Lecture 13

ELIMINATION REACTIONS

1
 E1

ALKYL HALIDES + WEAK BASE

(SOLVOLYSIS)

The removal of a β -hydrogen becomes difficult

without a strong base and a different mechanism
(ionization) begins to take place

….. if the substrate is capable. 2

 Mechanisms of Elimination—E1

An E1 reaction exhibits first-order kinetics:

rate = k[(CH3)3CI]
The E1 reaction proceed 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.
3
The E1 Elimination Reaction (two steps)
B:
H H
slow
C C C C + :X
Weak base +
X carbocation

fast

unimolecular
rate = k [RX] C C

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5
 Mechanisms of Elimination—E1

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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REGIOSELECTIVITY

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 Mechanisms of Elimination—E1
• E1 reactions are regioselective, favoring
formation of the more substituted, more stable
alkene.
• Zaitsev’s rule applies to E1 reactions also.

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 THE E1cB MECHANISM

Elimination, unimolecular, of the

conjugate base.
Carbanion mechanism

B: proton halogen
H second
first
C C C C C C
X X

carbanion
Regioselective and stereselective reaction

A regioselective reaction forms more of one

constitutional isomer than the other.
A B + C more ‘B’ is formed than ‘C’, where
B and C are constitutional isomers.
A stereoselective reaction forms more of one
stereoisomer than the other.
A B+ C more ‘B’ is formed than ‘C’, where B
and C are stereoisomers.
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 Stereospecific reaction
In a stereospecific reaction, each
stereoisomeric reactant forms a different
stereoisomeric product or a different set of
stereoisomeric products.
A B
C D
‘A’ AND ‘C’ ARE STEREOISOMERS
‘B’ AND ‘D’ ARE STEREOISOMERS
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Alkene synthesis by elimination
reactions

12
Acid Catalyzed Dehydration of Alcohols

Typical acids used in dehydration are

sulfuric acid and phosphoric acid
Primary alcohols are most difficult to
dehydrate, tertiary are the easiest.
Rearrangements of the carbon skeleton
can occur
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Acid Catalyzed Dehydration of Alcohols
The temperature and concentration of
acid required to dehydrate depends on the
structure of the alcohol

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Mechanism for Dehydration of Secondary and
Tertiary Alcohols: An E1 Reaction
Only a catalytic amount of acid is required
since it is regenerated in the final step of the
reaction
The second step of the E1 mechanism in
which the carbocation forms is rate
determining
Tertiary alcohols react the fastest because
they have the most stable tertiary
carbocation - like transition state in the
second step
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E1 Mechanism

16
Carbocation Stability and the
Transition State
Recall the stability of carbocations
is:

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 The relative heights of ΔG‡ for the second step
of E1 dehydration indicate that primary alcohols
have a prohibitively large energy barrier

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A Mechanism for Dehydration of Primary
Alcohols: An E2 Reaction

Primary alcohols cannot undergo E1

dehydration because of the instability of
the carbocation-like transition state in the
2nd step.

In the E2 dehydration the first step is

again protonation of the hydroxyl to yield
the good leaving group water

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20
 E2: Vicinal Dibromides
• Remove Br2 from adjacent carbons.
• Bromines must be anti-coplanar (E2).
• Use NaI in acetone, or Zn in acetic acid.

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E2: Vicinal Dibromides

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Dehydrohalogenation of alkyl halides

Removing HX via E1

• Secondary or tertiary halides

• Formation of carbocation intermediate
• May get rearrangement
• Weak nucleophile
• Usually have substitution products too.

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24
 Removing HX via E2
• Strong base abstracts H+ as X- leaves from
the adjacent carbon.
• Tertiary and hindered secondary alkyl halides
give good yields.
• Use a bulky base if the alkyl halide usually
forms substitution products.

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 Removing HX via E2
Bromocyclohexane, a secondary alkyl
halide, can undergo both substitution and
elimination
E2 is favored over substitution using bulky
base diisopropylamine
H H
Br (iPr)2NH, heat
+ [(CH3)2CH]2NH2Br
H
H H

bromocyclohexane Cyclohexene
(93%) 26
 Formation of Hofmann Product
• Bulky bases abstract the least hindered H+
• Least substituted alkene is major product.

