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Chapter 8

Alkyl Halides
and
Elimination 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.

Equations [1] and [2]


elimination reactions.

illustrate

examples

of

In both reactions a base removes the elements of an


acid, HX, from the organic starting material.

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.

The most common bases used in elimination


reactions
are
negatively
charged
oxygen
compounds,
E.g.: HO and its alkyl derivatives, RO, called
alkoxides.

To draw any product of dehydrohalogenation :


(i) Find the carbon.
(ii) Identify all carbons with H atoms.
(iii) Remove the elements of H and X from the and
carbons and form a bond.

AlkenesThe Products of Elimination


Recall that the double bond of an alkene consists of a
bond and a bond.

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

Because of restricted rotation, two stereoisomers of


2-butene are possible.
cis-2-butene and trans-2-butene are diastereomers
they are stereoisomers that are not mirror images of
each other.

When the two groups on each end of a carboncarbon double bond are different from each other,
two diastereomers are possible.

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In general, trans alkenes are more stable than cis


alkenes
The groups bonded to the double bond carbons in
trans alkenes are further apart, reducing steric
interactions.

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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.
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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trans-2-butene is more stable than cis-2-butene


(disubstituted alkenes), but both are more stable
than 1-butene (a monosubstituted alkene).

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Mechanisms of Elimination
There are two mechanisms of eliminationE2 and
E1.
E2 mechanismbimolecular elimination
E1 mechanismunimolecular 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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Mechanisms of EliminationE2
The
most
common
mechanism
dehydrohalogenation is the E2 mechanism.

for

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 concertedall bonds are broken and


formed in a single step.

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Figure 8.3: An energy diagram for an E2 reaction:

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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 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.

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Figure 8.4: An E2 elimination with DBN used as the base

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The SN2 and E2 mechanisms differ in how the R group


affects the reaction rate.

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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.

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Increasing the number of R groups on the carbon with


the leaving group forms more highly substituted, more
stable alkenes in E2 reactions.
Hence, 3 alkyl halides reacts faster than the 1 alkyl
halide.

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Table 8.2 summarizes the characteristics of the E2 mechanism.

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The Zaitsev (Saytzeff) Rule


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 productthe one
with the more substituted double bond.
This phenomenon is called the Zaitsev rule.

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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.

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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.

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Mechanisms of EliminationE1
An E1 reaction exhibits first-order kinetics:
rate = k[RX]
The E1 reaction
mechanism:

proceeds

via

two-step

(i) the bond to the leaving group breaks


(ii) bond is formed.
The slow step is unimolecular, involving only the
alkyl halide.
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Figure 8.6: Energy diagram for an E1 reaction.


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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.
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E1 reactions are regioselective, favoring formation


of the more substituted, more stable alkene.
Zaitsevs rule applies to E1 reactions also.

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Table 8.3 summarizes the characteristics of the E1 mechanism.

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SN1 vs E1 Reactions
SN1 and E1 reactions have exactly the same first step
formation of a carbocation. They differ in what happens
to the carbocation.

E1 reactions often occur with a competing SN1 reaction,


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

Stereochemistry of the E2 Reaction


The transition state of an E2 reaction consists of four atoms
from an alkyl halideall aligned in a plane. There are two ways
for the CH and CX 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
Allows the incoming base and leaving group to be further away
from each other.
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Figure 8.7: Two possible geometries for the E2 reaction.

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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


CH 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
elimination must occur from the less stable conformer, B.

that
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Figure 8.8: The trans diaxial geometry for the E2 elimination in chlorocyclohexane
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E2 dehydrohalogenation
methylcyclohexane.

of

cis-

and

trans-1-chloro-2-

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.

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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.

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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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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.

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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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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.

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Two elimination reactions are needed to remove two


moles of HX from a dihalide substrate.
Two different starting materials can be useda
vicinal dihalide or a geminal dihalide.

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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.

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Reason : The transition state for the second elimination


reaction includes partial cleavage of the CH
bond.
However, the carbon atom is sp2 hybridized
sp2 hybridized CH bonds are stronger than sp3
hybridized CH bonds.
A stronger base is needed to cleave this bond.

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Figure 8.9: Example of dehydrohalogenation of dihalides to afford alkynes.

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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 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.

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Figure 8.10: Determining whether an alkyl halide reacts by an SN1, SN2, E1, or E2 mechanism.
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Figure 8.10-8.10 continued

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Figure 8.10-8.10 continued

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1. What is the IUPAC name for the structure below?

2. What is the starting material in the reaction below?

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3. What is the product?

4. What is the product?

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Provide the structure of the major organic product in the


following reaction.

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Q: When 1-iodo-1-methylcyclohexane is treated with

NaOCH2CH3, the more highly substituted alkene


product predominates. When KOC(CH3)3 is used
instead, the less highly substituted alkene product
predominates. Offer an explanation.

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