ALKYNES

5.1 INTRODUCTION
A large number of naturally occurring compounds containing triple bonds have
been isolated from plant kingdom. For example, a triyne from safflower has
considerable activity against nematodes and evidently forms part of the plant’s
chemical defence against infestation.

You will see in this unit that the carbon-carbon triple bond reacts with many of the
reagents that react with alkenes. You will also study the most unique aspect of the
chemistry of alkynes, the acidity of terminal alkynes.

5.2 TYPES OF ALKYNES

Alkynes, also known as acetylenes, constitute the homologous series of open chain
unsaturated hydrocarbons that contain one or more carbon-carbon triple bond. Alkynes
may be of two types: terminal and internal. In the terminal alkynes, the triple bond lies at
the end of the carbon chain and in the internal alkynes, the triple bond lies anywhere
except at the terminal position.

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CH3C≡CH CH3CH2C≡CCH2CH3 CH3C≡CC≡CCH3
1-propyne 3-hexyne 2,4-hexadiyne
(terminal alkyne) (internal alkyne) (internal alkyne)

5.3 NOMENCLATURE OF ALKYNES

Alkynes are named in much the same way as alkenes. The name of the alkyne is
obtained by replacing the –ane ending of the corresponding alkane by –yne.

The lower number of the two carbon atoms of the triple bond is used to designate the
location of the triple bond. Some examples are:

Parent alkane Alkyne

CH3CH3 ethane HC≡CH ethyne

CH3CH2CH2CH2CH3 pentane CH3CH2C≡C─CH3 2-pentyne

(pent-2-yne)

When substituents are present, these are incorporated into the names as it was done
for alkenes. Some examples are:

Cl─CH2CH2C≡CH 4-chloro-1-butyne (4-chlorobut-1-yne)

CH3C≡CCH2Cl 1-chloro-2-butyne (1-chlorobut-2-yne)

CH3─CH─CH2CH2C≡CH 5-methyl-1-hexyne (5-methylhex-1-yne)

│
CH3

CH3
│
CH3─C─CH2C≡CH 4,4-dimethyl-1-pentyne
│ (4,4-dimethylpent-1-yne)
CH3

When a double bond and a triple bond are present in the same molecule, then if there is a
choice, then, the double bond is given the lower number. For example:

CH≡CCH2CH=CH2 1-penten-4-yne (pent-1-en-4-yne)

If a hydrocarbon chain contains more than one triple bond, the infixes -adiyne, -atriyne
and so forth, are used. For example:

CH≡CCH2CH2CH2C≡CH 1,6-heptadiyne

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5.4 PHYSICAL PROPERTIES

The increase in boiling point with increase in molecular weight is due to

increased London forces, as discussed in Unit 1 of this course.

Fractional distillation is the method of separating the components in a liquid mixture

using the difference in their boiling points.

The physical properties of alkynes are similar to those of corresponding alkenes. They are
all colourless and odourless (except ethyne). The first three members, i.e., ethyne,
propyne and 1-butyne are gases at room temperature; the next eight members are liquids
and the higher members are solids. The physical constants like melting points, boiling
points and densities increase gradually with the increase in molecular weight. Alkynes
have slightly higher boiling points than the corresponding alkenes and alkanes. Terminal
alkynes have lower boiling points than the isomeric internal alkynes and can be separated
by careful fractional distillation. Alkynes share with alkanes and alkenes the properties of
low density and low water solubility. They are nonpolar and dissolve readily in typical
organic solvents, such as diethyl ether, chlorinated hydrocarbons, etc.

5.5 PREPARATION OF ALKYNES

Organic synthesis makes use of two major reaction types: One is functional group
transformation and the other is carbon-carbon bond forming reaction. Both these
strategies are applied to the preparation of alkynes. In this Unit, we shall discuss how
alkynes are prepared by elimination reactions and by adding alkyl group(s) to the smaller
ethyne unit. Some important methods of preparation of alkynes are:

(i) Dehydrohalogenation of dihalide

(ii) Dehalogenation of tetrahalide

(iii) Alkylation of ethyne

5.5.1 Dehydrohalogenation of Dihalides

You have already seen in Unit 4 that an alkene can be prepared by the elimination of HX
from an alkyl halide. Similarly, an alkyne can be prepared by the elimination of two
molecules of HX from a dihalide. The dihalide may be of the geminal or vicinal type.

• Geminal dihalide: One in which both the halogen atoms are substituted on
the same carbon atom.
• Vicinal dihalide: One in which halogen atoms are substituted on adjacent carbon
atoms.

