Hydration of Alkynes

Alkynes, unlike alkenes, are not hydrated readily in aqueous acid unless a mercuric salt is present as a catalyst. Also, the products that are isolated are either aldehydes or ketones instead of alcohols. Even though the addition of one molecule of water to ethyne probably gives ethenol (vinyl alcohol) initially, this compound is unstable relative to its structural isomer (ethanal) and rapidly rearranges:

Similarly, addition of water to propyne leads to 2-propanone by way of its unstable isomer, 2-propenol:

In general, the position of equilibrium for interconversion of a carbonyl compound with the corresponding alkenol (or enol), having the hydroxyl group attached to the double bond, lies far on the side of the carbonyl compound:

Because mercuric salts catalyze the hydration of alkynes, they probably are acting as electrophiles. Mercuric salts are known to add to both alkenes and alkynes, and if the reaction mixture is acidic, the carbon-mercury bond is cleaved to form a carbon-hydrogen bond. The overall sequence in propyne hydration may be written as follows: