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MEKANISME KIMIA ORGANIK

Elimination Reactions
Elimination reactions involve the loss of elements from
the starting material to form a new bond in the product.
General Features of Elimination
2
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.
General Features of Elimination
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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.
General Features of Elimination
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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.
General Features of Elimination
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To draw any product of dehydrohalogenationFind the
carbon. Identify all carbons with H atoms. Remove
the elements of H and X from the and carbons and
form a bond.
General Features of Elimination
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Alkenes are classified according to the number of
carbon atoms bonded to the carbons of the double bond.
AlkenesThe Products of Elimination
Classifying alkenes by the
number of R groups bonded
to the double bond
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Whenever the two groups on each end of a carbon-
carbon double bond are different from each other, two
diastereomers are possible.
AlkenesThe Products of Elimination
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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.
AlkenesThe Products of Elimination
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The stability of an alkene increases as the number of R
groups bonded to the double bond carbons increases.
AlkenesThe Products of Elimination
The higher the percent s-character, the more readily an atom
accepts electron density. Thus, sp
2
carbons are more able to
accept electron density and sp
3
carbons are more able to
donate electron density.
Consequently, 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 (a disubstituted alkene) is more stable
than cis-2-butene (another disubstituted alkene), but
both are more stable than 1-butene (a monosubstituted
alkene).
AlkenesThe Products of Elimination
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There are two mechanisms of eliminationE2 and E1,
just as there are two mechanisms of substitution, S
N
2
and S
N
1.
E2 mechanismbimolecular elimination
E1 mechanismunimolecular elimination
The E2 and E1 mechanisms differ in the timing of bond
cleavage and bond formation, analogous to the S
N
2 and
S
N
1 mechanisms.
E2 and S
N
2 reactions have some features in common, as
do E1 and S
N
1 reactions.
Mechanisms of Elimination
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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.,
Mechanisms of EliminationE2
rate = k[(CH
3
)
3
CBr][OH]
The reaction is concertedall bonds are broken and
formed in a single step.
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Mechanisms of EliminationE2
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Mechanisms of EliminationE2
An energy diagram
for an E2 reaction:
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There are close parallels between E2 and S
N
2 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 likeOH and OR. Two strong sterically hindered
nitrogen bases called DBN and DBU are also sometimes
used.
Mechanisms of EliminationE2
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Mechanisms of EliminationE2
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The S
N
2 and E2 mechanisms differ in how the R group
affects the reaction rate.
Mechanisms of EliminationE2
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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 E
a
,
which increases the rate of the reaction.
Mechanisms of EliminationE2
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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.
In the reactions below, since the disubstituted alkene is more
stable, the 3 alkyl halide reacts faster than the 1
0
alkyl halide.
Mechanisms of EliminationE2
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Table 8.2 summarizes the characteristics of the E2 mechanism.
Mechanisms of EliminationE2
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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 productthe one with
the more substituted double bond.
This phenomenon is called the Zaitsev rule.
The Zaitsev (Saytzeff) 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.
The Zaitsev (Saytzeff) Rule
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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.
The Zaitsev (Saytzeff) Rule
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The dehydrohalogenation of (CH
3
)
3
CCI with H
2
O to form
(CH
3
)
2
C=CH
2
can be used to illustrate the second general
mechanism of elimination, the E1 mechanism.
An E1 reaction exhibits first-order kinetics:
Mechanisms of EliminationE1
rate = k[(CH
3
)
3
CCI]
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.
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Mechanisms of EliminationE1
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.
Mechanisms of EliminationE1
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 H
2
O 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.
Mechanisms of EliminationE1
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Table 8.3 summarizes the characteristics of the E1 mechanism.
Mechanisms of EliminationE1
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S
N
1 and E1 reactions have exactly the same first stepformation
of a carbocation. They differ in what happens to the carbocation.
S
N
1 and E1 Reactions
Because E1 reactions often occur with a competing S
N
1 reaction,
E1 reactions of alkyl halides are much less useful than E2
reactions.
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The transition state of an E2 reaction consists of four atoms
from an alkyl halideone hydrogen atom, two carbon atoms,
and the leaving group (X)all aligned in a plane. There are two
ways for the CH and CX bonds to be coplanar.
Stereochemistry of the E2 Reaction
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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Stereochemistry of the E2 Reaction
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.
Stereochemistry of the E2 Reaction
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 that elimination must occur from the
less stable conformer, B.
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Stereochemistry of the E2 Reaction
The trans diaxial geometry
for the E2 elimination in
chlorocyclohexane
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Now consider the E2 dehydrohalogenation of cis- and trans-1-
chloro-2-methylcyclohexane.
Stereochemistry of the E2 Reaction
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 H
a
and H
b
, 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.
Stereochemistry of the E2 Reaction
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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.
Stereochemistry of the E2 Reaction
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.
Stereochemistry of the E2 Reaction
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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.
When is the Mechanism E1 or E2?
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Zaitsev's rule
Alexander Mikhaylovich Zaytsev