ELIMINATION

REACTION
 Learning objectives
Recognise, differentiate and explain the different
reaction elimination mechanism involving alkyl
halides and alcohols
Illustrate the different reactions and mechanisms
using examples
Draw mechanism of reactions

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 ALKYL HALIDES
Elimination Reactions
We had mentioned earlier that alkyl halide can undergo two
main type of reactions, nucleophilic substitution and
elimination.

Substitution
- -
Nu + C X Nu + X

H
Elimination - Nu H
-
Nu + C C + + X
X

Elimination reactions usually gives mixtures of alkene products

We can predict the major product in the reactions by using
Zaitsevs rule.
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 Zaitsevs rule state that, in the elimination of HX from an alkyl
halide, the more highly substituted alkene product predominates.

The reactions can take place by two common pathways: E1 and

E2 reactions.

Br -
CH3CH2O Na+
H3CH 2CHC CH 3 H3CHC CHCH 3 + H3CH 2CHC CH 2
CH3CH2OH
81% 19%

Br
- CH 3 CH 3
H3CH 2CC CH 3
CH3CH2O Na+
H3CHC CCH 3 + H3CH 2CC CH 2
CH 3 CH3CH2OH
70% 30%

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 The E2 reaction

This is elimination bimolecular reaction.

Occurs when an alkyl halide is treated with a strong base
such as OH- or OR-.
The most commonly occurring pathway for elimination

B: +
R B H R
H R R
R ...... R
C C R + B H + X
R
R X R X - R R

Transition state neutral alkene is produced when

Base X attack hydrogen, the C-H bond is fully broken and
start to remove the H, X group has departed with the
alkene double bond start C-X bond elecron pair
to form and X start to leave

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E2 takes place in one step without intermediates and the
reaction show second order kinetics.

Rate = k [RX] [Base]

E2 reactions always occurs with a periplanar geometry, all four

reacting atoms hydrogen, the two carbon, and the leaving
group lie in the same plane.

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Two such geometries are possible:
a. syn periplanar geometry in which the H and the X
are on the same side of the molecule
b. anti periplanar geometry in which the H and the X
are on the opposite side of the molecule.
H HX

H X
H
X
X

Anti periplanar geometry Syn periplanar geomtry

(staggered, lower energy) (eclipsed, higher energy)

For example, meso-1,2-dibromo-1,2-diphenylethane

undergo E2 elimination on treatment with base to give
only the pure E-alkene.
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This is due to anti periplanar arrangement of the eliminated
atoms, H and Br, with lower energy.
For the isomeric Z alkene to form, H and Br should have syn
periplanar arrangement with higher energy, thus not preferable.

H H Ph H
KOH Ph
Br Ethanol Br
Br Ph Ph

H
H Ph
KOH Br Ph
H Ph
Ethanol
Br Ph
Br
(E)-1-Bromo-
meso-1,2-Dibromo- 1,2-diphenylethene
1,2-diphenylethane
(Antiperiplanar geometry)
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 The E1 reaction

The E1 reaction (elimination unimolecular) is a close analog of

SN1 reaction.
E1 reaction begin in similar fashion with SN1 with the
occurrence of dissociation to give carbocation and followed by
the loss of H+ instead of substitution.

Rate determining Base

CH3 H CH3
step H CH3
Fast
H3C C Cl C+
- C C
H C + Cl
CH3 H CH3 H CH3
Carbocation

Dissociation of 3o alkyl Loss of H+ in a fast step

halide to form carbocation to give alkene. Electron pair
from C-H bond goes to form
in rate determining step the bond.
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E1 and SN1 normally occurred together whenever alkyl
halide is treated with nonbasic nucleophile in protic solvent.
For example, treatment of 2-chloro-2-methylpropane with
warm aqueous ethanol at 65 oC will give mixture of
elimination and substitution products.
CH3 CH3 H CH3
H2O, Ethanol
H3C C Cl H3C C OH + C C
o
65 C
CH3 CH3 H CH3

E1 showed first order kinetics, consistent with rate determining

spontaneous step dissociation process:
Rate = k[RX]
There is no geometric requirement on the E1 reaction because
the halide and hydrogen are lost in separate steps.
The reaction products also follow Zaitsevs rule.
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Primary alkyl halides
SN2 occurs if a good nucleophile is used such as RS-, I-,
CN-, NH3, or Br.
E2 takes place if a strong, hindered base is used such as tert-
butoxide.
-
Na+ CN
CH3CH2CH2CH2CH2Br CH3CH2CH2CH2CH2CN
THF-HMPA

-
(CH3)3CO K+
CH3CH2CH2CH2CH2Br CH3CH2CH2CH=CH2

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Secondary alkyl halides

SN2 and E2 occur together to give mixture of products.

If a weakly basic nucleophile is used in a polar aprotic
solvent, SN2 predominates.
If a strong base such as CH3CH2O-, OH-, or NH2- is used, E2
predominates.
O O
- O C CH3
H3C C O
H3C C CH3 + H3CHC CH2
Br Weak base H
100% 0%
H3C C CH3
H
- OCH2CH3
CH3CH2O
H3C C CH3 + H3CHC CH2
Strong base H
20% 80%

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Tertiary alkyl halides

E2 occurs when a base such as OH- or RO- is used.

Reaction under neutral condition leads to mixture of
products from both SN1 and E1.

- CH 3 CH 3
CH3CH2O
H3C C OCH 2CH 3 C CH 2
Ethanol
CH 3 CH 3 CH 3
H3C C Br 3% 97%
CH 3 CH 3 CH 3
CH3CH2OH
H3C C OCH 2CH 3 C CH 2
Heat
CH 3 CH 3
80% 20%

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 Summary of substitution and elimination reactions

Halide type SN1 SN2 E1 E2

RCH2X Do not occur Highly favored Do not occur Occur when strong
(Primary) bases are used

R2CHX Can occur with Occur in competition Can occur with Favored when
(Secondary) benzylic and allylic with E2 benzylic and allylic strong bases are
halides halides used

R3CX Favored in Do not occur Occur in competition Favored when

(Tertiary) hydroxylic solvents with SN1 bases are used

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 Reactions of Alcohol
Dehydration to alkene
Oxidation to aldehyde, ketone
Substitution to form alkyl halide
Reduction to alkane
Esterification
Tosylation
Williamson synthesis of ether

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Summary Table

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 Reactions of alcohols: Dehydration
1. E1 mechanism/ acidic condition
The C-O and a neighboring C-H bonds are broken, and a new
alkene pi () bond is formed.
This is acid-catalyzed reaction (normally using warm aqueous
H2SO4) in THF.
H3C OH CH 3

H3O+, THF
50oC
The reaction yield the more substituted alkene as the major product.
CH 3 CH 3 CH 3
+
H3O , THF
H3C C CH 2CH 2CH 3 H3C C CHCH 2CH 3 + H2C C CH 2CH 2CH 3
o
OH 50 C
Major Minor
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 Follow Zaitsevs rule
E1 mechanism via carbocation intermediate
3 alcohol dehydrate readily; 2 alcohol need severe condition
(75% H2SO4, 100 C) and 1 alcohol need harsher cond. (95%,
150 C)

H+
OH OH2 H H

CH CH C C
H3C CH3 H3C CH3 H2C CH3 H2C CH3

H
H2 O

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2. E2 mechanism of dehydration of 2 and 1 alcohol

Gentler method for dehydration- under milder and basic condition

Use POCl3 in pyridines

Pyridine act as base and solvent

Cl
H N
O P Cl
Cl
OH OPOCl2

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