Organic Chemistry, 6th Edition

L. G. Wade, Jr.

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.
=>
Chapter 9 2
 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.
=>
Chapter 9 3
 Name these:
CH3 C CH
propyne
CH3 C C CH2 CH2 Br
5-bromo-2-pentyne
5-bromopent-2-yne
CH3 CH3
CH3 CH CH2 C C CH CH3

2,6-dimethyl-3-heptyne
2,6-dimethylpept-3-yne =>
Chapter 9 4
 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.

=>

Chapter 9 5
 Examples
CH3
CH2 CH CH2 CH C CH

4-methyl-1-hexen-5-yne
4-methylhex-1-en-5-yne
OH
CH3 C C CH2 CH CH3

4-hexyn-2-ol
hex-4-yn-2-ol
=>

Chapter 9 6
 Common Names
Named as substituted acetylene.

CH3 C CH
methylacetylene
(terminal alkyne)
CH3 CH3
CH3 CH CH2 C C CH CH3

isobutylisopropylacetylene
(internal alkyne) =>
Chapter 9 7
 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.
=>
Chapter 9 8
 Acetylene
• Acetylene is used in welding torches.
• In pure oxygen, temperature of flame
reaches 2800C.
• It would violently decompose to its
elements, but the cylinder on the torch
contains crushed firebrick wet with
acetone to moderate it.
=>

Chapter 9 9
 Synthesis of Acetylene
• Heat coke with lime in an electric
furnace to form calcium carbide.
• Then drip water on the calcium carbide.
3 C + CaO CaC2 + CO
coke lime

* CaC2 + 2 H2O H C C H + Ca(OH)2

*This reaction was used to produce light
for miners’ lamps and for the stage. =>
Chapter 9 10
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.

=>
Chapter 9 11
 Bond Lengths
• More s character, so shorter length.
• Three bonding overlaps, so shorter.

Bond angle is 180, so linear geometry. =>

Chapter 9 12
 Acidity of Alkynes
• Terminal alkynes, R-CC-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.
=>

Chapter 9 13
Acidity Table

=>
Chapter 9 14
Forming Acetylide Ions
• H+ can be removed from a terminal alkyne by sodium
amide, NaNH2.

• NaNH2 is produced by the reaction

of ammonia with sodium metal.

=>
Chapter 9 15
 Alkynes from
Acetylides
• Acetylide ions are good nucleophiles.
• SN2 reaction with 1 alkyl halides
lengthens the alkyne chain.

=>
Chapter 9 16
 Must be 1
• Acetylide ions can also remove H+
• If back-side approach is hindered,
elimination reaction happens via E2.

=>
Chapter 9 17
 Addition to Carbonyl
Acetylide ion + carbonyl group yields an
alkynol (alcohol on carbon adjacent to
triple bond).
R C C + C O R C C C O

H
O
H2O + R C C C O H H
H

=>
Chapter 9 18
 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
H
H
H2O + CH3 C C C O H O
H
H H

=>
Chapter 9 19
 Add to Aldehyde
Product is a secondary alcohol, one R
group from the acetylide ion, the other R
group from the aldehyde.
CH3 CH3
CH3 C C + C O CH3 C C C O
H
H
CH3
H
H2O + CH3 C C C O H O
H
H H
=>
Chapter 9 20
 Add to Ketone
Product is a tertiary alcohol.
CH3 CH3
CH3 C C + C O CH3 C C C O
CH3
CH3
CH3
H
H2O + CH3 C C C O H O
H
CH3 H

=>
Chapter 9 21
 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.
=>
Chapter 9 22
 Reagents for
Elimination
Br Br
KOH (fused)
CH3 CH CH CH2 CH3 CH3 C C CH2 CH3
200°C

• Molten KOH or alcoholic KOH at 200C

favors an internal alkyne.
• Sodium amide, NaNH2, at 150C, followed
by water, favors a terminal alkyne.
1) NaNH2 , 150°C
CH3 CH2 CH2 CHCl2 CH3 CH2 C CH
2) H2O
=>
Chapter 9 23
Migration of Triple Bond

=>
Chapter 9 24
 Addition Reactions
• Similar to addition to alkenes.
• Pi bond becomes two sigma bonds.
• Usually exothermic.
• One or two molecules may add.

