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Q.(a) Explain why :

(i) Carboxyl group in benzoic acid is meta directing.
(ii) Sodium bisulphite is used for the purification of aldehydes and ketones.
(iii) Carboxylic acids do not give characteristic reactions of carbonyl group.
(OR)
(b) An organic compound 'A' with molecular formula C3H8OC_3H_8O on reaction with Cu at 573 K gives 'B'. 'B' does not reduce Fehling's solution but gives a yellow precipitate of compound 'C' with I2I_2/NaOH. Deduce the structures of A, B and C.
CBSECBSE Class XII Board 2023Subjective· 3mImportance★★★★★
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Part (a): −COOH-\text{COOH} is meta-directing because resonance withdrawal deactivates o/p most; NaHSO3\text{NaHSO}_3 forms reversible crystalline adducts used to purify carbonyl compounds; carboxylic acids fail carbonyl tests because −OH-\text{OH} resonance lowers the carbonyl's electrophilicity. Part (b): A = propan-2-ol, B = propanone, C = iodoform.

Part (a)

(i) −COOH-\text{COOH} is meta-directing

The carboxyl group is a strong deactivator (both −R-\text{R} and −I-\text{I}). Drawing the resonance structures of the substituted benzene shows the developing positive charge (electron depletion) sits at the ortho and para carbons; the meta carbon is spared. So although the whole ring is deactivated, meta is the least deactivated, and the incoming electrophile chooses it. "Meta-directing" means meta is preferred, not that meta is activated.

(ii) NaHSO3\text{NaHSO}_3 for purification

Aldehydes and most methyl ketones undergo nucleophilic addition of bisulphite to give crystalline, water-soluble adducts:

R-CHO+NaHSO3→R-CH(OH)-SO3Na\text{R-CHO} + \text{NaHSO}_3 \to \text{R-CH(OH)-SO}_3\text{Na}

Non-carbonyl impurities stay behind; the adduct is filtered, and treatment with dilute acid or base regenerates the pure carbonyl compound. Because the addition is reversible, the pure aldehyde/ketone is recovered — the basis of the purification.

(iii) Carboxylic acids don't give carbonyl reactions

In −COOH-\text{COOH} the hydroxyl oxygen lone pair conjugates with the C=O\text{C=O}:

R-C(=O)-OH↔R-C(-O−)=O+H\text{R-C(=O)-OH} \leftrightarrow \text{R-C(-O}^-\text{)=}\overset{+}{\text{O}}\text{H} …

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