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Q8.14(ii):
How will you prepare the following compounds from benzene? You may use any inorganic reagent and any organic reagent having not more than one carbon atom (ii) m-Nitrobenzoic acid

Solution :

Given Target: Synthesis of m-Nitrobenzoic acid from Benzene

To synthesize $m$-nitrobenzoic acid ($C_7H_5NO_4$) starting from benzene ($C_6H_6$), we must observe the directing influence of substituents. The carboxyl group ($-COOH$) is meta-directing, and the nitro group ($-NO_2$) is also meta-directing. The strategic sequence involves introducing an alkyl group, oxidizing it, and then performing nitration.

Step 1: Friedel-Crafts Alkylation of Benzene

Benzene is reacted with methyl chloride ($CH_3Cl$) in the presence of an anhydrous Lewis acid catalyst, aluminum chloride ($AlCl_3$), to yield toluene ($C_6H_5CH_3$).

$C_6H_6 + CH_3Cl \xrightarrow{AlCl_3} C_6H_5CH_3 + HCl$

[Justification: Electrophilic Aromatic Substitution mechanism where $CH_3^+$ acts as the electrophile].

Step 2: Oxidation of Toluene to Benzoic Acid

Toluene is subjected to vigorous oxidation using alkaline potassium permanganate ($KMnO_4$) followed by acidification ($H_3O^+$). This converts the methyl group into a carboxylic acid group.

$C_6H_5CH_3 \xrightarrow[2. H_3O^+]{1. KMnO_4, OH^-, \Delta} C_6H_5COOH$

[Justification: The oxidation of the benzylic carbon occurs regardless of the length of the alkyl chain, provided at least one benzylic hydrogen is present].

Step 3: Nitration of Benzoic Acid

Benzoic acid is treated with a nitrating mixture consisting of concentrated sulfuric acid ($H_2SO_4$) and concentrated nitric acid ($HNO_3$) at $273-283 K$.

$C_6H_5COOH + HNO_3 \xrightarrow{conc. H_2SO_4} m-NO_2-C_6H_4-COOH + H_2O$

[Justification: The $-COOH$ group is a strong electron-withdrawing group, which deactivates the ring and directs the incoming nitronium ion ($NO_2^+$) to the meta-position].

Visual Representation of the Reaction Sequence

Benzene Toluene Benzoic Acid m-Nitrobenzoic Acid + CH3Cl / AlCl3 KMnO4 / H+ HNO3 / H2SO4

Summary of Reaction Conditions

Step Reagents Product
1 $CH_3Cl, AlCl_3$ Toluene
2 $KMnO_4, OH^-, H_3O^+$ Benzoic Acid
3 $Conc. HNO_3, Conc. H_2SO_4$ $m$-Nitrobenzoic Acid

Final Solution: The synthesis is achieved via Friedel-Crafts alkylation of benzene, followed by the oxidation of the side chain to benzoic acid, and finally, meta-selective nitration of the benzene ring.


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