The carbon-carbon triple bond results from the interaction of two sp hybridized carbon
atoms. 180 degree angle. Linear.
The carbon-carbon triple bond is the shortest and strongest known
carbon-carbon bond. Why? It has the highest percentage of s character.
Nomenclature
Alkynes are named like alkenes with the following adjustments: 1) Number the carbons
on the chain so that the triple bonded carbons receive the lowest possible numbers, 2)
Indicate the location of the triple bond by writing the number of the lowest numbered
carbon making up the triple bond in front of the name of the parent chain. 3) Change the
ending from –ene to –yne.
Reactions to Know
Preparation of Alkynes
Synthesis of Alkynes:
R Br
2 Alc. KOH
C C R C C R
Br H
H R
Note: vic-dihalides are prepared from alkenes. Thus, in effect, this is a conversion of
alkene to alkyne.
Reactions of Alkynes
1. Hydrohalogenation:
X H
2 HX
R C C R R C C R
X H
(Geminal Dihalide)
OH O
H2O, H2SO4
R C C H R C C H R C C CH3
HgSO4 H2
H
Enol
(Ketone)
The enol is an intermediate in the reaction. However, it immediately rearranges to form
the a ketone through a process called keto-enol tautomerism.
OH O
1) BH3
R C C R R C C R R C C R
2) H2O2, OH H2
H
Enol
(Ketone)
As in the mercury-catalyzed reaction, the enol is an intermediate which quickly
undergoes keto-enol tautomerism to form the ketone.
OH
H BR2
1) BH3 2) H2O2, OH R C C R
R C C R C C
R R H
Enol
R C C R
H2
Examples:
a) Internal alkyne to ketone
OH O
1) BH3
H3C C C CH3 H3C C C CH3 H3C C C CH3
2) H2O2, OH
H2
H
Enol
b) Terminal alkyne to aldehyde
OH O
1) BH3
H C C CH3 H C C CH3 H C C CH3
2) H2O2, OH
H2
H
Enol
4. Hydrogenation:
H H
2 H2/ Pd
R C C R R C C R (Alkane)
H H
H H
H2
R C C R C C (Cis Alkene)
Lindlar's cat.
R R
6. Hydrogenation Using Lithium and Ammonia (Na can be used instead of Li):
H R
R C C R C C (Trans Alkene)
Li, NH3
R H
O O
KMnO4 or
R C C R' R C OH + R' C OH
O3
(Carboxylic Acid)
O
KMnO4 or
R C C H R C OH + CO2
O3
(Carboxylic Acid and CO2)
1) NaNH2, NH3
R C C H R C C CH2R'
2) R'CH2Br
Practice Problems:
Since s orbitals are nearer the positive nucleus and are lower in energy than p orbitals, the
negative charge is stabilized to a greater extent.
C C
H
2) How could you prepare H from H3CH2CC CH and any
needed reagents?
Answer
Answer
H CH2CH3
H3C C C CH2CH3 C C
Li, NH3
H3C H
Return to Problem
Answer
KMnO4 or CO2
H3C C C H H3C C OH
O3
Return to Problem
Answer
c)
1) BH3 ?
H C C CH2CH3
2) H2O2, OH
O
1) BH3
H C C CH2CH3 HC CH2CH2CH3
2) H2O2, OH
Return to Problem
Answer:
H3CH2C CH3
C C
H
2) How could you prepare H from H3CH2CC CH and any
needed reagents?
NaNH2
H3CH2CC CH H3CH2CC C BrCH3
H3CH2C CH3
C C
H2
H3CH2CC CCH3
H Lindlar's Catalyst
H
Return to Problem