CHEMISTRY TEXTBOOK

Problem 10.4 : Primary allylic and

primary benzylic halides show higher

reactivity by SN^1 mechanism than

other primary alkyl halides. Explain.

Solution : SN1 reaction involves

formation of carbocation

intermediate. The allylic and benzylic

carbocation intermediate formed are

resonance stabilized, and hence SN 1

mechanism is favoured.

CH 2 = CH - CH 2 CH 2 - CH = CH 2

⊕ ⊕

Resonance stabilization of allylic carbocation

CH 2 CH 2 CH 2

CH 2 CH 2

⊕

⊕

⊕ ⊕

⊕

Resonance stabilization of benzylic carbocation

relief from steric crowding present in the
tertiary halide substrate).

Secondly the carbocation intermediate is
stabilized by +I effect of alkyl substituents
and also by hyperconjugation effect of alkyl
substituents containing α-hydrogens. As a
result, SN1 mechanism is most favoured
in tertiary halides and least favoured in
primary halides. This can be represented
diagramatically as shown below.

SN 1 rate increases

CH 3 - X 1^0      20      30

SN 2 rate increases

Tertiary halides undergo nucleophilic
substitution by SN1 mechanism while primary
halides follow SN2 mechanism. Secondary
halides react by either of the mechanism or
by mixed mechanism depending upon the
exact conditions.

(a)

(b)

crowding and destabilization increases

steric relief, stabilization by +I and hyperconjugation of

α - hydrogens increases

H

H

C

H

Nu X

1

2

1

2

H

H H

H

C

C

H

Nu X

1

2

1

2

H

H H

H H

H

C

C

C H

Nu X

1

2

1

2

H

H H

H HH H

H H

C

C

C C

Nu X

1

2

1

2

H

H

C

H

⊕

H

H H

H

C

C

H

⊕

H

H H

H H

H

C

C

C H

⊕

α

α

H

H H

H HH H

H H

C

C

C C

⊕

α

α

α

Fig. 10.6 : Influence of substrate in SN1 and SN2 (a) Transition states (T.S.) in SN 2

(b) Carbocation intermediates in SN 1