To synthesize luminol from 3-nitrophthalic acid and hydrazine, you can follow a three-step protocol involving the formation of the anhydride, reaction with hydrazine, and reduction of the nitro group to an amino group. Below is a detailed synthesis procedure:

Materials Required:

3-Nitrophthalic acid

Hydrazine hydrate (80% aqueous solution)

Ethanol

Concentrated hydrochloric acid (HCl)

Iron powder (Fe)

Sodium hydroxide (NaOH)

Distilled water

Ice bath

Reflux apparatus

Filtration setup



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Step 1: Formation of 3-Nitrophthalic Anhydride

Procedure:

1. Dehydration of 3-Nitrophthalic Acid:

Place 3-nitrophthalic acid (e.g., 10 g) in a dry round-bottom flask.

Heat the flask gradually to 200–220°C under reduced pressure to remove water and form the anhydride.

Maintain the temperature until no more water distills off.



2. Cooling:

Allow the flask to cool to room temperature.

The residue is 3-nitrophthalic anhydride, which can be used directly in the next step.





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Step 2: Synthesis of 3-Nitrophthalhydrazide

Procedure:

1. Reaction with Hydrazine:

Dissolve the 3-nitrophthalic anhydride in 50 mL of ethanol in a round-bottom flask.

Add hydrazine hydrate (excess, e.g., 5 mL) to the solution.

Attach a reflux condenser to the flask.



2. Reflux:

Heat the mixture under reflux for 2–3 hours.

Monitor the reaction progress (optional) using thin-layer chromatography (TLC).



3. Cooling and Isolation:

Allow the reaction mixture to cool to room temperature.

Pour the mixture into 200 mL of ice-cold water with stirring.

Collect the precipitated 3-nitrophthalhydrazide by filtration.

Wash the solid with cold water to remove impurities.

Dry the product under vacuum or in a desiccator.





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Step 3: Reduction to Luminol

Procedure:

1. Preparation of Reduction Mixture:

Suspend the dried 3-nitrophthalhydrazide in 100 mL of aqueous ethanol (50% ethanol in water) in a round-bottom flask.

Add iron powder (excess, e.g., 15 g) to the suspension.

Add concentrated hydrochloric acid (e.g., 20 mL) carefully to the mixture.



2. Heating:

Heat the mixture under reflux with stirring for 2–3 hours.

The nitro group will be reduced to an amino group, forming luminol.



3. Filtration:

While still hot, filter the mixture to remove the iron salts (iron oxides).

Wash the residue with hot water to extract any remaining product.



4. Neutralization:

Combine the filtrates and cool them in an ice bath.

Slowly add a solution of sodium hydroxide (10% NaOH) to the filtrate until the pH reaches around 8–9.

Luminol will precipitate out of the solution.



5. Isolation and Purification:

Collect the precipitated luminol by filtration.

Wash the solid with cold water to remove any remaining impurities.

Recrystallize the product from a suitable solvent (e.g., ethanol) if higher purity is desired.

Dry the purified luminol under vacuum.





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Safety Precautions:

Perform reactions involving hydrazine and concentrated acids in a well-ventilated hood.

Wear appropriate personal protective equipment (lab coat, gloves, safety goggles).

Handle hot equipment and reactions with care to avoid burns.



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Summary:

1. Convert 3-nitrophthalic acid to its anhydride by heating, removing water.


2. React the anhydride with hydrazine to form 3-nitrophthalhydrazide.


3. Reduce the nitro group to an amino group using iron and hydrochloric acid, yielding luminol.



This protocol efficiently synthesizes luminol from 3-nitrophthalic acid and hydrazine through accessible laboratory procedures.