Br Br

-...,,_-=-= + 2HB r
X
Propyne Hydrogen 2,2- Dibromopropane ( 100%)
bromide

Section 9.11 Hydration of alkynes in the presence of Hg2+ salts yields ketones by way of an unstable enol intermediate. The enol arises by
addition of water to the double bond according to Markovnikov’s rule.

1-Hexyne Water 2-Hexanone

(80 %)

Section 9.12 Addition of 1 mol of chlorine or bromine to an alkyne yields a trans dihaloalkene. A tetrahalide is formed on addition Page 350
of a second equivalent of the halogen.

+ 2Cl2
Cll yCI
Cl
Propyne Chlorine I , 1,2,2-Tetrachloropropane
(63 %)

Section 9.13 Carbon–carbon triple bonds can be cleaved by ozonolysis. The cleavage products are carboxylic acids.

0
+
2. Hp
~OH
2-Hexyne Butanoic acid Acetic acid

Section 9.14 Alkylation of acetylene followed by functional-group transformations involving the triple bond of the resulting alkyne can be
applied to the synthesis of a wide range of organic compounds.

PROBLEMS

Structure and Nomenclature

9.16 Provide the IUPAC name for each of the following alkynes:
(a) CH,CH2CH~= CH
(b) CH,CH2C=CCH3
(c) CH3C= CCHCH(CH3)2
11
I

(•)o
CH3 (f)
(d) [:>-CH 2 CH 2CH 2C - CH (g)
) (

9.17 Write a structural formula for each of the following:

(a) 1-Octyne
 (e) 2,5-Dimethyl-3-hexyne
(b) 2-Octyne
(f) 4-Ethyl-1-hexyne
(c) 3-Octyne
(g) Ethynylcyclohexane
(d) 4-Octyne
(h) 3-Ethyl-3-methyl-1-pentyne

9.18 All compounds in Problem 9.17 are isomers except one. Which one?

9.19 Oropheic acid is the common name of a naturally occurring acetylenic carboxylic acid having the molecular formula C18H22O2. Its
systematic name is 17-octadecene-9,11,13-triynoic acid. What is its structural formula?

Reactions

9.20 Write structural formulas for all the alkynes of molecular formula C8H14 that yield 3-ethylhexane on catalytic hydrogenation.

9.21 An unknown acetylenic amino acid obtained from the seed of a tropical fruit has the molecular formula C7H11NO2. On catalytic
hydrogenation over platinum, this amino acid yielded homoleucine (an amino acid of known structure shown here) as the only product.
What is the structure of the unknown amino acid?

Homoleucine

9.22 Oleic acid and stearic acid are naturally occurring compounds, which can be isolated from various fats and oils. In the Page 351
laboratory, each can be prepared by hydrogenation of a compound known as stearolic acid, which has the formula
CH3(CH2)7C C(CH2)7CO2H. Oleic acid is obtained by hydrogenation of stearolic acid over Lindlar palladium; stearic acid is
obtained by hydrogenation over platinum. What are the structures of oleic acid and stearic acid?

9.23 The alkane formed by hydrogenation of (S)-4-methyl-1-hexyne is optically active, but the one formed by hydrogenation of (S)-3-methyl-
1-pentyne is not. Explain. Would you expect the products of hydrogenation of these two compounds in the presence of Lindlar palladium
to be optically active?

9.24 Write the structure of the major organic product isolated from the reaction of 1-hexyne with
(a) Hydrogen (2 mol), platinum
(b) Hydrogen (1 mol), Lindlar palladium
(c) Sodium amide in liquid ammonia
(d) Product in part (c) treated with 1-bromobutane
(e) Product in part (c) treated with tert-butyl bromide
(f) Hydrogen chloride (1 mol)
(g) Hydrogen chloride (2 mol)
(h) Chlorine (1 mol)
(i) Chlorine (2 mol)
(j) Aqueous sulfuric acid, mercury(II) sulfate
(k) Ozone followed by hydrolysis

9.25 Write the structure of the major organic product isolated from the reaction of 3-hexyne with
(a) Hydrogen (2 mol), platinum
(e) Chlorine (1 mol)
(b) Hydrogen (1 mol), Lindlar palladium
(f) Chlorine (2 mol)
(c) Hydrogen chloride (1 mol)
 (g) Aqueous sulfuric acid, mercury(II) sulfate
(d) Hydrogen chloride (2 mol)
(h) Ozone followed by hydrolysis

9.26 When 2-heptyne was treated with aqueous sulfuric acid containing mercury(II) sulfate, two products, each having the molecular formula
C7H14O, were obtained in approximately equal amounts. What are these two compounds?

