708 Chapter 14 • the Chemistry of alkynes

lenic Grignard or organolithium reagents can be formed • Acetylenic anions are good nucleophiles and react with
by the reactions of 1-alkynes with alkylmagnesium primary alkyl halides and sulfonates in SN2 reactions to
halides and alkyllithium reagents, respectively. form new carbon–carbon bonds.

reaction review For a summary of reactions discussed in this chapter, see the Reaction Review section
of Chapter 14 in the Study Guide and Solutions Manual.

ADDitioNAl ProBlemS

14.26 Give the principal product(s) expected when 1-hexyne or (b) a chiral alkyne of six carbon atoms
the other compounds indicated are treated with each of the (c) an alkyne of six carbon atoms that gives the same
following reagents: single product in its reaction either with BH3 in THF
(a) HBr (b) H2, Pd/C followed by H2O2 / – OH or with H2O/Hg2+/H3O+
(c) H2, Pd/C, Lindlar catalyst (d) a six-carbon alkyne that can exist as diastereomers
(d) product of part (c) 1 O3, then (CH3)2S
(e) product of part (c) 1 BH3 in THF, then H2O2 / – OH 14.30 On the basis of the hybrid orbitals involved in the bonds,
arrange the bonds in each of the following sets in order of
(f) product of part (c) 1 Br2
increasing length.
(g) NaNH2 in liquid ammonia
(a) C ¬H bonds of ethylene; C ¬H bonds of ethane;
(h) product of part (g) 1 CH3CH2I C ¬H bonds of acetylene
(i) Hg2+, H2SO4, H2O (b) C ¬C single bond of propane; C ¬C single bond of
(j) disiamyl borane, then H2O2 / – OH propyne; C ¬C single bond of propene
(k) CH3CH2MgBr in ether
(l) product of part (k) with ethylene oxide, then H3O+ 14.31 Rank the anions within each series in order of increasing
basicity, lowest first. Explain.
14.27 Give the principal products expected when 4-octyne or the (a)
other compounds indicated are treated with each of the
(b)
following reagents:
(a) H2, Pd/C catalyst
(b) H2, Lindlar catalyst
(c) product of (b) 1 O3, then H2O2 /H2O 14.32 Using simple observations or chemical tests with read-
(d) Na metal in liquid NH3 ily observable results, show how you would distinguish
between the compounds in each of the following pairs.
(e) Hg2+, H2SO4, H2O
(Don’t use spectroscopy.)
(f) BH3, then H2O2 / – OH
(a) cis-2-hexene and 1-hexyne
14.28 In its latest catalog, Blarneystyne, Inc., a chemical com- (b) 1-hexyne and 2-hexyne
pany of dubious reputation specializing in alkynes, has (c) 4,4-dimethyl-2-hexyne and 3,3-dimethylhexane
offered some compounds for sale under the following (d) propyne and 1-decyne
names. Although each name unambiguously specifies a
structure, all are incorrect. Propose a correct name for 14.33 Outline a preparation of each of the following compounds
each compound. from acetylene and any other reagents.
(a) 2-hexyn-4-ol (a) CH3CH2CD2CD2CH2CH3 (b) 1-hexene
(b) 6-methoxy-1,5-hexadiyne (c) 3-hexanol (d) 1-hexyne
(c) 1-butyn-3-ene (e)
(d) 5-hexyne

14.29 In each case, draw a structure containing only carbon and (f) (CH3)2CHCH2CH2CH2CH “O
hydrogen that satisfies the indicated criterion. (g) cis-2-pentene (h) trans-3-decene
(a) a stable alkyne of five carbons containing a ring (i) meso-4,5-octanediol (j) (Z)-3-hexen-1-ol
 aDDitional problems 709

14.34 Using 1-butyne as the only source of carbon in the reac- 14.36 A box labeled “C6H10 isomers” contains samples of three
tants, propose a synthesis for each of the following compounds: A, B, and C. Along with the compounds are
compounds. the IR spectra of A and B, shown in Fig. P14.36. Frag-
(a) CH3CH2C‚C ¬D (b) CH3CH2CD2CD3 mentary data in a laboratory notebook suggest that the
(c) compounds are 1-hexyne, 2-hexyne, and 3-methyl-1,4-
pentadiene. Identify the three compounds.

(d) 1-butoxybutane (dibutyl ether) 14.37 You have just been hired by Triple Bond, Inc., a company
that specializes in the manufacture of alkynes containing
(e) the racemate of
five or fewer carbons. The President, Mr. Al Kyne, needs
an outlet for the company’s products. You have been asked
to develop a synthesis of the housefly sex pheromone,
muscalure, with the stipulation that all of the carbon in
(f) octane (g) the product must come only from the company’s alkynes.
The muscalure will subsequently be used in a household
fly trap. You will be equipped with a laboratory containing
all of the company’s alkynes, requisition forms for other
14.35 (a) Draw the structures of all enols that would sponta-
reagents, and one gross of fly swatters in case you are suc-
neously form the following ketone, including
cessful. Outline a preparation of racemic muscalure that
stereoisomers.
meets the company’s needs.

