306 Chapter 8 Alkyl Halides and Elimination Reactions

Alkenes
8.28 Which double bonds in the following natural products can exhibit stereoisomerism? Farnesene is found in the waxy coating of
apple skins and geranial is isolated from lemon grass.

a. b. CHO

farnesene geranial

8.29 Label each pair of alkenes as constitutional isomers, stereoisomers, or identical.

CH3 CH2
a. and c. and

H CH3
CH3CH2 CH3 CH3CH2 CH2CH3 C C
CH3 H
b. C C and C C d. and
CH3 CH2CH3 CH3 CH3

CH3 CH3

8.30 Draw all isomers of molecular formula C2H2BrCl. Label pairs of diastereomers and constitutional isomers.
8.31 PGF2α is a prostaglandin, a group of compounds that are responsible for inrammation (Section 19.6). (a) How many tetrahedral
stereogenic centers does PGF2α contain? (b) How many double bonds can exist as cis and trans isomers? (c) Considering both
double bonds and tetrahedral stereogenic centers, what is the maximum number of stereoisomers that can exist for PGF2α?
OH

CH2CH CH(CH2)3COOH

HO CH CHCH(OH)(CH2)4CH3
PGF2α

8.32 Rank the alkenes in each group in order of increasing stability.

CH3CH2 H CH3CH2 CH3
a. CH2 CHCH2CH2CH3 C C C C
H CH3 H H

b. CH2 C(CH3)CH2CH3 CH2 CHCH(CH3)2 (CH3)2C CHCH3

8.33 ∆H° values obtained for a series of similar reactions are one set of experimental data used to determine the relative stability of
alkenes. Explain how the following data suggest that cis-2-butene is more stable than 1-butene (Section 12.3A).

CH2 CHCH2CH3 + H2 CH3CH2CH2CH3 ∆H° = –127 kJ/mol

1-butene

CH3 CH3
C C + H2 CH3CH2CH2CH3 ∆H° = –120 kJ/mol
H H
cis-2-butene

E2 Reaction
8.34 Draw all constitutional isomers formed in each E2 reaction and predict the major product using the Zaitsev rule.
Cl I CH3
(CH3)3CO– –
OH –
OH
a. c. e. I

–
DBU OC(CH3)3 Br –
OH
Cl
b. d. f.
Cl
O O

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 Problems 307

8.35 For each of the following alkenes, draw the structure of two different alkyl halides that yield the given alkene as the only product
of dehydrohalogenation.

a. (CH3)2C CH2 b. CH CH2 c.

8.36 Explain why (CH3)2CHCH(Br)CH2CH3 reacts faster than (CH3)2CHCH2CH(Br)CH3 in an E2 reaction, even though both alkyl
halides are 2°.
8.37 Consider the following E2 reaction.
–OC(CH )
3 3
Br (CH3)3COH

a. Draw the by-products of the reaction and use curved arrows to show the movement of electrons.
b. What happens to the reaction rate with each of the following changes? [1] The solvent is changed to DMF.
[2] The concentration of –OC(CH3)3 is decreased. [3] The base is changed to –OH. [4] The halide is changed to
CH3CH2CH2CH2CH(Br)CH3. [5] The leaving group is changed to I–.
8.38 Dehydrohalogenation of 1-chloro-1-methylcyclopropane affords two alkenes (A and B) as products. Explain why A is the major
product despite the fact that it contains the less substituted double bond.

K+ –OC(CH3)3 +
CI
A B
1-chloro-1-methyl-
cyclopropane

8.39 What is the major stereoisomer formed in each reaction?

H
KOH NaOCH2CH3
a. CH3CH2CH2 C b.
Br Cl

E1 Reaction
8.40 What alkene is the major product formed from each alkyl halide in an E1 reaction?
CH3
Br
Cl Cl
a. b. c.
CH3

E1 and E2
8.41 Draw all constitutional isomers formed in each elimination reaction. Label the mechanism as E2 or E1.
– –
OCH3 I OC(CH3)3 –
OH
a. c. e. Cl
Br