9.27 All the following reactions have been described in the chemical literature and proceed in good yield. In some cases the reactants are more
complicated than those we have so far encountered. Nevertheless, on the basis of what you have already learned, you should be able to
predict the principal product in each case.
I
(a) NaC=CH + Cl~

(b) Br'
,. . . _I ,. . . _. . . _,1, . . . _, ,
, Br 1. excess NaNHi, NH 3
2.H20
Br
Cl
KOC(CTl 3h, DMSO
(c) C>---i-CI heat

I. 03
(e) Cyclodecyne 2.1½()
CH
$
(f) rvc
\____/\OH
j \JOH
(g) ~

(h)Q 0 O(CHz.)sCI
( ·1) p roduct o f part {b) Lindlar
H2 Pd

Page 352
9.28 Compound A has the molecular formula C14H25Br and was obtained by reaction of sodium acetylide with 1,12-
dibromododecane. On treatment of compound A with sodium amide, it was converted to compound B (C14H24). Ozonolysis
of compound B gave the diacid HO2C(CH2)12CO2H. Catalytic hydrogenation of compound B over Lindlar palladium gave compound C
(C14H26), and hydrogenation over platinum gave compound D (C14H28). C yielded O CH(CH2)12CH O on ozonolysis. Assign
structures to compounds A through D so as to be consistent with the observed transformations.

Synthesis

9.29 When 1,2-dibromodecane was treated with potassium hydroxide in aqueous ethanol, it yielded a mixture of three isomeric compounds of
molecular formula C10H19Br. Each of these compounds was converted to 1-decyne on reaction with sodium amide in dimethyl sulfoxide.
Identify these three compounds.

9.30 Show by writing appropriate chemical equations how each of the following compounds could be converted to 1-hexyne:
(a) 1,1-Dichlorohexane
(c) Acetylene
(b) 1-Hexene
(d) 1-Iodohexane
 9.31 Show by writing appropriate chemical equations how each of the following compounds could be converted to 3-hexyne:
(a) 1-Butene
(b) 1,1-Dichlorobutane
(c) Acetylene

9.32 Diphenylacetylene can be synthesized by the double dehydrohalogenation of 1,2-dibromo-1,2-diphenylethene. The sequence starting from
(E)-1,2-diphenylethene consists of bromination to give the dibromide, followed by dehydrohalogenation to give a vinylic bromide, then a
second dehydrohalogenation to give diphenylacetylene.

(E}-1 ,2-Diphenylethene me.ro-l ,2-Dibrorno-

1,2-<liphenylethane
-KOH
e thanol

I C 14H 11 Br
Vinylic bromide
l-
KOH
190°C Q-c-c-Q
Diphenylacetylene

(a) What is the structure, including stereochemistry, of the vinylic bromide?

(b) If the sequence starts with (Z)-1,2-dibromo-1,2-diphenylethene, what is (are) the structure(s) of the intermediate dibromide(s)? What
is the structure of the vinylic bromide?

Page 353
9.33 (Z)-9-Tricosene [(Z)-CH3(CH2)7CH CH(CH2)12CH3] is the sex pheromone of the female housefly. Synthetic (Z)-9-tricosene
is used as bait to lure male flies to traps that contain insecticide. Using acetylene and alcohols of your choice as starting
materials, along with any necessary inorganic reagents, show how you could prepare (Z)-9-tricosene.

9.34 The ketone 2-heptanone has been identified as contributing to the odor of a number of dairy products, including condensed milk and
cheddar cheese. Describe a synthesis of 2-heptanone from acetylene and any necessary organic or inorganic reagents.

~
2-Heptanone

9.35 Assume that you need to prepare 4-methyl-2-pentyne and discover that the only alkynes on hand are acetylene and propyne. You also have
available methyl iodide, isopropyl bromide, and 1,1-dichloro-3-methylbutane. Which of these compounds would you choose in order to
perform your synthesis, and how would you carry it out?

