Ryan & Connolly — Action of Oxides, &c., on Ethyl- Phenylur ethane. 127 



The substance was tlierefore a niononitro-ethyl-phenylurethane, and was. as is 

 shown later, the 4-nitro derivative of the iirethane. 



A-Nitro-ethyl-phenylurdliane crystallises from alcohol in large, colourless, 

 rhonibohedral, platy crystals, which are insoluble in water, dilute acids or alkalies, 

 sparingly soluble in peti-oleum ether or benzene, soluble in ligroin, chloroform, or 

 alcohol, and very soluble in hot alcohol and ether. 



A mixture of this substance with 2-nitro-phenylurethane, which melts at 58° C, 

 melted about 35°-38° C. 



The mononitro-ethyl-phenylurethane was decomposed by heating it for four or 

 five hours with alcoholic potash (4 parts) under a reflux condenser. When the 

 reaction product was poured into water, a bright yellow crystalline substance 

 separated. The solid was filtered, washed, and recrystallised from hot alcohol, from 

 which it separated in the form of sulphur-yellow prismatic crystals, which melted 

 at 96° C, and gave on analysis the following results : — 



0'1'242 g. of the substance gave 1 7'7 c.c. of moist nitrogen at 1 7° C. and 776 mm., 



corresponding to N 17T. 

 CsHioNjO, requires N 16-9. 



The substance was therefore identical with nitro-ethyl- aniline, for which 

 A. Weller gave the melting point 95°-96° G. [Ber. d. Dtsch. Chem. Ges., xvi (1883), 

 p. 32; cf. E.N Siting and Collin, «6«/.,xvii (1884), p. 267]. 



By addition of an aqueous solution of sodium nitrite to a cold solution of the 

 amine in dilute hydrochloric acid the nitrosamine separated in the form of light 

 yellow crystals, which, when filtered, washed, and recrystallised from alcohol, were 

 obtained as cream-coloured, almost white, needles. Its melting point, 119°-120° C, 

 was identical with that found by E. Meldola and S. Streattield [Jour. Chem. Soc, 

 45, p. 61] for p.-nitro-ethyl-phenyl-nitrosamine. 



The substance, which melted at 88'-89°,C., consisted of colourless rhombic prisms, 

 which were less soluble in alcohol than the mononitro compound described above. 

 It was insoluble in water, dilute alkalis, or acids, sparingly soluble in carbon 

 tetrachloride or ligroin, and very readily soluble in chloroform, ether, or acetone. 



On analysis it gave the following results : — 



0T007 g. of the substance gave 12-8 c.c. of moist nitrogen at 15° C. and 722 mm., 



corresponding to N 14'9. 

 C^^Hj^gNgOg requires N 14-8. 



The substance was therefore a dinitro-ethyl-phenylurethane, but attempts to 

 convert it into 2.4-dinitro-ethyl-aniline by the interaction of it with alcoholic 

 potash have not hitherto been successful. 



B,— ACTION OF NITRIC ACID ON ETHYL-PHENYLURETHANE. 



I. — WitJiout a Solvent; 



Fuming nitric acid was added slowly with continuous shaking to 10 c.c. of 

 ethyl-phenylurethane, the temperature being kept as low as possible during the 

 reaction. The mixture, which was allowed to remain at the laboratory temperature 

 for a few days, acquired a greenish colour and an oily consistency. The product, 

 which separated when the contents of the flask were poured into water, was filtered, 

 washed, and dissolved in boiling alcohol. The relatively small amount of crystals 

 which separated when the solution was cooled consisted of dinitro-ethyl-phenyl- 

 urethane, melting at 88°-89°. The main product of the reaction, which was separated 

 by slow evaporation of the alcohol, consisted of 4-nitro- ethyl-phenylurethane, 

 melting at 55°-56° C. 



