14

The Chemistry of
Alkynes
An alkyne is a hydrocarbon containing a carbon-carbon triple bond; the simplest member of
this family is acetylene, H-C-C-H. The chemistry of the carbon-carbon triple bond is
similar in many respects to that of the carbon--carbon double bond; indeed, alkynes and
alkenes undergo many of the same addition reactions. Alkynes also have some unique chemistry, most of it associated with the bond between hydrogen and the triply bonded carbon, the

:C-H
14.1

bond.

NOMENCTATURE OF ATKYNES
In common nomenclature, simple alkynes are named as derivatives of the parent compound
acetylene:

H3C-C:C-H
methytacetylene

HrC-C:C-CH:
dimethylacetylene

CH3CH2-C:C-CH:
ethylmethylacety-lene

Certain compounds are named as derivatives of the propargyl group, HC:C-CH'-,

the common system. The propargyl group is the triple-bond analog of the allyl group.

644

HC Q-CH,-Cl

H,C-CH-CH,-Cl

propargyl chloride

allyl chloride

in

14.1 NOMENCLATURE OF ALKYNES

645

We might expect the substitutive nomenclature of alkynes to be much like that of alkenes,
and it is. The suffix ane in the name of the corresponding alkane is replaced by the suffix
yne, and the triple bond is given the lowest possible number.

HgC-C-Q-H

cH3cH2cH2cH2-Q-C-CH:

propyne

HrC-CH2-Q-C-H
l-butfne

2-heptyne

HEC-CH-C-Q-CHr
"l

HC-Q-CH z-CHz-C-Q-CH:
1,S-heptadiyne

CH:
4-methyl-2-pentyne

Substituent groups that contain a triple bond (called alkynyl grcups) are named by replacing the final e in the name of the corresponding alkyne with the suffix yl. (This is exactly analogous to the nomenclature of substituent groups containing double bonds; see Sec. 4.2A.) The
alkynyl group is numbered from its point of attachment to the main chain:

HC-C-

HC-C-CH2-

ethynyl group
(ethynf + yl)

2-propynyl group

t2

cH2c-cH
3

- (2-

f\
I

propyny')cyclohexanol

\position of triple bond within the substituent

position ofthe 2-propynyl group on the ring

As with alkenes, groups that can be cited as principal groups, such as the
group in
-OH
the following example (as well as in the previous one), are given numerical precedence over
the triple bond. (See Appendix I for a summary of nomenclature rules.)

OH

HC:C-CHz-CH-CH3
5 4
2\
'
,{-pentyn-2-ol
\ OH group receives
r

numerical priority

When a molecule contains both double and triple bonds, the bond that has the lower number at first point of difference receives numerical precedence. However, if this rule is ambiguous, a double bond receives numerical precedence over a triple bond.

646

CHAPTER

14

O THE CHEMISTRY OF ALKYNES

j-l

ttl45

HC-C-CH:CHCHT
I

rll

cH3c

tli45

HzC:CHCH2C-CH

-c-cH-cHr

1-penten-4-yne

1-penten-3-yne

-pentyn-3-ene

precedence is given to the double bond

when numbering is ambiguous

precedence is given to the bond that has

lower number at first point of difference

a lrwis structure for each of the following alkynes.

(a) isopropylacetylene (b) cyclononyne (c) 4-methyl-1-pntyne
(d) l-ethynylcyclohexanol (e) 2-butoxy-3-heptyne (f) l,3-hexadiyne

14.1 Draw

14.2 hovide the substitutive

name for each of the following compounds. Also provide cofllmon

names for (a) and (b).

(a) cHrcHrcHrcHrc-cH (b)

(c)

OH

"t

cH3cHrcHrcHrc-ccH2cH2cH2cH3

(d)

HC-

H:C-A-Q-C-CH:

"r.\C:C i

CH:

(e)

/\

CH2OCH3

oH
I

HC-C-CH-

14.2

CCHCH2CHzCHT

CH:CH,

STRUCTURE AND BONDING IN ATKYNES

Because each carbon of acetylene is connected to two groups-a hydrogen and another carbon-the H-C:C bond angle in acetylene is 180o (Sec. 1.3B); thus, the acetylene molecule

is linear.

il.ro4

H\cT9-\t

i;A,

The C:C bond, with a bond length of t.ZO A, is shorter than the C:C and C-C bonds,
which have bond lengths of 1.33 A and 1.54 A, respectively.
Because of the 180" bond angles at the carbon--carbon triple bond, cis-trans isomerism
cannot occur in alkynes. Thus, although 2-butene exists as cis and trans stereoisomers, 2-butyne does not. Another consequence of this linear geometry is that cycloalkynes smaller than
cyclooctyne cannot be isolated under ordinary conditions (see Problem 14.3).
The hybrid orbital model for bonding provides a useful description ofbonding in alkynes.
We learned in Secs. 1.9B and 4.1A that carbon hybridization and geometry are correlated:
tetrahedral carbon is sp3-hybridized, and trigonal planar carbon is sp2-hybridized. The linear
geometry found in alkynes is characterized by a third type of carbon hybridization, called sp
hybridiTation Imagine that the 2s orbital and one 2p orbital (say, the 2p, orbital) on carbon
mix to form two new hybrid orbitals. Because these two new orbitals are each one part s and
one partp, they are called sp hybrid orbitqls. Two of the 2p orbitals (2prand2pr) are not included in the hybridization.

14.2

STRUCTURE AND BONDING IN

ALKYNES 647

nn.rftcctrrr,l br. hvlt rid i zirti on

2p

)6
)6 '-t',
*t

)n
-f--r

^, \
/(spl
^
--f-

I hl"hricl
j.,ibitul,

-f$-

2s

rrrraffcctcd

L-r'

hi'Lrn riiz;rtion

ls

ls

r-

tl
Tf-

carbon in acetylene

atomic carbon:
(1s)?(2s)t(2p*)(2py)

An sp hybrid orbital, then, is an orbital derived from the mixing of one s orbital and a p orbital of the same principal quantum number.
An sp orbital has much the same shape as an sp2 or sp3 orbital (Fig. 14.1; compare with
Figs. 1.16a and4.4a). However, electrons in an,1p hybrid orbital are, on the average, somewhat
closer to the carbon nucleus than they are in sp2 or sp3 hybrid orbitals. In other words, qp orbitals are more compact than sp2 or qp3 hybrid orbitals. The reason is that an sp orbital contains a greater fraction ofs character than an sp2 or ansp3 orbital, and 2s electrons are, on the
average, closer to the nucleus than 2p electrons. An ,qp-hybridized carbon atom, shown in Fig.
14.1c, has two sp orbitals at a relative orientation of 180". The two remaining whybidized2p
orbitals lie along axes that are at right angles both to each other and to the sp orbitals.
The o bonds in acetylene result from the combination of two sp-hybridized carbon atoms
and two hydrogen atoms (Fig. 14.2, p. 648). One bond between the carbon atoms is a o bond
resulting from the overlap oftwo sp hybrid orbitals, each containing one electron. This bond
is an qp-^1p o bond. The remaining ,sp orbital on each carbon overlaps with a hydrogen ls orbital to form a carbon-hydrogen obond. These bonds are sp-1s o bonds. Because electron
density in an sp hybrid orbital is closer to the nucleus than electron density in other hybrid orbitals, the C-H bond in acetylene is shorter (1.06 Al than the C-H bonds in ethylene (1.08
A) anA ethane (l.ll A). Table 5.3 (p.213) shows that the C-H bond in acerylene, with a
bond dissociation energy of 558 kJ mol-r (133 kcal mol-r), is also stronger than the C-H
bonds of ethylene (463 kJ mol-r, I I I kcal mol-r; or ethane (423kl mol-r. l0l kcal mol-r).

2p orbitals
peak

/
wave

sp

orbital

sPo rbiral

,/

trough---_\

nodal

\_/

surface
(a)

(b)

(c)

Figure 14.1 (a) A perspective representation of an sp hybrid orbital. (b) A more common representation of an
sp hybrid orbital used in drawings. (c) The two sp hybrid orbitals shown together.The "leftover" (unhybridized) 2p
orbitals are shown with dashed lines. Notice that the
colors represent wave peaks and wave troughs.

ip hybrid orbitals

are oriented at 180'.The blue and green

548

CHAPTER

14

THE CHEMISTRY OF ALKYNES

2p orbitals

sp-ls tr bond

2p orbitals

Fltwe 14.2

sp-sp a bond

The o-bond framework of acetylene (shown in blue). Overlap of carbon sp hybrid orbitals gives the

o bond, and the overlap of carbon sp hybrid orbitals with hydrogen ls orbitals gives the
carbon-hydrogen o bonds.Two 2p orbitals on each carbon, shown as dashed lines, do not participate in o bondcarbon-carbon

ing. (5ee Fig. 1a3.)

