[ 297 "] 



No. 37. 



THE ACTION OF THE OXIDES AND THE OXYACIDS OF NITR0C4EN 

 ON ETHYL-/3-NAPHTHYLETHER. 



By HUGH RYAN, D.Sc, 



AND 



JOHN KBANE, Ph.D., 

 University CoUege, Dublin. 



(Bead December 18, 1923. Printed February 27, 1924.) 



Introduction. 



In the preceding comiminieation we showed that phenylbenzylether reacts 

 with nitrogen peroxide vapour with formation of a mononitro derivative and 

 oxidation products of the ether, while with a solution of the peroxide it 

 gives a dinitro derivative. Similar results were obtained by the action of 

 nitric acid on solutions of the ether in carbon tetraclrloride. It was only 

 by the action of concentrated nitric acid on the ether, or its nitro derivative, 

 that a trinitro- or a pentanitrophenylbenzylether could be obtained. 



In the present communication we describe the results of similar experiments 

 which were carried out with ethyl-/3-naphthylether with a view to determining 

 whether ethers of the naphthols nitrated at the ordinary temperature more 

 easily than ethers of the phenols. 



Several nitro derivatives of ethyl -|3-naphthylether have been alreadv 

 described. Thus Wittkampf [Ber. Dtsch. Chem. Ges., xvii (1884), p. 394] 

 obtained l-nitroethyl-ci-naphthylether by the action of nitric acid on the ether, 

 and established its constitution by converting it into l-nitro-/3-naphthylamine. 

 In a similar experiment F. Gaess [Journ. f. pr. Chem. (2), xliii, p. 23] obtained 

 8-nitroethjd-/3-naphthylether and crystals, melting at 114° C, which probably 

 consisted of 6-nitroethyl-|3-naphthylether. Gaess also obtained 1-6- and 1-8-di- 

 nitroethyl -/3-naphthylether. 



Staedel [Ber. Dtsch. Chem. Ges., xiv (1881), p. 900] prepared a trinitroethyl- 

 /3-naphthylether, melting at 186° C., but did not determine the orientation of 

 the nitro groups in his compound. 



In our experiments we have found that ethyl -/3-naphthylether reacted with 

 nitrogen peroxide vapour more readily than phenylbenzylether, forming 1-6- 

 and l-8-dinitroethyl-/j-naphthylether. In a similar experiment in carbon 

 tetrachloride solution, the 1-nitro and 1-8-dinitro derivatives were the main 

 products. 



With one molecular amount of nitric acid in carbon tetrachloride solution 

 and at the ordinary temperature the ether was converted into its 1-nitro 

 derivative, while with four molecular amounts of the acid 1-6- and IS-dinitro- 

 ethyl -/3-naphthylether were formed in nearly equal amounts. The same two 

 nitro compounds were also formed by the action of nitric acid on a dilute 

 carbon tetrachloride solution of the mononitro ether. 



3CIENT. PROC. R.D.S., VOL. XVII, NO. 37. 3 L 



