62 XK.-On the Resin of Ficus rubiginosa anda new Homolbgue of Benzylic Alcohol. BY WARRENDE LA RUE,Ph.D. F.R.S.,Treasurcr of the Chemical Socicty Secretary of thc Royal Astronomical Society &.,and HUGOMULLEH,lJh.D. F.C.S. (Abetncted from the Philosophial Traneactione 1880 Part I.) AMONGthe interesting collcction of natural products contributed to the Paris Universal Exhibition of 1855 by the British Colonics waa a gum presenting some remarkablc qualities. This substance waa stated by the exhibitor to be a ncw species of gutta percha in consequence of its becoming plastic when masticated and on this account it attractcd considerable attention. It hul been contri- buted by Dr. Stephenson of Manning River N.S.W. who had obtained it from a specics of Ficus known as F.rubiyinosa. The tealous Commissioner for New South Wales Mr. (now SirWilliam) Macarthur brought this gum undcr our notice with the vicw of obtaining some information respecting its chemical properties. A few preliminary experiments which were made in Paris at once showed us that this substance had vcry little in common with gutta percha and moreovcr its chemical propcrties wcre found to be entirely diffcrent from those of that gum. Although our ex- periments did not allow us to hold out hopes to Mr. Macarthur of the gum becoming a valuablc articlc for cxportation from the colony they offered somc iriduccmcnt to us to make a more rigor-ous investigation of it on purely scictititic grounds. On communi-cating this view to Mr. Macartliur hc liberally placcd at our disposal the remainder of thc spccinien exhibitctl.In pursuing suliscqucntly the study of this subjcct we iliscovcred one of the proximate coristitucnts to bc a natural acctic ether of a new radical homologous to benzyl (C 11,). Thc peculiar in- tercst which attaches to this class of compounds induces us to bring under the notice of thc Socicty the results of our investigation. This gum or rcsiii exhibits on tlic first glance great similarity in its general appcarancc to ‘‘Gum Euphorbium,” occurring like that substance in irrcgular picccs generally pierced with holcs ; some specimens also exhibiting a stalactitic formatiou. The holes in the fragments of this rcsin are protluccd by a small beetle of the tribe ‘‘Curculio,” which apparcntly feeds upon and lives in ON THE BESIN OF FICU8 ILUBIGINOSA.this resin as it oozes in a semifluid state from the branch of the tree. We had no means of ascertaining whether or not this insect causes the secretion of the resin by puncturing the branches of the tree in the same manner as the Coccus~cusdoes for the pu'poe of depositing its ova. The colour of the gum varies from a dirty yellow or red almost to white. It is solid and brittle but some of the larger pieces exhibit especially in the interior a degree of toughness which renders it difficult to powder. It is opaque the fracture being dull and wax-like. At a temperature of about 30" C. (86' Fahr.) this resin becomes soft when it resembles gutta percha being plastic without.becoming sticky provided it has been previously wetted with water. In its natural condition it has neither taste nor odour ; but when heated it evolves a wax-like odour arid on being masticated evinces a characteristic taste. In hot or cold water it is perfectly insoluble; but warm alcohol ether oil of turpentine and other solvents of resioous substances dissolve it with facility. Solutions of caustic alkalies have DO effect on it even when aided by heat. When left for some time in contact with cold alcohol of ordinary strength the greater part of the resin is dissolved whilst a white flocculent substance remains undissolved. By employing this solvent we succeeded in separating several distinct classes of substances from the Ficus resin.,The constituent readily soluble in cold alcohol formed an amorphous resinous substance when separated from the solvent by distillation or precipitation with water. The white insoluble part when further treated with boil-ing alcohol is in part dissolved particles of bark sand and other accidental impurities remaining undissolved. The alcoholic solution of the white substance deposits on cooling a white crystalline mass which by repeated crystallization may be obtained in beautiful scaly crystals. From the residue insoluble in boiling alcohol bisulphide of carbon or chloroform extr'acts a small quantity of caout c houc. A quantitative experiment by the above method yielded the following approximate per-centage red t :-Resinous substance readily soluble in cold alcohol .73 White crystalline substances insoluble in cold alto-hol but soluble in warm alcohol 14 Caoutchouc fragments of bark sand and loss 13 DE LA RUE AND BIULLER ON The resinous substance readily soluhlc in cold alcohol which forms according to this analysis by far the principal constituent of our resin ofl’ered but little incluccment for chcmical investigation. However a number of experiments were made which although unproductire