed out of the water solution as the mixture become alkaline. The meth can be extracted out with toluene; filtered if need be, and then bubbled with dry HCI gas to get crystals of meth hydrochloride. If the yield is unexpectedly low, it may be due to meth being trapped in the calcium hydroxide sludge. This could be recovered by use of steam, or by making (he sludge acidic again with hydrochloric acid. This will redissolve the sludge, and then by again adding lye to pH 13 plus another load of meth could be pulled from the water solution with toluene.
- That was a surprisingly simple and high yielding recipe! It did use calcium hydride, but sodium borohydride could be used in its place using virtually identical reaction conditions. It wouldn't form that troublesome sludge upon making the reaction mixture alkaline to extract out the meth, and it is a pretty commonly used lab chemical. The hydride example shows that active hydrogen being pumped to palladium chloride and the palladium black catalyst it produces will convert chloroephedrine to meth in very high yield at normal pressure and temperature. There is another way to produce this active hydrogen. It is very easy and it uses only the simplest of materials and equipment. That is by electric generation of the hydrogen directly in the reaction mixture in contact with the palladium chloride and chloroephedrine. The negative pole of an electric cell will fizz wildly with active hydrogen in a solution containing water. It will do this at very low DC voltages easily obtained from a battery charger so long as the cell divider, which separates the solution in contact with the anode (the plus or red pole) from the
- catholyte, which is the solution in contact with the black pole, will pass electric current without much
- resistance. This electric reduction is the most low profile method possible for converting ephedrine or pseudoephedrine to meth. It uses no iodine or red phosphorous or anhydrous ammonia in the process, and the source of hydrogen for the palladium chloride is electrically generated directly in the reduction mixture.
- To do this method, one needs chloroephedrine as in the previous examples. There is a difference, however, in that it has to be fairly free of excess hydrochloric acid. That is because in an electric cell,
- chlorides such as hydrochloric acid which come into contact with the anode or red pole will be converted
- to chlorine at that pole. One might as well be adding bleach to the reaction mixture as this chlorine will destroy the product just as surely. A less permeable cell divider such as porous deglazed pottery would function both to keep hydrochloric acid away from the anode, and any chlorine generated there away from the goods, but thesc kinds of dividers have a good amount of resistance and would require more voltage to run than could be obtained from a battery charger. In this process, the desired divider is a Kling Tite sheep gut condom. It has very low electric resistance even when doubled up. It will also serve to keep the solution in contact with the anode separate from the reduction mixture for the half hour to 4S minute reaction lime.
- Chloroephedrine hydrochloride made by the methods using PCIS or thionyl chloride could be simply added to the catholyte solution described in the next paragraph. Glacial acetic acid chloroephedrine reaction mixture can be treed of excess dry HCI gas just by bubbling air through the mixture. An
- Chapter Fifteen Methamphetamine from Ephedrine or Pseudoephedrine Amphetamine ji-am PPA
- aquarium pump and some glass tubing will do the job in about under half an hour. Lucas reagent reaction mixture is more problematic. It has to be based and extracted. Strong base and chloroephedrine is a bad combination as it will produce toxic aziridine. To base Lucas reagent, dilute it with ten volumes of water, then add washing soda slowly to the reagent mixture. It will fizz a LOT. Once the fizzing upon additions of further portions of washing soda has stopped, it is time to move the mixture to a sep funnel. Shake it some more. If the washing soda has stopped producing fizzing, it is time to add toluene to extract out the product. The zinc carbonate sludge in the mixture will make this difficult, but shake nonetheless. Now after making sure that the neutralization mixture is cool, add lye with shaking, small portions at a time. This will convert the zinc carbonate to zincate. This is soluble in water and so dissolves the sludge so Ihal extraction can be complete. One could add a bit more water if the sodium carbonale left noating around is troublesome. This toluene extract containing the chloroephedrine is next separated, washed with water, and can be added to the catholyte as described in the next paragraph. The amount of chloroephedrine made by chlorinating anywhere from one to three grams of ephedrine or pseudoephedrine will lit nicely into the batch size I am describing here. Since the hydrogen is generated electrically and so is virtually limitless, one does not have to be precise on the amount of chloroephedrine
- added.
- Mix up a solution of 5 ml of concentrated sulfuric acid in 150 ml of water. Pour 50 ml into one beaker. That is the anolyte, or solution which will be in contact with the anode. Pour the other 100 ml into another beaker and add roughly a tenth gram or so of palladium chloride to it and let it dissolve. This will take some time for all of it to go into solution even with stirring. A brown tinted with yellow solution will result. That is the catholyte, the mixture which will reduce the chloroephedrine to meth. Take a 250 ml beaker and place it on a magnetic stirrer, clip a well scrubbed Kling-Tite Naturalamb rubber in one
- side of the beaker and put a piece of graphite rod about y,-inch in diameter and a few inches long, inside
- Ihe rubber. One can get graphite rod from welding suppliers or by taking apart a dry cell battery. Its diameter is not really important, but it must not have sharp points which would rip the rubber. Blow down into the top of the rubber as you insert it so as to innate the condom and avoid rips and holes. A doubled up Kling Titc will serve better to keep catholyte from the anode. On the opposite side of the beaker, stand up a Kennedy half dollar. These are clad with nickel, and it is the cathode. Using alligator clips, make contact with the half dollar, and with the graphite rod.
- Now it is time to add the catholyte or reduction mixture to the beaker. If it is chloroephedrine made by PCI5 or SOCl2, just add it to the 100 ml beaker mentioned above containing the PdCI2 solution. If it is from acetic acid solution, simply add that to the same beaker. If one has the toluene extract from Lucas reagent, pour the 100 ml of dilute sulfuric acid containing the palladium chloride into a sep funnel and
- then add the toluene solution, shake and the chloroephedrine will pull out of the toluene into the sulfuric
- acid solution, which is the bottom layer. Pour whichever source of chloroephedrine one has into the 250 ml beaker. Then using a pipette or by careful filling, pour the condoms full of the anolyte solution which comains no palladium. The Kennedy half dollar should be over half immersed.
- A glass beaker isn't the only reaction vessel which can be used. The only requirements are that it be non-conductive so that the cell doesn't short out, and it must also be inert to the dilute acetic and sulfuric acid used in the process. A measuring cup with a pour lip would be a quite good substitute, and a drink tumbler would also be serviceable:
- Chapter Fijleen Methamphetaminefrom Ephedrine or Pseudoephedrine Amphetaminefrom PPA
- directly by being charged with DC current. Some of it just floats around in solution and picks up hydrogen from the bubbles being produced at the half dollar. Some of the palladium black is attracted by electric charge and sticks to the half dollar. There it sits and fizzes active hydrogen of its own. This layer of electrically attracted Pd black is easily removed from the half dollar at the end of the reaction just by using a toothbrush and a squirt bottle of water.
- One could just as well use a reaction mixture which produces the acetic acid ester of ephedrine or pseudoephedrine in these methods. The hydrogenation of the acetic acid ester of pseudoephedrine has been detailed in US Patent 6,399.828 using palladium. One should know first that making the acetic acid ester of pseudoephedrine is not as easy as with ephedrine. Ephedrine will react with glacial acetic acid and a couple of drops of sulfuric acid to give the desired ester in reasonable yield by heating the mixture to boiling for 15 minutes or so. Pseudoephedrine requires a lab acetylating chem, such as acetic anhydride. The Patent also notes that retaining the acetic acid into the reduction mix lowers the yield of product. The yield of ester reduction at its best was 60 or 70%, while chloroephedrine will give 90% at its best. and with higher conversion numbers to the desired derivative versus the acetic acid ester.
- The reduction to meth will be complete after about half an hour to 45 minutes of hard fizzing from the Kennedy half dollar. Pull out the condoms and the anode rod. Brush off the layer of palladium black from the front face of the Kennedy half dollar, and squirt it back into the catholyte with a stream of water. Let the palladium black catalyst settle. Then filter your product off of the settled palladium black. This valuable material can be recycled.
- The reaction mixture should be poured into a sep funnel, and approximately 20% solution of NaOH (lye) in water should be added with shaking until the mixture is strongly (13+) alkaline to pH paper. Then extract with one or two portions of toluene. Fifty to one hundred ml of toluene is more than enough to extract one gram of product. The toluene extracts are next bubbled with dry HCI to get the crystalline hydrochloride product. After filtering and rinsing them off with some fresh toluene. they are spread out to dry.
- The reductions using palladium chloride with aluminum, boro hydrides or hydrogen all leave a recoverable and recyclable palladium black sludge sitting on the bottom of the reaction vessel. To
- reCOver and recycle this palladium, simply tilter it out using coffee filters. Once one has accumulated a
- reasonable quantity of the used palladium catalyst, it can easily be reconverted into palladium chloride. To do this. just take the coffee filter containing the palladium black and wrap it around a graphite rod. The bottom of the rod should go right to the bottom of the filter, and the rest of the filter containing the palladium is next pushed against the graphite rod. One wants the palladium in direct contact with the graphite rod. Hold the jilter paper in place with a few rubber bands. Now go to Chapter Five. This filter paper containing the used palladium now takes the place of the palladium ingot or coin. Applying a few volts oj' DC current will cause the palladium metal to dissolve into the hydrochloric acid just as with an ingot or coin. A brownish tinted with yellow solution will result as the palladium dissolves back into palladium chloride.
- (i) Definitions
- Anode: the electrode in an electrochemical cell which is attached to the positive pole of a DC
- transformer or rectifier. Oxidations occur here. Cathode: the electrode in an electrochemical cell which is attached to the negative pole of a DC transformer or rectifier. Reductions occur here.
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- Divided Cell: a method of constructing an electrochemical cell wherein the solution in contact with the
- anode is kept separate from the solution in contact with the cathode. A cell divider is used to keep the
- two solutions separate. It must pass current, and be unaffected by the solutions used. Rubbers are the
- cell dividers most otten used in this book. Electrolyte: a material added to the solutions in an electric cell which allows the solutions to carry clirrent. Pure water or other solvents just aren't conductors. Dilute acids or bases make good
- electrolytes in water, as do salts.
- Anolyte: the solution in a divided cell which tills that portion of a divided cell in contact with the anode.
- Catholyte: the solution in a divided cell which fills that portion of a divided cell in contact with the
- cathode. The anolyte and catholyte are otten pretty much identical with the exception of the substrate
- or precursor being acted upon.
- Method 3: Direct Reduction of Ephedrine With Palladium
- These methods arc pretty similar to the indirect reduction of ephedrine, racephedrine, pseudo¬ephedrine and PPA presented earlier. The difference here is that these variations on that theme are one¬pot methods. For example, chlorination and reduction can be done simultaneously in a solution containing dry HCI gas and palladium in a hydrogenation bomb. Other variants use sulfuric, perchloric or phosphoric acid to either first form an ester with the ephedrine, or whatever, which is then reduced to meth in the hydrogenation bomb, or these same substances act as promoters to cause the direct reduction of the benzyl alcohol (ephedrine, or whatever) to the meth or benzedrine. The exact mechanism of how this actually works is a matter for debate in the patent literature.
- These direct routes have the advantage of using very common materials as feed stocks. The various chlorinating agents given in the indirect-reduction section aren't particularly common lab chemicals. Also, chloroform is becoming less commonly used in industry with the new ozone-depletion rules.
- There are a few drawbacks to this method. First and foremost, in one of these procedures the contents of the bomb must be heated to about 80-900 C during the reaction. This leads to the danger that the champagne bottle hydrogenation bomb may crack and burst due to heat stress. This is a possibility even i I' the outside of the bottle is coated with fiberglass resin. Another problem is the high cost and suspiciousness of purchases of the various palladium catalysts used in these methods. This can be avoided by getting one's palladium chloride from the plater's supply outfits mentioned earlier in the palladium-catalyst section. One note on this source of palladium, platers tend to use archaic or weird technical language. For example, a company may offer what he calls 60% PdCI2. This refers to the Pd content of the PdCI2, and indicates that it is actually quite pure.
- A big improvement to this procedure is to use "The Poor Man's Hydrogenation Device" detailed in the second edition of Practical LSD Manufacture and also in Advanced Techniques ol Clandestine
- & Amphetamine Manulacture. With this improvement, the danger of breaking champagne bottles under heat is removed. A geniune Parr hydrogenation device from a scientific supply outfit is even better. A heavy walled pyrex filtering flask is also suitable for use. The top would have to be stoppered, and then the stopper wired into place. The vacuum nipple could be used as a hydrogen inlet. This is a cheap and otf the shelf alternative to a Parr hydrogenation device.
- For this particular application, I would use a tire extinguisher having a bottle made out of a non¬magnctic stainless steel. The technical sheet that comes with the extinguisher will state what the bottle is made out of. and a magnet will tell you if it is a non-magnetic alloy. A non-magnetic stainless steel will pass a magnetic field, so magnetic stirring will be possible.
- The reason for choosing stainless steel over aluminum in this application is the corrosive nature of the hydrogenation mixtures used in these direct reductions. Acetic acid is the solvent used in these
- Chapter Fijieen Methamphetamine from Ephedrine or Pseudoephedrine Amphetamine from PPA
- procedures, and it will dissolve aluminum. The promoters used in these procedures, either HCI, sulfuric or perchloric acid, all eat away at aluminum as well. If the coating should fail inside the bottle, then a hole could be rapidly eaten through the pressure bottle if it were made of aluminum. The light weight of the bottle will quickly tell you if it is made of aluminum rather than stainless, although a magnetic field passes much better through aluminum than stainless steel.
