Two statements — Statement-I: Oxidation of p-nitrotoluene with acidic KMnO₄ gives an acid that is stronger than benzoic acid. Statement-II: Reduction of p-nitrotoluene with Sn/HCl followed by neutralization gives an amine that is more basic than aniline. Choose the most appropriate answer:

Solution & Explanation

This is a two-statement (correct/incorrect) item; evaluate each. Statement-I — Oxidation of p-nitrotoluene with acidic KMnO₄ oxidises the –CH₃ to –COOH, giving p-nitrobenzoic acid. The –NO₂ group is strongly electron-withdrawing (–I and –M). It pulls electron density away from the –COO⁻ formed on ionisation, stabilising the carboxylate anion and so making the acid MORE ionised, i.e. a STRONGER acid than benzoic acid. Statement-I is CORRECT. Statement-II — Reduction of p-nitrotoluene with Sn/HCl (then base) converts –NO₂ to –NH₂, giving p-toluidine (4-methylaniline). The –CH₃ at the para position is electron-DONATING (+I and hyperconjugation); it pushes electron density onto the nitrogen lone pair, increasing the availability of that lone pair, so the amine is MORE basic than aniline (which has no such donor). Statement-II is CORRECT. Both statements are correct → answer A. Key idea: electron-withdrawing groups increase acidity of an acid; electron-donating groups increase basicity of an amine.