(b) Would alkyne hydration be a good preparative method

for this compound? If so, give the reaction. If not,
explain why.

wavelength, micrometers
2.6 2.8 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 1516
100
percent transmittance

80

60

40

20
compound A
0
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600
wavenumber, cm–1

wavelength, micrometers
2.6 2.8 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 1516
100
percent transmittance

80

60

40

20
compound B
0
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600
wavenumber, cm–1
figure p14.36 ir spectra for problem 14.36.
710 Chapter 14 • the Chemistry of alkynes

14.38 Outline a preparation of racemic disparlure, a pheromone
of the gypsy moth, from acetylene and any other com-
pounds containing not more than five carbon atoms.
O IR: 2125, 3300 cm–1
CH3(CH2)9 C C (CH ) CH(CH )
2 4 3 2
H H
disparlure
14.39 In the preparation of ethynylmagnesium bromide by the
transmetallation reaction of Eq. 14.24, ethylmagnesium
bromide is added to a large excess of acetylene in THF
solution. Two side reactions that can occur in this proce-
dure are shown in Fig. P14.39.
(a) Suggest a mechanism for reaction (1), and explain why
an excess of acetylene is important for avoiding this
reaction.
(b) Suggest a mechanism for reaction (2), and explain why
an excess of acetylene is important for avoiding this
reaction.
(c) Tetrahydrofuran (THF) is used as a solvent because
the undesired by-product, BrMg ¬C‚C ¬MgBr,
is relatively soluble in this solvent. Explain why it is
important for this by-product to be soluble if both side
reactions are to be minimized.
14.40 (a) When the reduction of alkynes to alkenes by Na in
liquid ammonia is attempted with a 1-alkyne, every
three moles of 1-alkyne give only one mole of alkene
and two moles of the acetylenic anion:
(b) C4H6O: liberates a gas when treated with EtMgBr
NMR: d 2.43 (1H, t, J 5 2 Hz);
d 3.41 (3H, s); d 4.10 (2H, d, J 5 2 Hz)
(c) C4H6O:
NMR in Fig. P14.42
IR: 2100, 3300 cm–1 (sharp), superimposed on a broad,
strong band at 3350 cm–1
(d) C5H6O
IR: 3300, 2102, 1634 cm–1
NMR: d 3.10 (1H, d, J 5 2 Hz); d 3.79 (3H, s);
d 4.52 (1H, doublet of doublets,
J 5 6 Hz and 2 Hz); d 6.38 (1H, d, J 5 6 Hz)
14.43 (a) Identify the compound C6H10 that shows IR absorp-
tions at 3300 cm–1 and 2100 cm–1 and has the follow-
ing 13C NMR spectrum: d 27.3, 31.0, 66.7, 92.8.
(b) Explain how you could distinguish between 1-hexyne
and 4-methyl-2-pentyne by 13C NMR.
14.44 Propose mechanisms for each of the following known
transformations; use the curved-arrow notation where
possible.
(a)
(b)

Explain this result using the mechanism of this reduc-

tion and what you know about the acidity of 1-alkynes.
14.45 A compound A (C6H6) undergoes catalytic hydrogenation
(b) When (NH4)2SO4 is added to the reaction mixture,
over Lindlar catalyst to give a compound B, which in turn
the 1-alkyne is converted completely into the alkene.
undergoes ozonolysis followed by workup with aqueous
Explain. (Hint: The pKa of the ammonium ion is 9.25.)
H2O2 to yield succinic acid and two equivalents of formic
acid. In the absence of a catalyst poison, hydrogenation of
14.41 Arrange the following three carboxylic acids in order of
A gives hexane. Propose a structure for compound A.
increasing acidity (decreasing pKa). Explain your reason-
ing. (Hint: Consider the electronegativity of the b-carbon.)

H2C CHCH2CO2H HC CCH2CO2H CH3CH2CH2CO2H

A B C

14.42 Identify the following compounds from their IR and pro-

14.46 An optically active alkyne A (C10H14 ) can be catalytically
ton NMR spectra.
hydrogenated to butylcyclohexane. Treatment of A with
(a) C6H10O: EtMgBr liberates no gas. Catalytic hydrogenation of A
NMR: d 3.31 (3H, s); d 2.41 (1H, s); over Pd/C in the presence of quinoline poison and treat-
d 1.43 (6H, s) ment of the product with O3 and then H2O2 gives an opti-
IR: 2110, 3300 cm–1 (sharp) cally active tricarboxylic acid C8H12O6. (A tricarboxylic

(1)

(2)

figure p14.39
 aDDitional problems 711

acid is a compound with three ¬CO2H groups.) Give the 14.47 Complete the reactions given in Fig. P14.47 using knowl-
structure of A, and account for all observations. edge or intuition developed from this or previous chapters.

chemical shift, Hz
2400 2100 1800 1500 1200 900 600 300 0

J = 6.7 Hz
3H

J= J=
6.7 Hz 2.1 Hz
absorption

J=
2.1 Hz
dry
dry wet
δ 2.61 1H
1H
wet
disappears
on D2O shake 1H

8 7 6 5 4 3 2 1 0
chemical shift, ppm (δ)

figure p14.42 the nmr spectrum for problem 14.42c. a trace of aqueous acid was added to the
compound before the spectrum was obtained. the integral (as the number of protons) is shown
in red over each absorption. the absorptions labeled “dry” were obtained on a very dry sample
before addition of the acid. the absorptions labeled “wet” were obtained in the presence of
aqueous acid.

(a)

(b)

(Hint: Tertiary silyl halides, unlike tertiary alkyl halides, undergo nucleophilic substitution reac-
tions that are not complicated by competing elimination reactions.)

(c)

(Hint: See Sec. 10.4C)

(d)

(e)

(Hint: See Sec. 9.5)

(f)

(Hint: See Sec. 9.9A)

figure p14.47