UNIVERSITY OF ZAMBIA

CHEMISTRY DEPARTMENT
Tutorial sheets on Radical Reactions 28th July 2020
Provide solutions to questions: 1, 2, 3a, b, & c, 4c, 5a, & 6

CHE 2511 BASIC ORGANIC CHEMISTRY

QUESTION ONE
a) Draw the important resonance structures of the following free radicals.

CH2
O
CH2=CH-CH2
H3C C O

b c d
a e
b) Classify the following radicals as primary, secondary or tertiary and list in increasing order of stability

a b c d e

c) Explain why there is the following distribution of products shown below:

Cl
Cl
Cl2 +
-HCl
1-chloro-1-phenylethane 1-chloro-2-phenylethane
(major product) (minor product)

QUESTION TWO
a) In the presence of a small amount of bromine, the following light-promoted reaction has been
observed.

H3C CH3 H3C CH3 H3C CH3

Br2
+
hv Br
Br
i) Write a mechanism for this reaction. Your mechanism should explain how both products are
formed. (Hint: Notice which H atom has been lost in both products.)
ii) Explain why only this hydrogen atom has been replaced, in preference to any of the other
hydrogen atoms in the starting material.

1
 b) For each compound, predict the major product of free-radical bromination. Remember that
bromination is highlyselective, and only the most stable radical will be formed.

i) cyclohexane (ii) methylcyclopentane (iii) 2,2,3-trimethylbutane (iv) decalin

(v) 3-methyloctane (vi) hexane

CH2CH3

(vii) (viii)

QUESTION THREE

When exactly I mole of methane is mixed with exactly 1 mole of chlorine and light is shone on the mixture,
a chlorination reaction occurs. The products are found to contain substantial amounts of di-, tri-, and
tetrachloromethane.

(a) Explain how a mixture is formed from this stoichiometric mixture of reactants, and propose
mechanisms for the formation of these compounds from chloromethane.

(b) How would you run this reaction to get a good conversion of methane to CH3Cl? and Methane to
CCl4?
(c) The chlorination of pentane gives a mixture of three monochlorinated products.
i) Draw their structures.
ii) Predict the ratios in which these monochlorination products will be formed, remembering that
a chlorine atom abstracts a secondary hydrogen about 4.5 times as fast as it abstracts a
primary hydrogen.

QUESTION FOUR

(a) Draw the structure of the transition state for the second propagation step in the chlorination of
methane.
CH3 + Cl2 CH3Cl + Cl
Show whether the transition state is product-like or reactant-like, and which of the two partial bonds
is stronger.

(b) Repeat for the second propagation step in the bromination of methane.

(c) Draw and name all monochloro products you would expect to obtain from radical chlorination of 2-
methylpentane. Which, if any, are chiral?

QUESTION FIVE
a) A chemist requires a large amount of 1-bromo-2-pentene as starting material for a synthesis and
decides to carry out an NBS allylic bromination reaction. What is wrong with the following synthesis
plan? What side products would form in addition to the desired product?
b) What percentages of 1-chloropropane and 2-chloropropane would you expect to obtain from the
chlorination of propane if 1° and 2° hydrogen atoms were equally reactive?

2
 Cl
Cl2
Cl +
h

c) What percentages of 1-chloro-2-methylpropane and 2-chloro-2-methylpropane would you expect

from the chlorination of 2-methylpropane if the 1° and 3° hydrogen atoms were equally reactive?

Cl2 +
Cl
h Cl

d) Compare these calculated answers with the results actually obtained in the table below and justify the
assertion that the order of reactivity of the hydrogen atoms is 3° 2° 1°.

Cl
Reaction (a) Cl

Actual product distribution 45% 55 %

Reaction (b) Cl
Cl

Actual product distribution 63 % 37 %

QUESTION SIX
a) When ethane is chlorinated, 1,1-dichloroethane and 1,2-dichloroethane, as well as more highly
chlorinated ethanes are formed in the mixture. Write chain reaction mechanisms accounting for the
formation of 1,1-dichloroethane and 1,2-dichloroethane.
b) Which of the following compounds can be prepared by radical halogenation with little complication
by formation of isomeric by-products?
Br
Br Br Cl
I

Cl
Br

c) Chlorination of (R)-2-chlorobutane yields a mixture of dichloro isomers

Cl
Cl2
C4H8Cl2
h

i) Taking into account stereochemistry, how many different isomers would you expect? Write the
structures.
ii) How many fractions would be obtained upon fractional distillation?
iii) Which of these fractions would be optically active?