Ryan and Gi.ovkr — Nitro- Derivatives of Diphenylamine. 10.5 



which at first was amber-coloured, gradually became paler, and a small 

 quantity of a brownish solid very slowly separated. After four weeks water 

 was added, and the solid was filtered, and washed with small quantities of 

 water, alcohol, ether, and chloroform. After several purifications from 

 alcohol and acetone it was finally obtained as yellow crystals, which melted 

 at 190° C, and gave on analysis the following results : — 



- 0701 g. substance gave 12 cc. moist nitrogen at 18° C. 

 and 7G4 m.m.p. 



corresponding to N19'9 

 C, 2 H 7 N 3 O s requires N 201. 



Owing to the small amount of substance obtained in the reaction, we were 

 unable to carry olit the analysis with a larger quantity than that mentioned. 



The tetmmitro-diphenylaminc consists of yellow prisms, which are only 

 slightly soluble in alcohol, soluble in chloroform, and readily soluble in 

 acetone. 



With alcoholic alkali it formed a blood-red coloured solution. 



G. Action of Nitrous Acid on Pier yl- Aniline. 



To 7 g. of picryl-aniline, and rather less acetic acid than that required to 

 completely dissolve it, 12 cc. of isoamyl nitrite was added, and the mixture 

 was allowed to remain at the room temperature for four weeks. 



A small quantity of a yellow crystalline solid separated. After re-crys- 

 tallisation of the solid it melted at 236° C, and probably consisted of 

 2.4.6.S.10-hexanitro-dipheiiylamine. 



The substance contained in the acetic acid filtrate was precipitated by 

 addition of water, and, after repeated crystallisation from acetone and 

 chloroform, it consisted of yellow prisms melting at 193-194° C. An analysis 

 which was made showed it to be a pentanitro-diphenylamine, very probably 

 2.4.6. 8.10-petanitro-diphenylamine, for which P. Juillard (loc. cit.) gave 193° C. 

 as the melting-point : — 



0T484 g. substance gave 28-0 cc. of moist nitrogen at 20° < '. 

 and 757 m.m.p. 



corresponding to N21 - o 

 C 12 H c N„0,„ requires N 21-3. 



In conclusion we wish to express our thanks to Nobel's Explosives Company 

 for a grant in aid of this investigation, and to Mr. liintoul, the Manager of 

 the Eesearch Section of that Company, owing to whose suggestion the work 

 was undertaken. 



B.I.A. PROC. VOL. XXXIV, SF.CT. B. [J'] 



