Tautomerism and Enols - July Dec Revision

Tautomerism

Tautomerism may be defined as the phenomenon in which a single compound exists in two readily interconvertible structures that differ markedly in the relative position of at least one atomic nucleus, generally hydrogen. The two different structures are known as tautomers of each other.

In the presence of acid or base, ketone or aldehyde with α-hydrogen is converted into hydroxyl ene (called enol), hence this type of isomerism in which keto and enol forms exist in dynamic equilibrium is also called ket-enol isomerism.


Enols

Preparation of aldehydes and ketones from alkynes

Hydration of alkynes in the presence of dilute sulphuric acid and HgSO4 as catalyst gives aldehydes and ketones.

Water adds to alkynes to form unstable enol intermediates which rearrange to form aldehydes or ketones.

Hydration of acetylene gives acetaldehyde.

Hydration of alkynes other than acetylene gives ketones.




Addition of water to alkynes (hydration of alkynes)

In the presence of acid (H2SO4) and HgSO-4, a molecule of water adds to the triple bond at 348K. The catalyst in this reaction is HgSO4 (Mercuric sulphate). The final products of this reaction are carbonyl compounds aldehydes and ketones.

Initially enol is formed which is raidly converted into an equilibrium mixture containing keto form in excess. Enol is so called because it contains 'ene' (double bond) and an alcoholic group (ol).



IIT JEE Revision - Acid Catalysed Hydration of Alkynes
In the presence of acid (H2SO4) and HgSO-4, a molecule of water adds to the triple bond at 348K.

The catalyst in this reaction is HgSO4 (Mercuric sulphate).

The final products of this reaction are carbonyl compounds aldehydes and ketones.

Initially enol is formed which is raidly converted into an equilibrium mixture containing keto form in excess.

Enol is so called because it contains 'ene' (double bond) and an alcoholic group (ol).

Example:
Addition of water to Ethyne or acytelene: Acetylene is passed into water (at about 330K) containing 60% H2SO4 and about 1% mercuric sulphate (HgSO4) as a catalyst, acetaldehyde is formed.

In the first step 'ethenol' is formed and in the second step the rearrangement of it takes place and its isomer 'acetaldehyde' is formed.

The conversion of enol form into keto form is termed tautomerism