Organic Chemistry

Chapter 9
Alkynes

Introduction
Alkynes contain a triple bond.
General formula is CnH2n-2
Two elements of unsaturation for each
triple bond.
Some reactions are like alkenes:
addition and oxidation.
Some reactions are specific to alkynes.
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Chapter 9

Nomenclature: IUPAC
Find the longest chain containing the
triple bond.
Change -ane ending to -yne.
Number the chain, starting at the end
closest to the triple bond.
Give branches or other substituents a
number to locate their position.
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Chapter 9

Name these:
CH3

C CH
propyne
CH3

C C CH2

CH2

Br

5-bromo-2-pentyne
CH3
CH3

CH CH2

CH3
C C CH CH3

2,6-dimethyl-3-heptyne
Chapter 9

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Additional Functional
Groups
All other functional groups, except
ethers and halides have a higher
priority than alkynes.
For a complete list of naming priorities,
look inside the back cover of your text.
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Chapter 9

Examples
CH3
CH2

CH CH2

CH C CH

4-methyl-1-hexen-5-yne
OH
CH3

C C CH2

CH CH3

4-hexyn-2-ol
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Chapter 9

Common Names
Named as substituted acetylene.
CH3

C CH

methylacetylene
CH3
CH3

CH CH2

CH3
C C CH CH3

isobutylisopropylacetylene
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Physical Properties
Nonpolar, insoluble in water.
Soluble in most organic solvents.
Boiling points similar to alkane of same
size.
Less dense than water.
Up to 4 carbons, gas at room temperature.
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Acetylene
Acetylene is used in welding torches.
In pure oxygen, temperature of flame
reaches 2800C.
It would violently decompose to its
elements, but the cylinder on the torch
contains crushed firebrick wet with
acetone to moderate it.
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Chapter 9

Synthesis of Acetylene
Heat coke with lime in an electric
furnace to form calcium carbide.
Then drip water on the calcium carbide.
CaC2 +

3 C + CaO
coke
* CaC2 +

CO

lime

2 H2O

H C C H + Ca(OH)2

*This reaction was used to produce light

for miners lamps and for the stage.
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Electronic Structure
The sigma bond is sp-sp overlap.

The two pi bonds are unhybridized p

overlaps at 90, which blend into a
cylindrical shape.

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Bond Lengths
More s character, so shorter length.
Three bonding overlaps, so shorter.

Bond angle is 180, so linear geometry.

Chapter 9

12

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Acidity of Alkynes
Terminal alkynes, R-CC-H, are more
acidic than other hydrocarbons.
Acetylene acetylide by NH2-, but not
by OH- or RO-.
More s character, so pair of electrons in
anion is held more closely to the
nucleus. Less charge separation, so
more stable.
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Acidity Table

Chapter 9

14

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Forming Acetylide Ions

H+ can be removed from a terminal
alkyne by sodium amide, NaNH2.
CH3

C C H + NaNH2

CH3

C C: Na

+ NH3

NaNH2 is produced by the reaction

of ammonia with sodium metal.
H N H

+ Na

Fe

+3

H N Na

+ 1/2 H2

H
Chapter 9

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15

Heavy Metal Acetylides

Terminal alkynes form a precipitate with
Ag(I) or Cu(I) salts.
Internal alkynes do not react.
Two uses:
Qualitative test for terminal alkyne
Separation of a mixture of terminal and
internal alkynes.
Chapter 9

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Qualitative Test
CH3

C C H

+ Cu

CH3

C C Cu

Reagent is AgNO3 or CuNO3 in alcohol, or

ammonia is added to form the complex ion.
The solid is explosive when dry.
Copper tubing is not used with acetylene.
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Separation of Mixtures
CH3

Cu

C C CH3
+

CH3

CH2

No reaction
+

C C H

Cu

CH3

CH2

C C Cu

red-brown precipitate

Filter the solid to separate, then regenerate the terminal

alkyne by adding dilute acid.
CH3

CH2

C C Cu

+ HCl

CH3

CH2

C C H

+ CuCl

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Alkynes from
Acetylides
Acetylide ions are good nucleophiles.
SN2 reaction with 1 alkyl halides
lengthens the alkyne chain.
CH3

C C: Na

CH3CH2

Br

CH3

C C CH2

CH3

+ NaBr

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Must be 1
Acetylide ions can also remove H+
If back-side approach is hindered,
elimination reaction happens via E2.
Br
CH3

C C: Na

CH3

CH CH3

CH3

C C H

H3C CH

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CH2

Addition to Carbonyl
Acetylide ion + carbonyl group yields an
alkynol (alcohol on carbon adjacent to
triple bond).
R C C

