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Some of the lower members of alkyne series can be synthesized by the

hydrolysis of carbides.

Calcium carbide on hydrolysis gives acetylene and magnesium carbide


on hydrolysis gives propyne.
CaC2 + 2H2O
Mg2C3 + 4H2O

HC CH + Ca(OH)2
CH3 - C CH + 2Mg(OH)2

The difference in the behavior of calcium carbide and magnesium


carbide is due to the differences in their structures. Both the carbides
are ionic in nature. In calcium carbide, the anion exists as -C C- while
in magnesium carbide, the anion exists as 3-C - C C-.

Aluminium carbide (Al4C3) and beryllium carbide (Be2C) do not form


any alkyne on hydrolysis, instead they form methane on hydrolysis.
This is due to the fact that their anions exist as C4-.

The two hydrogen atoms of acetylene are acidic in nature and can be
replaced by a strong base like sodium or sodamide.

HC CH + Na
HC CH + NaNH2

HC C-Na+ + H2
HC C-Na+ + NH3

Sodium acetylide when treated with primary alkyl halide gives 1-alkynes
following nucleophilic substitution reaction by SN2 mechanism.
Secondary alkyl halide gives poor yield of 1-alkyne because substitution
reaction is accompanied by elimination reaction with acetylide ion
(HC C-) functioning as a strong base. Tertiary alkyl halides do not
undergo any substitution reaction because of steric hindrance. Instead
they undergo elimination reaction easily forming alkene as the only
product.
HC C- + CH3CH2CH2 - Cl

HC C - CH2CH2CH3 + Cl-

The alkyne formed as a result is still 1-alkyne. So using NaNH2 again


we can introduce another alkyl group in it.

Both vicinal dihalides and geminal dihalides undergo


dehydrohalogenation reaction with a strong base to give alkyne in
fairly good yield. The reaction follows 1, 2-elimination mechanism.
In the first step, the base employed is alcoholic KOH while in the
subsequent step, we use NaNH2
H H
H
CH3C CH

alc. KOH

CH3C CH

Br Br

NaNH2

CH3CCH

Br

vic. dibromide

Br
CH3C CH2CH3
Br
gem. dibromide

alc. KOH

CH3C CHCH3
Br

NaNH2

CH3CCCH3

Why doesnt alc. KOH do both the eliminations?

NaNH2 is a stronger base than RO-.

Vinylic halides are less acidic.


CH3 - CH = CH
Br

CH3 - CH - CH
Br

The lone pair - double bond conjugation enables Br to show its +R


effect thereby causing the carbon, from which the proton is to be lost,
to become negatively charged. True that for halogens -I dominates
over +R but compared to the saturated dihalide vinylic halides are less
acidic as in the former only -I effect occurs.

But the why cant we just use NaNH2? If it can abstract proton from
less acidic vinylic halides it can certainly do so from the more acidic
saturated dihalide.
We dont use NaNH2 because that would cause an increase in the
concentration of NH2- which would then behave as a nucleophile than
as a base and cause substitution to yield amines.

Then why doesnt NaNH2 cause substitution in vinylic halide?

Because the vinylic carbons are electron rich due to electron cloud so
nucleophiles cannot approach them directly. Moreover the C - Br bond
is partially double so it wont be a good leaving group.

Vicinal tetrahalides are compounds containing two halogen atoms


attached to each of the two adjacent carbon atoms. They loose all the
four halogen atoms forming alkynes when treated with either (i) NaI in
acetone/methanol, or (ii) Zn dust and ethanol. The mechanism is very
similar to the one discussed in the lesson on Alkenes.
Br Br
CH3C CCH3
Br Br
vic. tetrabromide

(i) NaI in Me2CO/CH3OH


or
(ii) Zn dust in C2H5OH

CH3CCCH3

Being compounds of low polarity, the alkynes have physical properties


that are essentially the same as those of the alkanes and alkenes. They
are insoluble in water but quite soluble in the usual organic solvents of
low polarity like ether, benzene, carbon tetrachloride etc. Their
densities are lower than that of water. Their melting points and boiling
points show the usual increase with increase in number of carbon
atoms and the usual effects of chain branching.

