34 ABSTRACTS OF CHEMICAL PAPERS.Organic Chemistry.Reactions of the Halogen-compounds of Olefines. 13yELTEKOFF (Deut. Chem. Ges. Ber., 11, 989-991) .-Recent experi-ments by the author have shown that the haloid compounds ofethylene, when heated with water and lead oxide, yield glycol andaldehyde ; whilst propylene chloride and bromide, under the samecircumstances, yield propyl glycol, acetone, and propaldehyde. Simi-larly isobutylene bromide yields isobutyl glycol and the corres-ponding aldehyde, and trimethylethylene bromide yields isopropyl-methyl ketone. From these results the author conclades that thefirst product of the action in every case is a glycol, which by elimina-tion of water is partially or entirely converted into aldehyde oracetone. J.R.A New Unsaturated Hexvalent Hydrocarbon, Diallylene,C,H,. By L. HENRY (Compt. rend., 87, 171--173).-The action ofPCI, on monallyl-acetone is energetic and regular a t ordinary tempera-tures, hydrochloric acid being abundantly disengaged. The product is amixture of allylmethylchloracetol, C3H5.CH2.CC1,.CH3, and mono-chlorodiallyl, C3H5.C3H4CI, resulting from the former by eliminationof HCI. The former is a colourless liquid, with a sharp smell andtaste, boiling a t 150" with partial decomposition. It is insoluble anddenser than water. The monochlorodiallyl, which constitntcs abont +thsof the product, is a colourless mobile liquid, lighter than and insolublein water, but soluble in alcohol and ether, and possessing a sharpsmell and tsste.Its sp. gr. a t 18.2" is -9197, and it boils a t 1.50"without decomposition. The vapour-density found is 4.15, calcu-lated 4.08. This body forms a tetrabromide, (C6H,C1Br4), which theauthor has not as yet solidified. It. disengages hydrochloric acid 'whentreated with sulphuric acid, forming probably a sulphate of acetonicalcohol. Heated with potash under pressure a t 100" i t yields ahydrocarbon of the formula C6H8.The author yegards monochlorordiallgl as a mixture of two isomericbodies :-(1). C3H5.CH2.CC1=CH2 ; and (2). C,H,.CH=CCl.CH,, re-sulting from allylic dimethyl chloracetol, C3H5.CH,.CCI2.CH3, by elimi-nation of HCl.According to the author the density of diallylene a t 18.2" is -8579 ;i t boils a t 70"; its vapour-density as found is 2.79, calculated 2.76.The author has not obtained the dibromide C,H,Br,, although thORGANIC CHEMISTRY.35tetrabromide is easily formed, and by further action of bromine con-verted into the hexabroruide ; both are viscous liquids. By the actionof ammonic cuprous chloride it yields a yellow precipitate, C6H,Cu +H,O, chara.cteristic of acetylene compounds, and with an alcoholicsolution of silver nitrate it gives a precipitate corresponding withCsH7Ag + C2H,(0H) ; with an aqueous solution it gives C6H,Ag +H,O. The author considers it probable that C,H8 contains two isomeridescorresponding with the formnlm-(a) CsH,.CH,.CECH.(6.) C,H,.C-C.CH,.corresponding to the two varieties of monochlorodiallyl above men-tioned. J. M. T.Action of Nitrous Acid on Unsaturated Hydrocarbons.ByP. TOKNIES (Deict. Chem, Ges. Ber., 11, 1511--1512).-When a con-centrated solution of potassium nitrite is poured into a glacial aceticacjd solution of furfurbutylene, the crystalline compound, C8HI0.NZO3,is obtained, which yields on reduction C8HloO(OH) (NH2). This bodyforms a platinum salt having the formula [CsHl0O(OH) (NH?)HCl],PtCI4.Phenylbutylene behaves in a similar way, forming CloH12, Nz03, and[CloH,,(OH) (NH,)HCl]J’tCl,.Styrol, tolylbutylene, anethol, and amylene also form crystallineaddition products with N203. w. c. w.Some Selenocyanates. By J. W. CLARKE (Deut. C’kem. Ges.Ber., 11, 1325-1326) .-Amongst the platinum thiocyanates thepotassium salt is the best known on account of its beauty and theease with which it may be obtained.It was thought of interest toprepare the corresponding selenocyanate, but some difficulty was ex-perienced in doing so. When alcoholic solutions of potassi~m seleno-cyanate and platinic chloride are mixed, a heavy red-brown precipitateis a t once formed, which becomes darker and partly dissolves on boil-ing. Crystals of the new salt separate out from the filtrate, mixed witha reddish selenium salt; these can be purilied by recrystallising fromalcohol, although they are rather easily decomposed. The crystals areordinarily small, but can be obtained as hexagonal tables, almost blackin reflected light, and dark garnet-red by transmitted light. Sp. gr.