Alkynes (CnH2n-2)

Electronic Structure of Alkyne

C C
sp sp
Physical Properties of Alkynes
-relatively nonpolar.
-have low density
- low water solubility
- soluble in most organic solvents including acetone, diethyl ether, dichloromethane,
chloroform and alcohols.
-acetylene, propyne and butyne are gases at room temperature

Example of Alkyne

Acetylene

H C C H

-Most important commercial alkyne

-used as fuel for oxyacetylene welding torch

-colorless
- foul smelling gas that burns in air with a smoky sooty flame. When flame is
supplied with pure O2, the color turns to light blue, flame temperature
increases dramatically

- oxyacetylene torch can reach as high as 2000oC.

\ -gives most heat per mole of product.

- source: calcium carbide.

Classification of alkynes

Terminal Alkyne Internal Alkyne

General formula General formula

R C C H R C C R'
where R is an alkyl chain where R and R’ are alkyl chains

Examples: Examples:

H3C C C H H3C C C CH3

CH3CH2 CH2 C C H H3C C C CH2CH3

H C C CH2CH2 CH2CH3 CH 3CH 2 C C CH2CH3

-Terminal alkynes are weakly acidic

-reacts only with very strong bases such as sodium amide (NANH2) in liquid
ammonia solution.

-Alkynide is electron rich and a potential nucleophile.

NH3
R C C H + Na+ NH2- R C C Na+ + NH3
terminal alkyne sodium amide sodium alkynide ammonia

Internal alkynes are not acidic at all.

Reactions of Alkynes
1. Addition of HX (Hydrohalogenation)

H R H X
HX HX
R C C R C C R C C R
where R X
HX = HCl,HBr or HI H X

Markovnikov's Addition
2. Addition of X2 (Halogenation)

X R X X
X2 X2
R C C R C C R C C R
where R X
X2 = Cl2 or Br2 X X
(Anti addition)

3. Addition of H2O catalyzed by HgSO4/H2SO4 (Hydration)

O
H2O HO H +
H
R C C H C C C
(HgSO4, H2SO4)
R H R CH3
Ketone
enol

4. Hydroboration/Oxidation
O
1. BH3 H OH
R C C H - C C CH2CH
2. H2O2, OH
R H R
Aldehyde
enol
Reactions of Alkynes (continuation.1)
5. Addition of H2 (Hydrogenation)
R R H H
H2 H2
R C C R C C R C C R
Lindlar H H
Catalyst H H
Syn Addition
Lindlar catalyst- finely divided palladium metal that has been precipitated onto a calcium
carbonate support and then deactivated by treatment with lead acetate, and quinoline, an
aromatic amine.

R R H H
2 H2 H2
R C C R C C R C C R
Pd/C H H
H H
Syn Addition

H H
H R'
Li Li R C C R
R C C R' C C
NH3 NH3
R H H H
anti-addition
6. Conversion into acetylide anions

NaNH2 +
R C C H R C Na C + NH3
NH3
sodium alkynide
7. Acetylide ion alkylation

R C C + R' CH2Br R C C CH2R' + NaBr

alkyl halide
must be primary

8. Reaction of Acetylide anions with epoxide

O
(1)
H C C H C C CH2CH2OH
(2) H2O * Opening of the ring occurs
from the back side at the les substituted end of the epoxide

9. Oxidation
R
(1) O3
O + CO2
R C C H
(2) H2O
HO
R R'
(1) O3
R C C R' O + O
(2) H2O
HO OH
Preparation of Alkynes
Dehydrohalogenation (E2)

H H
Na+ -NH2
R C C R R C C R
2 equiv
X X

H X
K+ -OC(CH3)3
(excess)
R C C R R C C R
DMSO
H X