CHAPTER-4

Elimination Reaction
 Chapter contents

 Introduction
 E1 versus E2 versus E1cb
 Saytzeff and Hoffmann elimination rules
 Dehydration of alcohols (C-O bond cleavage)
 Dehydrohalogenation of alkyl halides
 Elimination of vicinal dihalides
 Ester/acetate pyrolysis
 Cope reaction of N-oxides (C-N bond cleavage,Syn-
elimination)
 Introduction

 Elimination reactions deal with the removal of two groups from a

reactant unlike to substitution reactions which involve the removal
of only one species
 Elimination reaction involves the deprotonation of hydrogen atoms
together with removal of a good leaving group
 Elimination reactions can be classified based on the structural
relationship between the proton and the leaving group
 Elimination can be three types: α-elimination, β-elimination or γ-
elimination which produce unstable divalent carbon species
(carbenes), carbon-carbon double bonds and cyclic alkane,
respectively
 The E2, E1 and E1cb Mechanisms
The ß-eliminations can be subdivided into E2, E1 and E1cb based on
the mechanisms involved

E2 mechanism (concerted): The two groups (H & X) are removed simultaneously

β-position

E1 mechanism (carbocation intermediate): The leaving group (X) is first removed and
carbocation is formed

E1cb mechanism (carboanion intermediate): The hydrogen atom is first removed

leading to carboanion (carbon nucleophile) formation
 Saytzeff versus Hoffmann rules
Saytzeff rule: The elimination reactions give the more substituted
alkene as the major product. This behavior is characteristic of E1
reactions and E2 reactions involving relatively good leaving groups,
such as halides and sulfonates. In such reactions, the C−X cleavage is
well advanced in the TS.

Hoffmann rule: If the E2 reaction involves poor leaving groups,

such as quaternary ammonium salts, it gives primarily the less-
substituted alkene. Such reactions can undergo through TSs with
E1cb character.

Saytzeff rule Hoffmann rule

 Dehydration of alcohols
• The dehydration of alcohols is an elimination reaction that takes
place under acidic than basic conditions and involves an E1
mechanism.
• The acidic reagent makes the hydroxyl group a better leaving group
via protonation
• This elimination reaction is the reverse of acid-catalyzed hydration
• Since a carbocation is the intermediate, the elimination step is
expected to favor the more-substituted alkene
• 30 > 20>10 in reactivity towards E1 mechanism
• The produced carbocation can be rearranged to the more stable
one acidic condition
+

protonated alcohol
rearrangement

R- trnsfer
 Elimination reactions other than C−H bonds

Vicinal dibromide elimination: It can be debrominated by certain

reducing agents like iodide ion

Vicinal debromination by
sodium iodide (NaI)

1,1,2-tribromocyclohexane

The above iodide-induced reduction is essentially the reverse of a halogenation

and the reaction proceeds through a bridged intermediate
Another example:

Trans
Anti-elimination Anti-elimination Cis

Ester/acetate pyrolysis (thermal decompositon)

Ester functional group is converted to alkene and carboxylic acid under high
tempreture. During this reaction, a six membered transition state is first formed
using the β-hydrogen atom.

β-hydrogen
O H R' OH
R R'
300 OC +
R H

O O
Alkene
Ester Carboxylic acid
 Cope elimination of N-oxides (C-N bond cleavage)
• The amine groups, especially their conjugate bases, are strong bases and poor
leaving groups. As a result, they cannot participate in an elimination
reaction
• On the other hand, Quaternary ammonium salts are good leaving group since
the departing nitrogen is charge-free and with a complete octet
• In this Cope eliminatiom, the amine group first reacts with hydrogen
peroxide which oxidizes it to a tertiary amine oxide. This oxide becomes a
strong base as well as a good leaving group on the form of a hydroxyl amine.
The amine oxide then undergoes elimination under heat which forms an alkene
and a N,N dialkylhydroxylamine
Mechanism O
O
N HO-OH
HO
N OH N
H Heat
N
H alkene
H H

(CH3)2N-OH
30 amine 3 amine oxide
0 Transition state
(quaternary (five membered ring)
ammonium salt) N,N-dimethylhydroxyl
amine