CHAPTER 9NUCLEOPHILIC SUBSTITUTION AND -ELIMINATION

MULTIPLE CHOICE
1. Which of the following reactions corresponds to a substitution?
a. propene 1,2-dibromopropane
b. 1-iodopropane propene
c. propene propane
d. 1-iodopropane 1-bromopropane
ANS: D
2. Which of the following reactions corresponds to a substitution?
a. tert-butanol tert-butyl chloride
b. tert-butanol 2-methylpropene
c. 3,3-dimethyl-2-butanol 2,3-dimethyl-2-butene
d. cyclohexene 1,2-dichlorocyclohexane
ANS: A
3. Which of the following statements related to SN1 reactions is not true?
a. The heterolysis of a bond between atoms which do not bear formal charges always
produces a cation and an anion
b. The charged carbon atom of a carbocation has a complete octet of valence shell electrons
c. Carbocations are Lewis acids
d. Nucleophiles seek centers of low electron density
ANS: B
4. Which of the following statements related to SN1 reactions is not true?
a. The SN1 reaction can be described as a heterolytic bond cleavage followed by nucleophilic
attack
b. Carbocations are electrophilic
c. The charged carbon atom of a carbocation has an unfilled valence shell
d. Nucleophiles are Lewis acids
ANS: D
5. What is the equation for the rate of formation of tert-butyl alcohol from the reaction of tert-butyl
bromide (t-BuBr) with water by an SN1 mechanism?
a. Rate = k [t-BuBr]
b. Rate = k [t-BuBr][H2O]
c. Rate = k [H2O]
d. Rate = k [t-BuBr]2
ANS: A
6. What is the equation for the rate of formation of 1-iodobutane from the reaction of 1-chlorobutane
(BuCl) with NaI by an SN2 mechanism?
a. Rate = k [BuCl]
b. Rate = k [BuCl][NaI]
c. Rate = k [NaI]
d. Rate = k [BuCl]2

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ANS: B
7. What is the equation for the rate of formation of 2-methoxypropane, (CH3CH(OCH3)CH3, from the
reaction of 2-bromopropane (i-PrBr) with sodium methoxide (NaOCH3)?
a. Rate = k [i-PrBr]
b. Rate = k [i-PrBr]2
c. Rate = k [NaOCH3]
d. Rate = k [i-PrBr][NaOCH3]
ANS: D
8. What is the equation for the rate of formation of 2-methoxypropane, CH3CH(OCH3)CH3, from the
reaction of 2-bromopropane (i-PrBr) with methanol?
a. Rate = k [i-PrBr]
b. Rate = k [i-PrBr]2
c. Rate = k [CH3OH]
d. Rate = k [i-PrBr][CH3OH]
ANS: A
9. The reaction of methyl iodide with sodium azide, NaN3, proceeds by an SN2 mechanism. What is the
effect of doubling the concentration of NaN3 on the rate of the reaction?
a. the rate remains the same
b. the rate decreases by a factor of 2
c. the rate increases by a factor of 2
d. the rate increases by a factor of 4
ANS: C
10. The reaction of 1-bromopropane with sodium iodide gives 1-iodopropane. What is the effect of
doubling the concentration of NaI on the rate of the reaction?
a. the rate remains the same
b. the rate decreases by a factor of 2
c. the rate increases by a factor of 2
d. the rate increases by a factor of 4
ANS: C
11. The reaction of tert-butyl bromide, (CH3)3CBr, with methanol in an inert solvent proceeds by an SN1
mechanism to give tert-butyl methyl ether, (CH3)3COCH3. What is the effect of doubling the
concentration of methanol on the rate of the reaction?
a. the rate remains the same
b. the rate decreases by a factor of 2
c. the rate increases by a factor of 2
d. the rate increases by a factor of 4
ANS: A
12. The reaction of tert-butyl chloride, (CH3)3CCl, with water in an inert solvent gives tert-butyl alcohol,
(CH3)3COH. What is the effect of doubling the concentration of water on the rate of the reaction?
a. the rate remains the same
b. the rate decreases by a factor of 2
c. the rate increases by a factor of 2
d. the rate increases by a factor of 4
ANS: A

