Hydration of Alkynes

Organic Chemistry I
Course Content
Reactions of Alkynes
1. Addition of hydrogen halide (HX):

a. Example
b. Mechanism
This reaction is very similar to alkene hydrohalogenation. With

one equivalent of hydrogen halide, this reaction can be stopped at
the production of the vinylic halide. If an excess of hydrogen
halide is used, then the geminal dihalide is produced.
2. Addition of halide (X2):
a. Example
b. Mechanism
test
3. Hydration:
A,,,,Example
a. Mechanism
Mercury (II) ion is the elctrophile in this reaction. It interacts with

the less highly substituted carbon atom of the triple bond. The
resulting vinylic carbocation is attacked by water, which is
subsequently deprotonated. The mercury ion is replaced by acidic
hydrogen to form an enol intermediate. The enol tautomerizes to
the more stable ketone.
Note: Hydration of terminal alkynes always leads to the
production of methyl ketones. Symmetrical alkynes lead to only
one ketone product, whereas unsymmetrical internal alkynes lead
to mixtures of ketones.
4. Hydroboration:
a. Example
b. Mechanism
Hydroboration of an alkyne involves the reaction of an alkyne with

borane. The boron atom has an empty p-orbital which acts as an
electrophile toward the triple bond. Hydride transfer from borane
to the other carbon atom of the triple bond occurs simultaneously
with bond formation to boron. A four-atom transition state closely
describes the bond-breaking and bond-forming interactions.
Because borane has three hydrogen atoms attached, each
borane molecule reacts with three alkynes to form a trialkenyl
borane. Hydrogen peroxide oxidizes the boron atom, and the
carbon-boron bonds are replaced with carbon-oxygen bonds. You
are not responsible for this portion of the mechanism. The
resulting enol tautomerizes to the more stable ketone.
Note: Hydration of terminal alkynes always leads to the

production of methyl ketones. Symmetrical alkynes lead to only
one ketone product, whereas unsymmetrical internal alkynes lead
to mixtures of ketones.
5. Oxidative cleavage with potassium permanganate:

a. Example
b. Mechanism
No mechanism is required for this reaction.

Potassium permanganate oxidative cleavage of an alkyne is a
very complicated chemical reaction. However, you must be aware
of the result: each carbon of the carbon-carbon triple bond is
oxidized up to the carboxylic acid. Additionally, all acetylenic
hydrogen atoms are replaced with -OH groups.
Note: In the case of a terminal alkyne, the terminal carbon atom is

removed as carbon dioxide. This is a chain-shortening reaction
(see top reaction above). This reaction works best for symmetrical
alkynes, because, in this case, only one product is produced (see
middle example above). For unsymmetrical alkynes mixtures are
formed (see bottom example above).
6. Hydrogenation to alkane:
a. Example
b. Mechanism
Hydrogen gas adsorbs onto the surface of the catalyst. The

hydrogen adds to the same face of the alkyne reducing it to an
alkene. The alkene can continue to react with more hydrogen to
reduce the alkene to the alkane.
7. Hydrogenation to (Z)-alkene:
a. Example
b. Mechanism
Hydrogen gas adsorbs onto the surface of the catalyst. The

hydrogen adds to the same face of the alkyne reducing it to an
alkene. The catalyst has been deactivated by treatment with lead
acetate and quinone, and is thus unreactive toward alkenes. The
reaction stops at the production of the (Z)-alkene
8. Hydrogenation to (E)-alkene:
a. Example
b. Mechanism
This reaction is often referred to as a "solvated electron" reaction.

Lithium metal donates an electron to the alkyne forming a radical
anion that is protonated by the solvent. Lithium metal again
donates an electron to the vinylic radical to form a new anion
which is again protonated by solvent.
Note: The trans-stereochemistry is determined when the more
stable trans- vinylic anion is formed. Equilibrium is not established
before protonation occurs, therefore, the trans- product is isolated.
Alkenes are much less reactive under these conditions, so the
alkene product is isolable.

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Organic Chemistry I

1. Addition of hydrogen halide (HX):

This reaction is very similar to alkene hydrohalogenation. With

Mercury (II) ion is the elctrophile in this reaction. It interacts with

Hydroboration of an alkyne involves the reaction of an alkyne with

Note: Hydration of terminal alkynes always leads to the

5. Oxidative cleavage with potassium permanganate:

No mechanism is required for this reaction.

Note: In the case of a terminal alkyne, the terminal carbon atom is

Hydrogen gas adsorbs onto the surface of the catalyst. The

Hydrogen gas adsorbs onto the surface of the catalyst. The

This reaction is often referred to as a "solvated electron" reaction.

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