CHEMISTRY

SEM-1

PAPER-101

UNIT-3 8 UN SA TU RA TE D HY DR OC AR BO NS

AL KY NE S

Prof.V.R.Parikh
Alkynes are unsaturated hydrocarbons in which there are triple bonds between
carbon - carbon i.e -C=C- .Carbon atoms shares three pairs of electrons.
In alkyne triply bonded carbon is SP hybridised.
The first member of the series is acetylene. (HC=CH), therefore they are also known
as "Acetylenes".
General formula is CnH2n -2.

Nomenclature:

They are named according to two systems:

1. IUPAC Nomenclature ( as discussed before)
2. As derivative of acetylene by replacement of one or both H atoms by alkyl groups

HC=CH HC=C-CH3 CH3-CH2-C=CH CH3-C=C-CH3

Ethyne Propyne But-1-yne But-2-yne
Acetylene Methy Acetylene Ethyl Acetylene Dimethyl Acetylene

For more complicated structure IUPAC Nomenclature is used.

Physica l properties :
• Their physical properties are almost same as alkanes and alkenes.
• They are insoluble in water, but quiet soluble in organic solvents like Ether,
benzene , CC'4.
• Alkynes are less dense than water.
• There B.P. increases as number of carbon atoms increases while B.P.
decreases as branching increases.

Industrial Preparation of Acetylene :

Acetylene is prepared by action of water on calcium carbide (CaC2).

HC=CH

Another method is from petroleum by partial oxidation of Methane at high

temperature.

1500°C .-·;> 2 HC:CH + CO + H2

Preparation of alkynes :

By dehyd rohalo genati on of alkyl halide (Remo val of HX )

NaNH 2 gives alkynes.

Vicinal dihalid e on reaction with alcoholic KOH and then with

alcoholic KOH + NaNH2

C H3-C H2-<;H-y H2
Br Br

CH3-CH2-C=CH + NaBr + NH3

Conve rsion : Propane Propyne

CH3-CH=CH2 + Br2 CH3-CH-CH2 alcoholic KOH CH3-C H=CH

Propne ~r Br er
+ NaNH2

l
CH3-C :CH
Propy ne
+NaB r + NH3

By the Dehalogenation of Tetrahalides

Tetrah alides on reaction with zinc metal gives alkyne s

R-C -C-R + 2 Zn ) R-C=C -R Alkyn e

HC-C H + HC=C H Ethyn e

CH3 - C - CH + 2 Zn Li ) CHJ-C =CH Propy ne

By reaction of Acetylides with Primary halide :

Acetylene on reaction with sodium in liquid ammonia gives sodium acetylide , which
on reaction with primary halide give alkyne with more number of carbon atoms.

HC=CH + Na liq.NH,_ HC=C-Na +1/2 H2 + CH3-CH2-Br ~ HC=C-CH2-CH3

Na-Acetylide But-1-yne
+NaBr

By this reaction alkyne with less number of carbon atoms can be converted into
alkynes with more number of carbon atoms.

Conversion : Propyne Hex-2-yne

CH3-C:CH + Na liq.NH3 ½ H2 + CH3-C=C-Na + Br-CH2-CH2-CH3

"

l
CH3-C:C-CH2-CH2-CH3 + NaBr
Hex-2-yne

Reactions of alkynes :

In alkyne there are three bonds between carbon-carbon i.e. -C=C-, out of which two
are pi bonds and one is sigma bond. Therefore due to presence of two pi bonds
alkynes are more reactive than alkenes and alkanes.
Generally alkynes give addition reactions.

Hydrogenation reaction or (Reduction) or ( reaction with hydrogen):

• Alkyne on complete hydrogenation in presence of Pt for Pd or Ni yatalyst

gives alkane.

R-C=C-R +2 H2 Pt /Pd /Ni R-CH2-CH2-R

Alkyne Alkane

HC=CH +2 H2 Pt /Pd /Ni CHJ-CH3

Ethyne Ethane
 -
catalyst (Pd+CaCQ3) produces Cis
• Hydrogenation in presence of Lindliar
in liq.NH3 produces Trans-isomer.
isom er while in presence of Na or Li
He
Pd / CaCQ3 3 'c
lindliar ca alyst 1-1 /

CH3-C=C-CH3 + H2
But-2-yne

Na or i
Liq.NH3

s Alkenes
• On partial hydrogenation Alkyne give

R-C= C-R + H2 PUsilica ) R-CH=CH-R

tion):
Reaction with Halogen or (Halogena

presence of CCl4 gives Tetra halide

Alkyne on reaction with halogen In

R-C=C-R + 2 X2 cc 14 R-C-C-R
/\f \
X XX) (

Tetra halide
Alkyne

CH 3-C :CH + 2 Br2 CC14 .H c- c -C \-f

I·
3 /\ A
Br Br_B.- Bi---
1, 1,2,2 tetra bromo propane
Propyne
Hydrohalogenation : or (Reaction with HX)

Alkyne on reaction with HX in presence of HgCl2 gives Dihalides.

