Organic Reactions & Mechanisms

Module 3.2: Addition and Substitution Reactions

An addition reaction is the one in which two substances are combined to

form a single compound. In general, an unsaturated organic compound like
alkene or alkyne undergoes addition reaction. These addition reactions are
divided into three types as given below depending on the nature of the
reagent.

(a) Electrophilic Addition Reactions

We already learnt about Electrophilic additions of olefins, Markovnikovs

law
and Kharasch effect.

Example: Electrophilic addition with rearrangement

Mechanism:

Migration of an alkyl group leads to the formation of a more stable product.

The stability order of carbocations is 10 < 20 < 30 < neo-

Michael reaction:

Reaction between an enol and an olefin is referred in this mechanism.

(b) Nucleophilic Addition Reactions

We already learnt about Nucleophilic addition reactions and their

mechanisms.
These reactions mainly occur in carbonyl compounds like aromatic
aldehydes.

In some Cannizaro reactions, out of the two reactants one of them need not
contain any -hydrogen.

Nucleophilic addition at carbon-carbon multiple bonds:

Example: Skraup synthesis

1. This reaction can be used for synthesis of a wide variety of quinoline

derivatives.
2. Quinoline derivatives are generally dyes, anti-malarials, anti-oxidants
etc.
3. Quinoline is obtained from the reaction of aniline, with glycerol, nitro
benzene, conc. H2SO4 and FeSO4.
The overall reaction is
Mechanism:

i) Dehydration of glycerol to form acrolein

ii) This reaction involves nucleophilic addition of aniline at -carbon of

acrolein.

iii) This step involves electrophilic aromatic substitution with ring closure.
iv) This reaction step involves oxidation of 1, 2-dihydroquinoline to
quinoline.

(c) Free Radical Addition Reactions

We already learnt about free radical addition reaction and free radical
mechanism; Anti Markovnikovs rule in alkenes.

Examples:
Polyethylene polymer is thermoplastic substance. Polyethylene is a non-
polar homo polymer.

Polyvinyl chloride is used in the preparation of polyvinyl chloride pipes.

Polystyrene is an artificial rubber

Uses:

Polymeric materials are used as

1. Electrical insulators
2. Synthetic fabrics
3. Furniture
4. Ion-exchange resins

Substitution reactions
An atom or a group of atoms is substituted by other atom or group in a
substitution reaction. Depending on the nature of substituting species,
substitution reactions are classified into following three types.

(a) Nucleophilic Substitution Reactions

Example 1: SN1 reaction

 SN1 reaction with rearrangement

Order of rate of SN1 reaction is 30 > 20 > 10 > CH3X

If polarity of the solvent increases, then the rate of SN1 reaction also
increases.

Example 2: SN2 reaction

Mechanism:

Configuration is reversed in the SN2 mechanism.

The reactivity order of alkyl halides in SN2 reaction is

Q. Identify the Nucleophile; transition state product in the following

reactions.
(b) Electrophilic Substitution Reactions

Based on the reactants involved in the rate determining step, electrophilic

substitution reactions are categorized into two types.

1. SE2
2. SE1
1. SE2 reaction: In these electrophilic substitution reactions, one
electrophile is substituted by another electrophile.

2. SE1 reaction: In this reaction mechanism two steps are present. First
step is formation of carbanion and 2nd step is the combination of carbanion
and an electrophile

For the reaction + +

In SE1 reaction, sometimes inversion process can take place.

SE1 with retention

For example in the following reaction the structure is retained.

Examples:

1. FreidelCraft alkylation with ring closure.

2. Preparation of vanillin

Assignment Questions:
1. What are addition reactions ? Write the different types of addition
reactions?
2. Write a note on Skraup synthesis.
3. Give any three examples for electrophilic substitution reactions.