Chemistry 1

Alkynes
Hydrocarbons with a carbon–carbon triple bond are alkynes.
Noncyclic alkynes have the molecular formula CnH2n-2.
Acetylene (HC≡ CH) is the simplest alkyne.
Compounds with the triple bond at the end of a carbon

chain (RC≡ CH) are monosubstituted, or terminal, alkynes.
Disubstituted alkynes (RC≡ CR′) have internal triple bonds.

Naming Alkynes
Replace the suffix –ane for the corresponding alkane

with –yne.
Naming Alkynes
Compounds that contain both an alkene and an alkyne

are numbered to give the first multiple bond the lowest
number and are named as an –enynes.
hept-1-en-5-yne
Physical Properties of Alkynes
Alkynes resemble alkanes and alkenes in physical

properties.
Low density and low water solubility.
Boiling points similar to the corresponding alkane.

Structure of Alkynes
Acetylene is linear.
Cyclononyne, the smallest stable cycloalkyne is strained

as the C-C≡ C-C unit is clearly bent.
Bonding in Alkynes
The C≡ C has two p-bonds and one s-bond. The s-bond
is formed by overlap of sp orbitals. The p-bonds are
formed by overlap of p orbitals. The p-bonds are
orthogonal to each other – shown in (b) and (c).
Bonding in Alkynes
The electrostatic potential maps shows the high electron

density (red) associated with the p-bonds.
Bonding in Alkanes, Alkenes and Alkynes
Bonding in Alkanes, Alkenes and Alkynes
For the series ethane → ethylene → acetylene the general

trends are:
1. The geometry at carbon changes from

tetrahedral → trigonal planar → linear.
2. The C-C and C-H bonds become shorter and stronger.
3. The acidity of the C-H bonds increases.

C-H Bond Lengths
C-H bond lengths are shortest for hydrogens bonded to

a sp C. The sp orbital has higher s character than sp2
orbitals so it is closer to the carbon atom.
Acidity of Alkanes, Alkenes and Alkynes
C-H bonds of alkanes, alkenes and alkynes are very weak

acids. The pKa of methane is estimated to be 60.
Because it is derived from a very weak acid the conjugate

base, a carbanion, is a very strong base.
Acidity Trend
The effective electronegativity of carbon increases with

increasing s-character (sp3>sp2>sp) therefore the pKa
decreases in the same order.
Acetylide Anions as Nucleophiles
Examples include:
The reagents are listed above and below the reaction

arrow in the order they are used. So, in the first reaction,
acetylene is first deprotonated with sodium amide in
ammonia and then reacted with ethyl bromide.
Preparation of Alkynes by Elimination
Alkynes can be prepared by double dehydrohalogenation

of either geminal dihalides or vicinal dihalides.
Preparation of Alkynes by Elimination
Three equivalents of base are required if the alkyne is
terminal since a terminal alkyne is deprotonated by the
base as soon as it is formed.
Protonation of the acetylide anion is then required as a
second step.
From Alkenes to Alkynes
Vicinal dibromides are formed on bromination of an

alkene so this gives us a way to transform an alkene
into an alkyne.
Reactions of Alkynes
Reactions of alkynes are similar to reaction of alkenes:

hydrogenation, hydration, halogenation, HX addition etc.
Hydrogenation of Alkynes
Alkynes are reduced to alkanes using hydrogen and a

transition metal catalyst.
For example:
Relative Stability of Alkynes
The heat of hydrogenation of 1- and 2-butyne can be

used to determine the relative stability of an internal and
a terminal alkyne (both yield butane as product).
Less heat is released by 2-butyne so that is the more

stable isomer.
Stereochemistry of Hydrogenation
Metal catalyzed hydrogenation is a syn addition process.

Hydrogenation with Lindlars Catalyst
Lindlar catalyst is a partially deactivated catalyst that

was developed for partial hydrogenation of alkynes to
alkenes.
Disubstituted alkynes yield cis-alkenes.

