CHAPTER 8—HALOALKANES, HALOGENATION, AND RADICAL REACTIONS

MULTIPLE CHOICE

1. What is the IUPAC name of the following compound?

a. (R)-1-chloro-3-methyl-2-cyclohexene
b. (S)-1-chloro-3-methyl-2-cyclohexene
c. (R)-3-chloro-1-methylcyclohexene
d. (S)-3-chloro-1-methylcyclohexene
ANS: C

2. What is the IUPAC name of the following compound?

a. (R)-2-bromo-2-vinylpentane
b. (S)-2-bromo-2-vinylpentane
c. (S)-3-bromo-3-propyl-1-butene
d. (R)-3-bromo-3-methyl-1-hexene
ANS: D

3. What is the IUPAC name of the following compound?

a. (E)-1-chloro-1,2,3-trimethyl-1-butene
b. (Z)-1-chloro-1,2,3-trimethyl-1-butene
c. (E)-2-chloro-3,4-dimethyl-2-pentene
d. (Z)-2-chloro-3,4-dimethyl-2-pentene
ANS: D

Brown Organic Chemistry 6e Test Bank 1

 4. What is the correct assignment of the names of the following compounds?

1. CH3Cl
2. CH2Cl2
3. CHCl3

a. 1 = methyl chloride; 2 = chloroform; 3 = methylene chloride

b. 1 = trichlor; 2 = chloroform; 3 = methylene chloride
c. 1 = methyl chloride; 2 = methylene chloride; 3 = chloroform
d. 1 = chloroform; 2 = methylene chloride; 3 = trichlor
ANS: C

5. Which of the following has the list of compounds in the correct order of decreasing boiling point
(higher boiling point > lower boiling point)?
a. chloromethane > chloroethane > 2-chloropropane > 2-chloro-2-methylpropane
b. 2-chloro-2-methylpropane > 2-chloropropane > chloroethane > chloromethane
c. chloroethane > chloromethane > 2-chloro-2-methylpropane > 2-chloropropane
d. chloromethane > 2-chloro-2-methylpropane > 2-chloropropane > chloroethane
ANS: B

6. Which of the following has the list of compounds in the correct order of decreasing boiling point
(higher boiling point > lower boiling point)?
a. 2-fluoropropane > 2-chloropropane > 2-bromopropane > 2-iodopropane
b. 2-chloropropane > 2-iodopropane > 2-fluoropropane > 2-bromopropane
c. 2-iodopropane > 2-chloropropane > 2-fluoropropane > 2-bromopropane
d. 2-iodopropane > 2-bromopropane > 2-chloropropane > 2-fluoropropane
ANS: D

7. Which of the following has the list of compounds in the correct order of decreasing density (higher
density > lower density)?
a. CH2Cl2 > CH2Br2 > CH2I2
b. CH2Cl2 > CH2I2 > CH2Br2
c. CH2I2 > CH2Br2 > CH2Cl2
d. CH2I2 > CH2Cl2 > CH2Br2
ANS: C

8. Which of the following has the list of compounds in the correct order of decreasing polarity (more
polar > less polar)?
a. CCl4 > CHCl3 > CH2Cl2
b. CH2Cl2 > CHCl3 > CCl4
c. CCl4 > CH2Cl2 > CHCl3
d. CHCl3 > CCl4 > CH2Cl2
ANS: B

9. Which of the following has the list of compounds in the correct order of decreasing molecular polar
(more polar > less polar)?
a. CH3I > CH3Br > CH3Cl > CH3F
b. CH3F > CH3Cl > CH3Br > CH3I
c. CH3Cl > CH3F > CH3Br > CH3I
d. CH3Cl > CH3I > CH3F > CH3Cl

Brown Organic Chemistry 6e Test Bank 2

 ANS: C

10. Which of the following bonds has the lowest bond dissociation enthalpy?
a. CH
b. CF
c. CBr
d. CI
ANS: D

11. Which of the following statements is not true?

a. homolytic cleavage of a bond in a neutral molecule gives two radicals
b. radicals have one or more unpaired electrons
c. movement of single electrons is depicted using a "fishhook arrow"
d. the CF bond is the weakest bond between carbon atom and a halogen
ANS: D

12. Which halogen is most useful in the regioselective radical halogenation of alkenes??
a. fluorine
b. chlorine
c. bromine
d. iodine
ANS: C

