Lecture 12

ELIMINATION REACTIONS

1
 ELIMINATION REACTIONS
An elimination reaction is one where starting
material loses the elements of a small
molecule such as HCl or H2O or Cl2 during
the course of the reaction to form the
product.

- HCl
C C C C
H Cl
TWO EXAMPLES FOLLOW
2
 ELIMINATION REACTIONS
TWO EXAMPLES
Alkyl halide + strong base & heat LOSS OF HCl
NaOH
CH3CH2CH2CH2 Cl CH3CH2 CH CH2
∆
NaOH
CH3CH2 CH CH3 CH3 CH CH CH3
∆
Cl

Alcohol + strong acid and heat LOSS OF H2O

H2SO4
CH3CH2CH2CH2 OH CH3CH2 CH CH2
∆ 3
 ELIMINATION REACTIONS

H H H H
| | | |
X – C α- Cβ – Y → C=C + X–Y
| | | |
H H H H
In this reaction, alkene formation requires
that X and Y be substituents on adjacent carbon
atoms.
4
 ELIMINATION REACTIONS

By assigning X as the reference atom and

identifying the carbon attached to it as α
carbon, the atom Y is a substituent on the β
carbon.
Carbon succeedingly more remote from
the reference atom are designated as γ , δ and
so on.
Our discussion will confine to β elimination
reactions (also called as 1,2 eliminations).
5
 THE REACTION IS A β-ELIMINATION

The β-hydrogen
is attached to the H
β-carbon. α-carbon
C C
β-carbon Cl The functional
group is attached
to the α-carbon.

Since the β-hydrogen is lost this reaction is

called a β-elimination.
Reagent = a strong base6
 MECHANISM
THE BASE TAKES THE β-HYDROGEN

B:
B H
H
C C C C
: Cl
.. :
..
: Cl
.. :

7
Alkenes—The Products of Elimination
Whenever the two groups on each end of a
carbon-carbon double bond are different
from each other, two diastereomers are
possible.

8
 Alkenes—The Products of Elimination
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.

9
Alkenes—The Products of Elimination

The stability of an alkene increases as the

number of R groups bonded to the double
bond carbons increases.

10
Alkenes—The Products of Elimination
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 a carbon atom
able to accept electron density makes the
alkene more stable.

11
 Mechanisms of Elimination

• There are two mechanisms of elimination E2

and E1
• E2 mechanism — bimolecular elimination
• E1 mechanism— unimolecular elimination
• The E2 and E1 mechanisms differ in the
timing of bond cleavage and bond formation

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 Mechanisms of Elimination—E2

E2 reactions are generally run with

strong, negatively charged bases like¯OH
and ¯OR.
The reaction 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.
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 Mechanisms of Elimination—E2

The base removes a proton from

the β carbon
The electron pair in the β C-H bond
forms the new π bond.
The leaving group comes off with
the electron pair in the C-X bond
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 The E2 Mechanism

.. –
R O
..
:
H

C C

: X:
..

Reactants
 The E2 Mechanism

.. –
R O
..
:
H

C C

: X:
..

Reactants
 The E2 Mechanism

δ..–
R O H
..
Transition state
C C

δ–
: X:
..
 The E2 Mechanism

..
R O H
..

C C

.. –
: X:
..

Products
Energy diagram for E2 reaction

19
 Mechanisms of Elimination—E2
Because the bond to the leaving group is
partially broken in the transition state, the
better the leaving group the faster the E2
reaction

20
 Mechanisms of Elimination—E2
The SN2 and E2 mechanisms differ in how the
R group 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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 Mechanisms of Elimination—E2

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.

22
 Mechanisms of Elimination—E2

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 on the next slide, since
the disubstituted alkene is more stable, the 30
alkyl halide reacts faster than the 10 alkyl
halide.

23
Mechanisms of Elimination—E2

24
Mechanisms of Elimination—E2

25
 REGIOSELECTIVITY

A reaction is regioselective when it yields

mostly one constitutional isomer when more
than one product is possible.

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WHAT HAPPENS IF THERE IS MORE
THAN ONE β-HYDROGEN ?

β β’
H H
C C C
Cl

Which one do we lose 27?

 Zaitsev’s (Saytzeff) rule
If more than one elimination
product is possible, the most-
substituted alkene is the major
product (most stable).

R2C=CR2 > R2C=CHR > RHC=CHR > H2C=CHR

tetra > tri > di > mono

28
Major (90%) Minor (10%)

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 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.

30
Stereochemistry of the E2 Reaction

ORBITAL ALIGNMENT

IN MOST CONCERTED REACTIONS THE

ORBITALS BECOME PREALIGNED FOR
A SMOOTH PROGRESSION OF EVENTS

A coplanar arrangement allows a

continuous movement of electrons from one
end of the system to the other.

31
 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.