- To coat the inside of the an aluminum pressure bottle, one has the choice of Teflon and Teflon-based paint, or high phosphorous electro less nickel. To pursue this latter alternative, one goes to the Yellow Pages and looks under electroplaters. Ask them if they do electroless nickel, if they have a high phosphorous (phosphorus content in alloy of about 12%) plating bath, and if they are set up to plate over aluminum. To plate aluminum, one must be prepared to enter the fumes of hell.
- If they answer yes to the above questions, you are set to go. Say you want the plating to make the extinguisher match your techno decor or some such cock and bull story. I work in this business and I've heard it all by now. Make sure that the inside of the bottle gets plated, as that is actually the priority item, not the outside. Also ask that threads be masked off so that you can screw the top back on the extinguisher after plating. Also ask for a plating thickness of about one thousandth of an inch for good protection. I have produced many thousands of these aluminum spray bottles at my day job. They can be found on line if one knows where to look. I will not torment a customer by giving his company name, but they are out there and easy to find. Their volumes are 500 ml and are perfect hydrogenation bottles. Let's look at variation number one of this procedure.
- To do this reaction, the chemist first prepares palladium black catalyst. This is done as follows: In a 2000 ml beaker, 50 grams of palladium chloride is dissolved in 300 ml of concentrated hydrochloric acid (laboratory grade, 35-37%). Once it has all dissolved, it is diluted with SOO ml of distilled water. Next, the beaker is nestled in a bed of ice that has been salted down. This is an ice-salt bath. The contents of the beaker are stirred occasionally. and once it is cold, 300 ml of 40% formaldehyde solution is added with stirring. After a few minutes, a cold solution of 350 grams KOH in 350 ml distilled water is added slowly over a period of 30 minutes. The palladium solution must be vigorously stirred during the addition. Now the beaker is removed from the ice and warmed up to 600 C for 30 minutes with occasional stirring during the heating.
- When the heating is complete the beaker is set aside to cool and to let the catalyst settle. Once the catalyst has settied, the chemist pours off as much of the water solution as possible, without losing any catalyst. Then fresh distilled water is added to the beaker, the catalyst is stirred up to wash it off, then the chemist lets it settle again and pours off the water. This washing is repeated a total of six times. Finally, the catalyst is suspended in a bit of fresh distilled water. and filtered, preferably through sintered glass to be sure of catching all the catalyst. Any catalyst still clinging to the sides of the beaker are rinsed down
- with water and poured in with the main body of catalyst. It is wise to rinse off the catalyst again with still
- another large portion of water while it is in the filtering funnel. This process yields 31 grams of palladium black catalyst, once it has dried. It is important that the catalyst be allowed to dry completely, because the presence of water in the reaction mixture is to be avoided.
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- I'm pretty sure that the mechanism whereby this hydrogenation works is that the sulfuric acid acts as a catalyst for the formation of an ester between the acetic acid solvent and the alcohol group in the ephedrine, or PPA. This benzyl ester then undergoes what is termed hydrogenolysis to yield meth or dexedrine. See Organic Reactions, Volume 7, for an anicle on hydrogenolysis of benzyl esters. This reaction mechanism is the basis for the Fester Formula, revealed in Advanced Techniques ul C/andestine Psvchedelic & Ampheramine Manufacture, and also the Advanced Fester Formula, given later in this chapter.
- Workup of the reaction mixture to isolate the meth product consists of first either letting the catalyst settle to the bottom. or filtering it out. It can be reused and when it wears out it can be reworked like platinum catalyst.
- Now the acetic acid solution containing the meth is poured into a distilling flask, and with the aid of vacuum, the acetic acid is distilled off. If the vacuum isn't really high, and if the condenser and receiving tlask are pretty cold, then most of the acetic acid should be recovered for reuse.
- Then to the residue left in the tlask after most of the acetic acid has distilled away, add a 20% solution of lye in water until the mixture is strongly alkaline. This would be best done in a sep funnel, with shaking between adds of lye solution. You now have meth free base. When the solution has cooled down a bit. add 200-300 ml of toluene and shake to extract the meth into the toluene, which will float on top of the water after the shaking stops. Separate this top layer of meth in toluene, and after any entrained water has settled out, bubble Hel gas through it to get meth hydrochloride crystals. Filter them out, and air dry as usual to get the product.
- My commentary on this procedure" That sure is a lot of acetic acid used, a lot of expensive catalyst used, and heating the hydrogenation bomb is a hassle that prevents the use of glass hydrogenation vessels. Also that need for distilling off all that excess acetic acid at the end of the hydrogenation is a lot of work, and it requires that one have a set of distillation glassware to do the hydrogenation. Let's get around all that.
- This hydrogenation works by way of the hydrogenolysis of the acetic acid ester of the benzyl alcohol of the ephedrine, or whatever. This hydrogenolysis is very easy, even easier than reducing a double bond by hydrogenation. It's the formation of the acetic acid ester that requires the heating of the hydrogenation mixture. Also, ephedrine hydrochloride isn't very soluble in cold acetic acid. That's why such a large amount of glacial acetic acid is used in the old standard recipes found in the patent literature. Let's get around all the practical cooking problems in one broad stroke just by preforming the acetic acid ester prior to hydrogenating the solution.
- The general method for producing an ester from an alcohol like ephedrine and an acid like acetic acid is to add a bit of sulfuric acid to the mixture of the alcohol and acid, and then heat the mixture. This will only work for ephedrine or PPA. Pseudoephedrine will not form an ester in decent yields by this simple method.
- The holders ofa recent Patent, US Patent 6,399,828 tried sulfuric acid in this method and agree that the use of this substance ruins the yield of product. They ascribe the problem as stemming from bad conversion to the ester when sulfuric acid is in the mixture. It may also be that the very bulky sulfate anion attached to the nitrogen atom of the pseudoephedrine has a steric effect which blocks the reduction of the neighboring alcohol group.
- In the recipes they give in their Patent, they formed the acetic acid ester of ephedrine or pseudoephedrine by reacting it with acetic anhydride. They did it as follows:
- Into a 100 ml flask they put 18 grams of ephedrine hydrochloride or pseudoephedrine hydrochloride. 18 011 or glacial acetic acid and 13 ml of acetic anhydride. The mixture was stirred magnetically during the addition of the ingredients, and then with continued stirring, the mixture was heated to 80 C. The mixture cleared as the ephedrine went into solution, and they continued heating at 80 C for two hours.
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- When two hours had passed, they slowly with strong stirring added 36 ml of heptane to the hot reaction mixture. Heptane could be replaced with naptha or even gasoline to make the method more clandestine. The addition of the heptane to the reaction mixture precipitated crystals of their product, the acetic acid ester of ephedrine, from the reaction mixture. They continued stirring as the reaction mixture cooled down. It was at this point a slurry. They kept the stirring going overnight at room temperature, and then filtered out the crystals of their product. Atler spreading the crystals out to dry on a plate, they got around I X grams of product, which works out to a 90% yield. The batch size in the example can be scaled up or down as desired.
- Then to make meth trom the ester, they tried two variations of the palladium hydrogenation. Both of them worked great, so pick the method most convenient to you.
- In their first example, they did catalytic transfer hydrogenation. They used ammonium formate to pump hydrogen to the palladium catalyst rather than using a pressurized vessel full of hydrogen gas. Into a 500 ml three necked tlask equipped with a condenser, stirrer, and addition funnel, they put 47 grams of the acetic acid ester of ephedrine or pseudoephedrine, 130 ml of water, and one gram of 10% Pd on carbon catalyst. Their catalyst as soaking wet with water, to the extent that half its weight was water. I'm pretty sure that one could also use Pd black catalyst made by adding some sodium borohydride to a water solution of PdCI2, and that Pd on carbon made by the same method with about 5 times the weight of activated carbon in the water solution as compared to the PdCI2 would work just fine.
- They made a solution of 15.5 grams of ammonium formate in 20 ml of water, and warmed the contents of their reaction tlask to 70 C using a hot water bath. When it had warmed up to 68 C, they took 6 ml of their ammonium formate solution and added it to the reaction flask in two ml portions at 5 minute intervals with good stirring. The mixture started fizzing, and as the fizzing slowed down, they dropwise added the remainder of their ammonium formate solution to the reaction. When the addition of the ammonium formate was complete, they continued stirring the mixture at 70 C in the hot water bath for another hour. Then they let the mixture cool down while continuing to stir.
- Several hours later, they filtered out their palladium on carbon catalyst, and kept the catalyst wet before transferring it to a glass bottle for storage under water in their fridge for reuse in the next batch.
- Then they took the filtered reaction mixture and put it into a sep funnel. Slowly, they added 20 grams of lye to the sep funnel to free base the meth. The mixture will get warm, and ammonia from the ammonium formate will also be free based. The addition of the lye should be done in roughly 5 gram portions, with hard shaking between each add.
- When all the lye has been added, the meth free base should be tloating atop the water in the sep funnel.
- For this size batch, it will be roughly 40 ml. When it has cooled down, one could add about 50 ml of toluene or xylene to the sep funnel and shake to get all the meth drawn together into the top floating toluene layer, and then drain off the water layer, and finally distill to get VERY pure meth free base which can then be mixed with toluene and bubbled with dry Hel gas to get crystals of meth hydrochloride.
- Alternatively, one could just add 50 ml of toluene or xylene to the sep funnel that contains the newly
- free based meth, and shake to get all the meth collected into the toluene solvent. After letting the layers
- settle, the water layer could be drained away. Pour the toluene layer which contains the meth into a
- beaker, and let it set for a while to drain entrained water and to fume off any ammonia which happened to
- be pulled into the "goods". A water wash of the toluene extract might be very helpful for removing
- ammonia. When the toluene no longer reaks of ammonia, it can be further diluted with a lew hundred ml
- of toluene, and then bubbled with dry HCI gas to get high quality meth hydrochloride crystals. The yield
- will be around 80%.
- Secrets of Methamphetamine Manufacture Eighth Edition
- reacts with water to form phosphorus acid and more hydroiodic acid. Since the hydrogen atom of the HI is being absorbed by the ephedrine, the red phosphorus acts as a recycler.
- In clandestine cooking, the need for HI is dispensed with just by mixing red phosphorus and iodine crystals in a water solution. The red phosphorus then goes on to make HI by the above-mentioned process. With a small amount of due care, this is an excellent alternative to either purchasing or stealing pure hydroiodic acid. This substance is on the List I of restricted chemicals, so buying it is just asking for trouble.
- This method has the advantage of being simple to do. It is generally considered the most popular method of making meth from ephedrine or pseudoephedrine. Now red phosphorus is on the List One of restricted chemicals, so an increased level of subterfuge is called for to obtain significant amounts. One might think that this is easily gotten around by making your own red phosphorus, but this is a process I would not want to undertake. Ever hear of phosphorus shells? I would much rather face the danger of exploding champagne bottles. Those who insist upon finding out for themselves, will see Journal vOhe American Chemical Society, Volume 68, page 2305. As I recall, The Poor Man 's James Bond also has a formula for making red phosphorus. Those with a knack for scrounging from industrial sources will profit from knowing that red phosphorus is used in large quantities in the fireworks and matchmaking industries. The striking pad on books of matches is about 50% red phosphorus.
- The determined experimenter could obtain a pile of red phosphorus by scraping off the striking pad with a sharp knife. A typical composition of the striking pad is about 40% red phosphorus, along with about 30% antimony sulfide, and lesser amounts of glue, iron oxide, Mn02, and glass powder. These contaminants can be removed from the red phosphorus by soaking the mixture in a 10% solution of hydrochloric acid for about an hour with stirring, then filtering out the red phosphorus and rinsing it with some water. This procedure is very stinky as the antimony sulfide gets converted to hydrogen sulfide and antimony chloride. Ventilation is mandatory. Various correspondents have written to tell that the glue holding the red phosphorus striking pads to the paper is soliened by soaking in rubbing alcohol, or acetone, or even hot water, and can then be easily scraped off.
- The red phosphorus can be replaced with a solution of hypophosphorous acid. It is generally sold as either 30% or 50% solutions in water. The later is preferable, although concentrated solutions of hypophosphorous acid can spontaneously burst into flames in contact with air. It reacts in the same way towards iodine as red P does, and so functions the same as red P in both making the HI solution, and in recycling the iodine formed during the course of the reaction with ephedrine or pseudoephedrine.
- Hypophosphorous acid isn't very commonly used industrially or in the lab. As a result, it too has become an item under intense suspicion. It has joined red phosphorus on the List One of restricted chemicals. No need to get discouraged at this point. The acid, H3P02, is easily made from its sodium salt, sodium hypophosphite, NaH2P02. This substance finds wide use industrially as thc reducer in electroless nickel-plating solutions. See Advanced Techniques of Clandestine Psychedelic & Amphetamine Manu!acllire
- for a fuller discussion of electroless nickel-plating solutions, but sutlice it here to say that they are generally sold as a three-component package. The A solution contains nickel sulfate, the B solution contains complexors to prevent the nickel from sludging out during operation of the bath, and the C component contains anywhere from 300 to 400 grams per liter of sodium hypophosphite in water solution. One can also get nickel bath "annihilator," which is used to plate the nickel out of spent electroless nickel-plating solutions. It will be a solution of about 50°/" by weight of sodium hypophosphite in water. This solution is also sometimes called "plate out" solution by the suppliers. One could also get pure sodium hypophosphite crystals from the same suppliers who sell electroless nickel-plating solutions, but sodium hypophosphite is also on the List One of restricted chemicals. It is when it is in solution in these electroless nickel plating products that it is free from restrictions. [( is suprisingly easy to go "shopping" for these electroless nickel products if one has a bit of
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- The result will be a solution of hypophosphorous acid in water somewhere between 30 and 50% strength, and it will work well for making meth. It should be carefully poured into a glass container, and stored in a freezer or refrigerator until ready for use.
