June 16, 1870.

General Sir EDWARD SABINE, K.C.B., President, in the Chair.

Dr. E. H. Greenhow, Dr. J. Jago, Prof. N. S. Maskelyne, the Rev. Dr. Parkinson, Capt. R. M. Parsons, Dr. W. H. Ransom, Mr. R. H. Scott, Dr. A. Voelcker, and Dr. S. Wilks were admitted into the Society.

The following communications were read :—

I. "On Compounds Isomeric with the Cyanuric Ethers." By A. W. HOFMANN and OTTO OLSHAUSEN. Received April 29, 1870. Some time ago M. Cloëz* described a remarkable body, which has the composition but none of the properties of ethylic cyanurate. This substance, which he called cyanetholine, is distinguished from cyanuric ether by its behaviour with alkalies, which, according to the observations of Cloëz, evolve from it ammonia and not ethylamine. Cyanetholine, according to Cloëz, combines with acids, forming crystallizable salts, none of which, however, up to the present time, has been more carefully investigated. It is rather strange how little the attention of chemists has been directed to this interesting compound. M. Cloëz contented himself with the discovery of cyanetholine and establishing its composition, but has not again reverted to the subject. Of the researches of other chemists who have touched upon cyanetholine, the only ones known to us are the few but rather important experiments of M. Galt. According to his observations, cyanetholine is changed by treatment with potash solution into potassium cyanide and alcohol, and by the action of hydrochloric acid into cyanuric acid and ethylic chloride; and Gal and Cloëz, in consequence of these reactions, are of opinion that cyanetholine is the true ether of cyanuric acid constructed upon the water type

whilst the earlier known ethylic cyanate of M. Würtz corresponds to the

It need scarcely be mentioned how completely this view has been confirmed by the subsequent discovery of the isonitriles and of the series of mustard oils isomeric with the sulphocyanic ethers.

The formation of cyanetholine, which, as is known, is obtained by the action of chloride of cyanogen on sodium ethylate, proves a close connexion

* Compt. Rend. xliv. p. 482, and Ann. Chem. Pharm. cii. p. 354.
+ Compt. Rend. lxi. p. 527, and Ann. Chem. Pharm. cxxxvii. p. 127.

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between this body and the ethylcyanamide, discovered by Messrs. Cahours and Cloëz*, which is formed by treating ethylamine with chloride of cyanogen. The same reagent acting on ethylated water and ethylated ammonia causes in the one case the formation of ethylic cyanate, and in the other that of ethylcyanamide. The close analogy between cyanetholine and ethylcyanamide, which is, perhaps, best represented by the formulæ CN(C, H2)O and CN(C2 H.)HN,

cannot possibly be doubted, and accordingly the easy polymerization of ethylcyanamide, which is readily converted into triethylmelamine, naturally raised the question as to whether cyanetholine could not be polymerized in a similar manner; in other words, whether there might not exist a series of combinations isomeric with the known cyanuric ethers.

The experiments undertaken for the solution of this question have been performed in the methyl-, ethyl-, amyl-, and phenyl-series.

We begin the communication of our observations by a description of the experiments made in the methyl-series; for although in the first instance we had worked in the ethyl-series, it was the investigation of the methylic compounds which yielded at once results that could not be mistaken.

Experiments in the Methyl-series.

When a stream of gaseous chloride of cyanogen is passed through a dilute solution of sodium methylate in methylic alcohol (we have generally dissolved 20 grms. of sodium in about 400 grms. of anhydrous methylic alcohol), a considerable quantity of common salt is separated. If the current of gas be continued until the solution smells of chloride of cyanogen, and the excess of methyl alcohol then distilled off, a brown oil remains behind, similar to that which Cloëz obtained by the corresponding experiment in the ethyl-series, and which he described as cyanetholine. This oil sometimes remains fluid for a long time, but generally solidifies on standing. Frequently, however, little or no oil is formed, and when the methyl alcohol is distilled off, there remains a residue which solidifies to a brown crystalline mass. The purification of this substance offers no difficulties; one or two crystallizations from boiling water, in which it is easily soluble, whilst it dissolves but slightly in cold water, and a final treatment with animal charcoal remove the colour. But these crystals, though perfectly colourless, prove, under the microscope, to be a mixture of two compounds, of which the one, crystallizing in fine needles, is the more easily soluble, whilst the other, consisting of rhombic tables, dissolves with greater difficulty. If an intermediate mixed product be sacrificed, they may, by repeated crystallizations from boiling water, be both obtained in a pure state. They are, however, better separated by the extraordinary difference of their solubility in ether, which dissolves the needles and leaves the rhombic tables behind.

* Ann. Chem. Pharm. xc. p. 91.