Chapter 10

Elimination
Reactions of
Alkyl
Halides
Competition
Between
Substitution and
PaulaElimination
Yurkanis Bruice
University of California,
Santa Barbara
2014 Pearson Education, Inc.

Alkyl Halides Undergo

Substitution and Elimination Reactions

In an elimination reaction, a halogen is removed from one carbon

and a hydrogen is removed from an adjacent carbon.

A double bond is formed between the two carbons
from which the atoms were removed.
2014 Pearson Education, Inc.

An E2 Reaction

2014 Pearson Education, Inc.

Mechanism for an E2 Reaction

2014 Pearson Education, Inc.

The Halogen Comes off the Alpha Carbon;

the Hydrogen Comes off the Beta Carbon

dehydrohalogenation

2014 Pearson Education, Inc.

The Weakest Base Is the Best Leaving Group

2014 Pearson Education, Inc.

An E2 Reaction is Regioselective

The major product is the most stable alkene.

The most stable alkene is (generally) obtained by removing a hydrogen
from the beta carbon that is bonded to the fewest hydrogens.

2014 Pearson Education, Inc.

The More Stable Alkene

Has the More Stable Transition State

2014 Pearson Education, Inc.

Alkene-Like Transition State

2014 Pearson Education, Inc.

More E2 Reactions

2014 Pearson Education, Inc.

Relative Reactivities of Alkyl Halides in an

E2 Reaction

2014 Pearson Education, Inc.

The More Stable Alkene

is the Major Product

The conjugated alkene is the more stable alkene (an

exception to Zaitsevs rule).
2014 Pearson Education, Inc.

The More Stable Alkene

is Not the Major Product

A sterically hindered alkyl halide and a sterically hindered base

forms the less stable alkene (another exception to Zaitsevs rule).

2014 Pearson Education, Inc.

Need a Lot of Steric Hindrance

forms the more stable alkene

2014 Pearson Education, Inc.

 2014 Pearson Education, Inc.

Fluoride Ion is a Poor Leaving Group

This is another exception to Zaitsevs rule.

2014 Pearson Education, Inc.

The Transition State is

Carbanion-Like

2014 Pearson Education, Inc.

Relative Stabilities of Carbocations

2014 Pearson Education, Inc.

Relative Stabilities of Carbanions

2014 Pearson Education, Inc.

How the Leaving Group Affects

the Product Distribution

2014 Pearson Education, Inc.

An E1 Reaction

2014 Pearson Education, Inc.

The Mechanism for an E1 Reaction

2014 Pearson Education, Inc.

How Does a Weak Base (Like Water)

Remove a Proton From an sp3 Carbon?

1. The presence of the positive charge greatly reduces the pKa.

2. Hyperconjugation weakens the CH bond by draining electron
density.
2014 Pearson Education, Inc.

An E1 Reaction is Regioselective

The major product is the more stable alkene.

The most stable alkene is obtained by removing a hydrogen
from the beta carbon that is bonded to the fewest hydrogens.

2014 Pearson Education, Inc.

The More Stable Alkene is the

Major Product

2014 Pearson Education, Inc.

The Weakest Base is the Best Leaving Group

2014 Pearson Education, Inc.

Benzylic and Allylic Halides

Undergo E2 Reactions

2014 Pearson Education, Inc.

Benzylic and Allylic Halides

Undergo E1 Reactions

2014 Pearson Education, Inc.

The E1 Reaction of Allylic Halides

Can Form Two Products

2014 Pearson Education, Inc.

The Reactivity of Alkyl Halides

in Elimination Reactions

2014 Pearson Education, Inc.

The Bonds to Be Broken

Must Be in the Same Plane

2014 Pearson Education, Inc.

Anti Elimination is Preferred

1. Anti requires the molecule to be in a staggered conformation.

2. Back-side attack achieves the best overlap of interacting orbitals (see Figure 9.1).
3. It avoids repulsion of the electron-rich base with the electron-rich leaving group.
2014 Pearson Education, Inc.

Anti Elimination

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.
2014 Pearson Education, Inc.

