By FREDERICK GUTHRIE'. 11. THEterms isotype and idiotype isotypic and idiotypic may be advantageously adopted to denote bodies which belong to similar types or to the same one and the relations kihich such bodies bear to one another. The application of' these expressions which we almost self-explicatory is best seen in examples. A body is idiotypic with all its replacement derivatives; the latter are of course idiotypic with one another ;the whole are idiotypes Bodies belonging to the same chemical series axe isotypic with one asother or are isotypes. Hence (1.) The idiotypes of the same body are idiotypes of one another. (2.) The isotypes bf the same body are isotypes of one another (3.) The idiotypes of the same body are isotypes of the idiotypes of an isotypic body.(4.) The isotypes of the same body are isotypes of the idiotypes of an idiotypic or isotypic body. In a paper read before the Chemical Society (March 3rd 1859,) I described the formation and some of the properties of the bodies C,H,Cl,S, Clo€IloC12S2 CloHloC1S2 and of some derivatives obtained from them. I purpose now resuming the consideration of this interesting class of bodies obtained by the action of the two chlorides of sulphur upon the olefines and rendering their history somewhat more complete before discussing the behaviour of the other compound halogens towards the same hydrocarbons. In the paper referred to it was asserted that bisulphide of chlorine is without action upon ethylene at temperatures between 0" and 100"C.The hope mas however expressed that the two might combine directly as is the case with amylene if they were subjected to increased pressure. I have since found that even at ordinary pressures an increased temperature is suEcient to deter- mine chemical recomposition ; and from analogies afterwards to be pointed out I conclude that the most probable interpretation of D2 GTJTHRTE ON SOME DERIVATIVES such recomposition is the direct union of the two reagents ethylene and bisulphide of chlorine and the simultaneous decomposition of the product formed. Action of bisukhide of chlorine upon ethylene.-Three or four ounces of bisulphide of chlorine are brought into a retort of two or three pounds capacity. The retort is connected with an inverted condense;.and through a tube passing through the tubulus into the bisulphide a rapid current of pure dry ethyleneis allowed to pass. On heating the bisulphide to ebullition the two substances are brought together in a gaseous state at a tempera-ture of about 139"C.; a condition which appears greatly to pro- mote their reaction. After about 200 litres of ethylene have passed through the liquid which has deepened in colour is trans- ferred to a smaller retort and heated till the boiling point rises to 18OoC. During this distillation as well as during the passage of the ethylene a disengagement of hydrochloric acid takes place. On allowing the residue in the retort to cool a considerable quantity of sulphur separates out. The distillate which contains only a small quantity of substance undecomposible by water may be employed in subsequent operations.In order to free the organic compound in the unvolatilized residue from still adhering bisulphide of chlorine it is after separation from the sulphur digested for many hours with water at 80'. After fresh portions of water no longer become acid the residue which is pasty and opaque is allowed to stand for two or three days in contact with dilute caustic soda. After drying it is digested with ether and the same process of purification followed which has been fre- quently described in my former paper. In burning this substance with oxide of copper it was weighed in an open boat and chlorate of potash was employed. This same method was used with the non-volatile bodies afterwards to be described.In the determination of the sulphur of this and other bodies I have employed carbonate of zinc in conjunction with chlorate of potash instead of the carbonates of soda or magnesia; the first of these attaclrs the glass and the subsequent separa- tion of silicic acid renders the filtration troublesome ; the second is so light as to be prone to projection from the tube; and both are difficult to procure free from sulphuric acid. The carbonate of zinc prepared from the chloride or the oxide of zinc prepared by the combustion of zinc may I think in all cases advantageously FROM THE OLEPINES. replace the before-mentioned carbonates for sulphur determinations. The zinc may also be used in union with oxide of mercury in Russell's method.In all cases however the combustion tube should be about 20 inches long and the anterior eight inches should be kept cold. I. 0.4637 grm. gave 0,3199grm. carbonic acid and 0.0980grm. water. 