106 PROCEEDINGS OF THE AMERICAN ACADEMY 



ash, and chloroform. Hofmann isolated only two products, namely, 

 phenyl and isoamylisocyanide, the first named substance, as will 

 be seen later, was not pure nor entirely free from aniline. It was 

 therefore necessary, in the first place, to find an exact method 

 for separating isonitriles from primary amines, which was readily 

 accomplished. It depends simply on the fact that the isonitriles 

 are not basic substances, so that, for example, an ethereal solution 

 of aniline and phenylisocyanide can be separated completely by 

 shaking once with a solution of dilute hydrochloric acid. It fol- 

 lows, therefore, that the hitherto accepted strong basic property of 

 the isonitriles is a mistake, and the energy with which these sub- 

 stances unite with haloid acids depends, not on their basic nature, 

 but on the presence of bivalent carbon. 



Gautier,* to whom unquestionably belongs the priority in the 

 discovery of the isonitriles, introduced the name carbylamines for 

 them because of their supposed strong basic properties. He re- 

 garded them as ammonia in which one hydrogen atom was replaced 



by alkyl, while the other two were replaced by C", ™, - N IIT , and 



supposed them to react with the haloid acids like ammonia, going 



"P "j 

 over thus from trivalent into pentavalent nitrogen, „,, [- N v , HX. 



This was the chief reason that led him to disregard the other 



possible formula, ^ 1V -] N v , for the isonitriles. 



In a similar manner Gautier t regarded the alkyl-cyanides (am- 

 monia, in which the three hydrogen atoms are replaced by trivalent 

 KrC-) as weak bases, because they unite with gaseous hydrochloric 



* Annales de Chim. et de Phys., [4.], XVII. 205. I cite here exclusively 

 from Gautier's paper in Annales de Chimie et de Physique, [4.], XVII. 103-260 

 (1869), which includes the following previous papers: 



Ann. Chem. (Liebig), 138.38 142.294 145.118 146.119,352 149.29,155 151.239 152.221 

 Bull, de la Soc Chim., 4.88 11.214 11.222 



Comptes Rendus, 63.920 65.410 It'lel" 72 67 713*804 



In this paper Gautier describes the compounds more fully, and corrects a 

 number of his previous statements. The statements of Gautier on prussic acid, 

 the nitriles and carbylamines in Beilstein, and other treatises on organic chem- 

 istry, are therefore incomplete, since remarkably enough this last paper has not 

 been taken into consideration. I regret that the These of Gautier (Paris, 1869), 

 which may possibly contain still more details, has not been accessible to me. 



t Ibid., pp. Ill, 118. 



