8 THE ROYAL SOCIETY OF CANADA 



(b) The compound obtained from the alcoholic extraction, when 

 purified in this solvent twice, melts at 179-180°; it is a reddish-brown 

 powder. The yield is not good. Its properties agree with those of the 

 Bis — 2,4 — tetranitrodiphenylamine, described by Hager.^ When dis 

 solved in Sodium Hydroxide and warmed in the presence of Ammon- 

 ium Hydroxide a scarlet-red colour is developed. 



This colour reaction and similarity of melting point indicate 

 undoubtedly that this compound is Bis — 2,4 — tetranitrodipheny- 

 lamine, (NH(C6H3(N02)2)2. 



HI. On nitrating diphenylamine three compounds were obtained. 



(a) A portion of the nitrated products is soluble in hot nitro- 

 benzene and is not deposited on cooling. Ethyl Alcohol, however, 

 precipitates it as a light reddish-brown powder; the yield is poor. 

 Analysis shows it to be a tetranitrodiphenylamine. Its melting 

 point is above 250°, for at this temperature no signs of melting were 

 visible. It is not described in the literature and is not identical with 

 any known tetranitrodiphenylamines. All these were prepared and 

 the mixed melting points taken, thus proving the lack of identity. 



(b) Ethyl acetate dissolves part of the nitration products and 

 from this solution a precipitate is obtained on adding Petroleum Ether 

 (b.p. under 90°). When this precipitate has been boiled in Alcohol 

 twice, it is a light-brown powder melting at 191-2°. This compound 

 dissolves in Sodium Hydroxide, giving a red colour on warming, and is 

 identical with the substance believed to be a symmetrical tetranitrodi- 

 phenylamine (cf. lia). 



(c) A portion recrystallized from Xylene twice, had a melting 

 point of 190-1°. It is a reddish-brown powder which dissolves in 

 Sodium Hydroxide and develops a red colouration on warming. 

 Mixed melting points show this substance is identical with those 

 described under Ha and 1 1 lb. 



(d) The remaining product of the nitration has a yellow-brown 

 colour and is insoluble in Benzene, but is very soluble in Acetone. 

 The yield of this compound is very poor, and as no solvent was found 

 from which to recrystallize it, nothing further was done. 



Experimental. 



The materials used in the experiments described below were 

 as follows: Sulphuric Acid sp.g. 1-84. Acetic Acid glacial (99-5 

 percent). Nitric Acid sp.g. 1-46 ( = 80 per cent HNO3). Oxalic 

 Acid was anhydrous. Alcohol 95 per cent by volume. The Trichlor- 

 acetic Acid was specially prepared from Trichloracetaldehyde and 



^Ber. n, 2629. 