13. What is the major organic product obtained from the following reaction?

a. 1
b. 2
c. 3
d. 4
ANS: B

Brown Organic Chemistry 6e Test Bank 3

 14. What is the major organic product obtained from the following reaction?

a. 1
b. 2
c. 3
d. 4
ANS: B

15. What is the major organic product obtained from the following reaction?

a. 1
b. 2
c. 3
d. 4
ANS: A

16. What are the major organic products obtained from the following reaction?

a. 1 and 2
b. 3 and 4
c. 1 and 3
d. 2 and 4
ANS: C

Brown Organic Chemistry 6e Test Bank 4

 17. What is the correct order of stability of the following radicals (more stable > less stable)?

a. 1>2>3
b. 1>3>2
c. 3>1>2
d. 3>2>1
ANS: D

18. What is the correct order of stability of the following radicals (more stable > less stable)?

a. 1>2>3
b. 2>1>3
c. 2>3>1
d. 3>2>1
ANS: C

19. What is the characteristic of a radical chain initiation step?

a. radicals are formed
b. substitution products are formed
c. a radical reacts with a molecule to give a new radical and a new molecule
d. two radicals combine to give a molecule
ANS: A

20. What is the characteristic of a radical chain propagation step?

a. radicals are formed
b. byproducts are formed
c. a radical reacts with a molecule to give a new radical and a new molecule
d. two radicals combine to give a molecule
ANS: C

21. What is the characteristic of a radical chain termination step?

a. radicals are formed
b. substitution products are formed
c. a radical reacts with a molecule to give a new radical and a new molecule
d. two radicals combine to give a molecule

Brown Organic Chemistry 6e Test Bank 5

 ANS: D

22. What type of reactive intermediate is formed in the reaction of propene with N-bromosuccinimide to
give 3-bromo-1-propene?
a. allylic carbocation
b. allylic carbanion
c. allylic radical
d. cyclic bromonium ion
ANS: C

23. What type of reactive intermediate is formed upon irradiation of a solution of toluene (Ph-CH3) and
bromine?
a. benzylic carbocation
b. benzylic carbanion
c. benzylic radical
d. cyclic bromonium ion
ANS: C

24. Which of the following alkanes does not undergo monobromination to form a single bromoalkane as
the major product?

a. 1
b. 2
c. 3
d. 4
ANS: D

25. Which of the following alkenes undergoes allylic bromination to form a single monobrominated
product?

a. 1
b. 2
c. 3
d. 4
ANS: A

Brown Organic Chemistry 6e Test Bank 6

 26. What is the major product formed upon radical bromination of (S) 3-methylhexane?
a. (S) 3-bromo-3-methylhexane
b. (R) 3-bromo-3-methylhexane
c. a mixture of (R) and (S) 3-bromo-3-methylhexane
d. (3R) 1-bromo-3-methylhexane
ANS: C

27. What is the geometry of the central carbon atom of a tert-butyl radical?
a. tetrahedral
b. trigonal planar
c. trigonal pyramidal
d. square planar
ANS: B

28. Which of the following statements is not true about the allyl radical
a. the carbon-carbon bond lengths are identical
b. the unpaired electron density is shared between carbons 1 and 2.
c. it undergoes reaction with bromine to give a single product
d. it is formed by abstraction of a hydrogen atom from the methyl group of propene
ANS: B

29. How many electrons does the allyl radical have in p orbitals
a. 1
b. 2
c. 3
d. 4
ANS: C

30. How many -bonding, non-bonding, and antibonding orbitals does the allyl radical possess?
a. one bonding, one nonbonding, and one antibonding
b. two bonding, no nonbonding, and no antibonding
c. two bonding, one nonbonding, and no antibonding
d. three bonding, no nonbonding, and no antibonding
ANS: A

31. What type of orbitals overlap to provide stability to the tert-butyl radical by hyperconjugation?
a. 3 C 2p atomic orbital + 3 C sp2 atomic orbital
b. 3 C 2p atomic orbital + methyl CH molecular orbital
c. 3 C sp2 atomic orbital + methyl CH molecular orbital
d. 3 C 2p atomic orbital + methyl C 2s atomic orbital
ANS: B

32. What type of orbital contains the unpaired electron of the tert-butyl radical?
a. s
b. p
c. sp3
d. 
ANS: B

Brown Organic Chemistry 6e Test Bank 7

 33. Which of the following is an accurate statement of Hammond's postulate?
a. the transition state of an exothermic reaction will resemble the starting materials
(reactants) more than the product
b. the transition state of an exothermic reaction will resemble the products more than the
starting materials (reactants)
c. the transition state of an endothermic reaction will resemble the starting materials
(reactants) more than the product
d. the difference in energy between the starting materials (reactants) and transition state
controls the rate of a reaction
ANS: A

34. Which of the following statements is not true regarding the halogenation of alkanes upon treatment
with halogen and light?
a. bromination is more selective for 3 positions than chlorination
b. the reaction proceeds via a radical intermediate
c. the reaction proceeds via a chain reaction
d. this is a useful process for the formation of fluorides, chlorides, bromides and iodides
ANS: D

