ALKYNE

INDEX
1. Introduction to alkyne
2. Nomenclature of alkynes
General naming(trivial name)

IUPAC nomenclature

3. Structure of alkynes
Terminal and internal alkynes

4. Isomerism in alkynes
chain isomer

position isomer

functional group isomer

geometrical isomer

5. Physical properties of alkynes

6. Chemical properties of alkynes
7. Reaction of alkynes
Hydrohalogination of alkynes

Halogination of alkynes

Combustion

Reduction

Complete hydrogination of alkynes

 Syn-hydrogenation of alkynes
Antihydrogenation of alkynes

Anion formation

Nitrile formation

Polymerization of alkyne due to triple

bond
8. Alkyne reaction summary

9. Reactivity of alkynes

10. Uses of alkynes

 INTRODUCTION TO ALKYNE
In organic chemistry, an alkyne is an unsaturated hydrocarbon containing at least
one carbon-carbon triple bond between two carbonatoms.The simplest acyclic alkynes
with only one triple bond and no other functional groups form a homologous series with
the general chemical formula CnH2n-2. Like other hydrocarbons, alkynes are generally
hydrophobic but tend to be more reactive.They exhibit neither geometric nor optical
isomerism. The simplest alkyne is ethyne (HCCH), commonly known as acetylene.

Ethyne
3D model of Ethyne

The alkynes are said to be unsaturated because of the existence of a multiple bond
in the molecule.The first member of the alkyne series is ethyne (previously called
acetylene).The names of all alkynes end in "-yne". Rules for the systematic naming of
alkynes are similar to those for alkenes. In the case of higher members of the alkyne series,
the triple bond may be between the terminal carbon atoms of the chain, or may be
between internal carbon atoms in the chain.

Ethyne HCCH
(Acetylene)

Propyne HCCCH3

1-Butyne HCCCH2CH3
1-Pentyne HCC(CH2)2CH3
1-Hexyne HCC(CH2)3CH3
1-Heptyne HCC(CH2)4CH3
1-Octyne HCC(CH2)5CH3
1-Nonyne HCC(CH2)6CH3
1-Decyne HCC(CH2)7CH3
2-Butyne CH3CCCH3
2-Pentyne CH3CCCH2CH3

Alkyne homologous series

 The bond formed between the hydrogen atom and the unsaturated carbon atom,
and first bond between the unsaturated carbon atoms in the ethynes are s bonds (sigma
bonds) and these bonds are formed by the end-on overlap of sp hybrid orbitals of the
carbon atoms and the bonds are arranged as far apart in space as possible (i.e. at 180
degree) to form a linear molecule. The second and third bonds that makes up the triple
bond of the unsaturated carbon atoms in alkenes are p-bonds (pi-bonds), formed by the
side-on overlap of the two p-orbitals on each of the carbon atoms. The p-bonds (pi-bonds)
are much more reactive than the s bonds (sigma bonds), and react readily in addition
reactions.

Acetylene is a linear molecule, all four atoms lying along a straight line. This linear
structure can only be explained by the existence of sp hybridisation of the orbitals of the
carbon atoms of ethyne.

The carbon-carbon triple bond is thus made up of one strong bond and two weaker
(bonds; it has a total strength 123 kcal. It is stronger than the carbon-carbon double bond
of ethylene 100 kcal or the single carbon-carbon bond of ethane 83 kcal, and therefore is
shorter than either.

The C-C distance is 1.2 A, as compared with 1.34 A in ethylene and 1.54 A in ethane
and is a more electronegative grouping than that formed by carbon atoms joined by either
a double or a single bond.

The hydrogen attached to the carbon-carbon triple bond in ethyne or in any alkyne
where the carbon-carbon triple bond is situated at the end of a carbon chain is able to
separate from the rest of the molecule as a hydrogen ion; the electronegative carbon is
able to retain both electrons from the broken covalent bond.

A significant result of this bonding is that ethyne can unite with metals and so be
distinguished from alkenes by chemical means.
 Nomenclatue of alkynes
1.General naming of alkynes
In this method the alkynes are named as acetylene derivatives. The lowest
alkyne with formula C2H2 is called acetylene and other compounds are named as
substituents of acetylenes. The naming of some alkynes is given below.

CH CH - Acetylene
CH3-C C-CH3 - Dimethyl acetylene
CH3-C C-CH2-CH3 - Ethyl methyl acetylene
CH3-CH2-CH2-C CH - Propyl acetylene
CH3-C CH - Methyl acetylene

The general naming of alkynes is restricted to some fewer alkynes and will
give complex results as many alkynes will be possible for complex structures like methyl
isopropyl acetylene.

