IvVAN & Kkane — Action of Oxides of Nitrogen on Ethyl- ^-Naphthylethcr. 29^ 



were obtained. This substance, which was also a dinitroethyl-/3-naphthylether, 

 gave on analysis the following results : — 



0-1512 g. substance gave 14 c.c. moist nitrogen at 13° C. and 760 m.m. 



corresponding to N 110 

 C12H10O5N, requires N 107. 



Since alcoholic ammonia converted it into l-8-dinitro-/3-naphthylamine, 

 melting at 223-224° C, it must have been l-8-dinitroethyl-/3-naphthylether. 

 It is sparingly soluble in cold alcohol, benzene, or acetic acid, and moderately 

 soluble in hot benzene or hot acetic acid. 



Nitrogen peroxide vapour, therefore, reacts easily and smoothly with 

 ethyl- /3-aaphthylether, converting it into its 1-6- and 1-8-dinitro derivatives. 



(b) In Glacial Acetic Acid Solution. — Vapour of nitrogen peroxide, generated 

 by heating lead nitrate, was passed for 20 minutes into a solution of 2 g. of 

 ethyl- /3-naphthylether in 50 g. of 95 per cent, acetic acid. Some crystals, 

 which separated on allowing the solution to remain overnight, were filtered 

 off. After recrystallisation from acetic acid they consisted of light yellow 

 platy prisms, which melted at 103-104° C, and gave on analysis the following 

 results : — 



0-2087 g. substance gave 11-9 c.c. moist nitrogen at 14° C. and 769 m.m. 



corresponding to N 678 

 C12H11O3N requires N 6-45. 



The substance proved to be l-nitroethyl-|:i-naphthyl ether. When heated 

 in a sealed tube to 180° C. for eight hours with 20 parts of alcoholic ammonia, 

 it was converted into l-nitro-/3-naphtliylamine, melting at 126-127° C. 1-nitro 

 /3-naphthylether is sparingly soluble in cold alcohol or acetic acid, and is 

 moderately soluble in carbon tetracliloride or ether. 



The parent liquid, from which the mononitro compound had separated, 

 was allowed to remain in a stoppered flask for several days. The solid matter 

 deposited was filtered off and recrystallised from glacial acetic acid. It melted 

 at 216-217° C, and proved to be 1-8-dinitroethyl -/3-naphthylether. 



The parent liquid was poured into water, and the precipitate was recrystal- 

 lised several times from alcohol. It melted at 144r-145° C, and proved to be 

 1 ■6-dinitroethyl -|3-naphthylether. 



In another experiment, in which anhydrous acetic acid was used as the 

 solvent, a dark-brown solution resulted. From this no crystalline nitro derivative 

 of ethyl-/3- naphthylether could be isolated. 



(c) In Carbon Tetrachloride Solution. — A solution of 2 g. of ethyl -/3- 

 naphthylether in 50 g. of carbon tetrachloride was saturated with nitrogen per- 

 oxide, and allowed to remain in a stoppered bottle for three weeks. The mixture 

 then contained a dark oily upper layer and a clear light-red lower layer. The 

 solvent was distilled under reduced pressure, and a red, oily solid remained. 

 Portion of this solid dissolved in warm alcohol, giving a clear red solution, 

 and the rest remained undissolved in the form of a brownish-white solid. The 

 latter, on recrystallisation from glacial acetic acid, was obtained as colourless 

 prisms, melting at 216-217° C, and these proved to be 1-8-dinitroethyl -/3- 

 naphthylether. 



A red -nscous mass with traces of a white solid was left by evaporation of 

 the reddish alcoholic solution. The solid was extracted with petroleum ether, 