Though alkynes have higher electron cloud density than alkenes,


they are less reactive than alkenes towards electrophilic addition
reactions. This is due to three reasons.
The two perpendicular electron cloud make the overall electron
cloud cylindrical in shape causing loss in surface area. This offers less
exposure to the incoming electrophiles.

Many electrophilic reactions of alkynes requires the presence of


catalysts.
Electrophilic addition reactions are either through carbonium ion
formation (like addition of HX) or through the three member bridged
ring intermediate (OMD, halogenation).
Vinylic carbonium ions are less stable than the typical ones as the
carbon is sp hybridized and is more electronegative.

Three member rings are more unstable is carbon is sp2 because it


would cause more strain.

Hydrogenation is non ionic reaction. It occurs faster for alkynes than


alkenes.

Alkynes can be reduced directly to alkanes by the addition of H2 in the


presence of Ni, Pt or Pd as a catalyst. The addition reaction takes place
in two steps. It is not possible to isolate the intermediate alkene under
the above reaction conditions.

Partial reduction of alkynes to alkenes has been discussed.

Addition of halogen acids to alkynes occur in accordance with


Markownikoffs rule. Addition of one molecule of halogen acid gives
an unsaturated halide, which then adds another molecule of hydrogen
halide to form gem and vicinal dihalides.
HBr in the presence of peroxide shows the typical peroxide effect.

CH3 - C CH + HBr

CH3 - C = CH2

HBr

Br
CH3 - C - CH3

Br
HBr

Br

Peroxide

Br
CH3 - CH - CH2
Br
CH3 - C CH + HBr

Peroxide CH3 - CH = CH

HBr

Br
CH3 - CH2 - CH

Br HBr Peroxide

Br

One or two molecules of halogens can be added to alkynes giving


dihalides and tetra halides respectively. Chlorine and bromine add
readily to the triple bond while iodine reacts rather slowly.
Cl
Cl Cl

CH3 - C CH + Cl2

CH3 - C = CH
Cl

Cl2

CH3 - C - CH
Cl Cl

Water adds to alkyne when alkyne is treated with 40% H2SO4


containing 1% HgSO4 (as a catalyst) to form a carbonyl compound.

The addition of water follows Markownikovs rule forming enol as


intermediate, which tautomerizes to give a more stable carbonyl
compound.

That is why we didnt prepare alkynes by the double dehydration of


vicinal or gem diol because the enol formed on the first dehydration
would tautomerize.

CH3 - C CH + H2O

H2SO4

CH3 - C = CH2

HgSO4

CH3 - C - CH3

OH

The reaction is believed to take place via the formation of a three


member ring involving Hg2+ ion.
Hg2+
2+

CC + Hg

Hg+
H2 O

C=C
+

OH2

Hg+
H+

C=C
OH

H3 O+
Hg2+

CH=C
OH
CH2C
O

Acetylene is the only alkyne forming an aldehyde in this reaction.


Higher homologues of acetylene either form a single ketone or a
mixture of ketones. For example, 2-pentyne gives a mixture of 2pentanone and 3-pentanone.

Diborane, the simplest hydride of boron reacts with alkyne to form


trialkenylborane. Diborane splits into two BH3 units and the addition
of BH3 takes place following Markownikoffs rule. The addition
continues as long as hydrogen is attached to boron atom.

3CH3 - C CH + BH3
(CH3 - CH = CH)3B
Trialkenyl boranes on hydrolysis yield alkenes.
3CH COOH

3
(CH3 - CH = CH)3B
3CH3 - CH = CH2
If the alkene can show stereochemistry then only cis alkene is formed.
Oxidation of trialkenylborane with alkaline H2O2 results in the
formation of carbonyl compounds. Terminal alkynes give rise to
aldehydes whereas internal alkynes give rise to ketones.
OH

