Chapter 11Homework and practice questions

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

SHORT ANSWER
Exhibit 11-1
Circle your response in each set below.
1.

Circle the least reactive compound in an SN2 reaction.

ANS:

2.

Circle the best leaving group in an elimination reaction.

ANS:

3.

Circle the best nucleophile in a substitution reaction at a primary carbon.

ANS:

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

4.

Circle the least reactive compound in an SN1 reaction.

ANS:

5.

Circle the best solvent for an SN2 reaction.

ANS:

Exhibit 11-2
Consider the pair of reactions below to answer the following question(s).
a.

or
b.

6.
a.
b.

Refer to Exhibit 11-2.

Which reaction would be predicted to be faster?
Explain your answer to the question in part a.

ANS:
a. b
b. SH is a better nucleophile than OH because nucleophilicity usually increases in going
down a column of the periodic table and sulfur is below oxygen in group 6A.
7. How do you define a chiral carbon?

Chapter 11

8.
a.
b.
c.
d.

Refer to Exhibit 11-2. The mechanism for these reactions is:

S N1
S N2
E1
E2

ANS:
b
Exhibit 11-3
Consider the pair of reactions below to answer the following question(s).
a.
or
b.

9.
a.
b.

Refer to Exhibit 11-3.

Which reaction above is faster?
Explain your answer to the question in part a.

ANS:
a.
b.

10.

a
The conversion of tert-butyl chloride to tert-butyl alcohol proceeds faster in 70% H2O/30%
CH3OH than in 50% H2O/50% acetone because SN1 reactions are faster in more polar
solvents. Acetone (dielectric polarization, P = 20.7) is less polar than CH3OH (P =
33.6), and the percentage of H2O is higher in the water/methanol system.
The original question has been combined with question #9 as part b. This placeholder
question is here to maintain the integrity of the numbering system between the printed copy
and ExamView. Therefore, it has been marked "do not use on test" in ExamView's question
information dialog. As a result, this placeholder question is automatically prevented from
being chosen as a test question.

ANS:
Answer not provided.
11.
a.
b.

Refer to Exhibit 11-3. The kinetics of these reactions are:

second-order
first-order in nucleophile

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

c.
d.

not measurable
first-order in alkyl halide

ANS:
d
Exhibit 11-4
Consider the pair of reactions below to answer the following question(s).
a.

or
b.

12.
a.
b.
c.
d.

Refer to Exhibit 11-4. The alkyl bromide starting materials in these reactions are classified
as:
3
2
1
4

ANS:
c
13.
a.
b.
c.
d.

Refer to Exhibit 11-4. The solvent in these reactions is:

nonpolar aprotic
polar aprotic
polar protic
nonpolar protic

ANS:
b
14.
a.
b.
c.
d.

Refer to Exhibit 11-4. The nucleophile in these reactions is:

K+
alkyl group
Br
I

ANS:
d

Chapter 11

15.

Refer to Exhibit 11-4. Which reaction is faster?

ANS:
b
16.
a.
b.
c.
d.

Refer to Exhibit 11-4. The mechanism for these reactions is:

S N2
E2
S N1
E1

ANS:
a
Exhibit 11-5
Consider the pair of reactions below to answer the following question(s).
a.

or
b.

17.
a.
b.

Refer to Exhibit 11-5.

Which reaction above is faster?
Explain your answer to the question in part a.

ANS:
a. b
b. Tosylate anion is a better leaving group than amide ion; tosylate is the weak conjugate base of
a strong acid, while amide is the strong conjugate base of a weak acid.

18.

The original question has been combined with question #17 as part b. This placeholder
question is here to maintain the integrity of the numbering system between the printed copy
and ExamView. Therefore, it has been marked "do not use on test" in ExamView's question
information dialog. As a result, this placeholder question is automatically prevented from
being chosen as a test question.

ANS:
Answer not provided.

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

19.
a.
b.
c.
d.

Refer to Exhibit 11-5. Doubling the concentration of potassium hydroxide in these reactions:
causes the reaction mechanism to change
halves the rate of reaction
has no effect on the rate of reaction
doubles the rate of reaction

ANS:
d
20.
a.
b.
c.
d.

Refer to Exhibit 11-5. The mechanism for these reactions is:

S N2
E2
S N1
E1

ANS:
b
Exhibit 11-6
Consider the reaction below to answer the following question(s).

21.