11. 0.2286 grm. gave 0.0443grrn. water. 111. 0.3960 grm. gave 0.2747 grm carbonic acid and 0.0735 grm. water. IV. 0.2564 grm. gave 0.4559grm. sulphate of baryta. V. 0.12876 grm. gave 0.6178 grm. chloride of silver. Calculated. Found. I. 11. 111. IV. v. Hean. C . . 18.45 18'81 , 18.92 , 72 18-86 H3. . 2-31 2.33 2.12 2.06 , ,2 2.17 Ss . C12. . 24.61 54.62 ,,,) ?t 2 )) 9 24.35 , a> 53.14 24.35 53-14 -__. 99'99 98-52 The substance analysed has accordingly the composition C4H3S2C12 having been formed according to the equation- C4H + 3s2cl = C4H,S2C1 + HC1 + 4s which also explains the liberation of hydrochloric acid and the separation of free sulphur described in the preparation of the body.Probably the most appropriate name for this body would be the bisu@hochloride of chlorethylene its formula being inasmuch as in all likelihood one atom of hydrogen has been replaced by one of chlorine and the so-formed chlorethylene has combined with the bisulphide of chlorine; OF the bisulphide of chlorine has combined with the ethylene to C,H,S,Cl and this body has decomposed two more atoms of bisulphide of chlorine forming hydrochloric acid and bisulphochloride of chlorethylene C,H,S,Cl + 2S2C1 = C {%)-S2C1 f-4s + HCl GUTHRIE ON sonm DERIVATIVES It is clear however that it may be viewed also; either as the bichlorosulphide of vinyl which mould hoPrever be without analogues or as the bisulphide of bichloreth pl Bisulphochloride of chlorethylene is a transparent liquid of light yellow colour.Its taste is sweet and pungent. Its smell when fresh is agreeable being between those of peppermint and of oil of lemons. Three or four drops when swallowed prwluce head- ache. It is soluble in ether and alcohol insoluble in water ; it does not 1-olatilize without decomposition. At 11"C. its specific gravity is 1.599. It is worthy of note that the bichlorosulphide of ethylene C,H,S,Cl obtained by the direct union of chloride of sulphur withi ethylene and described in the former paper differs from the body just described only in having one more atom of hydrogen a differ- ence which might not appear on analysis.The specific gravity of the latter body however is only 1408 its smell is quite distinct and it is much less soluble in ether. The determination of the composition of bisulphochloride of chlorethylene suggested three questions :-(1.) Is its forination preceded by that of the bisulphochloride of ethylene C4H4S2Cl,which undergoes decomposition on heating in presence of two additional molecules of S,C1? (2.) May it be regarded as a sul)stitution-l?roduct of bisnl-phide of ethyl being in fact the bisulphide of bichlorethyl (3.) Does it admit of further exchange of hydrogen for chlorine whether such chlorine replacement-products be identical or not with the hitherto hypothetical chlorine substitution-products of bisuphide of ethyl.*? * Ann.Ch. Phys. [3] xviii. Cahours mentions that chlorine acts upon the bisulphide of ethyl ; but the products do riot appear to have been examincd. FROM THE OLEFINES. The question (1)may be answered approximately by submitting the bisulphochloride of amylene C,,H,,S2Cl described in the former paper to the action of two additional molecules of bisulphidc of chlorine at a high temperature. Question (2) must be answered by submitting bisulphide of ethyl to chlorine. To answer question (3) bisulphochloride of chlorethylene must be acted on by chlorine. On passing dry chlorine into bisulphochloride of chlorethylene a rapid disengagement of hydrochloric acid results accompanied by a liberation of heat which undcr favourable circumstances may raise the temperature of the liquid from 12°C.to 85"C.; at the same time the liquid loses almost all its colour. In the following experiments the reaction mas carried on in the dark Through eight or ten grammes of hisulphochloride of chlor-ethylene dry chlorine was passed until the heat at first developed had abated and the ordinary temperature was re-established. The tube containing the product was then heated in a water-bath to 100"C. and a rapid current of dry chlorine was passed through for two hours. The product was freed from dissolved hydrochloric acid and chlorine by being again heated to 100' C.and subjected to a rapid current of dry carbonic acid for two hours. Even after all the hydrochloric acid was expelled the carbonic acid in passing through the liquid at 100"C. continued to carry off a vapour which both fumed with ammonia and reddened litmus paper. This is due to the vapours of chloride of sulphur and oxychloride of sulphur as we shall presently see. The cold gas-exit-tube became coated with a layer of yellowish transparent ci ystals too small in quantity for examination and consisting probably of oxychloride of sulphur whose formation was due to a trace of moisture After the carbonic acid had passed through duriiig the time mentioned a drop of the liquid did not give up any hydrochloric acid to water It was however digested with warm water dissolved in ether then dried and purified as before.On analysis this body showed the following composition :-grm. grm. grm. I. 0.3737 gave 0.2182 carbonic acid and Q*Q374 water. If. 0.5184 ) 0.4116 sulphate of baryta. 