H2O +

C O

R C C C O

R C C C O H

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H
H

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Add to Formaldehyde
Product is a primary alcohol with one
more carbon than the acetylide.
H

H
CH3

C C

C O

CH3

C C C O
H

H
H2O + CH3 C C C O H
H

H
H

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Add to Aldehyde
Product is a secondary alcohol, one R
group from the acetylide ion, the other
R group from the aldehyde.
CH3

C C

CH3

CH3
C O
+
H

CH3

C C C O
H

CH3
H2O + CH3 C C C O H
H
Chapter 9

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H
H

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Add to Ketone
Product is a tertiary alcohol.
CH3

C C

CH3

CH3
C O
+
CH3

CH3

C C C O
CH3

CH3
H2O + CH3 C C C O H

CH3

H
H

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Synthesis by
Elimination
Removal of two molecules of HX from a
vicinal or geminal dihalide produces an
alkyne.
First step (-HX) is easy, forms vinyl
halide.
Second step, removal of HX from the
vinyl halide requires very strong base
and high temperatures.
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Reagents for
Elimination
Br
CH3

Br

CH CH CH2 CH3

KOH (fused)
200C

CH3

C C CH2

CH3

Molten KOH or alcoholic KOH at 200C

favors an internal alkyne.
Sodium amide, NaNH2, at 150C, followed
by water, favors a terminal alkyne.
CH3

CH2

CH2

CHCl2

1) NaNH2 , 150C

Chapter 9

2) H2O

CH3

CH2
26

C CH

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Migration of Triple Bond

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Addition Reactions

Similar to addition to alkenes

Pi bond becomes two sigma bonds.
Usually exothermic
One or two molecules may add.

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Addition of Hydrogen
Three reactions:
Add lots of H2 with metal catalyst (Pd,
Pt, or Ni) to reduce alkyne to alkane,
completely saturated.
Use a special catalyst, Lindlars catalyst
to convert an alkyne to a cis-alkene.
React the alkyne with sodium in liquid
ammonia to form a trans-alkene.
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Lindlars Catalyst
Powdered BaSO4 coated with Pd,
poisoned with quinoline.
H2 adds syn, so cis-alkene is formed.

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Addition of Halogens
Cl2 and Br2 add to alkynes to form vinyl
dihalides.
May add syn or anti, so product is
mixture of cis and trans isomers.
Difficult to stop the reaction at dihalide.
CH3

C C CH3

Br2

CH3
Br

Br
C C
CH3

CH3

C C

Br
Br2

CH3
Br
Br Br

CH3

C C CH3
Br Br

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Addition of HX
HCl, HBr, and HI add to alkynes to form
vinyl halides.
For terminal alkynes, Markovnikov
product is formed.
If two moles of HX is added, product is
a geminal dihalide.
CH3

C C H

HBr

Br
CH3

C CH2

Br

HBr

CH3

C CH3
Br

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HBr with Peroxides

Anti-Markovnikov product is formed with a
terminal alkyne.
CH3

C C H

HBr
ROOR

CH3

C C

HBr

Br ROOR

H Br
CH3

C C H
H Br

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Hydration of Alkynes
Mercuric sulfate in aqueous sulfuric
acid adds H-OH to one pi bond with a
Markovnikov orientation, forming a vinyl
alcohol (enol) that rearranges to a
ketone.
Hydroboration-oxidation adds H-OH
with an anti-Markovnikov orientation,
and rearranges to an aldehyde.
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Oxidation of Alkynes
Similar to oxidation of alkenes.
Dilute, neutral solution of KMnO 4
oxidizes alkynes to a diketone.
Warm, basic KMnO4 cleaves the triple
bond.
Ozonolysis, followed by hydrolysis,
cleaves the triple bond.
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Reaction with KMnO4

Mild conditions, dilute, neutral
CH3

C C CH2

CH3

O O

KMnO4

CH3

H2O, neutral

C C CH2

CH3

Harsher conditions, warm, basic

CH3

C C CH2

CH3

KMnO4 , KOH
H2O, warm

O
CH3

C O

O
+ O C CH2

CH3

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Ozonolysis
Ozonolysis of alkynes produces carboxylic
acids (Alkenes gave aldehydes and ketones)
CH3

C C CH2

CH3

(1) O3
(2) H2O

O
CH3

C OH

O
+ HO C CH2

CH3

Used to find location of triple bond in an

unknown compound.
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End of Chapter 9

Chapter 9

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