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13. Which of the following alkyl halides undergoes the fastest SN2 reaction with sodium azide, NaN3?
a. 1-fluorohexane
b. 1-chlorohexane
c. 1-bromohexane
d. 1-iodohexane
ANS: D
14. Which of the following alkyl halides undergoes the fastest SN2 reaction with sodium cyanide, NaCN?
a. methyl iodide
b. ethyl iodide
c. 2-iodopropane
d. tert-butyl iodide
ANS: A
15. Which of the following alkyl halides undergoes the fastest SN2 reaction with sodium methylthiolate,
NaSMe?
a. methyl iodide
b. ethyl iodide
c. 2-bromopropane
d. tert-butyl chloride
ANS: A
16. Which of the following alkyl halides undergoes the fastest solvolysis reaction with formic acid,
HCOOH?
a. tert-butyl fluoride
b. tert-butyl chloride
c. tert-butyl bromide
d. tert-butyl iodide
ANS: D
17. Which of the following alkyl halides undergoes the fastest solvolysis reaction with methanol, CH3OH?
a. methyl chloride
b. ethyl chloride
c. 2-chloropropane
d. tert-butyl chloride
ANS: D
18. Which of the following alkyl halides undergoes the fastest solvolysis reaction with ethanol,
CH3CH2OH?
a. methyl fluoride
b. ethyl bromide
c. 2-chloropropane
d. tert-butyl bromide
ANS: D
19. Which of the following is best set of conditions for the preparation of tert-butanol?
a. tert-butyl fluoride in water
b. tert-butyl bromide in water
c. tert-butyl fluoride and NaOH in DMSO
d. tert-butyl bromide and NaOH in DMSO

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ANS: B
20. Which of the following is the best set of conditions for the preparation of tert-butyl methyl ether?
a. tert-butyl fluoride and NaOCH3 in CH3OH
b. methanol and sodium tert-butoxide in tert-butanol
c. fluoromethane and sodium tert-butoxide in tert-butanol
d. tert-butyl bromide and CH3OH
ANS: D
21. What is the major product formed upon treatment of (R) 1-bromo-4-methylhexane with sodium
cyanide?
a. (R) 1-cyano-4-methylhexane
b. (S) 1-cyano-4-methylhexane
c. (R) 4-methyl-1-hexene
d. (S) 4-methyl-1-hexene
ANS: A
22. What is the major product formed upon treatment of (R) 2-bromohexane with sodium cyanide?
a. (R) 2-cyanohexane
b. (S) 2-cyanohexane
c. 1-hexene
d. 2-hexene
ANS: B
23. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B

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

a.
b.
c.
d.

1
2
3
4

ANS: A
25. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: A
26. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B

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

a.
b.
c.
d.

1
2
3
4

ANS: C
28. What is the major organic product(s) obtained from the following reaction?

a.
b.
c.
d.

1-hexyne
2-hexyne
propene + propyne
propane + propyne

ANS: B
29. What is the major organic product(s) obtained from the following reaction?

a.
b.
c.
d.

3-methyl-1-pentyne
3-methyl-2-pentyne
1-propene + propyne
4-methyl-2-pentene

ANS: C

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30. What is(are) the major organic product(s) obtained from the following substitution reaction?

a.
b.
c.
d.

only 1
only 2
only 3
a mixture of 1 and 2

ANS: A
31. What is(are) the major organic product(s) obtained from the following substitution reaction?

a.
b.
c.
d.

only 1
only 2
only 3
a mixture of 1 and 2

ANS: D
32. What is(are) the major organic product(s) obtained from the following substitution reaction?

a.
b.
c.
d.

only 1
only 2
only 1 and 2
1, 2 and 3

ANS: D

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33. What is(are) the major organic product(s) obtained from the following substitution reaction?

a.
b.
c.
d.

only 1
only 2
only 1 and 2
1, 2 and 3

ANS: D
34. In which of the following solvents would the reaction of 1-bromobutane with sodium azide, NaN3,
proceed the fastest?
a. acetic acid
b. ethanol
c. water
d. acetonitrile
ANS: D
35. Which of the following solvents is the best choice for the reaction of 1-chlorohexane with sodium
bromide?
a. dimethylsulfoxide
b. water
c. hexane
d. toluene, PhCH3
ANS: A
36. Which of the following solvents is the best choice for the reaction of 1-chlorohexane with sodium
bromide?
a. water
b. N,N-dimethylformamide
c. hexane
d. toluene, PhCH3
ANS: B
37. Which of the following anions is the most nucleophilic in polar protic solvents?
a. F
b. Cl
c. Br
d. I
ANS: D