Br
I
HC::CH + HBr HgCh> CH2=yH + HBr HgCl2> CHJ-CH
Br sr
Br
CH3-C::CH + HBr HgCl2 CH3-y=CH2 + HBr CH3-C-CH3
Br er
(Geminal dihalide)

(In asymmetric alkynes addition of asymmetric reagent takes place according to

Markonikov's rule.)

Reaction with HCN :

Alkynes on reaction with HCN in presence of Cu2Cl2 and NH4CI forms Vinylcyanide.
(Acrylonitrile ).

HC::CH + HCN CH2 = yH Vinyl cyanide or acrylonitrile

CN

CH3-C=CH + HCN 2-Cyano propene

Hydration reaction or (Reaction with water) :

Alkyne on reaction with water molecule in presence of H2SQ4 and HgS04 gives
"enol' (a compound having two functional group alkene (-ene) and alcohol(-ol) which
on rearrangement, converted into keto ( C=O) group produces either Aldehyde or
ketone .This rearrangement is known as Keto-Enol Tautomerism.

• Acetylene Acetaldehyde

keto-enol
HC:CH tautomerism

Acetylene Vinyl alcohol Acetaldehyde

 • Propyne - - - Acetone

keto-eno ~
CH3-C=CH2 tautomer ism CH3-C-CH3
CH3-C=CH + H20
(H+QH-) 6~ 8
Acetone
Propyne

Hydroxy halogenation (Reaction with Ch + H20 or Br2 + H20):

C'2 + H20 ~ HOCI + HCI or Br2 + H20 --:7 HOBr + HBr

HC:::CH + HOCI -➔ H~~ b~ + HOCI -- ➔Gil~ ~ CH-CH

/\_ II
CICI 0
1-
2,2 dichloro
acetalde hyde

Oxidation reaction : (Bayer's Test):

Alkynes on oxidation in presence of KMnQ4 gives carboxylic acid. The reaction is

carried out as follows:

HC=CH + 4 (0) cold,dil,alkaline KMNQ4

+H20 6 ooH
OOH
Oxalic acid

HC:CH +H2~ fH=yH CHO +2(0) gooH

--~ ~2i CH@ I
~
(0) OH OH (0) c@ -2 H2O CHO OOH
'f ..,.
Acetylen e glyoxal oxalicacid
Ozonalysis:

It i~ the reaction in which ozone (03) is employed to cleave the unsaturated bonds of
akyne.
Alkyne on ozonalysis gives carboxylic acid and/or CO2.

• If =CH group is present at the end of alkyne chain than Co2 is obtained.

• If =CH group is not present at the end of alkyne chain than carboxylic acid is
obtained after hydrolysis.
Zn+ H20
HC=CH CO2 + CO2

Zn
CH3-C=CH + Q3 followed by hydrolysis CH3CQOH + CO2
Zn
CH3-C=C-CH3 + Q3 followed by hydrolysis -➔ 2 CH3CQOH

Polymerization:

It is a process in which the smaller molecules ( monomers) combine with each other
chemically to produce a very large molecule is called polymer and the process is
known as polymerization.

• Two molecules of acid in presence of Cu2Cl2 and NH4CI gives Vinyl acetylene
(dimer)

HC=CH + HC::CH CH2=CH-C=CH Vinyl acetylene

• Three molecules of acid lean on polymerization in presence of Cu2C'2 and
NH4CI gives Divinyl acetylene( trimer )as follows:

HC=CH + HC=CH CHi=CH-C=CH + HC=CH

Cu2Cl2
NH4CI

CH2=CH-C=C-CH=CH2
Divinyl acetylene

• when three molecules of acetylene combine with each other in presence of

Fe or Cu at 500°C Benzene is formed.

Cli CH
-~ / ~ ;,

11~ C;H Fe/C_y

500°C
CH
II
CH
I
CH
CH CH CH
v-'~ ,{/
CH
"' CH

Benzene

• Four molecules of acetylene combine with each other in presence of Ni(CN)4

at 60 to 70°C and 15 to 20 atm pressure,forms 1,3,5,7 cyclo octa-tetraene.

HC=CH HC= CH

c0 '--:i CH
Ni(CN)4
HC / " CH
Ill
CH
(Ill
CH
60-70oC
15-20 atm
I
HC
II
CH

~
HC=CH "HC=CH I
1,3,5,7 cyclo octa-tetraene
Reaction of terminal acetylene :
OR Formation of metal Acetylides
OR Acidicity of terminal alkynes
OR Substitution reaction of terminal alkynes

• Alkynes with =CH at the end gives acetylides with heavy metal in presence
of
liquid ammonia.
• In =CH the hydrogen atom attached to triply bonded carbon is slightly acidic
and it reacts with strong base to form metal acetylides as follows:

HC=CH + Na liq.NH3 HC=C-Na + 1/2 H2

- -> Na-acetylide

CH3-C:::CH + AgNQ3 alco.NH3 CH3-C=C-Ag + HN03

Ag-acetylide
,,
CH3-CH 2-C=CH + Cu2Cl2 alco.NH3 CH3-CH 2-C=C-Cu + 2NH4C r
---> Cu-acetylide

• This reaction is useful to prepare higher alkyne as discussed in preparation of

alkynes .
• This reaction is also very useful to distinguish between alkynes and 1-alkynes.