[ 164 ] 



THE ACTION OF NITEOUS ACID AND XITEOI'S FUMES ON 

 UEETHAXES AXD OTHEE BODIES. 



By HUGH ETAX, D.Sc, and MAEGAEET EGAlv^, D. es. Sc, 

 University College, Dublin. 



[Eead Febriaut 25. PuUished May 23, 1924.] 



In previous communications from this laboratory the action of nitrogen 

 peroxide and nitric acid on some secondary amines, urethanes, ethers and ureas 

 has been described (Proe. E.I.A., xxxiv, B Nos. 8, 10, and 12 ; Proc. R.D.S. 

 xvii, X.S., Xos. 14-19, 36-4:0). The reactions were studied more especially 

 at the ordinary temperature and at low concentrations of the bodies. The 

 behaviour of these substances towards nitrous acid was not, however, examined. 



The present commimication deals with the action of nitrous acid and 

 nitrous fumes on the more important of these substances, and in this respect 

 completes the series of investigations already published. 



In our experiments, butyl nitrite was the source of the nitrous acid, in 

 nearly ever}' case ; the acid was set free by hydrochloric or glacial acetic 

 acid. The action of nitrous fumes on five or ten per cent, solutions of some 

 of the above-mentioned substances in the common organic solvents at 0' G, 

 and at the ordinary temperature, was also investigated. 



By the action of nitrous fumes on an ethereal solution of plienylurethane, 

 Behrend [Liebig's Annalen der Chemie. eexxxiii fl 886), p. 9] obtained 4-nitro- 

 phenylurethane. Willstatter [Ber. der Dtsch. Chem. Ges., xlii (1909), p. 4b76] 

 prepared by the same reaction, using glacial acetic acid as solvent, a very 

 unstable phenylnitroso-urethane in the form of light, yellow needles, melting 

 at 6 P-62' C. We found that nitrous fumes readily converted phenylurethaue 

 (five or ten per cent, solutions) in ether, carbon tetrachloride, glacial acetic 

 acid, and in petroleum ether solution into 4-nitro-phenylurethane. Attempts 

 to isolate Willstatter's compound by allowing the reaction to proceed for 

 shorter periods, and otherwise varying the conditions of the experiments, 

 were unsuccessful. Phenylurethaue, dissolved in alcohol, or in glacial acetic 

 acid, did not react with nitrous acid, even when the mixture had been allowed 

 to remain at the room temperature for two months in each case. In carbon 

 tetrachloride solution, nitration proceeded slowly, however, the urethane being 



