GGTHRIE ON SOME DERIVATIVES FRON TOE OLEFINES 129 XV.-On some derivatives from the OZeJines. BY FREDERICK GUTHRIE. 1x1. THEintroduction of nitroxine* into organic bodies and the forma-tion of the so-called nitro-compounds has been hitherto effected with apparently a single exceptiont by the action of iiitric acid either alone or in presence of sulphuric acid The reason of this is obvious :-such introduction has in every case .consisted in the replacement of hydrogen by nitroxine. The nitric acid offers its fifth atom of oxygen to the hydrogen being replaced while the nitiwxine replaces it. Such replacement is of course double recomposition expresssed generally by the equation and is quite parallcl to the reaction attending the formation of *It will be found conrenient to call NO nitrozine a compact term recalling the analogy which this molecule bears to chlorine iodine etc.Accordingly the nitrites MONO, will be nitroxides MNO as has been sometimes proposed. Further regarding the nomenclature as with the chlorides C H&12is bichlor-ethy!ene C,H,CI bichloride of ethylene etc.:-So with the nitroxides C,,H7N0 Nitroxinapthaline loH,,2N0, Binitroxide of Amylene etc. 'k See below ;nitroxinapthaline. VOIJ. XZlI. H GUTHRIE ON SOXE DERIVATIVES the chlorine substitution derivatives obtained by the action of chlorine C,. ...H + p(C1 Cl) = C,. *..H,-,Cl + pHCl and probably also to that which occurs when chlorine is introduced by means of hypochlorous acid. The formation of binitroxide of amylene C,,H1,.2N0, by the action of nitric acid upon amylene * immediately suggested the question:-May the olefines whose privilege it is to combine directly with two atoms of the halogens without elimination of hydracids behave in a similar manner towards nitroxine ? If nitroxine prepared by heating anhydrous nitrate of lead be passed through an empty bottle and then into a flask containing amylene the gas is instantly absorbed and the amylene gradually becomes converted into a pasty mass of minute crystals.To avoid loss the flask containing the amylene should be surrounded by a freezing mixture. The product is thrown upon a filter washed with cold alcohol in order to remove an oily liquid which accompanies the crystals then recrystallised from boiling ether and dried in vacuo over sulphuric acid.I. 0.2682 grm. gave 0.3664grm. carbonic acid and 0.1572water. 11. 0.2290grm. gave 32.3 cc. of nitrogen at 760 mm. and 0" C which gives Calculated Found I. 11. c, . 37.09 37.26 ti 'I 'I JY H, 6.18 6.51 N* . 17~28 Ji 17.66 0 ' Yi >Y 3 This substance is therefore the binitroxide of amylene CloHlo. 2N0 and is identical with the crystalline body obtained by the action of nitric acid upon amylene (see 11). It is curious as being the only known nitroxine-isotype of Dutch liquid but more remarkable in this latter manner of its formation as furnishing the only instance in organic chemistry of the behaviour of free nitroxine as a halogen without the elimination of hydrogen.Bintroxide of amylene is but slightly soluble in cold but readily in boiling alcohol ;it dissolves in ether and in bisulphide of carbon *See 11. FROX THE OLEFINES. but is perfectly insoluble in water. It crystallises in small square and rectangular colourless transparent plates. Heated by itself in a dry tube binitroxide of amylene decom- poses exactly at 95OC. giving rise to a gas and to a liquid heavier than water. The decomposition of a portion having been effected in a very strang sealed tube by heating to loo* C. the tube on opening gave off much gas which reddened moist litmus paper. Another portion was treated in the same way in presence of' water. After opening the tube neutralizing the acid water with ammonia filtering and evaporating to dryness on a water bath a residue was obtained which gave off nitrogen on being heated.Accordingly the gas evolved from the binitroxide of amylene was nitrous acid NO, or nitroxhydric acid HNO,. The next point was to determine the nature of the liquid product the supplementary factor to binitroxide of amylene which