Chemistry

Alkynes

Session objectives
1. Preparation of alkynes by

(a) Kolbes method

(b) dehydrohalogenation of vicinal dihalide (c) dehydrohalogenation of geminal dihalide 2. Chemical reactions of alkyne (a) Addition of halogen, hydrogenhalides. (b) Ozonolysis

3. Confirmatory test for alkyne

General characteristics of alkynes

General formula CnH2n2 sp hybridization CC bond length 1.2 A0 Shows chain and functional isomerism

Chain isomerism

CH3

CH2

CH2

CH

CH3

CH CH3

CH

Functional group isomerism

CH3 C CH
CH2 C CH2

Preparation
Kolbe electrolysis

At anode CHCOO Na Current CHCOO CHCOO

At cathode 2Na
2e C2Na

CH COO Na
Sodium maleate

.
CH

-2eCHCOO

CH

H2 O

.
CH

CH

2CO 2

.
CHCOO

2NaOH H2

Dehydrohalogenation of vicinal dihalides

2KOH (alc)

CH3

CH Br

CH2 Br

CH3

CH + 2KBr + 2H2O

From gem dihalides

Cl

CH3 Cl

alc.KOH

+ 2 KCI + 2 H2O

Miscellaneous methods

Miscellaneous methods From CaC2

CaC2 H2O HC CH Ca(OH)2

Lime

Chemical properties
Addition Reactions (i) Addition of hydrogen
CH3C CH + 2H2 Ni CH3CH2CH3

Propyne

Chemical properties
Lindlar catalyst (H2/Pd/BaSO4) partially reduces a disubstituted alkyne to a cis-alkene.
H2 / Lindlar Catalyst H3 C C H C H CH3

CH3 C

C CH3

CH3 C

C CH3

Na/NH3 (liq.)

H3 C C H C

CH3

Trans-2-butene

Chemical properties
Addition of halogens
Br Br |
HC CH
2

| |

2Br

HC C H | Br Br

Addition of hydrogen halides

HC

CH3CH Br2 CH 2HBr

Mechanism
HBr CH3 C CH CH3 C Br HBr Br CH3 C Br Major product CH3 CH2

Br

CH3

CH3

CH3

CH Br

CH2

Br (2) more stable

(1) less stable

Peroxide CH3 C CH + HBr

CH3

CH

CHBr

(Anti Markownikoff addition)

Addition of water

HC

CH + H2O

HgSO4 H2SO4

CH2
O

CHOH

CH3 CHO

Unstable
H2O/H+ CH3 C C CH3 HgSO4 CH3 C CH2CH3

O CH3C CCH2CH3 H2O/H+ HgSO4

CH3CH2CCH2CH3+ CH3CCH2CH2CH3

(Major)

(Minor)

Hydroboration oxidation

CH3C

R2BH C H 0-10C

CH3 CH

CH

BR2

H2O2/OH-

CH3 CH

CH :O : H

Tautomerization CH3 CH2 CHO Aldehyde

Oxidation of alkynes

HC

alk. CH KMnO 4
alk.KMnO

COOH COOH

Strong heating

CO2 + H2O

CH3C

4 CH3COOH + CO 2 + H2O CH

CH3C

CCH3

alk . KMnO4

CH3COOH + CH3COOH

Ozonolysis of alkynes

O RC CR + O3 R C C R OO H2O R C C R + H2O2 O O

RCOOH + RCOOH

O HC CH + O3 HCCH OO H2O H2O2 H C C H + HCOOH O O Major

Minor

Formation of alkynides

2 RC

CH + AgNO3 + 2 NH4OH (Tollens' reagent)

2 RC

+ C Ag + 2 NH4CI + 2 H2O

White ppt

Formation of alkynides

2 RC

CH + Cu2 Cl2 + 2 NH4OH

+ CCu + 2 NH4Cl + 2H2O 2 RC Red ppt

Acidity of Alkynes

H : H C

H H C H

H CH :

C H

Acetylide anions

Vinyl anion

Ethyl anion

- > CH = CH- > HC CC2H5 2

HC CH>CH2 =CH2 >CH3 - CH3

Acidity of Alkynes

HC CH Na

HC C

Na

1 H2 2

sodium. acetylide

Acidity of Alkynes
The order of boiling point among hydrocarbons is alkynes > alkenes > alkanes. These hydrocarbons also possess low dipole moment.
CH3CH2C CH CH3CH2CH CH2 CH3C C CH3

= 0.80 D

= 0.30 D

= 0.0 D

Acetylene having two hydrogen atoms is more acidic than a mono substituted acetylene.

Class exercise

Class exercise 1
How will you effect the following conversions?
(a) CH4
CH2 CH2

(b) CH3C

CH

CH3COCH3

Solution: (a) (i) Cl2 + hn (ii) Wurtz reaction (iii) Cl2 + hn (iv) alc. KOH, heat (b) (i) HgSO4, H2SO4 (20%)

Hence, the answer is (c)

Class exercise 2
Write the structural formula of the main organic product.
CH3

H2O/H+ CH HgSO4

(i)

(ii) CH3C
(iii) CH3C

CH

2 HOCl
H2/Lindlar's

CCH2CH2 CH3

Catalyst

Solution:

Hence, the answer is (b)

Solution

(i)
O

(ii)

CH 3 C CHCl2 O

(iii)
H H

Class exercise 3
Give a chemical test to distinguish between 1-butyne and 2-butyne.

Solution:

1 butyne will give white ppt. with ammonical AgNO3.

Class exercise 4
A cylinder contains one of the following gases propyne, propene, propane. What chemical test would you apply to identify the gases? Solution:

AgNO3 (ammonical) is used for alkyne, alk. KMnO4, and heat is applied for alkene. No reaction takes place with propane with the above mentioned reagents.

Class exercise 5
Write the product of the following reaction.
CH3CH2CHCl2 Alkali Boil

Solution: CH3CH2CHO

Class exercise 6
What reaction of an appropriate alkyne would lead to the following product?
H3C C Br C CH2CH3 Br

Solution:

CH3C

CCH2CH3

Class exercise 7
An organic compound (A) having molecular formula when treated with NaNH2/ NH3 followed by reaction with n-propyl bromide yielded (B) . Compound (A) gives a ketone (C) when treated with acidified HgSO4. (B) on oxidation with hot alk. KMnO4 gives two isomeric acids (D) and (E). Deduce structures from (A) to (E). Solution:

A:

B:
COOH

C
O

D
COOH

E:

Class exercise 8
Write the correct product of the following reaction.

HC

CH + 2HOCl

Product

Solution: Cl2CHCHO

Class exercise 9
Write the products of the following reaction.
H C C H Na (A) C 2H 5Br (B) O3, distillation (F) + (G)

KMnO4, Hot (C) + (D) + (E)

Solution:

C is CO2
+ C Na
C C2H5

A is H C
B is
H C

D is C2H5CO2H E is H2O

F is HCOOH
G is C2H5COOH

Class exercise 10
Write the intermediate steps of the following reaction
C 6H5CHC OH CH H3O+ C 6H5CH CHCHO

Solution:

Solution
C 6H 5CH C OH CH C 6H 5CH C CH

OH 2 H2O

C 6H 5 CH C

C 6H 5CH C

CH

+ CH
H 2O , H C 6H 5CH

+
C CH OH

C 6H 5CH

CH CH

Thank you