Ryan &Cur,MNANE — Action of Oxides of Nitrogen onDiphenylene Oxide. 326 



(c) In Carbon Tetrachloride Solution. — A solution containing 1 g. of 

 diphenylene oxide and 1 molecular amount of fuming nitric acid in 100 g. of 

 carbon tetrachloride was prepared. This solution was also allowed to remain 

 at the room temperature for 5 months, when, on evaporation of the solvent, 

 a red oil remained. After extracting this with ligroin, the parent substance 

 was obtained from the ligroin extract, and a small quantity of the mononitro 

 derivative previously mentioned was isolated from the undissolved portion 



A similar experiment was also performed with the employment, however, 

 of 4 molecular amounts of fuming nitric acid. After 5 months the yellow 

 solution was evaporated, leaving a yellowish-white solid. This was washed 

 with ligroin, a small quantity of the original oxide being isolated from the 

 extract. The undissolved residue consisted of mononitrodiphenylene oxide, 

 melting at 182° C. 



(d) An almost quantitative yield of mononitrodiphenylene oxide was obtained 

 by the following method : — 5 g. , of the oxide were dissolved in 20 c.c. of 

 glacial acetic acid, and 5 c.c. of fuming nitric acid were added slowly with 

 shaking. 'N\nien the initial violent reaction ha.d subsided, the mixture was 

 heated for 5 minutes on the water-bath, and on cooling a yellow solid cake 

 was formed. It was washed with water and recrj^stallised from glacial acetic 

 acid, and was then found to be pure mononitrodiphenylene oxide. 



(e) An equally good yield of the mononitro compound was obtained by 

 substituting carbon tetrachloiide for acetic acid as the solvent. In this case 

 the solid cake was deposited during the addition of the acid. On reerj^stallising 

 this from glacial acetic acid it gave the pure mononitro compound. 



4. Preparation of the Nitro Derivative.'?. 



(a) Dinitrodiphenylene Oxide. — This compound was readily obtained in the 

 following manner : — To a concentrated solution of 5 g. of the mononitro 

 derivative in glacial acetic acid 25 c.c. of fuming nitric acid was added slowly. 

 A somewhat ^agorous reaction occurred, and, when it had subsided, the mixture 

 was heated for about 20 minutes on the water-bath. The white crystalline 

 deposit formed on cooling was washed with water, and recrystallised from 

 acetic acid. The product consisted of fine white needles of dinitrodiphenylene 

 oxide, melting at 245° C. The yield was 3 g. 



Dinitrodiphenylene oxide is almost insoluble in ligroin, slightly soluble in 

 alcohol, moderately soluble in glacial acetic acid or xylene, and readily 

 soluble in acetone. 



(b) Trinitrodiphenylene Oxide.. — Fuming nitric acid (10 c.c.) was added 

 slowly with shaking to 2 g. of mononitrodiphenylene oxide. A vigorous 

 reaction ensued with evolution of heat. The reddish-yellow solution was 

 allowed to remain at the room temperature for a few minutes, and was then 

 poured into water. The solid product was washed several times with boiling 

 alcohol. The residue was extracted with boiling benzene, from which a 

 small quantity of colourless blunt prisms, melting at 223° C, was isolated. 

 The alcoholic extract contained dinitrodiphenylene oxide. The portion left 

 undissolved by the benzene crystallised from xylene, yielding a small amount 

 of colourless thin plates, melting at 283° C. The compound melting at 223° C. 

 was a trinitrodiphenylene oxide, and it gave on analysis the following results : — 



01027 g. substance gave 12-3 c.c. moist nitrogen at 18° C. and 766 m.m. 



corresponding to N14-1 

 CioHjOjNj requires N 139. 



SCIENT. PEOC. R.D.S., VOL. XVII, NO. 40. 3 P 