32
Stereochemistry of the E2 Reaction

C C
syn elimination
H Cl not common
HCl
H H
anti elimination
C C
observed
Cl most often
Cl
anti-coplanar 33
Syn Elimination

34
Anti Elimination

35
 STEREOCHEMISTRY

ACYCLIC HALIDES

36
ACYCLIC MOLECULES MAY HAVE TO ROTATE
IN ORDER TO REACT

Cl H Cl

anti-coplanar

37
 2-Bromo-3-phenylbutane

two stereocenters RS SS enantiomers

SR RR
diastereomers
* *CH
CH CH 3
NaOEt
EtOH
CH3 Br

C CH CH 3 +
*CH CH CH 2
CH 3 CH 3

Major Product Minor Product

Zaitsev
38
Z or E ?
 2S,3R-DIASTEREOMER
R S
CH 3 CH 3 CH 3
CH 3
C C H C C
Ph
Ph H
H Br

rotate not observed

H Ph CH3
CH3 NaOMe
Ph C C H C C
CH3 MeOH CH 3 H
Br
observed
anti-coplanar major product
(Z)-2-phenyl-2-butene
(plus some 1-butene due to β-H on the CH3)39
MAKING THE 2S,3S-DIASTEREOMER
R S S S
CH 3 CH 3 Ph CH3
Ph C C H R S CH3 C C H
H Br H Br
make
H
diastereomer
Ph C C H
CH 3 ( change one ? Z or E
CH 3 Br stereocenter )

Ph CH 3
C C Will the 2S,3S-diastereomer
CH 3 H give the same product as
(Z) its 2S,3R diastereomer? 40
 2S,3S-DIASTEREOMER
S S
Ph Ph CH3
CH3
C C H C C
CH3
CH3 H
H Br

rotate not observed

H CH3 CH3
CH 3 NaOMe
CH3 C C H C C
Ph MeOH Ph H
Br
observed
anti-coplanar major product
(E) -2-phenyl-2-butene
(plus some 1-butene) 41
CONVERTING THE ALKYL HALIDE TO AN ALKENE
VISUALIZING THE PRODUCT THAT FORMS
H (top)
H
CH3 CH3
Ph CH3 CH3
H
Ph H
Cl
alkyl halide alkene Cl (bottom)

The methyl groups (blue) are in back in both

structures. The phenyl and the hydrogen (black)
are in front in both. 42
ANOTHER VISUALIZATION OF THE REACTION

2S,3R CH3 H
H back
C
CH3 H carbon
C
Ph CH3 front Ph CH3
Cl carbon
same same
side side
2S,3S
H CH3 H
CH3 H C
CH3 Ph C
Cl CH3 Ph
same
side same 43
side
 CYCLIC HALIDES

The stereochemical requirement of an anti

periplanar geometry in an E2 reaction has
important consequences for compounds
containing six-membered rings.

44
Stereochemistry of the E2 Reaction
Chlorocyclohexane exists as two chair
conformers.
Conformer A is preferred since the bulkier Cl
group is in the equatorial position.

45
Stereochemistry of the E2 Reaction

For E2 elimination, the C-Cl bond must be

anti periplanar to the C—H bond on a β
carbon
This occurs only when the H and Cl
atoms are both in the axial position.
The requirement for axial geometry
means that elimination must occur from the
less stable conformer.

46
Stereochemistry of the E2 Reaction

47
Stereochemistry of the E2 Reaction

48
 Stereochemistry of the E2 Reaction
1-Bromo-2-methylcyclohexane
The expected result (naïve) :
CH 3 CH 3 CH 3
+
Br

drawn flat without major product minor

stereochemistry Zaitsev

The result actually depends on the

stereochemistry of the starting material. 49
 cis stereoisomer
The elimination needs to have H and Br anti-
coplanar
H CH3
H
CH3
H
Br major product (Zaitsev)
cis + CH3

The other chair

won’t work. Why? Minor 50
 trans stereoisomer

CH3
H CH3

H
H
H
Br
only product
trans CH3

The other chair not formed

won’t work. Why?
51
Reaction does not occur easily if
anti-coplanar geometry cannot be achieved

Br is not axial,
trans (e,e) H no anti-coplanar H
CH 3 NaOEt
Br no reaction
CH 3 C Et OH

CH 3 H3C
Br CH3
NaOEt C
CH 3
H EtOH
CH3
CH 3 C C
H
CH 3 H

THESE RINGS WILL NOT INVERT

cis (e,a) 52
Both green hydrogens
are anti to chlorine.
Elimination by path (a) and (b)
give different products 53
54
 syn Elimination

More difficult than anti-coplanar elimination,

but do occur in some circumstances.

Br Na+OCH3
H + CH3OH
H
H
D D + NaBr

55
DO NOT DRAW THE ALKENES IN
CHAIR CONFORMATION

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