CHEMICAL REACTIONS OF ALKYNES

04-04-2020 SKS
 1. Electrophilic Addition Reactions
a. Electrophilic Addition of Bromine and Chlorine to Alkynes
Alkynes show the same kind of addition reactions with chlorine and bromine
that alkenes do.
 With alkynes the addition may occur once or twice, depending on the number of
molar equivalents of halogen we employ:

Anti-addition takes place:

mechanism is same as the
addition of Cl2 / Br2 takes
place on alkenes.

04-04-2020 SKS
 b. Addition of Hydrogen Halides to Alkynes

 Alkynes react with one molar equivalent of hydrogen chloride or hydrogen

bromide to form haloalkenes, and with two molar equivalents to form geminal
dihalides.

 Both additions are regioselective and follow Markovnikov’s rule:

04-04-2020 SKS
Mechanism of Electrophilic Addition of Hydrogen Halides to Alkynes:

R1 R1 H
R1 R2 + H X or + X-
H R2 R2
1 mole
A vinylic cation (Search for the more stable carbocation)

R1 X R1 X X H R1 X R1 H
or
H H
H R2 H R2 H R2 X R2
Resonance stabilized
+ X-

R1 X
H X
H R2

04-04-2020 SKS
Q1: The addition of HCl to 3,3-dimethyl-1-butyne gives the following products: 2,2-dichloro-3,3-
dimethylbutane (44 %), 2,3-dichloro-2,3-dimethylbutane (18 %) and 1,3-dichloro-2,3-dimethylbutane (34
%). Account in detail for the formation of these products.

Q2. The addition of 1.0 equivalent and excess HBr to 1-butyne gives 2-bromo-1-butene and 2,2-
dibromobutane (a geminal dihalide), respectively. Account in detail for the formation of these products.

Q3. Write the structure of the product along with the stereochemistry when 1.0 equivalent of HCl is
reacted with 2-butyne. Give explanation.

Q4. Give the mechanism for the formation of 1-bromo-1-butene, when 1 equivalent of HBR is reacted
with 1-butyne in the presence of organic peroxide.

04-04-2020 SKS
c. Addition of H2O
 Like alkenes, alkynes can also be hydrated.

 This is an example of electrophilic addition reaction.

 Alkynes undergo acid-catalysed addition of H2O.

 Terminal alkynes are less reactive than the internal alkyne towards the addition of H2O. Terminal alkynes will
add water if Hg2+ is added to the acidic mixture. The Hg2+ acts as a catalyst to increase the rate of the addition
reaction.
 Acetylene give acetaldehyde, whereas other alkynes (both internal and terminal) give ketone.

04-04-2020 SKS
 Mechanism

Practice Problem:
Q. Write the mechanism of
hydration of ethyne, 1-
butyne and 2-butyne.

enol
H
H H
H
Ketone
04-04-2020 SKS
2. Nucleophilic addition reactions:
 The sp-hybridised carbon atoms of the triple-bond render alkynes more electrophilic than similarly
substituted alkenes because the electronegativity of sp-hybridized orbital is more than sp2, hence pi-
electrons will be more close to the carbon nucleus.

C2H5O-K+
HC CH H2C C OC2H5
in C2H5OH H
at high temp
HCN
Cat. NaCN

H2C C CN
H
Practice problem:
Write the chemical reaction involved when acetylene is
reacted with C2H5S-Na+ in ethanol.
04-04-2020 SKS
3. Reduction of Alkynes

Reduction using Na/ Liq. NH3 (Birch Reduction):

 Na / Liq. NH3 or Li / Liq. NH3 is used to carry out reduction of alkynes into alkenes.
 Alkynes are selectively converted into trans-alkenes.
 Na / liq NH3 is the source of ammoniated electrons.
 Na in ethanol can also be used.

2-Butyne

trans-2-Butene

04-04-2020 SKS
 Mechanism

trans-Vinylic radical anion is more stable as

the –ve charge and radical are at the anti-
position, so no electronic repulsion.

OR
Mechanism

04-04-2020 SKS
Reduction using Lindlar’s catalyst H2/ Pd(BaSO4)
 H2/ Pd(BaSO4) partially deactivated (poisoned) by quinoline is used to carry out
reduction of alkynes into cis-alkenes.
 Alkynes are selectively converted into cis-alkenes.
 syn-addition of H2 takes place.

04-04-2020 SKS
Mechanism:

The quinoline serves to prevent complete hydrogenation of the alkyne to an alkane.