111. 0.4453 , 1.2957 chloride of silver. 40 GUTFIRIE ON SOME DERIVATIVES Calenlated. Found. I. 11. 111. C . . 16*16 15.94 ?Y > H . 1.35 1-11 ?I , S Cl . . . . 10.76 71.73 J) 1 10.88 )7 ,,71.98 - I__.- 9991 100*00 The action of chlorine therefore under these circumstances upon the bisulphochloride of chlorethylen is to replace one atom of hydrogen by chlorine and to eliminate half the sulphur ; thus giving rise to a body whicli may be called the chlorosu&hide of bichlorethy lene.The reaction takes place according to the equation C4H3C12S2+ 3C1 = C,H,Cl,S + HC1 + 3C1 The chlorosulphide of bichlorethylene is a yellowish almost colourless transparent liquid of pungent suffocating and most persistent smell. It mixes with ether and alcohol but is insoluble in water. Although not volatile when heated alone it may be volatilized almost without residue in a current of dry carbonic acid. Its specific gravity is 1.225 at 13*5"C. In order to compare the products of the action of chlorine upon bisulphide of ethyl with those of its action upon the bisulpho- chloride of chlorethylene ten or twelve grammes of the bisulphide of ethyl were exposed to the action of chlorine in the same appa- ratus and as nearly as possible under the same physical conditions as obtained during the action of chlorine upon the bisulphochloride of chloret hylene.On passing a rapid current of dry chlorine into the above quan-tity of bisulphide of ethyl the temperature was raised from 14" to 78' CJabundance of hydrochloric acid being evolved. The first bubbles of chlorine passed through the liquid became opales- cent owing to the separation of sulphur. As however the temperature rose this opalescence speedily disappeared. At one stage the liquid became much darker in colour than the sulphide FROM TEE OLEFINES. of ethyl ; subsequently it regained its light straw-colour ;when this happened the evolution of heat ceased. The liquid product so formed was thereon heated to 100"C.in a water-bath and the current of chlorine continued for two hours; it was then freed from hydrochloric acid and chlorine by a stream of carbonic acid as described in the preparation of the chlorosulphide of bichlor- ethylene. A product was thus obtained having the same colour and yre- cisely the same exceedingly characteristic smell as the chloro- sulphide of bichlorethylene formed as already described by the action of chlorine upon the bisulphochloride of chlorethylene. Its specific gravity was found to be 1.219 at 13.5"C. which is identical with that of the chlorosulphide of bichlorethylene,* Analysis also showed the two to contain the elements carbon hydrogen sulphur and chlorine in the same proportions as they exist in the chloro- sulphide of bich lore t h ylene.I. 0.3623grm. gave 0,2177 grm. carbonic acid and 0.0329grm. water. 11. 0.4073 grm. gave 0.4113 grm. sulphate of baryta. 111. 0.2762 grm. gave 0.7702 grm. chloride of silver. Calculated. Found. I. 11. 111. c4 . 16-16 . . 16.38 1 3 H . 1.35 . . 1-00 7 >¶ s. . 10.76 . ' ,I 11.10 >J >> 69.00 Cl . . 71.73 . -,J 100*00 97-43 This liquid has therefore the formula :-having been formed according to the equation :-C4H5S2+ 7C1 = C4 {%) S + SC1. + 3HC1 and being in accordance with its derivation the suZphide of ter-chlorethy l. * For exact cornparigon the specific gravities of the tao substances were taken in the same vessel and nearly at the mme time GCTTIIRIE ON SOME DERIVATIVES I can detect no difference whatever between the substance just described and that whose analysis was given on page 40 and named the chlorosulphide of bichlorethylene.The empirical formulae of the two are identical C,H,Cl,S ; but if we insist upon evidencing the different sources of the two bodies in their formulze and nariles me must write the oiie :-Chlorosulphide of bichlorethylene SCl the other C (:$-Sulphide of terchlorethyl . c4 -@I s* That these two bodies are identical I believe no one who has had them in his hands will doubt. I must reserve the confirma-tory evidence resulting from the apparent identity of some oxygen derivatives obtained in the same manner from both for another occasion. But from the above facts alone we are perhaps justified in giving an affirmative answer to the question (2) above proposed ; that is we may