9.36 Show by writing a suitable series of equations how you could prepare each of the following compounds from the designated starting
materials and any necessary organic or inorganic reagents:
(a) 2,2-Dibromopropane from 1,1-dibromopropane
(b) 2,2-Dibromopropane from 1,2-dibromopropane
(c) 1,1,2,2-Tetrachloropropane from 1,2-dichloropropane
(d) 2,2-Diiodobutane from acetylene and ethyl bromide
(e) 1-Hexene from 1-butene and acetylene
(f) Decane from 1-butene and acetylene
(g) Cyclopentadecyne from cyclopentadecene

(h)
D; from

Mechanism

9.37 Alkynes undergo hydroboration to give alkenylboranes, which can be oxidized to give carbonyl compounds with hydrogen peroxide. The
net result of the two-step sequence is hydration, which gives aldehydes from terminal alkynes.
 R 0
R - C::CH
R

>=<
H
y H
H BR'2
Alkenylborane

The oxidation step involves an enol intermediate. Using Mechanism 9.1 as a guide, write the structure of the enol that is formed in the
conversion of 1-hexyne to hexanal.

~H

1-Hexyne Hexanal

Page 354
Descriptive Passage and Interpretive Problems 9

Thinking Mechanistically About Alkynes

The preparation and properties of alkynes extend some topics explored in earlier chapters:

Alkynes can be prepared by elimination reactions related to the E2 dehydrohalogenation of alkyl halides used to prepare alkenes.
Alkynes can be prepared by SN2 reactions in which a nucleophile of the type RC C:− reacts with a primary alkyl halide.
Alkynes undergo addition reactions, especially electrophilic addition, with many of the same compounds that add to alkenes.

The greater s character of sp hybrid orbitals compared with sp3 and sp2 gives alkynes certain properties beyond those seen in alkanes and alkenes. It is
convenient to think of sp-hybridized carbon as more electronegative than its sp2 or sp3 counterparts.

The C–H unit of an alkyne is more acidic than a C–H unit of an alkene or alkane, allowing acetylene and terminal alkynes to be converted to their
conjugate bases C:− by NaNH2.
• Unlike alkenes, alkynes are reduced by metals, especially Li, Na, and K.
Unlike alkenes, alkynes can undergo nucleophilic as well as electrophilic addition.

~
-C =C -
f:;ru ,J
E+ is an electrophile Nu ,- is a nucleophile

Problems 9.38–9.42 emphasize mechanistic reasoning. By thinking mechanistically you reduce the need to memorize facts while increasing your
ability to analyze and understand new material. Nucleophilic addition to alkynes, for example, is not covered in this chapter but is the focus of Problem
9.42, which can be solved by thinking mechanistically.

9.38 Which of the following best describes what happens in the first step in the mechanism of the reaction shown?

~Br + 3NaNH2
Br

~ Br
:Br:

A. B. C. D.

9.39 Which of the following best describes what happens in the first step in the mechanism of the hydrogen–deuterium exchange reaction
shown?
 D CI-l3
------
NaNH 2
NH3
H CH3

(\ ~
D CH3 H2f./'o ~ - CH3 D - CH3 D CH3
H2NJH ~ l : NH2 H2N =J
A. B. C. D.

9.40 Electrophilic addition of fluorosulfonic acid (FSO2OH) to propyne proceeds by way of a very unstable vinyl cation Page 355
intermediate. What is the most reasonable structure, including geometry, of this intermediate? (Hint: Use VSEPR to deduce
the geometry.)

H CH3 CH3

H
)={ i=<H
H
B. C. D.

9.41 Rates of Br2 addition were measured for a series of alkynes, giving the data shown.

Relative rate of Br2 addition

1.0 13.4 120 558

Assuming that Br2 addition to alkynes proceeds through rate-determining formation of a cyclic bromonium ion, what generalizations can
you make about the structure of the rate-determining transition state?

Positive charge development More important effect

at carbons In original of substltuents on
triple bond triple bond

A. One carbon only Electron donation

B. One carbon only Sterle hindrance

C. Both carbons Electron donation

D. Both carbons Sterle hindrance

9.42 Nucleophilic addition can occur with alkynes that bear strong electron-attracting substituents such as CF3 on the triple bond. Predict the
product of nucleophilic addition of CH3OD to 3,3,3-trifluoropropyne. The stereochemistry of addition is anti, and the first step in the
mechanism is bond formation between CH3O− and one of the carbons of the triple bond.

A. B. C. D.