Free Radical

Chlorination
 Experimental Evidence
Helps to Determine

Mechanism
Chlorination does not occur at room
temperature in the dark.
The most effective wavelength of light is
blue that is strongly absorbed by Cl 2 gas.
The light-initiated reaction has a high
quantum yield (many molecules of
product are formed from each photon of
light).
Free Radical Species are
Constantly Generated
Throughout the Reaction
Propagation
Termination: Reaction of any 2
Radicals
Chlorination of Propane

30%

70%
Hs are not abstracted at the
same rate.
For secondary:
70%/4H = 17.5
For primary:
30%/6H = 5.0
Therefore
Relative rate of H abstraction for 1o : 2o is
1 : 3.5
 Chlorination of
Methylpropane
.
CH3 CH2 CH3
CH3 C H + Cl . CH3 C H + CH3 C.

CH3 CH3 CH3

.
CH2 CH2Cl
CH3 C H + Cl2 CH3 C H 65% + Cl .

CH3 CH3
CH3 CH3
CH3 C. + Cl2 CH3 C Cl 35% + Cl .

CH3 CH3
3o Radicals are Easiest
to Form
Tertiary Hs removed five times
more readily than primary Hs in
chlorination reactions
Relative reactivity of 1o H abstraction:
65% / 9H = 7.2

Relative reactivity of 3o H abstraction:

35% / 1H = 35
Therefore
Relative rate of H abstraction for 1o : 3o
1:5
Stability of Free
Radicals
Bromination is Very
Selective
RDS in Bromination is highly
endothermic
Consider the free radical
monochlorination of 2,2,5-
trimethylhexane. Draw all of the
unique products (ignore
stereoisomers; use zig-zag
structures please) and predict the
ratio or percent composition of the
2.(12) Consider the free radical
monochlorination of 1,4-
dimethylcyclohexane. The reaction
affords three different products (all
C8H15Cl). In this reaction, the rates of
hydrogen abstraction of primary :
secondary : tertiary are 1 : 3.5 : 5.
Draw the three products and predict the
percent composition (or ratio) of the
product mixture. (Disregard cis / trans
isomers for this problem.)