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Jully Tan
School of Engineering
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Alkynes
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Naming Alkynes
Step 1: Find the longest chain containing the triple bond.
Step 2: Change ene or -ane ending to -yne.
Step 3: Number the chain, starting at the end closest to the triple bond.
Step 4: Give branches or other substituents a number to locate their
position.
Example
CH
3
C CH
propyne
CH
3
C C CH
2
CH
2
Br
5-bromo-2-pentyne
CH
3
CH
CH
3
CH
2
C C CH
CH
3
CH
3

2,6-dimethyl-3-heptyne
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Step 5: Substitutive nomenclature: As a substituent, an alkyne is named alkynyl.

Step 6: The double bond has a priority over the triple bond when numbered (Follow whichever that
nearest to the end of the chain in determines the direction of numbering). The lowest numbers are
given to the multiple bonds Whether double / triple. When there is a choice, HOWEVER, The
double bond takes precedence!!!

C C H CH
2
CH C H
2
1-Pentene-4-yne
1
2 3
4
5
There are no cis -
trans
-isomers, because the triple bond is linear
C C H
CH
2
C C H Ethynyl
2-propynyl
CH
2
CH CH
2
CH
CH
3
C CH
4-methyl-1-hexen-5-yne
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Example of Naming Alkynes
The lowest numbers are given to the multiple bonds
Whether double / triple. When there is a choice,
HOWEVER, The double bond takes precedence!!!
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Carbon-carbon triple bond results from sp orbital on each C forming a sigma bond and
unhybridized p
X
and p
y
orbitals forming bonds.
The remaining sp orbitals form bonds to other atoms at 180 to C-C triple bond.
The bond is shorter and stronger than single or double
Breaking a bond in acetylene (HCCH) requires 318 kJ/mole (in ethylene it is 268 kJ/mole)

2


C H
3
CH
3
C H
2
CH
2
C H CH
1.54 1.33 1.20
1. Electronic Structure Of Alkynes
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Alkynes show three types of isomerism,
Chain isomerism
Position isomerism
Functional isomerism.
Chain isomerism It is due to the different arrangement of carbon atoms in the
chain i.e., straight chain or a branched-chain.





Position isomerism It is due to the difference in the location of the triple bond
2. Isomerism in Alkynes
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Functional isomerism Alkynes are isomeric with alkadienes both being
represented by the general formula CnH2n-2. So there can be a difference in the
nature of the bond (triple to double) giving different functional properties.
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Boiling points of alkynes are close to the boiling points of alkenes and alkanes.
C C H H
IR characteristic bands:
Stretch ~2100 cm
-1
Strech ~ 3300 cm
-1
3. Boiling Point of Alkynes
Alkyne have lower densities, than water and they are insoluble in water.
4. Density & Solubility
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Additional to Triple Bond
Hydrogen
Halogen
Hydrogen Halide (HX)
Hydration
Oxidation of triple bond


Synthesis
Dehydration of alkyl dihalides
Reaction with 1 alkyl halides

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Synthesis of Alkynes
Method 1: Dehydration of alkyl dihalides using a strong base

1. Vicinal dihalides (compounds with halogen atoms on adjacent carbon atoms)
2. Treatment of vicinal dihalides with strong bases, alcoholic KOH and sodium amide
results in alkynes.
3. Vicinal dihalides obtained from addition of halogen to alkenes.
NaBr
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Method 2: Reaction of sodium acetylide with 1 alkyl halides

1. Acetylene & monosubstituted acetylenes contains a H atom attached to triple
bonded C atom: Acetylenic hydrogen
2. Acetylenic H are acidic and replaced by certain metals forming salts: metal
acetylides.

R C CH
Na
R C C Na
+
R C C Na
+
+
R' CH
2
X
R C C CH
2
R' + NaX
+ H
2
Terminal
Alkyne
Methyl
or
Primary
Alkyl
Halide
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Show how to synthesis 3-decyne from ethyne and any necessary alkyl halide
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Addition Reaction (i) Hydrogenation
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Conversion of Alkynes to cis-Alkenes
Addition of H
2
using chemically deactivated palladium on calcium carbonate as a
catalyst (the Lindlar catalyst) produces a cis alkene
The two hydrogens add syn (from the same side of the triple bond)
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Conversion of Alkynes to trans-Alkenes
Anhydrous ammonia (NH
3
) is a liquid below -33 C
alkaline metals dissolve in liquid ammonia and function as reducing agents
Alkynes are reduced to trans alkenes with sodium or lithium in liquid ammonia
The reaction involves a radical anion intermediate
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Addition Reaction (ii) Halogenation
Alkynes reacts with equivalent of halogens forming tetrahalides.
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Electrophilic addition to triple bonds proceeds slower, than addition to double bonds and
often requires a catalyst. The Markovnikovs rule is as valid as for the addition to double
bonds. HBr in the presence of peroxides adds against the rule.

2 Step involved:
Step 1: producing of haloalkene stage
Step 2: Producing gem-dihalide stage (twin =both halogen at the same
Addition Reaction (iii) Hydrohalogenation
C H
3
C CH
3
Br
Br
HBr
C H
3
C
CH
2
Br
C H
3
C CH
HBr
peroxides
C H
3
C
CHBr
H
74%
C H
3
C CH
3
Br
Br
HBr
C H
3
C
CH
2
Br
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Addition Reaction (iv) Hydration
Differences from hydration of alkenes:
1. A Hg
2+
catalyst is required
2. The product of addition is unstable and isomerizes.
3. Water adds and loses a proton.
4.A proton from aqueous acid replaces Hg(II)

RC CH O H
2
HgSO
4
, H
2
O
C C
R
O H
H
H
C C
R
O
H
H
H
+
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Mechanism of Mercury(II)-Catalyzed Hydration of Alkynes
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Oxidative Cleavage of Alkynes
Strong oxidizing reagents (O
3
or KMnO
4
) cleave internal alkynes, producing two carboxylic
acids
Terminal alkynes are oxidized to a carboxylic acid and carbon dioxide
Neither process is useful in modern synthesis were used to elucidate structures because the
products indicate the structure of the alkyne precursor
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Visual Test
1. Bromine test
2. Rxn with H2SO4 (to differentiate alkanes and alkynes)
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