148 CHAPTER 4 | Reactions of Alkenes and Alkynes

Additional Problems
N AMING A LKENES 4.27 Give IUPAC names for the following compounds:
AND A LKYNES
(a) H3C CH3 (b) CH2CH2CH3
H C C H CHCH2C CH
C C H C C
H3C H H3C H

(c) H CH3 (d) CH3

C C C HC CCH2C CCHCH3
H CH3

4.28 Draw structures corresponding to the following IUPAC names:

(a) 3-Ethylhept-1-yne (b) 3,5-Dimethylhex-4-en-1-yne
(c) Hepta-1,5-diyne (d) 1-Methylcyclopenta-1,3-diene
4.29 The following two hydrocarbons have been isolated from plants in the
sunflower family. Name them according to IUPAC rules.
(a) CH3CHPCHCqCCqCCHPCHCHPCHCHPCH2 (all trans)
(b) CH3CqCCqCCqCCqCCqCCHPCH2
4.30 Draw and name all the possible pentyne isomers, C5H8.
4.31 Draw and name the six possible diene isomers of formula C5H8. Which of
the six are conjugated dienes?
4.32 Draw three possible structures for each of the following formulas:
(a) C6H8 (b) C6H8O
P REDICT THE P RODUCTS 4.33 Predict the products of the following reactions. Indicate regioselectivity
where relevant. (The aromatic ring is inert to all the indicated reagents.)

H2/Pd
(a) ?
H
Br2
C H (b) ?
C

H HBr
(c) ?
Styrene KMnO4
(d)
NaOH, H2O
?

4.34 Using an oxidative cleavage reaction, explain how you would distinguish
between the following two isomeric cyclohexadienes:

and
 | Exercises 149

4.35 Formulate the reaction of cyclohexene with (i) Br2 and (ii) meta-chloro-
peroxybenzoic acid followed by H3Oⴙ. Show the reaction intermediates
and the final products with correct cis or trans stereochemistry.
4.36 What products would you expect to obtain from reaction of cyclohexa-
1,3-diene with each of the following?
(a) 1 mol Br2 in CH2Cl2 (b) 1 mol HCl
(c) 1 mol DCl (D ⫽ deuterium, 2H) (d) 2 mol H2 over a Pd catalyst
4.37 Predict the products of the following reactions on hex-1-yne:

(a) 1 equiv HBr (b) 1 equiv Cl2 (c) H2, Lindlar catalyst
? ? ?

4.38 Predict the products of the following reactions on dec-5-yne:

(a) H2, Lindlar catalyst (b) 2 equiv Br2 (c) H2O, H2SO4, HgSO4
? ? ?

4.39 Suggest structures for alkenes that give the following reaction products.
There may be more than one answer for some cases.
H2/Pd catalyst
(a) ? 2-Methylhexane

Br2 in CH2Cl2
(b) ? 2,3-Dibromo-5-methylhexane

HBr
(c) ? 2-Bromo-3-methylheptane

(d) CH3 HO OH
KMnO4, OH–
? CH3CHCH2CHCHCH2CH3
H2O

P REDICT THE R EACTANTS 4.40 Draw the structure of a hydrocarbon that reacts with only 1 equiva-
lent of H2 on catalytic hydrogenation and gives only pentanoic acid,
CH3CH2CH2CH2CO2H, on treatment with acidic KMnO4. Write the reac-
tions involved.
4.41 Give the structure of an alkene that yields the following keto acid on reac-
tion with KMnO4 in aqueous acid:

O O
KMnO4
? HOCCH2CH2CH2CH2CCH3
H O+
3
150 CHAPTER 4 | Reactions of Alkenes and Alkynes

4.42 What alkenes would you hydrate to obtain the following alcohols?

(a) OH (b) OH (c) OH

CH3CH2CHCH3
CH3

4.43 What alkynes would you hydrate to obtain the following ketones?

(a) CH3 O (b) O

CH3CHCH2CCH3 C
CH3

4.44 Draw the structure of a hydrocarbon that reacts with 2 equivalents of H2

on catalytic hydrogenation and gives only succinic acid on reaction with
acidic KMnO4.

O O
HOCCH2CH2COH Succinic acid

S YNTHESIS 4.45 In planning the synthesis of a compound, it’s as important to know what
not to do as to know what to do. What is wrong with each of the following
reactions?

(a) CH3 CH3

HBr
CH3C CHCH3 CH3CHCHCH3

Br

(b) H
OH
KMnO4
H2O, OH–
H
OH

(c) CH3 CH3 O

H2O, H2SO4
CH3CH2CHCH2C CH CH3CH2CHCH2CH2CH
HgSO4

4.46 How would you prepare cis-but-2-ene starting from propyne, an alkyl
halide, and any other reagents needed? (This problem can’t be worked in a
single step. You’ll have to carry out more than one reaction.)
4.47 Using but-1-yne as the only organic starting material, along with any
inorganic reagents needed, how would you synthesize the following com-
pounds? (More than one step may be needed.)
(a) Butane (b) 1,1,2,2-Tetrachlorobutane
(c) 2-Bromobutane (d) Butan-2-one (CH3CH2COCH3)
 | Exercises 151

R ESONANCE 4.48 Draw the indicated number of additional resonance structures for each of
the following substances:

(a) + (b) O (c) O –

O
C ⴚ H
H3C C

(two) (one) (two)

4.49 One of the following pairs of structures represents resonance forms, and
one does not. Explain which is which.

(a) + (b)
+
? ?

4.50 Draw three additional resonance structures for the benzyl cation.

+
CH2
Benzyl cation

4.51 In light of your answer to Problem 4.50, what product would you expect
from the following reaction? Explain.

+ HCl ?