- When starting with sodium hypophosphite solutions in water, such as one would obtain from electroless nickel products, a very similar procedure is used. In this case, add one ml of hydrochloric acid to each ml of ammonia free electroless nickel product. For example, 100 ml of electroless nickel plate out solution is mixed with 100 ml of 35% hydrochloric acid. The 31 % hardware store muriatic acid can be used instead and one still get a good product.
- Now one pours this mixture into a glass baking dish, and simmers it down just as in the previous example until half of the solution has evaporated away. When it has cooled, the salt is tiltered off. The tiltered hypophosphorous acid solution is then poured into a glass container and stored in a freezer until ready for use. It will be roughly 30% strength hypo, but may vary depending upon how much sodium hypophosphite was in the electro less nickel product.
- Ether starting fluid could also be used as an extractant for the hypophosphorous acid made by this procedure. One could extract out the hypo acid from the simmered down solution, and then take the ether extract and shake it with the water which is going to be used to cook the HI. The water will pull most of the hypo acid from the ether on the first go. Then when the water has been reacted with some iodine and cooled down, an additional quantity of hypo acid could be extracted into the batch water by another shaking of the ether extract with the batch water.
- The iodine one needs to do this reaction can be obtained at farmers' supply stores and similar outlets.
- Gone are the days when iodine crystals could be picked up straight off the shelves, but iodine tinctures and iodine disinfecting solutions are still widely used and available. It is now very hard to find iodine solutions stronger than 2'% on the shelf. This is by federal decree. When shopping for iodine, one needs to do some careful label reading. The solutions one wants contain iodine, one needs to do some careful label reading. One does not want povidone-iodine, nor does one want complexes which contain some iodine. The solutions one wants contain iodine, generally at about 7% strength (more would be better!), along with roughly three times that much potassium iodide, KI. The KI is in the mixture to keep the iodine in water solution. Without it, the iodine doesn't dissolve at all in water. All tinctures stronger than 2% are now impossible to find on shelves in the US, but the one or two percent of KI in them pushes the total amount of available iodine up to about 3%.
- The tirst thing one wants to do to these iodine tinctures/disinfectants is to knock out the KI, and convert it to more iodine. To do that, one can make use of the following reaction:
- 2KI + CuS04 c) CuI + Y,/2 + K2S04
- In script, that reads potassium iodide plus copper sulfate react to make copper iodide and iodine. Copper sulfate crystals can be obtained for about $20 per five pound container. It is found at the hardware store as root killer for clogged drains. The large blue crystals of copper sulfate are easy to recognize, even though the label should identity the contents. The other popular drain opener is sodium hydroxide.
- Let's say one has a gallon jug of iodine disinfectant, containing 20% KI. At eight pounds per gallon, that's 1.6 pounds of KI per gallon. Half of that will be converted to iodine by reaction with copper sulfate, and we can add in the roughly half pound or so of iodine originally present in the disinfectant to give a total iodine yield of over a pound and a quarter from this very cheap jug of iodine disinfectant. More concentrated disinfectant would yield proportionally more.
- NLlw to convert the KI in this hypothetical example jug containing 20% Kl, one would slowly with stirring and cooling add 550 grams of copper sulfate crystals. After about a half hour of stirring, the KI
- Chapter Fifteen Methamphetamine/",m Ephedrine or Pseudoephedrine Amphetamineji-om PPA
- present in the mixture has been converted to iodine and copper iodide, and the iodine is no longer soluble in the water,
- To then use the iodine, one first puts the mixture into a large sep funnel. Add a couple hundred ml of toluene and shake. The toluene will dissolve about 40 grams of iodine. Separate off this toluene solution. In the example batch given in this section, we are using 300 ml of water and 30 grams red P. Add the toluene to the 300 ml of water and 30 grams of red P. Then shake to react the iodine with the phosphorous. Keep the mixture cool. Then separate off the toluene from the water/HI mixture. Wash it with a 300 ml portion of water which will be used in the next batch.
- This will remove HI from the toluene, and save it for the next batch. Finally, pour the toluene back into the sep funnel with the iodine and shake to get another load of iodine. One repeats this process until all the red P has been consumed. Then enough iodine will have been added to do the example batch given in this section. Finally add another 30 grams of red P to the mixture, and it is ready to cook ephedrine or pseudoephedrine to meth.
- After a while, the iodine produced in our hypothetical jug of iodine disinfectant will begin to run out.
- The toluene extracts of the jog solution will no longer be so darkly violet in color. Then it is time to get the roughly one pound of iodine which is in the form of copper iodide in this jug. That is the tan colored solid which has been floating around in the solution.
- To tum the copper iodide into iodine, first add hydrochloric acid to the jug solution until the pH is down to one, the tan solid will then dissolve. Next slowly with stirring add hydrogen peroxide solution to the jug solution. Make sure the pH of the solution stays in the region of one. It will tend to rise during the reaction. If it rises too much, a lot of gas bubbles will form from the peroxide, and it will be wasted. If the pH rises too much, just add more hydrochloric acid. Two hundred ml of 30% hydrogen peroxide should be enough to convert the copper iodide to iodine. Two thousand ml of 3% hydrogen peroxide would do the same thing. When enough has been added, a clear green-colored solution will result, and the iodine will fall out of solution in the form of big nuggets. To get these nuggets of iodine, just pour off the green-colored water. Then rinse the iodine nuggets with clean water. They are now ready to use just the same as iodine crystals one might buy.
- Many people use a simpler and more direct method for getting iodine crystals from their tinctures containing iodine plus KI. They omit the copper sulfate, and go directly to the portion of the procedure using hydrochloric acid and hydrogen peroxide. They first add hydrochloric acid to the tincture until the pH is around I. Then they add hydrogen peroxide with stirring to get crystals and nuggets of iodine to fall out of the solution.
- The dilute tinctures now on the store shelves will not make a good yield of iodine crystals. However, the iodine produced is easily extracted with toluene and can then be carried into the batch water containing the red P or hypo acid. You can check out my Cookin' Crank video to see how this is done.
- When working with iodine, one must follow some precautions. Overexposure to the substance can poison you! Use good ventilation, and keep upwind. This shouldn't be done in a basement or closet. Rubber gloves will keep the tingers from becoming stained with the iodine. Such stains are not only incriminating, they also pose a health hazard. Store the iodine nuggets and crystals in a sealed glass container until ready for use.
- One problem with the HI/red P method is that it can produce a pretty crude product if some simple precautions are not followed. From checking out typical samples of street meth, it seems basic precautions are routinely ignored, I believe that the byproducts in the garbage meth are iodoephedrine, and the previously mentioned aziridine, (See the earlier section concerning chloroephedrine.)
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- I don't think that even a good tractional distillation will remove these byproducts from the meth. The aziridine has to have a boiling point very near that of meth, and so is unremovable by that method. I also think that the heat of distillation would cause the iodoephcdrine byproduct to form more aziridine, which would then distill with the meth. Steam distilling the meth produced by this method has become very popular, and is recognized as "the" way to get the contaminants removed from the product.
- To some extent, these byproducts can be avoided in the first place, if when making hydroiodic acid from iodine and red phosphorus, the acid is prepared tirst, and allowed to come to complete reaction for 20 minutes before adding the ephedrine to it. This will be a hassle for some, because the obvious procedure to follow is to use the water extract of the ephedrine pills to make HI in. This should never be done, especially with the doctored pills now on the market. Pure ephedrine, racephedrine, pseudoephedrine or PPA hydrochloride made according to the directions at the beginning of this chapter must be used. Impure raw material leads to big reductions in yield, and isolation problems at the end of the reaction. Recent DEA publications state that the pill gaks have become so toxic to this reaction that a pressure reaction vessel may be required to get good yields. Since the production of HI from iodine and red phosphorus gives off a good deal of heat, it is wise to chill the mixture in ice, and slowly add the iodine crystals to the red phosphorus-water mixture.
- To do the reaction. a 1000 ml round bottom flask is tilled with 150 grams of ephedrine hydrochloride (or psuedoephedrine-HCI). The use of the sulfate salt is unacceptable because HI reduces the sulfate ion, so this interferes with the reaction. Also added to the flask are 40 grams of red phosphorus. and 340 ml of 50%+ hydroiodic acid. This same acid, which by the way, is on the chemical diversion list and should never be purchased. can be made by adding 300 grams of iodine crystals to 50 grams of red phosphorus suspended in 300 ml water. After allowing the iodine and red phosphorous to react together for an additional 20 minutes after the last of the iodine has been added to the red phosphorus, the ephedrine or pseudoephedrine can then be added to the mixture. A more refined procedure is to react 300 grams of iodine with 30 grams of red phosphorus in 300 ml water, and then distill this mixture. collecting the first 2/3 of it, and leaving the phosphonlS-acid byproduct behind in the distilling flask. This home brew acid smells bad, but works really well. It loses its bad smell shortly after the beginning of the reflux in the reaction with ephedrine. When using this more refined procedure, remember that 20-30 grams of red phosphorus must be added to the reaction mixture. The 40 grams cited above is overkill, but the unused portion can be reused by filtering it out at the end of the reaction.
- With the ingredients mixed together in the flask, a condenser is attached to the tlask, and the mixture is boiled for one day. This length of time is needed for best yields and highest octane numbers on the product. While it is cooking. the mixture is quite red and messy looking from the red phosphorus floating around in it. It is best to take about an hour to warm up the reaction mixture to the boiling point, as this reduces the amount of by-products made.
- The progress of the reaction can be followed by watching the consumption of the red phosphorus. The majority of product is obtained in about 10 hours; after 16 hours over % is obtained, and after 24 hours, the reaction is done.
- When one day of boiling under reflux is up, the flask is allowed to cool; then it is diluted with an equal volume of water. Next, the red phosphorus is filtered out. A series of doubled-up coffee filters will work to get out all the red phosphorus. but real tilter paper is better. The tiltered solution should look a golden color. A red color may indicate that all the phosphorus is not out. If so, it is tiltered again. The filtered¬out phosphorus can be saved for use in the next batch. If filtering does not remove the red color. there may be iodine floating around the solution. It can be removed by adding a few dashes of sodium bisulfite or sodium thiosulfate.
- Of these two. the thiosulfate is much preferred because it has the ability to destroy aziridine along with the iodine in the solution. You see. iodoephedrine makes aziridine (dimethylphenyl aziridine) by reaction
- Chapter Fifteen Methamphetamine from Ephedrine or Pseudoephedrine Amphetuminefrom PPA
- between the iodine atom and the amino group. See earlier in this chapter for the drawing of the aziridine in question. The high temperature at which this reaction works encourages its formation.
- The best way to add the thiosulfate or bisulfite is along with the sodium hydroxide or lye solution used to neutralize the reaction mixture. That is our next step. For the batch size given here, using 300 grams of iodine in 300 ml of water and about 150 grams of ephedrine hydrochloride, over ISO grams of lye or sodium hydroxide will be required to make the solution strongly alkaline (ph 13+). This amount of lye should be dissolved in about 600 ml of water and allowed to cool down.
- Now add the few grams of sodium thiosulfate or sodium bisulfite to the cooled-down lye mixture and stir until it dissolves. Slowly and with periodic shaking or strong stirring, add the lye solution to the ti ltered reaction mixture. If one prefers, one could also do the opposite and add the reaction mixture to the lye water with shaking and stirring.
- Some fizzing may be noted here as the reaction takes place. Then as the great heat produced by the neutralization reaction allows, the rest of the sodium hydroxide solution should be added with stirring or shaking to the reaction mixture. The meth free base which forms will float to the top of the water solution. Strong and prolonged shaking of the mixture is necessary to ensure that all the meth has been converted to free base.
- Then check the pH of the water layer using pH papers. It should read strongly alkaline. If not, add more lye, and continue shaking.
- With free base meth now obtained, the next step, as usual, is to form the crystalline hydrochloride salt of meth. To do this, a few hundred mls of toluene is added to the batch, and the meth free base extracted out as usual. If the chemist's cooking has been careful, the color of the toluene extract will be clear to pale yellow. If this is the case, the product is sufficiently pure to make nice white crystals just by bubbling dry HCI gas through the toluene extract as described in Chapter Five. If the toluene extract is darker colored, a distillation is called for to get pure meth free base. The procedure for that is also described in Chapter Five. The yield of pure meth hydrochloride should be from 100 grams to 130 grams.
- If gummy binders from the stimulant pills are carried over into the reaction mixture, they produce a ncxt-to-impossible-to-break emulsion of meth, gum, toluene, and water when the reaction is done and it is time to extract out the meth. It is absolutely necessary that the pill-extraction procedure given in this book he followed. If this emulsion is encountered, the only way to break it is to first let the emulsion sit in a sep funnel for a few hours. Water will slowly work its way out and settle to the bottom where it can be drained away. The stubborn residual emulsion should be transferred to a distilling flask, and the toluene slowly distilled otT through a fractionating column. This removes water from the emulsion as the toluene-water azeotrope. It may be necessary to add additional toluene to the distilling flask to get all the water removed. The gum sticks to the glass flask, and causes no further problem. Once the emulsion is broken, distilling should be stopped. The toluene-meth solution should be poured from the distilling flask, and the meth precipitated as hydrochloride as per the usual dry HCl bubbling method.