= 3.377 a t 10“ (weighed in benzene). Analysis gives numbers indi-cating the formula K2Pt(CSeN)+ The attempt to prepare gold com-pounds was only partially successful.When an alcoholic solution ofpotassium selenocyanate is mixed with neutral gold chloride, a red prc-cipitate falls, consisting mostly of pure selenium. On gradual evapo-ration, the orange-yellow filtrate deposits a crust of small, dark redprisms, which decompose so easily that only a small quantity was ob-tained, and this not pure. Analysis gave only approximate numbers,but sufficiently near to indicate that the salt was KAu(CSeN),,considering the impurity (metallic gold) present, for this salt wasd 31; ABSTRACTS OF CHEJIICAL PAPERS.prepared by a method precisely analogous to that bz which Cleveprepared his thiocyanste.The attempt to prepare a seleniocyanatesimilar to the potassiiim chromothiocpnate, K,Cr(CSN),,.8H20, ofRoeslar was unsuccessful. Aqueous solutions of chrome alum andpotassium selenocyanate mixed together gave rise only to a precipitateof seleuium. w. s.Alcohols in Potato Fusel-oil. By L. RARUTEAU (Camp!. ye11(7.,87, 501).-The following table shows the nature, boiling-point, andquantities of the products found in 1 litre of potato fusel-oil:-Boiling points. Quantities.Degrees. c. c.Tsopropjl alcoliol ...................... 8.3 150Propyl alcohol ........................ 97 30Ordinary but$ alcohol ................. 109 50Normal butyl alcohol .................. 106.9 65Methylpropyl carbinol .................. 120 60Ordinary amyl alcohol .................128-132 275Products boiling above 132", and retaining179Water - 12.3........................ amyl alcohol -................................Aldehyde, ethyl acetatc, and e t h j l alcohol - 75TrimethylcarbinoI also appears to be present. R. R.Etherification Of Primary Alcohols. By N. MENSCHUTKrN(Deut. Chem. Ges. Be?.., 11,1507-l~ll).-The author has repeated hisexperiments on the etherification of alcohols by acetic acid at. 154"(Ber., 11, 732), and finds that his former results were not quite cor-rect. He now obtains tlie following numbers for the (I) absolute,(TI) relative initial rate, and (111) limit of etherification.Methyl alcohol ....Ethyl . . . . . .Propyl . . . . . .Normal butyl . . . . . .Octyl . . .. . .Cetyl . . . . . .Isobntjl . . . . . .Ally1 . . . . . .Benzyl . . . . . .I.53.5346.95469246.8546.5944.3635.7238.64-IT.70.5270.1869-6164-4066.6660.12G3.96--TIT.69-5966-5766.8567.3072.3480.3967-3859.4160.75From these numbers i t is seen that all the primary normal saturatedalcohols, except methyl alcohol, have the same absolute initial rate ofetherification, but the absolute initial rate of isohutyl alcohol is lessthan that of the normal alcohols. The relative initial rate decreaseswith the increase in niolecular weight. The rate of et<herification ofthe unsaturated primary alcohols is less than that of the saturated.The limits of etherification increase with the molecular weight of thORG.WlC CHEMISTRY.37alcoliol (methyl alcohol forming a n exceptionj, but the limits arelower for tlie unsaturated than for the saturated alcohols. w. c. w.Amyl-compounds. By FLAwITzKY (Deut. Cliem. Ges. Ber., 11,!W.L).--The author has o'Jtained from ethylamyl oxide an amyl iodide,having tlie specific rotatory power + 0.07. This iodide yields apentylene which boils a t 'LO.?", has the sp. gr. 0.648 a t O", and is con-verted by oxidation witlh chromic acid into acetone, acetic acid, andanother acid, probably isobutyric. The corrcsponding g i p 1 boils at2Ol", and yields by oxidation acetone, traces of an a1deh-j-de, and acids,chiefly isobutvic.Flawitzky finds that diluted sulphui-ic acid (1 part of H,SC), and1 part of H20) is the best deliydrating agent for the gl-jcols.With it,trimethylethylene and isopropylethylcnc gljcols Field tlic same pro-clucts as with 1)hosphorus pentoxide or zinc chloride, but in muchlarger quantities. J. R.Oxidation Products of Diethyl Sulphide and AnalogousCompounds. By E:. 0. BEChalAxS ( J . pr. Chem [a], 17, 439-4i7).- 'l'lie author's iwearches have added the substance phenylefligl-sdphitZs to tlie list of sulphides of alcoholic radicles. This bodx is1)roduced by heating sodium phenrlmercaptide with three times its\\eight of ethyl iodide a t 120" iii sealed tubes : the new sulpliide boils; i t 204" (barometer = i43 S mm.), has a sp. gr. of 1.0315 a t lo", andIS a strongly refractive liquid with aii exceedingly disag yeeu'uleo lour.The me1 tiiig point of clil'.rol).2lfylsir711~~~~Z~, ( C,H9B),S0, is deter-mined to be G8.5', and not 41", as stated by Saytzeff aiid Grabowskyv(,iu?~uZen, 171, 235) : this substance is but slightly soluble in hotuater, while at the ordinary temperature 2 parts of water dissolve1 part of the sulphoxide.1 he author shows that sulphoxides, as also the corresponding su!