158 PROCEEDINGS OF THE AMERICAN ACADEMY. 



The Action of Phosgene on Ethylisocyanide. 



On adding slowly 5 c.cm. phosgene (cooled to — 15°) to 10 c.cm. 

 ethylisocyanide (cooled to —19°), reaction takes place always with 

 explosive violence. Even when the isocyanide is diluted with an 

 equal volume of absolute ether and the solution is cooled to — 19°, 

 a very energetic union takes place on adding the phosgene, which 

 makes it difficult to regulate the reaction. A yellow sharp-smelling 

 liquid is formed, which does not boil without decomposition. On 

 pouring it into water a brown solution containing much hydrochlo- 

 ric acid is formed, from which ether extracts nothing, and which 

 gives no precipitate with phenylhydrazine. The products, which are 

 in all probability all derivatives of mesoxalic acid,* were not further 

 investigated. 



The Action of Chlorocarbonic Ether on Ethylisocyanide. 



An addition of fhlorocarbonic ether, or of alkyliodides or chlorides, 

 to aromatic derivatives of isocyauogen could not be accomplished, be- 

 cause a reaction takes place only at high temperatures, and this must 

 result in the formation of much resinous polymeric products, as well 

 as in the decomposition of the addition products first formed. t 



An addition of chl(M'Ocarbonic ether to ethylisocyanide has, however, 

 been accomplished, and with the following experiences. Chlorocarbonic 

 ether reacts, already, at ordinary temperatures, on ethylisocyanide and 

 the mixture becomes colored yellow. On heating at 100°, complete 

 reaction takes place in a very short time, but the addition product first 



formed, 



C2H5N : CCl 

 I 

 OiCOCsHj, 



is completely split into carbondioxide, ethylchloride, and ethyliso- 

 cyanide, C2H5N : C, which, generated in the nascent state, mostly 

 polymerizes. Klinger has already observed an entirely analogous 

 decomposition in the case of oxanilethane-imidechloride, 



CeHjN : CCl 

 I 

 O : COC0H5, 



on heating it to 120°. J 



* Ann. Chem. (Liebig), CCLXX. 286-29.5 and 315 



t Ibid., CCLXX. 280, et seq. Cf. also Wallach, Ibid., CLXXXIV. 8C, 108, 

 CCXIV 283 



J Ibid., CLXXXIV. 283 



