Radical Reactions

Chapter 15
Smith

1
 Introduction
• A radical is a chemical species with
a single unpaired electron in an
orbital.
• Two radicals arise when a bond is cleaved
homolytically.

Cl-Cl + heat  Cl• + Cl•

2
 1o, 2o and 3o Radicals
H
CH3 C CH3 C CH3 CH3 C CH3
H H CH3
1o 2o 3o

The number of carbon atoms bonded to the carbon with the

lone electron determines the kind of radical.

Order of stability is the same as for carbocations: a tertiary

radical is more stable than a secondary radical, and a secondary
radical is more stable than a primary radical
3
 Radical Reactions
• Radical reactions are initiated with heat
(∆ ) or light (hν ) and often with a
peroxide (RO-OR) initiator.
• Once formed, a radical reacts to form a
new radical.
• A radical formed by an initiation reaction
may abstract an H• radical from a C-H
bond or bond to a π electron of a π
bond. A new σ bond is formed in both
cases.

4
 Step 1. Initiation Reaction: Formation of chlorine radical
heat
Cl Cl 2 Cl

H H
H C H + Cl H C + H Cl
H H

Step 2. Radical makes a radical: Chlorine radical reacts

to form methyl radical
or Cl
C C + Cl C C

Step 2. Radical makes a radical: Chlorine radical adds to

double bond to form a new radical

5
 Two Radicals May React with
Each Other
Step 3. Termination: Radical reacts with radical

Cl + Cl Cl Cl

O O + Cl O O Cl
Oxygen is a radical inhibitor, it reacts with a radical such as
Cl thereby keeping it from reacting with another species.

Compounds that prevent radical reactions are called

radical inhibitors or radical scavengers.
Vitamin E is a radical scavenger. 6
 Monohalogenation of Alkanes
(Replacement of one H with Br or Cl)

heat CH3Br
CH4 + Br2 + HBr

hν
+ Cl2 Cl + HCl

All Hydrogens are alike, replacement of any one gives the same product.

Halogenation of an alkane is a substitution reaction.

7
 Show the monohalogenation products
for the following reaction.
Cl2

heat or UV light

Cl Cl
Cl + +

+ Cl
Cl
Five different H atoms produce five unique products.

Rule: We only make monohalogenation products in this course.

8
Example of a Radical Reaction
• Halogenation (bromination or
chlorination) of alkanes.

• CH4 + Br2 + heat or UV light  CH3Br +

HBr

•To do a halogenation, use a halogen (X2).

9
 How do halogenation reactions
occur?
• Three essential steps :
• 1. Radical Initiation (heat or UV light)
• 2. Radical Propagation (two steps)
• 3. Radical Termination (three ways)

10
 Radical Initiation
• Halogen + heat or UV light  radical

∆
Br2 or Br
hν

Br = Br

Initiation: Two radicals are formed by homolysis of a σ bond, starting the rxn.
11
 Radical Propagation
homolytic clevage
H of blue bond

(a) Br + H + H Br
C
H sp H sp C H
2

H
3
H
homolytic clevage
H of pink bond
Br
(b) C H Br
H C H
+ Br Br +
H
H

Propagation: A radical reacts with a reactant, forming a new σ bond and

a radical. (A radical makes a radical in propagation sub-steps.
12
 Radical Termination
(a) Br + Br Br Br

Br
(b) H C H Br H C H
+
H H
H H
(c) H H C H C C
C H + H H
H H H H

Termination: Two radicals combine to form a stable bond.

13
 Energy Profile of Propagation
transition state [1] CH4 + Br2 + heat
CH3Br + HBr
Ea[1]
Energy

transition state [2]

CH4 + Br
Ea[2]

o
CH3
∆H overall

BrCH3

Reaction coordinate

Two propagation steps; the first is rate determining.

14
 The weaker a C-H bond, the
easier it is to remove H
Increasing strength of C-H bonds

H H H CH3 CH3
H C H H C C H H3C C H H3C C H
H H H H CH3
methyl H's primary H's secondary H's tertiary H's

Increasing ease of removal of H

Use this information to predict the product distribution when more

than one kind of H is present in the substrate.
15
 Predict which H is easiest to
abstract in each compound.

Tertiary H is easier to remove than secondary, and secondary is

easier to remove than primary H.

16
Bromination vs Chlorination
• Bromination is slower and more
selective than chlorination.
• Selectivity is in the order IIIo > IIo
> Io, the order of radical stability.
• The selectivity of bromination can be
explained by Hammond’s postulate,
because alkyl radical formation in
bromination is endothermic and in
chlorination is exothermic.
17
 Halogenation in Synthesis
• Convert alkanes (usually symmetrical) into
alkyl halides, from which alcohols, ethers
and alkenes can be formed in one step.
Br2
Br
heat

HO- (SN2) OH

Br RO-
OR
-
t-BuO (E2)

18
Make trans-1,2-dibromocyclohexane
from cyclohexene

Classroom Activity

19
 Stereochemistry of Halogenation
Starting Result
material
a. Achiral Product is achiral or a racemic mixture
(not chiral)
b.1.Chiral w/rxn Configuration at * (stereogenic center) is
away from * retained

b.2. Chiral w/rxn Configuration at * depends on the

at * center mechanism of the reaction.
20
 Halogenation of an Achiral Compound
hν +
+ Cl2 Cl + Cl
Cl
butane 1-chlorobutane (R)-2-chlorobutane (S)-2-chlorobutane
(achiral) (racemic mixture of R and S enantiomers)

Halogenation of a Chiral Compound

* hν Br Cl
+ Br2 * + * + * + *
Cl Cl Br * Cl * Cl
(R)-2-chlorobutane reaction at * gives a Br Br
creation of a new * gives
racemic mixure of enantiomers
a pair of diastereomers
Halogenation at Io carbon away from * retains the R configuration.

21
 Problems
• Work problems 15.1 through 15.18 in
Smith.

22