Rvan and Duumm — Derivatives of P]wny1r2-Naphthylamine, 167 



By the action of nitric acid on a solution of phenyl-2-naphthylamine 

 Streiff (Liebig's Annalen der C'lieniie, CCIX, 1881, p. 157) obtained a 

 mononitro-phenyl-2-naphthylanhne melting at 85° C. and a dinitro-phenyl- 

 2-naphthyl-amine melting at 192-195° C. In the course of the present work 

 the action of nitric acid on phenyl-2-naphthylamine in acetic acid solution 

 was examined; a red compound, probably the dinitro compound of Streiff, 

 was isolated, but the yellow mononitro body of Streift" was apparently not 

 formed under the conditions obtaining in our experiment, but instead of it 

 an orange trinitro derivative melting at 179' C. was found in relatively 

 large amount. As already stated, this trinitro compound was of special 

 interest, since it was one of the two substances formed by the action of 

 nitrogen peroxide on an alcoholic solution of the stabiliser. 



Heim (Ber. d. Dtsch. Chem. Ges., XXI, 1888, p. 589), from 1-bromo- 

 2.4-dinitro-benzene and 2-naphthylamine, and Ernst (Ber. d. Dtsch. Chem. 

 Ges. XXIII, 1,^90, p. ••5429) (from 2.4-dinitro-l-chloro-benzene), obtained 2'.4.'- 

 dinitrophenyl-2-naphthylamine, melting at 169.5° C. (Heim), 179° C. (Ernst). 

 We obtained it incidentally by the latter method ; it consisted of orange-red 

 prisms melting at 171" C. 



By heating /3-naphthylamine with picryl chloride or with ruethy- 

 picrylnitrosamine, E. Bamberger and J. Mueller (Ber. d. Dtsch. Chem. Ges. 

 XXXIII, 1900, p. 107) obtained 2'.4'.6'-trinitrophenyl-2-naphthylamine in 

 the form of brick-red diamonds, or as orange-yellow prisms, melting at 

 233° C. This picryl compound was prepared during the course of the 

 present work. It crystallised as brick-red prisms from glacial acetic acid, 

 and in the form of the yellow variety from aqueous acetic acid. The 

 melting-point of either variety was 2^0° C. (uncorr.). 



Although picryl chloride reacted readily with 2-naphthylamine, we did 

 not succeed in getting it to combine with l-mononitro-2-naphlhylamine, even 

 when the substances were heated together in boiling nitrobenzene. 



In many cases organic halogen compounds, such as bromobenzene, do not 

 react easily with primary amines, such as naphthylanune. In such cases, how- 

 ever, the desired reaction between the amine and the halogen compound can 

 often be effected by a metliod due to I. Goldberg (Ber. d. Dtsch. Chem. 

 Ges., XL, 1907, p. 4541), in which the reaction between the amine and the 

 halogen compound proceed.- in nitrobenzene solution in the presence of copper 

 dust, potassium iodide, and potassium carbonate. The following compounds. 

 which could not be got by direct heating of a mixture of their components. 

 were prepared successfully by this method : — 



l-nitro-2-naphthylaniline, 4'-nitro-2-naphthylaniline, and 2'.4'.l-trinitro- 

 2-naphthylaniliue. 



[S2] 



