Chapter 4.

1: Substitution Reactions

Learning Objectives

By the end of this section, you should be able to:

 Define free radicals and differentiate the relative stabilities of methyl 1 0/20/30 radicals
 Describe how and under what conditions free radicals are produced
 Draw the initiation, propagation and termination stages of the free radical substitution
mechanism of alkanes

Introduction to free radicals

 A free radical are highly reactive, short-lived, electrically neutral intermediates (neither
electrophilic or electrophilic) , that exist as a neutral atom or group that has an unpaired
electron.
E.g. chlorine atom, Clᐧ
bromine atom, Brᐧ
methyl group radical, ᐧ CH3
ethyl group radical, CH3CH2ᐧ or ᐧ C2H5

 Free radicals are formed by the homolysis of a covalent bond.

 Alkyl radicals are classified as: methyl, primary (1 0), secondary (20) and tertiary (30) by
the number of (R) groups bonded to the carbon with unpaired electrons.
 The stability of the free radicals are:
Determine the stability by looking
Methyl < 10 < 20 < 30 at the carbon with the free radical

 FYI:
 The lower the bond dissociation energy (Energy required to break or form a bond) of a
C-H bond to form a carbon radical, the more stable the resulting carbon radical.
 This is because lower dissociation energy implies that central carbon is less e -
withdrawing, allowing for easier homolytic bond breaking initially and better dispersion
of e- later when the radical is formed.
 Note that the BDE of C-H bonds decreases as we go from methyl to primary to tertiary.

 Unlike carbocations, less stable radicals do not rearrange to more stable carbon radicals
Free radical substitutions

 Free radical substitutions include reactions such as oxidation which involves the
homolysis of non-polar bonds to form radical intermediates. Some industrial
applications include:
 Styrofoam
 Polyethylene
 Industrial preparation of alkyl halides
 In this module, the only free radical substation touched on is Halogenation of alkanes
CANNOT substitute a H on benzene (aromatic) rings, but can do so for grps attached.

Halogenation of alkanes

(a) It is a type of radical substitution reaction in the presence of light or heat

where a gaseous halogen atom (X) replaces a hydrogen atom in alkanes to
form alkyl halides.

Halogens Cl2 and Br2 are more commonly used. Reactions with F2 are too
violent and reactions with I2 are too slow

(b) An alkane with different types of H can react with Cl2 to give a mixture of
alkyl chlorides. Recall Chem II  finding the number of possible products

(c) Bromination is a highly selective process, where 30 H (H bonded to 30 Carbon)

is preferentially replaced by Br. Other H can also can also be substituted.

Chlorination is less selective and occurs more quickly than bromination

Preference for replacing H for bromination: 30H > 20H > 10H

(d) In excess, Cl or Br can further substitute all H atoms present

Free radical substitution Mechanism (For Halogenation of alkanes)

 It is a self-propagating reaction  it is a free-radical chain reaction so use half arrows

 3 stages
REMEMBER to write You NEED to write the title,
UV and Br for overall initiation, propagation, and
(a) Initiation reaction!
termination
 Step 1:
Homolytic fission of halogen molecule (Cl2) by heat or light produces 2 radical
halogen (Cl) atoms:
REMEMBER to
write UV for
initiation!
UV
(b) Propagation
 Step 2:
Radical halogen (Cl) atoms abstracts H atom from alkane R-H to give H-X (HCl) &
alkyl radical

 Step 3:
Alkyl radical abstracts halogen (Cl) atom from Cl2 to give alkyl halide (R-Cl) and
radical halogen (Cl) atom

Side propagation (same as previous 2 steps, further substitution generating new

products, DO NOT NEED TO WRITE IN EXAMS UNLESS STATED/IMPLIED)

 Radical Cl atoms can react with alkyl halide molecules (R-Cl) to generate more
radicals, producing polysubstituted alkanes R-Cln ,until all H are substituted.
 The radicals can also go on to react with other molecules

(c) Termination
 Step 4:
2 radicals react in 3 possible ways to remove radicals and stop propagation