Ryan & Keane — Actmi of Oxides of Nitrogen on Phenylbenzylether. 295 



being added to a cold mixture of 4 c.c. of fuming nitric acid (Sp. g. 1-52) and 

 4 c.c. of fuming sulphuric acid in a small round flask. 



No heat was evolved ; the light-yellow solution was allowed to stand overnight, 

 during which time colourless crj'stals separated. The contents of the small 

 flask were then poured into a mixture of ice and water, a voluminous yellowish- 

 white precipitate resulting. The precipitate was filtered, washed free from 

 acid, and dried. On crystallising the dried product from chloroform, colourless 

 monoclinic plates were olstained, which melted with decomposition at 146° C. 



They were fairly soluble in boiling chloroform, and somcAvhat more so in 

 glacial acetic acid and hot benzene. 



0-1239 g. of the substance gave on analysis 181 c.c. of nitrogen at 17° C. 

 and 775 m.m. 



corresponding to N 171 

 CijHyOiiN^ requires N 171. 



The compound is therefore a pentanitro derivative of phenylbenzylether. 



On subjecting 2-4-2'-trinitrophenylbenzylether to the same treatment as 

 2-44'-trinitrophenylbenzylether, the same pentanitro . compound, melting at 

 146° C, is formed ; therefore this body must contain nitro groups in the positions 

 2-4-2'-4' respectively. 



7. Action of Nitric Acid on the Pentanitro Compound. 



In the Absence of Solvents. — 1 g. of the pentanitro compound was heated 

 on a water-bath for 12 hours with 4 c.c. of fuming sulphuric acid and 4 c.c. 

 of fuming acid (Sp. g. 1-52) in a small round flask. 



After 6 hours fuming acid (4 c.c) was again added, and the heating was 

 continued. The contents of the flask were finally poured into water, yielding 

 a clear yellow solution, from which, by extraction with ether, a yellow oily 

 compound was isolated. This separated from chloroform in almost colourless 

 crystals, which melted with decomposition at 139-140° C. A mixture of this 

 substance with the pentanitro compound melted at 122-125° C It dissolved 

 in dilute aqueous potash, giving a deep-red coloured solution. It was probably 

 a decomposition product of nitrated phenylbenzylether, but it was not obtained 

 in sufficient quantity for analysis. 



Summary. 



1. Nitrogen peroxide converted phenylbenzylether into 4-nitrophenylbenzyl- 

 ether, and this in turn into its 4-4'-dinitro derivative together with some benzoic 

 acid and a little oily matter. 



2. A similar result was obtained by the action of nitric acid on a carbon 

 tetrachloride solution of the ether, but in glacial acetic acid or ether solution 

 on short standing no appreciable nitration occurred. 



3. Nitric acid converted 4-nitro- and 2-nitrophenylbenzj'lether into 2-4-4'- 

 and 2-4-2'-trinitrophenylbenzylether, and these were both converted by a 

 mixture of concentrated sulphuric and nitiic acids into the same pentaiiitro- 

 phenylbenzylether. 



4. Attempts to prepare a hexanitro derivative of tlie ether led to the 

 formation of decomposition products. 



The above investigation was undertaken at the request of the Reseai'ch 

 Section of Nobel's Explosives Company, to whom we are indebted for the 

 materials employed in the research. 



SOIENT. PECO. R.D.S., VOL. XVII, NO. 36 3k 



