Alkynes

Alkynes are hydrocarbons that contain carbon–carbon triple bonds. Alkynes are also
called ‘acetylenes’ because they are derivatives of acetylene, the simplest alkyne.
Alkynes are not as common in nature as alkenes, but some plants do use alkynes to
protect themselves against disease or predators.

 Chemistry of the C≡C triple bond is similar to that of the double bond. Alkynes
undergo most of the same reactions as alkenes (additions and oxidations).

 Reactions those are specific to alkynes depend on

 Unique characteristics of the C≡C triple bond
 Unusual acidity of the acetylenic ≡C-H bond

A triple bond gives an alkyne four fewer hydrogens than the corresponding alkane
(molecular formula: CnH2n-2). The triple bond contributes two elements of unsaturation.

Nomenclature of Alkynes
1. The IUPAC nomenclature for alkynes is similar to that for alkenes. We find the
longest continuous chain of carbon atoms that includes the triple bond and
change the -ane ending of the parent alkane to –yne. The chain is numbered
from the end closest to the triple bond. Substituents are given numbers to
indicate their locations.

Old IUPAC name: ethyne (acetylene) 2-butyne 6-bromo-2-methyl-3-heptyne

New IUPAC name: ethyne But-2-yne 6-bromo-2-methylhept-3-yne

2. When additional functional groups are present, find the longest continuous chain
containing both functional groups and put both suffixes at the end of the name.
If the two functional groups are a double bond and a triple bond, number the
chain in the direction that produces a name containing the lower number. Put
the “ene” ending first, with the terminal “e” omitted.

If the same low number is obtained in both directions, number the chain in the direction
that gives the double bond the lower number.
1 PHRM103: Organic Pharmacy I
Abdullah-Al-Faysal, Lecturer, DOP, EWU
The structure of alkynes
Each carbon atom is bonded to only two atoms: a hydrogen and another carbon. Each
carbon atom needs two hybrid orbitals to form the sigma bond framework.
Hybridization of the s orbital with one p orbital gives two hybrid orbitals, directed 180°
apart. Overlap of these sp hybrid orbitals with each other and with the hydrogen s
orbitals gives the sigma bond framework.

Two pi bonds result from overlap of the two remaining unhybridized p orbitals on each
carbon atom. These orbitals overlap at right angles to each other, forming one pi bond
with electron density above and below the C-C sigma bond, and the other with electron
density in front and in back of the sigma bond. The shape of these pi bonds is such that
they blend to form a cylinder of electron density encircling the sigma bond between the
two carbon atoms.

Cylindrical e- density
distribution of π e-s
Acidity of Alkynes

The hybridization of an atom affects the acidity of a hydrogen bonded to it because

hybridization affects electronegativity:

2 PHRM103: Organic Pharmacy I

Abdullah-Al-Faysal, Lecturer, DOP, EWU
The most acidic compound is the one with its hydrogen attached to the most
electronegative atom. Electronegativity is a measure of the ability of an atom to pull the
bonding electrons toward itself. Thus, the most electronegative atom will be the one
with its bonding electrons closest to the nucleus. Pulling the electrons closer to the
nucleus stabilizes the carbanion. Therefore, a sp hybridized atom with 50% s character is
the most electronegative.

If we want to remove a proton from an acid, we must use a base that is stronger than
the base that is formed when the proton is removed. Very strong bases (such as sodium
amide, NaNH2) deprotonate terminal acetylenes to form carbanions called acetylide
ions. Hydroxide and alkoxide ions are not strong enough bases to deprotonate alkynes.

Acetylide ions are strong nucleophiles. In fact, one of the best methods for synthesizing
substituted alkynes is a nucleophilic attack by an acetylide ion on a primary alkyl halide.

Alkynes are less reactive than alkenes

Alkynes, like alkenes, undergo electrophilic addition reactions because of their relatively
weak π bonds. The same electrophilic reagents that add to alkenes also add to alkynes.
For example,

An alkyne is less reactive than an alkene. Because, a positively charged intermediate—a

vinylic cation is formed. A vinylic cation is less stable than a similarly substituted alkyl
cation because a vinylic cation has a positive charge on a sp carbon. A sp carbon is more
electronegative than the sp2 carbon of an alkyl cation and is, therefore, less able to bear
a positive charge.

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Abdullah-Al-Faysal, Lecturer, DOP, EWU
The addition of water to an alkyne

Alkynes also undergo the acid-catalyzed addition of water.

The initial product of the reaction is an enol. An enol has a carbon–carbon double bond
with an OH group bonded to one of the sp 2 carbons. The enol immediately rearranges to
a ketone. A ketone and its corresponding enol are called keto–enol tautomers.
Tautomers are constitutional isomers that are in rapid equilibrium. Interconversion of
the tautomers is called tautomerization.

The addition of hydrogen halides to an alkyne

The product of the electrophilic addition reaction of an alkyne with HCl is an alkene.
Therefore, a second addition reaction can occur if excess hydrogen halide is present.
The second addition—like other addition reactions to alkenes—is regioselective: the H +
adds to the sp carbon that is bonded to the most hydrogens. The product of the second
addition reaction is a geminal dihalide.

If the alkyne is a terminal alkyne, the first electrophilic addition reaction is also
regioselective: the H+ adds to the less substituted sp carbon.

Oxidation of alkynes

Under mild conditions, potassium permanganate oxidizes alkenes to glycols, compounds

with two –OH groups on adjacent carbon atoms. A similar reaction occurs with alkynes.
Hydroxylated product then losing two molecules of water to give the diketone.

4 PHRM103: Organic Pharmacy I

Abdullah-Al-Faysal, Lecturer, DOP, EWU
The addition of hydrogen to an alkyne
Alkynes can be reduced by catalytic hydrogenation just as alkenes. The initial product of
hydrogenation is an alkene, but it is difficult to stop the reaction at this stage because of
hydrogen’s strong tendency to add to alkenes in the presence of these efficient metal
catalysts. The final product of the hydrogenation reaction, therefore, is an alkane.

a) Catalytic Hydrogenation to cis Alkenes

The palladium on calcium carbonate poisoned with lead acetate (block the most active
catalyst sites and reduces the amount of hydrogen content in the Pd) and quinoline
(lowers the reduction rate but efficiently enhances the selectivity) is referred to as the
Lindlar catalyst. Hydrogenation of alkynes follows the same principle as that of alkenes
with platinum and both proceed with syn stereochemistry.

The selective reduction of triple bonds is the result of stronger bonding to the metal
surface but not higher reactivity of the bond. As long as the reaction mixture contains
alkyne molecules, available active metal centers will be occupied by alkyne. Only after
all alkyne is reduced to alkene, further hydrogenation of the alkene can take place.
Therefore, it is very important to stop the reaction after uptake of one equivalent of H2.

b) Metal–Ammonia Reduction to trans Alkenes

Internal alkynes can be converted to trans alkenes using sodium (or lithium) in liquid
ammonia. The reaction stops at the alkene stage because sodium reacts more rapidly
with triple bonds than with double bonds (formation of a vinylic radical and anion).

5 PHRM103: Organic Pharmacy I

Abdullah-Al-Faysal, Lecturer, DOP, EWU