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Q.

Which of the following statements is not correct?

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a

Amides are much stronger bases than amines

b

PhCONH2 is a stronger base than CH3CONH2

c

N, N-Dimethylaniline is only slightly more basic than aniline whereas 2,6-dimethyl-N,N-dimethylaniline is much more basic than 2,6-dimethylaniline.

d

p-Nitroaniline is a weaker base than p-cyanoaniline.

answer is A.

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Detailed Solution

(a) The adjacent C=O weakens the basicity by delocalisation of electron density from N to O.

(b) The ability of C=O to cause base-weakening is attenuated by the phenyl group, making benzamide a stronger base than acetamide

(c) Phenyl group has a base-weakening effect because of its ability to form extended p-bonding between the amino N and the phenyl ring

Question Image

In the structure II, N-H bonds are in the plane of benzene ring. In 2, 6-dimethyl- N,N-dimethylaniline, the formation of extendedπ-bonding is sterically hindered and thus interfere with the base-weakening extended π-bonding making this compound much more basic than 2, 6-dimethylaniline.

( d) The nitro group is more effective than cyano group in weakening the basic nature of aniline.

Question Image

In nitroaniline, electron delocalisation ends up with the negative charge on the more electronegative oxygen atom whereas in cyanoaniline, the negative charge ends up in the nitrogen atom (which is less electronegative than oxygen).

 

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