Alkyne Reactions

On the basis of presence of single and multiple covalent bonds in the aliphatic
hydrocarbon, they can be classified as alkanes, alkene and alkynes. Alkanes
are saturated hydrocarbons in which all carbon atoms are bonded with single
covalent bond. Due to saturation, they are usually giving substitution reactions
and less reactive compare to other aliphatic hydrocarbons. Another type of
hydrocarbons is unsaturated hydrocarbons which contain either double or triple
covalent bond in between at least two carbon atoms. Alkynes have at least one
triple bond between two carbon atoms such as ethyne (CH=CH). Alkenes contain
at least one double covalent bond between two carbon atoms.

We know in multiple bonds like in a triple bond, there is one pi bond with two
sigma bond. Similarly in a double bond, there is one pi bond with one sigma
bond. Pi bonds are weaker compared to sigma bond and readily cleave than
sigma bond. That is the reason; alkenes and alkynes are more reactive
comparable to alkanes which are saturated hydrocarbons.

Alkenes are mainly involved in additional reactions such as hydrogenation,
halogenations etc. They can also give some substitution reactions but with less
speed compare to addition reactions. Addition reactions play an important role in
our daily life also such as hydrogenation of vegetable oil, hydrogenation of
alkenes etc. Lets discuss some common addition reactions of alkenes with their
mechanism.

Hydrogenation
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Hydrogenation of alkyne can be done in two ways.


1. Complete reduction or hydrogenation

On reacting with strong reducing agents like palladium, platinum, nickel or
rhodium alkynes are reduced to alkanes. For example propyne is reduced to
propane.

CH
3
-C = CH + 2H
2
$\to $ CH
3
-CH
2
-CH
3

The heats of hydrogenation is double that of corresponding alkenes. Like alkenes
the heats of hydrogenation depends on nature of branching in alkynes. Due to +I
effect the alkyl release electrons to carbon atom and hence the heats of
hydrogenation is reduced. So the heats of hydrogenation of 1-pentyne will be
more than that of 2-pentyne.

CH
3
-CH
2
-CH
2
-C = CH > CH
3
-CH
2
-C = C-CH
3



2. Partial reduction or hydrogenation

Alkynes on partial reduction with poor catalysts give alkenes. The
partial reduction of alkynes can be done in two ways.
By reacting with Palladium in Calcium carbonate / Palladium in barium
sulphate. Alkynes on treating with palladium in barium sulphate give cis alkenes.
For example 2-Butyne on reacting with palladium in barium sulphate gives cis 2-
Butene.
CH
3
-C = C-CH
3
+ H
2
[Math Processing Error]


By reacting with alkali metal in liquid ammonia. Alkynes on treating
with alkali metals in liquid ammonia give trans alkenes. For example 2-butyne on
reacting with sodium in liquid ammonia give trans-2-butene.
CH
3
-C = C-CH
3
+ H
2
[Math Processing Error]
Halogenation
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Alkynes undergo addition with halogen to give tetra halo derivatives. For example
acetylene on reacting with chlorine give 1,1,2,2 tetra chloro ethane (Westron)
which on further reacting with alcoholic KOH give westrol ( 1,1,2 trichloro
ethene). Westron and westrol are used as solvents for organic compounds.
CH CH + 2Cl
2
CHCl
2
-CHCl
2

CHCl
2
-CHCl
2
+ KOH CHCl=CCl
2

Similarly alkynes also add with bromine water in carbon disulphide. This is the
characteristic test to determine unsaturated compounds as the color of the
bromine water will be decolorized.
Hydrohalogenation
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Alkynes on reacting with hydrogen chloride give vinyl chloride which may
undergo polymerization to give polyvinyl chloride or it can undergo addition with
HCl again to give ethyledene chloride. For example the reaction of acetylene with
hydrogen chloride is given below.
CH CH + HCl CH
2
= CH-Cl
CH
2
= CH-Cl [CH
2
-CH(Cl)-]
n
or
CH
2
= CH-Cl + HCl CH
3
-CH-Cl
2

Hydrolysis
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Alkynes react with water in the presence of HgSO
4
to give a alcohol with double
bond. This alcohol is called as enol (en for double bond and ol for alcohol). This
reaction is called as Kocharov's reaction. For example acetylene on hydrolysis
with mercuric sulphate gives an enol as given below.
CH CH + H
2
O CH
2
=CH-OH
This enols are highly unstable and undergo migration to give carbonyl
compounds ( aldehydes and ketones). The migration of enol to carbonyl
compound and vice versa is called tautomerism, a type of isomerism. Some type
of enols are stable and acidic and can be isolated by adding suitable base. For
example the enol formed due to hydrolysis of acetylene changes to acetaldehyde
as given below.

CH
2
= CH-OH CH
3
-CHO
Similarly 2-Butyne on hydrolysis followed by tautomerism gives butanone.
CH
3
-C C-CH
3
+ H
2
O CH
3
-CH = C(OH)-CH
3

CH
3
-CH = C(OH)-CH
3
CH
3
-CH
2
-CO-CH
3

Ozonolysis
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Alkynes on ozonolysis gives ozonides which on further hydrolysis give
carboxylate ions. From the nature of carboxylate ions the position and nature of
triple bond in an organic compound can be determined. For example the
ozonolysis of propyne is given below.

In the first step the ozone adds with alkyne to give ozonide which on further
hydrolysis gives carboxylic acids.

Polymerization
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Alkynes undergo two type of polymerization reaction.


1. Linear polymerization

Acetylene on linear polymerization give vinyl acetylene which on further
polymerization give polyvinyl acetylene. This is linear polymerization.

CH = CH [Math Processing Error] [-CH = CH-]n
2. Cyclic polymerization

Acetylene when passed through red hot tube undergoes cyclic polymerization to
give benzene.
3 CH=CH ? C
6
H
6



Similarly propylene on cyclic polymerization gives mesitylene.
Oxidation
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The triple bond between carbon atoms can be easily oxidized by oxidizing agents
like alkaline potassium permanganate to give carboxylic acids. The alkaline
potassium permanganate is called Bayer's reagent and it is decolorized when
acetylene gas is bubbled through the Bayer's solution.

CH CH COOH-COOH
Alkyne Reaction Summary
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The reaction of alkynes can be summarized below.

1. Alkynes on adding with hydrogen undergo hydrogenation to give
alkanes. The heats of hydrogenation is more than alkenes. Similarly the partial
hydrogenation give alkenes.
2. Alkynes can undergo addition reaction with 2 moles of chlorine and
hydrogen halides to give addition product.
3. Similarly they can undergo oxidation reaction with alkaline potassium
permanganate to give carboxylic acids.
4. Alkynes can undergo linear and cyclic polymerization to give polymers.
5. Alkynes can react with ozone to give ozonides which on hydrolysis give
carboxlic acids. This reaction can be used to identify the position and nature of
triple bond.
6. Alkynes add with water in the presence of mercuric sulphate to give
enols (an organic compound containing both alcohol group and double bond).
This enols are unstable and undergo tautomerism to give carbonyl compounds
(ketones or aldehydes). The presence of enol form can be proved by separating
it with the help of a strong base.
Alkyne Addition Reactions
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In an addition reaction atom/groups are added across an unsaturated bond
(double/triple) in an organic compound. Alkynes have a triple bond in their
structure and can add 2 moles of compound to become saturated. This addition
reaction can be of following types.

1. Addition of hydrogen (hydrogenation)
2. Addition of halogen (halogenation)
3. Addition of hydrogen halides
4. Addition of water (hydration)
As alkynes are rich source of electrons, all the addition reactions stated above
are electrophilic addition reactions.