Ryan and O'Rioijdan — Action of Bromine on Diphenylamine. 223 



IV. Action of Bromine on 2.^-Dinitro-Dij)hc»ylamine. 



Five grams of bromine in 20 c.c. of chloroform were added to a solution 

 of 1 gram of 2'4-dinitro-diphenylamine in 20 c.c. of chloroform. Hydro- 

 bromic acid was freely evolved during the addition of the bromine. The 

 mixture was placed in bright sunlight, and allowed to stand for six hours. 

 Fumes of hydrobromic acid were evolved, and an orange solid separated. 

 The mixture was allowed to remain overnight, the solid was then filtered, 

 washed with alcohol and ether, and dried. It melted at 1955° C. A further 

 quantity of this substance was obtained from the parent liquid. The total 

 weight of substance obtained was 1*6 grams, which corresponds to the 

 formation of a dibromo-dinitro-diphenylamine. The body is orange in colour, 

 and crystallises in rhombic prisms which are slightly soluble in alcohol and 

 soluble in benzene and ether. A determination of bromine in the compound 

 gave the following result : — 



0T916 gram of the substance on treatment with sodium and alcohol gave 

 an amount of sodium bromide which, on precipitation with silver nitrate, 

 yielded 0"1722 gram of silver bromide, 



corresponding to Br 38 -4 

 C 12 H 7 Br (N0 2 ) 2 NH requires Br 236 

 PislleBr, (N0 8 ) 2 NH requires Br 38-3 

 C 13 H,Br, (N0 3 ) 2 NH requires Br 484 



The substance is, therefore, a dibromo-2.4.dinitro-diphenylaimiie. 

 Leymann (Ber. d. Dtsch. Chem. Ges. XV, 1882, p. 1236) obtained a 

 substance melting at 196° C, by the bromination of dinitro-diphenylamine. 

 It is not explicitly stated that the 2 - 4-dinitro compound was that used, but 

 from the context it appears to have been so. In this case it is probably 

 identical with our substance. 



V. Action of Bromine on 2A0-lJinitro-lHpheni/lamine. 



10 c.c. of a solution of bromine in chloroform (containing 40 grams of 

 bromine in 100 c.c.) was added to 1 gram of 2.10-diuitro-diphenylamine in 

 20 c.c. of chloroform. The substance, which is only slightly soluble in 

 chloroform, dissolved on adding the bromine solution. The mixture was 

 allowed to remain in a bright place for two days, during which time hydro- 

 bromic acid was evolved, and a yellow solid separated. The solid was 

 recrystallised a couple of times from chloroform, li consisted of yellow, 



