Ryan and Dkumm — Derivatives of Phenyl-2-Naphthylamine, 171 



Tlio more sparingly soluble solid crystallized from glacial acetic acid in 

 orange prisms melting at 179-180° 0., and proved to be identical with the 

 trinitro compound of the same melting-point formed by the action of nitrogen 

 peroxide on an alcoholic solution of the stabiliser. 



1). Action of Nitric Acid on Plienyl-B-NapMhylnitrosamme. 



1. In Alcoholic Solution. 



To a solution of 4 grams of the nitrosamine in 100 e.c. of absolute alcohol 

 10-12 grams of nitric acid (sp. gr. 1-43) were added. In the course of a few 

 hours a reddish, amorphous solid separated. The parent liquid was filtered, 

 and the solid was purified by crystallisation from glacial acetic acid. It was 

 finally obtained in the form of brownish prisms, melting about 170-180° C, 

 with much decomposition, and it gave on analysis the following results : — 



0-1670 grams of the substance gave 19'3 c.c. of moist nitrogen 

 at 17° C. and 750 m.m.p. 



corresponding to N 13T6. 

 C 16 H n N b 4 requires N 13-59. 



The compound analysed was therefore a dinitro derivative of phenyl-2- 

 naphthylamine. 



2. In Acetic Acid Solution. 



Three solutions, each containing 2 grams of phenyl-2-naphfhylnitrosaniine 

 in 20 c.c. of glacial acetic acid, were prepared. 



One molecular quantity of nitric acid was added to the first solution, two 

 to the second, and six to the third. The solutions, contained in stoppered 

 flasks, were allowed to remain at the room temperature for two days, by the 

 end of which time a yellow powder had separated in each case. The parent 

 liquids were filtered, and the solids were purified by recrystallisation from 

 glacial acetic acid. In each case yellow prisms, melting at 242-243° C, were 

 obtained. This compound was identical with the yellow trinitro compound 

 of the same melting-point got by the action of nitrogen peroxide on an 

 alcoholic solution of the stabiliser. 



When 4-6 molecular quantities of nitric acid were employed in the nitra- 

 tion the yield of the trinitro compound was almost quantitative. 



E. Orientation. 

 1. Phcni//-2-nap/it hi/In itrosainine. 



Twelve grams of pure phenyl-2-naphthylamino were heated with a mixture 

 of 50 c.c. of absolute alcohol and 20 c.c. of iso-amyl nitrite, under a rellux 



