Alkynes

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 -bonds and one -bond. The -bond
is formed by overlap of sp orbitals. The -bonds are
formed by overlap of p orbitals. The -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 -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.
 Acidity of Alkynes
Terminal alkynes RC≡ CH are similar to acetylene in acidity.

After deprotonation the acetylide electron pair is in a sp

orbital.
 Acid-Base Reactions of Alkynes
In order to form the acetylide anion the base must be
strong enough. The conjugate acid of the base should
have pKa greater than the pKa of the alkyne.

Hydroxide is too weak and the equilibrium lies to the left.

Amide is strong enough and the equilibrium lies to the right.

 Practice Question
Which one of the following is the strongest
acid?

A) water
B) ammonia
C) 1-butene
D) 1-butyne
 Acetylide Anions as Nucleophiles
Acetylide anions react with methyl and primary alkyl
halides to form substituted alkynes.

This is an SN2 type of reaction.

 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.
Elimination Reactions with Acetylide Anions

Acetylide anions are very basic so they act as bases if

the alkyl halide is secondary or tertiary.
 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, ozonolysis.
 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

Lindlars 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.
 Ozonolysis of Alkynes

Ozonolysis also cleaves alkynes. The alkyne carbons are

tranformed into carboxylic acid carbons. The end carbon of
a terminal alkyne becomes carbonic acid which dissociates
to CO2 and H2O.
 Applications of Alkynes in Synthesis
Retrosynthesis
Example: Outline a synthesis of 1,2-epoxybutane using
ethyl bromide and acetylene as sources for all the carbon
atoms.

The epoxide may be formed from the corresponding

alkene:

The alkene could be made from the corresponding alkyne

which could itself be prepared from an acetylide anion:
 Applications of Alkynes in Synthesis
Now list the reactions in the “forward” direction starting
from acetylene.