ALKYL HALIDE, E1 and E2

Organic Chemistry, Second Edition
Janice Gorzynski Smith

University of Hawai’i
Chapter 8
Alkyl Halides, E1 & E2
Prepared by Rabi Ann Musah
State University of New York at Albany
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
1
Alkyl Halides and Elimination Reactions
Chapter 8 Topics:
• Elimination reactions.
• Dehydrohalogenation with base.
• Stability of alkenes.
• Elimination mechanisms, E1 and E2.
• Zaitsev’s rule.
• Summary E2 and E1 mechanisms.
• Stereochemistry of E2.
• Summary of factors for E2 & E1.
• Summary SN1, SN2, E1 and E2.
• Alkyne synthesis. 2
General Features of Elimination:
• Elimination reactions involve the loss of elements from the starting
material to form a new  bond in the product.
• Alkyl halide + base 
3
• 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.
4
• 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.
5
• The most common bases used in elimination reactions are
negatively charged oxygen compounds, such as HO¯ and its
alkyl derivatives, RO¯, called alkoxides.
6
• 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.
7
Alkene: The Products of Elimination
• Recall that the double bond of an alkene consists of a  bond
and a  bond.
8
Classification of Alkenes:
• Alkenes are classified according to the number of carbon atoms
bonded to the carbons of the double bond.
Figure 8.1 Classifying alkenes by the number

of R groups bonded to the double bond
9
• Recall that rotation about double bonds is restricted.
Figure 8.2 Rotation

around C-C and C=C
compared
10
• Because of restricted rotation, two stereoisomers of 2-butene are
possible. cis-2-Butene and trans-2-butene are diastereomers, because
they are stereoisomers that are not mirror images of each other.
11
• Whenever the two groups on each end of a carbon-carbon
double bond are different from each other, two diastereomers
are possible.
• Conversely, when one carbon of a double bond has two
identical groups attached, cis-trans isomers are not possible.
12
• 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.
13
• The stability of an alkene increases as the number of R groups bonded
to the double bond carbons increases.
• 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.
• Consequently, increasing the number of electron donating groups on an
sp2 carbon atom makes the alkene more stable.
14
• trans-2-Butene (a disubstituted alkene) is more stable than cis-2-
butene (another disubstituted alkene), but both are more stable than
1-butene (a monosubstituted alkene).
15
Stability of Alkenes
Heats of Hydrogenation
Structural H°
Name Formula [kJ (kcal)/m ol]
Ethylene CH2 =CH2 -137 (-32.8)
Propene CH3 CH=CH2 -126 (-30.1)
1-Butene -127 (-30.3)
cis-2-Butene -120 (-28.6)
trans-2-Butene -115 (-27.6)
2-Methyl-2-butene -113 (-26.9)
2,3-Dimethyl-2-butene -111 (-26.6)

16
Mechanisms of Elimination:
• There are two mechanisms of elimination—E2 and E1, just as there
are two mechanisms of substitution, SN2 and SN1.
• E2 mechanism—bimolecular elimination
• E1 mechanism—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.
17
Mechanisms of Elimination: E2
• 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, i.e.,
rate = k[(CH3)3CBr][¯OH]
• The reaction is concerted—all bonds are broken and formed in a

single step.
18
19
Figure 8.3 An energy diagram for an E2 reaction:
20
• 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.
• The base appears in the rate equation, so the rate of the E2 reaction
increases as the strength of the base increases.
• E2 reactions are generally run with strong, negatively charged bases
like ¯OH and ¯OR. Two strong sterically hindered nitrogen bases
called DBN and DBU are also sometimes used.
1,8-diazabicyclo[5,4,0]undec-7-ene
1,5-diazabicyclo[4,3,0]non-5-ene
21
22
• The SN2 and E2 mechanisms differ in how the R group affects the
reaction rate.
23
• 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. Thus,
increasing the stability of the double bond with alkyl substituents
stabilizes the transition state (i.e., lowers Ea, which increases the rate of
the reaction.
24
• 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.
25
Table 8.2 summarizes the characteristics of the E2 mechanism.
26
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.
27
The Zaitsev (Saytzeff) Rule:
• The Zaitsev rule: the major product in  elimination has the more
substituted double bond.
• 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.
28
Stereoisomer products:
• When a mixture of stereoisomers is possible from a dehydrohalogenation,
the major product is the more stable stereoisomer.
• A reaction is stereoselective when it forms predominantly or exclusively
one stereoisomer when two or more are possible.
• The E2 reaction is stereoselective because one stereoisomer is formed
preferentially.
29
• The dehydrohalogenation of (CH3)3CCI with H2O to form (CH3)2C=CH2 can
be used to illustrate the second general mechanism of elimination, the E1
mechanism.
• An E1 reaction exhibits first-order kinetics:
rate = k[(CH3)3CCI]
• The E1 reaction proceeds via a two-step mechanism: the bond to the
leaving group breaks first before the  bond is formed. The slow step is
unimolecular, involving only the alkyl halide.
• The E1 and E2 mechanisms both involve the same number of bonds broken
and formed. The only difference is timing. In an E1, the leaving group
comes off before the  proton is removed, and the reaction occurs in two
steps. In an E2 reaction, the leaving group comes off as the  proton is
removed, and the reaction occurs in one step.
30
31
Figure 8.6 Energy
Diagram for an E1
reaction:
32
• The rate of an E1 reaction increases as the number of R
groups on the carbon with the leaving group increases.
• 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, whereas weaker bases like H2O and
ROH favor E1 reactions. 33
• E1 reactions are regioselective, favoring formation of
the more substituted, more stable alkene.
• So, Zaitsev’s rule applies to E1 as well as E2 reactions.
34
Table 8.3 summarizes the characteristics of the E1 mechanism.
35
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.
• Because E1 reactions often occur with a competing SN1 reaction, E1