This bond-strength effect occurs because the C-H bond in acetylene contains a greater percentage of the lower-energy 2s orbital than the bonds derived from sp: or sp3 hybrid orbitals.
which, in contrast, contain progressively more high-energy 2p character. Notice that the linear
geometry of acetylene results from the 180o orientation of the sp orbitals on each carbon.
Again: hybridization and geometry are correlated.
The leftover 2p orbitals on each carbon overlap to form z'bonds. Because each carbon of
acetylene has two 2p orbitals, two rbonds are formed. Like the 2p orbitals from which they
are formed, they are mutually perpendicular. The two bonding z'molecular orbitals that result
from this overlap are shown in Fig. 14.3. Notice that the acetylene molecule is literally surrounded by z'electrons. The total electron density from all of the z'electrons taken together
forms a cylinder, or barrel, about the axis of the molecule (Fig. 14.3c). This cylinder of z-electron density is particularly evident in the electron potential map (EPM) of acetylene. Compare
this with the EPM of ethylene, which has a'-electron density above and below the plane of the
molecule.
ring of rr-electron densi6.

/
zr-electron clensity
ilbove ancl belou'
the plane of the rnolecLlle

EPM of acetylene
EPM of ethylene

The following heats of formation show that alkvnes are less stable than isomeric dienes:

H-Q-C-CH2CHzCH:
AHT

l-pentyne
144 kJ mol-t

(34.5 kcal

mol-l)

H:C-C-Q-CHzCH:
2-pentyne

1,4-pentadiene

+ I29 kl mol-t
(30.S kcal mol-l

HzC-CH-CH ?- CH:CHz
+ 106 kJ mol-l

(25.4 kcal mol-t

14,3 PHYSICAL PROPERTIES OF ALKYNES

649

+
(b)

(a)

(c)

Figure14.3 Thetwobondingz'molecularorbitalsinacetylene.(a)

Aperspectiveview.(b) An"end-on"viewas
indicated by the eyeball in (a). The blue and green colors in (a) and (b) represent wave peaks and wave troughs.
(c) The total r-electron density in acetylene. Acetylene is completely surrou nded by zr electrons.

In other words, the sp hybridization state is inherently less stable than the sp' hybridization
state, other things being equal. These heats of formation also show that a triple bond, like a
double bond, is more stable in the interior of a carbon chain than at the end.

@l4.3(a)Attempttobuildamodelofcyclohexyne.Explainwhythiscompoundisunstable.
(b) Build a model of cyclodecyne. Compare its subility qualitatively to that of cyclohexynrc;
explain your answer.

14.3

PHYSICAL PROPERTIES OF ALKYNES

A. Boiling

Points and solubilities

The boiling points of most alkynes are not very different from those of analogous alkenes and
alkanes:

HC-C(CHr):CH:

HzC-CH(CHz):CH:

H:C-CHz(CHz):CH:

1-hexfne

1-hexene
63.4 "C
0.6731 g ml-l

hexane
68.7 "C

point:
density:

boiling

71.3 "C

0.7155 g

ml-t

0.6603

I ml-t

Like alkanes and alkenes. alkvnes have much lower densities than water and are also insoluble in water.

B. lR spectroseopy of Alkynes
C:C

stretching absorption in the 2100-2200 cm-r region of the infrared

cm-t in the IR spectrum of loctyne (Fig. 14.4, p. 650). However, this absorption is very weak or absent in the IR spectra of
many symmetrical, or nearly symmetrical, alkynes because of the dipole moment effect (Sec.
12.38). For example, 4-octyne has no C:C stretching absorption at all.

Many alkynes have

spectrum. This absorption is clearly evident, for exapple, at2l20

650

CHAPTER

14

THE CHEMISTRY OF ALKYNES

wavelength, micrometers

2.6 2.8

3.5 4

4.5

5 5.5 6

8 910

13 14

15 16

100
q.)

H80
(\t
H60
(s
L{

q)

(J

b20
Or
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200
wavenumber,

1000

800

600

cm-l

Figule 14.4 The lR spectrum of l-octyne.The two key absorptions indicated

are absent in the spectrum

of

+octyne.

C:C sftetching absorption (2120 cm-') lies at considerably higher frequency than
C:C stretching frequency (I&C-1,675 cm-r). This is a clear manifestation of the bond-

The
the

strength effect on absorption frequency. (See Sec. 12.34 and Srudy Problem 12.1, p. 5a6.)
A very useful absorption of l-alkynes is the
stretching absorption, which occurs
at about 3300 cm-I. This strong, sharp absorption, very prominent in the spectrum of l-octyne
(Fig.14.4), is well separated from other C-H stretching absorptions. Because alkynes other
than l-alkynes lack the unique
bond, they do not show this absorption.

:C-H

:C-H

C.

NMR Spectroscopy of Allqnes

Pnoton NMR Spectloscopy Compare the typical chemical shifts observed in the proton
NMR spectra of alkynes with the analogous shifts for alkenes:

C-Q-H
I

-C -f, -q | -

acefylenic protons
6 1.7-2.5

propargylic protons
6 r.8-2.2

\/f-f
U-U
/\
\/
\--\,
/\

H
vin1,lic protons
6 4.s-5.5

l^-l^

(-

alll4ic protons
6 1.8-2.2

./Y -H
I

Although the chemical shifts of allylic and propargylic protons are very similar (as might be
expected from the fact that both double and triple bonds involve n'electrons), the chemical
shifts of acetylenic protons are much smaller than those of vinylic protons.
The explanation for the unusual proton chemical shifts observed in alkynes is closely re-

latedtotheexplanationforthechemicalshiftsofvinylicprotons(Fig.13.I4,p.613),although
the effect is in the opposite direction. An alkyne molecule in solution is tumbling rapidly, but
alkyne chemical shifts are dominated by the effects resulting from one particular orientation
of the alkyne molecule relative to the magnetic field, as shown in Fig. 14.5. When an alkyne
molecule is oriented in the applied field Bo as shown in this figure, an induced electon circu-

14.3 PHYSICAL PROPERTIES OF ALKYNES 651

--

\/\.
/
r .-. \.\
ii / t// \,\
\,\
\l

/
/ / - -\
/,/
\
l,/
\

\\

z^t

_-\

ll /-''.

Ji\ ,/ \\\\liil l' ".

i I i\c\ i)

:i*?fff

B1 (indr-rc-ecl

ti!'

",',,'

circulation

fielcl)

llqii

Irrllllrl

s\f
I rlzrl

\\
,t. \
\

tr \,
t\

I
\
r'i'lH\,',\,
lr.t "',\ l\'.\
/
1 t ll
t-,/
\1
\"/ ll
p/
\r

ti

\'-

\.tt't

-/r/

\r--t'

- -

,'

\--l

+
I

8,,

aprprlie

11

field

Figure 14.5 Explanation of the chemical shift of acetylenic protons.The induced field B, of the circulating z'
electrons (red) opposes the applied field Bo (b/ue) from the spectrometer in the region of space occupied by
acetylenic protons. As a result, the local field at an acetylenic proton is reduced. Hence, acetylenic protons have
NMR absorptions at relatively small chemical shift.The same effect accounts for the chemical shifts of acetylenic
r3C
NMR spectra of alkynes.
and propargylic carbons in the

lation is set up in the cylinder of zr electrons (Fig. 14.3c) that encircles the molecule. The resulting induced field B, opposes the applied field along the axis of this cylinder. Because the
acetylenic proton lies along this axis, the local field at this proton is reduced. Consequently, by
Eq. 13.4, p. 583, acetylenic protons have NMR absorptions at smaller chemical shift than they
would have in the absence of this effect.

f,

Carbon NMR Spectroscopy Chemical shifts of alkynes in

13C

NMR are subject to the

in double bonds have

same influences as proton chemical shifts. Although carbons involved

chemical shifts in the 6 100-145 range, carbons involved in triple bonds absorb at considerably lower chemical shift, in the 6 65-85 range. Propargylic carbons, like acetylenic hydrogens, also have smaller chemical shifts, typically by 5-15 ppm. The chemical shifts in 2heptyne are typical:
propargyilc carDons
5

r8.7 31.7 22.3 13.8

CH3
- \/= - CH 2- CH2-

3.3

----_------r-

H3C

'

75.2
C

79.2
C

:etvler-ric carbirns

CH2

2-heptyne

Compare, for example, the chemical shift of the propargylic methyl carbon (6 3.3) with that of
the other methyl carbon (5 13.8), which is much like that of an alkane methyl group.
The explanation for these chemical-shift effects is the same one (Fig. 14.5) discussed for
the proton chemical shifts in alkynes.

652

cHAprER 14

THE cHEMrsrRy oF ALKyNES

wavelength, micrometers

2.62.83

100
c.)

H80
(s
.E

H60
cd

:40

3.5 4 4.5 5 5.5 6

T1: n

IImi{^

8 910 11 12 l3t4

Il l,{ li.
.x1,ilj-,].'|-L..lJilI,[
Ii- lf.[ llf
,.i i,
,,j{ilf-,
t.

a,)

(,

b20

il; ,iti, r

3800 3400 3000 2600 2200 2000 1800 1600 1400 1200
wavenumber.

lR spectrum

for Problem

800

600

14.4.

Fig. 14.6 and the following NlvtR spectmm: 6 1.X)

1000

cm-l

14.4 Identify tbe compound with a molecular mass of 82 that

f?|F

Figure 14.6 The

15t6

has the

IR spectn,* shown in

(|If, s); 6l.2l (9H, s)

(a) March each of the following r3C NIvIR spectra to either 2-hexyne or 3-hexyne. Explain.

SpearumA.' 63.3, 13.6,21.1,22.9,75.4,79.1

Speannt

B:

6 12.7, 14.6, 81.0

O) Assign each of the resonances in the two spectra to the appropriate carbon atoms.

