Radical Reactions

Chapter 11: Radical Reactions

MULTIPLE CHOICE
1. What are the products of cleavage of the radical species shown?

a.
b.
c.

d.

e.

ANS: A

DIF: Easy

REF: 11.2

2. What is the name of the process shown here?

a. disproportionation
b. hydrogen abstraction
c. cleavage
ANS: D

DIF: Easy

d. dimerization
e. pyrolysis
REF: 11.2

3. The disproportionation product(s) of the alkyl radical shown here will be

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a. 2 alkanes.
b. an alkane and an alkene.
c. 1 alkane.
ANS: B

DIF: Easy

d. 1 alkene.
e. 2 alkenes.
REF: 11.2

4. Use the numbering system in the structure shown here to identify any and all carbon atoms.

a. 1
b. 2
c. 3
ANS: E

d. 1 and 2
e. 1 and 3
DIF: Easy

REF: 11.2

5. Which of the following is least likely to be a radical initiator?

a.

b.
c.

d.

e.

ANS: B

DIF: Easy

REF: 11.2

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6. Which of the indicated CC bonds requires the least amount of energy to break homolytically?

a. A
b. B
c. C
ANS: B

d. D
e. E
DIF: Easy

REF: 11.2

7. Which of the following transformations is a disproportionation?

a.

b.

c.

d.

e.

ANS: B

DIF: Medium

REF: 11.2

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8. Cyclopropylmethyl radical, shown here, decomposes rapidly through a cleavage process. Which of the
following structures is the product of this process?

a.

d.

b.

e.

c.

ANS: A

DIF: Medium

REF: 11.2

9. Which of the following radicals is most stable?

a.
d.

b.

e.

c.

ANS: B

DIF: Easy

REF: 11.3

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10. Which CH bond is easiest to break homolytically? (For clarity, not all CH bonds in the molecule are
shown.)

a. A
b. B
c. C
ANS: A

d. D
e. E
DIF: Medium

REF: 11.3

11. What orbitals are involved in hyperconjugative stabilization of the radical shown here?

a. filled CC and empty 2p

b. filled CC and empty CH
c. filled CH and half-filled 2p
ANS: C

DIF: Difficult

d. filled CC and half-filled 2p

e. filled CH and empty 2p
REF: 11.3

12. Which of the following is a termination step in a radical chain reaction?

a.

b.

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c.

d.

e.

ANS: C

DIF: Easy

REF: 11.4

13. What is a radical inhibitor?

a. A chemical species that prevents an initiation step in a radical chain reaction.
b. A chemical species that terminates the chain in a radical chain reaction.
c. A chemical species that prevents chain termination in a radical chain reaction.
d. A chemical species that accelerates one or more propagation steps in a radical chain
reaction.
e. A chemical species that produces radicals.
ANS: B

DIF: Easy

REF: 11.4

14. Which of the following do you expect is least likely to act as a radical inhibitor?
a.
d.

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Radical Reactions
b.

e. All these molecules are equally likely to

act as radical inhibitors.

c.

ANS: D

DIF: Medium

REF: 11.4

15. What is the most likely stereochemical outcome of the following reaction?

a. An unequal mixture of enantiomers.

b. An equal mixture of enantiomers.
c. An unequal mixture of diastereomers.
ANS: C

DIF: Medium

d. An equal mixture of diastereomers.

e. b or d are both likely.
REF: 11.4

16. Which of the following statements about the anti-Markovnikov addition of HX to alkenes is false?
a. The reaction must be run in the presence of peroxides.
b. The regiochemistry is the result of the formation of the most substituted carbocation in the
rate-limiting step.
c. The halogen atom attaches to the less substituted side of the alkene.
d. The reaction is only successful when HBr is used.
e. An alcohol is formed as a byproduct.
ANS: B

DIF: Medium

REF: 11.5
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17. Which of the following monomers will react to provide the polymer shown here?

a.

d.

b.

e.

c.

ANS: D

DIF: Medium

REF: 11.5

18. Predict the product of the following reaction:

a.

d.

b.

e. Both b and d

c.

ANS: E

DIF: Medium

REF: 11.6

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19. Which of the following monobrominated products forms fastest under the conditions shown?

a.

d.

b.

e. All form at equal rates.

c.

ANS: B

DIF: Easy

REF: 11.7

20. Which of the following is a propagation step?

a.

b.

