Organic Chemistry

Sixth Edition
Janice Gorzynski Smith
University of Hawai’i

Chapter 8
Lecture Outline
Prepared by Andrea Leonard
University of Louisiana at Lafayette

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permitted without the prior written consent of McGraw-Hill Education.
1
 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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 Elimination of HX
In both example reactions a base removes the elements of
an acid, HX, from the organic starting material.

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

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 Common Bases for
Dehydrohalogenation
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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 Drawing Products of
Dehydrohalogenation
Find the α carbon.
Identify all β carbons with H atoms.
Remove the elements of H and X from the α and β carbons
and form a π bond.

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 Alkenes
Alkenes are hydrocarbons containing a carbon-carbon
double bond.
Each carbon of the double bond is sp2 hybridized.
The alkene carbons are trigonal planar.
The bond angles are 120 degrees.

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 Alkene Structure
The double bond of an alkene consists of a σ bond and a π
bond.

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 Classifying Alkenes
Alkenes are classified according to the number of carbon
atoms bonded to the carbons of the double bond.

Figure 8.1

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 Restricted Rotation About Double
Bonds
Recall that even though there is free rotation around single
bonds, rotation about double bonds is restricted.
Figure 8.2

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 Stereoisomers of Alkenes
Because of restricted rotation, two stereoisomers of 2-
butene are possible.
cis-2-Butene and trans-2-butene are diastereomers (i.e.,
non-mirror image stereoisomers).

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 Alkene Diastereomers
Whenever the two groups on each end of a carbon-carbon
double bond are different from each other, cis-trans
isomers are possible.

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 Stability of Trans Alkenes
In general, trans alkenes are more stable than cis alkenes
because the groups bonded to the double bond carbons
are further apart, reducing steric interactions.

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 Stability in Alkenes
The stability of an alkene increases as the number of R
groups bonded to the double bond carbons increases.

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 Stability in Alkenes-1
The higher the percent s-character, the more readily an
atom accepts electron density.
Thus, sp2 carbons are more able to accept electron density
and sp3 carbons are more able to donate electron density.
Increasing the number of electron donating groups on a
carbon atom able to accept electron density makes the
alkene more stable.

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 Relative Stability of Butenes
The 2-butenes (disubstituted) are more stable than
1-butene (monosubstituted).
trans-2-Butene is more stable than cis-2-butene
(less crowding).

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 Elimination Mechanisms
There are two mechanisms of elimination—E2 and E1, just
as there are two mechanisms of substitution, SN2 and SN1.

The E2 mechanism is called bimolecular elimination.

The E1 mechanism is called unimolecular elimination.
The E2 and E1 mechanisms differ in the timing of bond
cleavage and bond formation, analogous to the SN2 and
SN1 mechanisms.

E2 and SN2 reactions have some features in common, as

do E1 and SN1 reactions.

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 E2 Mechanism
The most common mechanism for dehydrohalogenation is
the E2 mechanism.
It exhibits second-order kinetics, and both the alkyl halide
and the base appear in the rate equation.

The reaction is concerted—all bonds are broken and

formed in a single step.

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 E2 Mechanism-1

There are close parallels between E2 and SN2 mechanisms

in how the identity of the base, the leaving group, and the
solvent affect the rate.

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 Energy Diagram for an E2 Reaction

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 Bases in E2 Mechanisms
E2 reactions are generally run with strong, negatively
charged bases like −OH and −OR.
The base appears in the rate equation, so the rate of the
E2 reaction increases as the strength of the base
increases.
Two strong, sterically hindered nitrogen bases called DBN
and DBU are also sometimes used.

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 E2 Reaction with DBN

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 Effects of Leaving Group and
Solvent on E2 Reactions
Because the bond to the leaving group is partially broken in
the transition state, the better the leaving group the faster
the E2 reaction.
Polar aprotic solvents increase the rate of E2 reactions.

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 Effect of Alkyl Halide Structure on
E2 Reactions
The SN2 and E2 mechanisms differ in how the alkyl halide
structure affects the reaction rate.
As the number of R groups on the carbon with the leaving
group increases, the rate of the E2 reaction increases.

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 Transition States in E2 Mechanisms
The increase in E2 reaction rate with increasing alkyl
substitution can be rationalized in terms of transition state
stability.
In the transition state, the double bond is partially formed.
This increases the stability of the double bond with alkyl
substituents stabilizing the transition state (i.e., lowers Ea),
which increases the rate of the reaction.

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 Product Stability and Rate of E2
Reactions
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 degrees alkyl halide reacts faster than the 1 degree alkyl halide.

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 E2 Mechanism Summary

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 E2 Reaction in Organic Synthesis
Elimination reactions are often steps in the synthesis of
complex natural products, like the E2 reaction in the
formation of the anti-malarial drug quinine:

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 The Zaitsev (Saytzeff) Rule
When alkyl halides have two or more different β carbons,
more than one alkene product can be formed.
The Zaitsev rule predicts that the major product in
β elimination has the more substituted double bond.
This is the more stable alkene.

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 Regioselectivity of E2 Reactions
A reaction is regioselective when it yields predominantly or
exclusively one constitutional isomer when more than one
is possible.
Thus, the E2 reaction is regioselective.

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 Stereoselectivity of E2 Reactions
A reaction is stereoselective when it forms predominantly or
exclusively one stereoisomer when two or more are
possible.
The E2 reaction is stereoselective because the more stable
stereoisomer is formed preferentially.