14.6 A student

consultd arwell-known compilation of reference spectra for the proton NMR spectrum of propyne and was surprised o find ttrat ttris $pectrum consists of a single unsplit resonan@ at 61.8. Believing this to be an error, he comes to you for an explanation. Explain to
him why it is reasonable that propyne could have this spectum.

71.4

INTRODUGTION TO ADDITION REACTIONS

OF THE TRIPLE BOND
In Chapters 4 and 5 we learned that the most common reactions of alkenes involve additions
to the double bond. Additions to the triple bond also occur, although in most cases they are
somewhat slower than the same reactions of comparably substituted alkenes. For example,
HBr can be added to the triple bond.

CH:(CHz)IC:CH

l-hexyne

* HBr TEHII-

CH3(CH2)3C:CHz (I4.I)
I

Br
2-bromo-l-hexene

The regioselectivity of the addition is analogous to that found in the addition of HBr to alkenes
(Sec. 4.7A): the bromine adds to the carbon of the triple bond that bears the alkyl substituent.
As in alkene additions, the regioselectivity is reversed in the presence of peroxides because
free-radical intermediates are involved (Sec. 5.6).

14.4 INTRODUCTION TO ADDITION REACTIONS OF THE TRIPLE

CHr(CHz):C-CH

+HBr

ffi

BOND 653

CHr(CHz)iCH:CHBr

l-hexFne

(r4.2)

I -bromo- I -hexene;
stereochemistry not determined
(7 4o/o yield)

Because addition to an alkyne gives a substituted alkene, a second addition can occur in many
cases.

Br

Br

HsC-C-C-CH: +HBr
2-butyne

H:C-C:CH-CH:
I

+ HBr

HrC-9-CHzCH:

(not isolated)

(excess)

(14.3a)

Br
2,2-dibromobutane
(600/o

yield)

The regioselectivity of this addition reaction is determined by the relative stabilities of the two
possible carbocation intermediates. One of the two possible carbocations (A in the following
equation) is stabilized by resonance. By Hammond's postulate (Sec. 4.8D), this carbocation is
formed more rapidly.
:

Br:

H:C-C

l\l

*Br,

1:B'r,

-CHCHT

lt
H:c-c-cHrcH,

Ltr.-9-cHzcH:

resonance- stabil ized carbo cation

l
I

:Br:

l*

H:C- CH-CHCH:
less stable carbocation B
I

I
I

rBr

Br:
I

H:C- C -CHzCHi
I

,J,,
ob*.**d product

HrC- CH -CHCHT

14.3b)

'P1,,

not formed

In the addition of a hydrogen halide or a halogen to an alkyne, the second addition is usually slower than the first. The reason is that the halogen that enters the molecule in the first addition exerts a rate-retarding polar effect (Sec. 3.6C) on carbocation formation in the second
addition. In other words, both carbocations A and B in Eq. I4.3b are destabilized by the polar
effect of bromine, and this polar effect is only partially counterbalanced by the resonance stabilization in carbocation A. Because the second addition is slower, it is possible to isolate the
product of the first addition if one equivalent of HBr is used, as in Eq. 14.1.

654

cHAprER 14

14.5

THE cHEMrsrRy oF ALKyNES

14.7

Give the product that results from the addition of one equivalent of Br, to 3-hexyne. What
are the possible stereoisomers that could be formed?

14.8

The addition of HCI to 3-hexyne occurs as an anri-addition. Give the structure, stereochemistry, and name of the product.

CONVERSION OF ALKYNES INTO

ALDEHYDES AND KETONES

A. Hydration

of Alkynes

Water can be added to the triple bond. Although the reaction can be catalyzed by a strong acid,
it is faster, and yields are higher, when a combination of dilute acid and mercuric ion (Hg2+)
catalysts is used.

\__J)-C-CH

(dilute)
lL > (
C-Cu,
f
\__J

+ H2o "o

Hs2+,r"Z""+'\""-.''
Hrso,

cyclohexylacetylene

14.4)

cyclohexyl methyl ketone

i9lo/o yreld)

The addition of water to a triple bond, like the corresponding addition to a double bond, is
called hydration. The hydration of alkynes gives ketones (except in the case of acetylene
itself, which gives an aldehyde; see Study Problem 14.7, p. 656).
Let's contrast the hydration reactions of alkenes (Sec. 4.9B) and alkynes. The hydration of
an alkene gives an alcohol.
HzSo+

R-cH:cH2 + H2o
an alkene

t R-cH-cH3

(14.5a)

OH
an alcohol

Because addition reactions of alkenes and alkynes are closely analogous, it might seem that an

alcohol should also be obtained from the hvdration of an alkvne:

OH

+ H2o
R-c:c-H
an alloTne

HzSOa' Hs2+

R-C:CH 2

o4.5b)

an enol

An alcohol containing an OH group on a carbon of a double bond is called an enol (pronounced

enols are formed in the hydration of alkynes. However, most enols cannot be
isolated because most enols are unstable and are rapidly converted into the coresponding
aldehydes or ketones.

Enl6l). In fact,

oH9
R-C:CH z T>
an enol

R-C-CU:
a

ketone

(14.5c)

KETONES 655

14.5 CONVERSION OF ALKYNES INTO ALDEHYDES AND

Most aldehydes and ketones are in equilibrium with the corresponding enols, but the equilibrium concentrations of enols are in most cases minuscule-typically, one part in 108 or less.
The relationship among aldehydes, ketones, and enols is explored in Chapter 22.T\e important point here is that, because most enols are unstable, if an enol isformed as the product of a
reaction, it is rapidly converted into the corresponding aldehyde or l<etone.
The mechanism of alkyne hydration is very similar to that of the oxymercuration of alkenes
(Sec. 5.4A). In the first part of the mechanism, mercuric ion reacts as an electrophile with the
zr electrons of the triple bond to form a carbocation, which could be in equilibrium with a
cvclic mercurinium ion:

----+ R-C-CH _
I
\\'Hg*
1' Hgr*

R-Q-CH

R-C-CH

\/Hgt*

(r4.6a)

The carbocation is formed at the carbon of the triple bond that bears the alkyl substituent. (Recall that alkyl substitution stabilizes carbocations; Sec. 4.7C.) This carbocation reacts with
water, and loss of a proton to solvent water gives the addition product. As a result, the oxygen
from water ends up on the carbon with the alkyl substituent.

l^
|

,o*fH

tOH

R-C-CH- 'Ou,

R-C-CH1

-:oH,
Hg*

Hro*

(14.6b)

R-C-CH
Hg*

Hg*

In the oxymercuration of alkenes, the reducing agent NaBI{o is the source of hydrogen that
replaces the mercury. However, the use of NaBHo is unnecessary in the hydration of alkynes.
The reason is that the presence of a double bond makes possible removal of the mercury by a
protonolysis reaction. This protonolysis occurs under the conditions ofhydration; a separate
procedure is not required. The first step in the mechanism of this protonolysis reaction is protonation of the double bond. This protonation occurs at the carbon bearing the mercury because the resulting carbocation is resonance-stabilized.

.\

*OH

/tOH
\'l

i,Hr0r,
t/
t(
+
R-C:CH
:ou

I
ll
R-C-CHzl

R-C-CHz
+ - <+

Hg*

. r.T;nce-stabilized carbocation

-l

Hs* I

(Recall that formation of a resonance-stabilized carbocation also explains the position of protonation in HBr addition; Eq. 14.3b, p. 653.) Dissociation of mercury from this carbocation
liberates the catalyst Hg2+ along with the enol.

OH

OH

+
R-Q;CHz
+Ll
I

Hg*

R-C-CHz + Hgt*
an enol

(14.6d)

656

CHAPTER

14 o

THE CHEMISTRY OF ALKYNES

Conversion of the enol into the ketone is a rapid, acid-catalyzed process. Protonation of the
double bond gives another resonance-stabilized carbocation:

,Qnrr r--tiu,
t(
R-C-CHz
< -+
a resonance*stabilized

carbocation

This carbocation is also the conjugate acid of a ketone. Loss of a proton gives the ketone
product.

f>H

:O'

'9H,

:o

tl

R-C-CH:

ll*

.F:-

R-C-CH: + Il-'--LlHl

14.6f)

The hydration of alkynes is a useful way to prepare ketones provided that the starting material is a l-alkyne or a symmetrical alkyne (an alkyne with identical groups on each end of
the triple bond). This point is explored in Study Problem 14.1.

@Whichoneofthefollowingcompoundscouldbepreparedbythehydrationofalkynessothatitis
uncontaminated by constitutional isomers? Explain your answer.
(b)
o
ll
ll
CH3CH
cH3cH2ccH2cH3

(a)

acetaldehyde

3-pentanone

SOlution First, what alkyne starting materials, if

any, would give the desired products? The

equations in the text show that the two carbons of the triple bond in the starting material corre-

C:O

spond within the product to the carbon of the

group and an adjacent carbon. Thus, for part
(a), the only possible alkyne starting maierial is acetylene itself, HC-CH. For part (b), the only

possible alkyne starting material is 2-pentyne, CI{,C-CCH'CH,.

Nexg it remains to be shown whether hydration of these alkynes gives ozly the products in the
problem. Remember, a good synthesis gives relatively pure compounds. The hydration of acetylene
indeed gives only acetaldehyde. (In fact, acetaldehyde is the only aldehyde that can be prepared by
the hydration of an alkyne.) However, hydration of 2-pentyne gives a mixture consisting of comparable amounts of 2-pentanone and 3-pentanone , because the carbons of 2-pentyne both have one

alkyl substituenl. Thus, there is no reason that the reaction of water at either carbon should be
strongly favored.

