1

13. ORGANI C CHEMI STRY

I V) ALKYNES
SYNOPSIS
Alkynes are commonly known as acetylenes. Acetylene is the simplest and important member of
the alkyne series.
Alkynes contain C C
General molecular formula of alkynes is C
n
H
2n2

Triple bonded carbons are sp hybridized and greater s character is associated with it.
Alkynes will exhibit chain, position and functional isomerism.
Their functional isomers are alkadienes and cyclo alkenes.
The minimum number of carbons required to exhibit chain isomerism by an alkyne is five.
Preparation of Acetylene or ethyne :
1. Industrial method : By the hydrolysis of calcium carbide
( )
2 2 2
OH Ca CH HC O H 2 CaC + +
Ca ( )
2
H
H
C
C
OH
OH
H
H
C
C
OH Ca ||| ||| + +

Even, other carbides like, MgC
2
, SrC
2
, BaC
2
on hydrolysis will give acetylene.
2. By the dehydrohalogenation of gem or vicinal dihalides.
i)
( )
CH CH
Br H
KOH . alc
Br CH
2
CH
HBr
. alc
KOH
Br
|
2
CH
Br
|
2
CH

+
ii)
( )
CH CH
HBr
KOH . alc
Br CH
2
CH
HBr
. alc
KOH
2
CHBr
3
CH

+
3. By the dehalogenation of acetylene tetrabromide
2 2 2
ZnBr 2 CH CH Zn 2 CHBr CHBr + +


4. Iodoform reacts with silver powder to give acetylene.
AgI 6 H C Ag 6 CHI 2
2 2 3
+ +


5. Kolbes electrolysis : Sodium or potassium salts of unsaturated dicarboxylic acids, on electrolysis
will give alkynes.
Potassium maleate or potassium fumerate on electrolysis gives acetylene

2
H KOH 2
2
CO 2
CH
CH
|||
is electrolys
H
H
HO
HO
COOK
COOK
CH
CH
|| + + +

at anode at cathode
Physical properties : Pure acetylene is colorless, odourless gas, presence of impurities such as H
2
S,
PH
3
will give garlic odour.
It is sparingly soluble in polar solvents like H
2
O, but readily soluble in non polar solvents like
alcohol, ether etc.
It is less volatile than ethylene and ethane.
Chemical properties :Acetylene undergoes addition reactions because it is unsaturated.
Acetylene undergoes both electrophilic additions and nucleophilic additions while ethylene
undergoes only electrophilic additions.
Organic Chemistry
2

H
C
|||
C
H
Reactivity : Acetylene is more reactive due to the presence of triple bond or 2 bonds.
But, acetylene is less reactive than ethylene due to shortening of C C bond length electrons
are strongly held.
Reactivity order :
H
2
C =CH
2
>HC CH >H
3
C CH
3
I) Addition reactions:
In these additions, two molecules of the reagent will be added to acetylene


3 3
Ni / H
2 2
Ni / H
CH C H CH C H
2 2
=
( )
2
westron
2
CCl / Cl
Cl
|
Cl
|
CCl / Cl
CHCl HC Cl CH HC
4 2 4 2
=
2 2
CCl / Br CCl / Br
CHBr HC Br CHBr BrHC ,
4 2 4 2
=
( ) hane dichloroet 1 , 1
2 3
HCl
ide Vinylchlor
2
HCl
CHCl CH Cl CH CH

=
( )
( )
2
4 2 4
rearrangement H O
2 3
1%HgSO 30%H SO
vinylalcohol Acetaldehyde
Unstable
CH CH OH CH CHO
+
=

( )
acetate ethylidene
2 3
OCOCH
|
CH C
3
H
te Vinylaceta
3
OCOCH CH C
2
H
Hg
COOH CH COOH
3
CH
2
3
=
+

ile Acrylonitr or cyanide vinyl
2
CuCN
HCN
CN CH C H =
lewisite
2
AsCl
AsCl CH ClHC
3
=
Reaction with H
2
O and HCN are nucleophilic additions.
II. Oxidation :
i) Acetylene is oxidised to oxalic acid with alkaline KMnO
4
. Pink colour of KMnO
4
is declorised .
( ) COOH HOOC O 4 CH HC
C 25 , OH
KMnO
0
4
+


ii) Acetylene is oxidised to acetic acid in presence of chromic acid.
( ) COOH CH O H O CH HC
3
acid chromic
2
+ +
III. Combustion : Acetylene burns in air to give oxy- acetylene flame, which is used in weldings and
cuttings.
flame ne oxyacetyle O H CO 2 O
2
5
CH CH
2 2 2
+ + +
( ) O H 1 n nCO O
2
1 n 3
H C
2 2 2 2 n 2 n
+

IV) Polymerisation : Acetylene when passed through red hot iron tubes, it trimerises to give benzene.

6 6 2 2
H C H C 3

In the above trimerisation, 3 bonds are broken and 3 bonds are formed.
Organic Chemistry
3

v) Ozonolysis : Acetylene on addition of ozone,
followed by reductive hydrolysis gives glyoxal.
HC CH+O
3

O
|
CH
O
O
|
HC

CHO
Glyoxal
OHC
Zn / O H
2

Acetylene ozonide
vi) Acidic nature of alkynes :
In alkynes, triple bonded carbons are sp hybridised.
Due to greater s character (50%), the hydrogens bonded to triple bonded carbons are slightly
acidic.
The hydrogens of acetylene or hydrogens bonded to triple bonded carbon of any other alkyne are
acidic hydrogens and they can be easily replaced by metal atoms like Ag, Na, Cu to give
corresponding metal acetylides.
Thus acetylene and terminal alkynes (Alk 1-ene) are acidic. Non terminal alkynes are not
acidic.
Acetylene is slightly acidic, but less acidic than even H
2
O.
a) With Na or NaNH
2
:
HC CH +Na NaC CH + H
2

HC CH +2Na NaC CNa +H
2

HC CH +NaNH
2
NaC =CH +NH
3
Sodium acetylides are useful in the preparation of higher alkynes.
i) HCCNa +CH
3
- Br HC C CH
3
+NaBr
Propyne
ii) NaCCNa+2CH
3
BrCH
3
-CCCH
3
+2NaBr
2 Butyne
iii) HCCNa +C
2
H
5
- Br HC C C
2
H
5
+NaBr
1 Butyne

b) with Tollens reagent (Ammonical silver nitrate):
HC CH +2AgNO
3
+2NH
4
OH AgC CAg +2NH
4
NO
3
+2H
2
O
Silver acetylide (white ppt)
c) with ammoniacal cuprous chloride :
HCCH+Cu
2
Cl
2
+2NH
4
OHCuC CCu+2NH
4
Cl+2H
2
O
Cuprous acetylide (red ppt)
The above reactions are substitution reactions.
Uses :
In oxyacetylene flame used in weldings and cuttings
In the preparation of compounds like acetaldehyde, aceticacid, ethyl aclcohol, benzene etc.
In the preparation of industrial solvents like westron and westrasol (1, 1, 2 trichloro ethene)
In Hawkers lamp for illumination purposes.