in their results may serve to characterize this sub-stance which possesses peculiarities distinguishing it from other bodies of like origin. In order to identify it hereafter we pro-pose to call this resiii Sy coret i 11. At the same time we must state that we were not succcssful for reasons hereinafter mentioned in obtaining this substance perfectly pure.Xycordin. Cold alcohol of moderate strength dissolves the principal part of the original resin forming a light brown solution which on precipitation with water or the separation of the alcohol by distillation yields the sycoretin. The alcoholic solution of this resin is perfectly neutral arid scarcely any precipitate is caused in it on the addition of an alcoholic solution of acetate of lead or acetate of copper. This behaviour indicated at orice that no acid compounds were present and that the resin is perfectly neutral. The minute precipitate which formed we ascertained to be tarmate of lend the source of the tannic acid being probably the bark which contaminated the resin.This resin was purified by redis-solving it in alcohol and in order to remove the small amount of colour the soliition 1%as treated with animal charcoal but this had no effect. No better result was obtained when a small quantity of acetate of lead was introduced into the solution and a basic lead- salt thrown down with ammonia. We afterwards found that the colour could be gradually removed by repeated precipitation of the resin from its dcoholic soliition by water. The decolorized resin was now redissolved in a just-suEcient quantity of alcohol and the solution left for some time in a cool place wheu a small amount of crystalline substance was deposited which was filtered off. By addition of a little water a small quantity of sycoretin was then thrown down in order to carry down the last traces of the less soluble crystalline compound in case ariy we1.E still present.After this treatment the solution was again allowed to stand for some time but no further precipitate was formed. The clear solution was now partly precipitated with water and the precipitate removed after it had subsided heat being used to facilitate the subsidence of the sycoretin by eausillg the THE 1tESIN OF FICUS RUBIGINUSA. precipitate to aggliitiiiate into one mass. That part of thc resin remaining in solution was aftcrwarils throwii doin1 with water and collcctetl separately. The two diff'crcrit lots of resin thus obtained had the sitme ap- pearance; both wcre brittle hut only the last bccaine sticky when masticated and tasted like the original resin.Both products were powclcrcd arid kept for some time in vacm over sulphuric acid in order to remove all traces of any adheriug water or alcohol. The analysis of the first prccipitatcd part (A) gavc the following per ceiitagcs :-Carbon . . 74-65 Hydrogen . . 10.11 The analysis of the portion last thrown down (B) gave the fol-lowing per-centages :-Carbon . . 77-89 Hydrogen . . 9.94 It will be observed from the preceding numbers that the resin wliich has the property of agglutinating on being masticated is richer in carbon than that first thrown down by water from the alcoholic solution. The peculiar characters of these substances did not however permit of any formulae being determined for them.Sycoretin is almost white ; it is very brittle. It melts in boiliiig water to a thick liquid floating on the surface and when powdered becomes so electric that it flies out of the mortar. In water dilute acids alkaline solutions or ammonia it is insoluble; but it is readily soluble in alcohol etlier chloroform oil of turpentine &c. In order to ascertain whether sjcoretin was allied to that class of bodies called glucosides (jalapin for example) the following experiments were made :-Action of Xu@huric Acid on kycoretin. A portion of the sycoretin prepared as stated above by frac- tional precipitation was added to conceritratcd sulphuric acid ; it was readily dissolved forming a fine deep red solution which gave off only a fairit odour of sulphurous .acid when kept for several days.By exposure to the air or on addition of water a brownish precipitate deposited which differed from the original solution by its lesser solubility; the aqueous liquid contained a trace of a 1)E LA RbE AND MULLEK OK sulpho-copulate acid but no snccliarinc snlntance could he dis-covered. Analogous results wcrc olitainctl l)y twatiiig it with a conccntratcd solution of potash. Tlicsc espcrinicnts sliow that sycoretin cannot he classec? with tlic glucosides ; iiiorcover dl at-tempts to placc this substarm in connciion nith sonic‘ of the clnssificd organic com1)ouiids wcrc unsucccssfiil and we arc tlicrc-forc constraincd to lcaw it for the przscitt anioiig tlic so callcd resins under which tcrm arc comprisctl all sorts of bodics wid and ncntrnl wliich haw notliing in comnion esccpt some physical 1’2sc113 bla11ce.Action of A\’&ic ~Icid on Sycoretin. It appears that the only products of tlic action of