2.IUPAC naming of alkyne

In IUPAC system the alkynes are named as derivatives of alkanes. The suffix
'ane' is replaced with 'yne' in the alkane name.
For example the following compound have three carbon atoms and hence
the root name is propane.
If the suffix 'ane' is replaced with 'yne' we will get the IUPAC name of the
compound as propyne.
CH3-C CH - Propyne.
If there is a substitute in the chain, the longest chain is selected in such a
way that the chain contains the triple bond.
Similarly the chain is numbered in such a way that the carbon containing the
triple bond gets the least number.
For example the following compound contains five carbon atoms in the
longest chain. Hence it is named as pentyne.
It is named from right to left so that the carbon containing triple bond gets
the number 1.
There is one substitute methyl group at 3rd carbon atom. Hence the name of
the compound is 3-methyl 1-pentyne.
CH3-CH2-C(CH3)-C CH - 3-methyl 1-pentyne.
 Structure of alkynes
In acetylene, the HCC bond angles are 180. By virtue of this bond angle, alkynes
tend to be rod-like. Correspondingly, cyclic alkynes are rare. Benzyne is highly unstable. The
CC bond distance of 121 picometers is much shorter than the C=C distance in alkenes (134
pm) or the C-C bond in alkanes (153 pm).

Alkynes: a-acetylene; b-two depictions of propyne; c-1-butyne;d-2-

butyne;e-the naturally occurring 1-phenylhepta-1,3,5-triyne; f-the
strained cycloheptyne. Triple bonds are highlighted blue.

The triple bond is very strong with a bond strength of 839 kJ/mol. The sigma bond
contributes 369 kJ/mol, the first pi bond contributes 268 kJ/mol and the second pi-bond of
202 kJ/mol bond strength. Bonding usually discussed in the context of molecular orbital
theory, which recognizes the triple bond as arising from overlap of s and p orbitals. In the
language of valence bond theory, the carbon atoms in an alkyne bond are sp hybridized:
they each have two unhybridized p orbitals and two sp hybrid orbitals. Overlap of an sp
orbital from each atom forms one sp-sp sigma bond. Each p orbital on one atom overlaps
one on the other atom, forming two pi bonds, giving a total of three bonds. The remaining
sp orbital on each atom can form a sigma bond to another atom, for example to hydrogen
atoms in the parent acetylene. The two sp orbitals project on opposite sides of the carbon
atom.

Terminal and internal alkyne

Internal alkynes feature carbon substituents on each acetylenic carbon. Symmetrical
examples include diphenylacetylene and 3-hexyne.
Terminal alkynes have the formula RC2H. An example is methylacetylene (propyne
using IUPAC nomenclature). Terminal alkynes, like acetylene itself, are mildly acidic, with
pKa values of around 25. They are far more acidic than alkenes and alkanes, which have
pKa values of around 40 and 50, respectively. The acidic hydrogen on terminal alkynes can
be replaced by a variety of groups resulting in halo-, silyl-, and alkoxoalkynes. The
carbanions generated by deprotonation of terminal alkynes are called acetylides.
 Isomerism in alkynes
Chain isomer:
Compounds having same molecular formula with difference in carbon chain
pattern like linear or branch are called chain isomers. 1-Pentyne is chain isomer for
3-methyl Butyne.
CH3-CH2-CH2-C CH and CH3-C(CH3)-C CH

Position isomer:
Compounds having same molecular formula with difference in position of the
functional group are called as position isomers. 1-Butyne and 2-Butyne are position
isomers.
CH3-CH2-C CH and CH3-C C-CH3

Functional group isomer:

Compounds having same molecular formula with difference in nature of functional
group are called as functional group isomers. Alkynes are functional group isomers
for cyclo alkenes. For example pentyne and cyclo pentene are functional group
isomers.

CH3-CH2-CH2-C CH and

Geometrical isomer:
The bond between carbon atoms in alkyne is rigid and cannot be rotated. Hence
there should be possibility of geometrical isomers. But the orientation of atoms
cannot be determined. Hence there is no possibility of geometrical isomerism in
alkynes.
 Physical properties
1.Alkynes are colorless gases with specific odor. They are insoluble in water and
soluble in most of the organic solvents like benzene and carbon tetra chloride.
2.The first four members are colorless gases and next five to six members are liquids.
The branched alkynes will have low boiling points then linear alkynes due to
compact packing efficiency.