appears in the preparation of that body. The filtrate and alcoholic washings from binitroxide of amylene after evaporation for some hours on a water bath washing with water and drying yielded an amber-coloured transparent liquid heavier than water and immiscible with it. Neither this liquid nor the binitroxide of amylene underwent any change on being kept for several days in an atmosphere of nitroxine.On analysing the liquid 0.2586 grm. gave 0.3882 grm. of carbonic acid and 0.1717 water. The substance whose composition corresponds most closely with these numbers is a mixture of equivalent quantities of bini-troxide of' amylene with nitrate of amyl. Found. 10H10*2N04 C,,H,,O*NO!, C . . 40.67 40.94 H.. 7.12 7.37 Although the presence of amyl would point to the disintegration of anather molecule of amylene the above given composition of this mixture is rendered probable on the following grounds :-On heating to 95' C.,* it undergoes decomposition whereupon the temperature rises spontaneously to 170" C. and the greater * Identical nith that at which C,,K,,.2NO4 is decomposed K2 132 GUTHRIE ON SOME DERIVATIVES quantity of the liquid passes over.On rectifying a portion was obtained which boiled almost constantly at 160' C. Of this 0.2263 grm. gave 03850 grm. carbonic acid and 0-1712grm. Found. C,OH,,ONOB C . . 4511 46-40 H.. 8.27 8.40 On boiling a portion of this distillate with an alcoholic solution of caustic potash nitrate of potash was formed. The original liquid also gave rise to nitrate of potash under the same circumstances. Nitrate of amyl also appears among the liquid products formed when binitroxide of amplene is heated by itself. Heated with quick lime binitroxide of amylene gives rise to an aromatic body differing from valeral and probable amylenic ether C,OH,,O,* The actions of sulphide of ammonium nascent hydrogen and other reducers upon binitroxide of amylene will be well worthy of study.As yet my attempts to combine nitroxine with ethylene have not been successful. Neither protoxide nor binoxide of nitrogen has any action upon amylene. The affinity of amylene for nitroxine is so great that by means of this hydrocarbon a very small trace of nitroxine may be detected in the above named nitrogen-oxides. Thus if amylene be added through a funnel tube to a flask containing copper and nitric acid which is kept quite cold and from which the evolved gas has expelled the air crystals of binitroxide of amylene are continuously though slowly formed; but if the binoxide of nitrogen be first absorbed by protosulphate of iron and then expelled thence by heat* and made to pass through amylene in an apparatus from which a current of carbonic acid has expelled the air no change occurs.Nitroxinapthalin. (Witronapthalin.) The laborious reseaches of Laurentt and others have long since established the claim of napthalin to be an olefine. It combines directly with chlorine to form bichloricie of napthalin C,H,Cl, 8nd although it may unite with four atoms of halogen as in the * Bunsen's Gas~m?~fy.Engl. Ed.p. 51. -t. Ann. Ch. Phys. '8'9 lix. FROM THE OLEFINES. quadrichloride C,H,Cl, in the tercliloro bromide C,oH,C1,Br and in their numerous idiotypes C,,H6Cl,C1 quadrictiloride af bichlornapthalin. C2,HGBr2C1 quadrichloride of bibronapthalin etc. etc. yet as we have already seen in examining the behaviour of ethylene and amylene towards chloride of sulphur ad as we shall abundantly see in the sequel this assumption of four haloid atoms is quite consistent with the nature of the olefines isotypic with ethylene.Like ethylene napthalin combines with anhydrous as well as with hydrated sulphuric acid and finally in napthalamim C,,H,HN me find it still preserving the biatomic character of an olefine taking the place of two atoms of hydrogen. Laureiit’s exaiuiuation of the action of nitric acid on napthaline resulted principally in the discovery of three nitroxine-replacemeut derivatives idiotypic not with the bichloride of napthalin but with napthalin itself. Nitroxinapthalin . . C20H,(N04) Bini t roxinap thalin . C,OHG(NO,) Triuitroxinapthalin .