CHAPTER 8:

ELIMINATION REACTION
 Recognize, 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 and Elimination Reactions

General Features of Elimination

• Elimination reactions involve the loss of elements from the starting material to form a new  bond
in the product.

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• Equations [1] and [2] illustrate examples of elimination reactions. In both reactions a
base removes the elements of an acid, HX, from the organic starting material.

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• Removal of the elements HX is called dehydrohalogenation.
• Dehydrohalogenation is an example of  elimination.
• The curved arrow formalism shown below illustrates how four bonds are broken or formed
in the process.

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• The most common bases used in elimination reactions are negatively
charged oxygen compounds, such as HO¯ and its alkyl derivatives, RO¯,
called alkoxides.

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• To draw any product of dehydrohalogenation—Find the  carbon. Identify
all  carbons with H atoms. Remove the elements of H and X from the 
and  carbons and form a  bond.

• Elimination reactions usually gives mixtures of alkene products

• We can predict the major product in the reactions by using Zaitsev’s rule.
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The Zaitsev (Saytzeff) Rule:
• Recall that when alkyl halides have two or more different  carbons,
more than one alkene product is formed.
• When this happens, one of the products usually predominates.
• The major product is the more stable product—the one with the more
substituted double bond.
• This phenomenon is called the Zaitsev rule.

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 E2 reaction
• This is elimination bimolecular reaction.
• Occurs when an alkyl halide is treated with a strong base such as OH- or
OR-
• E2 takes place in one step without intermediates and the reaction show
second order kinetics.
Rate = k  [RX]  [Base]
• The most commonly occurring pathway for elimination
B: +
H R B......H R

....
...... R R R

.
R + B H + X

.
C C

....
R R
X - R R

.
R

.
R X

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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Stereochemistry of the E2 Reaction

• The transition state of an E2 reaction consists of four atoms from an alkyl halide—
one hydrogen atom, two carbon atoms, and the leaving group (X)—all aligned in a
plane. There are two ways for the C—H and C—X bonds to be coplanar.

• E2 elimination occurs most often in the anti periplanar geometry. This arrangement
allows the molecule to react in the lower energy staggered conformation, and
allows the incoming base and leaving group to be further away from each other.
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 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 H CH3
step Fast
H3C C Cl H C C+
- C 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
65oC
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 Zaitsev’s rule. 13
 When is the Mechanism E1 or E2?

• The strength of the base is the most important factor in determining the
mechanism for elimination. Strong bases favor the E2 mechanism. Weak
bases favor the E1 mechanism.

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Predicting the Mechanism from the Reactants—SN1, SN2, E1 or E2.

• Good nucleophiles that are weak bases favor substitution over

elimination—Certain anions generally give products of substitution because
they are good nucleophiles but weak bases.
• These include I¯, Br¯, HS¯, ¯CN, and CH3COO¯.

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• Bulky non-nucleophilic bases favor elimination over
substitution—KOC(CH3)3, DBU, and DBN are too sterically
hindered to attack tetravalent carbon, but are able to remove
a small proton, favoring elimination over substitution.

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 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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 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 CH3

H3O+, THF
50oC

The reaction yield the more substituted alkene as the major product.
CH3 CH3 CH3
+
H3O , THF
H3C C CH2CH2CH3 H3C C CHCH2CH3 + H2C C CH2CH2CH3
OH 50oC
Major Minor
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• Follow Zaitsev’s 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
H2O

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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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