35. What type of reactive intermediate is formed in the reaction of propene with hydrogen bromide in the
presence of peroxides to give 1-bromopropane?
a. 1 radical
b. 1 carbocation
c. 1 radical
d. 2 radical
ANS: D

36. What is the major product obtained from the reaction of 2-methyl-2-butene with hydrogen bromide in
the presence of peroxides?
a. 2,3-dibromo-2-methylbutane
b. 2-bromo-3-methylbutane
c. 2-bromo-2-methylbutane
d. (E)-1-bromo-2-methyl-2-butene
ANS: B

37. Which of the following statements is not true?

a. Bromine radicals add to the least substituted end of a carbon-carbon double bond of an
alkene.
b. The major anti-Markovnikov product obtained upon addition of HBr to alkenes in the
presence of a peroxide is formed in a radical termination step.
c. Two radicals combine in radical termination steps.
d. Alkoxy radicals remove a hydrogen atom from HBr to give an alcohol and a bromine
atom.
ANS: B

38. Which of the following compounds is most susceptible to autooxidation?

a. propene
b. 1,3-butadiene
c. 1,4-pentadiene
d. 1,5-hexadiene

Brown Organic Chemistry 6e Test Bank 8

 ANS: C

39. What is the reactive intermediate in the autooxidation of cyclohexene?

a. an allylic radical
b. a 2 carbocation
c. a carbocation
d. a diene
ANS: A

40. What is the major product of autooxidation of cyclohexene?

a. 1
b. 2
c. 3
d. 4
ANS: C

41. What is the major organic product obtained from the following reaction?

a. 1
b. 2
c. 3
d. 4
ANS: C

Brown Organic Chemistry 6e Test Bank 9

 42. What is the major organic product obtained from the following reaction?

a. 1
b. 2
c. 3
d. 4
ANS: C

43. What is the major organic product obtained from the following reaction?

a. 1
b. 2
c. 3
d. 4
ANS: A

44. What are the major products formed upon treatment of (E) 3-methyl-2-hexene with HBr in the
presence of peroxides?

1. (S,S) 2-bromo-3-methylhexane
2. (S,R) 2-bromo-2-methylhexane
3. (R,S) 2-bromo-2-methylhexane
4. (R,R) 2-bromo-2-methylhexane

a. only 1 and 2
b. only 1 and 4
c. only 2 and 3
d. a mixture of 1, 2, 3, and 4
ANS: D

Brown Organic Chemistry 6e Test Bank 10

 45. What are the major products formed upon treatment of (E) 3-methyl-2-hexene with HBr in the absence
of peroxides?

1. (S) 3-bromo-3-methylhexane
2. (R) 3-bromo-2-methylhexane
3. 2-bromo-3-methylhexane

a. only 1
b. only 2
c. a mixture of 1 and 2
d. only 3
ANS: D

46. Which of the following accounts for the anti-Markovnikov regiochemistry of the reaction of an alkene
with HBr in the presence of peroxides?
a. the alkene reacts with HBr to give a carbocation
b. the alkene reacts with a bromine atom to give a radical
c. the alkene reacts with a hydrogen atom to give a radical
d. the alkene reacts with peroxide to five an allylic radical
ANS: B

PROBLEM

1. Provide the IUPAC name of the following compound.

ANS:
(S)-4-bromo-2-methylhexane

2. Provide the IUPAC name of the following compound.

ANS:
(S)-2-chloro-4-methylpentane

3. Provide the IUPAC name of the following compound (shown as a Fischer projection).

ANS:
(S)-2-fluorobutane

Brown Organic Chemistry 6e Test Bank 11

 4. Provide the IUPAC name of the following compound (shown as a Fischer projection).

ANS:
(S)-2-iodopentane

5. What is the structure of all of the monobrominated products, including regioismers and stereoisomers,
obtained from the following reaction?

ANS:

6. What is the structure of all of the monobrominated products, including regioismers and stereoisomers,
obtained from the following reaction?

ANS:

7. What is the major organic product obtained from the following reaction?

ANS:

Brown Organic Chemistry 6e Test Bank 12

 8. What is the major organic product obtained from the following reaction?

ANS:

9. What is the major organic product obtained from the following reaction?

ANS:

10. What is the major organic product obtained from the following reaction?

ANS:

11. Provide neatly drawn resonance structures of the key intermediate in the following reaction.

Brown Organic Chemistry 6e Test Bank 13

 ANS:

12. What is the structure of the key intermediate in the following reaction?

ANS:

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