RvAN&KiiANE — Action of Oxides of Nitrogen onEthjl-^-NapUhyUther. 301 



acid (Sp. g. 1-52) was added to a solution of 2 g. of ethyl -^-naphthylether 

 in 50 g. of carbon tetrachloride, contained in a stoppered flask. The colour of 

 the solution was at first yellow, but it quickly deepened to orange, and finally 

 to red. Dark oily particles gradually appeared together with traces of 

 crystalline matter. The contents wex-e examined after remaining 6 days at 

 the room temperature. The ciystalline matter, which was isolated by filtration, 

 melted at 205° C, and seemed to be impure l-8-dinitroethy]-/j-naphthylether. 

 (Its formation was due no doubt to the unequal distribution of the nitric 

 acid.) The carbon tetrachloride was distilled under reduced pressure, a red 

 oily solid remaining in the distilling flask. The solid was dissolved in warm 

 alcohol, and the solution on cooling yielded brownish-white prisms, melting 

 at 103^° C. A mixture of these with l-nitroethyl-/j-naphthykther melted at 

 the same temperature, the two bodies being, therefore, identical. 



1 molecular amount of nitiic acid then reacts with ethyl -/3-naphthylether 

 in carbon tetrachloride solution, forming principally the 1-nitro derivative, 

 with 5-10 per cent, of oily or tarry substances, and about 1 per cent, of a 

 crystalline product, which is probably the 1-8-dinitro derivative of the ether. 



In a similar experiment 19 c.c. (4 molecular amounts) of nitric acid 

 (Sp. g. 1-52) was added to 2 g. of ethyl -/3-naphthyl ether in 50 g. of carbon 

 tetrachloride. 



The solution was at first orange-yellow, and finally brownish-red. After 

 5 minutes a copious brown coloured precipitate was thi'own down. The 

 carbon tetrachloride was distilled off after 3 days, leaving a nearly white 

 solid residue. On fractionating from warm alcohol, two kinds of crystals were 

 obtained— slender acicular prisms, melting at 143° C, and long slender 

 rectangular prisms, melting at 217° C. The first mentioned prisms proved to 

 be 1-6-dinitro-, and the last l-8-dinitroethyl-/3-naphthylether. 



By the action of 4 molecular amounts of nitric acid, then, on a 4 per cent, 

 carbon tetrachloride solution of ethyl -/S-naphthylether, the 1-6-dinitro- and the 

 1-8-dinitro derivatives of the ether are formed in nearly equal quantities. 



4. Action of Nitric Acid on 1-Nitroetliyl-^-napMhyletlier. 



(a) In the Absence of Solvents. — About 5 g. of l-nitroethyl-/3-naphthylether 

 were added slowly to 25 c.c. of fnming nitric acid in a small roiind flask cooled 

 by immersion in water. The clear red solution was allowed to remain at the 

 room temperature overnight, and was then poured into water. The orange 

 red precipitate which formed was filtered, washed with water, and dried. A 

 portion of this solid separated from hot alcohol in the form of colourless, 

 apparently rectangular prisms, melting at 189-190° C. Another portion 

 crystallised from benzene as monoclinic plates or leaves, which also melted at 

 189-190° C. A mixture of the two products melted at 189-190° C. The 

 apparent diiference in the crystalline structure of the two substances was only 

 one of habit, since both gave oblique extinction, and therefore belonged to the 

 monoclinic system. The two bodies were therefore identical, and gave on 

 analysis the following results :— 



00962 g. substance gave 11-6' c.c. nitrogen at 12° C. and 728 m.m. 



corresponding to N 13-82. 

 CiaHgO.N, requires N 137. 



The substance was therefore a trinitro derivative of ethyl-j3-naphtliylether, 

 and, since it was obtained by the nitration of both the 16- and 1-8-dinitro- 

 ethyl-j3-naphthjdether (see 5 and 6 below), it must have been 1-6-8-trinitro- 



