ALKYL HALIDES –

ELIMINATION REACTIONS
Common reaction :
Elimination of alkyl halide: Dehydrohalogenation, Dehydrohalogenation is an
example of  elimination.
H X
C C + B C C + BH + X

Strong
product
Alkil halide base
(alkene)
mechanism

E1 E2
 E1 Mechanism

Carbocation stability order

E1 mechanism need two step mechanism
First step (rate determining step), slow step, rate determining step entails
one species – the alkyl halide.

Heterolysis C – I bond form an intermediete carbocation, this is the same step as

SN1 mechanism.
 Energy diagram
for an E1 reaction:
 H Br H
H C C CH3 H C C CH3
H CH3 H CH3
Halide ion leaves, forming carbocation. The more stable the carbocation
is, the easier it is to form, and the faster the E1 reaction will be.

H O H H CH3
+
C C + H 3O
H C C CH3
H CH3
H CH3

•Base removes H+ from adjacent carbon.

•Pi bond forms
 H

H O H H CH3
+
C C + H3O
H C C CH3
H CH3
H CH3
 SN1 and E1 Reactions

SN1 and E1 reactions have exactly the same first step—formation of a

carbocation. They differ in what happens to the carbocation.
 E2 Mechanism
• E2 Mechanism – Bimolecular Elimination (2nd order).
Rate = k [RX] [Nu:-]

• E2 reactions occur when a 3° ,2° or 1° alkyl halide is treated with a strong

base such as OH-, OR-, NH2-, H-, etc.
• The reaction is concerted—all bonds are broken and formed in a single step.

B:- 
+
B
H R R
H R R
C C R C C C C + B H + X-
R R R
R R
X R X R
-

Step the E2 reaction :
• The base OH- removes a proton from the β carbon , forming H2O (a by-product)
• The electron pair in the β C-H bond forms the new π bond
• The leaving group Br- comes off with the electron pair in the C-Br bond
Figure 1. An energy diagram for an E2 reaction:

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12
The SN2 and E2 mechanisms differ in how the R group affects the
reaction rate.

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• Increasing the number of R groups on the carbon with the leaving group
forms more highly substituted, more stable alkenes in E2 reactions.
• In the reactions below, since the disubstituted alkene is more stable, the
3° alkyl halide reacts faster than the 10 alkyl halide.

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 Kinetic Isotope Effects

• Kinetic Isotope Effects is the difference in the rate of reaction

between compounds containing different isotopes.
For example : Differences in elimination rate between alkyl halides
deuterium and not deuterium.
• Deuterium ( atau D ) is a hydrogen isotope that essentially
consists of one proton and one neutron. C-D bond is stronger than
the C-H bond by 1.2 kcal / mol.
• If H were to be eliminated was replaced with D, break the bond
stronger C-D was asking for more energy. So Eakt must be higher
and the elimination reaction rate will be lower.
 Kinetic Isotope Effects

• examples of elimination reactions 2- bromopropane with CH3CH2O - as a

base.
 H Br CH3
H -
H C C CH3 C C + H2O + Br
H H CH3
H CH3
O

If the t-butyl bromide undergo elimination, only will produce

the kind of product alkene possible.
In reactions of removal of hydrogen halides from alkyl halides or the removal of
water from alcohols, the hydrogen which is lost will come from the more highly-
branched b-carbon.

More branched Less branched

H H H H
   
H C C C C H
CH3 A. N. Zaitsev -- 1875
H X H
 HO
H H H CH3
 C
H3C  H
C C C H
 H  C + H2O
H
Br H + Br
CH3
more substituted alkene
more stable
SAYTZEFF PRODUCT
and/or
OH
H H H H

  C
H3C H
C C C H CH3CH2
 C + H2O
H
Br H H + Br
less substituted alkene
less stable
HOFMANN PRODUCT
When remove a hydrogen atom from the more branched position, you are
forming a more highly substituted alkene.
 Rules of Saytzeff
• In 1875 a chemist russian, Alexander saytzeff formulate :
“Alkenes that having alkyl groups most at double bond carbon atoms, present in
the largest amount in product mix elimination reactions.” Alkene is referred to as
more substituted alkenes.
Has established that alkenes higher substituted are more stable than alkenes less
substituted.
State transitions that produce more stable alkene has a lower energy. Reactions
that lower energy transition state will go faster. Therefore more stable alkene is a
product that is more abundant
• Most often substituted alkenes can form cis and trans diastereomers (geometric
isomers). Experimentally it was determined that the trans alkene is generally
more stable than their cis isomers.
Hofmann's Rule implies that steric effects have the greatest influence on the outcome
of the Hoffman or similar eliminations. The loss of the β-hydrogen occurs preferably
from the most (least substituted) position [-CH3 > -CH2-R > -CH(R2)]. The product
alkene with fewer substitutents will predominate.
When the base is very bulky, then the H’s on the less substituted  carbon are almost
exclusively removed, and the less substituted (Hofmann) alkene product
predominates.

Et
CH3
H Et C O K H  CH
H 3

H3C C C C H Et H3C C C

CH3 C H
CH3 Cl H 
H

97% less substituted alkene

HOFMANN PRODUCT