Ryan & Connolly — Action of Oxides, S)-c., on Ethyl-Phenylurethane. 129 



The oils which separated from the sohitioiis containing one and two molecular 

 proportions of nitric acid respectively did not crystallise, and apparently consisted 

 largely, if not entirely, of unchanged ethyl-phenylurethane. 



When the yellow-coloured solution, obtained by allowing a solution of 5 grams 

 of ethyl-phenylurethane with three molecular amounts of nitric acid in 100 grams 

 of acetic acid to remain for five months at the temperature of the laboratory, was 

 poured into water, an oil separated. The oil was extracted with etlier, and the 

 oil, wliich again separated on evaporation of the ether, was dissolved in alcohol from 

 which 4-nitro-ethyl-phenylurethane, melthig at 55°-56° C, separated. 



Similarly from the solutions to which four and five molecular proportions of 

 nitric acid had been added to 5 grams of ethyl-phenyhirethane an oil separated 

 when the solutions, after standing, were poured into water. The oil was extracted 

 with ether, the solvent was allowed to evaporate, and the residue was dissolved in 

 alcohol. Crystals of dinitro-ethyl-phenylurethane, melting at 88°-89° C, were in 

 each case obtained. 



III. — III Carbon Tetrachloride Solution. 



Fourteen cubic centimetres (approx. four molecular proportions) of fuming nitric 

 acid 'were added slowly to a solution of fifteen cubic centimetres of ethyl-phenyl- 

 urethane in carbon tetrachloride. The mixture consisted of a small upper aqueous 

 and a large lower carbon tetrachloride layer. After remaining a couple of days at 

 the temperature of the room, a small amount of large, colourless, platy crystals 

 separated, the quantity of which did not, however, appreciably increase during the 

 remainder of the time reaction was allowed to continue. At the end of three weeks 

 the crystals were separated from the liquid. They melted at about 101° C, but 

 their amount was not sufficient for a further examination. The carbon tetrachloride 

 layer was washed with dilute sodium carbonate, filtered through a dry filter paper, 

 and distilled. The oily residue which was left in the distilling flask was dissolved 

 in alcohol. During the spontaneous evaporation of the solution colourless crystals 

 of 4-nitro-ethyl-phenylurethane were obtained. 



C — ACTION OF NITRIC ACID ON 4.-NITR0-ETEYL-PHENYLURETBANE. 



(a) Two grams of 4-nitro-ethyl-phenylurethane were dissolved in concentrated 

 sulphuric acid, and to the mixture, which was kept cold, 10 c.e. of fuming nitric 

 acid were added with constant stirring. The mixture was allowed to remain 

 overnight at the temperature of the room. It was then poured into water, and 

 the oil which separated was extracted with ether. The residue left after evapo- 

 ration of the ether was dissolved in boiling alcohol, from which colourless acicular 

 crystals separated. The crystals thus obtained melted at 109°-111'^ C, and this 

 melting point was not altered by the addition to the substance of 2.4-dinitro- 

 phenylurethane, which was prepared by the method described below. The 

 substance was, therefore, 2.4-dinitro-plienylurethane. 



(b) More or less prolonged action (three days) of the nitric acid on the 

 2-4-dinitro-phenyhirethane obtanied in the last experiment converted it into 

 colourless felted needles, which, when recrystallised from alcohol, melted at 

 145°-146° 0., and proved to be identical with the 2.4.6-trinitro-phenylurethane 

 obtained as described below. 



B.— ACTION OF NITRIC ACID ON NITRO-PRENTLURETHANE. 

 2-Nitro-phenylurethane was prepared according to the method of Eudolph 

 [Ber. d. Dtsch. Chein. Ges., xii (1879), p. 1295] by boiling a benzene solution 

 of nitraniline and chloroformic ester under a reflux condenser for four hours. 



SOIIiNT. PROC. R.D.S., VOL. XVII, NO. 16. 2 B 