-pliides, are generally oxidised to sulphories by the action of potassinriipermanganate ; sulphones have been thus produced from sulphidwcontaining one or two alcoholic radicles derived from primary orsccondary isoalcohols.The following new sulpliones have been ob-tained by the author's method :-Diisou?iz2/ZsuZ~l/o~ie (the action of nitricitcid upoii diisoamylsulphoxide, at nloderately high temperatures, resultsi r t the formation of isoarnplsulphonic acid), t Z i i s , ~ b u t y l s u ~ ~ I ~ ~ ~ ~ i e , i s o m l y l -etlrplsulpho~~e, tli;sl)~,,.o~lllszil1Jlronc, m e t h ~ l e t l i ! l l s i L l p l ~ ~ ~ ~ ~ , ~ ) ? i e ~ ~ ? j l ~ ~ t ~ ~ l 1' ho 11 e, and e t li e I 1 rd ie f h?j Zsa Zp I1 o TI c .T lie s u 1 plio i i e s are produced byheating an aqueous solution of the corresponding sulphides with i~slight excess of potassium permangnnate also in aqueous solufioii.Details of the purification of each suiphone are given in the originalpaper.Sulphones are stable bodies which may be distilled without decom-position; they are not reduced by the action of zinc and dilute sul-phuric acid or by hyclriodic acid ; neither arc they attacked by phospho-r u s pentachloride : sulphoxitles on the other hand, arc reduced by thereagents namcd, and are readily recmverted into sulphides by theaction of phospliorus pcntachloride.Former experimeiits which werer 38 ABSTRACTS OF CHEMICAL PAPERS.said to result in the prodnction of diethyl- and dimethyl-sulphide fromthe corresponding sulphones, by reduction, were certainly erroneous :the sulphones employzd probably contained traces of sulphoxides.Sulphides which contain acid radicles are energetically attackedby potassium permanganate, and are therefore not capable of takingup oxygen without molecular decomposition ; benzo?/lethylsulpkide, forinstance, is split up by permanganate into benzoic and ethylsulphonicacids. Saytzeff (Zeitschr. f.Chem., 1868, 642) has shown that thesesulphides are also decomposed by the action of nitric acid.In connection with this behaviour of acid sulphides, the authorexamined the action of barium dioxide upon thiscetic anhydride dis-solved in absolute ether. The action is an energetic one ; the productsare barium acetate, and acetyl persulphide ( C2H302)cS2.The author's investigations do not determine wit,h certainty whethersulphones do or do not form compounds with nitric acid.Sulphoxides containing only univalent radicles form somewhatunstable compounds with nitric acid, containing the elements of onemolecule of nitric acid combined with one molecule of sulphoxide.The following are the leading properties of the new sulphones pre-pared by the author.Diisou.ni~Z.sul~hone, ( C5Hl,6),SO2, crystalljses in groups of longneedles, which are unchanged in air, odourless, but possessed of asweetish yet burning taste.A t 31" the sulphone melts to a colour-less liquid, which boils a t 295" with very slight decomposition. Water,hot or cold, and aqueous solutions of alkalis, scarcely dissolve diiso-amylsulphone, but it is largely soluble in alcohol, ether, benzene,chloroform, and carbon bisulphide ; also in concentrated nitric, sul-phuric, and acetic acids, from which solvents it is reprecipitated byxddition of water.I)iisobutlJl.~SLlyhone, (C,H,B)?SO,, is a colourless syrupy liquid re-sembling glycerin, having a faint pleasant odour ; when surroundedwith a freezing mixture the sulphone solidifies to a crystalline massmelting at 17".The sp. gr. of the sulphone a t 18" is 1.0056 : theliquid boils at 265" without material decomposition. Hot water dissolvesbut small quantities of the sulphone, although it is soluble in two partsof water at ordinary temperatures : it is readily soluble in ether, andbehaves generally towards solvents similarly to diisoamylsulphone.SO2, is a thick, colonrless liquid with-out smell, which in a freezing mixture solidifies to a crystalline mass :the solid sulphone melts at 13*5", the liquid has a sp. gr. of 1.0515 a t18", and boils at 270". The action of solvents upoii this sulphone issimilar to their action, already described, upon diisoamyl, and diiso-butylsul phone.Diisopopy Zsulphnne, ( C,H,)2~SOz, forms colourless crystals withoutodour.It melts a t 36", forming a liquid which often remains for dayswithout solidifying. This snlphone is readily soluble in cold and inhot water, as also in alcohol, ether, benzene, chloroform and carbonbisulphide : concentrated nitric, sulphui*ic, or acetic acid likewisedissolves the sulphone, which is not reprecipitated by the addition ofw at e r .Isoanz~Zetl~ybulphone, c5H'1sC2& ORGANIC CHEMISTRY. 