- When using hypophophorous acid instead of red phosphorus, a very similar procedure is followed. First, SO%+ hydroiodic acid solution is made. To do this, put 3S ml of the 30 -SO%hypophosphorous acid solution into a flask. Then slowly and with stirring add about 40 grams of iodine crystals to the hypophosphorous acid solution. The red color produced by the iodine will be sucked up as the hypophosphorous acid reacts with it to make hydroiodic acid. As the solution gets hot, cool it down in ice water. After about half an hour, a fairly clear to yellowish solution should result. If it is still red with iodine, the hypophosphorous acid solution you made wasn't strong enough and needs to be evaporated down some more. One could check for strength of the hypophosphorous acid by first reacting 3.S ml of the solution with 4 grams of iodine, before moving on to the full batch given here.
- Chapter Fifteen Methamphetamine/rom Ephedrine or Pseudoephedrine Amphetamine/rom PPA
- See Inorganic Syntheses, Volume I. The first of these methods involves bubbling H2S gas into a suspension of iodine in water. The H2S gas is made by dripping HCl onto iron sulfide and piping the gas into solution just like the HCl gas made in Chapter Five. The excess H2S gas dissolved in the product acid is then boiled out of solution under a reflux. This method is quite good.
- The alternate method directly produces a very pure acid by direct union of H2 gas with 12 vapor in the Pt catalyst bed. This is really good if you aren't afraid of putting together some glass tubing.
- There are a few variations upon the standard HI/red P recipe that I have just given. Some people like to use the free base of ephedrine or pseudoephedrine rather than the hydrochloride crystals. This gives them a somewhat better yield of product in the reaction. When using the free base rather than hydrochloride crystals, one has to increase the strength of the acid a bit to compensate for the HI which will be consumed by the free base. In the example batch given, increasing the amount of iodine used to 380 grams will cover the amount sucked up by the free base.
- Another variation is to do the heating of the ephedrine/HI/red P mixture inside a pressure vessel able to withstand at least 50 pounds of pressure. This is said to greatly speed up the reaction. This variation has never become very popular because such pressure vessels aren't easily found on store shelves. If one should rupture a pressure vessel containing a cooking batch, a most regrettable fire is likely to result.
- The HI/red P variation that was really popular in the mid '90's is called the Push Pull method. Our ti'iend ReadyEddie would like to share his Push Pull recipe for making 10 gram batches. It is a lot faster than the standard HI/red P method, and the equipment used is pretty basic. Do note that the more concentrated conditions of the push pull make the pill "gaks" even more effective for killing the reaction. Push Pull by ReadyEddie. The push/pull does not take a lot of skill but does take a bit of understanding of what one is dealing with. First of all this method does require some very watched items. Red phosphorous and iodine crystals can bring unwanted attention if ordered from different supply companies. If by chance one can't seem to obtain these items anywhere, there is still hope. These items can be obtained OTC (over the counter) at your nearest supermarket. If one can get one's hands on lab grade without getting a one-way ticket to the slammer, it's well worth it.
- The striking pads of matchbooks contain a small amount of red phosphorous. It's not pure, so it should be cleaned up before use. Iodine crystals can be converted from iodine tinctures. Tinctures can be found on the shelf in many different supermarkets, and come in 2 % strength in a 30 ml bottle.
- Tinctures can also be found at cattle supply houses, in pint and gallon sizes, and comes in a 7 % strength. Sometimes iodine powder or pellets can be found in cattle supply stores as well. It's called iodine prill and works great just the way it is.
- There are many different ways to collect red phosphorous off of matchbooks. An easy way is to just scrape it off with a razor blade. A better way is to cut the strikers off and soak them in acetone until the red phosphorous falls off. It takes a very large amount of strikers to obtain a large enough pile to do anything with, but it can be done and has been done by many.
- After all falls off the paper, take the paper out and filter the acetone/red phosphorous through two conee filters and now rinse with distilled water and let dry. Now mix up a solution of 20% sodium hydroxide. That is 20% grams of sodium hydroxide in 100 ml of distilled water. Place the dry red phosphorous that was collected in a beaker or flask of choice and add the hydroxide solution to it, heat on low heat for a few hours then filter through two coffee filters again. When dry, rinse with hot distilled water a few times and let dry. This will give a pretty pure powder that will fire off a push/pull reaction.
- Chapter Fifteen MethamphetamineJrom Ephedrine or Pseudoephedrine AmphetamineJrom PPA
- As one can see from Figure 40, it is very easy to construct the apparatus for this reaction. A small clear beer bottle can replace the flask if one is not on hand. This setup can also be made larger or smaller for different size batches.
- If, for example, one wants to do a 20 gram batch, use a 500 ml flask or bottle and two 64-oz. plastic Gatorade jugs. Make sure all the hoses are sealed in place because one doesn't want any leaks. The reaction can be very quick, but other times it may not be. Keep a bucket of dirt or sand around in case it is needed to smother a phosphorous fire. This is a slim possibility, but be on the safe side.
- With lab grade red phosphorous and iodine crystals, the ratios by weight are I gram pseudo¬(ephedrine) HCl to I gram of iodine crystals to 0.5 gram of red phosphorous. With OTC chemicals, the ratios are I gram pseudo-( ephedrine) HCl to 1.5 grams of iodine crystals to 0.7 gram of red phosphorous.
- So now let's get started with the reaction. First thing to do is set up the push/pull vessel. Fill the first water tank with distilled water % of the way full. The second one leave empty. The drain hose from the second tank is put down the drain past the u trap or in a bucket of cat litter. Weigh out the pseudo¬(ephedrine) HCl and place inside the flask or bottle, no more than a 10 gram batch in a 250 ml size flask or bottle. Next weigh out the iodine crystals and put them inside with the pseudo-(ephedrine) HCl. Mix them together very well and stopper the flask or bottle and place it in the freezer for around 3-4 minutes. Weigh out the red phosphorous. Take the flask from the freezer, the reactants should be dark and may be a dark thick-looking mud. Place the red phosphorous in the flask, mix in good with a glass rod and hook it up to the water tanks. If the drain hose is down the drain, it's time to tum on the water to keep the fumes down.
- I f using lab grade chemicals, one may have to add a few drops of distilled water to get the reaction going. For OTC chemicals, no water should be needed; just heat the reactants a little and it should fire. Do not flood the reaction with water! Place the flask on a coffee cup warmer or in a hot water bath. When the reaction starts, take it off the heat.
- During the first phase of the reaction, the mixture turns to a thick liquid and starts bubbling. The small bubbles will be kind of silvery looking. Some gas may now be pushing into the first water tank and water into the second. The contents inside the flask will rise some. A light yellow-colored mist and white fog inside the flask is normal. Continue to add, on and off, heat to maintain an easy bubbling reaction, at least around 15-20 minutes or until bubbling begins to slow.
- In the next phase, increase heat to the flask; slowly raise it up to between 160°-1 80° F. The reaction should begin to bubble very rapidly. The color of the reaction will change to a dark purple or reddish with a yellow tint. The small reaction bubbles will start turning into big bubbles that collapse into large holes. The reaction should be pushing gas into water tanks, but a lot harder this time. The contents will rise quickly, and may start to smoke. If so take off the heat and swirl the contents around in the flask to get the smoking to stop. Swirling will also keep the reactants from rising too high. Let react until all seems to be dead inside the flask (no reaction) even with applied heat. A pull may be noted. If not, that's alright too. Sometimes there is no pull with small reactions. Tilt the flask, if reactants are not longer stuck and slowly flow off the bottom and sides, it should be finished. Let cool to room temperature and then add 100 ml of distilled water. Next, heat on a water bath at 1500 F in an open flask for 30 minutes to tree the contents. Filter all the red phosphorous out of the mix. A couple of coffee filters work well for this.
- After filtering the red phosphorous out, the color should be clear to pale yellow. If one gets a dark orangeor red color that does not filter out, the reaction may not be done or the adulterants in the pill mayhave messed it up. If this is the case try putting the red phosphorous back into the water it was filtered out of. Heat it up to about 2000 F for two hours to complete it. If this doesn't work, the gak in the pills may have messed the reaction up.
- Chapter Fifteen Methamphetamine/rom Ephedrine or Pseudoephedrine Amphetamine/rom PPA
- Begin fast magnetic stirring, then toss a piece of sodium borohydride about the size of a split pea into the flask, and quickly stopper the flask to hold in the hydrogen generated. When the fizzing stops, add another piece of sodium borohydride, continue this until the balloon stays inflated with hydrogen.
- Now Ii Iter out the palladium black for reuse. Put the filtered batch in a sep funnel, and add lye solution with shaking until the mixture is strongly alkaline. Extract out the meth with toluene, separate off the toluene layer, and bubble it with dry HCI gas to get about 10 grams of a very nice meth. You'll like this recipe! If you should have trouble getting the PdCI2 to dissolve in the water, add a few drops of HCI, that will make it dissolve.
- One can get closer to the Patent's procedure by using Pd on carbon rather than Pd black. To do that, simply add activated carbon powder to the PdCI2 solution mentioned 4 paragraphs ago. In this recipe example, it would be 112 gram PdCI2 and 2.5 grams activated charcoal powder. When using this variation, it's hard to tell when all the PdCl2 has been reduced to Pd metal by the borohydride, so you have to let the carbon settle in the solution to see if the brown color of the PdCI2 has all been removed trom the water. Catalyst formation is complete when the water solution is clear atter the Pd on carbon has settled.
- Another pretty useful procedure for converting ephedrine or pseudoephedrine to meth is to convert the ephedrine to chloroephedrine using Lucas Reagent. This reagent has the advantage of being much more easily obtained than thionyl chloride or PCI5, so that scientilic supply houses can be left out of the supply loop. One can then pretty easily hydrogenate the chloroephedrine to meth.
- The method was originally introduced by Wizard X, so due credit should be given to him. The cooking procedures can be found in Vogel's Textbook of Practical Organic Chemistry, 5th edition page 555. Lucas Reagent is a mixture of concentrated 35% lab grade hydrochloric acid, and a chloride salt. Zinc chloride is the preferred chloride for this mixture, but calcium chloride and nickel chloride work as well.
- To make chloroephedrine trom ephedrine or pseudoephedrine, put 25 ml of lab strength hydrochloric acid into a round bottom flask, then add 8 grams of anhydrous calcium chloride. Calcium chloride is commonly sold at gas stations and hardware stores as ice melter during the winter months. As it, it usually has roughly 20% water contained within the pellets. This can be removed by grinding the pellets and putting them into a glass baking dish. Bake the powder in an oven at 350 to 400 F for a few hours to drive off the water, then scoop the dried powder into a dry glass container with a lid for storage. The powder will suck up water trom the air, so work quickly.
- When the anhydrous calcium chloride has been added to the flask, then add 10 grams of ephedrine HCl or pseudoephedrine HCI. Attach a reflux condenser to the flask, and heat the mixture in a boiling water bath fl)f about 10 hours.
- Once the mixture has cooled down, it's time to get the product, chloroephedrine. Mix up a concentrated solution of sodium carbonate in water. The most convenient source for sodium carbonate is Arm and Hammer washing soda found in the detergent section of the grocery store. Lye shouldn't be used for free basing chloroephedrine because it can cause aziridine to be formed. Slowly add the sodium carbonate solution to the reaction mixture. It will fizz a lot as it neutralizes the hydrochloric acid.
- When enough sodium carbonate solution has been added so that the fizzing upon addition of more solution stops, it's time to shake the solution hard for a couple of minutes. Stop from time to time to vent off any additional C02 which may be produced. Then stop and let the solution settle.
- The chloroephedrine should be floating atop the water as an oily layer. Check the pH of the water layer with pH paper. It should read around 12. Now extract the chloroephedrine by adding 50 to 100 ml of toluene or xylene, and shaking. The chloroephedrine free base will go into the toluene or xylene. Allow the layers to settle, and then drain olT the water. Now add about 50 ml of clean water, and shake to wash the toluene solution. Allow it to settle, and then drain olfthe water layer.
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- The toluene layer containing the chloroephedrine should be poured into a clean beaker and allowed to sit for a few hours to shed entrained water. Then it is poured into another clean beaker, and dry HCI gas is bubbled through it to get crystals of chlorephedrine HC!. They are rinsed with some clean toluene and then spread out on a plate to dry. The yield will be about 75% and the hydrogenation procedures for reducing chloroephedrine to meth can then be followed.
- A more direct one pot method shows some promise for this reaction pathway. That method is to replace the calcium chloride with nickel chloride. Then after heating the reaction mixture to make chloroephedrine, zinc dust could be added to the reaction mixture to produce nickel catalyst and hydrogen for the reaction. I have not yet had the opportunity to personally check out this interesting possibility.
- Secrets of Methamphetamine Manufacture Eighth Edition
- Pseudoephedrine can also be used to make cat. The pills containing this starting material must be extracted according to the directions given in Chapter Fifteen, and then converted to racemic ephedrine (called racephedrine) by heating with HCI solution as also described in that chapter. This will yield dl or racemic cat, which is almost as potent as cat made from ephedrine.
