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No. 40. 



THE ACTION OF THE OXIDES AND THE OXYACIDS OP NITROGEN 

 ON DIPHENYLENE OXIDE. 



By HUGH RYAN, D.Sc, 



NICHOLAS CULLINANE, Ph.D., 

 University College, Dublin. 



(Read Decembef. 18, 1923. Printed Makch 3, 1924.) 



Introduction. 

 A COMPARISON of nitration under similar conditions has shown [H. Ryan and 

 P. Ryan, Proe. R.I.A., xxxiv, B, pp. 194, 212] that diphenylnitrosamine is 

 more smoothly nitrated than diphenjdamine. Interesting results have also been 

 obtained by comparing the ease of nitration of other substituted diphenylamines, 

 e.g., urethanes, with diphenylamine and diphenylnitrosamine. Thus H. Ryan 

 and A. Donnellan [Proc. R.D.S., xvii, N.S., p. 113] found that diphenylurethane 

 was less easily nitrated than diplienylamine, while in the paper preceding th"^; 

 present one H. Ryan and P, J. Drumm describe an investigation on diphenyl- 

 ether, which differs from diphenylamine only by the substitution of an oxygen 

 atom for an imino radicle. 



In the present investigation a similar ether, diphenylene oxide, was 

 examined, and its behaviour towards nitrating agents was compared with that 

 of diphenylether. In the case of diphenylene oxide, unlike that of diphenyl- 

 ether, there was a complete absence of decomposition products, derivatives of 

 the former being evidently less easily decomposed than those of the latter 

 substance. Also diphenylene oxide was less easily nitrated than diphenylether, 

 for concentrated nitric acid in the cold was almost without action upon it. 

 Furthermore, the highest nitro derivative of diphenylene oxide we were able 

 to obtain was the tetranitro compound, while in the case of diphenylether a 

 pentanitro compound was prepared. We also found that, as in the case of 

 diphenylether, nitrations in carbon tetrachloride solutions gave higher nitro 

 derivatives than those under similar conditions where the solvent was glacial 

 acetic acid. Hence, it is evident that the solvent exercises an influence upon 

 the reaction. 



Diphenylene oxide has been obtained, mostly in small yield, by various 

 methods, e.g., by the distillation of calcium phenolate [Niederhauseru, Ber, 

 Dtsch. Chem. Ges., xv (1882), p. 1120] ; by heating 2-2'-dihydroxydiphenyl with 

 zinc chloride [Kraemer and Weissgerber, Ber. Dtsch. Chem. Ges., xxiv (1891), 

 p. 1663] ; by passing diphenjdether through a red-hot tube [Tauber and 

 Halberstadt, Ber. Dtsch. Chem. Ges., xxix (1896), p. 1876] ; and by the oxidation 

 of diphenylene [Dobbie, Pox, and Gauge, Joum. Chem. Soc, ciii (1913), p. 41]. 

 A good yield of diphenylene oxide was obtained by Sabatier and Mailhe 



SCIENT. PROC. R.D.S., VOL. XVII. NO. 40. 3o 