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 E1 Mechanism
The dehydrohalogenation of (CH3)3CCI with H2O to form
(CH3)2C=CH2can be used to illustrate the second general
mechanism of elimination, the E1 mechanism.
An E1 reaction exhibits first-order kinetics:

The E1 reaction proceeds via a two-step mechanism: the

bond to the leaving group breaks first before the π bond is
formed.
The slow step is unimolecular, involving only the alkyl
halide.
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 E1 Mechanism-1

In an E2 reaction, the leaving group comes off as the β

proton is removed, and the reaction occurs in one step.
However, in an E1, the leaving group comes off before the
β proton is removed, and the reaction occurs in two steps.
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 Energy Diagram for an E1 Reaction

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 Effect of Alkyl Halide Structure on
E1 Reactions
The rate of an E1 reaction increases as the number of
R groups on the carbon with the leaving group increases.

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 Effect of Base on the E1 Reaction
The strength of the base usually determines
whether a reaction follows the E1 or E2 mechanism.

Strong bases like −OH and −OR favor E2 reactions.

Weaker bases like H2O and ROH favor E1

reactions.

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 Regioselectivity of E1 Reactions
Zaitsev’s rule applies to E1 reactions also.
E1 reactions are regioselective, favoring formation of the
more substituted, more stable alkene.

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 E1 Mechanism Summary

Because E1 reactions often occur with a competing SN1

reaction, E1 reactions of alkyl halides are much less useful
than E2 reactions.

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 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.

In an SN1 reaction, a nucleophile attacks the carbocation,

forming a substitution product.
In an E1 reaction, a base removes a proton, forming a new
pi bond.
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 Stereochemistry of E2 Reactions
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.

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 Two Possible Geometries for E2
Reactions
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.
Figure 8.6

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 Anti Periplanar Geometry
The requirement of anti periplanar geometry in an E2
reaction has important consequences for compounds
containing six-membered rings.
• Chlorocyclohexane exists as two chair conformations.
• Conformation X is preferred since the bulkier Cl group is in the
equatorial position.

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 Trans Diaxial Geometry for E2
Reactions-1
For E2 elimination, the C—Cl bond must be anti
periplanar to the C—H bond on a β carbon, and
this occurs only when the H and Cl atoms are both
in the axial position.
The requirement for trans diaxial geometry means
that elimination must occur from the less stable
conformer.

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 Trans Diaxial Geometry for E2
Reactions-2
Figure 8.7:
The trans diaxial geometry for the E2 elimination in
chlorocyclohexane.

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 E2 Reactions of Cis and Trans
Isomers
Consider the E2 dehydrohalogenation of cis- and trans-1-chloro-2-
methylcyclohexane.

The cis isomer exists as two conformations, A and B, each of which

has one group axial and one group equatorial.
E2 reaction must occur from conformation B, which contains an axial Cl
atom.

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 Regiochemistry of E2 Reactions on
Cyclohexanes
Because conformation B has two different axial β
hydrogens, labeled Ha and Hb, E2 reaction occurs in two
different directions to afford two alkenes.
The major product contains the more stable trisubstituted
double bond, as predicted by the Zaitsev rule.

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 Axial Leaving Groups for E2
Reactions

The trans isomer of 1-chloro-2-methylcyclohexane exists

as two conformers: C, having two equatorial substituents,
and D, having two axial substituents.
E2 reaction must occur from D, since it contains an axial Cl
atom.
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 Anti Zaitsev Products for E2
Reactions
Because conformer D has only one axial β H, the
E2 reaction occurs only in one direction to afford a
single product.
The most substituted, “Zaitsev” alkene is not the
major product in this case.

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 Comparison of E1 and E2
Mechanisms
The strength of the base is the most important factor in
determining the mechanism for elimination.

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 E2 Reactions and Alkyne Synthesis
A single elimination reaction produces a π bond of an
alkene.
Two consecutive elimination reactions produce two
π bonds of an alkyne.

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 E2 Reactions and Alkyne Synthesis-1
Two elimination reactions are needed to remove two moles
of HX from a dihalide substrate.
Two different starting materials can be used—a vicinal
dihalide or a geminal dihalide.

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 Bases for Alkyne Synthesis
Stronger bases are needed to synthesize alkynes by
dehydrohalogenation than are needed to synthesize
alkenes.

The typical base used is −NH2 (amide), used as NaNH2.

KOC(CH3)3 can also be used with DMSO as solvent.

Stronger bases are needed to break the stronger sp2

hybridized C—H bonds in the second elimination reaction.

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 Dehydrohalogenation of Dihalides

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 When is the Reaction 𝐒𝐍𝟏, 𝐒𝐍𝟐, E1,
or E2?
Good nucleophiles that are weak bases favor
substitution over elimination.
These include I−, Br−, HS−, −CN, and CH3COO−.

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

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 Predicting Reaction Mechanisms
(𝐒𝐍𝟏, 𝐒𝐍𝟐, E1, or E2)
Tertiary Alkyl Halides:

Access the text alternative for slide images.

Access the text alternative for slide images.

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 Predicting Reaction Mechanisms
(𝐒𝐍𝟏, 𝐒𝐍𝟐, E1, or E2)-1
Primary Alkyl Halides:

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 Predicting Reaction Mechanisms
(𝐒𝐍𝟏, 𝐒𝐍𝟐, E1 or E2)-3
Secondary Alkyl Halides Part 1:

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 Predicting Reaction Mechanisms
(𝐒𝐍𝟏, 𝐒𝐍𝟐, E1 or E2)-4
Secondary Alkyl Halides Part 2:

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 Predicting Reaction Mechanisms
(𝐒𝐍𝟏, 𝐒𝐍𝟐, E1 or E2)

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