- Note in the patent that for each molecule of ephedrine or racephedrine in the reaclion mixture, there are .66 atoms of Cr+6 in the solution. As a result, the amount of Cr+6 substance used in this reaction will vary with the compound used. For example, in the one-tenth mole-size batch given here, 20 grams of ephedrine or rae ephedrine hydrochloride will react with:
- 10 grams ofNa2Cr207e2H20 10 grams ofNaCr04
- 22.8 grams ofNaCr04elOH20
- 12.9 grams of KCr04
- to grams of K2Cr207
- 6.6 grams of Cr03
- There are two main precautions to be adhered to in doing this reaction. The first one is the need to keep the temperature of the reaction mixture below 1000 F. It is better to keep it well below that. To keep the reaction temperature down, the glass container in which the reaction is done should be packed in ice. I have also heard that very fast stirring will so speed up the reaction that the ice bath fails to keep the temperature down. This is only a problem with large-size batches about one mole in size or larger. In these big batches, a favorite agitation technique was to put the reaction mixture contained in a glass jug surrounded by ice in a cooler into the trunk of a car and spend a few hours driving on rough back roads to stir the mix.
- The other main precaution is to add the Cr+6 solution slowly to the ephedrine or racephedrine with stirring. It is best to do the addition dropwise, but with larger batches, this is just not practical. In any case, use some common sense as to the rate of add for the chrome.
- To do the reaction, 20 grams of ephedrine or racephedrine hydrochloride is dissolved in 50 ml of water, then 5 ml of concentrated sulfuric acid is slowly added to it with stirring. The beaker containing this mixture should then be nestled in ice to cool down. Then, in another beaker mix 45 ml of water with
- 7.5 ml of sulfuric acid and the amount ofCr+6 compound listed above.
- Begin stirring the ephedrine solution, and then dropwise add the Cr+6 solution to it. The addition should take about Y2 hour. The chrome solution will be clear orange-red going into the mix, but it soon darkens to a blackish-red. The stirring should be continued for a reaction time of four hours. Shortening this reaction time gives poor yields and incomplete oxidation. Exceeding this reaction time causes destruction of the product, and again poor yields. The preferred solution temperature during the 4 hour reaction time is 80-90° F. The amount of cooling required will depend on the batch size.
- When the reaction time is over, a 20% solution of lye in water should be added to the reaction mixture with stirring until it is strongly alkaline to litmus. Now pour the mixture into a sep funnel, and shake vigorously for a couple of minutes to ensure complete conversion of the cat to free base. The chrome will come out of solution as a greenish sludge. Extract this mixture with two 50 ml portions of toluene. The extracts should have a mild yellowish tint. The pooled toluene should then be washed once with 100 ml of water and then the toluene layer should be poured into a beaker to sit for about an hour. This will allow entrained water to settle and stick to the glass. Now pour the toluene solution into a fresh, clean beaker and bubble dry HCI gas through it, as described in Chapter Five, to get crystalline cat hydrochloride to precipitate out of solution. Filter this out as also described there, and spread the crystals out on a plate to dry. The yield of white to maybe slightly yellow-tinted crystals is a little over 10 grams.
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- 180
- Chapter Seventeen Brewing Your Own Ephedrine
- I love to guzzle beer. Not that mass produced swill, but real beer turned out in small batches by microbrewers and homebrewers. Beer that has some body, flavor, and a real kick! Homebrewing is just a joy, as lots of people have found out. Stores selling supplies to the homebrewer have sprung up in every backwater town. They are just all over the place, and newspapers catering to the homebrewer or fans of microbrews can be picked up for free at the local liquor store. The ads in these newspapers are predominately for mail-order brewing supplies at discount prices.
- What a fortunate coincidence that the industrial process for making ephedrine is just a fermentation process using brewer's yeast. This process is much cheaper than extracting ephedrine from Ma Huang, and yields I-ephedrine as the product. Other chemical processes give product mixtures that consist of d and I ephedrine and pseudoephedrine. If one wishes to scale up production beyond that which can be sustained by scrounging pills and extracting them, this fermentation is a very viable alternative.
- This process uses benzaldehyde as the starting material, so essentially one could consider this method as an alternative to the Knoevenagel reaction back in Chapter Nine. The fermentation action of the brewer's yeast takes the place of that List I chemical nitroethane.
- Benzaldehyde is easily available, in spite of the fact that it too is a List I chemical. Oil of bitter almonds can be used as is, once the HCN it contains is removed by applying a vacuum to the oil. On a larger scale, the electric oxidation of toluene procedure given in Chapter 9 would give all the benzaldehyde that could ever be desired.
- The fermentation action of brewer's or baker's yeast converts benzaldehyde to I-I-phenylpropanol-I¬one-2 in a yield corresponding to about 70% by weight of the benzaldehyde added to the fermentation mixture. This phenyl acetone derivative is then reductively alkylated with methylamine by any one of several procedures to give I-ephedrine.
- @-qH o
- Yeast
- Benzaldehyde
- @-'OH 0II
- o
- CHC CH3
- 1-1.Pheny1 propanol 1-ooe-2
- OHH, ,CH3
- N
- @-CH2CH CH3
- I-Ephednne
- One would think that the reductive alkylation of that phenylacetone derivative would yield d,l¬ephedrine, and then that reduction of that d,l-ephedrine would then give d,l-meth, that same racemic meth that results
- Chapter Seventeen Brewing Your Own Ephedrine
- from reductive alkylation of phenyl acetone. (Your Uncle prefers the buzz produced by the racemate over the harsher, more nerve jangling buzz produced by d-meth.) Apparently, this isn't the case. The references
- for this process claim that solely I-ephedrine is produced, and then reduction of this I-ephedrine, which is identical to natural ephedrine, yields that potent but harsh d-meth.
- To start with this project, one would first want to read a home beer brewing book, such as Belter Beer and How to Brew II. since the processes are so similar and much of the same equipment and materials will be used. I have this book, and it is good. This is all you need to sound like a real brewer when you head down to the Brew Shop in your town to pick up supplies.
- As with regular beer brewing, one starts with a brew vat, five gallon plastic pails work just tine for this purpose. They should be cleaned. then rinsed with bleach diluted with several volumes of water to disinfect the surfaces, then rinsed some more with clean water to remove the bleach residue.
- Next till the pails with tap water until they are half to 2/3 full. We are now ready to brew. See Drug Trade News, Volume 16, Number 16, page 27 (1941), (I love that reference) and Wallerstein Labs. Commun, Volume 4, Number 13, page 213 (1941). Also see Chemical Abstracts, Volume 17, page 1484, and Biochemische Zeilschriji, Volume 115, page 282 (1921), and Volume 128, page 6\0 (1922). These articles will give you some historical perspective on the process. Then go to Biotechnology and Bioengineering, Volume 34, pages 933-41 (1989) and World Journal of Microbiology and Biotechnology, Volume 16, pages 499-506 (2000) for more contemporary techniques.
- Into the pail the brew mixture is made up by adding molasses to clean wann water. Add roughly 31
- grams of molasses for each quart of water in the pail, and till the pail no more than 3/4 full of water
- because there will be frothing and foaming when the yeast starts to grow. Then live baker's yeast is added. The best yeast to use are the cakes of refrigerated yeast found in the grocery store rather than the freele dried packets, although both would work. It takes a lot of yeast to do the chemical transformation, so stir in the package of yeast, and let the yeast grow at about 80 F, like one would when making bread.
- When the brew mixture in the pail has been fennenting for about 8 hours at wann room temperature, it's time to add the benzaldehyde. Start with about 4 ml of benzaldehyde for each quart of water in the pail. Once the benzaldehyde has been added, bubble some air through the culture using an aquarium pump. Then add about 1/2 ml of acetone per quart of water. Acetone is found in the hardware store's paint section and a bit of it in the mixture increases the yield of product. Also add about 1/4 gram of epsom salts for each quart of water. The magnesium in epsom salts aids the conversion of the benzaldehyde. Allow the yeast to work for about 4 hours and then add an additional 4 ml of benzaldehyde for each quart of water in the pail. Adding all the benzaldehyde at once would tend to poison the growing yeast and ruin the yield. Then continue the aeration with the aquarium pump tor at least another 8 hours as the yeast completes the conversion of the benzaldehyde.
- During the course of the tennentation, an enzyme called carbo ligase (pyruvate decarboxylase) produced by the yeast converts the benzaldehyde to phenylpropanol-l-one-2. [t is believed that the enzyme links acetaldehyde or acetic acid made by the fennenting yeast with the benzaldehyde to give the product. In any case, in less than a day, one gets a yield of product amounting to 70% of the amount of benzaldehyde used.
- When the fermentation is completed after about 12 hours or so, it's time to recover the phenylpropanol-l -one-2 trom the brew mixture. The yeast in the mixture is a problem. With regular beer brewing, the yeast just settles to the bottom of the fermenter when the fennentation is complete. Siphoning is then done to remove the clear beer from the settled yeast. If you have days to let the yeast settle, that may be an option. The industrial process uses centrifugation of the fennentation mixture to force the yeast to the bottom. I'm sure that works well for them, because once the centrifuge is installed, no materials need be purchased from then on to settle the yeast. The centrifuge pays for itself.
- Chapler Seventeen Brewing Your Own Ephedrine
- methylamine used. There are about two moles of the phenylacelOne derivative, but they don't even use one mole of methylamine. It should be the other way around, an excess of methylamine. Perhaps this is how they only get I-ephedrine from the phenyl acetone derivative. In any case, ['d much rather have 300 grams of racephedrine than 11 0 grams of l-ephedrine. My thoughts are that one would be better served just going to Chapter Eleven, and just plug in this phenyl acetone derivative for the regular phenylacetone. That means two or three moles of methylamine for each mole of phenyl acetone. alcohol as solvent, and a bit more platinum catalyst in the mixture.
- In the patent, they give another reductive alkylation example. They use amalgamated aluminum as the reducer. just like in Method Three in Chapter Twelve. They take 120 grams of the undistilled fermentation product containing the l-phenylpropanol-l-one-2, and drip it over the course of two hours into a solution of 10 grams of methylamine in 500 ml of ether in the presence of 20 grams of activated aluminum amalgam. Simultaneously, they drip into the mixture 20 to 30 ml of water. Stirring of the mixture is required.
- The vigorous reaction that sets in is moderated by periodic cooling. When the reaction is complete after a few hours. they filter the mixture to remove the aluminum. Then they shake the ether solution with 10% HCI solution to draw the ephedrine into the water. The ether layer is separated, then the dilute acid boiled off. The residue is thinned with a little alcohol. then dissolved in a lot more ether. Bubbling with dry HCI gives 25 to 45 grams of I-ephedrine hydrochloride crystals.
- My commentary on this procedure is identical to the last one. So little methylamine used! I haven't tried this, but I would be surprised to say the least if more methylamine didn't greatly increase the yield
- of product. I would also think that any one of the activated aluminum procedures given in Chapter
- Twelve could be used. just by plugging in this phenylacetone derivative for the regular phenyl acetone. Also the use of ether is to be avoided when possible. One could also use one of the reduction methods from Chapter Twelve which make use of sodium cyanoborohydride or sodium borohydride to reduce a mixture of methylamine plus l-phenylpropanol-I-one-2 to ephedrine. Of the two choices. sodium borohydride would be best because it is easily available and produces good yields of product. See "The Journal of Chemical Technology and Biotechnology", Volume 77, pages 137 to 140 (2002) for a sample recipe using sodium borohydride to do this reduction. Note that they zapped the reaction mixture in a microwave oven to kick start the reduction.
- Chapter Eighteen Cooking Your Own Ephedrine
- dimethylalanine will give no reaction. Check out the Journal of the Phannaceutical Society of Japan Vol. 12, pages 812 to 815 (1952) for a complete discussion of these results.
- A great stroke of luck for meth cooks was published in 2007. It is a very easy and very high yielding procedure for making N-methylalanine. It can be found in Tetrahedron Letters, Volume 48, pages 7680¬
- 82. The reaction uses formaldehyde and zinc dust to do the methylation in water solvent containing partly neutralized phosphoric acid. Formaldehyde can be picked up on the internet or from other sources at low cost and with no heat attached as of 2009. A little bit goes a long way and the other materials can be picked off shelves at stores.
- The following procedure has been found to be an easy and very productive method tor making N¬methylalanine. It is given on a 10 gr scale because larger amounts are not done easily with a magnetic stirrer. The zinc dust is quite dense, but must be kicked up into solution to react.
- To 200 ml water in a beaker or other container, add 16 ml phosphoric acid. The hardware store dairy mi IkslOne remover phosphoric would work if account was taken of its weaker strength, and the detergent extracted. Next add 9.5 gr of NaOH to form the monobasic sodium phosphate. Lye would substitute as would bicarb or washing soda so long as the amount added was adjusted. Stir constantly. One should be able to make a roughly equivalent buffer solution by adding 40 grams of hardware store trisodium phosphate (TSP) to 200 ml of water, and then adding roughly 30 ml of hardware store hydrochloric acid. I haven't tried this variation, but it should work and would be entirely supplied right off the hardware store shelf.
- Now to this mixture add 10 gr alanine (. 11 mole) from the health food store. It dissolves quite easily, and the solution should be around 30 C from the neutralization of the phosphoric acid solution by lye.
