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.
3
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
4
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
5
X +
Carbocation
H +
Carbanion
6
2. Reaction Intermediates:
Free radicals
Carbocations
Carbanions
7
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)
10
Apart from alkyl free radicals, other important free radicals are :
Allyl and benzyl free radicals are highly
stable due to resonance.
12
13
14
15
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
16
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.
21
Neet 2013
22