coiicentratcd nitric acid arc a peculiar :iitro-compounu arid a small quaiitity of odic acid no picric acid bcing formed. On submitting sycoretin to the action of nitric acid the pow- dered resin was iutroclueed in small quantities into tlie acid at tlie ordinary ternpcrature and whcn the action had somewhat subsided the acid was boiled for some time when every particle of resin disappeared. The resulting yellow liquid vns mixed with water when a copious precipitate of a pale yellow dour was formed. The precipitate was filtercd off and washed with water.The fil-trate when freed from nitric acid by evaporation gave an addi- tional precipitate of the nitro-compound on admixture with water. The nitro-compound has slightly acid pruperties and ip readily soluble in solutions of potash and ammonia. Carbonate of potash also dissolves it but there is no evolution of carbonic acid even when the solution is warmcd. All the solutions in alkalies are dark yellowish brown and leave on evaporation an amorphous re-sidue. Lead and other metallic salts give coloured precipitates with its solution but as might be expected no dcfinite compounds could be 2roduced in this way. Thc compound with potash when heated on platinum-foil melts takes fire pufls up and burns with the vivacity of other nitro-compounds.Action of Heat on Sycoretin. When heated in a retort spcoretin melts below looo C. and at a temperature of a few degrees higher froths considerably giving off water which retains the peculiar odour perceptible on heating the original resin. On raising the temperature much higher it becomes quiet and begins to decompose giving off at THE RESIN OF FICUS BUBIQLNOSA. first a mobile liquid and towards the end a dark yellow tar-like substance leaving only a small quantity of charcoal behind. The distillate so obtained has a disagreeable smell somewhat like burnt india-rubber acetic acid being also present in considerable quan- tity. By treating it with R solution of carbonate of aodium the acetic acid is removed a dark brown oily liquid remaining which pa-sesses now a less disagreeable odour.This oily liquid submitted to a new distillation gives at first a very mobile liquid possessing in every respect the properties of caoutchin and then a thick oily liquid which soon becomes dark brown when exposed to the air. Acetate of Sycoceryl. We assign this name for reasons hereafter to be mentioned to the crystallizable substance which as already mentioned is obtained when the residue left after the treatment of the original resin with cold alcohol is dissolved in boiling alcohol and the solution allowed to cool. For the preparation of this substance the original resin is coarsely powdered arid extracted with cold alcohol in order as far as possible to remove the sycoretin.The undissolped residue is then exhausted with boiling alcohol. The several solutions thus obtained are filtered and allowed to cool when a white deposit is formed which generally shows but little indication of crystallba-tion. This white deposit is again dissolved in a large quantity of boiling alcohol and left in a quiet place to cool slowly when a more perfect crystallization is obtained. Towards the latter part of the crystallization a substance is de-posited of different appearance being of a more flocculent nature and altogether different from the crystals first deposited. This substance is present only in very small quantity and its separation from the other crystallizable constituents of the resin is attended with great dificulties.Iu order to effect this separation the alco- holic solution is allowed to cool to about 40" C. (lO-ko Fahr.) and then the crystals which may have formed are separated by strain- ing off the liquor as quickly as possible through a piece of gauze. The mother-liquor on further cooling will now deposit the floc-culent substance contaminated however with the first substance. By repeating this operation a perfect separation of this second substance may be effected. By repeated solution in and recrystallization from hot alcohol the crystalline substance (acetate of sycoceryl) was obtained DE Id RUE AND MULLEI~ON perfectly white and transparent and apparently pare. h a&-nation with the microscope however proved tJmt another foreign body had deposited in smaller crystals on the faoe8 of the ~~pposed pure substance.This new body proved to be much less soluble in different vehicles than our acetate of sycoceqd but being present only in very small quantity its separation caused us at ht very greRt perplexity but finally we found the following method per-fectly efflcacions for that purpose. The dry crystals were placed in a flask,and a quantity of ether inaufficient to dissolve the whole substance was introduced the temperature being maintained at about 30' C. (86" Fahr.! ;more ether was cautiously added from time to time until the larger crystals had just disappeared leaving the smaller ones of the new eubstance undissolved. The