- Next add 10 ml (.14 mole) 37% tonnaldehyde, follow that with 15 gr zinc dust andstir for 45 minutes. I know that is more than the Tetrahedron Letters article specified, but the amount of formaldehyde has been backed down from the 1.5 molar excess stated in that article to around 1.2. Fonnaldehyde is toxic and no doubt folks would do it in a kitchen. Less is more ... so increase reaction time ... besides that is the ingredient that one would need to purchase.
- One will note a constant fizzing noise from the reaction vessel as the zinc dust reacts and makes hydrogen. The zinc gradually changes from grey to blue, and this is zinc phosphate. Zinc dust is easily had, but one can make one's own by taking a piece of zinc metal such as pennies and grinding on a wheel or with a file until they are reduced to grit and dust.
- Now let the zinc settle, then filter the almost clear water solution leaving the zinc on the bottom of the flask. It should filter clear water white through a couple of coffee tilters.
- Add 50 ml of hot water to the settled blue zinc sludge on the bottom of the flask, and swirl for a bit.
- Then let that settle. Filter off the water, and add this to the main charge of filtered water.
- Now tor the important part. .. add bicarb powder slowly and with stirring until the pH reaches roughly pH 7. One will need a pH meter, and make sure it is calibrated. Tap water should read within a few tenths ofpll 7, but buffer solutions are easy to get to calibrate a pH meter.
- Once the pH has been adj usted to around 7, let the water clear solution sit in the fridge overnight. Great hcavy masses of long needle shaped N-methyl alanine will form. Let the mass grow to its greatest extent. It may take more than 12 hours to get the crystal growth to kick off. If one has a seed crystal, it would be
- very convenient.
- When the crystal mass has stopped growing, filter it off. Then rinse it with some alcohol. .. at least 70'Yo . .. and set the crystals on a plate to dry. The alcohol dries the crystals and keeps them from becoming bacteria food as they dry. Usc less than 50 mi.
- Now the filtered liquid should be boiled down. This is another reason for using less fonnaldehyde.
- Boiling the mixture makes the residual formaldehyde become part of the steam given off The mixture will now be kind of yellow colored. Reduce the liquid volume by half and then add the alcohol rinse from
- Secrets or Methamphetamine Manufacture
- Eighth Edition
- the first crop of crystals. Then put this boiled down water liquid in the fridge to collect another crop of crystals of N-methyl alanine. Total yield is about 10 gr after the crystals have dried. This would react with benzaldehyde in OMSO solvent to give yields of ephedrine and pseudoephedrine which have not been seen since the mid 90's.
- This newer and much better cooking procedure was covered in detail during two conferences sponsored by the Pharmaceutical Society of Japan in 2006 and 2007. The abstracts were published on line as "Proceedings of the Symposium on Progress in Organic Reactions and Syntheses". The two papers in question were presented at the 32" " and 33'd Symposiums by Yokoyama and Tsubaki. The easiest way to google up these abstracts is by searching 33'd symposium or 32" " symposium. To get the full cooking details requires some hands on cooking since they are less than willing to give the text of their proceedings. Go figure on that one!
- The preferred procedure is to react one mole of benzaldehyde with two moles of N-methylalanine in DMSO solvent. Let's take a small scale example using 30 ml of benzaldehyde. It would react with 60 grams ofN-methylalanine to give roughly 25 to 30 grams of a mixture of ephedrine and pseudoephedrine hydrochloride.
- Now place 250 ml of OMSO into a suitable heating vessel such as a round bottom flask with reflux condenser ... or a lava lamp if you are ghetto ... add a magnetic stir bar. .. and 60 gr of N-methyl alanine. Then add 10 ml of the 30 ml of the benzaldehyde. It is best to add it in portions to save on the total amount of OM SO solvent used. This makes the clean up at the end of the reaction much more practical.
- Heat this mixture to about 130 C if one is using piperonal, but benzaldehyde will react at a lower temperature. Look for the fizzing of C02 as your visual clue, and go with the lower temperature. Let it fizz for an hour or so, then add the next \0 ml portion of the 30 ml total benzaldehyde add. Let it similarly fizz for an hour before adding the last 10 ml portion of benzaldehyde.
- After the last addition of benzaldehyde, let the mixture heat at the lowest tizzing temperature, and then tum up the heat slowly. The max with benzaldehyde should be at about 130 C. Piperonal would react much more easily, but allow the mixture to tizz to complete reation. Take no more than 6 hours on this stage of the reaction. Just push up the heat to get it going.
- Now for the new part of the reaction Uust discovered), "Vinegar", yes the really cheap distilled white vinegar at the grocery store, greatly increases yield by breaking up a dimer complex the product forms. At this scale, add 500 to 600 ml of that cheap grocery store vinegar, and swirl to mix it in. Then add from 50 to 100 ml of toluene or xylene. This solvent serves as a catcher for the BS we don't want.
- You will note that after adding the two volumes of vinegar, the toluene or xylene now form a layer on top of the DMSO and product layer. This is important as it is the crap catcher. The mixture now must be heated to reflux boiling temperature for 3 to 6 hours to break up the dimer and give the greater yields one wants. A lava lamp is unsuitable for this purpose.
- Heat the mixture to boiling gently for three to six hours. Then let it cool. This has broken up the dimer.
- Add about a shot glass of hardware store hydrochloric acid to the mixture and mix it in. This will assure that all the ephedrine stays out of the toluene layer.
- Now put the reaction into a sep funnel and shake it. Let this settle and the toluene layer on top would have crap and unreacted benzaldehye in it. Put it aside for further work, the water layer underneath has the product.
- Next base the OMSO and water solution containing the ephedrine and pseudoephedrine. Add a solution of lye to it with sirring and shaking until the pH is 13 plus. This should not take all that much lye to reach that level. Then add about 100 ml of toluene or xylene to extrtact the product. Save it. Extract again with 50 ml of toluene or xylene.
- Chapter Eighteen Cooking Your Own Ephedrine
- Wash the combined extracts with some water to rid them of DMSO, then let then sit to shed water and then transfer to a dry beaker minus the water droplets, and bubble with dry HCL to give about 30 grams of pure pseudoephedrine and ephedrine mixture as hydrochloride crystals. Keep water out of the dry HCI bubbling mixture!
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- Chapter Niueteen MDA, Ecstasy (XTC), and Other Psychedelic Amphetamines
- The psychedelic amphetamines are a fascinating and largely ignored group of drugs. They all have the basic amphetamine carbon skeleton structure, but show effects that are more akin to LSD than to the amphetamines. The LSD-like effect is due to the presence ofa variety of "add ons" to the benzene ring of the basic amphetamine structure. Generally, these "add ons" are ether groupings on the 3, 4, or 5 positions on the benzene ring. Because of these "add ons" one can consider these compounds more closely related to mescaline than to amphetamine. Consider the mescaline molecule pictured below.
- Mescaline should by all rights be considered an amphetamine derivative. It has the basic phenethylamine structure of the amphetamines with methyl ether groupings on the benzene ring at the 3, 4, 5 positions. To be a true amphetamine, it would only need its side chain extended by one carbon, putting the nitrogen atom in the central, isopropyl position. Such a compound does in fact exist. It is called trimethoxyamphetamine or TMA for short. Its effects are very similar to mescaline in much lower dosage levels than the Y, gram required for pure mescaline. Its chemical cousin, TMA-2 (2, 4, 5 trimethoxyamphetamine) has similar awe-inspiring characteristics, More on this subject later.
- The most popular and, in my opinion, the best of the psychedelic amphetamines are the members of the MDA family. This family consists of MDA, and its methamphetamine analog, XTC, or Ecstasy, or MDMA. MDA (3,4 methylenedioxyamphetamine) gives by far the best high of this group. Its effects can best be described as being sort of like LSD without the extreme excited state caused by that substance. It was popularly known as "the love drug" because of the calm state of empathy so characteristic of its effect. It could also be a powerful aphrodisiac under the right circumstances.
- This substance gradually disappeared during the early 80s due to an effective crimping upon the
- chemicals needed for its easy manufacture.
- This crimping, and the drug laws in effect at the time, gave rise to a bastard offspring of MDA. This substance was XTC, or MDMA, the so-called Ecstasy of the drug trade. This material was a designer variant of MDA, and so was legal. The chemicals needed to make it could be obtained without fear of a bust. It also lacked the best qualities of its parent. While the addition of a methyl group of the nitrogen of the amphetamine molecule accentuates its power and fine effect, the addition of a methyl group to the MDA molecule merely served to make it legal. As fate would have it, the hoopla surrounding the subsequent outlawing of this bastard child served to make it a more desired substance than MDA. This is typical of black-market, prohibition-driven demand.
- To understand the various routes which can be followed to make these substances, note the structures of MDA and MDMA shown below:
- At the time of the writing of the second edition, the latest drug craze was the smoke-able form of methamphetamine called "'ice." At the writing of this seventh edition, this material was still popular, with most usage being confined to those with serious drug problems.
- I'm not going to endorse or encourage the foolhardy practice of smoking meth. Seeing firsthand what this stuff does to rubber stoppers, corks, and razor blades, I can only imagine what it does to lung tissue. My opinion on this practice is similar to my opinion on injecting the substance. If snorting the hydrochloride salt doesn't get you as wired as you could ever want to get, it is time to give up and find something else to fill your spare time with.
- I have never made nor used "'ice" as such, but I can tell you how to get smokable forms of meth. Since the godless importers of this stuff have already created a market for it, it's only right that I help American technology catch up.
- The regular hydrochloride salt is not ideally suited for smoking, as a lot of the product will get charred during the heating. The free base is quite smokable, but it is a liquid, and as such is not easily sold, as it is unfamiliar. I will cover this matter from two angles: a home technique that works well to base your personal stash for smoking, and a more large-scale procedure for commercial use.
- To base your stash and smoke it, mix your stash with an equal amount of bicarb, and then with a dropper, drip a little water onto it with stirring to make a paste. Now take some aluminum foil, and with your finger indent a well into it about an inch deep. Into this well put some of the paste, and heat it tram underneath with a lighter. Suck up the smoke with a straw.
- For making a crystalline yet volatile derivative of meth similar to crack rocks, one just recrystallizes the nicely small crystals one gets by bubbling dry HCI through toluene. Crank rocks similar to crack rocks are pretty simple to make also. These would be just big crystals of pure meth hydrochloride. To get such big rocks, just dissolve the meth hydrochloride into a minimum amount of alcohol. Then let the alcohol evaporate away. As it evaporates away, it will make pretty large crystals of meth hydrochloride. An alternative recrysallization solvent would be acetone containing a bit of water. This will evaporate away faster, but give more of a tell tale smell.
- Chapter Twenty One Calibrating the Vacuum
- His vacuum should be 50 torr or lower to be able to make methamphetamine. If his vacuum reading is more than 50 torr, he gets a new aspirator or changes the oil in the vacuum pump.
- The chemist can lise this information to adjust the temperature at which he collects his distilled product. The boiling temperature of phenyl acetone is about 105° C at 13 torr, and about 1150 C at 20 torr. The boiling temperature of N-methylforrnamide is about lOT C at 20 torr. The boiling temperature of methamphetamine is about the same as phenyl acetone. Phenylacetone and methamphetamine should be collected over a 20-degree range centered on their true boiling points. This makes sure that the chemist gets all of it. The purilleation scheme he goes through before distilling removes all the impurities with boiling points close to that of his product.
- Chapter Twenty Two Production from Allylchloride and Benzene
- caps of pipes have the thickest amount of zinc on the inside. I strip zinc off steel all the time at work. The end caps should have been completely stripped within a couple of hours using 5-7% HCI. That's conc. HCI diluted 6 to 7 times. Under that zinc is mild steel. It too will fizz in HCI solution, but much slower. Using a scrub pad, one can go into that end cap and scrub off the surface layer of gunk that forms while metals are being stripped. Zinc while it dissolves will be black. Exposed iron or mild steel will be a brighter color. After rinsing, application of some copper sulfate solution will show exposed steel. The old copper displacement reaction, leaving a copper deposit. For a part to take two days to strip in HC!, either such a small amount of HCI solution was used that it has been exhausted by the stripping action, or the dissolution of the underlying iron has been mistaken for more stripping of zinc.
- This possible source of confusion can be eliminated by using stainless-steel pipes and caps rather than galvanized steel. These can be used as is, without any treatment.
- Now with the reaction mixture inside the pipe, it's time to heat the mixture. For production of meth or benzedrine from l-phenyl-2-chloropropane, the preferred heating procedure is to heat at 1600 C for about 9 hours. For production of MDA or MDMA from bromosafrole, the preferred heating is at about 1250 C for 3 to 4 hours. One does this heating by putting a pan with cooking oil on a stove burner, and then immersing the pipes in the cooking oil. The temperature of the oil bath is then held at the desired temperature for the required period of time.
- Alier the cooking period is complete, the pipes are removed from the heating bath, and allowed to cool down. Once they have cooled, they can be opened, and the contents poured into a distilling flask. Most all of the alcoholic ammonia or methylamine should be distilled otT. In the case of methylamine, great care should be taken to catch its vapors for reuse. This is done using that apparatus shown in Chapter Four, making a fresh load of methylamine in alcohol for use in the next run. The last portion of alcohol should be removed using a vacuum, down to a volume of about 100 ml.