3.The H/C ratio is least in alkynes and hence they will burn with sooty flame due to
incomplete combustion.

4.The alkynes having triple bond in the last carbon atom are called as terminal
alkynes.

5.The hydrogen atom attached with carbon in terminal alkyne is polarized due to
high electronegative nature of carbon.

6.The hydrogen gets partial positive charge and can be removed easily by strong
bases like soda amide. Hence alkynes are more acidic then alkenes and alkanes.

CH CH and CH2=CH2 and CH3-CH3

pKa-46,54,65

Chemical properties
Liquid alkynes are non-polar solvents, immiscible with water. Alkynes are,
however, more polar than alkanes or alkenes, as a result of the electron density
near the triple bond.
Alkynes with a low ratio of hydrogen atoms to carbon atoms are highly
combustible. Carbon-carbon triple bonds are highly reactive and easily broken or
converted to double or single bonds. Triple bonds store large amounts of
chemical energy and thus are highly exothermic when broken. The heat released
can cause rapid expansion, so care must be taken when working with alkynes
such as acetylene.
One synthetically important property of terminal alkynes is the acidity of their
protons. Whereas the protons in alkanes have pKa's around 60 and alkene
protons have pKa's in the mid-40's, terminal alkynes have pKa's of about 25.
Substitution of the alkyne can reduce the pKa of the alkyne even further; for
example, PhCCH has a pKa around 23, and Me3SiCCH has a pKa around 19. The
acidity of alkynes allows them easily to be deprotonated by sufficiently strong
 bases, such as butyllithium BuLi or the amide ion NH 2-. More acidic alkynes such
as PhCCH can even be deprotonated by alkoxide bases under the right
conditions.

Reaction of alkynes
Hydrohalogination of alkynes
Alkynes react very quickly and to completion with hydrogen halides. Addition is anti,
and follows the Markovnikov Rule.
RCCH + H-Br (1 equiv) --> RCBr=CH2
RCCH + H-Br (2 equivs) --> RCBr2CH3
Adding a halide acid such as HCl or HBr to an alkyne can create a geminal dihalide
via a Markovnikov process, but adding HBr in the presence of peroxides results in the Anti-
Markovnikov alkenyl bromide product.

Halogination of alkynes
Adding diatomic halogen molecules such as Br 2 or Cl2 results in 1,2-dihaloalkene, or,
if the halogen is added in excess, a 1,1,2,2-tetrahaloalkane.
Adding H2O along with the diatomic halide results in a halohydrin addition and an -
halo ketone

Combustion
Alkynes burn in air with a sooty, yellow flame, like alkanes. Alkenes also burn
yellow, while alkanes burn with blue flames. Acetylene burns with large amounts of
heat, and is used in oxyacetylene torches for welding metals together, for example,

in the superstructures of skyscrapers.

2 C2H2 + 5 O2 --> 4 CO2 + 2 H2O

Reduction
Alkynes can be hydrogenated by adding H2 with a metallic catalyst, such as
palladium-carbon or platinum or nickel, which results in a both of the alkyne
carbons becoming fully saturated. If Lindlar's catalyst is used instead, the alkyne
hydrogenates to a Z enantiomer alkene, and if an alkali metal in an ammonia
solution is used for hydrogenating the alkyne, an E enantiomer alkene is the result.
 Complete Hydrogenation of Alkynes
As mentioned above, alkynes are reduced to alkanes in the presence of an
active metal catalyst, such as Pt, Pd, Rh, or Ni in the presence of heat and pressure.
RCCR' + 2 H2 (Pt cat.) --> RCH2CH2R'

Syn-Hydrogenation of an Alkyne
There are two kinds of addition type reactions where a -bond is broken and
atoms are added to the molecule. If the atoms are added on the same side of the molecule
then the addition is said to be a "syn" addition. If the added atoms are added on opposite
sides of the molecule then the addition is said to be an "anti" addition. Hydrogen atoms
can be added to an alkyne on a one mole to one mole ratio to get an alkene where the
hydrogen atoms have been added on the same side of the molecule. Isotopic identification
allows chemists to determine when this syn-hydrogenation has occurred.
As mentioned above, alkynes can be reduced to cis-alkenes by hydrogen in
the presence of Lindlar Pd, i.e. palladium doped with CaSO 4 or BaSO4.
RCCR + H2 ---> cis-RCH=CHR

Anti-Hydrogination of alkynes
In regards to the syn-hydrogenation, anti is hydrogenation when one hydrogen is
added from the top of the pi bond and the other is added from the bottom.

