Practicing Success

Target Exam

CUET

Subject

Chemistry

Chapter

Organic: Amines

Question:

For the same alkyl group, all the three primary, secondary and tertiary amines are more basic than ammonia in aqueous solutions. Their relative basicity, however, depends upon a combination of three factors: +I-effect of alkyl groups, the stability of the ammonium cation (formed after accepting a proton) due to H-bonding with water molecules and the steric effect of the alkyl groups which tend to reduce the extent of H-bonding. All these three factors are favourable for secondary amines thereby making them the strongest bases. Since methyl group has the smallest size, there is no steric hindrance to H-bonding. Consequently, stability of the ammonium cation due to H-bonding with water predominates over the +I-effect of the methyl group thereby making methylamine more basic than trimethylamine. If, however, the alkyl group is bigger than the methyl group, +I-effect of the alkyl group outweighs stability of the ammonium cation due to H-bonding there making tertiary amines more basic than the primary amines. Due to delocalization of lone pair of electrons of the nitrogen atom on the benzene ring, aniline is a weaker base than ammonia. The basic strength of the substituted anilines, however, depends upon the nature of the substituent. Whereas electron-donating groups tend to increase, electron-withdrawing groups tend to decrease the basic strength. The base strengthening effect of the electron-withdrawing groups and base weakening effect of the electron-withdrawing group is, however, more pronounced at p-than at m-position. However, due to ortho-effect, o-substituted anilines regardless of the nature of substituent whether electron-donating or electron-withdrawing.   

Among the following, the strongest base is 

Options:

C6H5NH2

p-NO2-C6H4NH2

m-NO2-C6H4NH2

C6H5CH2NH2

Correct Answer:

C6H5CH2NH2

Explanation:

Both p-nitroaniline and m-nitroaniline are much weaker bases than aniline due to the electron withdrawing nature of -NO2. Benzylamine is, however, a stronger base than aniline because in benzylamine, lone pair of electrons on the N-atom is not delocalized over the benzene ring while in aniline it is.