look upon bisulphochloride of chlorethylene in its behaviour towards chlorine as a chlorine-substitution-product of bisulphide of ethyl.That we do not obtaiii the bisulphochlo- ride of chlorethylene by acting upon bisulphide of ethyl with chlorine is accounted for by the fact already proved that the bisulphochloride of chlorethylene is itself attacked by chlorine. It is highly probable however that the darkening of the liquid mentioned above at one stage of the action of chloriiie upon the bisulphide of ethyl is owing to the formation of the bisulpho- chloride of ehlorethylene which subsequently undergoes further hydlrogen-replacement and elimination of sulphur being convcrted into the chlorosulphide of bichloret hylene.I did not however seek to intercept the process at this point because no criterion could be formed of the intcgral nature of the action and because even if a body of the anticipated composition had been formed it might still have been a mixture of t?le higher substitution-product with the original substance. The identity of the chlorine-substitution-products of C4c,] S,C1 I1 and C,H,S is further of considerable interest inasmuch as it shows that towards chlorine the two are essentially idiotypic and that consequently while we have seen in the case of amylene that a body C,H,S,Cl acts towards oxides and hydrated oxides as the FROM TI-TE OLEFIKES.chloride of a sulphur-radicle; towards chlorine such a body acts as the subhide of a chlorine-radicle. This line of evidence will be more complete after studying the action of chlorine upon the bisulphochloride of amylene previously described If a rapid current of dry chlorine be passed through bisulpho- chloride of amylene C,,H 1oS2Cl hydrochloric acid is evolved. In order to compare this reaction with the action of chlorine upon bisulphide of ethyl and bisulphcchloride of chlorethylene ten or twelve grammes of the bisulphochloride of amylene mere brought into the same apparatus arid subjected to the action of chlorine under tlie same circumstances as attended the action of that ele-ment upon the bodies mentioned. The action was attendcd by an evolution of heat which raised the liquid from 12"to 70" C.The colour changed from a light straw-yellow to a garnet-red at this point I suppose the liquid to consist principally of an intermediate snbstitution-product C * {:f 1S,Cl) arid then became almost' of its original paleness. At this point no more heat m-as evolved. The product being then heated ii? a water-bath the stream of chlorine was continued for two hours. After standing in a stoppered bottle for twelve hours it still smelt strongly of chlorine. The excess of chlorine and the hydrochloriG acid formed mere finally expelled by a stream of dry carbonic acid at 100" C. and the product was purified as before. G1X.I. Grm. Grm I. 0.4853 gave 0.4334carbonic acid and 0.1572water. 11.0,3299 , 0.3228 , , 0.1137 , '111. 0.4241 , 0.3850 , , 0.1368 , IV. 0*5011 , 1.2995 chloride of silver. v. 0.3940 ., 0.2274 sdphate of baryta. VI. 0.6996 , 0.4031 , 9 VII 0.4942 , 0.2810 , 1 GUTHRlE ON SOXE DERIVATIVES The possible substance whose composition approaches most newly to this is the chlorosu@hide of terchloramylene or according to what has been shown concerning the ethylene compounds the sulphide of puudrochloramyt? for these two bodies to whose identity analogy points require C, . . 26.66 H .. 3.11 Cl .. 63.11 S .. 7.11 99.99 The sulphide of quadrochlorarnyl or chlorosulphide of terchlor- amylene closely resembles in smell taste and physical properties the ethylene substitution-products already discussed.It is a trans-parent non-volatile light yellow liquid of specific gravity 1.406 at 16O C It is insoluble in water miscible with ether and soluble in hot alcohol. Fourteen grammes of amylene were gradually mixed at the closed end of a combustion-tube four feet long with more than three equivalents of bisulphide of chlorioe. The mixture having been kept boiling for eight hours (during which hydrochloric acid was copiously evolved) was transferred to a retort and heated till its temperature rose to 190°-C After cooling and decanting from the small quantity of separated sulphur the product was washed with ‘aqueous caustic soda etc. 0.4148 grm. gave 0-4411 grm. of carbonic acid and 0.1680 grm. water. 0.7006 grm. gave 0.6362 grm. of chloride of silver.These numbers show 28-76per cent. of carbon 4.50 per cent. of hydrogen and 22.46 per cent. of chlorine; a result which points to no simple formula. The product was probably a mixture. It is very worthy of notice that the body resulting from the action of chlorine upon the bisulphochloride of amylene is not an FROM THE OLEFINES. analogue of that derived by chlorine from the bisulphochloride of chlorethylene (i.e. from the bisulphide of bichlorethyl) and from the bisulphide of ethyl. Comparing their general formulze we have i2-41 for the first C, S and for the second Czm{c";;.