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38. Which of the following anions is the most nucleophilic in polar aprotic solvents?
a. F
b. Cl
c. Br
d. I
ANS: A
39. Which of the following compounds is the most nucleophilic in polar protic solvents?
a. H2O
b. NH3
c. H2S
d. PH3
ANS: D
40. Which of the following is the most nucleophilic?
a. sodium ethoxide
b. acetic acid
c. methanol
d. water
ANS: A
41. Which of the following anions is the best leaving group in an SN1 reaction?
a. F
b. HO
c. NH2
d. Cl
ANS: D
42. Which of the following is the best leaving group in an SN2 reaction?
a. F
b. H3C
c. CH3O2SO
d. HO
ANS: C
43. Which of the following statements is true regarding the reactivity of 1 and 2 with potassium tertbutoxide?

a.
b.
c.
d.

1 reacts faster than 2

1 and 2 give different dehydrochlorinated products
2 reacts by elimination whereas 1 reacts by substitution
1 reacts by elimination whereas 2 reacts by substitution

ANS: A

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44. What is the major elimination product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B
45. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: A
46. Which of the following alkyl bromides reacts the slowest with NaSCH3 in DMF?

a.
b.
c.
d.

1
2
3
4

ANS: A

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47. Which of the following is most likely to undergo rearrangement during reaction with methanol?

a.
b.
c.
d.

1
2
3
4

ANS: B
48. Which of the following compounds undergoes the most rapid hydrolysis reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B
49. Which of the following statements is not true regarding the SN2 reaction of (R)-2-bromobutane with
sodium cyanide?
a. the reaction proceeds with inversion of configuration
b. the rate is proportional to the concentration of sodium cyanide
c. the rate is proportional to the concentration of (R)-2-bromobutane
d. the rate of the reaction is independent of the identity of the solvent
ANS: D
50. Which of the following statements is true regarding the reaction of tert-butyl bromide with water?
a. the rate is proportional to the concentration of tert-butyl bromide
b. the rate is proportional to the concentration of water
c. the rate is independent of the identity of the solvent
d. the rate of the reaction is independent of the temperature
ANS: A
51. Which of the following is not a characteristic of SN2 reactions?
a. the electrophilic carbon undergoes inversion of stereochemistry
b. the rate is proportional to the concentration of substrate
c. the rate is proportional to the concentration of nucleophile
d. the rate is independent of the solvent
ANS: D

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52. Which of the following is not a characteristic of SN1 reactions?

a. the electrophilic carbon undergoes inversion of stereochemistry
b. the rate is proportional to the concentration of substrate
c. the reaction proceeds faster in a more polar solvent
d. the rate is independent of the concentration of nucleophile
ANS: A
53. What is the role of tetrabutylammonium chloride as a phase transfer catalyst in the reaction of 1chlorooctane and sodium cyanide in a mixture of water and CH2Cl2?
a. it transfers 1-chlorooctane into the aqueous phase
b. it transfers cyanide anion into the organic phase
c. it makes water and dichloromethane miscible
d. it transfers the sodium cation into the organic phase
ANS: B
54. Which of the following statements is not true regarding SN2 reactions?
a. A carbocation intermediate is formed.
b. The mechanism has only one step.
c. Aprotic solvents are good choices for SN1 reactions.
d. The stereochemical outcome is inversion at the carbon bearing the leaving group.
ANS: A
55. Which of the following statements is not true regarding SN1 reactions?
a. A carbocation intermediate is formed.
b. The mechanism has only one step.
c. Polar, protic solvents are good choices for SN1 reactions.
d. The stereochemical outcome is racemization at the carbon bearing the leaving group.
ANS: B
56. Which of the following energy diagrams represents the course of an exothermic SN1 reaction?

a.
b.
c.
d.

1
2
3
4

ANS: A

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57. Which of the following energy diagrams represents the course of an exothermic SN2 reaction?

a.
b.
c.
d.

1
2
3
4

ANS: C
58. Which of the following energy diagrams represents the course of an exothermic E2 reaction?

a.
b.
c.
d.