N N
H
04-04-2020 Quinoline SKS1,2-Dihydroquinoline
Hydroboration-oxidation of alkynes:

Hydroboration of internal alkynes is not a particularly useful procedure because

a mixture of products will often be obtained, unless the triple-bond is
symmetrically substituted.

O
1. BH3 in THF
H3C C C CH3
2. H2O2 / NaOH
Disiamylborane is preferred over BH3 to
04-04-2020 SKS avoid the possibility of further addition
Oxidative Cleavage of Alkynes
Treating alkynes with hot basic potassium permanganate followed by acid, leads to cleavage at the carbon–
carbon triple bond. The products are carboxylic acids. Whereas under neutral condition it gives 1,2-diketo
compounds (in case of internal alkyne), b-keto acids (in case of terminal alkynes), respectively.

Alkaline condition
O O
hot R1 C O- R1 C OH
KMnO4 / -OH O O KMnO4 / -OH + H3O+ +
R1 C C R2 R1 C C R2 O O
R2 C O- R2 C OH

hot
KMnO4 / -OH O O KMnO4 / -OH O O
R C C H R C C H R C C O-

KMnO4 / -OH

O O
OH + CO2 H3O+ O- + CO2
R C R C
04-04-2020 SKS
 O Ozonolysis of alkynes
KMnO4 /H2O
R C C R R
Neutral Condition
R O
O R1 C OH
O3
R1 C C R2 +
O
KMnO4 /H2O dil. CH3COOH O
R C C H OH
Neutral Condition
R or H2O R2 C OH
O

O3 O
H3C C C CH3 H3C C OH
dil. CH3COOH
2 moles
or H2O

O3 O
H3 C C C H H3C C OH + CO2 + H2O
dil. CH3COOH
or H2O

04-04-2020 SKS
Distinction between terminal and internal alkynes
 Terminal alkynes react with Tollens reagent (ammoniacal silver nitrate solution) to form silver alkynides
as a white precipitate, whereas internal alkynes do not react with Tollens reagent.

R1 C C H + [Ag (NH3)2]+ -OH R1 C C Ag + 2NH3 + H2O

Tollens reacgent Silver alkynide
White ppt
R1 C C R2 + 2 [Ag (NH3)2]+ -OH No Reaction
Tollens reacgent

H C C H + 2 [Ag (NH3)2]+ -OH Ag C C Ag + 4NH3 + 2H2O

Tollens reacgent Silver alkynide
White ppt

04-04-2020 SKS
 R1 C C H + [Cu (NH3)2]+ -OH R1 C C Cu + 2NH3 + H2O
Tollens reacgent Silver alkynide
Red ppt
R1 C C R2 + [Cu (NH3)2]+ -OH No Reaction
Tollens reacgent

H C C H + 2 [Cu (NH3)2]+ -OH Cu C C Cu + 4NH3 + 2H2O

Tollens reacgent Silver alkynide
Red ppt

04-04-2020 SKS
Reactions of terminal alkynes with sodamide, Sodium hydride, n-BuLi and Grignard
reagent:

NaNH2 / liq. NH3

R1 C C Na R1 C C Na + NH3

NaH
R1 C C Na + H2
R1 C C H
acidic hydrogen n-BuLI
R1 C C Li + n-butane

RMgX
R1 C C MgX + RH

04-04-2020 SKS
 Conversion of terminal alkynes into internal alkynes

NaNH2 / liq. NH3

R1 C C H R1 C C Na + NH3

acidic hydrogen Act as nucleophile

Terminal alkyne
R2-X
Nucleopholic substitution reaction

R1 C C R2 + NaX
Internal alkyne

Practice problems:
1. Convert 1-butyne into 2-pentyne.
2. Convert propyne into 2-butyne.
3. Convert ethyne into n-butane.

04-04-2020 SKS
Reactions of ethyne (Acetylene)
1. Addition of Arsenic trichloride

HgCl2
H C C H + ASCl3 Cl C C AsCl2  Learn about British
H H anti-lewisite (BAL).
b-Chlorovinyldichloroarsine (trans)

Lewisite

2. Dimerisation of Acetylene

CuCl + NH4Cl H2
H C C H H2 C C C C H H2C C C CH2
H Pd-BaSO4 H H
Vinylacetylene 1,3-Butadiene

Practice Problems:
1. What happen when ozonolysis of acetylene is carried out ?
2. What happen when acetylene is heated with hot alkaline potassium permanganate solution?
3. How will you distinguish between ethane, ethene and ethyne ? Explain.
04-04-2020 SKS