392l~et7~ytetlryZsu~7Lone, CH3 ] SO,, crys tallises in small brilliant C2H5needles which melt at 3rio-(th; liquid often remaining for days with-out solidifying). It is devoid of odour, and very soluble in water andin alcohol. This sulphone is scarcely soluble in cold ether or in car-bon bisulphide, but is dissolved in almost all proportions by benzene,chloroform, a d acids.Nitric acid very slowly attacks the sulphone,long continued heating in sealed tubes being necessary for the com-plete decomposition of the substance.Plienylethybu~hone, C6H5 } SO,, crystallises in thick colourlesstables, devoid of odour (m.p. 42"). The solubility of the sulphone isalmost the same a6 that exhibited by diisopropylsulphone ; it is how-ever reprecipitated by water from its solution in acids.SO2, is produced by the action ofpotassium permanganate upon diethyl sulphide at the ordinary tempera-ture; it crystallises in short, hard, colourless needles. It melts a t 136.5",and distils unchanged a t a higher temperature. This sulphone is solublein hot alcohol and water ; it is scarcely dissolved by ether, benzene,chloroform, or carbon bisulphide, but is readily soluble in concen-trated nitric and sulphuric acids, less so in hydrochloric acid, and withj e t greater difficulty in acetic acid : it is decomposed by warm solutionsof the alkalis.M. M. P. M.Glucoside of Buckthorn Berries and Rhamnodulcite. By C.LIEBERMANN and 0. HORMANN (Deut. Chew. Ges. Ber., 11, 952-958).-An examination by the authors of the glucoside extracted byalcohol from the berries of buckthorn (Rhamnus infectorius) has led tosome results differing from those arrived at by previous experimenters.The glucoside was first prepared pure by Gellatly, who called itzanthorhanznin, the name adopted by the authors.It is identical withSchutzenberger's a-rhamnegin. The properties of the substance, asdescribed by these chemists, agree with the observations of theauthors.When boiled withdilute sulphuric acid it readily breaks up into rhamnetin and sugar(rhamnodulcite), the former of which is deposited in tufts of lemon-yellow needles, agreeing in composition with Schutzenberger's formula,C12H1005.Rhamnodulcite the authors find to be (contrary to the observationsof Gellatly and Schutzenberger) a crystallisable sugar. It is solublein water and absolute alcohol, and crystallises from the latter in herni-liedral tables. The aqueous solution yields holohedral crystals, whichmelt a t 92-93". Dried in the air, the sugar has the formula CSH,,O6.When heated, it melts, and at 108' gives off 1 mol.of' water: theresidual C,H,,05 solidifies on cooling to a brittle glassy mass, theaqueous solution of which again yields crystalline sugar. Rhamno-dulcite is very sweet and agreeable in taste. It does not ferment withyeast. Its action on polarised light is dextro-rotatory. It reducesh'ehling's solution on warming. Xanthorhamnin yields about 57 perccnt. of the sugar.C2H5EthyZenedL'ethyZsu2;piLone, CzH4 (C2& )2 }Xanthorhamnin does not ferment with yeast.J. R40 ABSTRACTS OF CIIEMICAL PAPERS.Isodulcite. By L. BEREND (Dcut. Chem. Ges. Bw., 11, 1353-1355).-Liebermann and Hormann obtained a beautifully crystallisedsugar, by the decomposition of the glucoside of buckthorn berries(12lmm?zus kfectorius) with acids, which was strikingly like the isodul-cite prepared by Hlasiwetz and Pfaundler from quercitrin.On accountof certain discrepancies, however, in melting point, &c., they termedi t rhamnodnlcite. On re-examining the isvdulcite of quercitrin theauthor. found that the two sugars are identical. The quercitrin employedwas prepared according to the method of Zwengler and Dronke, aridthe isodulcite therefrom according to that of Hlasiwetz and Pfaundler.Melting points (93-94”) and crystalline forms of the isodulcite andrhamnodulcite were found to be the same. Hlasiwetz and I’faundlerfound the melting point to be 10.5”. The specific rotatory power inSoleil-Scheibler’s apparatus was [aIu = 8.04. The name rhamnodul-cite can thus be dispensed with.Liebermann also points out in afootnote that Schiitzenberger’s rhamnegin-sugitr is probably only im-piire isodulcite, in spite of the difference in its properties. JV. S.‘ l Mercurialine ”. (Methylamine). By E. ScHxIDrr (L;e/,ig’s AIL-? ( d e n , 193, 73--86).