292 Scientific Proceedings^ Royal Duhlin Society. 



The red oily portion, which was not volatile with steam, was dissolved in 

 chloroform and washed with dilute potash. The portion soluble in chloroform 

 proved to be 4-nitrophenylbenzylether (about 1-2 g.), whilst the potash fraction 

 yielded a small quantity of oily red plates. 



{d) In Acetic Acid Solution. — 1-8 e.c. (4 molecular amounts) of nitric acid 

 (Sp. g. 1-5) were added to a solution of 2 g. of phenylbenzylether in 50 g. 

 of glacial acetic acid. The mixture was allowed to remain in a stoppered 

 flask for three weeks. The contents of the flask were at first deep purple 

 in colour, but gradually changed to light-red. The colour changes indicated 

 the formation of an oxonium salt, but when the mixture was poured into 

 water phenylbenzylether was recovered unchanged. 



Experiments with smaller molecular amounts of nitric acid were also 

 performed and, as might be expected, .yielded negative results. 



On repeating the experiment, this time allowing the mixture to stand six 

 weeks and then evaporating the solvent in a vacuum over soda-lime, yellowish- 

 white prisms, melting at 94-96° C, were obtained. The green oily residue, 

 left after removal of the er^'stals, had a distinct smell of benzaldehyde. On 

 dissolving the crystalline matter in ether and washing with dilute potash, 

 the ethereal layer on evaporation gave white crystals melting at 107-109° C, 

 while the potash layer gave reddish oily crystals, melting at 101-109° C. Both 

 fractions seemed to be mixtures of decomposition products of phenylbenzyl- 

 ether and its nitro derivatives; the quantities produced, however, were too 

 small to establish the identity of its constituents. 



4. Action of Nitric Acid on 4-Nitrophenylhenzylether. 



(a) In Carhon Tetrachloride Solution. — 0-57 c.c. (6 molecular amounts) of 

 nitric acid (Sp. g. 1-5) were added to 05 g. of 4-nitrophenylbenzylether and 

 50 g. of carbon tetrachloride. The mixture was shaken automatically for 

 four weeks in a stoppered flask. Much white matter separated. The carbon 

 tetrachloride was driven off under reduced pressure, and a little alcohol was 

 added to the white residue in the distilling flask. The mixture was warmed 

 slightly and filtered while hot. A white compound remained on the filter, 

 whilst a yellowish-white substance separated from the filtrate on cooling — the 

 latter proved to be unchanged 4-nitrophenylbenzylether. 



The white compound left on the filter melted at 167-177° C, and after 

 repeated crystallisation from chloroform, colourless needles, melting at 186° C, 

 were obtained. A mixture of the latter with 4-4'-dinitrophenylbenzyl ether 

 melted at the same temperature, the two substances being therefore identical. 

 Under these conditions nitric acid reacts with 4-nitrophenylbenzylether forming 

 4-4'-dinitrophenylbenzylether. 



(i) In Acetic Acid Solution. — 1-14 e.c. (6 molecular amounts) of nitric 

 acid (Sp. g. 1-5) were added to a solution of 1 g. of 4-nitrophenylbenzylether 

 in 55 g. of glacial acetic acid. The mixture was allowed to remain in a 

 stoppered flask for four weeks, during which time it developed no coloration. 

 On pouring the mixture into water a white precipitate was formed, which 

 was filtered, washed free from acid, and recrystallised from methylated spirits. 

 Prismatic cr^^stals were obtained, which melted at 105-106° C, and a mixture of 

 them with 4-nitrophenylbenzylether melted at the same temperature. Apparently, 

 therefore, 4-nitrophenylbenzylether is unaffected by nitric acid in acetic acid 

 solution. 



(c) In Alcohol Solution. — 09 c.c. (4 molecular amounts) of nitric acid 