H2O2 in NaOH

(CH3 - CH = CH)3B

3CH3 - CH2 = CH

O
3CH3 - CH2 - CH

Acetylene dimerises when treated with a mixture of Cu2Cl2 and NH3


and later acidified to give vinyl acetylene.
CH3
Cu2Cl2 + NH3

2CH3 - C CH
+
Mechanism H3O
CH3 - C CH
CH3 - C CH

NH3
Cu+

CH3 - C CCu+
CH3 - C = CH
Cu+

CH3 - C C-

2CH3 - C C -C = CH2

CH3 - C = CH

CH3 Cu

CH3 - C C - C = CH
H+

CH3
CH3 - C C - C = CH2

Alkynes are oxidised by hot alkaline KMnO4, which causes cleavage of


-CC- resulting in the formation of salts of carboxylic acids. The salts
on acidification are converted into acids. Non-terminal and internal
alkynes give mixture of carboxylic acids while terminal alkynes give a
carboxylic acid and the terminal C-atom is oxidised to CO2 and H2O.
KMnO4 in OH-,

CH3 - C CH

CH3 - C C - CH3

CH3 - COOH

H+

KMnO4 in OH-,
H+

O
CH3CCH + O3

CH3C
O

CH
O

CO2

2CH3 - COOH

H2O

CH3COOH + HCOOH

However, if ozonide is hydrolysed with Zn and H2O, a diketone is


formed. This is called reductive ozonolysis.
O

O
CH3CCCH2CH3 + O3

CH3C
O

Ethyne behaves differently. Ozonolysis followed by oxidative


hydrolysis of ethyne gives a mixture of glyoxal and formic acid.
HC CH

CCH2CH3 Zn/H2O CH3CCCH2CH3

(i) O3

OHC - CHO + HCOOH

(ii) H2O

Hydrochloric acid adds to acetylene in the presence of Hg2+ ion as


catalyst to form vinyl chloride. Polymerisation of vinyl chloride results
in the formation of polyvinyl chloride (PVC).

HC CH + HCl

Hg2+

H2C = CHCl

Polymerization

- H2C - CH Cl
n

Addition of HCN to ethyne is catalysed by Cu2Cl2 in HCl. The product


obtained is acrylonitrile, which on polymerisation gives
polyacrylonitrile (PAN).

HC CH + HCN

Cu2Cl2
HCl

H2C = CHCN

Polymerization

- H2C - CH NC
n

Acetic acid adds to ethyne in the presence of Hg2+ ion to give vinyl
acetate, which is used as monomer in the preparation of polyvinyl
O
acetate (PVA).
Hg2+
H2C = CH - O - C - CH3
HC CH + CH3COOH

- H2C - CH H3C-C-O
O

Acetylene when passed through a hot metallic tube polymerizes to give


benzene.
3HC CH

Red Hot tube

Higher homologues of acetylene also polymerize under similar


conditions to give derivatives of benzene.
3 CH3 - C CH

3 CH3 - C C - CH3

Red Hot tube

1,3,5-Trimethylbenzene

Red Hot tube


1,2,3,4,5,6-Hexamethylbenzene

Alkynes react with hypohalous acid in the molar ratio of 1 : 2 to give


dihalo ketones. Acetylene forms dihaloaldehyde.
O
OH
OH

R - C CH + X2

Water

R - C = CHX

R - C - CHX2

-H2O

R - C - CHX2

OH

Non-terminal alkynes are converted to terminal alkynes by the


treatment of NaNH2 and the reverse is achieved by alc. KOH.

CH3CH2CH2 - C C - CH3

NaNH2

Alc. KOH

CH3CH2CH2 - CH2 - C CH

Mechanism

CH3CH2CH2 - C C - CH2

NH2-

CH3CH2CH2 - C C - CH2

H
CH3CH2CH2 - C = C = CH2
NH2-

NH3

CH3CH2CH2 - C = C = CH2

CH3CH2CH2 - C = C = CH
H

CH3CH2CH2 - C - C CH
H
Alc. KOH

NH3

CH3CH2CH2 - CH2 - C CH

Terminal alkynes are weakly acidic. pKa values are : Acetylene: 25;
H2O: 15.7; Alcohols: 16-19; NH3: 34; Ethylene: 44; CH4: 50.