CH3OH CH2CH2CH3 H2O –

OH
b. d. Cl f.
Br
CH3 Cl

8.42 Rank the alkyl halides in each group in order of increasing E2 reactivity. Then do the same for E1 reactivity.
CH3

a. b. CH3 Br
Br Cl
Br Cl CH3
Br

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 308 Chapter 8 Alkyl Halides and Elimination Reactions

8.43 Which elimination reaction in each pair is faster?

CH3 Cl
–
OH H2O –
OH
a. Cl b. c. (CH3)3CCl
H2O

CH3 Cl Cl H2O –OH

–OH
(CH3)3CCl
DMSO

8.44 In the dehydrohalogenation of bromocyclodecane, the major product is cis-cyclodecene rather than trans-cyclodecene. Offer
an explanation.
8.45 Explain the following observation. Treatment of alkyl chloride A with NaOCH2CH3 yields only one product B, whereas treatment
of A with very dilute base in CH3CH2OH yields a mixture of alkenes B and C, with C predominating.
Cl

A B C

Stereochemistry and the E2 Reaction

8.46 What is the major E2 elimination product formed from each halide?
CH3 Br C6H5
C6H5 Br H CH3 CH3 H
a. b. c.

H CH2CH3 C6H5 CH3 CH3 Br

CH3 CH2CH3 CH2CH3

8.47 Taking into account anti periplanar geometry, predict the major E2 product formed from each starting material.
Cl Cl D D

a. b. c. d.
CH3 CH3 Cl Cl
CH(CH3)2 CH(CH3)2 D D

8.48 a. Draw three-dimensional representations for all stereoisomers of 2-chloro-3-methylpentane, and label pairs of enantiomers.
b. Considering dehydrohalogenation across C2 and C3 only, draw the E2 product that results from each of these alkyl halides.
How many different products have you drawn?
c. How are these products related to each other?

8.49 Which stereoisomer—cis- or trans-1-bromo-3-tert-butylcyclohexane—will react faster in an E2 elimination reaction? Offer an

explanation.

Alkynes
8.50 Draw the products of each reaction.
CH2CHCl2 NaNH2 CI
NaNH2
a. (2 equiv)
c. CH3 C CH2CH3
(excess)
CI

CH3 H H
NaNH2 NaNH2
b. CH3CH2 C CHCH2Br d. C C
(2 equiv) (2 equiv)
CH3 Br Cl Cl

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 Problems 309

8.51 Draw the structure of a dihalide that could be used to prepare each alkyne. There may be more than one possible dihalide.
CH3
a. CH3C CCH3 b. CH3 C C CH c. C C
CH3

8.52 Under certain reaction conditions, 2,3-dibromobutane reacts with two equivalents of base to give three products, each of which
contains two new π bonds. Product A has two sp hybridized carbon atoms, product B has one sp hybridized carbon atom, and
product C has none. What are the structures of A, B, and C?

SN1, SN2, E1, and E2 Mechanisms

8.53 For which reaction mechanisms—SN1, SN2, E1, or E2—are each of the following statements true? A statement may be true for
one or more mechanisms.
a. The mechanism involves carbocation intermediates.
b. The mechanism has two steps.
c. The reaction rate increases with better leaving groups.
d. The reaction rate increases when the solvent is changed from CH3OH to (CH3)2SO.
e. The reaction rate depends on the concentration of the alkyl halide only.
f. The mechanism is concerted.
g. The reaction of CH3CH2Br with NaOH occurs by this mechanism.
h. Racemization at a stereogenic center occurs.
i. Tertiary (3°) alkyl halides react faster than 2° or 1° alkyl halides.
j. The reaction follows a second-order rate equation.
8.54 Draw the organic products formed in each reaction.

– CH2CH3 – Cl Cl
Br OC(CH3)3 OC(CH3)3 KOC(CH3)3
a. e. h.
Br (2 equiv)
DMSO

–
Br I
OCH2CH3 CH3CH2OH CH3CH2OH
b. I f. CH2CH3 i.

Cl –NH
2
2 NaNH2 H2O
c. CH3 C CH3 g. (CH3)2CH CHCH2Br j.
(2 equiv) Cl
Cl Br

Br DBU
d.

