CHAPTER-5

Addition Reactions
 Chapter Content

 Introduction
 Reactivity and reaction mechanism
 Markovnikov’s rule
 Addition of halogens, hydrogen halides and hypohalous
acids
 Hydration of alkenes
 Michael addition
 Introduction

• Addition reaction involves the introduction of adjacent (vicinal) groups to a

carbon-carbon double bond
• The reaction can undergo by electrophilic polar (heterolytic), radical (homolytic),
nucleophilic and concerted mechanisms
• The electrophiles can be protic acids, halogens, sulfenyl and selenenyl reagents,
epoxidation reagents, mercuric and related metal cations, diborane and alkylboranes
 Addition of hydrogen halides to alkenes
Markovnikov’s rule
• The main aspect of addition of hydrogen halide is its regioselectivity, that is, the
direction of addition
• A regioselectivity reaction means if an unsymmetrical alkene gives a
predominance of one of the two isomeric addition products
• In the addition of hydrogen halides to alkenes, the nucleophilic halide ion
becomes attached to the more-substituted carbon atom which is known as
Markovnikov’s rule
More substituted & stable carbocation

According to Markovnikov rule

Skeletal rearrangements are also possible in hydrogen halide additions
if hydride or alkyl migration can give a more stable carbocation

Hydride migration

Alkyl migration

Mechanism
Acid-catalyzed hydration and related addition reactions

-The reaction is carried out through the carbocation intermediate in which the
alkene is protonated and the carbocation then reacts with water. Such reaction is
governed by the Markovnikov’s rule in which the more highly substituted
alcohol is formed from unsymmetrical alkenes

Acid-catalyzed hydration

Trifluoroacetic acid can also be added to alkenes without the necessity of a stronger acid.
Otherwise, the reaction mechanism is similar to addition of water catalyzed by strong acids.
 Addition of halogens

 Alkene chlorinations and brominations are very general reactions.

 The order of reactivity is F2 > Cl2 > Br2 > I2.
 But, fluorination is strongly exothermic and difficult to control, whereas for
iodine the reaction is easily reversible.
 The initial step in bromination is the formation of a complex between the
alkene and Br2.
 Addition of hypohalous acid to alkene

• Hyphalous acids are another halogen containing reagents with the

genral formula, HOX (X= Cl, Br, I)
• It is another electrophilic addittion to alkene to form halohydrins.
• The addition mechanism is carriedout through the Markovnikov
rule in which the OH group is attached at the more substituted
carbon of the alkene.
HO-Cl

-OH Cl Cl
Cl
OH
Halohydrins
OH

• But, sometimes, halohydrins are not formed by directly adding a hypohalous

acid, instead the alkene is reacted with Br2 or Cl2 in the presence of water.
 Addition reactions involving epoxides

 Epoxidation is also an electrophilic addition which is closely related to

halogenation in that the electrophilic attack results in the formation of a three-
membered ring
 However, unlike to halogenation, the resulting epoxides are neutral and stable
and normally can be isolated
 The epoxides are susceptible to nucleophilic ring opening so the overall pattern
results in the addition of OH+ and a nucleophile at the double bond
 The oxygen is regioselectively introduced at the more-substituted carbon
 Epoxides from alkenes and peroxidic reagents
• The most widely used reagents for conversion of alkenes to epoxides are
peroxycarboxylic acids.
• m-Chloroperoxybenzoic acid (mCPBA) is a common reagent
• No ionic intermediates are involved in the epoxidation of alkenes
• The oxidation is considered to be a concerted process.
 Michael addition (conjugate addition)
• Michael additiion undergoes via addition of carbon nucleophile to
the conjugate or alkene of an α, β-unsaturated carbonyl
compounds rather than adding directly to the carbonyl group.

O O O O O
O
H Na/KOH

O O O O

Protonation H

O OH
O O
H
Transfer O
O