Ryan & 0' Donovan — Action of Oxides, ^"c, on Phenyl-hensylurethane. 135 



(3) In a similar experiment at a somewhat higher temperature the nitrating 

 mixture became a yellow viscid mass, which was then divided into two portions. 



One part was freed from volatile matter by distillation in a current of steam, 

 and from the more soluble matter by extraction with hot alcohol. By re- 

 crystallising the residue a few times from glacial acetic acid the tetranitro-phenyl- 

 benzylurethane just described was obtained. The substance which was obtained 

 by concentrating the parent liquids separated from hot acetone in the form of 

 yellowish-white silky needles, which melted with decomposition at 274° C, and 

 pi'oved to be a pentanitro-phenyl-benzylamine, as the following analysis indicates: — 



0-0978 g. of the substance gave 16'8 c.c. of moist nitrogen at 14° C. and 768 mm., 



corresponding to N 20-43. 

 CaUsO.oNc requires N 20-6. 



Pencanitro-phenyl-benzylamine is soluble in hot alcohol, glacial acetic acid, and 

 acetone. It is almost insoluble in ether or chloroform. 



The more soluble matter contained in the alcoholic extracts mentioned above 

 was dissolved in aqueous potash, and from the filtered solution, by acidification and 

 recrystallisation from alcohol, almost colourless crystals, melting at 238° 0. and 

 containing S'? p.c. of nitrogen, were obtained. This substance was probably 4-nitro- 

 benzoic acid, which melts at 238° C. and contains 8-53 p.c. of nitrogen. 



The second part of the yellow viscid mass was heated with fuming nitric acid 

 for some days on the water-bath, and was then poured into water. From the hard, 

 yellow, solid product crystals, melting at 238° 0. (probably 4-nitro-benzoic acid), 

 were extracted by means of alkali, and the residue was separated by alcohol into 

 2-4-diuitro-phenylurethane and a mixture which, when heated with potash, gave a 

 small amount of a reddish crystalline solid melting at 228°-330" C, together with 

 yellow felted needles, which melted with decomposition at 264° (J. The latter 

 substance gave the following results on analysis : — 



0-1104 g. of the substance gave 16-6 c.c. of moist nitrogen at 17° 0. and 767 mm., 



corresponding to N 17-6. 

 C,6H„0,„Na requires N 17-5. 

 CsHioOoNi requires N 17-6. 



It is doubtful whether this substance is pentanitro-phenyl-benzylurethane or 

 a triiiitro-phenyl-benzylamiue. 



II. — In the Presence of Solvents. 



(a) In glaeial acetic acif?.— Quantities of fuming nitric acid (sp. g. 1-52), 

 corresponding to one, two, three, four, and six molecular amounts of the solid, were 

 added respectively to five solutions, containing in each case 5 grams of phenyl- 

 benzylurethane, dissolved in 50 grams of glacial acetic acid. The solutions, which 

 varied in colour from orange-red to yellow, were allowed to remain at the tempera- 

 ture of the room for four months. 



From the solutions to which four and six molecular amounts of the acid had 

 been added we obtained in each case about half a gram of 4-nitro-phenyl-benzyl- 

 urethane in a pure state. The oil obtained from the solution to which two 

 molecular amounts of the acid had been added did not crystallise, but from it by 

 hydrolysis with potash we obtained 4-nitro-phenyl-benzylamine. The oil from 

 the solution to which one molecular amount of the acid had been added also refused 

 to crystallise. 