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c.

d.

e.

ANS: C

DIF: Easy

REF: 11.7

21. Which of the following concepts should be used to correctly describe the reason for enhanced
regioselectivity of photobromination versus photochlorination?
a. relative bond strengths of Cl2 and Br2
d. Hammond postulate
b. energy released on termination steps
e. steric hindrance
c. overall enthalpy of reaction
ANS: D

DIF: Difficult

REF: 11.7

22. Which of the following compounds is the product of this reaction?

a.

d.

b.

e. Both a and b would be produced.

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Radical Reactions
c.

ANS: E

DIF: Easy

REF: 11.8

23. What is the stereochemical outcome of the following reaction?

a.
b.
c.
d.
e.

Enantiomers are produced in equal amounts.

Diastereomers are produced in equal amounts.
A single product forms.
Enantiomers are produced in unequal amounts.
Diastereomers are produced in unequal amounts.

ANS: E

DIF: Difficult

REF: 11.8

24. Which of the following statements about allylic bromination using NBS is false?
a. Molecular bromine concentration must be low.
b. Allylic rearrangements may occur.
c. HBr is required in trace amounts.
d. Symmetrical alkenes are the most suitable substrates for the reaction to avoid mixtures of
products.
e. Bromine radical is produced by homolytic cleavage of the NBr bond in Nbromosuccinimide.
ANS: E

DIF: Difficult

REF: 11.8

25. Which of the following statements about rearrangements is false?

a. Hydrogen atom shifts in radicals are not observed.
b. 1,2-vinyl group shifts in radicals have been observed.
c. Methyl group shifts in radicals are not observed.
d. Radical rearrangements are disfavored because of the transition state for the
rearrangement is destabilized.
e. Carbocation rearrangements are favored because the transition state for the rearrangement
is stabilized.
ANS: E

DIF: Difficult

REF: 11.9

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Chapter 11
SHORT ANSWER
1. Draw the products of the following reaction:

ANS:

DIF: Easy

REF: 11.2

2. Draw an arrow-pushing mechanism for the transformation shown here.

ANS:

DIF: Medium

REF: 11.2

3. Predict the most likely products of cleavage of the radical shown here and draw an arrow-pushing
mechanism to illustrate their formation.

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Radical Reactions

ANS:

DIF: Medium

REF: 11.2

4. When a sample of diethyl ether is allowed to stand, over time it reacts with molecular
oxygen to form peroxides:

Propose an arrow-pushing mechanism to illustrate the formation of the peroxide from the ether starting
material. Use R as the initiator. Show all curved arrows and single electrons.
ANS:

(continued)

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Chapter 11

DIF: Difficult

REF: 11.2

5. Predict the product of the following reaction:

ANS:

DIF: Easy

REF: 11.4

6. Devise a multistep synthesis of the target molecule from the given starting material. Show the reagents
needed for each step and the product of each step.

ANS:

DIF: Medium

REF: 11.4

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Radical Reactions
7. Devise a multistep synthesis of the target molecule from the given starting material. Show the reagents
needed for each step and the product of each step.

ANS:

DIF: Medium

REF: 11.4

8. Unsaturated fats in food react with oxygen to form alkylperoxy radicals. These radicals can then react
further with compounds in the food to degrade its taste. To prevent this process, preservatives like BHT
(butylated hydroxytoluene) that act as radical inhibitors are added to some foods.
Provide a mechanism to show how an alkylperoxy radical like the one shown here
is quenched by BHT.

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Chapter 11
ANS:

DIF: Difficult

REF: 11.4

9. Devise a multistep synthesis of the target molecule from the given starting material. Show the reagents
needed for each step and the product of each step.

ANS:

DIF: Difficult

REF: 11.4

10. Anti-Markovnikov addition of HX to an alkene only works with HBr in the presence of peroxides as a
radical initiator. Use the bond dissociation data provided to explain why the reaction fails with HCl and
HI.