reactions of alkyl halides are much less useful than E2 reactions. 36
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
37
and leaving group to be further away from each other.
Figure 8.7 Two possible geometries for the E2 reaction
38
• The stereochemical requirement of an anti periplanar geometry
in an E2 reaction has important consequences for compounds
containing six-membered rings.
• Consider chlorocyclohexane which exists as two chair
conformations. Conformation A is preferred since the bulkier
Cl group is in the equatorial position.
• For E2 elimination, the C-Cl bond must be anti periplanar to the

C—H bond on a  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 39
the less stable conformer, B.
Figure 8.8 The trans diaxial geometry for the E2 elimination in chlorocyclohexane
40
• Now consider the E2 dehydrohalogenation of cis- and trans-1-
chloro-2-methylcyclohexane.
• This cis isomer exists as two conformations, A and B, each of

which as one group axial and one group equatorial. E2 reaction
must occur from conformation B, which contains an axial Cl
atom.
41
• Because conformation B has two different axial 
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.
42
• 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.
43
• Because conformer D has only one axial  H, the E2
reaction occurs only in one direction to afford a single
product. This is not predicted by the Zaitsev rule.
44
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.
45
Factors in predicting E1 vs E2 mechanisms:
Base:
E1 Base strength not important
E2 Needs a strong base
Substrate:
E1 3o > 2o (1o C+ is unstable)
E2 3o > 2 o > 1 o
Solvent:
E1 Enhanced by polar protic solvent
E2 Solvent may vary, aprotic preferred
Leaving Group:
E1 Good LG important to form C+
E2 Good LG enhances reaction
46
Alkyl Halides and Nucleophilic Substitution
Results of E1 vs E2 mechanisms:
Kinetics:
E1 rate = k[RX]
E2 rate = k[RX][B:]
Alkene Orientation:
E1 Zaitzev
E2 Zaitzev
Stereochemistry:
E1 No requirement for C+
E2 Anti, coplanar arrangement is best
Rearrangements:
E1 rearrangements common
E2 rearrangements not possible
47
Predicting the Mechanism for 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¯.
48
• Bulky nonnucleophilic 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.
49
Figure 8.10 Determining whether an alkyl halide reacts

by an SN1, SN2, E1, or E2 mechanism
50
Figure 8.10 continued
51
Figure 8.10 continued
52
Alkyl Halides and Nucleophilic Substitution
Summary for predicting SN1, SN2, E1 & E2:
Halide Conditions Mechanism
1o strong nucleophile SN2

strong bulky base E2
2o strong base & nucleophile SN2 & E2

strong bulky base E2
weak base and nucleophile SN1 & E1
3o weak base and nucleophile SN1 & E1

strong base E2
Higher temp. favors elimination over substitution.

53
E2 Reactions and Alkyne Synthesis:
• A single elimination reaction produces a  bond of an
alkene. Two consecutive elimination reactions produce
two  bonds of an alkyne.
54
SUMMARY
55
• 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.
56
• Stronger bases are needed to synthesize alkynes by
dehydrohalogenation than are needed to synthesize
alkenes.
• The typical base used is ¯NH2 (amide), used as the
sodium salt of NaNH2. KOC(CH3)3 can also be used
with DMSO as solvent.
57
• The reason that stronger bases are needed for this
dehydrohalogenation is that the transition state for the
second elimination reaction includes partial cleavage
of the C—H bond. In this case however, the carbon
atom is sp2 hybridized and sp2 hybridized C—H bonds
are stronger than sp3 hybridized C—H bonds. As a
result, a stronger base is needed to cleave this bond.
58

Figure 8.9 Example of dehydrohalogenation of dihalides to afford alkynes
59
Organic Chemistry, Second Edition
Janice Gorzynski Smith

University of Hawai’i
End Chapter 8
Prepared by Rabi Ann Musah

State University of New York at Albany
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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Organic Chemistry, Second Edition

Janice Gorzynski Smith

Figure 8.1 Classifying alkenes by the number

Figure 8.2 Rotation

cis-2-Butene -120 (-28.6)

trans-2-Butene -115 (-27.6)

2-Methyl-2-butene -113 (-26.9)

2,3-Dimethyl-2-butene -111 (-26.6)

• The reaction is concerted—all bonds are broken and formed in a

• The strength of the base usually determines whether a reaction

• Because E1 reactions often occur with a competing SN1 reaction, E1

• E2 elimination occurs most often in the anti periplanar geometry.

• For E2 elimination, the C-Cl bond must be anti periplanar to the

• This cis isomer exists as two conformations, A and B, each of

• E2 reaction must occur from D, since it contains an axial

• Good nucleophiles that are weak bases favor

• Bulky nonnucleophilic bases favor elimination over

Figure 8.10 Determining whether an alkyl halide reacts

Halide Conditions Mechanism

1o strong nucleophile SN2

2o strong base & nucleophile SN2 & E2

3o weak base and nucleophile SN1 & E1

Higher temp. favors elimination over substitution.

E2 Reactions and Alkyne Synthesis:

Janice Gorzynski Smith

Prepared by Rabi Ann Musah

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