-I5. Reichardt has described (Jour. J: p v k t .C‘hern., 104, i4Ol) a, volatile allraloid “ mercurialine,” whicli he ob-tained from Mem(ria1is anwua and ilfercurialis pereniks, as having thesame composition as methylamine, but differing from it in being anoily colourless liquid a t the o r d i n q temperature, and in forming tinoxalate and sulphate whose cr.ystitllisiiig characters were riot i n accord-ance with those given by JVurtz for the corresponding salts of methyl-amine.The author has separated a large quantity of the alkaloid whichexists in JIercuriczZis annua, and has compared it with pure methyl-amine prepared from caffeine.The results proye that the two alka-loids and their corresponding salts are in every respect identical, andthat Reichardt’s “ mercurialine ” is none other than an aqueous solu-tion of methylamine. I t was also found that the oxalate and sulphateof methylamine do not bclis\.c ; r i tiic manner stated by Wurtz (Atznnh,76, 324), but that they are readily crj-stallisablc from water ; in fact,agreeing with the results obtained by Reichardt with the oxalate andsulphate of “ mercurialine.”“rimethylamine in small quantity was also obtained from Illei*curialiscmuua, and its presence there, together with a considerable quantity ofthe primary base induces the supposition that diniethy lamine mayalso be present.I n many plants which the author has examined, hehas found a small quantity of trimethylamine accompanying ammo-nium salts, but has met with no species of plants other than thoseabove mentioned, which contain methylamine, although no doubtmethylamine is not confilled to them. A. J . C.Trimethylcarbarnine. By W. RUDNEFF (Deut. Chein. Ges.Ber., 11, %%).--This body was first obtained by Butlerow as a bye-product in the preparation of trimethylacetic acid. According t o theauthor’s observations, it, boils a t 45”. Its hydrochloride, CaH9NH2.HC1,crj-stallises from alcohol in small lamine. Its platinum salt forms ORGAXIC CHEMISTRY.41yellow crystalline powder. The amine combines with carbon bisul-phide to form the compound CS(NHC4N,) (SNH,C,H,), from which, b yz e a n s of mercuric chloride, tertiary butylthiocarbimide, C( CH:,j3N.CS,is obtained. This last boils a t 142", melts a t 10.5", and has an agree-able aromatic odour. J . R.Sulphuretted Dicyanodiamine. By B. RATHKE (Deut. Clzem.Ges. Ber., 11, 962--967).-The author has obtained a body to whichhe assigns the constitutional formula, NH,.CS.NH.C( NH)NH2, by theaction of thiocarbonyl chloride or phosphorus pentachloride on thio-carbamide. The reaction with phosphorus pentachlo ride is representedThe new product is a base forming transparent monoclinic crystals,which dissolve in water and sparingly in alcohol, and yield a stronglyalkaline solution.When heated above loo", it melts and is com-pletely transformed into the isomeric guanidine thiocyanate.The i ~ y d r o c l ~ l o ~ i ~ l e , C2H6N,S.H C1, forms fine transparent rhombiccrystals, which dissolve freely in water and alcohol. With platinicchloride it gives an amorphous dark-coloured precipitate. Tlie o.ca,Zate,C2H6N,S.C2H,0, -t +HLO, forms small granular crgst,als, sparinglysoluble in water. Both salts have an acid reaction.thus: 3CS(NH,), + PC1, = C?SN,H,.HCl + CS(NH,)?.HCl+ PSCI?.J. R.Butylchloral Hydrocyanide. By A. PIKNER and F. KLEIN(Deut. Chenz. G'es. Bey., 11, 1488-1499 j .-Butylchloral hydrocyanideprepsred by digesting butylchloral hydrate with aqueous hydrocyanicacid a t 100" for several days, forms crystalline plates which dissolvereadily in alcohol and in ether, sparingly in water and in benzene, butare insoluble in petroleum ether.This substance melts a t 101-102",and boils with decomposition a t 230".Action of Amrnomk-When ammonia gas is passed into a solutionof butylchloral hydrocyanide in absolute alcohol, ammonium chloride,ammonium cyanate and monochlorocrotonamide (m. p. 112") areformed, C,H5Cl3(0H)CN + INH, = C,H,ClO.NH, + 2NH,CZ +NH,CN.A good yield of chlorocrotonamide can be obtained by gently heat-ing a mixture of dry butylchloral hydrocyanide and ammonium carbo-nate in a sulphuric acid bath, until hydrocyanic acid is no longerevolved, and extracting the residue with ether.No crystalline compound is formed by the actioii of aniline on theh y d rocy anid e.Monochlorocrotouzyl carbamide, CO( NHE,)NH.C4H,C10, is obtained byheating a mixture of butylchloral hydrocyanide with urea at 105-110", until all the hydrocyanic acid is evolved, the residue being thentreated with alcohol, and tJhe ammonium chloride washed away bywater.With acetyl chloride, butylchloral hydrocyanide forms the com-pound C4H5CI3(OC,H3O)CN. It is a yellow oil, boiling with decom-position between 240" and 250".When a solution of the hydrocyanide in concentrated sulphuric acidis poured into water, tricTLloroxyvcLleramide or tril;hlorou~lerolactamide,C~H5Cl,(OH)C0.NH2 (m.p. l l 9 O ) crjstallises out. It is very solubleThis carbamide melts wit8h decomposition at 216"42 ABSTRACTS OF