tautomerism

tautomerism, the existence of two or more chemical compounds that are capable of facile interconversion, in many cases merely exchanging a hydrogen atom between two other atoms, to either of which it forms a covalent bond. Unlike other classes of isomers, tautomeric compounds exist in mobile equilibrium with each other, so that attempts to prepare the separate substances usually result in the formation of a mixture that shows all the chemical and physical properties to be expected on the basis of the structures of the components.

The most common type of tautomerism is that involving carbonyl, or keto, compounds and unsaturated hydroxyl compounds, or enols; the structural change is the shift of a hydrogen atom between atoms of carbon and oxygen, with the rearrangement of bonds as indicated:

In many aliphatic aldehydes and ketones, such as acetaldehyde, the keto form is the predominant one; in phenols, the enol form, which is stabilized by the aromatic character of the benzene ring, is the major component.

An intermediate situation is represented by ethyl acetoacetate, which at room temperature contains about 92.4 percent keto and 7.6 percent enol; at −78 °C (−108 °F), the interconversion of the two forms is slow enough for the individual substances to be isolated. The enol form is stabilized by hydrogen bonding between the hydrogen of the ―OH (hydroxyl) group and the oxygen of the C=O (carbonyl) group.

In addition to keto-enol tautomerism, several other types are well known, including those of aliphatic nitro compounds and those involving ring and chain structures, especially of molecules of sugars.