Basic concepts of

organic reactions
What is a chemical reaction?
• A chemical reaction is a process by which some existing bonds in the reacting molecules are
broken and new bonds are formed.
• In a chemical reaction, a reactant is converted into a product.
• This conversion involves one or more steps.
• In general an organic reaction can be represented as

Substrate + Reagent → Intermediates → Product

Substrate → an organic molecule which undergoes chemical change.

Reagent → may be an organic, inorganic or any agent like heat, photons etc., that

brings about the chemical change

Intermediates → species which are formed during the reactions but cannot be isolated, as
they
are extremely reactive, unstable and therefore, short-lived.
Solvents polar →(protic or aprotic) or nonpolar
Steric hinderance is there. 2
Mechanism:

“  Many chemical reactions are depicted in one or more simple steps.

 The series of simple steps which collectively represent the chemical change, from substrate
to product is called as the mechanism of the reaction.

 The slowest step in the mechanism determines the overall rate of the reaction.

 It is the theoretical pathway which describes the changes occurring in each step during the
course of the chemical change.

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 1. Fission of a covalent bond
 All organic molecules contain covalent bonds which are formed by the mutual sharing of
electrons between atoms.
 These covalent bonds break in two different ways, namely homolytic cleavage
(symmetrical splitting) and heterolytic cleavage (unsymmetrical splitting).
 The cleavage of a bond in the substrate is influenced by the nature of the reagent
(attacking agent).

Bond Cleavage

Homolytic cleavage Heterolytic cleavage

Free radicals Cations & Anions

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Homolytic Fission or Homolysis:

 The covalent bond is broken in such a way that each resulting species gets its own
electron.
 This leads to formation of odd electron known as free radical.
 They are reaction intermediates, highly unstable and highly reactive.
 They are formed when the electronegativity of the atoms is almost zero.
 Homolytic bond fission takes place in gaseous phase and the initiator are Heat, Electricity,
Light, Peroxide and free Radical.
 
─ → + 

Methyl free radicals

 As a free radical with an unpaired electron and unstable, it has a tendency to gain an
electron to attain stability.
 Organic reactions involve homolytic fission of C-C bonds to form alkyl free radicals. The
stability of alkyl free radicals is in the following order

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 X +
Carbocation
 H +
Carbanion

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2. Reaction Intermediates:

Free radicals
Carbocations
Carbanions

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Free radicals
An atom (or group of atoms) having an unpaired electron is called as Free Radical. These are
formed via homolytic fission.

 
─ → +
 

methyl free radicals are produced

  of free radical (alkyl) is hybridised and hence the shape is planar, having an unhybridized‘p’
‘C’
p-orbital containing an odd electron (Paramagnetic in nature)

Tertiary alkyl free radicals are more stable than others.

The stability of free radicals follows the order:

C   0
120
 
The stability of free radicals is explained via hyperconjugation effect. In methyl free radical, there
is no hyperconjugation, as there is no -C-H bond. Let us draw various hyperconjugation structure of
ethyl radical.
 
Hyperconjugation: alkyl groups (R) with at least one hydrogen (H) atom on the α- carbon,
attached to an unsaturated carbon atom (i.e., having a - C = C - bond), or positive charge (as
in carbocation, ) or odd electrons (as in free radicals, ) are able to release electrons as in
electromeric effect (delocalization)

Let us draw various hyperconjugation structure of ethyl radical.

 
Similarly a radical is more stable than radical, which is more stable than a alkyl radical (as number of
alpha H-atoms are increasing, the hyperconjugation effect is increasing and hence stability increases)
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Apart from alkyl free radicals, other important free radicals are :

Allyl and benzyl free radicals are highly

stable due to resonance.
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Arrange the following free radicals in order
of stability:
(1) Benzyl
(2) Allyl
(3) Methyl
(4) Vinyl

(a) 4 > 3 > 2 > 1

(b) 1 > 2 > 3 > 4
(c) 1 > 3 > 4 > 2
(d) 4 > 3 > 1 > 2

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The most stable free radical When a methyl radical is formed from
among the following is CH3Cl, select the correct statement:

(1) Bond angle of 109º28’ is retained

(2) Number of sigma bonds is three
(3) Carbon undergoes geometric change from
tetrahedral to planar
(4) Hybridization changes sp3 to sp2

(a) 2, 3 and 4
(b) 1, 3 and 4
(c) 2 and 4
(d) 3 and 4
3. Arrange the following free radicals in increasing In which cases, free radicals can be formed by
order of stability: homolytic fission

A- PHENYL, B- ALLYL(2), C-VINYL

D- ALLYL(1), E- SEC

B undergoes resonance

(a) A < C < E < D < B

(b) E < C < D < B < A
(c) C < A < B < E < D
(d) B < A < D < E < C
The decreasing order of stability of the following The increasing order of stability of the following
free radicals is free radicals is

a. I < II < III < IV

b. II < III < IV< I
c. III < II< I < IV
d. IV< I < II < III
 Arrange the following free radicals in increasing order of
their stability

a. I < II < III < IV

b. II < III < IV< I
c. III < IV< I < II
d. IV< III < II < I

D= This free radical has two effects that make it most

stable, i.e the free radical is allylic as well as tertiary.
C= It is the only allylic position. So, it is 2nd most stable 
B= It is tertiary free radical.
A= It is secondary free radical.
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Neet 2013

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