separation of the two substances is not however perfect in a single operation; for when the flask iu allowed to cool a small part of this parasitical body depsita.After d$tilling the filtered etheric solution the acetate of sycoceryl is obtained in a state of perfect purity and by recrystallization from alcohol ether or chloroform it may be procured in beautifid crystals. Acetate of sycoceryl so obtained is perfectly colourless and crystallizes from ether in flat prisme which generally appear a~ six-sided plates. When crystallized from alcohol the crystals are thin and scaly like mica and have the greatest resemblance to cholesterin. Acetate of sycoceryl is brittle yet difficult to powder on account of its becoming highly electric when triturated. It melts at 118" -120" C. (244"4-248" Fahr.) and is still fluid when cooled down to 80"C.(176" Fahr.). It eolidifies at first to a transparent mass which however after a short time becomes opaque and crystalline especially if scratched with a hard body. Heated considerably above its melting-point it boils and distils almost without decomposition. The distillate is at first liquid but solidifies after 8ome time and becomes gradually crystalline. When not perfectly pure or if the heat is applied too rapidly it givea out a rancid odour in which that of acetic acid is recognisable. Hot alcohol ether chloroform benzel acetone oil of turpentine and concentrated acetic acid dissolve the acetate of sycoceryl with great facility. The alcoholic solution is perfectly neutral and gives no precipitate with alcoholic solutions of the acetates of lead or copper.Sulphuric acid dissolves it readily forming a viscid colourlem solution wliit~li gets grntlitnlly IJIWWII and tliw giws off trams of sulpliiiroiis atit1 acetic acids. \\Iwii tlic siilpliiiric soliit ion is miscd wit11 water n siibstnncc is thrown tlowi wliic4i is Iwrfcctly liartl at coniinon tcmp:mtiirCs hiit niclts bolow lo()?(:. (213"k'ithr.1 ant1 is very tliiliciiltly soltiblc iii alcoliol hut rc;ulily so in clilorofoi m ant1 I)ciizol. Nitric acid wlicii tlilutccl lias no cffcct nt ortlinary tcmpcra- turcs 011 acctittc of syc*occrFl ; hit if warm it cvolves nitrous fiimcw and prod iiccs a ycllow rcsiiious compoiiiitl. k'iitning nitrom acid Iio\vcvcr dissolves it rcadily at ordinary tcmpcraturcx giving n yellow soliition from wliicli water tlirows down a flocculent amorplious ycllow nit ro-coml)oiiiid.IIylrocliloric acid has no cflcct on acctatc of sycoccryl. Cliloritic bromiiic aiitl iotliiic iii coutact with this siihstancc act npoii it witli violcticc cspccinlly tlic two first-uamerl rcagcnts; the procliicts Jiowcvcr procurd in this matincr arc oiily rcsiti .like compounds iiot atlaptcd for aniilysis. If Iio\vcvcr a wiirni alcoliolic soliition of tlic acctatc of sycoccryl is cmployccl ant1 tlic 1)roiiiiiic or iociiiic also adtlccl iii solution and iii small qiiaiitititts at a tirnc the coloiir of tlicsc two rcagcnts tlisappcnrs and aftcr cooliiig a IICW hino-or iodo-compound as tlic cnsc niay be is tlepsitetl in small crpt:ds.Tlic iodine-corn-poiintl is y~llow,the 1)romiiic-coniponiitl colourlcss. l'lic purifica-catioii of tho two proiiiisiiig conipoiiiids ant1 tticir scpariition froiii t1ic 1111nl tcrcvl ()rigin;il siihi;tal iccs aid mi0t licr rcsi nou Y hodp f'ormctl at tlic samc tinic was imfortuiiatdy not possildc witti tlic liiiiitctl qiiniitity of nintcrial that coiiltl bc dcvotcd to their pl.cl):lratiOTi. Poliitioi~of potmli cvcn whcn boilcrl for a long time with the sitl)staiicc iiiitlcr coiisitlcrntioii tlocs riot act iipoii it. If hydrate of pot:i4i Iiowcwr is mcltcd with it a tlccomposition takes ~IRCC and if tlic tcwil)crritnrc is raised sonic liytlrogcii is given off. The protluct' of this reaction trcatcd wit11 water leaves bcliind a coloiii*lcss anioi.ptioiis I~otly,wliicli could not hc ohtaincd in a cryp t;dliiic stntc 01' siificiciitly pirc for aidysis.Thc alkaline mother- liqiior snturatcd with rliliitctl siilpliuric acid bccamc slig1itly turbi(J aid the prcscncc of ncctic acid was tlicii pcrccptible. Soda-tartrntc of coppcr gave no rcnction indicatiiig the presence of siigai*iii the solution. 'l'lius far vc did not siicccctl in producing any derivative which would tlirow light upon tlic tlicoretical composition of our substance ant1 fiirnisli us with the nieans of ascertaining its rational formula. DE LA RUE AND MULLER ON Analysis gave numbers which agree with the empirical for-mula C, H,60,* our substance bcing accordingly isomeric with camphor to which howcver it has no further resemblance.This composition varics also widely from that of the crystalline snbstanccs procured from analogous sources and which have a great rescmblancc to OUT sabstaiicc,-for instance the crystalline resins on the one hand Chinese wax and waxes generally on the other. We have mentioned above in spcaking of the action of various reagcnts on our new substance the occurrence of acetic acid under two different