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Since an alkyne contains a triple bond as compared to the double bond in alkenes, two
molecules of HX must be eliminated. Therefore, stronger conditions are required to
remove the second HX molecule. For example, when 1,2-dibromopropane reacts with a
strong base, a two-fold elimination occurs and as a result a propyne is produced.

H H H
│ │ NH3(ℓ) │ NaNH2
H─C─C─CH3 + NaNH2 H─C=C─CH3 H─C≡C─CH3
│ │ -33ºC │
Br Br Br

You have studied in Unit 4 that dihalides are prepared by the addition of halogen to
an alkene. Thus, the overall sequence of halogenation-dehydrohalogenation provides
an excellent method for going from an alkene to an alkyne. For example:

Br2 2 NaNH2
CH3(CH2)3CH=CH2 CH3(CH2)3CHCH2Br CH3(CH2)3C≡CH
│ -2 HBr
Br

You may recall that alkenes can be prepared by elimination reactions of alkyl halides,
which again, can be obtained from alkanes. Thus, we can say that alkane can serve as
a starting material for the preparations of alkynes.

hν base Br2
CH3─CH3 + Br2 CH3─CH2Br CH2=CH2 CCl4
base
BrCH2─CH2Br CH≡CH

Different bases can be used for dehydrohalogenation; sodium amide is preferred, since
it usually gives a higher yield.
The two-fold dehydrohalogenation follows the same mechanism as the
dehydrohalogenation of alkyl halide to alkenes mentioned in Unit 4.

5.5.2 Dehalogenation of Tetrahalides

Alkyne can also be prepared by dehalogenation of tetrahalides. For example, propyne is
formed when the vapours of 1,1,2,2-tetrabromopropane are passed over heated zinc.

Br
│ Zn
Br─CH─C─CH3 CH≡C─CH3
│ │ ∆
Br Br
1,1,2,2-tetrabromopropane

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This reaction does not have any synthetic importance, since the tetrahalides themselves
are usually prepared from alkynes. However, it provides a method for the purification
of alkynes.

5.5.3 Alkylation of Ethyne

Reactions that lead to the attachment of an alkyl group to a molecular fragment are
called alkylation.

In this sub-section, we shall see how alkynes are prepared by combining smaller units
to build larger carbon chains. One of these structural units is ethyne itself. By attaching
alkyl group to ethyne, more complex alkynes can be prepared. For example,

CH3(CH2)2CH2I
- + + -
HC≡CH + NaH HC≡C Na HC≡CCH2(CH2)2CH3 + Na Br

Alkylation is a two-step process. In the first step, ethyne reacts with sodium amide to
give a sodium ethynide ion, the conjugated base of ethyne. .

In the second step, sodium ethynide ion attacks the C-1 carbon atom of 1-iodobutane and
pushes out the, iodide ion giving an overall 86% yield of 1-hexyne.
Again, l-hexyne can itself be converted into an alkynide anion, and can be alkylated a
second time to yield an internal alkyne. A different alkyl halide can be used this time.
NaH CH3CH2Br
- +
CH3(CH2)3C≡CH CH3(CH2)3C≡C Na
+ -
CH3(CH2)3C≡CCH2CH3 + Na Br

This reaction gives good yields of alkyne only with primary alkyl bromides and iodides.
Alkylation can also be carried out by reacting ethyne and Grignard reagent, followed by
the reaction with an alkyl halide.

RX
CH≡CH + RMgX CH≡CMgX CH≡C─R + MgX2

SAQ
Suggest a method for preparation of the following alkynes starting with ethyne. Use any
alkyl halide needed.

(a) 2-Heptyne

(b) 3-Heptyne

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5.6 REACTIONS OF ALKYNES
Due to the presence of loosely held π electrons, alkynes undergo reactions similar to
those of alkenes. You will see in this Unit that some of the chemical characteristics of
alkynes are similar to those of alkenes. Characteristic reactions of alkynes include
electrophilic additions, reduction and oxidation. Some important reactions of alkynes are:

(i) Electrophilic addition reactions (ii) Hydrogenation (iii) Ozonolysis

5.6.1 Electrophilic Addition

Electrophilic addition reactions are characteristic of alkynes. Some common electrophilic
addition reactions are discussed below.