%OH (NO,) Bearing in mind on the one hand the analogy which these bodies have to the chlorine-idiotypes of ethylene and on the other the above described direct union of mnylene with nitroxine we might h priori expect to obtain nitroside of napthalin or binitroxide of napthalin by the action of nitroxine on napthalin. So that although Laurent gives this reaction as a method of preparing nitroxinapthalin yet as no analysis appears to have been made of the body so produced I thought it worth while to comfirm Laurent’s experiment. If napthalin be thrown into a ffask containing aa excess of nitroxine considerable heat is developed scanty white fumes are formed which quickly subside and an oily liquid resdts whioh solidifies on cooling.To ensure complete reaction the flask is corked with an excess of nitroxine and the product is repeated13 shaken and melted. After re-fusion under water drying and recrystallisa- tion from ether a product was obtained which gave on analysis 0.4202 grm gave 1.0707 grm. CO and 0.1590 grm water. C,,H (N 0,) Found. C . . 69-36 69.49 H . . 4.05 4.20 134 GUTHRIE ON SOME DERIVATIVES FROM OLEFINES. The substance formed is therefore undouhtedly nitroxinapthalin. We accordingly find that nitroxine in its behaviour towards napthalin more closely resembles bromine than chlorine ; for while the former gives bromonapthalin the latter gives bichloride of napthalin c20€€, + 2c1 = C2,€€,Cl2 C2,Hs + 2Br = C,,H,Br -/-HBr CmH8 + 2NO,= C,,H,NO + HNO, BisdphoclzkmYe of Ethylene.Although as before shown,* ethylene and bisulphide of chlorine are without appreciable action on one another under ordinary circumstances of temperature etc. and although a temperature of 139"C. effects a disintegration of the ethylene-moleculet. I have again sought to unite the two directly because the result- ing body if it resemble its amylene-isotype would give rise to a highly important series of derivatives. $ If bichloride of sulphur be exposed in a stoppered bottle in an atmosphere of dry ethylene to direct sunlight the two unite slowly but almost completely hydrochloric acid however being liberated. If a few grammes of bisulphide of chlorine be placed in a well-stoppered bottle which is then filled by displacement with ethylene the waxed stopper inserted and covered with sheet-caoutchouc and the whole be completely immersed for twenty hours in boiling water very complete absorption is found to have taken place on opening the bottle while only a trace of hydrochloric acid is formed.The bottle may be then refilled with ethylene and the same operation repeated three or four times. The resulting product is then shaken up with warm water dried digested with ether filtered evaporated in vacao till the ether is expelled dissolved again in a minimum of ether filtered and evaporated in vacao. gm. grm. m. 1. 0.3058 gave 0.2908 carbonic-acid and 0.1184 water. 11. 0.2197 , 0.2356 water. 111. 0.1798 , 0.2638chloride of silver. IV. 0.2829 , 0.6934 sulphate of baryta.* Niernann. Ann. Ch. Pharm. cxiii. 3; F. Gnthrie ibzd. +Chem. Yoc. Qu. J. March 1860. $ See Memoir iv. HOWARD ON THE HISTORY OF CINNAMIC ACID. 135 Found. C4H,S,C1 I. 11 111. IV. C = 25.13 25.93 1 J> >J H= 419 4.30 (4.33) 9) ?J S = 33-51 I JJ >Y 33-47 C1= 37.17 JY >> 36.29 92 100*00 100~01 This substance is according to the previously adopted nomenclature the bisulphochloride of ethylene C4H4.S,Cl. Bisulphochloride of ethylene has a not unpleasant but indescribable smell ; its taste is intensely sweet and pungent. Like the bichlorosulphide of ethylene its annoying effect upon the eyelids is very enduring ;* Its colour is a pale yellow ; specific gravity 1.846at 19 C.* Like the previously described chlor-sulphur compounds of the olefines it is decomposed by heat and gives off an insupportable smell. In the next communication I shall describe the action of anhydrous and hydrated oxides upon this substance and the behaviour of it and its isotype bisulphochloride of amylene upon some of the metal-radicles.