circumstances; we did not attach much importance to this fact at the time because this acid occurs so frequently among the products resulting from the breaking up of organic substances ;nevertheless we subsequently repeated these experiments on a somewhat larger scale chiefly however with the view of stndying the other products of decomposition which are formed.In order to eliminate as much as possible the effect of temperature we made use of that powerful reagent the so-called ('sodium-alcohol,'' which is ohtained by dissolving sodium in absolute alcohol. Sodium-alcohol and potassium-alcohol at ordi- nary temperatures are for the most part equivalent in their reac- tions to the hydrates of those alkalies when in a state of fusion and hence present the advaiitage of etfecting decompositions in a more simple manner the effect of a high temperature not inter- fering with the final result as is somctimes the case when the fusing hydrated alkalies are employed. Some experiments of this kind performed with great care convinced us that the occurrence of acetic acid could not be attributed to the effect of empyreumatic decomposition but that it actually existed as an integral proximate coiistituent of our crystallizable substance.This led us at once to suspect that our substance was in reality an ether-like compound. This supposition was confirmed hy the separation of a body which might be con-sidered as the hydrated oxide of a radical; moreover we were ultimately enabled to give the fullest coiifirniation to this theoreti- cal speculation by actually producing the original substance in a manner suggested by this view. It should be stated that sodium-alcohol dissolves our substance with the greatest facility and even at a temperature of 30" C. * Carbon = 12 Oxygen = 16. TIlE RESIN OF FICUS RURIQINOSA. (86" Fahr.) decomposition takcs placc the reaction being unac-collll)ii~li(d by the cvolution of gas.On cooling the solution coritiiiucs liquid altliough il largc qnantity of the substance mfiy have Imn emyloycd; hut on addition of watcr a white flocculent substance scpimatcs from the colourless alkaline mother-liquor. The flocculciit substaricc is insoluble in water but readily soluble evcn in cold alcohol. IVlicn it is dissolvd in a quantity of boiling alcoliol just sufficient to tnkc it up tlic solution on cooling solidi-fies complctely to a mass of beautiful silky crystals quite different from those of the origiiial substancc this new derivative proved to bc the nmv alcokol which we proposc to call Sycocerylic A1 c o 1101. Thc aqueous liquor from wliieli the flocculent precipitate was separated rcmains almost pcrfcctly clear on saturation with a mine-ral acid ; 011 examination no othcr product bcsidcs a volatile organic acid coiilcl be found in it.Thc existence of a volatile acid with tlie odour of acctic acid was rendered evidcnt by saturating the alkaline rnothcr-liquor with phosphoric acid and distilling ;the distillatc was saturated with carbonate of barium and evaporatcd to the crystallizatioii poirit wlien prismatic crystals of the charac-teristic form of acetatc of barium were obtained. A barium determination gave riumbers which agree with the formula c I€ BaO,. Alcohol of Sycocmyt. The preparation of this substaiwe has been already detailed. In order to render it prc it is orily necessary after it has been pre- cipitatcd from the solution of sodium-alcoliol to wash it well with watcr in order to rcniove dl traces of fixcd alkali ;then to crystal- lizc it a few timcs from warm alcohol.The crystals usually occur aggrcgatctl iii splicrical inasses like the miricral Wavellite ; they are vcry tliin aid have a great rcsernblancc to caffcine. In sevcral iiistiuices (luring the earlier stages of its purification or wllcii dilute alcoliol is employccl for its solution it was noticed that tlic suhstaiicc did iiot dcposit in crystals but the transparent liqitid coiigcalccl to a jelly. Tliis jelly however after some time became crystalliiic the crystallization commcncing in several points of the inass and cstending gradually throughout the whole ; ulti-mately a crystallization was obtaincd of the same appearance as occurs undcr othcr circumstances.In the dctcrminatioii of the rational formula of this substance DE LA BUE AND MULISB ON we took cognizance of the fact that beside acetic acid it waaJ the only other product obtained in the decompoeition of the origid compound which we have deuominated acetate of sycoceryl and the analysis of which led to the empirical formula C, H,60. From the nature of this compound we inferred that it contained the radical of acetic acid in a state similar to that in which it exieta in acetic ether; that in fact we had to deal with a compound containing acetic wid miniia one atom of hydrogen and a radical. According to this view the empirical formula C, H160 would have to be doubled whereby we obtain Cm Hm Oa and if we now deduct the elementst of acetic acid minus hydrogen .) = C