H:C- C-C-CHzCHr
one alkyl substituent
on each carbon

HO
\-al
/\
HrC
Hgl
\:a'

Hg*

H:C

OH

/\

CH2CH3

H:o+

tl

cH3ccH2cH2cH3
2-pentanone

CH2CH3

Hro+

tl

cH3cH2ccH2cH3
3-pentanone

Q4'7)

14.5 CONVERSION OF ALKYNES INTO ALDEHYDES AND

KETONES 657

I{ence, hydration would give a mixture of constitutional isomerr that would have to be separated,
and the yield of the desired product would be low. Consequently, hydration would nar be a good
wey tb Fepare 3-pentanone. (However, 2.pentanone could be preparod by hydration of a different
alkyne; see Problem 14.9a).

EEEil

r+.>

auq/ne oourq e,acn or

;ffJ"

(nl" $',

(b)

"

Dc

prpeu Dy a",o-c$aryzoo

O
ilt1

tl

(cH3)3c-c-cHr

cH3ccH2cH2cH3

(c)

rr* rorowrng compouxls

ou"trotrVor)A-*o2eH2cH,.
14.10 Thc hydration of

H3

an alkyne is not a reasonabfe prepar*ive rrcnoA for eacb of the folloudng

compoxnds, Explain
(c}
{a)CF{sCHtCH-g'(b)

yhy.

.
O

"

ll',,c(cH3)3
o
ii li;) #; ue'srmqys or 1rj epqtfe{n*ior ur*eu@ i, fi!ffi *;*;
,(cHj)5f, ;;' 5

{4f

cHrcHr-c-cH(cH3L
O) Would alkyne hydration te

a gooA preparative method

for this coryound? Explain.

Hydroboration-oxidation of Al kynes
The hydroboration ofalkynes is analogous to the same reaction ofalkenes (Sec. 5.4B).

CH,CH\

3CH3CH2C-CCH2CH3

+ BH3 -THF*

icr"cu"
I
" --gr"\J

t\tls

t'o.rul

\H/3

As in the similar reaction of alkenes, oxidation of the organoborane with alkaline hydrogen
peroxide yields the corresponding "alcohol," which in this case is an enol. As shown in Sec.
14.5A^, enols react

[cH,c*ro

\,I

CH,CH\

l--'---'\

t\

further to give the corresponding aldehydes or ketones.

cH3crHz cH2cH3

H':o'?loH->
|
b:a1
\/\ INHOH
/3

an

enol

o
tl

----> cHrcH2cH2-c-cH2cH3
(14.8b)

6s8

CHAPTER '14

THE CHEMISTRY OF ALKYNES

Because the organoborane product of Eq. 14.8a has a double bond, a second addition of
BH, is in principle possible. However, the reaction conditions can be controlled so that only
one addition takes place, as shown, provided that the alkyne is not a 1-alkyne.
If the alkyne is a I -alkyne (that is, if it has a triple bond at the end of a carbon chain), a second addition of BH, cannot be prevented.

R-C:CH

BH3 ---------> multiple addition reactions

a l-a$me

Howeveq the hydroboration of l-alkynes can be stopped after a single addition provided that
an organoborane containing highly branched groups is used instead of BHr. One reagent developed for this purpose is disiamylborane, represented with the skeletal structure shown in
Eq. 14.9. (How would you synthesize disiamylborane? See Sec. 5.4B.)

cH,

/ll
u
-(.-c
\ll
\ CHt

(.

B-H

represented

as (+)
\

BH

14.e)

tz

disiamylborane

The disiamylborane molecule is so large and highly branched that only one equivalent can
react with a l-alkyne; addition of a second molecule results in severe van der Waals repulsions. In many cases, van der Waals repulsions, or steric effects, interfere with a desired
reaction; in this case, however, van der Waals repulsions are used to advantage, to prevent an
undesired second addition from occurring:

f!-)
\l /z

rrH

cH:(cHz)5-Q-CH

THF

cH:(cHz)s\
t

C:C

H/

cH:(cHz)s
\/

STUDY GUIDE LINK 14.1

Functional Group
Preparations

\
+

L)H
(an enol)

t-(+)
|

+ Hr( )r
oH-

lz

t^-f
U-U

cHr(cHz)s-cHz-cH-L)

(14.10)

octanal
(an aldehyde; 70o/o yield)

Notice from this example that the regioselectivity of alkyne hydroboration is similar to that
observed in alkene hydroboration (Sec. 5.4B): boron adds to the unbranched carbon atom of
the triple bond, and hydrogen adds to the branched carbon.
Because hydroboration-oxidation and mercury-catalyzed hydration give different products
when a l-alkyne is used as the starting material (why?), these are complementary methods for
the preparation of aldehydes and ketones in the same sense that hydroboration-oxidation and
oxymercuration-reduction are complementary methods for the preparation of alcohols from
alkenes.

14.6 REDUCTION OF ALKYN ES

65

o
tl

2) HzOz

cH:(cHz)scHz-c-H

/OH-

cH:(cHz)s-c-c-H

(14.1l)

tl

cH:(cHz)s-c-cH:
Notice that hydroboration--oxidation of a l-alkyne gives an aldehyde; hydration of any l-alkyne
(otherthan acetylene itself) gives aketone.

14.12 Compare the results of hydroboration-oxidation and mercuric ion-catalyzed hydratioa for
(a) cyclohexylacdylene and @)
.,,,

,,

2-butyne.

14.6

REDUCTION OF ATKYNES

A. Catalytic Hydrotenation

of Allrynes

Alkynes, like alkenes (Sec. 4.9A), undergo catalytic hydrogenation. The first addition of hydrogen yields an alkene; a second addition ofhydrogen gives an alkane.

H2,

R-c:c-R

catalvst.

Hz,

R-cH:cH-R

catalvst

> R-cH2-cHr-R

(r4.r2)

The utility of catalytic hydrogenation is enhanced considerably by the fact that hydrogena-

tion of an alkyne may be stopped at the alkene stage if the reaction mixture contains a catalyst poison: a compound that disrupts the action of a catalyst. Among the useful catalyst poisons are salts of Pb2+, and certain nitrogen compounds, such as pyridine, quinoline, or other
amines.

\r
pyriaine

quinoline

These compowds selectively block the hydrogenation of alkenes without preventing the hydrogenation of alkynes to alkenes. For example, a Pd/CaCO, catalyst can be washed with
Pb(OAc), to give a poisoned catalyst known as Lindlar catalyst. In the presence of Lindlar
catalyst, an alkyne is hydrogenated to the corresponding alkene:

H, + CH3CH2CH2C-CCH2CH2CH3
4-octFne

Lindlar catalyst or
Pd/C, pyridine
ethanol

cH3cH

zc.Hz cH2cHzcHi
\- /
C:C.
/\
HH
cis-4-octene

14.13)

660

CHAPTER

14 o

THE CHEMISTRY OF ALKYNES

As Eq. 14.13 shows, the hydrogenation of alkynes, like the hydrogenation of alkenes
(Sec. 7.9E), is a stereoselective syn-addition. Thus, in the presence of a poisoned catalyst, hydrogenation of appropriate alkynes gives cis alkenes. In fact, catalytic hydrogenation of allcynes is

one ofthe best ways to prepore cis alkenes.

In the absence of a catalyst poison, two equivalents of H, are added to the triple bond.
Pd/c

2Hz

noPoison

+ cH3cH2cH2c-ccH2cH2cH3

cH3cH2cH2CH2cH2cH2cH2cH3 04.14)
octane

4-octyne

The catalytic hydrogenation of alkynes can therefore be used to prepare alkenes or alkanes by
either including or omitting the catalyst poison. How catalyst poisons exert their inhibitory ef'fect on the hydrogenation of alkenes is not well understood.

l@I.**,nr,

/-\

w*o*i*,"r***o*

{.) C*n(CdjsC=
I-S$[!P!
:, .

,
.::

+' '

.r*nofthefol@ins.$astiw
ft) snne as part (a)'with

no poison

C:-CH

Reduction of Allqnes wlth Sodlum in tiquid Ammonla

Reaction of an alkyne with a solution of an alkali metal (usually sodium) in liquid ammonia
gives a trans alkene.

cH3cHzcHz

CH3CH

zCHz-C-Q-CH

zCHzCHr

2Na

+ zNn,

+C:C+

\'

/\
H
(97o/o

2Na+

-Nn,

CH2CHzCHT
yield)

(14.1s)

The reduction of alkynes with sodium in liquid ammonia is complementary to the catalytic
hydrogenation of alkynes, which is used to prepare cis alkenes (Sec. 14.6A).

R-Q-C-R

Na/NHy'

RH r
\/l^-f
U-U
/\
HR

trans alkene

\ Hrlpoisoned

catalyst
(Sec. 14.6A)

RR\
\/f-f
U-U
/\
HH

(14.16)

cis alkene

The stereochemistry of the Na/NH, reduction follows from its mechanism. If sodium or
other alkali metals are dissolved in pure liquid ammonia, a deep blue solution forms that contains electrons complexed with ammonia (solvated electrons).

