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Intext Questions · 8.5

Q.Predict the products of the following reactions:

Intext 8.5 (i): structure(s) drawn as printed in the NCERT textbook, with the labels O
Figure
Intext 8.5 (ii): structure(s) drawn as printed in the NCERT textbook, with the labels O, NH2—NH, O2N, NO2
Figure
(iii) R−CH=CH−CHO + NH2−C∥O−NH−NH2→H+\mathrm{R{-}CH{=}CH{-}CHO\ +\ NH_2{-}\overset{\overset{\displaystyle O}{\parallel}}{C}{-}NH{-}NH_2 \xrightarrow{H^{+}}}
Intext 8.5 (iv): structure(s) drawn as printed in the NCERT textbook, with the labels
Figure
Odisha ChseTextbookSubjective· 3mImportance★★★★★
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All four reactions are nucleophilic addition–elimination of an ammonia derivative H2N−ZH_2N{-}Z on a carbonyl compound: the products are (i) cyclopentanone oxime, (ii) cyclohexanone 2,4-dinitrophenylhydrazone, (iii) the semicarbazone of the α,β-unsaturated aldehyde, and (iv) the N-ethylimine (Schiff base) of acetophenone — each with a molecule of water eliminated.

The carbonyl group of an aldehyde or ketone is attacked by the lone pair of the nitrogen of an ammonia derivative (H2N−ZH_2N{-}Z). The initially formed addition product (a carbinolamine, >C(OH)−NH−Z>C(OH){-}NH{-}Z) rapidly loses water in the weakly acidic medium, leaving the condensation product >C=N−Z>C{=}N{-}Z. The optimum pH matters: the acid protonates the carbonyl oxygen (activating the carbonyl), but too much acid would protonate the amine nucleophile itself.

(i) Cyclopentanone + HO−NH2HO{-}NH_2 (hydroxylamine), H+H^+

Hydroxylamine's nitrogen adds to the ring carbonyl carbon; dehydration then gives the oxime: the ring C=OC{=}O becomes C=N−OHC{=}N{-}OH.

cyclopentanone+HO−NH2→H+cyclopentanone oxime+H2O\text{cyclopentanone} + HO{-}NH_2 \xrightarrow{H^+} \text{cyclopentanone oxime} + H_2O

(ii) Cyclohexanone + 2,4-dinitrophenylhydrazine

The terminal −NH2-NH_2 of the hydrazine adds to the carbonyl; loss of water gives the 2,4-dinitrophenylhydrazone, ring C=N−NH−C6H3(NO2)2C{=}N{-}NH{-}C_6H_3(NO_2)_2. 2,4-DNP-derivatives are yellow, orange or red crystalline solids — this is exactly the reaction behind the classical 2,4-DNP (Brady's) test for the carbonyl group.

(iii) R−CH=CH−CHOR{-}CH{=}CH{-}CHO + semicarbazide, H+H^+ …

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