Refer to Exhibit 11-6. The substrate in the reaction is:

ANS:
A
22.
a.
b.
c.
d.

Refer to Exhibit 11-6. Compound B is the:

SN2 product
SN1 product
E2 product
E1 product

ANS:
b
23.

Refer to Exhibit 11-6. Compound C is the:

Chapter 11

a.
b.
c.
d.

SN2 product
SN1 product
E2 product
E1 product

ANS:
d
24.

Refer to Exhibit 11-6. Write the complete reaction mechanism for the formation of
Compound C in this reaction.

ANS:

Exhibit 11-7
To answer the following question(s) consider the data below:
Reaction of bromomethane with sodium hydroxide in water forms methanol. If sodium iodide is
added to the reaction mixture, the rate of methanol formation is dramatically increased (i.e. sodium
iodide is a catalyst).
25.
a.
b.
c.
d.

Refer to Exhibit 11-7. The mechanism involved in the reaction of CH3Br and NaOH is:
S N1
S N2
E1
E2

ANS:
b
26.

Refer to Exhibit 11-7. Write a reaction pathway that accounts for the effect of added NaI.

ANS:

27.

Refer to Exhibit 11-7. Draw a reaction energy diagram showing the two different reaction
pathways (i.e. catalyzed and uncatalyzed). Indicate structures for all energy minima in the
diagram.

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

ANS:

28.

Refer to Exhibit 11-7. Explain why adding NaI increases the reaction rate.

ANS:
Iodide is a better nucleophile than hydroxide so we expect reaction between CH3Br and iodide to
proceed faster than the reaction between CH3Br and hydroxide. CH3I is a more reactive alkyl
halide than CH3Br because iodide is a better leaving group than bromide so when CH3I forms it
reacts with hydroxide faster than CH3Br to form CH3OH. The overall result is faster formation of
CH3OH from CH3Br when NaI is added.
29.

Refer to Exhibit 11-7. Would you expect the same catalytic effect on this reaction if you
added NaCl instead? Explain your answer.

ANS:
No. Chloride ion is a poorer nucleophile as well as a poorer leaving group than bromide ion.
Exhibit 11-8
Consider the reaction below to answer the following question(s):

Chapter 11

30.

Refer to Exhibit 11-8. Write the product that results from the electron flow in the reaction,
clearly indicating any stereochemistry.

ANS:

31.

Refer to Exhibit 11-8. Draw a Newman projection of the reactive conformation of the
starting material.

ANS:

32.
a.
b.
c.
d.

Refer to Exhibit 11-8. The mechanism of this reaction is:

S N1
S N2
E1
E2

ANS:
d
Exhibit 11-9
Consider the reaction below to answer the following question(s).

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

33.

Refer to Exhibit 11-9. Write the complete stepwise mechanism for this reaction. Clearly
show the formation of both products. Show all electron flow with arrows and draw all
intermediate structures.

ANS:

34.
a.
b.
c.
d.

Refer to Exhibit 11-9. This reaction obeys a rate law of the form:
rate = k[RCl][CH3CH2OH]
rate = k[RCl][H2O][CH3CH2OH]
rate = k[RCl]
rate = k[RCl][H2O]

ANS:
c
Exhibit 11-10
Draw the structure of the major organic product(s) for each of the following reactions. Indicate the
stereochemistry for each reaction when appropriate.

35.
ANS:

10

Chapter 11

36.
ANS:

37.
ANS:

38.
ANS:

39.
ANS:

11

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

40.
ANS:

41.
ANS:

42.
ANS:

43.
ANS:

44.
ANS:

12

Chapter 11

PRACTICE QUESTIONS
Exhibit 11-11
Consider the reaction below to answer the following question(s).

45.

Refer to Exhibit 11-11. List all chirality centers in the starting material by number.

ANS:
Carbon 2 is a chirality center.
46.

Refer to Exhibit 11-11. As indicated by the carbon numbers, during the course of this
reaction the bond between the nitrogen atom and carbon 3 is broken and a bond between the
nitrogen atom and carbon 2 is formed. On the structures provided below, draw arrows
showing electron flow for the mechanism that accounts for these bonding changes.

ANS:

47.

Refer to Exhibit 11-11. If the absolute configuration at carbon 2 in the starting material is R,
what is the absolute configuration at carbon 2 in the product?

ANS:
The absolute configuration at carbon 2 in the product is S because an intramolecular SN2 reaction
occurred in the first step of the reaction to invert the configuration at that carbon.