14.6 REDUCTION OF ALKYNES

Na' + nNH3 (liq) --*

Na+

e-(NH3)o

561

(r4.r1)

solvated electron

The solvated electron can be thought of as the simplest free radical. Remember that free radicals add to triple bonds (Eq. 14.2, p.653). The reaction of solvated elecffons with the alkynes
begins with the addition of an electron to the triple bond. The resulting species has both an
unpaired electron and a negative charge. Such a species is called a radical anion:

e- Na+

1n\
R-C:=C-R
(

.i

R-C-C-R

Na+

(r4.1 8a)

a radical anion

The radical anion is such a strong base that it readily removes a proton from ammonia to give
a vinylic radical-a radical in which the unpaired electron is associated with one carbon of a
double bond. The destruction of the radical anion in this manner pulls the unfavorable equilibrium in Eq. 14.18a to the right:

H'

'-J
R-C-C-R

a"

NHr

R-C:C
.

--+

Na+
a

.o

\*

+ -NHr

Na+

14.18b)

vinylic radical

The vinylic radical, like the unshared electron pair of an amine (Sec. 6.10B), rapidly undergoes inversion, and the equilibrium between the cis and trans radicals favors the trans radical
for the same reason that trans alkenes are more stable than cis alkenes: repulsions between the
R groups are reduced.

RH
\p
c-c

ffi\
*.ZR

frl
V/

AH

R-C:C
\JR

/w-c/\
RR

A\

L-U

trans vinylic radical

transition state
for inversion

(strongly favored

cis

(14.1 8c)

vinylic radical

at equilibrium)

Next, the vinylic radical accepts an electron to form an anion:

R
C
I

\_

-r

/
\

,\/ RH
(
t.\

Na+

Na+

14.18d)

solvated

electron

This step of the mechanism is the product-determining step of the reaction (Sec. 9.68). The
rate constants for the reactions ofthe cis and trans vinylic radicals with the solvated electron
are probably the same. However, the actual rate of the reaction of each radical is determined
by the product of the rate constant and the concentration of the radical. Because the trans

662

cHAprER 14

THE cHEMtsrRY oF ALKYNES

vinylic radical is present in much higher concentration, the ultimate product of the reaction,
the trans alkene, is derived from this radical.
The anion formed in Eq. 14.18d is also more basic than the amide anion and readily removes a proton from ammonia to complete the addition.

RH
\/
Na+ C:C
(-\
\R
\

RH
..
\
/
c:c. + -JJH, Na+
/\
HR

trans alkene

H,

pK"

/\..

I NHz

pK.

(14.18e)

42

35

Because ordinary alkenes do not react with the solvated electron (the initial equilibrium
analogous to Eq. 14.18a is too unfavorable), the reaction stops at the trans alkene stage.
The Na/NH, reduction of alkynes does not work well on l-alkynes unless certain modifications are made in the reaction conditions. (This is explored in Problem 14.39.) However, this
is not a serious limitation for the reaction, because the reduction of l-alkynes to l-alkenes is
easily accomplished by catalytic hydrogenation (Sec. 14.64).

@l4.14Whatproductisobtainedineachcasewhen3-hexyneistreatedineachofthefollowing
ways? (Hint: The products of the two reactions are stereoisomers.)
{a} with sodium in liquid ammonia and the product of that reaction with D, over Pd/C
(b) with H, over Pd/C and quinoline and the product of that reaction with D, over Pd/C

14.7

ACIDITY OF I.ALKYNES
A. Acetylenic Anions
Most hydrocarbons do not react as Br@nsted acids. Nevertheless, let's imagine such
in which a proton is removed from a hydrocarbon by a very strong base B:-.

-p-H
//

B:-

------->

-C:-

B-H

reaction

(14.19)

a carDanlon

In this equation, the conjugate base of the hydrocarbon is a carbon anion, or carbanion. Recall
from Sec. 8.8B that a carbanion is a species with an unshared electron pair and a negative
charge on carbon.
The conjugate base of an alkane, called generally an allql anion,has an electron pair in an
sp3 orbital. An example of such an ion is the 2-propanide anion:

*
O
V_

sP3

orbital

,,,''b("cHj
H -t
CH,

Z-propanide anion
(an alkyl anion)

14.7 ACIDITY OF 1-ALKYNES

653

The conjugate base of an alkene, called generally avinylic anion, has an electron pair in an sp2
orbital. An example of this type of carbanion is the l-propenide anion:

H:C,,

(:) *
\C:C_t-/

sp2

orbital

d\

l-propenide anion
(a vinylic anion)
The anion derived from the ionization ofa l-alkyne, generally called an acetylenic anion,has
an electron pair in an sp orbital. An example of this type of anion is the l-propynide anion:
sp

orbital

_t

cH3c-c
l-propynide anion
(an acetylenic anion)

The approximate acidities of the different types of aliphatic hydrocarbons have been measured or estimated:

R:C-H

/
R'C-C
.\

R-Q

C-H

14.20)

H
type of hydrocarbon

approximate pK.

alkane

alkene

alkyne

>55

42

25

These data show, first, that carbanions are extremely strong bases (that is, hydrocarbons are very
weak acids); and second, that alkynes are the most acidic ofthe aliphatic hydrocarbons.
Alkyl anions and vinylic anions are seldom if ever formed by proton removal from the cor-

responding hydrocarbons; the hydrocarbons are simply not acidic enough. However, alkynes
are sufficiently acidic that their conjugate-base acetylenic anions can be formed with strong
bases. One base commonly used for this purpose is sodium amide,.or sodamide, Na* -:NHz,
dissolved in its conjugate acid, liquid ammonia. The amide ion, -:NHz, is the conjugate base
of ammonia, which, as an acid, has a pK" of about 35.
STUDY GUIDE LINK 14.2

Ammonia, Solvated
Electrons, and

Amide Anion

B:-+:I.{Ha:-:NHr+B-H
pK. - 35
amide ion

(r4.2r)

Because the amide ion is a much stronger base than an acetylenic anion, the equilibrium for
removal of the acetylenic proton by amide ion is very favorable:

n-c:C\u'lNH,

11u*

--N!4!L R-C:e:

Na+

iriH,

(14.22)

In fact, the sodium salt of an alkyne can be formed from a l-alkyne quantitatively with
NaNHr. Because the amide ion is a much weaker base than either a vinylic anion or an alkyl
anion, these ions cannot be prepared using sodium amide (Probleml4.l7).
The relative acidity of alkynes plays a role in the method usually used to prepare acetylenic
Grignard reagents, which are reagents with the general structure R-C:C-MgBr. Recall
from Sec. 8.8A that Grignard reagents are generally prepared by the reactions of alkyl halides

664

cHAprER 14

THE

cHEMlsrRy oFALKyNES

with magnesium. The "alkyl halide" starting material for the preparation of an acetylenic
Grignard reagent by this method would be a l-bromoalkyne-that is, R-C:C-Br. Such
compounds are not generally available commercially and are difficult to prepare and store.
Fortunately, acetylenic Grignard reagents are accessible by the acid-base reaction between a
l-alkyne and another Grignard reagent. Methylmagnesium bromide or ethylmagnesium bromide are often used for this purpose.

CH1CH2CH2CH2-C

-C-

H + CH-ICH

CH3CH2CH2CH2-C-C-MgBr +

2-MgBr ffi

an acetylenic Grignard

CH3CH3

reagen,

gthane
(a gas)

(t4.23)

H-C:C-H

H-C:C-MgBr

+ CH3CH2-MgBr -T"F*

+ CH3CH3

04.24)

ethynylmagnesium bromide

This reaction is extremely rapid and is driven to completion by the formation of ethane gas
(when CH,CHTMgBT is used as the Grignard reagent). This reaction is an example of a transmetallation: a reaction in which a metal is transferred from one carbon to another. However.
it is really just another Br0nsted acid-base reaction:

{_\

,"-._.---r-

BrMg+ :CH.,CH1

-R

-4

ii-('Hr('Hr + BrMg+

-r-:R

(11.25)

Although Grignard reagents are covalent compounds, the two Grignard reagents in this equation are represented as ionic compounds to stress the acid-base character of the equilibrium.
This reaction is similar in principle to the reaction of a Grignard reagent with water or alcohols (Eq. 8.27,p.363). Like all Brgnsted acid-base equilibria, this one favors formation of the
weaker base, which, in this case, is the acetylenic Grignard reagent. The release of ethane gas
in the reaction with ethylmagnesium bromide makes the reaction irreversible and at one time
was also a useful test for l-alkynes. Alkynes with an internal triple bond do not react because
they lack an acidic acetylenic hydrogen.
What is the reason for the relative acidities of the hydrocarbons? Sec. 3.6,4. discussed two
important factors that affect the acidity of an acid A-H: the A-H bond strength and the
electronegativity of the group A. Bond dissociation energies show that acetylenic C-H
bonds are the strongest of all the C-H bonds in the aliphatic hydrocarbons:
R
I

R:C-H

-C-C-H

H
acetylenic C
(548 kJ mol-l,
l3 l kcal mol-1)

vinylic
(460

kl mol-l,

110 kcal

mol-l

(r4.26)

H
alkyl C
eA2-41S kl mol-l,
96-100 kcal mol-l)

If bond strength were the major factor controlling hydrocarbon acidity, then alkynes would

be

the least acidic hydrocarbons. Because they are in fact the most acidic hydrocarbons, the elec-

tronegativities of the carbons themselves must govern acidity. Thus, the relative electronegativities of carbon atoms increase in the order sp3 < sp2 < sp, and the electronegativity differences on aciditv must outweish the effects of bond strensth.