-3] s. But; this difference which might seem to indicate an anomalous behaviour in the two cases really results from the symmetry of the two recompositions effected by chlorine ; a symmetry which ex-tends moreover to the chlorine-substit ution-products of the mono- sulphide of ethyl studied by Regnault." Putting the reations together :-is into by the ex-4 H for 3 €I for 3 C1 H for C1 3 H for 3 C1 change of 14C1 and SC1 for C1 and SCl for Cl C1 for SC1 Thus in all cases but the third a fourfold exchange is effected; and that here merely a twofold exchange occurs may be attri- buted to the body reckoned from the bisulphide of ethyl having already suffered a two-fold replacement.It has been already shown in the first paper that SC1 is monomolecular and may be replaced by a single atom of chlorine. Particularly remarkable is the analogy between (2) and (4) proving as it does that these two substances are towards ciitorine isotypic.The above bodies furnish examples of the proneness which chlorine has to replace even numbers of molecules. ?n order to throw some more light upon the constitution of bisulphochloride of amylene I have subjected that body to the action of nitric acid; but before describing the products obtained by this reaction it will be well to consider briefly the action of nitric acid upon amylene itself. The temperature at which nitric acid and amylene act upon one another is so far above the boiling point of the latter body that great loss of amylene results if the two are heated together * Ann. Ch.Phys. [3] Ixxi 387. GUTHRIE ON SOXE DERIVATIVES even in capacious vessels until the reaction commences.If five or six grammes of amylene be shaken in a bolt-head with four OT five times the volume of fuming nitric acid and heat be applied until the acid boils a sudden evolution of nitrogen-oxides results thc neck of the bolt-head becomes coated iiith a thin layer of fatty white crystals and green oily drops heavier than nitric acid appear in that liquid. For the above-mentioned reason however this method of tracing the reaction was abandoned and the following one employed. Air dried by passing over chloride of calcium in the tube a is made to bubble through amylene contained in the bulbs 6 and being thus charged with the vapour of amylene it is led through fuming nitric acid in the retort c which has previously been heated to boiling and which is kept so during the passage of the The retort is connected with a condenser.If the volume of gas. the nitric acid be about seven times as great na that of the amylene and if the current of air and the heat of the retort be so regulated that the amylene and nitric acid are volatilized nearly together almost the whole of the non-gaseous products consists of the white fatty crystalline substance before mentioned which coats the surface of the receiver ; the greater quantity however is deposited in the tube of the condenser and may thence be washed into. the receiver. Water is added to the latter and it is vigorously shaken until the product cakes together. Although heavier than water it generally floats upon its surface owing to the presence of small gas-bubbles.After washing with cold water on a funnel and drying between blotting paper it is strongly pressed to remove traces of the liquid product mentioned before and then recrystallized from boiliug anhydrous ether. If the ethereal solution be allowed to cool without evaporation the substance crystallizes out in long rectangular prisms. If the FROM TIIE OLEFINES. crystallization be helped by evaporation it separates as flat rectan- gular tables. Under the microscop;= no other than right anglen could be observed in either case. Burnt with oxide of copper metallic copper being employed ia the anterior of the tube I. 0.3680 grm. gave 0.5019 grm. carbonic acid and 0.2056grm. water. 11. 0.1330 grm. gave 19.1 cc of nitrogen at OOC.and 760 mm Calculated. I. 11. c,o ' . 37-09 37-20 , HI0 . 6-18 6.24 1 N2 . 17.28 > 18'0h 0 This substance may therefore be called binitroxamylene its formula being- A portion of the nitric acid is deoxidized to NO,; this com- bines with the oxygen of the excess of air to form NO,; and the latter molecule urzites directly with a fresh portion of arnylene. This same substance which can be obtained only in small quantities by the above process may be prepared in any desired quantity by the direct union NO with arnylcne. The latter method of preparing this body together with some of its pro- perties will appear in the next communication.