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 Hofmann Elimination
• A quaternary ammonium salt has a good
leaving group - a neutral amine.
• Heating the hydroxide salt produces the
least substituted alkene.

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29
Hofmann Elimination

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E2 Mechanism

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E2 Mechanism

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 Cope Elimination
Amine oxides undergo elimination to form
the least substituted alkene under milder
conditions than the Hofmann reaction.

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DIFFERENCES BETWEEN
E1 AND E2

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 Structure of substrate
R H H
R-C-X R-C-X R-C-X
primary secondary tertiary
R R H
E1 formation of carbocation intermediate
rate :tertiary > secondary > primary > methyl

But this same order holds for E2 also.

H
H H
tertiary has more H C
more opportunites
β -hydrogens H
H
C C Br
for reaction
C
EtO- H H 35
H
 ALKYL HALIDE + BASE

strong base weak base

or
solvolysis
E2 mechanism E1 mechanism
anti-coplanar must be able to make
requirement “good” carbocation
stereospecific not stereospecific
regioselective regioselective 36
 E1 or E2?
• Tertiary > Secondary • Tertiary > Secondary
• Weak base • Strong base required
• Good ionizing solvent • Solvent polarity not
important
• Rate = k[halide] • Rate = k[halide][base]
• Zaitsev product • Zaitsev product
• No required geometry • Coplanar leaving groups
(usually anti)
• Rearranged products • No rearrangements

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 Elimination vs. Substitution
SN2 and E2

favored over SN1 and E1 by a strong

base/Nu
SN2 is slowed by steric hindrance, but
E2 is not
Stronger bases favor E2 over SN2
higher temperatures favor elimination

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 Elimination vs. Substitution

S N2 E2
weaker bases stronger bases

less steric more steric

hindrance hindrance

lower temperature higher temperature

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 Elimination vs. Substitution
Benzylic halides undergo substitution
reactions without competition from elimination.
10 benzyl halides react via SN2 pathway.

CH2Cl CH2OCH3
-
SN2 condition
+ CH3O + Cl-

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20 and 30 benzyl halides react via SN1
pathway, without benzylic rearrangement

CH2Cl CH2+
SN1 condition
+ Cl-

CH3OH

CH2OCH3
+ H+

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Rearranged products are possible from Allyl
halides

H2O
Cl Na2CO3 HO

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Vinyl halides and aryl halides do not undergo
SN2 reaction because the nucleophile
approaches the backside of sp2 carbon and is
repelled by the π electron cloud of the double
bond or the aromatic ring

Br

X + Br-

R CH CHCl X R C CHCl + Cl-43

Aryl and vinyl halides do not undergo SN1
reactions, two reasons:
1. Vinylic and aryl carbocations are very
unstable due to positive charge on sp carbon
atom.
2. sp2 carbon atom makes stronger bond
than sp3.
H H
C + 372 kJ
H
C C H
H H

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+ 464 kJ
 An exceptionally stable cation triphenylmethyl cation
used to form ether with a primary alcohol by an SN1
reaction.
Ph Ph
slow Ph fast
Ph Cl -
Ph Ph O R
-Cl Ph
Ph Ph H
HO R
Py fast

Ph
Ph O R

Ph
PhH2C-X Ph2HC-X Ph3C-X
kSN1 1 1000108 45
Apocamphyl chloride is inert to hydroxide ion
Steric hindrance from backside of the
C-Cl prohibits SN2 reaction.
Carbenium ion produced by SN1 is not
planar, therefore is unstable.
Larger bicyclic system undergo slow SN1
at bridged head position.

Cl
SbF6

Apocamphyl chloride 1-bicyclo

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[3.2.2]nonyl cation
 Substitution or Elimination?
• Strength of the nucleophile determines order:
Strong nucleophile, bimolecular, SN2 or E2.
• Primary halide usually SN2.
• Tertiary halide mixture of SN1, E1 or E2
• High temperature favors elimination.
• Bulky bases favor elimination.
• Good nucleophiles, but weak bases, favor
substitution.

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