14.7 ACIDITY OF 1-ALKYNES

555

This trend in electronegativity with hybridization can be explained in the following way.
The electrons in sp-hybridized orbitals are closer to the nucleus, on the average. than sp2 electrons, which in turn are closer than spr electrons (Sec. 14.2). In other words, electrons in orbitals with larger amounts of s character are drawn closer to the nucleus. This is a stabilizing
effect because the interaction energy between particles of opposite charge (electrons and nuclei) becomes more strongly negative (that is, favorable) as the distance between them decreases (the electrostatic law; Eq.3.40, p. 113). Thus, the stabilization of unshared electron
pairs is in the order sp3 I sp2 ( sp. In other words, unshared electron pairs have lower energy
when they are in orbitals with greater s character.

14.15 Each of the following compounds protonates on nitrogen. Draw the conjugate acid of
which compound is m:l:!3el1ft:rtut

"

ta
-:ti-i?rt
H:c-cH-NH
^
A

rr

"'t

each.

^-\r.

-t;*t. nrri,L
,,rr.
B
lg,trl

14.16 (a) Ion A is more acidic than ion B in the gas phase. Is this the acidity order predicted by
hybridization arguments? Explain.

++
H:C-OHz

H:C-CH:OH

(b) Ion .B is less acidic

(c)

because it is stabilized by resonance, whereas ion A is not. Show the

resonance structure for ion B, and, with the aid of an energy diagram, show why stabilization of ion B should reduce its acidity.
In aqueous solution, ion A is less acidic than ion B. Explain.

14.17 (a) Using the pK" values of the hydrocarbons and ammonia, estimate the equilibrium constantfor(l)thereactioninEq. 14.22and(2)theanalogousreactionofanalkanewith
amide ion. (Hint: See Study Problem 3.6, p. 91)
(b) Use your calculation to explain why sodium amide cannot be used to form alkyl anions

from alkanes.

B. Acetylenic Anions as Nucleophiles

Although acetylenic anions are the weakest bases of the simple hydrocarbon anions, they are
nevertheless strong bases-much stronger, for example, than hydroxide or alkoxides. They undergo many of the characteristic reactions of strong bases, such as S*2 reactions with alkyl
halides or alkyl sulfonates (Secs. 9.4, 10.34). Thus, acetylenic anions can be used as nucleophiles in S*2 reactions to prepare other alkynes.

'/-;----\
| ..

CH3CH2CH2CHrIB.I:
I

-bromobutane

Na+

:C:CH -"il'r)-

sodium acetylide

CH3CH2CH2CH2-C:CH

Na+

(14.21)

l-hexFne
(640/o yielcl)

n.
- :'zt-.------'Na+ + H.,t f B-r: ------->

CH3CH2CH2CH2-C:C

CH3CH2CH2CH2-

C:C-

CH r

Na+

14.28)

The acetylenic anions in these reactions are formed by the reactions of the appropriate 1alkynes with NaNH, in liquid ammonia (Sec. 14.7A). The alkyl halides and sulfonates, as in most
other S"2 reactions, must be unhindered primary compounds. (Why? See Secs. 9.4D,9.5G.)

666

cHAprER 14

THE cHEMtsTRy oF ALKyNES

The reaction of acetylenic anions with alkyl halides or sulfonates is important because i/ ls
another method of carbon-carbon bond formation. Let's review the methods covered so far:

l.

cyclopropane formation by the addition of carbenes to alkenes (Sec. 9.8)

2. reaction of Grignard reagents with ethylene oxide and lithium organocuprate reagents
with epoxides (Sec. 11.4C)

3. reaction ofacetylenic anions with alkyl halides or sulfonates (this section)

14. I

Give the structures of the products in each of the following reactions.

(a)cHrc:e:

Na+ + cH3cH2-I ------->

(b)butyltosylate + Ph-C:C: Na+ ------->
(cl

CH3C:C-MgBr

(d) Br(CHz)sBr

ethylene

+ HC:C:

oxide ------->

Hro+

Na+(excess) ------->

14.19 Explain why graduate student Choke Fumely, in attempting to synthesize 4,4-dimetfil-2pentyne using the reaction of H.C-C-C: Na+ with tert-bvtyl bromide, obtained none of
the desired product.

14.20 Propose a synthesis of 4,4-dimethyl-2-pentyne (the compound in Problem 14.19) from an

alkyl halide and an alkyne.

14.21 Outline two different preparations of2-pentyne that involve an alkyne and an alkyl halide.
14.22 Propose another pair of reactants that could

be used to prepare 2-heptyne (the product in

Eq

14.2$.

14.8

ORGANIG SYNTHESIS USING ATKYNES

Let's tie together what we've learned about alkyne reactions and organic synthesis. The solution to Study Problem 14.2 requires all of the fundamental operations of organic synthesis: the
formation of carbon--carbon bonds, the transformation of functional groups, and the establishment of stereochemistry (Sec. 11.9).
Notice that this problem stipulates the use of starting materials containing five or fewer carbons. This stipulation is made because such compounds are readily available from commercial sources and are relatively inexpensive.

@outlineasynthesisofthefollowingcompoundfromacetyleneandanyothercompoundscontaining no more than five carbons:

cH3(cH2)6\
/cr{2crl2c}l(cH)2
C:C

/\
HH

cis-2-methvl-5-tridecene

Solution As usual, we stafi with the target molecule and work backward. First, notice the stereochemistry of the target molecule: it is a cis alkene. We've covered only one method of preparing
cis alkenes free oftheirtrans isomers: the hydrogenation ofalkynes (Sec. 14.6.4). This reaction,
then, is used in the last step of the synthesis:

14.8 ORGANIC SYNTHESIS USING

cH3(cH2)6.
J\

CH3(CH

z)e-C-f,

Lina#Ltahst

cH2cH2cH(cH3)2
-

-."\

C:C
/\
HH

-CH2CH2CH(CH3)2

2-niethyl-S -tridegrne

ALKYNES 667

(14.29a)

(target molecule)

t1t" **1task is to preparc *rc alkyne used

as the

sarting naferial in Eq. 14.29a. Because the desired

alkyne contains 14 carbons and the problem stiprlates the use of compormds with five

fswr carbons,

we'll have to use several reaptions that forrn carbon<a6on bonds. Ttrerc are two pimary alkyl groups
on the tiple bond; the oderin which they ae intoduced is abitrary. It's infrodrce the fue+arbon
fiagment on tlre right-hand side of this alkyne in tbe las step of the alkyne qmfuis. This is accomplisbed by forming tlrc conjugate.base aoetylenic anion of l-noryrne and alowing it to rcact with the ap
prcpriate commercially available ve-cabon alk;f halide, l-bromo3-meflrylbutane (Sec. 14.78):
Br-CHzCHzCH(CHE)z
-bromo-3-methylbutane

--.

CH3(CHz)o-C:C-H

CHI(CHa)5C-C:

ffi

1-nonlare

CH3(CH2)6-C:-C-CHzCHzCH(CH3)2 04.29b)
The staning material for this reaction, l-nonyne, is prepared by the reaction of l-bromohoptane

with the sodium salt ofacetvlene itself.

H-c-c-H ffi

Na+

:e-c-H

cHr(cHz)oBr

t cH3(cHr6-c-c-H

(14.29c)

(rarge excess

relative to NaNHu)

The large excess ofacetylene relative to sodium amide is required to ensure formation ofthe
monoanion-thatis, the anion derived from the removal of only otu acetylene p'roton. If there

dianion:f,:f,: could fonn, and other reactions

would occur. (What are they?) Because acetylene is cheap and is easily separated ftom the products (it is a gas), use of a large oxcess presents no practical problem.
Because the l-bromoheptane used in Eq. 14.29c haq 1161p than five carbons, it must be prewere more sodium amide than acetylene, some

pared as well. The following sequence of reactiols

cH3cH2cH2cH2cH2-Br

A
Hrc-cH:t

will accomplish this objective.

H:o+t

l-bronopentane
coac HBr

CH3CH2CH2CH2CH2GH2CH2-oH

Hzsor

> CH3CH2CH2CH2CH2GH2CH2-B1

(14.29d)

l-bromoheptane

1-heptanol

The synthesis is now complste. To summarize:

HC-CH

(excess)

ffi

cHr.(94r)eBr(Pqrl+tzgd)

CH3(CHz)'C-CH
H2

BTCHzCHzCH(CHr)z

cH3(cHz)oc-ccHzcH2cH(cHr)z

Lindlar catalvst

NaNHr
NHr (liq)
-

cH3(cH2)q cH'cH2cH(cH3)2
\/
C:C

/\

HH

(14,29e)

568

CHAPTER

14

THE CHEMISTRY OF ALKYNES

14.23 Outline a synthesis of each of the following compounds from acetylene and any other compounds containing five or fewer carbons.