X
Cl
Br
I

First propagation step: X + H2C=CH2 XCH2CH2

Bond dissociation energy,
Bond dissociation energy,
XC in XCH2CH2,
bond, kcal/mol
kcal/mol
66
85
66
72
66
57

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Radical Reactions

X
Cl
Br
I

Second propagation step: HX + XCH2CH2 HCH2CH2X

Bond dissociation energy,
Bond dissociation energy,
HX bond, kcal/mol
HC in HCH2CH2X,
kcal/mol
103
98
87
98
71
98

ANS:
For HI, the reaction fails because the first step is endothermic (+9 kcal/mol compared to exothermic
values for HBr and HCl); because this step is so slow, the termination steps will be competitive and the
reaction does not proceed. For HCl, the second step is endothermic (+5 kcal/mol, compared to
exothermic values for HI and HBr), again slowing the overall reaction.
DIF: Difficult

REF: 11.4

11. In a radical chain reaction, termination steps are exothermic, yet propagation steps can be endothermic.
Despite this energetic difference, propagation steps can compete successfully to continue the chain
reaction, resulting in the eventual product. Explain.
ANS:
Propagation steps involve the reaction of a radical with a nonradical to form a new radical and a new
nonradical. Termination steps involve the collision of two radicals to form a nonradical. In typical chain
reaction conditions, radicals are more likely to encounter nonradicals than they are to encounter other
radicals, which are in low concentration. Thus, propagation events compete successfully with
termination events and the reaction can proceed.
DIF: Easy

REF: 11.5

12. Provide an arrow-pushing mechanism for the formation of polystyrene from styrene in
the presence of AIBN.

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Chapter 11

ANS:

DIF: Difficult

REF: 11.5

13. Devise a multistep synthesis of the target molecule from the given starting material. Show the reagents
needed for each step and the product of each step.

ANS:

DIF: Easy

REF: 11.6

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Radical Reactions

14. Devise a multistep synthesis of the target molecule from the given starting material. Show the reagents
needed for each step and the product of each step. Explain why the target cannot be made from the
starting material in one step.

ANS:
The anti-Markovnikov addition of HI to an alkene in the presence of peroxides fails because the first
propagation step of the reaction is exceedingly slow; thus, the termination steps prevail and the addition
fails. Therefore, the starting alkene must first be converted to a primary alkyl bromide followed by
treatment with sodium iodide in acetone (a Finkelstein reaction). Sodium bromide precipitates from
solution, allowing the product iodide to form irreversibly.

DIF: Difficult

REF: 11.6

15. Draw an arrow-pushing mechanism to show the transformation of dibromomethane to bromoform in the
presence of molecular bromine and bromine radical.
ANS:

DIF: Easy

REF: 11.7

16. What is the principal monobrominated product that would result from the conditions shown?

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Chapter 11

ANS:

DIF: Easy

REF: 11.7

17. Provide the structures of all monochlorinated products that would result from the conditions shown.
Assume that all chiral products are formed as racemic mixtures.

ANS:

DIF: Easy

REF: 11.7

18. Predict the product of the following reaction:

ANS:

DIF: Easy

REF: 11.7
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Radical Reactions

19. Using the bond dissociation energies provided below, draw an energy diagram for the two propagation
steps in the following reaction:
CH4 + Br2 CH3Br + HBr
Show the correct relative energies of intermediates, starting materials and products. Estimate the Hrxn.
Bond dissociation energies (kcal/mol)
CH3H, 105
BrBr, 46
CH3Br, 69
HBr, 85
ANS:
Estimated Hrxn is 3 kcal/mol.

DIF: Medium

REF: 11.7

20. Predict the product of the following reaction.

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Chapter 11
ANS:

DIF: Easy

REF: 11.8

21. Devise a multistep synthesis of the target molecule from the given starting material. Show the reagents
needed for each step and the product of each step.

ANS:

DIF: Easy

REF: 11.8

22. Predict the product of the following sequence of reactions.

ANS:

DIF: Medium

REF: 11.8

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Radical Reactions
23. Devise a multistep synthesis of the target molecule from the given starting material. Show the reagents
needed for each step and the product of each step.

ANS:

DIF: Medium

REF: 11.8

24. Predict the major organic product and provide a mechanism to illustrate its formation under the
conditions shown. Show all curved arrows, lone pairs and single electrons, and any nonzero formal
charges.

ANS:

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Chapter 11

DIF: Difficult

REF: 11.8

25. In an allylic bromination, why is it essential to keep the concentration of molecular

bromine relatively low?
ANS:
Alkenes react with Br2 to produce vicinal dibromides, and if the bromine concentration is high, this
process will compete with allylic bromination.
DIF: Easy

REF: 11.9

268