CHEMICAL PAPERS.in alcohol and ether, and sparingly soluble in benzme and in 1vate.r.The hydrochloride is precipitated from the alcoholic solution of theamide by gaseous hydrochloric acid.The amide prepared from acetyl-butylchloral cyanide melts at 96",and is probably a physical isomeride of the preceding compound.A mixture of trichloroxyvaleramide, and trichlor-oxyvalerimido-etheris formed by passing hydrochloric acid into an alcoholic solution ofbutylchloral hydrocyanide.Tric7~lorobz~t~Zide?zi~~tide, C4H5C13NH, obtained by heating a mixtureof dry ammonium acetate with butylctilornl hydrocyanide, and pour-ing the product into water, is a crystalline body, which melts at 164-165", and decomposes on exposure to the light, or when heated to 192".If is sparingly soluble in cold water and in cold benzene, but dissolvesreadily in alcohol, ether, glwcial acetic acid, in hot water and in hotbenzene.Trichloroxyvnleric or T?.icliZorvalel.olnctic; acid, C5HiC1303, describedby Pinner and Bischoff, forms the following salts: C,H,NaCI,O, +H20, loses its water of crystallisaLioa a t 100".The ammonium saltforms small granular crystals, and the lead salt is an amorphous pre-cipitate. The acetyl compound, C4H5Cl,(OC2H30jCOOH + H20,which crystallisps in white needles (m. p, 84"), is prepared by digest-ing the acid with acetic anhydride and pouring the product into coldwater. It is insoluble in cold water, and is slowly decomposed byboiling with water. The anhydrous compound forms a thick uncrys-tallisable syrup.Ethyl trichloroxllvcclerate, C5H6C1303.~2H5, forms long prismatic crys-tals, which melt at 40" and boil a t 255".If this ether is dissolved inalcoholic ammonia, and the solution left a t rest for several weeks, awhite crystalline crust is formed, which consists of a mixture ofammonium chloride and the amide of ~no~zochZorinaidoa~ayeZic acid,C5H,C1N,0. The amide is soluble in hot benzene, and is reprecipitatedby the addition of light petroleum to this solution. I t melts at 118"with decomposition. Platinum chloride and silver nitrate produceprecipitates in the aqueous solution. The ketone of monocldorangelac-tamide is obtained on evaporating the alcoholic solution of the smideof monochlorimidangelic acid, C5H7C1N20 + H20 = C5H6C1NO2 + NH,.When this body is heated, it decomposes without melting.Mo~~o~hZorn~zgelnctic acid, C5H7 ClO,, prepared by the reductionof trichlor-oxyvalerianic acid (Ber., 7, 589) forms the followingsalts : ( C5H,C10,),Zn, anhydrous crystals, very soluble in water ;(C5H6Clo3)2Cu, pale bliie powder insoluble in water and in alcohol:C5H9C103.Ag, deposited from a hot aqueous solution in pearly needles,is decomposed by boiling with excess of silver oxide, forming mono-chlorocrotonaldehyde or monochlorocrotonic acid.Ethyl monochlorange~actnte, C&I,C~O~.C2H5, is a heavy oil, boilingwith decomposition at 230", and is slowly decomposed by water. Theisobutyb ether boils a t 235-240', and is not decomposed by water atthe ordinary temperature.Monochloro-dibrom-oxyvaleric acid, C5H7C1Br203, is prepared by add-ing bromine to a solution of monochlorangelactic acid ia glaciaORGANIC CHEMISTRY.43acetic acid. It is soluble in ether, insoluble in benzene, and melts a t169".DichZorangeZic acid, C,H,CI,O,, is formed when t,he crude product ofthe action of phosphorus pentachloride on monochlorangehctic acid ispoured into water. It is an oily liquid, which does not form additionuroducts with bromine.MonocldorangeZic acid, C5H, ClO?, probably CH3. C ClZC H. C H?.COOH.The ether G f this acid is prepared by the action of zinc and hydro-chloric acid on the alcoholic solution of dichlorangelic acid. The freeacid obtained by saponifying the ether melts a t 103", and is soluble inhot benzene.w. c. w.Chloralide and its Derivatives. By 0. WALLACH (Liebig'sAnnalen, 193, 1-61> .-This paper consists of an historical sum-mary of the work of other chemists on chloralide, and contains also arecapitulation of the author's investigations on the subject, of whichabstracts have already appeared in this Journal.The Acids of Wood-vinegar and their connection with theso-called Wood-oils. By C. KRXMER and M. GRODZKI (Deuf.Chmz. Ges. Bey., 11, 1356--1362).