P OLYMERS 4.52 Plexiglas, a clear plastic used to make many molded articles, is made by
polymerization of methyl methacrylate. Draw a representative segment of
Plexiglas.

H 2C C
C OCH3 Methyl methacrylate
CH3

4.53 What monomer unit might be used to prepare the following polymer?

CH3 CH3 CH3 CH3 CH3

CH2CCH2CCH2CCH2CCH2C

Cl Cl Cl Cl Cl
152 CHAPTER 4 | Reactions of Alkenes and Alkynes

4.54 Poly(vinyl pyrrolidone), prepared by from N-vinylpyrrolidone, is used both

in cosmetics and as a synthetic blood substitute. Draw a representative
segment of the polymer.

N CH CH2 N-Vinylpyrrolidone

G ENERAL P ROBLEMS 4.55 Reaction of 2-methylpropene with CH3OH in the presence of H2SO4 cata-
lyst yields methyl tert-butyl ether, CH3OC(CH3)3, by a mechanism analo-
gous to that of acid-catalyzed alkene hydration. Write the mechanism.
4.56 Compound A has the formula C8H8. It reacts rapidly with acidic KMnO4
but reacts with only 1 equivalent of H2 over a palladium catalyst. On
hydrogenation under conditions that reduce aromatic rings, A reacts with
4 equivalents of H2, and hydrocarbon B, C8H16, is produced. The reaction
of A with KMnO4 gives CO2 and a carboxylic acid C, C7H6O2. What are the
structures of A, B, and C? Write all the reactions.
4.57 Compound A, C9H12, absorbs 3 equivalents of H2 on catalytic reduction
over a palladium catalyst to give B, C9H18. On reaction with KMnO4,
compound A gives, among other things, a ketone that was identified as
cyclohexanone. On treatment with NaNH2 in NH3, followed by addition of
iodomethane, compound A gives a new hydrocarbon C, C10H14. What are
the structures of A, B, and C?
4.58 The sex attractant of the common housefly is a hydrocarbon named musca-
lure, C23H46. On treatment of muscalure with aqueous acidic KMnO4, two
products are obtained, CH3(CH2)12CO2H and CH3(CH2)7CO2H. Propose a
structure for muscalure.
4.59 How would you synthesize muscalure (Problem 4.58) starting from acety-
lene and any alkyl halides needed? (The double bond in muscalure is cis.)
4.60 Draw an energy diagram for the addition of HBr to pent-1-ene. Let one
curve on your diagram show the formation of 1-bromopentane product
and another curve on the same diagram show the formation of 2-bromo-
pentane product. Label the positions for all reactants, intermediates, and
products.
4.61 Make sketches of what you imagine the transition-state structures to look
like in the reaction of HBr with pent-1-ene (Problem 4.60).
4.62 Methylenecyclohexane, on treatment with strong acid, isomerizes to yield
1-methylcyclohexene. Propose a mechanism by which the reaction might
occur.

CH2 CH3
Acid

Methylenecyclohexane 1-Methylcyclohexene
 | Exercises 153

4.63 ␣-Terpinene, C10H16, is a pleasant-smelling hydrocarbon that has been

isolated from oil of marjoram. On hydrogenation over a palladium catalyst,
␣-terpinene reacts with 2 mol equiv of hydrogen to yield a new hydro-
carbon, C10H20. On reaction with acidic KMnO4, ␣-terpinene yields oxalic
acid and 6-methylheptane-2,5-dione. Propose a structure for ␣-terpinene.

O O O O

C C CH3CCH2CH2CCHCH3
HO OH CH3

Oxalic acid 6-Methylheptane-2,5-dione

4.64 Prelaureatin, a substance isolated from marine algae, is thought to arise

from laurediol by the following route. Propose a mechanism.

OH OH

“Br+”
HO Bromo- O
peroxidase Br

Laurediol Prelaureatin

4.65 Hydroxylation of cis-but-2-ene with basic KMnO4 yields a different prod-

uct than hydroxylation of trans-but-2-ene. Draw the structure, show the
stereochemistry of each product, and explain the result. We’ll explore the
stereochemistry of the products in more detail in Chapter 6.
IN THE M EDICINE C ABINET 4.66 The oral contraceptive agent Mestranol is synthesized by addition of
acetylide ion to a carbonyl group.

OH
CH3
C CH
H
Mestranol

H H

CH3O

(a) To understand the acetylide-addition reaction, first draw a resonance

structure of the C⫽O double bond based on electronegativity values,
indicating where the ⫹ and ⫺ charges belong in the circles on the
following abbreviated structure:

CH3 O CH3 O
154 CHAPTER 4 | Reactions of Alkenes and Alkynes

(b) Then draw a two-step mechanism for the addition of acetylide

ion to this resonance structure and subsequent protonation of the
intermediate with acid.
IN THE F IELD 4.67 Oct-1-en-3-ol, a potent mosquito attractant commonly used in mosquito
traps, can be prepared in two steps from hexanal, CH3CH2CH2CH2CH2CHO.
The first step is an acetylide-addition reaction like that described in Prob-
lem 4.66. What is the structure of the product from the first step, and how
can it be converted into oct-1-en-3-ol?

OH

CH3CH2CH2CH2CH2CHCH CH2 Oct-1-en-3-ol

4.68 As we saw in the Interlude at the end of this chapter, natural rubber is a
polymer of 2-methylbuta-1,3-diene that contains Z double bonds. Synthetic
rubber, by contrast, is similar to natural rubber but contains E double
bonds. Draw the structure of a representative section of synthetic rubber.