H 0 we have c, H,, for the radical of our new alcohol whose formula would come- quently be C, H,,O.The analysis of the supposed alcohol obtained from acetate of sycocerpl gave results which support this view. Accordirig to the formula C,,H, 0 the new alcohol would be homologous with benzylic alcohol obtained from ''oil of bitter aimonds." Alcohol of sycoceryl is perfectly insoluble in water the fixed alkalies aud ammonia ; but alcohol especially when warm ale0 ether benzol chloroform and naphtha are good solvents for it. At a temperature of about 90"C. (194"Fahr.) sycocerylic alco- hol melts to a liquid heavier than water and solidifies on cooling to a crystalline mass especially if any fragments of crystals have remained unfnsed because they hecome the foci of a new crystal- lization.When however the heat is increased only a little beyond the fusion point it remains perfectly transparent and amorphous. By contact with alcohol this glassy condition is changed to the normal crystalline structure. When it is heated considerably above its melting-point a portion distils unchanged and a hrownish residue is left in the retort. Potassium brought in contact with this substance when in a state of fusion disengages hydrogen and hecorncs covered with a white crust; but when heat is applied in order to fuse tbe so-formed potassium-compound of the sycocerylic alcohol the reaction becomes so violent that the mass blackens and even catches fire.THE RESIN OF FICUS RCBTGTN0S.l. Heated with hydrate of potash above the melting-point of the latter it evolves hydrogen and decomposes; it appears that this reaction does not stop with the probable formation of an acid which unites with the potash but goes further; for in the product of this reaction me did not find the expected acid; but it is our intention to pursue this subject if ever we are so fortunate as to procure a larger supply of material. Concentrated sul phuric acid easily dissolves sycocerylic alcohol with evolution of heat forming a brown liquid which remains un- altered for some time. The liquid yields c?n addition of water 8 resinous viscid substance which melts at the temperature of boil- ing water and is but very sparingly soluble in alcohol.Ether and chloroform dissolve it with facility and on evaporating merely leave the resinous product in its original amorphous state. The aqueous liquor saturated with carbonate of barium gave no indi- cations of the presence of a conjugated sulphuric acid. Chlorine bromine and iodine act readily on sycocerFlic alcohol if solutions of these reagents are used crystalline compounds are formed. The iodine-compound is of a yellow colour. Action of Chloride of Phosphorus on Sycocerylk Alcohol. For the purpose of preparing the chloride of sycoceryl me em- ployed pentachloride of phosphorus and a solution of sycocer-ylic alcohol in benzol.At common temperatures no reaction took place but when the temperature mas raised to about 60" C. (140" Fahr.) hydrochloric acid mas given off and the pentachloride gradually di3appeared. After the disengagement of' hydrochloric acid had ceased the liquid was removed from the remaining penta- chloride and washed with water aud afterwards with an alkaline solution. After tlie benzol had been got rid of by keeping the liquid for some time in a warm place a viscid residue was obtained which was soluble with great difficulty in alcohol but easily soluble in ether or chloroform. These solutions after evaporation depo-sited this substance again in its original sticky state. In the first experiments which were carried out only on a very small scale a crystalline substance mas formed besides the amorphous greenish compound.This crystalline substance differed in its properties from the original alcohol. It therefore seems probable that a slight excess of pentachloride (or the phosphoric acid formed during the reaction) destroys to a great extent the chloride of sycoceryl formed during the reaction ; or at all events phosphate 74 DE LA RUE AND MULLER ON of sycoceryl which is produced simultaneously and predominates cannot be separated from the chloride. We are therefore at pre- sent unable to give a description of the chloride of sycoceryl in its pure state. Benzoate of Sycoceryl. Chloride of benzoyl dissolves with the greatest facility a large quantity of sycocerylic alcohol at common temperatures but no hydrochloric acid is disengaged j probably therefore no reaction takes place at ordinary temperatures but if heat is applied the liquid soon commences to give off hydrochloric acid.When the evolution of hydrochloric acid has ceased the mixture is allowed to ~001 when it solidifies to a fibrous crystalline mass. Any excess of chloride of benzoyl is removed after the reaction by throwing the mixture into a solution of bicarbonate of potassium whereby a resinous mass separatcs. The whole being kept warm for several hours all the chloride of benzoyl is decomposed. During this process a slight smell