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Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

Exhibit 11-12
For each substrate below, choose which reaction type is favored. Place the letter of the reaction
type in the blank to the left of the substrate.
a.
b.
c.
d.

S N1
S N2
E1
E2

48.

______

ANS:
b

49.

______

ANS:
d
50.

For the substitution reaction:

Draw the structure present at the point indicated by the asterisk (*) on the following energy
diagram. Identify the reactant as R or S or neither.

14

Chapter 11

ANS:

The reactant is the R enantiomer.

51.

For the substitution reaction:

Draw the structure present at the point indicated by the asterisk (*) on the following energy
diagram.

15

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

ANS:

52.

For the elimination reaction:

Draw the structure present at the point indicated by the asterisk (*) on the following energy
diagram.

16

Chapter 11

ANS:

53.

For the elimination reaction:

Draw the structure present at the point indicated by the asterisk (*) on the following energy
diagram

ANS:

17

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

MULTIPLE CHOICE
1.

Consider the two lines shown on the energy diagram below.

In an SN2 reaction, these compare the effect of the:

a. substrate.
b. nucleophile.
c. leaving group.
d. solvent.
e. nucleophile or solvent
f. substrate or leaving group
ANS: F
2.

Consider the two lines shown on the energy diagram below.

In an SN2 reaction,
a. the upper left line could represent Cl and the lower left line I.
b. the upper left line could represent OH and the lower left line CH3COO .
c. the upper left line could represent H2O and the lower left line H2S.
d. the upper left line could represent (CH3)2NH and the lower left line (CH3)2N.
ANS: B

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Chapter 11

3.

Consider the two energy diagrams below for an SN2 reaction.

A

Which of the following is correct?:

a. The change in the variable shown in A affects the transition state while that of B affects
the reactant.
b. The change in the variable shown in A affects the reactant while that of B affects the
transition state.
c. The changes in the variables shown in both A and B affect the transition state.
d. The changes in the variables shown in both A and B affect the reactants.
ANS: A
4.

Consider the two lines shown on the energy diagram below.

In an SN2 reaction, these lines could compare the effect of which of the following solvents?
a. CH3OH and CH3CH2OH
c. CH3OH and CH3CN
b. CH3OH and H2O
d. DMSO and CH3CN
ANS: C

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Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

5.

Consider the two energy diagrams labeled A and B given below.

A

Which of the following is correct with respect to these diagrams?

a. A represents an SN2 reaction.
b. B represents an SN1 reaction.
c. B represents an SN2 reaction.
d. A represents an SN1 reaction.
e. both a and b
f. both c and d
ANS: F
6.

20

Consider the substitution reaction:

Chapter 11

The product(s) of the reaction is(are):

a. R enantiomer

e. S enantiomer

b. S enantiomer

f.

R enantiomer

c. An equimolar mixture of a and b.

g. An equimolar mixture of e and f
d. A mixture of the major product a with the h. A mixture of the major product f with the
minor product b.
minor product e.
ANS: C
7.

Consider the substitution reaction:

The product(s) of the reaction is(are):

a. S enantiomer

e. R enantiomer

21

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

b. R enantiomer

f.

c.

g.
A equimolar mixture of a and b.

d.

S enantiomer

A equimolar mixture of e and f.

h.

A mixture of the major product a with the

minor product b.

A mixture of the major product f with the

minor product e.

ANS: B
8.

Consider the two energy diagrams given below.

A

Which of the following is correct with respect to these diagrams?

a. A could represent an E2 reaction.
b. B could represent an E1 reaction.
c. A could represent an E1cb reaction.
ANS: C
9.

Consider the elimination reaction:

The product(s) of the reaction is(are):

a.

22

Chapter 11

b.

c. An equimolar mixture of a and b.

d. A mixture of the major product a with the minor product b.
e. A mixture of the major product b with the minor product a.
ANS: D
10.

Consider the elimination reaction:

The product(s) of the reaction is(are):

a.
b.
c. An equimolar mixture of a and b.
d. A mixture of the major product a with the minor product b.
e. A mixture of the major product b with the minor product a.
ANS: D
11.
a.
b.
c.
d.

Nucleophilic substitution and elimination reactions often complete with one another. In
general, which of the following would enhance the rate of the E2 reaction over the SN2
reaction?
use of a weak nucleophile
branching at the or carbon
use of a weak base
All of the above would enhance the E2 rate.

ANS: B

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