If one of the carbon atoms involved in double bond formation (with another carbon atom)
carries a positive charge, then the species is called alkenyl cation. For example:
+
H2C=CH
(i) Hydrohalogenation

Halogen acid (HX) can add on to alkynes. The addition of halogen acid cannot take
place in the dark, light or metallic halides. Like alkenes, the addition is in accordance
with Markownikoff’s rule; for example, ethyne combines with hydrogen bromide to
form first 1-bromoethene and then 1,1-dibromoethane.
HBr
HC≡C─H + HBr H2C=CHBr CH3CHBr2
ethyne 1-bromoethene 1,1-dibromoethane

The mechanism of these reactions is the same as in the hydrohalogenation of alkenes, i.e.,
+
CH≡CH + H─Br CH=CH2 + Br-

+
-
CH=CH2 + Br CHBr=CH2
Addition of another molecule of hydrogen bromide could give either CH3CHBr+ (a
+
secondary carbocation) or CH2CH2Br (a primary carbocation). Since the secondary
carbocation is more stable than the primary carbocation, the reaction proceeds via
the secondary carbocation to form 1,1-dibromoethane. Thus;
+ +
CHBr=CH2 + HBr CHBrCH3 (CH─CH3 CH─CH3)
│ ║+
Br: Br
resonance stabilized
+
-
CHBrCH3 + Br CHBr2CH3
The other alternative way of explaining this addition of the halogen atoms on to the same

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carbon atom is as follows:
-
Br
CH=CH2 + H──Br CH─CH3) CHBr2CH3
│ ║
+
Br Br

In this way, the bromine atom increases the nucleophilic nature of the double bond
by using its lone pair of electrons.

Because of the electron-withdrawing nature of bromine atom, the availability of π

electrons in 1-bromoethene is less than that in ethene. Hence, the electiophilic addition
(of HBr) to 1-bromoethene is much slower than that to ethene.

In the presence of free radical initiators such as peroxides, anti-Markownikoff addition of

HBr is observed as with alkenes. For example, addition of HBr in the presence of
peroxides to 1-butyne gives 1,2-dibromobutane, as shown below:

peroxide
CH3CH2C≡CH + HBr CH3CH2CHBrCH2Br

You may be aware that bromine atom is grouped as ─ I group. Recall what you
have studied under inductive effect in Unit 1.

(ii) Halogenation
Alkynes react with chlorine and bromine to yield tetrahaloalkanes. Two molecules of
halogen add to the triple bond. A dihaloalkene is an intermediate and can be isolated
using proper reaction conditions. Ethyne, for instance, on treatment with bromine
water gives only 1,2-dibromoethene whereas with bromine alone, it forms 1,1,2,2-
tetrabromoethane.

H2O
HC≡C─H + Br2 HC=CH
│ │
Br Br

HC≡C─H + Br2 Br2HC─CHBr2

The addition of halogens to ethyne is stereoselective; the predominant product is the

trans isomer.

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 Br H3 C Br
Br
H3C C C CH3 + Br Br CC C C
Br CH3
H3C CH3
trans product
a bridged bromonium
ion intermediate

(iv) Hydroboration
Addition of borane to alkynes gives alkenyl boranes, which can be oxidised by basic
hydrogen peroxide to ketones via their enol. For example:

H O
1. BH3 │ ║
CH3C≡CCH3 CH3C=C─CH3 CH3CH2CCH3
2. H2O2, NaOH │
OH

The symmetrical internal alkynes give a single product while unsymmetrical

internal alkynes give a mixture of both the possible ketones. For example, 3-hexyne
gives 3-hexanone while 2-hexyne gives a mixture of 2-hexanone and 3-hexanone.

O
1. BH3 ║
CH3CH2C≡CCH2CH3 CH3CH2CCH2CH2CH3
2. H2O2, NaOH 3-hexanone

O O
1. BH3 ║ ║
CH3C≡CCH2CH2CH3 CH3CCH2CH2CH2CH3 + CH3CH2CCH2CH2CH3
2. H2O2, NaOH 2-hexanone 3-hexanone

The terminal alkynes on hydroboration give aldehydes.