The More Stable Product is

Easier to Form

2014 Pearson Education, Inc.

E2 and E1 Reactions are Regioselective

2014 Pearson Education, Inc.

E2 and E1 Reactions are Regioselective

2014 Pearson Education, Inc.

The Major Product of an E2 Reaction

(Largest Groups Are on Opposite Sides)

2014 Pearson Education, Inc.

When Only One Hydrogen is Bonded to the -Carbon,

the Major Product of an E2 Reaction Depends on the
Structure of the Alkene

2014 Pearson Education, Inc.

When Only One Hydrogen is Bonded to the

-Carbon, the Major Product is
Still the More Stable Alkene

2014 Pearson Education, Inc.

Summary of Stereochemistry

2014 Pearson Education, Inc.

E2 Elimination from Six-Membered Rings

Both groups being eliminated must be in axial positions.

2014 Pearson Education, Inc.

H and Cl Must Both Be Axial

2014 Pearson Education, Inc.

The Value of Keq Depends on Whether the Reaction

Takes Place Through the More Stable
Conformer or Through the Less Stable Conformer

Keq is large
2014 Pearson Education, Inc.

Keq is small

Neomenthyl Chloride is Faster

Elimination occurs through the more stable conformer.

2014 Pearson Education, Inc.

Menthyl Chloride is Slower

Elimination occurs through the less stable conformer.

2014 Pearson Education, Inc.

E1 Elimination from Six-Membered Rings

The H and Cl do not have to be in axial positions

because the reaction is not concerted.

2014 Pearson Education, Inc.

Proof That the E2 Reaction is Concerted

A carbon deuterium bond (CD) is stronger

than a carbon hydrogen bond (CH).
The deuterium kinetic isotope effect = 7.1.
Therefore, the CD bond is broken in the rate-limiting step.
2014 Pearson Education, Inc.

Alkyl Halides in SN2 and E2 Reactions

2014 Pearson Education, Inc.

Under SN2/E2 Conditions

Primary Alkyl Halide = Primarily Substitution

2014 Pearson Education, Inc.

Steric Hindrance Favors Elimination

2014 Pearson Education, Inc.

Under SN2/E2 Conditions

Secondary Alkyl Halide = Substitution and Elimination

Substitution is favored by a weak base.

Elimination is favored by a strong base.
2014 Pearson Education, Inc.

Bulky Bases are Used to Encourage Elimination

2014 Pearson Education, Inc.

Although They are Neutral Bases,

They are Strong Bases

2014 Pearson Education, Inc.

A High Temperature Favors Elimination

Why? Because elimination has a greater S.

2014 Pearson Education, Inc.

Under SN2/E2 Conditions

Tertiary Alkyl Halide = Only Elimination

2014 Pearson Education, Inc.

Under SN1/E1 Conditions Tertiary Alkyl Halides

Undergo Substitution and Elimination

2014 Pearson Education, Inc.

Tertiary (SN1/E1): Substitution is Favored

Tertiary (SN2/E2): Only Elimination

2014 Pearson Education, Inc.

Summary of the Products Obtained

From Substitution and Elimination Reactions

2014 Pearson Education, Inc.

William Ether Synthesis:

an SN2 Reaction

2014 Pearson Education, Inc.

Forming an Alkoxide Ion

2014 Pearson Education, Inc.

Synthesizing Butyl Propyl Ether

2014 Pearson Education, Inc.

Synthesizing tert-Butyl Ethyl Ether

The less hindered group should be provided by the alkyl halide.

2014 Pearson Education, Inc.

Synthesizing an Alkene

The more hindered group should be provided by the alkyl halide.

2014 Pearson Education, Inc.

Synthesizing an Alkene

If the reactant is a tertiary alkyl halide,

use SN2/E2 conditions because it gives only elimination.

2014 Pearson Education, Inc.

Synthesizing an Alkyne

2014 Pearson Education, Inc.

Converting an Alkene to an Alkyne

2014 Pearson Education, Inc.

Designing a Synthesis

2014 Pearson Education, Inc.

Designing a Synthesis

2014 Pearson Education, Inc.

Designing a Synthesis

2014 Pearson Education, Inc.

Designing a Synthesis

2014 Pearson Education, Inc.