(a) CHTCH'CH'CH2CH2CH2CH2CH2CH2-OH (b)

l-nonanol

o
tl

HrC-C-(CHz)sCH:
2-undecanone

14,9

PHEROMONES
As Problems 14.24 and 14.25 on p. 664 illustrate, the chemistry of alkynes can be applied to
the synthesis of a number of pheromones--rchemical substances used in nature for communication or signaling. An example of a pheromone is a compound or group of compounds
that the female of an insect species secretes to signal her readiness for mating. The sex attractant of the female Indian meal moth (Plodia interpunctella, a common pantry moth in the
United States) is such a compound:

H.
6Hz, CH2CH2CH2CH2CH2CH2CH2CH2-O-C-CU'
\/\/
C:C
C:C
/\/\
H:C
HH
H
(9 Z,l2E) -9,12 -tetradecadienyl acetate
(mating pheromone of the female Indian meal moth)

Pheromones are also used for defense, to mark trails, and for many other purposes. It was discovered not long ago that the traditional use of sows in France and Italy to discover buried
truffles owes its success to the fact that truffles contain a steroid that happens to be identical to
a sex attractant secreted in the saliva ofboars during premating behavior!
About three decades ago, scientists became intrigued with the idea that pheromones might
be used as a species-specific form of insect control. The thinking was that a sex attractant, for
example, might be used to attract and trap the male of an insect species selectively without affecting other insect populations. Alternatively, the males of a species might become confused
by a blanket of sex attractant and not be able to locate a suitable female. When used successfully, this strategy would break the reproductive cycle of the insect. The harmful environmental effects and consequent banning of such pesticides as DDT stimulated interest in such
highly specific biological methods.
Although experimentation has shown that these strategies are not successful for the broad
control ofinsect populations, they are successful in specific cases. For example, local infestations of the common pantry moth can be eradicated with commercially available traps that utilize the female sex attractant (Fig. A.7).In large-scale agriculture, traps employing mating
pheromones are useful as "early-warning" systems for insect infestations. When this approach
is used, conventional pesticides need be applied only when the target insects appear in the
traps. This strategy has brought about reductions in the use of conventional pesticides by as
much as 70Vo in many parts of the United States. Sex pheromones, aggregation pheromones
(pheromones that summon insects for coordinated attack on a plant species), and kairomones
(plant-derived compounds that function as interspecies signals for host plant selection) are
used commercially in this manner. Attractants for more than 250 different species of insect
pests are now available commercially.

14.9 PHEROMONES 669

pad impregnated with

mating pheromone

Figure 14.7 An infestation of the Indian meal moth, a common pantry moth. is controlled with a commercially
available trap.The pad on the trap is impregnated with the female mating pheromone. Males attracted to the
pheromone are immobilized and die on the sticky surface of the trap.The mating cycle of the moth is thus broken.Through use of these traps, fumigation ofthe pantry with insecticides is unnecessary.

l4.U

ln the course ofthe synthesis ofthe sex athactant ofthe grape berry moth, both the cis and
trans isomers of the following alkene were needed.
I

CH3CH2CH: CHCH2CH2CH2CH2CH2CH2CH zCHz-O

^ O)

(a) Outline a synthesis of the cis isomer of this alkene from the following alkyl halide and any
other organic compounds.

Br

CHZCH2CH2CH2CH2CH2CH2CH

z-." -l-

,-,

(b) Outline a synthesis of the trans isomer of the same alkene from the same alkyl halide and
any other organic compounds.

14.25 The following compound is an intermediate in one synthesis of the mating pheromone of the
female Indian meal moth (structue on p. 668). Show how this compound can be converted
into the pheromone in a single reaction.

HC
H2- Q
-C\/
C:C
/\
HrC
H

CHzCH2CHzCH2CH2CH2CH2CHz- O

tl

-C-

CH'

67

14.

cHAprER 14

10

THE cHEMtsrRy oF ALKyNES

OCCURRENCE AND USE OF ALKYNES

Naturally occurring alkynes are relatively rare. Alkynes do not occur as constituents of
petroleum, but instead are synthesized from other compounds.
Acetylene itself comes from two corlmon sources. Acetylene can be produced by heating
coke (carbon from coal) with calcium oxide in an electric furnace to yield calcium carbide,
CaCr.

cao + 3c

heat

> cac2 + co

*'il

gfiffi

(14.30)

-T;:r?"

Calcium carbide is an organometallic compound that can be regarded conceptually as the calcium salt of the acetylene dianion:
Q22+

3(l:Q;

calciurn carbide

Like any other acetylenic anion, calcium carbide reacts vigorously with water to yield the hydrocarbon; the calcium oxide by-product ofthis reaction can be recycled in Eq. 14.30.
The carbide process is widely used in Japan and eastern Europe, and it may become more important in the United States as the use of coal as a carbon source grows.
The second process for the manufacture of acetylene, and the predominant process used in the
United States, is the thermal "cracking" (that is, decomposition) of ethylene at temperatures above
1400 "C to give acetylene and Hr. (This process is thermodynamically unfavorable at lower temperatures.)

The most important general use of acetylene is for a chemical feedstock (starting material), as illustrated by the following examples:

:ffi:
'

+ HCr Hscr:'

(1431)

::;:::

(a monomer uded in the manufacture

of poly(vinyl chloride), PVC)

2HC:CH catalvst > HC:c-cH:cHu

vinylacetylene
acetylene

HCI

> Hrc:c-cH:cHz

e4.32)

Cl
chloroprene

I::ll"',9:'ffi:1T3.:ig$
Oxygen-acetylene welding is an important use of acetylene, although it accounts for a relatively small percentage of acetylene consumption. The acetylene used for this pulpose is supplied in cylinders, but it is hazardous because, at concentrations of 2.5-80Vo in air, it is explosive. Furthermore, because gaseous acetylene at even moderate pressures is unstable, this
substance is not sold simply as a compressed gas. Acetylene cylinders contain a porous material saturated with a solvent such as acetone. Acetylene is so soluble in acetone that most of it
actually dissolves. As acetylene gas is drawn off, more of the material escapes from solution
as the gas is needed-another example of Le Chdtelier's principle in action!

ADDITIONAL

Alkynes are compounds containing carbon-carbon

triple bonds. The carbons of the triple bond are

Catalytic hydrogenation of alkynes gives cis alkenes

when a poisoned catalyst is used. When a poison is

not used, hydrogenation to alkanes occurs. The reduction of alkynes with alkali metals in liquid ammonia, a reaction that involves radical-anion intermediates, gives the corresponding trans alkenes.

The sp hybridization state is less stable than the sp2 or

sp3 state. For this reason, alkynes have greater heats of
formation than isomeric alkenes.

2. reactions at the acetylenic

base sodium amide (NaNHr). ln a related transmetallabe

formed in the reactions of 1-alkynes with alkylmagne-

sium halides.

-C-H

bond

1 -Alkynes, with pq values nea r 25,are the most acidic

of the aliphatic hydrocarbons. Acetylenic anions are
formed by the reactions of 1-alkynes with the strong

tion reaction, acetylenic Grignard reagents can

Alkynes have two general types of reactivity:

1. addition to the triple bond

Both the hydration and hydroboration-oxidation of

alkynes yield enols, which spontaneously form the
isomeric aldehydes or ketones.

The carbon-carbon triple bond in an alkyne consists of

one o bond and two mutually perpendicular rr bonds.

The electron density associated with the rr bonds resides in a cylinder surrounding the triple bond.The induced circulation of these n electrons in a magnetic
field shields acetylenic protons as well as acetylenic
and propargylic carbons, and results in the relatively
small chemical shifts observed in NMR spectra.

sp-

hybridized. Electrons in sp orbitals are held somewhat

cfoser to the nucleus than those in spz or sp3 orbitals.

PROBLEMS 67

Acetylenic anions are good nucleophiles and react

with alkyl halides and sulfonates in Sr2 reactions to
form new carbon-carbon bonds.

Useful additions to the triple bond include Hg'*catalyzed hydration, hydroboration, catalytic hydrogenation, and reduction with sodium in liquid ammonia.

F'l

ii

REACTTON

{n}

REVTEW

For a summary of reactions discussed in this chapter, see Section R, Chapter 14, in the Study
Guide and Solutions Manual.

11.26 Give the principal product(s) expected when 1-hexyne

or the other compounds indicated are treated with each

of the following reagents:

HBr

(b) Hz,Pd/C
(c) Hz, Pd/C, Lindlar catalyst
(d) product of part (c) + Or, then (CH3)2S
(a)

(e) product of part (c)

+ BH, in THF,

then HzO?l-OH

1,4.21 Give the principal products expected when 4-octyne or

the other compounds indicated are treated with each of
the following reagents:
(a) Hz, Pd/C catalyst

(b) Hr, Lindlar catalyst

(c) product of (b) + Or, then H'O'/FI2O
(d) Na metal in liquid NH,

(f) product of part (c) * Br,

(e) Hg2+, HrSOo,HrO

(g) NaNH, in liquid ammonia

(h) product of part (g) + CH3CH2I
(i) Hgt*, H2SO4,Hro

(0 BH:, then HzOzl-OH

(j) disiamyl

borane, then HzOzl-OH

14.28 In its latest catalog, Blarneystyne, Inc.,

a chemical

company of dubious reputation specializing in alkynes,

67

cHAprER 14

THE cHEMtsrRy oF ALKyNES

has offered some compounds

for sale under the follow-

ing names. Although each name unambiguously specifies a structure, all are incorrect. Propose a correct

(f) (CH3)2CHCH2CH2CHTCH-O
(

g)

cls-2-pentene (h) trans-3-decene

(il meso-4,5-octanediol ( j) (Z)-3-hexen- 1-ol

name for each compound.

