Organic Chemistry

4th Edition
Paula Yurkanis Bruice

Chapter 11
Elimination Reactions
of Alkyl Halides
Competition Between
Substitution and
Elimination

Irene Lee
Case Western Reserve University
Cleveland, OH
2004, Prentice Hall

In addition to substitution, an alkyl halide can undergo an

elimination reaction

The E2 Reaction

The weaker the base, the better it is as a leaving group

The Regioselectivity of the E2 Reaction

The major product of an E2 reaction is the most stable

alkene
The greater the number of substituents, the more stable
is the alkene

Reaction coordinate diagram for the E2 reaction of

2-bromobutane and methoxide ion

The Zaitsev Rule

The more substituted alkene product is obtained when a
proton is removed from the -carbon that is bonded
to the fewest hydrogens

The most stable alkene is generally (but not always) the

most substituted alkene

Conjugated alkene products are preferred over the

more substituted alkene product

Do not use Zaitsevs rule to predict the major product

in these cases

Steric hindrance also affects the product distribution

Another exception to Zaitsevs rule

Consider the elimination of 2-fluoropentane

A carbanion-like transition state

Relative stabilities of carbanions

R
R C: R
tertiary
carbanion

least
stable

<

R
R C: - <
H
secondary
carbanion

R
H C: H
primary
carbanion

<

H
H C: H
methyl
anion

most
stable

The E1 Reaction

Reaction coordinate diagram for the E1 reaction of

2-chloro-2-methylbutane

Because the E1 reaction forms a carbocation

intermediate, we need to consider carbocation
rearrangement

Competition Between E2 and E1

Reactions

Stereochemistry of the E2 Reaction

The bonds to the eliminated groups (H and X) must be
in the same plane
HX

X
the more stable conformation

The anti elimination is favored over the syn elimination

Another view of the E2 reaction mechanism

The best overlap of the interacting orbitals is achieved

through back side attack
Anti elimination avoids repulsion of the electron-rich
base

Consider the regioselectivity of the E2 reaction

The alkene with the bulkiest groups on opposite sides of

the double bond will be formed in greater yield, because
it is the more stable alkene

Reaction coordinate diagram for the E2 reaction of

2-bromopentane and ethoxide ion

The particular alkene isomer that is formed depends on

the configuration of the reactant

Stereochemistry of the E1 Reaction

Elimination from Cyclic Compounds

In an E2 reaction, groups to be eliminated must be trans
to one another

H
Br

H
Br

E1 Elimination from Cyclic Compounds

An E1 reaction involves both syn and anti elimination

Utilization of kinetic isotope effect to study a reaction

mechanism
CH2CH2Br

CD2CH2Br

+ CH3CH2O

+ CH3CH2O

kH

kD

CH CH2

+ Br- + CH3CH2OH

CD CH2

+ Br- + CH3CH2OD

A carbon deuterium bond (CD) is stronger than a

carbon hydrogen bond (CH)
The deterium isotope is 7.1, indicating that CH (or CD)
bond must be broken in the rate-determining step

Competition Between Substitution and

Elimination
Alkyl halides can undergo SN2, SN1, E2 and E1
1) decide whether the reaction conditions favor SN2/E2 or SN1/E1
SN2/E2 reactions are favored by a high
concentration of nucleophile/strong base
SN1/E1 reactions are favored by a poor
nucleophile/weak base
2) decide how much of the product will be the substitution product
and how much of the product will be the elimination product

Consider the SN2/E2 conditions

A bulky base encourages elimination over substitution

A weak base encourages substitution over elimination

Cl
CH3CHCH3 + CH3CH2O-

OCH2CH3
CH3CHCH3

+ CH3CH CH2 + CH3CH2OH

+ Cl-

strong
base

Cl
O
CH3CHCH3 + CH3C O-

weak
base

O
OCCH3
CH3CHCH3 +

Cl-

Consider SN1/E1 conditions

Substitution and Elimination Reactions

in Synthesis

In synthesizing an ether, the less hindered group should

be provided by the alkyl halide
CH3
CH3CH2Br + CH3COCH3

CH3
Br- + CH3COCH2CH3 + CH2 CH2
CH3

CH3
CH3CH2O- + CH3CBr
CH3

CH3
Br- + CH3C CH2

+ CH3CH2OH

However, the most hindered alkyl halide

should be used if you want to synthesize an alkene

Consecutive E2 Elimination Reactions

Intermolecular Versus Intramolecular

Reactions

A low concentration of reactant favors an intramolecular

reaction
The intramolecular reaction is also favored when a fiveor six-membered ring is formed

Three- and four-membered rings are less easily formed

Three-membered ring compounds are formed more
easily than four-membered ring compounds
The likelihood of the reacting groups finding each other
decreases sharply when the groups are in compounds
that would form seven-membered and larger rings.

Now we can design a synthesis

?

CH3

CH3
Br
Br