-1n a previous paper on crudewood-spirit (ibid., 9, 1920), the authors indicated the possibility thatthe intermediate bodies corresponding with xylene and cymene couldbe obtained by condensation of aldehyde and acetone (methyl-ethplketone).The first opinion-that only saturated acids took part in the formx-tion of these bodies-was found untenable, and the authors weregradually led to assume that unsaturated acids must also be present inthe mother-substances, a supposition confirmed by experiment.Ander-son found that salts could be obtained from the acid fractions of wood-vinegar boiling up to above 160", which certain1.y contained propionicand bntyric acids, and probably valerianic acid ; but he did not isolatethe pure acids. The authors therefore examined certain liquors fromthe works of Kahlbaum, in Berlin, which had been obtained in thepreparation of sodium acetate or calcium acetate from wood-vinegar,and laid aside as refusing to crystallisefurther. After the greater partof the sodium acetate had been removed, the mother-liquors yielded anoil on addition of sulphuric acid, from which the following acids wcreobtained in the pure state and in considerable quantities :-A.J. C.Experiments in this direction failed.'Suturuted : Formic, acetic, propionic, bu tyric, and valeric acids.Unsaturated : Crotonic and angelic acids.The latter, however, has been recognised only by examination of itssalts.Both crotonic and isocrotonic acids were found to be present, andtheir occurrence is explained by considering them as formed by thesplitting off of two hydrogen-atoms from the normal butyric acid,CH3.CHI,.CH,.COOH, which first furnishes the unstable isocrotonicacid, CHz~CH.CH2.COOH, which becomes converted into the stablecrotonic acid, CH,.CH=CH.COOH.For this reason the occurrenc41 ABSTRACTS O F CHEMICAL PAPERS.of meth-j-1-acrylic acid, CH,=C(CH,) .COOH, would be excluded, andiiideed not a trace could be detected.1 he well-crystallising calcium salt of angelic acicl was found to havethe composition of tlie known one, (C5H802)2C:> + 2H,O. The silversalt of the acid was also obtained, and gave sufficiently good numbersfor angelic acid. It differs considerably, however, in several respects,both in behaviour and properties, from the two angelic acids known.Thus the two latter are solid, and melt a t 45' ancl 62', but this, theformer, remained fluid. Fittig has observed that by heating, thelower meltiiig acid passes over into the higher melting one, and thatthere is an intermediate stage a t which the acid remains fluid.The authors, however, did not redise this in their case.Even onheating for a clay t h e acid failed to pass from the liquid t o the solidmodification. Also on treating with bromine, a remarkable differenceis noticed. Whilst angelic acid gives a solid crystalline dibrorno-com-pound with 1 mol. of bromine, tile acid obtained by the authors re-mained liquid. Towards a l l ~ ~ . l i , hQwever, the latter brominated acidbehaves exactly like the dibromangelic acid, viz., it loses CO, andleaves behind an oil, which to all appearance is identical with crotonylbromide. Alhough i t is possible that the presence of some impurity mayoccasion the above differences, yet it is quite possible also that the acidin question may he a t,liird angelic acid analogous to isocrotonic acid.This demonstration of the occurrence of normal acids and the corre-sponding unsaturated acids iii the complex process of the splitting upof the cellulose molecule by dry distillation is interesting in severalways.Whilst in the butyric acid fermentation, only those fatty acidsare formed that have even numbers of carbon-atoms (raleric and pro-pionic acids nL)t being produced), in t h i s case the fatty acids with evenand those also with odd numbers of carbon-atoms appear, just as inalcoholic fermentation, in which, however, tlie alcohols correspondingwith these higher acids belong, not to the normal, but to the iso-series.Starting then from the same cellulose molecnle on the one handand the same sugar molecule on the other, three different kinds ofdecomposition occur :-I.By A l c o l ~ d i c ~er~~~entation.-Alcohols with even and odd numbersof carbon-atoms arise, i e . , besides ethyl and prop91 z~lcohols, also iso-butvl and isoamyl alcohols.11. By Butyric Acid ~~e,.)?zentutio,i.-Besides acetic acid, normalbutyric acid and normal caproic acid are formed, i.e., acids with evennumbers of carbon-at,oms.111. L'y Dry DistlZZation.-Acids with even and odd numbers ofcarbon-atoms : besides acetic acid, propionic, normal butyric, aiitlnormal vsleric acids were found.I n No. 111 a method of complete separation by fractional distillationwas found wholly impossible, so heterogeueous is the mixt'ure ofbodies, ancl so many boii at about the same temperature. There arethe saturated and unsaturated acids, together with bodies taken upfrom that portion of the distillate known as the " wood-oils,)) ketonesof the fatty and of the oleic scries, as well as mixed ketones of bothgroups, and also condensation-compounds, all probably present to-r igether.IV. sORGANIC CHEMISTRY. 