14.34 Using 1-butyne

(a )

2-hexyn-4-ol

(b )

6-methoxy- 1,5-hexadiyne

as the

only source of carbon in the re-

actants, propose a synthesis for each of the following

compounds.

} 1-butyn-3-ene
(d) 5-hexyne
{e

(a)

CHTCHTC:C-D
o

(b) CHTCH2CDTCD,

(c)

14.29 In each case, draw

a structure containing

only carbon

and hydrogen that satisfies the indicated criterion.

{a) a stable alkyne of five carbons containing a ring

(b) a chiral alkyne of six carbon atoms
(c,l an alkyne of six carbon atorns that gives the same
single procluct in its reaction either with BH, in
THF followed by HrOr/-OH or with

tl

cH3cH2cH2coH
(d) 1-butoxybutane (dibutyl ether)
(e)

the racemate of (3R,4S) -CHTCH2CHCHCH2CH2CHtCH:

tt

DD
(f )

octane (g)

H,o/Hg2*/H.o*

O
tl

cHrcH2ccH3

(d ) a six-carbon alkvne that can exist as diastereomers

14.30 On the basis of the hybrid orbitals involved in the

lrl.35 A box

labeled "CuH,n isomers" contains samples

of

bonds, arrange the bonds in each of the following sets

three compounds: A, 8,, and C. Along with the com-

in order of increasing length.

(a) C-H bonds of ethylene; C-H bonds of ethane;
C- H bonds of acetylene
(b) C-C single bond of propane; C-C single bond
of propyne; C-C single bond of propene

pounds are th.e IR spectra of A and B, shown in Fig.

14.31 Rank the anions within each series in order of increasing basicity, lowest first. Explain.

tal CH:CHzQ:-,
(b) cH:(cHr)3c

HC-a:, :it:-

ci

cHrqcHr;ncHr,

cH-.(cHz)_,cH-cH
14.32 Using simple observations or chemical tests with read-

P14.35. Fragmentary data in a laboratory notebook

suggest that the compounds are 1-hexyne, 2-hexyne,
and 3-methyl- 1,4-pentadiene. Identify the three compounds.

14.-16 You have just been hired by Triple Bond, Inc., a company that specializes in the manufacture of alkynes
containing 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, m"uscalure, wrth the stipulation that all of the carbon in the product must come
only from the company's alkynes. The muscalure will

ily observable results, show how you would distin-

subsequently be used in a household

guish between the compounds in each of the following

pairs. (Don't use spectroscopy.)
(a ) cris-2-hexene and 1-hexyne
(b) I -hexyne and 2-hexyne

be equipped with a laboratory containing all of the

(c )

4,,4-dimethyl-2-hexyne and 3,3-dimethylhexane

company's alkynes, requisition forms for other

fly swatters in case you are
successful. Outline a preparation of racemic muscalure

reagents, and one gross of

that meets the company's needs.

(cl) propyne and 1-decyne

14.33 Outline

a preparation

(cHr),rcH:
cH:(cHz)z
\/C-C
/\
HH

of each of the following com-

pounds from acetylene and any other reagents.

(a) CHTCH'CD'CD,CHTCH, (b) 1-hexene

muscalure

(c) 3-hexanol (d) 1-hexyne

(e)

fly trap. You will

cH3(cH)t-c-oH
I

14.37 Outline

a preparation of racemtc disparlnre, a

pheromone of the gypsy moth, from acetylene and any

ADDITIONAL

other compounds containing not more than five carbon

atoms.

A
_(CH3(CH)i'J"
(-

occur in this procedure are shown in Fig. P14.38,

(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 avoid-

-t'(CH2)4CH(CH3)2
H

PROBLEMS 67 3

urrnurlure

ing this reaction.

(c) Tetrahydrofuran (THF) is used as a solvent because
the undesired by-product,

14.38 In the preparation of ethynylmagnesium bromide by

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.

the transmetallation reaction of Eq. 14.24,

ethylmagnesium bromide is ad&d to a large excess of

acetylene in THF solution. Two side reactions that can

wavelength, micrometers

2.6 2.8

3.5

55.s678

4.5

l0

l1

t2

13

t4 1516
l

100
a,)

H80
(g

.:

860
(d
Lr

:40
q)

b20
o..
0

3800 3400 3000 2600 2200 2000 1800 1600 1400 1200
wavenumber, cm-

1000

800

2.6 2.8

3.s 4

wavelength, micrometers
4.5

5 5.56

l0

ll

12 13 14 1516

100
a.)

H80
(g

.:

E60

tr
(
L{

:40
q.)

(J

b20
a
0

3800 3400 3000 2600 2200 2000 1800 1600 1400 1200
wavenumber, cmFiSure P14.35

lR spectra

(l) H-C-Q-MgBr
(2)

2H-C-C-MgBr

Flgure P14.38

1000

800

for Problem 14.35.

----> CHTCH3 + BrMg-C-C-MgBr

+ BrMg-C-C-MgBr
H-.-C-H

+ CH3CHz-MgBr

rr*

67

cHAprER 14

THE cHEMtsrRy oF ALKyNES

(b) C4H.O: liberates a gas when treated with

14.39 (a) When the reduction of alkynes to alkenes by Na in

CrHsMgBr

liquid ammonia is attempted with a l-alkyne, every

three moles of l-alkyne give only one mole of
alkene and two moles of the acetvlenic anion:

2RC=
RCH-CH, + 2RC-Q:
3RC-(T'
lH -FffNU * RCH:CHz

NMR: 62.43 (IH,t, J

ZHz):

63.41 (3H, s); 64.10 (2H, d, J

IR:

Na+

ZHz)

125,3300 cm-r

(c) CoHuO:

NMR in Fig. P14.40

IR: 2100, 3300 cm ' lsharp), superimposed on a
broad, strong band at 3350 cm-r

Explain this result using the mechanism of this reduction and what vou know about the aciditv of 1alkynes.

(b) When (NHo)rSOo is added to the reaction mixture,

(d) csH6o

the 1-alkyne is converted completely into the

alkene. Explain.

IR: 3300,2102, 1634 cm-I

NMR: 53.10 (1F1, d, J - 2Hz); 63.79
64.52 (lH, doublet of doublets,

14.40 Identify the following compounds from their IR and

proton NMR spectra.

(a) CuH,oO'

6HzandZHz);66.38 (IH,d,J

(3F1, s);

6Hz)

14.41 (a) Identify the compound CuH,n that shows IR ab-

NMR: 63.31 (3lll, s); 52.41

(1F1, s);

sorptions at 3300 cm-r and 2100 cm-r and has the

following t'C NMR spectrum: 6 2l .3, 31.0, 66.7 ,

5 1.43 (6F1, s)

IR: 2110, 3300 cm t (sharp)

92.8.

(b) Explain how you could distinguish between

1-hexyne and 4-methyl-2-pentyne by '3C NMR.

chemical shift, Hz

2400

100

800

1s00 1200

900

600

300

6.7 Hz

disappears
on D2O shake

dry

43
chemical shift, ppm (6)

FiSure P'|4.40 The NMR spectrum for Problem 14.40c. 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.

ADDITIONAL

14.42 Propose mechanisms for each of the following known

transformations: use the curved-arrow notation where
possible.

oo
illl
HOC-CHzCHz-COH

H-COH

succinic acid

formic acid

(a)

Ph-C-CH

Hzo

Brz

t Ph-A-cH2Br
+

Ph-Q-C-H

THF

ph_e_C_D

14.43 A compound A (C6H) undergoes catalytic hydrogenation over Lindlar catalyst to give a compound B, which
in turn undergoes ozonolysis followed by workup with
aqueous HrO, to yield succinic acid and two equivalents of formic acid. In the absence of a catalyst poison, hydrogenation of A gives hexane. Propose a structure for compound A.

(a) cH3cH2cH

(b)

cHrcHzMgBr

zcH2c-cH

o
ll

14.44 An optically active alkyne A (Cr'Hr+) can be catalytically hydrogenated to butylcyclohexane. Treatment of
A with C2HsMgBr liberates no gas. Catalytic hydrogenation of A over Pd/C in the presence of quinoline
poison and treatment of the product with O, and then
HrOrgives an optically active tricarboxylic acid
CsHr2Oo. (A tricarboxylic acid is a compound with

HBr

(b)
NaOD,
DzO (large excess),

PROBLEMS 67 5

H"i;|"?'jl il::il1,:i::

the structure orA' and

14.45 Complete the reactions given in Fig. P14.45 using

knowledge or intuition developed from this or previous
chapters.

DzO

t
(CH3)3SiCl

CH3CH2CHzCHz-C-Q-H + CH3CH2CH2CHz-Li

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

reactions.)

(c)

tl

CH3CH2-O-S-O-CHzCHr
A

cH3(cH

(Hint:
(d)

z)o-.c-cH

diethylsulfate t

See Sec. 10.3C.)

ri-c-cH
(

NaNHz

+ F-(cHz)s-cl

-*

I equivalent)

(e)

neutralize

Ph-cH:cHz + Brz 1

NaNHz

(H:o+)

(Hint: See Sec. 9.5)

(f)

p'_c-e_ph

+ HCCI3

(Hint: See Sec. 9.8A)

Figure P14.45

K+(cHr)rco-

(a hydrocarbon not
containing bromine)