Metal-Ammonia Reduction of Alkynes
Group I metals in liquid ammonia reduce alkynes to trans

alkenes exclusively.
The key intermediate is the vinyl radical which prefers the

less hindered trans conformation.
Practice Question
How would you accomplish the following
conversion?
A) NaNH2
B) H2, Lindlar Pd
C) Na, NH3
D) either B or C
Practice Question
Select the most effective way to synthesize cis-2-
pentene from 1-propyne.
A) 1) NaNH2 2) CH3CH2Br 3) H2, Pd
B) 1) NaNH2 2) CH3Br 3) H2, Lindlar Pd
C) 1) NaNH2 2) CH3CH2I 3) H2, Lindlar Pd
D) 1) NaNH2 2) CH3CH2Br 3) Na,NH3
Practice Question
What is the structure of Compound Y in the
following synthetic sequence?
A) pentane
B) cis-2-pentene
C) trans-2-pentene
D) 2-pentyne
Addition of Hydrogen Halides
Hydrogen halides add to alkynes to form alkenyl halides.
The reaction follows Markovkovs Rule (the proton adds

to the carbon that initially has the most hydrogens).
Addition of HX to Alkynes
Excess HX leads to geminal dihalides.
Since each addition of HX follows Markovnikov’s rule

both protons are added to the same carbon.
Free Radical Addition of HBr
Anti-Markovnikov addition of HBr is performed with

peroxide initiation.
Hydration of Alkynes
Hydration of alkynes yields a special alcohol – an enol.

The enol has an –OH attached to an alkene carbon.
The enol rapidly isomerizes to the keto form. This

equilibration is keto-enol tautomerism.
Tautomers are constitutional isomers that equilibrate by

migration of an atom or group.
Hydration of Alkynes
In general the keto form is more stable so it will be drawn
as the product of a hydration reaction.
The reaction follows Markovnikov’s rule so terminal

alkynes yield methyl ketones not aldehydes.
Practice Question
What is the product of the acid catalyzed
hydration of 1-hexyne?
A) B)
C) D)
Addition of Halogens to Alkynes
Two molecules of halogen react with one alkyne to yield

a tetrahaloalkane.
Addition of Halogens to Alkynes
An anti dihaloalkene can be isolated if exactly one

equivalent of halogen is used.

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Alkynes

Hydrocarbons with a carbon–carbon triple bond are alkynes.

Noncyclic alkynes have the molecular formula CnH2n-2.

Acetylene (HC≡ CH) is the simplest alkyne.

Compounds with the triple bond at the end of a carbon

Disubstituted alkynes (RC≡ CR′) have internal triple bonds.

Replace the suffix –ane for the corresponding alkane

Compounds that contain both an alkene and an alkyne

Alkynes resemble alkanes and alkenes in physical

Low density and low water solubility.

Boiling points similar to the corresponding alkane.

Cyclononyne, the smallest stable cycloalkyne is strained

The electrostatic potential maps shows the high electron

For the series ethane → ethylene → acetylene the general

1. The geometry at carbon changes from

2. The C-C and C-H bonds become shorter and stronger.

3. The acidity of the C-H bonds increases.

C-H bond lengths are shortest for hydrogens bonded to

C-H bonds of alkanes, alkenes and alkynes are very weak

Because it is derived from a very weak acid the conjugate

The effective electronegativity of carbon increases with

The reagents are listed above and below the reaction

Alkynes can be prepared by double dehydrohalogenation

Vicinal dibromides are formed on bromination of an

Reactions of alkynes are similar to reaction of alkenes:

Alkynes are reduced to alkanes using hydrogen and a

The heat of hydrogenation of 1- and 2-butyne can be

Less heat is released by 2-butyne so that is the more

Metal catalyzed hydrogenation is a syn addition process.

Lindlar catalyst is a partially deactivated catalyst that

Disubstituted alkynes yield cis-alkenes.

Group I metals in liquid ammonia reduce alkynes to trans

The key intermediate is the vinyl radical which prefers the

Hydrogen halides add to alkynes to form alkenyl halides.

The reaction follows Markovkovs Rule (the proton adds

Since each addition of HX follows Markovnikov’s rule

Anti-Markovnikov addition of HBr is performed with

Hydration of alkynes yields a special alcohol – an enol.

The enol rapidly isomerizes to the keto form. This

Tautomers are constitutional isomers that equilibrate by

The reaction follows Markovnikov’s rule so terminal

Two molecules of halogen react with one alkyne to yield

An anti dihaloalkene can be isolated if exactly one

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