Anion Formation
Because of the acidity of the protons of terminal alkynes, they are easily converted
into alkynyl anions in high yield by strong bases.
Examples:
RCCH + NaNH2 -> RCCNa + NH3 C4H9Li + RCCH -> C4H10 +RCCLi
Alkynes are stronger bases than water, and acetylene (ethyne) is produced in a
science classroom reaction of calcium carbide with water.
CaC2 + 2 H2O --> Ca(OH)2+ C2H2
Alkynyl anions are useful in lengthening carbon chains. They react by nucleophilic
substitution with alkyl halides.
R-Cl + R'CCNa --> RCCR' + NaCl
The product of this reaction can be reduced to an alkane with hydrogen and a
platinum or rhodium catalyst, or an alkene with Lindlar palladium.
Nitrile formation
When a slight excess of ethyne and ammonia are passed over an alumina catalyst at
573 degK, ethanonitrile (i.e. acetonitrile) is produced.
 573 degK

HCCH + NH3 ==> CH3CN + H2

Ethyne Ethanonitrile

Polymerization
The products obtained by polymerising ethyne depend on the conditions
used.
When ethyne is passed through a glass tube at 4000C a little benzene is
formed. This is not a suitable way to make benzene in quantity but it is an
example of direct conversion from an open chain to an aromatic compound,
i.e. one with a closed-ring benzenoid structure)
400 degC

3 C 2H 2 ====> C 6H 6

Ethyne Benzene

Two molecules of ethyne can be combined to produce vinyl ethyne,

HCCCH=CH2, by passing the ethyne into a saturated solution of cuprous
chloride in ammonium chloride continuously in such a way that low
conversions of starting material occur.
NH4Cl , Cu2Cl2

2 HC CH ==> HCCCH = CH2

Ethyne Vinyl Ethyne

This linear polymerisation can be extended by altering the conditions of

reaction. For example
HCCCH=CH2 + HCCH ==> CH2=CHC(CCH=CH2)

Vinyl Ethyne Ethyne DiVinyl Ethyne

 Alkyne reaction summary
1.Alkynes can undergo addition reaction with 2 moles of chlorine and hydrogen
halides to give addition product.

2.Similarly they can undergo oxidation reaction with alkaline potassium

permanganate to give carboxylic acids.

3.Alkynes can undergo linear and cyclic polymerization to give polymers.

4.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.

5.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.

6.Alkynes on adding with hydrogen undergo hydrogenation to give alkanes. The

heats of hydrogenation is more than alkenes. Similarly the partial hydrogenation
give alkenes.

Reactivity of alkynes
The unsaturated nature of alkynes means that most of their reactions will be similar
to those of alkenes (i.e. electrophilic addition), because of the availability of the loosely
held pi-electrons. The carbon to carbon triple bond is less reactive than the carbon to
carbon double bond towards electrophilic reagents. As well as the addition reactions,
alkynes undergo reactions that are due to the acidity of a hydrogen atom attached to the
triple bonded carbon.
The carbon-carbon triple bond in ethyne is thus made up of one strong sigma-bond
and two weaker pi-bonds. It has a total strength 123 kcal/mole. This is stronger than the
carbon-carbon double bond of ethylene which has a total strength of 100 kcal/mole or the
single carbon-carbon bond of ethane which has a total strength of 83 kcal/mole.
The ethynyl radical, CHC*, is a more electronegative group than that formed by
carbon atoms joined by either a double or a single bond. Thus, the hydrogen attached to
the carbon-carbon triple bond in ethyne, or in any alkyne where the carbon-carbon triple
bond is situated at the end of a carbon chain, is able to separate from the rest of the
molecule as a hydrogen ion, so that the alkyne shows acidic properties. The electronegative
carbon is able to retain both electrons from the broken covalent bond. A significant result
of this bonding is that ethyne can form compounds with metals and so be distinguished
from alkenes by chemical means.
 Uses of alkyne
1.Chlorinated acetylene is used as solvent. Similarly acetylene is a starting material
in the synthesis of polyvinyl chloride and polyacrylo nitrile which are used as
polymers.

2.Alkyne carbanions are very good nucleophiles and can be used to attack carbonyl
compounds, alkyl halides to give addition product and thus they are important
material in the chain expansion of organic compound.

3.Acetylene is used in oxy-acetylene torch. When acetylene is burnt in sufficient

oxygen we can get the temperature of around 3000oC which can be used to melt
and join the metal parts.