CBSE Class 12 Chemistry 2018 Solved Paper

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Question : 18
Total: 26
(A), (B) and (C) are three non-cyclic functional isomers of a carbonyl compound with molecular formula C4H8O. Isomers (A) and (C) give positive Tollens' test whereas isomer (B) does not give Tollens' test but gives positive Iodoform test. Isomers (A) and (B) on reduction with Zn(Hg)∕ conc. HCl give the same product (D).
(a) Write the structures of (A), (B), (C) and (D).
(b) Out of (A), (B) and (C) isomers, which one is least reactive towards addition of HCN ?
Solution:  
(b) (B) as ketones are less reactive towards addition of HCN than aldehydes and alkane due to higher hinderance caused by steric effect and inductive effect.

(c) The possible non-cyclic functional isomers of a carbonyl compound having molecular formula.

‌C4H8O‌ are ‌−
‌
CH3−CH2
(I)
−CH2
−CHO

CH3−
O
∥
C
(II)
−CH2
−CH3


CH−
CH
|
CH3
−CHO
(III)

Since isomer (B) does not give Tollen's test, it must be a ketone but it gives positive iodofo on test, so it must be methyl ketone. Hence, structure of (B) is (II).
The isomers (A) and (C) give positive Tollen's test so both the isomers are aldehyder. Since isomers (A) and (B) on reduction with Zn∕Hg / conc. HCl give the some product (D).
CH3−
O
∥
C
−CH2
−CH3
(B)
‌
Zn(Hg)
────▸
‌ conc. ‌HCl
CH3−CH2−CH2−CH3
(D)

∴ Structure of (A) is (I) and Structure of (C) is (III).
Hence,
A‌⇒CH3−CH2−CH2−CHO
B‌⇒CH3−C−
O
∥
O
−CH
2
−CH3

C‌⇒CH3−
CH
|
CH3
−CHO

D‌⇒CH3−CH2−CH2−CH3
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