1
2
3
4

ANS: C
59. Which of the following energy diagrams represents the course of an exothermic E1 reaction?

a.
b.
c.
d.

1
2
3
4

ANS: A

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60. Which of the following represents the transition state of the rate-determining step in the SN1 reaction
between tert-butyl chloride and water?

a.
b.
c.
d.

1
2
3
4

ANS: B
61. Which of the following represents the transition state of the rate-determining step in the reaction
between tert-butyl bromide and methanol?

a.
b.
c.
d.

1
2
3
4

ANS: A

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62. Which of the following represents the transition state of the reaction between methyl iodide and
ammonia?

a.
b.
c.
d.

1
2
3
4

ANS: C
63. Which of the following represents the transition state of the reaction between methyl bromide and
sodium methylthiolate, NaSCH3?

a.
b.
c.
d.

1
2
3
4

ANS: D

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64. Which of the following represents the transition state of the rate-determining step in the reaction
between 2-bromopropane and sodium methoxide leading to elimination?

a.
b.
c.
d.

1
2
3
4

ANS: A
65. Which of the following represents the transition state of the rate-determining step in the reaction
between 2-chloropropane and sodium amide leading to elimination?

a.
b.
c.
d.

1
2
3
4

ANS: C

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66. Which of the following represents the transition state of the rate-determining step in the reaction
between tert-butyl bromide and methanol leading to elimination?

a.
b.
c.
d.

1
2
3
4

ANS: B
67. Which of the following represents the transition state of the rate-determining step in the reaction
between tert-butyl iodide and water leading to elimination?

a.
b.
c.
d.

1
2
3
4

ANS: A
68. Which of the following sets consists of only polar aprotic solvents?
a. water, hexane, methanol
b. acetic acid, DMF, toluene
c. DMSO, ethanol, acetonitrile
d. DMF, acetonitrile, DMSO

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ANS: D
69. Which of the following sets consists of only polar protic solvents?
a. water, DMF, DMSO
b. acetic acid, methanol, water
c. DMSO, ethanol, acetonitrile
d. DMF, acetonitrile, DMSO
ANS: B
70. Which of the following most favors elimination rather substitution in a reaction with 2-bromopropane?
a. sodium methoxide
b. sodium ethoxide
c. sodium isoproxide
d. sodium tert-butoxide
ANS: D
71. Which of the following most favors elimination rather substitution in a reaction with sodium
methoxide?
a. bromomethane
b. bromoethane
c. 1-bromopropane
d. 2-bromopropane
ANS: D
72. What is the best choice of reagent to perform the following transformation?

a.
b.
c.
d.

H2SO4
H2O
NaOCH3
KOtBu

ANS: D
73. What is the best choice of reagent to perform the following transformation?

a.
b.
c.
d.

H2SO4
H2O
NaOCH3
KOtBu

ANS: A

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PROBLEM
1. Draw all of the chloroalkanes that undergo base-promoted dehydrochlorination to form the following
alkene?

ANS:

2. Draw all of the chloroalkanes that undergo base-promoted dehydrochlorination to form the following
alkene?

ANS:

3. Draw all of the chloroalkanes that undergo base-promoted dehydrochlorination to form the following
alkene?

ANS:

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4. Draw all of the chloroalkanes that undergo base-promoted dehydrochlorination to form the following
alkene?

ANS:

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

ANS:

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

ANS:

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

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ANS:

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:
ANS
11. What is the major organic product obtained from the following reaction?

ANS:

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

ANS:

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

ANS:

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

ANS:

15. Provide a neatly drawn mechanism for the following reaction, including curved arrows to show the
movement of paris of electrons and the structure of reactive intermediates.

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ANS:
The reaction proceeds in three steps:
1. Dissociation by cleavage of the carbon-chlorine bond to afford a tertiary carbocation
2. Nucleophilic addition of water to the carbocation
3. Deprotonation of oxygen

16. Provide a neatly drawn mechanism for the following reaction, including curved arrows to show the
movement of paris of electrons and the structure of reactive intermediates.

ANS:
The reaction proceeds in a single step:
Concerted nucleohpilic attack on the electrophilic carbon atom with departure of bromide anion as the
leaving group.

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