somewhat like benzoate of ethyl is percep-tible. The resinous mass after removal from the saline liquors is washed several times with warm water ;it is now free from ben- zoic acid and chloride of benzoyl.On boiling the resinous mass with absolute alcohul a trace of a yellowish secondary product dissolves leaving the principal quantity undissolved which then appears as a white crystalline mass. When the product thus obtained is boiled with a large quantity of ether and the solution allowed to cool small crystals are. depo- sited which are soluble with difficulty in ether. Absolute alcohol dissolves only a trace of this substance and when boiled with it deposits the dissolved part on cooling in minute spherical aggre- gations of crystals which under the microscope are seen to be prismatic. The best solvent for this cotnpound is banzol it being soluble in all proportions in this liquid.On evaporating the solution the substancc is left behind in fine prismakic crystals. Chloroform behaves like benzol but the crystals obtained from this solvent are much finer and can be obtained of considerable size. In order to ascertain the nature of the compound produced by the action of chloride of benzoyl on sycocerylic alcohol we decom- posed it by means of sodium-alcohol which we found to be pre- ferable to any other form of caustic alkali. Even with this reagent the decomposition is effected only with dificulty possibly 011 account of the new substance being only sparingly soluble and THE RESIN OF FICUS BUBIGlNOdh. also 011 account of the resulting bnzoate of sodiuin not being much more soluble in the alcohol.IIowcver after boiling for some timc the bcitzoate of sycoceryl disappcaru. On additiou of water a bulky su1)staiice was sepmtltcd which provcd to hc tlic rcgcncratcd alcohol of sycoceryl. Thc aqueous liquid saturatctl with an acid sooii formed a crystal-liiic yrcciyitate which 0x1 removal with ether proved to be benzoic acid. Tlic foregoiug experimciits bear couclusive evidciice that thc alcohol of sycoccry1 behaves towarch chloride of berizoyl iii a manner perfectly analogous to that of other members of the alco- holic group producing that is to say a bcrizoatc of the ether- radicle. After haviiig sliown that the substancc separated li,~sodium-alcoliol may bc rcgardcd as the alcohol of the ncw radiclc sycoccryl it became dcsiralile to have a syntlietic proof of this tlicory; and it occurred to us tliat if we could succecd iu combiriitig the spco-ccrylic alcoliol again with tlie racliclc of acetic acid ad thus repro- ducc tlic origiiial substancc wliicli wc haw cnllcd acctate of syco-ccryl it would be the licst possihlc coiifirinatioii of our views.1x1 ordcr to test this we accordiiigly brought chloride of acetyl in contact with sycoccrylic alcoliol. At ordinary temperatures no action took placc ; but wlicii a littlc llciit was applied tlic alcoliol was dissolved arid the liquid coilirnciicctl to boil giving off copious fumes of hgdrocliloric acid. Aftcr tlic rciictioti liad ccascd heat was agaiu applied aiid tlic wliolc subjectctl to tlic boiling tcmpcra- tiire for soine time iu ordcr to gct rid of tlic excess of cliloridc cf acetyl.After cooliiig the resiil ting protluct was lioilctl with water alicn a heavy oily hody scpnratcd. The boiling with wtitcr was continucd for sonic timc uiitil at last thc oily liyiiid hcciinle per-fectly solid arid bcautifully crystalliiic iiidictitiitg at once that a siil~tance had been forni(v1 diffcriiig fi*oni t lic origi~ial alcollo] I\ liich it will IIC rcnicmbcrcd is fluid at thc tcnipcrnturc of boiliiig \vater. This white crystullinc substancc wits now tlissoliwl iii boilirig nl- cohol of wliicli it rcqiiirccl a considcrahle quantity rwl su1)scquciltly allowcd to cool. TVlicn almost tlic wl~olc1i:id clissolvecl a srnzlll quantity of a compouid was left beliiiid wliicli at last nicltctl being evidently a I~CWsubsta~icc tlic pro1)al)Ie protlilct of the actiori of a small quantity of os~cliloridc or pliosyliorus wliicli contanii- riated the chloridc of acetgl.1113 LA HUE AND MULLEU ON On cooling tlic filtcrcd liqnid bcpn to crystallize yielding bcautiful iridcscciit flat 1)risniiLtic crystals wliicli sparklad with the colours of tlic rainbow in tlic solution likc cliloratc of potash in the act of crptalliziiig. The crpcidlizcd suhtaiicc lwohccd iu tliiu cxpcrimcnt proved to bc in cvcry rcspcct identical with tlic iiatural acetatc of sycoccryl aid thiis pvc tlic most dircct confir- mation to our tlieorctical yicws. Haviug tiins cstilbli~licd tlic iiatiirc of the sycoccrylic :dcoliol it becamc dcsirnble to prodiice also tlic acid wliich moiild be homo-logous with benzoic acid ;ind woiilrl bcar to this acid a rclatioii similar to that wliich pahitic acid bcars to tlic lowcr mcmbcra of tlic series to 17-hicli it liclongs.A sniall quaiitity of tlic alcohol was tlicreforc boiled fbr ilhtit six lioiirs with dilutc nitric acid. A fccble rcrrctioii was iiidicrrtccl by tlic