- The residue in this flask should be shaken very vigorously with 10')'0 HCI solution. This converts the amine products into their hydrochlorides, which are water-soluble. The shaking should continue for at least 5-10 minutes to get all of the product extracted out of the gunky tar matrix. Now extract this 10% solution which contains the product with a couple 50 ml portions of toluene. This removes entrained gunk. Finally, make the solution strongly alkaline to litmus with lye. This generates a lot of heat, and should be done cautiously with shaking between adds of lye. When the solution is strongly alkaline, shake vigorously for about 5 minutes more, then check again the pH of the water to make sure it is still quite alkaline. There should be a healthy amphetamine layer floating on top of the water. With the hot water, it will give a strong aroma of amphetamine when sniffed. Cool the solution, and extract with two 50 ml portions of toluene.
- The toluene extracts contain the amphetamine. This should be distilled in the usual manner as described in Chapter Five to yield about 25 ml of amphetamine or meth. This is converted to the hydrochloride salt as also described in Chapter Five, to give about an ounce of pure benzedrine or meth. This procedure can be scaled up as desired. In case you were wondering, the boiling point of benzedrine free base is about 15° C lower than meth.
- Distilling must be done when using this method, because there is just no other way to remove the higher amines made as byproducts. If one is making MDA by this method, those higher amines produce a scary and paranoid trip. If one can't distill, this method shouldn't be used.
- Making Bromosafrole from Safrole, and I-phenyl-2-bromopropane From Allylbenzene
- To lise this "pipe bomb" method to make MDA or MDMA from bromosafrole or amphetamine and meth tram l-phenyl-2-bromopropane, one of course first needs the bromo compound. Good luck tinding that stllff Luckily, it's not a very complicated procedure to cook your own. Let's take, for example,
- Chapter Twenty Two Production from Allylchloride and Benzene
- The amount of dry HCI produced by dripping sulfuric acid onto salt will vary with the exact conditions, so the batch should be checked for reaction before quenching it on ice. It doesn't hurt to add too much dry HCI, within limits, but too little won't dehydrate the acid sufficiently. To check this, atler the day of stirring is done, pour some of the reaction mixture into a beaker, then from the beaker, return it to the reaction vessel. This leaves a coating of the reaction mixture on the glass in the beaker. Fill the beaker with water to rinse away the fuming acids, empty it, and snitI' inside the beaker for the aroma of the organics clinging to the glass. If it still smells like the candyshop fragrance of sassafras oil, an additional bubbling with dry HCl is going to be required, followed by another day of stirring in the cold. After the first batch or two, it's easy to gauge how much dry HCI one is getting. If the aroma has changed to something more chemical and fruity, yes, just like phenyl acetone, sufficient HCl has been added.
- When two days of stirring are completed, the batch is poured onto crushed ice, as in the other methods. When the ice has melted, a little bit of toluene is added (a volume about equal to the amount of sassafras oil used), and the water-bromosafrole mixture shaken. Prior to adding toluene, the bromosafrole will likely be on the bottom of the container, but after adding toluene and shaking, it should be floating on top. It's still burgundy-colored. Separate the bromosafrole layer with a sep funnel, and then wash it with about 3 volumes of water. Add bicarb slowly until the fizzing stops. This will knock out the carried-over HBr, HCl and acetic acid. Shake some more, then add a little more bicarb to make sure all the acid has been neutral ized.
- Separate the toluene-bromosafrole, and place it in a distilling t1ask. Distill off the toluene at normal pressure, then vacuum-distill the remaining bromosalrole. A vacuum that distills safrole at 11 00 C will distill bromosafrole at about 140-145° C. Some chlorosafrole distills at about 125° C. It can be used as is, or the chlorosafrole can be converted to iodosafrole according to the directions found in Chapter Eighteen in this book. The yield is about 66-75% conversion to bromosafrole, with the remainder being unconverted salrole and chlorosafrole. Bromosati'ole smells a lot like phenyl acetone. It may tum pink on standing, and should be stored in a freezer until used.
- Last, but certainly not least, check out the Pugsley Bromosalrole Recipe in Advanced Techniques of Clandestine Psychedelic & Amphetamine Manufacture. People have been getting very good results using this procedure. Essentially, it involves reacting sulfuric acid with sodium or potassium bromide in ice cold DMSO solvent to give anhydrous HBr solution. Sassafras oil is then added to the reaction mixture to give virtually 100% yields of bromosafrole.
- Secrets ofMethamphetamine Manufacture Eighth Edition
- Chapter Twenty Three
- Phenyl acetone from Benzene and Acetone
- This procedure makes use of the simple and common solvents, benzene and acetone, and links them together to form phenyl acetone. Back when I was cooking phenyl acetone, I often fantasized about how this could be done. Little did I know that it had been accomplished by a couple of Russians a few years before my cooking began.
- This isn't a procedure to get overly excited about, as the yields are low (36% based upon the manganese III acetate used), and a quite dilute solution is required. This procedure is most suited to someone willing to do large-scale cooking, not the typical basement experimenter.
- The interested reader should see Chemical Abstracts, Volume 77, column number 151620 (1972), and Journal of the American Chemical Society, Volume 93, pages 524 to 527 (1971), and Bulletin of the Academy of Science of the USSR, Volume 21, number 7, page 1626 (1972).
- In a large glass pot, as for instance one could get from people who sell milk pipeline equipment to dairy farmers, place 20 moles of acetone (900 ml). Hardware store acetone can be used by drying it with 111 0 volume of calcium chloride, also available at the hardware store as ice melt. Then add 5 moles of benzene (340 ml), and 1000 ml of glacial acetic acid, and one mole of manganese 1lI acetate (268 grams; price about $500). Equip the flask with a reflux condenser.
- These ingredients are mixed together, and then heated at 70° C until the brown color of Mn+3 disappears (about 2 to 3 hours). Then the contents are poured into a large stainless-steel distillation set up as described in Chapter One of this book, and the acetone, benzene, and part of the acetic acid are distilled off under reduced pressure. The weak vacuum produced by cheapie vacuum pumps, or low¬powered aspirators, is about right for this vacuum distillation. By chilling the receiving flask in ice, the unused acetone and benzene can be recovered for reuse.
- Then the residue, which consists of phenylacetone and other organic products dissolved in acetic acid along with Mn(II) acetate, should next be diluted with several volumes of water. The product phenylacetone can then be extracted from this watery mixture, with toluene. The extracts should next be washed with dilute sodium hydroxide solution, and then the toluene-phenylacetone solution can be distilled to yield around 25 ml phenylacetone.
- To get decent results from this reaction, the amount of water in the reaction mixture should be held to under I%, and preferably under v,%. Improperly dried acetone is a prime culprit when tracking down sources of water in the reaction mixture. Water introduced from Mn(H) acetate can be removed by distilling off the water-acetic acid azeotrope at 76° C.
- The other main problem with this reaction, besides the large dilution used, is the need for Mn(llI) acetate. This expensive material isn't something one can find on hardware store shelves. Mn(H) acetate, on the other hand, is a very common industrial chemical, used as a mordant in dying, and as a drier for paints and varnishes. It's also pretty cheap, so long as one doesn't want 99.9% pure chemical.
- To get Mn(llI) acetate from Mn(U) acetate, we return to a recurring theme in industrial chemistry -the electric generation of Mn(lII) Ii'om Mn(H). We saw one example of this kind of conversion back in Chapter Nine in the benzaldehyde recipe. For this next one see Acta Chemica Scandinavica B 33 (1979), pages 208-212. At a graphite or platinum anode in a simple, undivided cell, using a cathode much smaller than the anode to minimize reduction of the Mn(lII) formed, the chemists produce Mn(llI) acetate from Mn(ll) in glacial acetic acid solvent.
- One mole ofMn(ll) acetate is dissolved in one liter of glacial acetic acid. A little bit of sodium lithium fluoroborate (a few grams) is added as current carrier to the solution. One could also try sodium or potassium acetate as current carrier; it may not interfere in this reaction. The fairly large graphite or
- Secrets of Metbamphetamine Manufacture
- Eighth Edition
- To recover the product, they start by adding bicarb to this reaction mixture until it is neutralized. This is when the added bicarb no longer causes fizzing. They next add salt until the solution can dissolve no more. Then they extract out the phenyl acetone with methylene chloride. One could also use toluene. Distilling this extract then gives them pure phenyl acetone, around 5 ml.
- As is, this isn't a clandestine-suitable process. It just uses way too much solvent to get such small amounts of product. If one could reduce the amount of benzene used from the thirty fold excess relative to the 2-nitropropene down to around 10 fold, and if then one could also reduce the amount of methanol used, this method would have some promise. Good luck and happy cooking!
- For another somewhat related reaction, I have only the abstract. The research was done in 1959 by Robert Levine. It gives a 34% yield of phenylacetone. To liquid ammonia, one first adds sodamide and acetone. This forms a sodio derivative of acetone. Next, bromobenzene is added. and the mixture allowed to react for 10 minutes. Then the reaction mixture is quenched by adding ammonium chloride. After the ammonia evaporates away, the residue is extracted with toluene. This extract is washed with some dilute hydrochloric acid to remove aniline and diphenylamine formed as byproducts. Then the toluene extract is distilled to get pure phenylacetone. DibenzyI ketone is formed as a byproduct also.
- Chapter Twenty Four Last Resort: Extracting I-Methamphetamine from Vicks Inhalers
- Chapter Twenty Four Last Resort -Extracting I-Methamphetamine from Vicks Inhalers
- By popular demand, this method of last resort will be covered in this edition. The Vicks Vapor Inhaler is available off the shelf at your local grocery or drug store in the cold-or allergy-remedy section. It contains 50 mg of the free base of the weaker isomer of meth, along with the "Vicks vapors" which are bOnlyl acetate, camphor, lavender oil, and menthol.
- Of the above ingredients, only the meth free base (I-desoxyephedrine) has a basic nitrogen, so separation is possible. To extract and separate the I-meth from the other ingredients, we first disassemble the inhaler to get at the cotton-like wadding that contains ingredients. This wadding should be immediately soaked in 10 ml of the 10% hydrochloric acid. The hardware-store brands of hydrochloric acid are about 20°;', -30% strength, so dilute accordingly. Using surgical gloves, squish up this wadding repeatedly to get the HCI into contact with the meth free base and convert it to the hydrochloride, which is water soluble. After a good thorough squishing, pour the hydrochloric acid into a sep funnel. If solids are t10ating around, tilter the solution. Now add another 10 ml of plain water to the wadding, squish it around again to rinse out more product, and pour this too into the sep funnel.
- Now extract out the entrained vapors with a couple of 20 ml portions of toluene. Throw away the toluene, and keep the hydrochloric acid solution. Now make this hydrochloric acid solution strongly basic to pH papers by adding some lye or lye solution, with strong shaking between additions of lye.
- The meth has now been free based, and is freed of most of the Vicks vapors. Extract out the meth free base with about 20 ml of toluene. Separate off the toluene, and bubble dry HCI gas through it as described in Chapter Five. The crystals of I-meth hydrochloride should be spread out to dry after filtering, and their aroma noted, once they are free of toluene. If they still smell like the Vicks vapors, one should first try drying them under a vacuum for an hour or so. If this still doesn't render them odor¬Iree, they can be recrystallized by first dissolving them in a minimum amount of alcohol (91 % isopropyl Irom the drug store shelves), and then adding toluene with shaking until about 10 volumes of toluene have been added. After some standing in the cold to get complete precipitation, the crystals can be filtered out. At this point the smell of Vicks vapors should be gone.
- I have heard an unconfirmed report from a correspondent named Tammy that new versions of this inhaler don't respond to HCI extraction so well. The wonders of polymer science. If this is the case, the first extraction should be with 91 % isopropyl alcohol. After two extractions with isopropyl alcohol, add a couple of drops of HCI and then this extract should be evaporated under a vacuum, or barring this, just mix with 20 ml of toluene.
- Now extract this toluene solution with two 20 ml portions of 10% hydrochloric acid. From here, proceed as with the 10% hydrochloric acid solution.
- Secrets of Metbamphetamine Manuracture
- Eighth Edition
- Chapter Twenty Five Keeping Out or Trouble
- Making methamphetamine, it should be remembered, could be a dangerous activity. But, in addition to any dangers inherent in the activity, underground chemists making methamphetamine face dangers of another sort. The sources of these other dangers are the agents of the various law enforcement agencies. This chapter will discuss some of the dangers and how underground chemists avoid them.
- How then does the underground chemist minimize his risks? The lirst and most important thing is to use hit-and-run tactics. He makes a lot of product at a time, and then closes up shop. It is much safer to spend a week or so on steady work and make a supply of product that will last for a while than to keep setting up and supplying a lab every few weeks to make smaller amounts. This cuts the chemist's exposure to a minimum. Secondly, all the chemicals to make methamphetamine are only brought together when the chemist is ready to begin production. Having all the chemicals together could result in a conspiracy charge. For example, having phenylacetic acid, acetic anhydride and pyridine together could result in a charge of conspiracy to manufacture phenyl acetone, if the knuckleheads at the state crime lab are aware of this method of making phenylacetone. To avoid this, phenylacetic acid and methylamine arc kept at one location, and the other chemicals and glassware at another. After the chemist is done making his supply of methamphetamine, he washes all the glassware in hot, soapy water, rinses them a couple of times with hot water and then with rubbing alcohol. He lets the glassware drip dry, and then bakes the glassware in the oven at 4000 F for an hour or so. This removes all traces of product from his glassware. The empty glass jugs of chemicals are rinsed out with water and the labels scraped off. Then they are broken and the pieces taken to a far away dumpster.
