Ryan & Keane — Action oj Oxides of Nitrogen on Phenytbenzylether. 293 



(Sp. g. 1-5) was added to a mixture of 1 g. of 4-nitrophenylbenzylether and 50 g. 

 of absolute alcohol — very little of the 4-nitroplieiiylbenzylether being soluble 

 in the cold alcohol. The mixture was shaken automatically for a fortnight 

 in a stoppered flask; it underwent no apparent change. The white matter 

 was isolated from the contents of ilask by nitration, and, after washing and 

 drying, melted at 104-105° C, whilst a mixture of it with 4-nitrophenylbenzyl- 

 ether melted at 105-106° C. Under these circumstances 4-nitrophenyibenzyi- 

 ether did not appear to interact with nitric acid. 



Proceeding as above, using, however, 6 molecular amounts of nitric acid 

 and increasing the period of automatic shaking to 6 weeks, 4-nitrophenyl- 

 benzylether was again recovered unchanged. 



Thus carbon tetrachloride again appears to exert a preferential nitrating 

 influence as compared with such solvents as alcohol, ether, and glacial acetic 

 acid. 



(cZ) In the Absence of Solvents. — 8 g. of 4-nitrophenylbenzylether was 

 slowly added to 48 g. of nitric acid (Sp. g. 1-5) in a small round flask. The 

 mixture was well shaken after each addition, and the temperature was not 

 allowed to rise above 0° C. The 4-nitrophenylben2ylether became dark-brown 

 on addition to the nitric acid, but, on shaking, a yellow solution was formed. 

 About 3 g. of the 4-nitrophenylbenzylether went into solution, but in another 

 experiment, in which the temperature was allowed to rise to 25° C, the whole 

 8 g. dissolved, giving a red-coloured solution; the products in each case, however, 

 were much the same. After allowing this yellow solution to stand overnight 

 the contents were poured into water, a white precipitate resulting. This white 

 substance was washed free from acid and dried. It was then boiled with a 

 little benzene, and filtered whilst hot. A white solid (A) was left on the 

 filter, while the filtrate on cooling yielded another white body (B). (A) 

 melted at 200-202° C, and after a few recrystallisations from glacial acetic 

 acid, gave white platy prisms, melting from 207-208° C. 



01289 g. of the substance gave on analysis 142 c.c. of nitrogen at 14° C. and 

 770 m.m. __ 



corresponding to N 131 

 CisHjO.Nj requires N 132. 



The substance is therefore a trinitro derivative of phenylbenzylether, and 

 since it was prepared by the nitration of 4'4'-diuitrophenylbenzylether and also 

 by the nitration of 2-nitrophenylbenzylether, it must be 2-4-4'-trinitrophenyl- 

 beruzylether. 



The other nitration product ' (B) was fractionated by means of alcohol. 

 One fraction soluble in hot alcohol had a semi-crystalline appearance and melted 

 at 157-160° C, but further recrystallisations from alcohol and glacial acetic 

 acid failed to improve its crystalline appearance or its melting-point. 



The other sub-fraction of B, insoluble in boiling alcohol, crystallised from 

 chloroform in long silky needles melting at 188° C. 



0-1487 g. of the substance gave 167 c.c. of nitrogen at 13° C. and 758 m.m. 

 corresponding to N 131 

 CiaHsOjNs requires N 132. 



The substance was therefore another trinitro derivative of phenylbenzyl- 

 ether, and since it was also prepared by the nitration of 2-nitrophenylben2yl- 

 ether (Par. 5) it must contain nitro groups in the positions 2 and 4. Since 

 it is not identical with 2-4-4'-trinitrophenylbenzylether (m.p. 207-208° C.) nor 

 with 2-4-6-trinitrophenyIbenzylether (m.p. 147° 0.) it must be 2-4-2'-trinitro- 

 phenylbenzylether. 