8.55 What is the major product formed when each alkyl halide is treated with each of the following reagents: [1] NaOCOCH3;
[2] NaOCH3; [3] KOC(CH3)3? If it is not possible to predict the major product, identify the products in the mixture and the
mechanism by which each is formed.
Cl
a. CH3Cl b. c. Cl d. Cl

8.56
(CH3)3C Br (CH3)3C Br

cis-1-bromo-4-tert-butylcyclohexane trans-1-bromo-4-tert-butylcyclohexane

a. The cis and trans isomers of 1-bromo-4-tert-butylcyclohexane react at different rates with KOC(CH3)3 to afford the same
mixture of enantiomers A and B. Draw the structures of A and B.
b. Which isomer reacts faster with KOC(CH3)3? Offer an explanation for this difference in reactivity.
c. Reaction of cis-1-bromo-4-tert-butylcyclohexane with NaOCH3 affords C as the major product, whereas reaction of
trans-1-bromo-4-tert-butylcyclohexane affords D as the major product. Draw the structures for C and D.
d. The cis and trans isomers react at different rates with NaOCH3. Which isomer reacts faster? Offer an explanation for the
difference in reactivity.
e. Why are different products formed from these alkyl halides when two different alkoxides are used as reagents?

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 310 Chapter 8 Alkyl Halides and Elimination Reactions

8.57 Draw all products, including stereoisomers, in each reaction.

Cl H CH3
–
OH CH3OH CH3COO–
a. c. e. Br
Cl
C6H5
Cl H
H 2O Br
b. d. NaOH f. KOH

Cl
D

8.58 Draw all of the substitution and elimination products formed from the following alkyl halide with each reagent. Indicate the
stereochemistry around the stereogenic centers present in the products, as well as the mechanism by which each product is
formed.

Cl a. CH3OH b. KOH

8.59 The following reactions do not afford the major product that is given. Explain why this is so, and draw the structure of the major
product actually formed.
CH3 CH3 CH3
–OC(CH ) –
3 3 Cl OH
a. Br OC(CH3)3 c.

–OCH
b. Br 3
d. I–

Cl

8.60 Draw a stepwise, detailed mechanism for each reaction.

CH3CH2OH
a. + + + HCl
Cl OCH2CH3

CH3 CH3 CH2

–OH
b. Cl + + H2O + Cl–

8.61 Draw the major product formed when (3R)-1-chloro-3-methylpentane is treated with each reagent: (a) NaOCH2CH3; (b) KCN;
(c) DBU.
8.62 Draw a stepwise, detailed mechanism for the following reaction.

H H H H
OH
H 2O
Br OH + + + HBr

H H H H

8.63 Explain why the reaction of 2-bromopropane with NaOCOCH3 gives (CH3)2CHOCOCH3 exclusively as product, but the reaction
of 2-bromopropane with NaOCH2CH3 gives a mixture of (CH3)2CHOCH2CH3 (20%) and CH3CH – – CH2 (80%).
8.64 Draw a stepwise detailed mechanism that illustrates how four organic products are formed in the following reaction.
CI OCH3

CH3OH
+ + + + HCI
OCH3

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 Problems 311

Challenge Problems
8.65 Although there are nine stereoisomers of 1,2,3,4,5,6-hexachlorocyclohexane, one stereoisomer reacts 7000 times more slowly
than any of the others in an E2 elimination. Draw the structure of this isomer and explain why this is so.
8.66 Explain the selectivity observed in the following reactions.
Br CH3
H CH3 H Br H
– –
O CH3O O O CH3O O
O O O O
H H H H

8.67 Draw a stepwise mechanism for the following reaction. The four-membered ring in the starting material and product is
called a β-lactam. This functional group confers biological activity on penicillin and many related antibiotics, as is
discussed in Chapter 22. (Hint: The mechanism begins with β elimination and involves only two steps.)
H H
N N S
C6H5O S DBN C6H5O
O N O N
O O O
C
CH2Cl
β-lactam O

8.68 Although dehydrohalogenation occurs with anti periplanar geometry, some eliminations have syn periplanar geometry. Examine
the starting material and product of each elimination, and state whether the elimination occurs with syn or anti periplanar
geometry.
H D CH3 CH3 CH3 H
D ∆ Zn
a. b. C C C C
SeOC6H5 H H H CH3
Br Br

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