Ryan & Swkknicy — Action of Oxides, Sfc, on Phenyl-Methylurea. 159 



II. — In Solution. 



Ca) Ether. — Dry nitrogen peroxide fumes were passed at intervals through a 

 solution of 2 g. of phenyl-methylurea in 75 e.e. of anhydrous ether, which was 

 allowed to remain for about two months at the temperature of the room. About 

 1 g. of crystals separated, which melted at 111° 0., and proved to be 2'4'6-trinitro- 

 methylaniline. 



By evaporating the ether filtrate and recrystallising the residue 2"4-dinitro- 

 methylaniline was obtained in the form of yellow crystals, melting at 175°. 



(b) Alcohol.— li\ another experiment 2 g. of phenyl-methylurea were dissolved 

 in 10 e.e. of alcohol, and nitrogen peroxide vapours were passed through the 

 solution, which was kept cold by immersing the tube containing it in water. The 

 solution effervesced briskly and turned brown in colour. It was concentrated 

 slightly. The yellow solid which separated, after recrystallisation from alcohol, 

 melted at 99^-100° C, and, as its melting point was not affected by mixing it with 

 4-nitro-phenyl-nitrosamine, it was identical with the latter substance. 



'B.— ACTION OF NITROUS ANHYDRIDE ON PHENYL-METHYLUREA. 



Fumes of nitrous anhydride, prepared by the action of nitric acid on arsenious 

 oxide, were passed for about an hour through a solution of 2 g! of phenyl-methyl- 

 urea in 10 c.c. of absolute alcohol, kept at the temperature of the room by 

 immersing the flask containing the solution in water. The mixture effervesced, 

 the colour changing through yellow to red. On allowing the solution to evapo- 

 rate, 4 nitro-phenyl-methyl-nitrosamine separated in the form of yellowish 

 crystals, melting at 99"-100°C. 



C— ACTION OF NITRIC AND NITROUS ACIDS ON PHENYL- 

 METHYLUREA. 



I. — In the Absence of Solvents. 



About 8 c.c. of fuming nitric acid (sp. g. 1"51) were added slowly to 2 g. of 

 phenyl-methylurea. The dark red mixture was allowed to remain overnight 

 and was then poured into water. T'he yellowish solid which separated was 

 filtered, washed with water and alcohol, and then recrystallised from acetone, fi'om 

 which it separated in the form of nearly colourless crystals, melting at 128°- 

 129° C. The yield was very good. As its melting point was not affected by 

 mixing the substance with pure tetryl, prepared from dimethylaniline by the 

 method described by M. C. F. van Duin [Kec. de trav. Chim. Pays Bas, xxxvii 

 (1917), p. Ill], the two bodies are therefore identical. 



II. — In the Presence of Solvents. 



(a) Water: (a) At ordinary concentrations. — 1. Phenyl-methylurea (lo'6 g.) was 

 dissolved in a mixture of 12 c.c. of concentrated hydrochloric acid and 24 c.c. of 

 water, and to the cold solution 7'5 g. of sodium nitrite, dissolved in a small amount 

 of water, were added slowly and with frequent stirring. The mixture rapidly 

 became turbid, with separation of a yellowish oil, which was extracted with ether; 

 the residue left on evaporation of the ether was reduced by means of tin and 

 hydrochloric acid to methylaniline, which boiled at 192°-194°0. 'The aqueous 

 solution, from which the nitrosamine had been separated by ether, contained a 

 small amount of the hydrochloride of methylaniline. 



