BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 32
Dr. Ajay K. Sah
BITSPilani, Pilani Campus

E1
ALKYL HALIDES + WEAK BASE
(SOLVOLYSIS)
The removal of a -hydrogen becomes
difficult without a strong base, a different
mechanism (ionization) begins to take
place
.. if the substrate is capable.2

Mechanisms of EliminationE1
An E1 reaction exhibits first-order
kinetics:
rate = k[(CH3)3CI]

The E1 reaction proceed via a twostep mechanism.

The bond to the leaving group breaks
first before the bond is formed.
The slow step is unimolecular,
involving only the alkyl halide.
3

The E1 Elimination Reaction (two steps)

rate = k [RX]
4

Mechanisms of EliminationE1
The rate of an E1 reaction increases
as the number of R groups on the
carbon with the leaving group increases.

REGIOSELECTIVITY

Mechanisms of EliminationE1
E1 reactions are regioselective, favoring
formation of the more substituted, more stable
alkene.
Zaitsevs rule applies to E1 reactions also.

Alkene synthesis by
Dehydration of Alcohols

Acid Catalyzed Dehydration of Alcohols

Typical acids used in dehydration

are sulfuric acid and phosphoric acid
Primary alcohols are most difficult
to dehydrate, tertiary are the easiest.
Rearrangements
skeleton can occur.

of

the

carbon
9

Acid Catalyzed Dehydration of Alcohols

The temperature and concentration of
acid required to dehydrate depends on the
structure of the alcohol

10

Mechanism for Dehydration of Secondary

and Tertiary Alcohols: An E1 Reaction

11

Mechanism for Dehydration of Secondary

and Tertiary Alcohols: An E1 Reaction

Carbocation Stability and the

Transition State
Recall the stability of carbocations
is:

12

Mechanism for Dehydration of Secondary

and Tertiary Alcohols: An E1 Reaction
Only a catalytic amount of acid is
required since it is regenerated in the final
step of the reaction
The second step of the E1 mechanism in
which the carbocation forms is rate
determining
Tertiary alcohols react the fastest
because they have the most stable tertiary
carbocation - like transition state in the
second step
13

The relative heights of DG for the second

step of E1 dehydration indicate that primary
alcohols have a prohibitively large energy
barrier

14

A Mechanism for Dehydration of Primary

Alcohols: An E2 Reaction
Primary alcohols cannot undergo E1
dehydration because of the instability
of the carbocation-like transition state
in the 2nd step.

In the E2 dehydration the first step is

again protonation of the hydroxyl to
yield the good leaving group water
15

16

E2: Vicinal Dibromides

Remove Br2 from adjacent carbons.
Bromines must be anti-coplanar (E2).
Use NaI in acetone, or Zn in acetic acid.

17

Removing HX via E2
Use a bulky base if the alkyl halide usually
forms substitution products.

18

Removing HX via E2
Bromocyclohexane, a secondary alkyl
halide, can undergo both substitution and
elimination
E2 is favored over substitution using
bulky base diisopropylamine
H
Br (iPr)2NH, heat
H
H

H
+ [(CH3)2CH]2NH2Br
H

bromocyclohexane Cyclohexene
(93%)

19

Formation of Hofmann Product

Bulky bases abstract the least hindered H+
Least substituted alkene is major product.

20

Hofmann Elimination
A quaternary ammonium salt has a good
leaving group - a neutral amine.
Heating the hydroxide salt produces the
least substituted alkene.

21

Hofmann Elimination

22

Hofmann Elimination

23

E2 Mechanism

24

E2 Mechanism

25

Cope Elimination
Amine oxides undergo elimination to form
the least substituted alkene under milder
conditions than the Hofmann reaction.

26

DIFFERENCES BETWEEN
E1 AND E2

27

Structure of substrate
R
H
H
R-C-X
R-C-X
R-C-X
tertiary
secondary
R
R
H

primary

E1 formation of carbocation intermediate

rate :tertiary > secondary > primary > methyl

But this same order holds for E2 also.

tertiary has more
b -hydrogens

H
H
H

C
H
H

EtO-

H
C
C
C
H

H
Br

more opportunites
for reaction

H
28

ALKYL HALIDE + BASE

strong base

weak base
or

solvolysis
E2 mechanism
anti-coplanar
requirement

stereospecific
regioselective

E1 mechanism

must be able to make

good carbocation
not stereospecific
regioselective

29