=>
Chapter 9 25
 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, Lindlar’s catalyst, to
convert an alkyne to a cis-alkene.
• React the alkyne with sodium in liquid
ammonia to form a trans-alkene.
=>
Chapter 9 26
 Lindlar’s Catalyst
• Powdered BaSO4 coated with Pd,
poisoned with quinoline.
• H2 adds syn, so cis-alkene is formed.

=>
Chapter 9 27
Na in Liquid Ammonia
• Use dry ice to keep ammonia liquid.
• As sodium metal dissolves in the
ammonia, it loses an electron.
• The electron is solvated by the
ammonia, creating a deep blue solution.
- +
NH3 + Na NH3 e + Na =>

Chapter 9 28
 Mechanism
Step 1: An electron adds to the alkyne, forming a radical anion

Step 2: The radical anion is protonated to give a radical

Step 3: An electron adds to the alkyne, forming an anion

Step 4: Protonation of the anion gives an alkene

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Chapter 9 29
 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.
Br2 CH3 Br CH3 CH3
CH3 C C CH3 C C + C C
Br CH3 Br Br
Br2
Br Br
CH3 C C CH3
Br Br
Chapter 9 30 =>
 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.
Br Br
HBr HBr
CH3 C C H CH3 C CH2 CH3 C CH3
Br
Chapter 9 31 =>
 HBr with Peroxides
Anti-Markovnikov product is formed with a
terminal alkyne.
H H
H Br
HBr HBr
CH3 C C H CH3 C C CH3 C C H
ROOR Br ROOR
H Br
mixture of E and Z isomers

=>
Chapter 9 32
 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.

=>
Chapter 9 33
 Mechanism for
Mercuration
• Mercuric ion (Hg2+) is electrophile.
• Vinyl carbocation forms on most-sub. C.
• Water is the nucleophile.
+ +
+2 Hg Hg
Hg CH3 C
+
C
CH3 C C H CH3 C C
H + H
O
H2O H H
+
H H3O
+ Hg
CH3 C C CH3 C C H2O
H H
OH OH

an enol
=>
Chapter 9 34
 Enol to Keto (in Acid)
• Add H+ to the C=C double bond.
• Remove H+ from OH of the enol.

H + H H
H3O
CH3 C C
H CH3 C C H CH3 C C H
OH
OH H OH H

H H2O

A methyl ketone CH3 C C H

O H
=>
Chapter 9 35
Hydroboration Reagent
• Di(secondary
isoamyl)borane, called H3C
HC CH3
disiamylborane. CH3
CH
• Bulky, branched reagent H3C B CH
adds to the least H CH
CH3
hindered carbon. H3C
• Only one mole can add.

=>
Chapter 9 36
 Hydroboration -
Oxidation
• B and H add across the triple bond.
• Oxidation with basic H2O2 gives the enol.

H H2O2 H
CH3 C C H Sia2 BH CH3 C C CH3 C C
H BSia2 NaOH OH
H
=>

Chapter 9 37
 Enol to Keto (in Base)
• H+ is removed from OH of the enol.
• Then water gives H+ to the adjacent
carbon.
H H H
CH3 C C CH3 C C CH3 C C
OH OH O O
H H H
H HOH
H
CH3 C C
An aldehyde O
H
=>
Chapter 9 38
 Oxidation of Alkynes
• Similar to oxidation of alkenes.
• Dilute, neutral solution of KMnO4
oxidizes alkynes to a diketone.
• Warm, basic KMnO4 cleaves the triple
bond.
• Ozonolysis, followed by hydrolysis,
cleaves the triple bond.
=>
Chapter 9 39
 Reaction with KMnO4
• Mild conditions, dilute, neutral
O O
KMnO4
CH3 C C CH2 CH3 CH3 C C CH2 CH3
H2O, neutral

• Harsher conditions, warm, basic

O O
KMnO4 , KOH
CH3 C C CH2 CH3 CH3 C O + O C CH2 CH3
H2O, warm

=>
Chapter 9 40
 Ozonolysis
• Ozonolysis of alkynes produces carboxylic
acids (alkenes gave aldehydes and ketones).
O O
(1) O3
CH3 C C CH2 CH3 CH3 C OH + HO C CH2 CH3
(2) H2O

• Used to find location of triple bond in an

unknown compound.

=>
Chapter 9 41
End of Chapter 9

Chapter 9 42