BPC 10 26 09 - WadeOC Lecture

Organic Chemistry,
9th Edition
L. G. Wade, Jr.
Chapter 9
Lecture
Alkynes
© 2017 Pearson Education, Inc.

Introduction
• Alkynes contain a triple bond.

• Their general formula is CnH2n–2.
• There are two elements of unsaturation for
each triple bond.
• Some reactions resemble the reactions of
alkenes, like addition and oxidation.
• Some reactions are specific to alkynes.
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.
Examples of Nomenclature
• All other functional groups, except ethers and

halides, have a higher priority than alkynes.
Physical Properties
• Nonpolar, insoluble in water

• Soluble in most organic solvents
• Their boiling points are similar to an alkane
of the same size.
• Less dense than water
• Up to four carbons, gas at room
temperature
Overlap of the p Orbitals
of Acetylene
Each carbon in acetylene has two unhybridized p orbitals

with one nonbonded electron. It is the overlap of the parallel
p orbitals that forms the triple bond (two pi orbitals).
Bond Lengths
• Triple bonds are shorter than double or single

bonds because of the two pi overlapping
orbitals.
Acidity of Hydrocarbons
Acidity of Alkynes
• Terminal alkynes are more acidic than other

hydrocarbons due to the higher s character of the
sp hybridized carbon.
• Terminal alkynes can be deprotonated
quantitatively with strong bases such as sodium
amide (–NH2).
• Hydroxide (HO–) and alkoxide (RO–) bases are not
strong enough to deprotonate the alkyne
quantitatively.
Formation of Acetylide Ions
• H+ can be removed from a terminal alkyne by
sodium amide, NaNH2.
• The acetylide ion is a strong nucleophile that

can easily do addition and substitution reactions.
Acetylide Ions in SN2
Reactions
• One of the best methods for synthesizing substituted

alkynes is a nucleophilic attack by the acetylide ion
on an unhindered alkyl halide.
• SN2 reactions with 1° alkyl halides lengthen the
alkyne chain.
• Unhindered alkyl halides work better in an SN2
reaction: CH3X > 1°.
Acetylide Ions as Strong
Bases
• Acetylide ions are also strong bases. If the SN2

reaction is not possible, then an elimination (E2)
will occur.
Solved Problem 1
Show how to synthesize 3-decyne from acetylene and any necessary alkyl halides.
Solution
Another name for 3-decyne is ethyl n-hexylacetylene. It can be made by adding an ethyl
group and a hexyl group to acetylene. This can be done in either order; we begin by adding
the hexyl group.
Addition to Carbonyl
Compounds
• Nucleophiles can attack the carbonyl carbon,

forming an alkoxide ion that, on protonation, will
form an alcohol.
Mechanism of Acetylenic
Alcohol Formation
Addition to an Aldehyde
• The product is a secondary alcohol with one

R group from the acetylide ion, the other R group
from the aldehyde.
Addition to a Ketone
The product is a tertiary alcohol.

Solved Problem 2
Show how you would synthesize the following compound, beginning with acetylene and any
necessary additional reagents.
Solution
We need to add two groups to acetylene: an ethyl group and a six-carbon aldehyde (to form
the secondary alcohol). If we formed the alcohol group first, the weakly acidic —OH group
would interfere with the alkylation by the ethyl group. Therefore, we should add the less
reactive ethyl group first and add the alcohol group later in the synthesis.
Synthesis of Alkynes by
Elimination Reactions
• Removal of two molecules of HX from a vicinal
or geminal dihalide produces an alkyne.
• Dehydrohalogenation of a geminal or vicinal
dihalide gives a vinyl halide.
• Under strongly basic conditions, a second
dehydrohalogenation may occur to form an
alkyne.
Reagents for Elimination
• 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.
KOH Elimination
The KOH elimination tends to give the most stable,

most highly substituted alkyne.
End 10/26 lecture

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Organic Chemistry,

© 2017 Pearson Education, Inc.

• Alkynes contain a triple bond.

• Find the longest chain containing the

• All other functional groups, except ethers and

• Nonpolar, insoluble in water

Each carbon in acetylene has two unhybridized p orbitals

• Triple bonds are shorter than double or single

• Terminal alkynes are more acidic than other

• The acetylide ion is a strong nucleophile that

• One of the best methods for synthesizing substituted

• Acetylide ions are also strong bases. If the SN2

• Nucleophiles can attack the carbonyl carbon,

• The product is a secondary alcohol with one

The product is a tertiary alcohol.

• Molten KOH or alcoholic KOH at 200 °C favors an

The KOH elimination tends to give the most stable,

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