- A very important precaution for the underground chemist is to keep his mouth shut. While his Iriends may mean him no harm, they would tell their friends and eventually the wrong ears would hear about it. The streets are crawling with snitches who keep themselves out of jail by reporting what they hear. Without a snitch, police agencies are incapable of detecting a cockroach crawling across a loaf of bread.
- The people to whom the chemist sells his products have no business knowing where it comes from. In fact. he is constantly on guard against his customers, because they are his main source of danger. If one of them should foul up, he may very well try to set up the chemist to get out of his own problems. This is the way that Johnny Law makes his busts, so the underground chemist is on guard. If one of his customers has a newfound buddy who wants to buy from him, he starts babbling crazy nonsense or claims ignorance. He decides how to deal with them later.
- As long as the chemist does not deal with strangers. the only way that the narcs can get at him is to have one of his customers make what is called a "controlled" buy on him. This is when they send his customer in to make a purchase from him while they wait and watch outside.
- The underground chemist protects himself by only making deliveries to his customer's home. He never does business out of his own home, or at bars, parks, parking lots or any other place suggested by his customers. He knows his dealers well, and knows their schedules. His dealer does not know exactly when he will be showing up with the next shipment; he just shows up unannounced and makes the delivery. A street-legal dirt bike is a good delivery vehicle. If the narcs try to jump the chemist at his customer's home, he takes off cross-country, leaving a cloud of methamphetamine powder behind him. He can melt the baggie on his tail pipe. If the narcs eventually catch him, he says they looked like a sleazy gang of hit men. He never lets his customers talk him into meeting at a bar, park or other public place where Johnny Law can watch and make a controlled buy. He ignores excuses such as not wanting a roommate to know about the shipment.
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- Currently, under federal laws, once an individual has been found guilty of manufacturing any amount of any drug, he may then be sentenced according to any amounts that can be established by a light standard of proof. The sentencing in all federal drug offenses (except simple possession) is governed by the drug weights involved. In my case, where no drug seizure was made, the drug quantity involved is estimated based on the lab seized or the established amount of precursor seized.
- In my case, Killion fingered me as having ordered mini-thins from two distribution companies (T &M and Olympus), and stated that I was in possession of a methcathinone lab. The first thing the Kansas OEA did was call and subpoena the companies' records, which showed that 39,000 mini-thins had been shipped to my parents' and sister's addresses (both living next door to me). Then the OEA simply awaited the next order and shipment.
- I was found guilty, based largely on the DENs surveillance of me picking up 3,000 mini-thins at the post office. Soon, after agents followed me to my sister's home, my wife was observed going to buy a can of Red Devil lye and delivering it to me. A warrant was sought, and seven hours later the DEA rushed in to find me in a detached garage on my sister's property, where two five-gallon paint buckets containing toluene paint thinner were discovered, along with some Batman drinking glasses (one with a trace amount of chrome salt), a jug of HCI, a container of water mixed with sodium hydroxide, and one broken-up, duct-taped 3,OnO ml flask.
- My point is that on a bust where these white-cross mini-thins are involved, the distribution company's records (and any other records that the law can obtain) are used to establish the amount of precursor that had been involved in the laboratory manufacture, and from this the total quantity of drugs involved is determined, which in turn sets the length of the sentence to be imposed. The same thing has been done with methamphetamine precursors for years, but the yields of cat from ephedrine have not yet been established.
- In early 1993, two cases of cat manufacture arose in Marquette, Michigan. One is published: US vs Baker, 852 F. Supp. 609 (W.o. Mic 1994). Affirmed on appeal in the Sixth Circuit, this case established that 50% of the weight of the ephedrine pills will reasonably equal the weight of the cat which could be produced from it. This amount was established by a government-employed chemist who testilied at the trials in these cases. The prosecutor in my case is using Baker to calculate my sentence. I do not feel that 50% is unreasonable, unless I could find proof that it is. I am now arguing that insufficient proof exists that the 39,000 white-crosses were actually dropped into a cooking pot! They were ordered COD over a four-month period in 3,000-lot batches. And white-crosses have been sold for many years themselves as a "'speed" on the black markets. The FDA, which is now blasting against these pills, is a good source for this information.
- I wrote the FDA for information about white-cross mini-thins being illegally abused and sold as speed and lookalike-speed. The FDA sent me a copy of their proposed laws or regulations on ephedrine under published law, from the Federal Register, part 310 & 34 1, Volume 70, October, 1994 or 1995, I believe (I sent it to my lawyer, so I'm going by memory). It's a section on bronchial medications which are sold over-the-counter (OTC). In the FDA's proposed regulations, they mean to designate all ephedrine, norephedrine, and racephedrine products as prescription drugs. I do not believe that the DEA will succeed in its proposal, but they also propose (and have moved forward considerably) to remove all single-ingredient ephedrine products from OTC sales. They focus on the white-cross thins (which companies are selling now as stimulants) being sold as bronchial-aid products. Well, it's obvious that the distributors of white-crosses that sold them as stimulants before they were outlawed by the FDA have now relabeled them as asthma medicine, and continued their sales. Stimulants were prescription drugs at the time of those former sales, and that's why white-crosses were commonly sold as speed on the black markets years ago. There have been official discussions about outlawing OTC sales of the white-cross bronchial products, as recently as November 14, 1995. Also noticeable is that the FDA has mentioned
- Chapter Twenty Five Keeping Oul of Trollble
- PENNYWISE AND POUND FOOLISH by Uncle Fester
- There once was a man named Jack who had the normally virtuous trait of thriftiness. When Jack was able to save a few cents on a small purchase, he felt that he had won a victory and held his head up high as he walked out the store. A penny saved is a penny earned, after all. Jack shopped sales, and Jack cut coupons, but above all Jack loved his "store card".
- Jack's fondness for his collection of "store cards" would have done him little harm except for one little detail.. . .Jack liked to cook some crank once in a while too! He picked up his packages of Sudafed as part of his weekly shopping runs and just tossed them in with all the other sruff he was buying. Jack thought that this would cause less suspicion towards him than if he just showed up at various stores and simply loaded up at the cold medicine counter. On this point Jack was right, but his penury was setting a trap for him because at each checkout he flashed his "store card" to get his few penny discounts.
- One day, Jack's girlfriend had all of his stinginess that she could take. The final straw was the anniversary gift he brought home from the rummage sale. She stormed out of the house, and vowed to make Jack's lite a living hell.
- Jack's former girlfriend knew all about Jack's meth hobby, and she ran to the police. After she told her talc, the police did some checking to gather evidence for a search and bust. When they checked Jack's garbage, it was simply pristine, as he rarely threw anything out. Watching and tailing Jack yielded them nothing either. He wasn't a "dealer" and lived a frugal and spartan life.
- Finally the narco swine stumbled upon Jack's Achille's Heel...his addiction to "store cards". You see, whenever that little card is flashed at the checkout, the entire purchase is recorded in the files of the central scrutinizers with your name attached. Once there, it could linger for centuries ...
- When Jack's "store card" records were checked, what a gold mine they stumbled into! Box after box of "cold medicines", bottles of ephedrine pills at the gas station, along with cans of solvents at the hardware store. acids and drain openers at other stores. It was a gold mine for them, and the shaft for Jack!
- Now Jack is whiling away some time at a place where he doesn't have to pay for his meals or housing.
- Thanks to those "store card" records, they were able to string together years of cooking and claim that he made outrageous amounts of go-go powder. They were proud to give him more time than his cellmate Bubba who stabbed three guys because he didn't like the way they had their hats screwed on. Welcome to the War on Drugs.
- The End
- Secrets of Methamphetamine Manufacture
- Eighth Edition
- Chapter Twenty Six Legitimate Uses of Some Chemicals
- Acetic Anhydride -commonly used in the chemical industry, especially for making dyes. * * * Benzene and ether -common solvents, but they are sometimes used for tree basing coke. * * Fomlic acid -used for taxidermy and tanning leather. * Hydrochloric acid and sulfuric acid -the two most common mineral acids, with too many uses to list. When buying them, underground chemists say they want them for electroplating. *
- You can pick up these two at the hardware store. Hydrochloric will often be labeled as muriatic acid, and will generally be 30% HC\. This is good enough for most uses. I found an industrial grade concentrated sulfuric at my local hardware store in the plumbing section. It was a product called Liquid Fire by Amazing Products. It sells for around $6 a pint, and is used as drain opener. This is plenty good enough for dripping on salt to make HCI gas.
- Methylamine -used in photography, as an additive to racing fuels, and as an ingredient in rocket fuel
- and tanning solutions. * * * * Phenylacetic acid-used in perfume to produce the smell of honey, and added to the nutrient broth of penicillin mold to increase the yield of penicillin. * * * *
- Platinum and Raney nickel -catalysts used in all hydrogenations. * * Pyridine -a common but expensive solvent and reagent. * * All other List I chemicals * * * *
- All other List II chemicals * * * One should obtain toluene and acetone at the hardware store in the paint section. There they carry zero stars, so long as you don't buy so much at one place that you get them wondering.
- * Least suspicious to purchase * * * * Most suspicious to purchase
- Learning about clandestine chemistry is a lot of fun, as you well know after finishing this book. It's also a lot of fun to follow along with conversations and "posts" that people put on the Internet. There are a few web sites exclusively devoted to such conversations and postings. They are great places to drop in on and spend hours keeping up with the latest news or reading about clandestine processes and equipment.
- Before you eagerly dive into the Internet, let me give you a few necessary caveats. To start with, go ahead and read, but keep your mouth shut. If you are doing any cooking, you certainly don't want to draw attention to yourself by posting questions or mentioning any results you are getting. These bulletin boards require registration before you are allowed to post. The heat trolls on these web sites, either by asking questions that giving an answer to would involve you in their "conspiracy," or by checking out the e-mail addresses of posters who seem like they are actively cooking. By keeping quiet and just reading, no one will know you are there.
- Caveat number two is a corollary to the first one. Since no one who is actively cooking would be stupid enough to wave around their e-mail address for everyone to see, the people doing the posting will fall into two classes: retired cookers who stil l love to talk about the excitement of their glory days and relate war stories, and simple students of the field, ranging from rank amateurs to the fairly advanced. The problem is to discern the two classes, and separate the wheat tram the chaff in the huge amount of material posted on these boards.
- Making this differentiation is a difficult task for the beginner. The second class tends to be skilled at sophistry, and in the process they give birth to misconceptions that carry onward in time with the tenacity of urban legends. Let me give you some help in this sifting process; a good source posting on the net will
- cite references I,)r the readers to follow up on rather than just making claims. This is the same style your
- Uncle uses in this book and all my other ones. It is the only legitimate style to use when making posts as well. Suspect sophistry and underlying agendas when references aren't mentioned during chemical discussions.
- Now that you have been suflicientiy warned, Jet me pass along two web sites where one can read about the world of clandestine chemistry at great length. Site number one is a site I like to visit and pass along cooking tips when I'm not busy writing books, raising my kids, working my day job, or running a publishing company. The site is commonly referred to as The Zonez, and is run by Android, or Andrew. depending upon how well you know him. This site has relatively low tranic with postings by old retired c.:{)uks.
- I\. much more active and current board is wetdreams.ws. It is moderated by old cooks, and most BS postings are removed by them. It also has a search engine and quite an archive of pill extraction methods. It is a great place to kcep current on the news which effects clandestine cooking.
- I\.nother site with a long history and a really extensive archive which could be accessed through their search engine was called The Hive. This site is now defunct after its founder got himself into trouble by going into the chemical sales tield. Enjoy the websites, and keep your mouth shut if you are cooking!
- SECRETS OF METHAMPHETAMINE MANUFACTURE
- Revised and Expanded
- Eighth Edition
- The classic text on clandestine chemistry just got even better. The Eighth Edition of Secrets of Methamphetamine ManufochUf! Including Rec ipes for MDA. Ecstasy. and Other Psychedelic Amphetamines contains the wisdom and recipes from Uncle Fester you've come to know and trusl, along with some totally new techniques you won't find anywhere else! The "War on Drugs" is really a war on our civil liberties. Uncle Fester shows in excruciating detail exactly how under-ground chemists will always stay one step ahead of the DEA. Everyone interested in the crucial issue of drug legalization will benefit immensely from reading this eye-opening manual.
- Only Fester can show you:
- • A new way to turn over-the-counter pills into meth
- • The innovative balloon technique
- • How to make your own ephedrine, so you'll never scrounge for pills again
- • How to make crank and other psychedelics from cinnamon oil and other common flavorings
- • The besl chemicals to use to avoid sales scrutiny
- • Why the government can never win the "War on Drugs"
- Uncle Fester writes in the Introduction: "Beyond any doubt, this is the best book ever written on the subject of clandestine chemistry, by anyone, anywhere, anytime, period! Your humble and gracious Uncle has been training champions for twenty years now, and this tour de force of clandestine ingenuity is living testament to the fact that the game hasn't passed me by."
- "Secrets of Methamphetamine Manufacture by Uncle Fester delivers the goods. Believe it or not, it was featured on CBS's 60 Minutes ... Every single way to making methamphetamines is here." -The Book Reader
- "A lot of 'underground manuals' ... just don 'I stack up. They offer common sense advice bUI hardly any hard-core instructions. This book is different. Uncle Fester gives detailed plans for making speed ..F ster makes sure to discuss the physical dangers of each chemical and the precautions you need to take to avoid getting busted. Outposts
- " Do we endorse the use of tweak? No! Do we enjoy thaI Festering Publications has the freedom to piss people off by publishing this? Very much." --High Times
- $30.00
- 䄀挀攀琀椀挀....
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