diglit evolution of nitrous fwncs aud aftcr SOXIIC tinic tlic sycoccrylic alcohol becamc.of a dark ycllow coloiw niid prcsciitcd a rcsiiious aspcct. At'tcr digest- iug for sin hours t-lic rcsiiious procliict was rcmoved waslicd with watcr and tiricd. This substuiicc was rcadily soluble in warm al-~01101 and oii cooling a white crrstalliiie substaucc was depositcd. This crystalliiie sul)stil11ce had all the cliamctcrs of an acid; it wiis perfectly soluhle in ail nqucoiis solatioii of potash or ammonia aud gave with an alcoholic solution of acetatc of lead a copious prc- cipitnte.Altlioiigli this rcactioii sliowcd that ivc had olitaiiicd aii acid wliich posscsscs all tlic propcrties that niiglit be anticipated of an acid corresyoiiding to oiir alcohol we could not with the wry siiiall quantity of substance at our disposal get ciiough of it in a pure state for analysis on accoiiiit of the ycllow nitro-conipound (iil)l)arc11tly the iiitro-acid of the ncw acid) arlhcriiig wiili great obstinacy to it md acconipaiiyiiig it in all its compouiids and solu-tions. ln ordcr to exclude tlic formation of this sccoudary product we tried tlie action of chromic acid ofi sgcoccrrlic alcahol; n smid1 quantity of tlie alcohol was boilcd with a moderatcly concentrated soiution of cliromic acid for about eight hours.The product so obtoiiicd was washed aid boiled with a clilute solution of potash but aftcr saturating this alkaline solution with an acid 110 prccipi.. tate was foriucd mid it was altogetlicr inipossiblc to clctcct any acid tliercforc wc must conclude that this acid was not formed by this treatment. On oiie occaaioii on repcating this experimciit we accidcntally ob-served among the products of tlie action of chromic acid on syco-cerylic alcohol a crystalline body j on trcating tlic mass with dilute THE REBIN OF FICUS EUBIOINOSA. alcohol this product was procured in large flat priiains resembling somcwhat in appcarance the acetate of sycocerpl but differing in its melting-point arid was perfectly ncntral.From the mode of formation it might I3c inferred that we had obtairicd the aldehyde (C18 H2RO) corresponding to our alcohol hut the minuteness of the quantity procmd rendered it impossible to decide this point; For the prcsetit we must contcrit ourselves with the foregoing account of tlie compounds of thc radiclc sycocoryl the very emall amount of the substatice at our disposal bcing barely sufficient for the performance of tliose exppiments which we have described. The grcat ititcrcst wliich naturally attaches to this new homo-lope of thc bciizyl-alcohol scrics will be a sufficient inducement for us to take up this suhjcct again for the purpose of studying its tlerivativcs should we be so fortuuate as,to obtain a further supply of raw material.On rcvicwing tlic members of which Cannizzaro's benzylic alcohol is the type arid with which our ~icwalcohol must be classed it will bc perccivcd that -tlierc are still niaiiy gq)s to be tilled up in their series. Bciizylic alcohol . c71r8 o Cumiiiylic alcoliol > uuknown. Sycoccrylic alcohol . Oil comparing tlie properties of our sycocerylic alcohol with those of benzylic alcoliol wry little rcscnihlaricc will at first be traceable between them ; but whi it is rcmcxntcred that thcre are not fewer than teri stcps bctwceii bcnzglic auil sycoccrylic alcohol this dif-fereiicc of piwpertics is easily accounted for ; more particularly if we takc into consideration a siniilar case in aiiotlier iiomologms wries the liiiks uf wliich are murc fully kiiowri.The change in thc properties of tlie acetic acid scries for examplc by each in-crcmeut of increase of C €I2 is quite as remarkable; and when we BENCE JONES ON CBYSTALLIZED XANTXIN compare acetic acid on the one hand with palmitic acid on the other the dissimilarity is not leas remarkable than if we compare sycocerylic alcohol C18H, 0 with benzylic alcohol C H 0. In conclusion we may mention that benzylic alcohol aud cow-quently also cuminylic alcohol are generally considered to be homologues of phenyl-alcohol (carbolic acid) ; cresyl-alcohol would be ivomeric with benzyl-alcohol and carvacrol and thymol with cuminylic alcohol.On comparing these substances we find that this view is not tenable and that there exist in reality at least two distinct series of isomeric compounds the types of which are ben-cylic alcohol on the one haud and phenylic alcohol on the other. The crystalline substance which adhered to the acetate of syco-ceryl and which it will be recollected was left in part undissolved when the acetate was dissolved out with ether can be obtained in only very small crystals. It is perfectly neutral and we did not succeed in obtaining any derivative from it calculated to throw light on its true nature. The quantity was indeed extremely small and we therefore content ourselves with giving the results of the ultimate analysis of this substance which was found to contain 75.56 per cent.carbon and 12.30per cent. hydrogen.