Question

Why 1chloro 4metylbenzene is major product than 1chloro 2methyl bezene?

Answer 1

12

Because of the great reactivity of the chlorine radical, abstractions of primary, secondary, and tertiary hydrogen atoms are all exothermic. Therefore, the stability of the product radical has less influence on the activation energy of the reaction. Thus, according to the Hammond postulate, the transition state is more reactant-like.

According to R. Brückner Advanced Organic Chemistry, the chlorination of isopentane has four monochlorination products:

22 % 2-chloro-2-methylbutane

33 % 2-chloro-3-methylbutane

30 % 1-chloro-2-methylbutane

15 % 1-chloro-3-methylbutane

The statistical factor is responsible for this.

If each hydrogen atom of isopentane could be substituted at the same rate, the ratio would be

1 hydrogen atom (8 %) → 2-chloro-2-methylbutane

2 hydrogen atoms (17 %) → 2-chloro-3-methylbutane

6 hydrogen atoms (50 %) → 1-chloro-2-methylbutane

3 hydrogen atoms (25 %) → 1-chloro-3-methylbutane

In terms per hydrogen atom, the experimental yield is

22 % / 1 = 22 % → 2-chloro-2-methylbutane

33 % / 2 = 16.5 % → 2-chloro-3-methylbutane

30 % / 6 = 5 % → 1-chloro-2-methylbutane

15 % / 3 = 5 % → 1-chloro-3-methylbutane

Thus, 2-chloro-2-methylbutane is indeed slightly preferred –