Ryan & Dhumm — Action of Oxides of Nitrogen on Diphenylether. 3 



5. Action of Nitric Acid on d-Nitrodiphenyteiher. 



19 



Aboiit 1 g. of 4-nitrodiphenylether was added to 5 g. of nitric acid 

 (Sp. g. 1-4), and tlie mixture was heated for an hour on tlie water-bath. The 

 colour of the solution became dark red, and oxides of nitrogen were evolved. 

 The solid which separated when the mixture was poured into water was filtered, 

 dried, and washed with ether. The undissolved portion, which was purified 

 by recrystallisation from benzene, melted at 143°C., and consisted of 4-10-dinitro- 

 diphenylether. The dissolved portion was recovered by evaporating the ether. 

 It melted about 95° C, and probably consisted of 2-10-dinitrodiphenylether 

 in a somewhat impure condition. 



In a similar experiment with fuming nitric acid, the mononitroether 

 dissolved with evolution of much heat. The solution was allowed to remain 

 overnight at the temperature of the room, and was then poured into water. 

 The yellow solid which separated was dried and recrystallised from benzene. 

 It melted at 195° C, and proved to be 2-4-810-tetra.nitrodiphenylether. 



6. Action of Nitric Acid on 2-4-Dinitrodiphenylether. 



By nitrating 2-4-dinitrodiphenylether by a method analogous to that of 

 the last experiment, a deep-red solution was obtained, and from this, by addition 

 of water, a light-yellow solid was precipitated. The solid was dissolved in 

 boiling alcohol, and the solution was allowed to crystallise. The first fraction 

 which separated consisted of rectangular prisms, which melted about 110° C, 

 and were found to be slightly impure 2-4-10-trinitrodiphenylether. The second 

 fraction was separated by means of alcohol into two substances. One of 

 these was 2-4S-10-tetranitrodiphenylether, melting at 195° C. The other melted 

 at 153° C, but, as its amount was not sufficient for an analysis, we were 

 unable to determine whether it was 2-4-6-trinitro- or 2-4-610-tetranitrodiphenyl- 

 ethei', each of which, according to "Willgerodt [Ber. Dtsch. Chem. Ges., xii (1879), 

 p. 1278; xvi (1884), p. 1766], melts at 153° C. 



7. Action of Nitric Acid on 2-4-6-Trinitrodiphenylether and 2i-10-Trinitro- 



diphenylether. 



(a) About 1 g. of 2-4-6-trinitrodiphenylether was added to 5 g. of fuming 

 nitric acid. On remaining at the room temperature a white solid separated. 

 The mixture was poured into water, the solid was filtered, and recrystallised 

 from acetic acid. It consisted of colourless needles, which melted at 210° C, 

 and were sparingly soluble in alcohol, but easily in acetone. It gave on 

 analysis the following results : — 



0-1200 g. substance gave 18-65 c.c. moist nitrogen at 15° C. and 754 m.m. 



corresponding to N 1805 

 CioH^OiiNs requires N 17-8. 



The substance was therefore a pentanitrodiphenylether. 



(&) The nitration of 2-4-6-trinitro-, or 2-4-6-S-tetranitrodiphenylether, with 

 a mixture of 5 parts of fuming nitric acid and 5 parts of concentrated sulphuric 

 acid, gave in each case the same pentanitrodiphenylether, melting at 210° C. 

 The latter compound was probably 2-4-6-8-10-pentanitrodiphenylether. 



(c) Fuming nitric acid converted 2-4-10-trinitrodiphenylether into 2-4-8-10- 

 tetranitrodiphenylether, melting at 195° C. 