Another reaction of organoboranes is protonolysis. That is, the alkenyl boranes, formed
after the addition of borane to alkynes, on treatment with ethanoic acid yield cis-alkenes.
This reaction sequence provides another method of converting alkynes to cis-alkenes.
For example:

H3CH2C CH2CH3
C C
THF
3 CH3CH2C≡CCH2CH3 + BH3 H B
R R
(R = cis-3-hexenyl group)
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 H3CH2C CH2CH3
3 CH3COOH 3 C C +(CH3COO)3B
H H

5.6.2 Hydrogenation
Like alkenes, alkynes undergo catalytic hydrogenation. The addition of hydrogen to an
alkyne takes place in two steps. First addition results in the formation of an alkene; since
an alkene can also undergo catalytic hydrogenation, the second addition gives an alkane.
By using a calculated amount of hydrogen and a poisoned catalyst, hydrogenation can
be stopped at the alkene stage. These catalysts selectively block the hydrogenation of
alkenes. For example:
H3C CH3
Lindler
CH3C≡CCH3 + H2 C C
catalyst
H H
cis-2-butene
This is a stereoselective addition reaction giving predominantly cis alkenes. In the absence
of a poison, catalytic hydrogenation of an alkyne gives the alkane. For example:

Pd, Pt or Ni
CH3C≡CCH3 + 2 H2 CH3CH2CH2CH3
pressure

Now you can ask: can we modify the reduction of alkynes so as to get only trans alkenes.
The answer is yes; we can get only trans products, but with a different reducing agent
and through a different mechanism.

If we carry out the reduction of an alkyne with sodium metal or lithium metal in liquid
Ammonia, trans alkene is almost an exclusive product. For example, 3-heptyne is
reduced to trans 3-heptene in the following way:

Na H3CH2C H
CH3CH2C≡CCH2CH2CH3 C C
NH3(ℓ)
H CH2CH2CH3
trans 3-heptene

In the first step of this mechanism, the alkyne accepts one electron to give a radical anion.

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The radical anion is protonated by ammonia solvent to give an alkenyl radical; which gets
further reduced by accepting another electron to give an alkenyl anion. This species is
again protonated to give the, alkene.

Reaction Mechanism: (trans addition)

1. A one-electron reduction of the alkyne to a radical anion.

+
H 3C C C CH3+Na H 3C C C CH3 + Na
(an alkenyl radical anion)

2. An acid-base reaction to form an alkenyl radical and amide ion.

CH3
H3CCCCH3 +HNH CC+ NH
H 2 2

H3C H
3. A second one-electron reduction to form an alkenyl anion.
CH3 CH3
Na + C C Na + C C

H3C H H3C H
an alkenyl anion
4. A second acid-base reaction to give the trans-alkene.

CH3 H CH3

H2NH+ CC NH2 + CC
H3C H H3C H
trans-2-butene
Formation of the trans alkene is due to the rapid equilibration of the intermediate alkenyl
radical between the cis-and trans-forms. The equilibrium lies on the side of the more
stable trans species.

In other words, we can say reduction of alkyne to double bond can yield either cis-alkene
or trans-alkene, depending upon the choice of the reducing agent.

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5.6.3 Ozonolysis
Reagents and reactions that lead to oxidative cleavage of alkenes also lead to cleavage of
alkynes. Addition of ozone to an alkyne produces the ozonide. The ozonides on
hydrolysis give 1,2-dicarbonyl compounds, which undergo oxidative cleavage to
carboxylic acids by hydrogen peroxide formed in the reaction. For example, 2-hexyne on
ozonolysis gives butanoic and ethanoic acids.

1. O3
CH3CH2CH2C≡CCH3 CH3CH2CH2CO2H + CH3CO2H 2.
H2O
2-hexyne butanoic acid ethanoic acid

Same products are obtained when alkynes are oxidized by alkaline permanganate and
then hydrolysed using mineral acid.
-
1. KMnO4, OH
CH3CH2CH2C≡CCH3 CH3CH2CH2CO2H + CH3CO2H 2.
+
H
Oxidative cleavage reactions are used as a tool in structure determination. The carboxylic
acids formed would tell us which of the carbon atoms were linked through the triple
bond in the origina1 alkyne.

SAQ
Propose structures for alkynes that give the following products on oxidative cleavage:

(a) CH3CO2H + CH3CH2CO2H

(b) 2 CH3CH2COOH

5.9 TERMINAL QUESTIONS

1. Predict the product of the following reactions of 1-butyne:

1. NaNH2
(i) CH3CH2C≡CH
2. CH3CH2Br

1. BH3
(ii) CH3CH2C≡CH
-
2. H2O2, OH
2. How will you convert?

(a) 2-Bromopropane to propyne

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 (b) l-Bromopropane to 2-hexyne.

3. Suggest steps for the following transformations:

(a) 2,3-dibromopentane to trans-2-pentene

(b) 3-methyl-1-butyne to trans-2-methyl-3-heptene

4. Show, by writing appropriate chemical equations, how each of the following

compounds could be converted to 1-butyne?

(a) 1,2-dibromobutane

(b) 1-butene