In 1863 Geuther, and, independently, Frankland and Duppa, made known the existence of _aceto-acetic ester_. By Geuther this compound was termed _ethyl-di-acetic acid_—
by Frankland and Duppa it was considered to be _acetone-carboxylic acid_—
The essential difference in these formulæ, as the two names respectively indicate, is that the first implies that the ester has an acidic or hydroxylic character, proved by its forming characteristic salts; the other that it contains the group CO, proved by its yielding acetone and the usual reactions of the ketones. The attempt to settle the constitution of this substance gave rise to much controversy, and, as it was found to be very reactive, led to a great amount of conflicting experimental work. The ultimate result was to show that both formulæ are correct: at the time of reaction the ester is sometimes hydroxylic, at other times ketonic, or, adopting the terminology of Brühl, it sometimes shows the _enol_ form, at other times the _keto_ form. Other substances were subsequently found to behave in the same way. In 1885 the question was discussed by Laar, who suggested the term _tautomerism_ (ταὐτό, the same; μέρος, a part) to denote the fact that one and the same substance could have structural formulæ varying with conditions of reaction and depending upon the migrations of certain of its atoms within the molecule. During the last twenty years a large number of examples of the kind have been discovered. They are found to occur, not only among aliphatic substances, but in cyclic and heterocyclic compounds. We now know that such intermolecular changes may occur by the migration of any of the elements or groups present in the molecule. Thus, to confine ourselves to simple and well-known examples, the transformation of sodium phenyl carbonate into sodium salicylate, discovered by Kolbe, is due to the wandering of an atom of hydrogen from the benzene residue to oxygen, thus:
The conversion of the nitriles into the cyanides by heating is due to the transference of the alkyl radical from the nitrogen atom to the carbon—
Alkyl groups may also be transferred from oxygen to nitrogen; a radical may detach itself from a carbon atom and wander to a nitrogen atom; radicals in cyclic compounds may be transferred from the side chains to the nucleus, etc.