166 Proceedings of the Royal Irish Academy. 



solvents. The main product of the reactions was 4-nitro-phenyl- 

 benzylurethaiie melting at 70°-71°C., and a trinitro derivative. We 

 recovered the urethane unchanged from solutions in glacial acetic acid, alcohol, 

 and carbon tetrachloride, after these had been mixed with butyl nitrite and 

 an acid for prolonged periods. Nitrous fumes converted 10 per cent, solutions 

 of phenyl-beuzylurethane in glacial acetic acid into the 4-nitro compound 

 already obtained by Eyan and O'Donovan. A dinitro derivative was not 

 obtained under the same conditions as those in which diphenylurethane 

 yielded 4-10-dinitrO-diphenylurethane. 



When the reactions of ethyl-phenylurethdne were examined in this 

 laboratory [H. Ryan and A. Connolly, Proc. K.D.S., xvii. No. 16], nitric acid 

 was found to have but a slow action on its solutions. With one and two 

 equivalents of nitric acid, the urethane was recovered unchanged from a five 

 per cent, acetic acid solution after five months. Three equivalents of the acid 

 gave 4-nitro-ethyl-phenylurethane, and four and five equivalents dinitro- 

 ethyl-phenylurethane. We found that six molecular proportions of nitrous 

 acid were without action on ethyl-phenylurethane in glacial acetic acid, 

 alcohol, or carbon tetrachloride solution, even after long periods. 



Nitro derivatives of o-tolylurethane were obtained, as already mentioned 

 [^toc. cit.'\, by the direct action of nitric acid or of nitrogen peroxide on 

 ethyl-o-tolylurethane, the ethyl radical being eliminated. Nitric acid did not 

 yield crystalline derivatives in presence of cold solvents. In our experiments, 

 the urethane was recovered unchanged after periods of two to three months, 

 when its solutions in alcohol, acetic acid, and carbon tetrachloride had been 

 treated with nitrous acid. 



H. Eyan and J. Keane examined [i'roc. E.D.S., xvii, No. 36] the 

 reactions of phemjl-henzyl ether with nitric acid, nitrogen peroxide, and 

 nitrous fumes. They found that nitrogen peroxide converted the ether 

 in 4 per cent, carbon tetrachloride solution into 4-nitro-phenyl-benzyl 

 ether, melting at 104°-106° C, which they also obtained synthetically 

 from potassium, 4-nitro-phenolate, and benzyl chloride. After four months 

 standing, the product obtained by the same reaction was 4-10-dinitro-phenyl- 

 benzyl ether, melting at 184°-186° C. When nitrous fumes were passed into 

 a four per cent, solution of the ether in acetic acid for half an hour, and the 

 product was allowed to remain in a stoppered vessel for six weeks, they obtained 

 the 4-nitro compound already mentioned, and benzoic acid. Two, three, and 

 four equivalents of nitric acid gave decomposition products of the ether when 

 allowed to remain mixed with its acetic acid solution for long periods, while 

 the same quantities of acid gave 4-nitro-phenyl-benzyl ether in carbon 

 tetrachloride solutions. Phenyl-benzyl ether was recovered unchanged from 