45Angelic Acids of Different Origin. By W. V. l l I r , L m (DeJit.Chet17. Ges. Bey., 11, 1526--1,728).-By oxidising fermentation vnlc-rianic acid with potassium perriianpnate, Neubauer (A1~?iaZm, 106,63) obtained carbon dioxide, oxalic, acetic, and butyric acids, andangelic acid (m. p. 69.5-i0"), which solidified in the condenser OILdistilling the product of oxidation with sulphuric acid.A hydroxy-mid is first formed, which on distillation with sulphuric acid loseswater and forms angelic acid. This acid can be isolated, if care istaken to avoid adding an excess of sulphuric acid to the oxidation-product, and the mixture is distilled with steam. Zlydroxyialeric acidis an oily liquid, which solidifies after remaining in 'ccIc?io many daysover sulphuric acid. It is neither identical with Rohrbeck's a-methyl-15'-oxybutyric acid (ihid., 188, 229), nor with tlie a-methyl-a-oxr-butyric acid of Frankland and Duppa (ihid., 136, 9), both of whichyield a-methylcrotonic acid on dry distillation.Neubauer's acid differs from z-methylcrotonic acid in melting pointand in its barium salt. Neubauer's barium salt contains two mole-cules of water, and crystallises in the monosymmetrical system,whereas barium methyl-crotonate crystallises with four molecules ofwater in the asymmetrical system.w. c. w.Monosulpholactic Acid. By C. BOTTINGER (Dezct. Chew. Ges.Bey., 11, 1561) .-The monosulpholactic acids from pyroracemic acidand from a-chloropropionic acid are identical. Schacht's acid (Annn-l e n , 129, 1) from a-chloropropionic acid was impure : hence the appa-rent difference between the acid from the two sources. w. c. w.Synthesis of Pyroracemic Acid. By L. CLAISEN and J. SHAD-WELL (Deut. Chem. Ges. Ber., 11, 1563--1568).-The authors haveaccomplished the synthesis of pyroracemic acid by means of acetylcyanide, and have thus proved the correctness of Wichelhaus'sassumption that this acid is identical with acetyl-formic acid.When acetyl cyanide prepared by Hiibner's process (Anwrrlen, 120,334) is mixed with the theoretical quantity of hydrochloric acid,sp.gr. 1.20, acetjlformamidc separates out: C,H,O.CN + H,O =C,H,O.CO.NH,. (In this operation an excess of acid is to be avoided,and the mixture must be well cooled.) The formamide is soluble inwater, ether, alcohol, chloroform, and in benzcne. The alcoholic solu-tion deposits transparent prisms or plates, which melt a t 12&125",and begin to sublime a t lOO", forming crystals resembling benzoicacid.The amide is converted into pyroracemic acid by the action of aslight excess of dilute hydrochloric acid a t 100" : C2H,0.C0.NH2 +HCl + HZO = C2H30.COOH. + NH4Cl.The acid was identifiedby conversion into uvitic and dibromo-pyroracemic acids, and intoBy C. BoT'rIxGER (Dezct. C'hem. Ges. Be?-., 11, 135.2-1.3j3).-P?/yofa~.ta,.~~mid.-When a mixture of p j rotartaric acid and phosphorus ppntn-sulphide is distilled in small retorts, an oil is obtained coiitai;~;~ gpentabromacetone. w. c. w.Action of Phosphorus Pentasulphide on Organic Acids46 ABSTRACTS OF CHENICAL PAPERS.suspended sulphur. It is insoluble in cold water, smells slightly ofhydrogen sulphide. On long digestion with hot water it dissolves,and small quantities of hydrogen sulphide escape. The solution oncooling deposits pyrotartaric acid in yellow crystals, to which traces ofa sulphurised body adhere ; 26 grams of pyrotartaric acid furnished18-7 grams crude pyrotartaric anhydride.Pyroracemic acid.-Only a small amount of dccornposition, and smallyield of sulphurised substance.80 grams of pyroracemic acid fur-nished 27 grams of distillate. This could be separated, by fractiona-ting, into acetic acid, pyroracemic acid, and a high-boiling sulphurisedbody. With the acetic acid and the pyroracemic acid, there is also Rsmall quantity of a sulphurised body. The sulphurised body wasa red neutral oil.Lactic Acid.-This acid decomposes almost completely, on distilla-tion with phosphorus pentasulphide, into gaseous and partially sulphu-rised products. The fluid distillate is very small, and contains an oilysulphurised body. The latter was dissolved in alcohol and the solutionplaced in the exsiccator.Besides the alcohol, some volatile sulphurcompounds escaped, communicating to the sulphuric acid an intensered coloration.Action of Zinc-methyl on the Bromides of MonobrominatedAcid Radicles of the a-Series. By M. KASCIIIRSKY (Dew!. Chem.Ges. Ber., 11, 984-987).-Zinc-methyl reacts with a-bromopropionicbromide to form a hexyl alcohol boiling at 118--119", and solidifyingbelow 2.5". The chloride derived from this alcohol boils a t about 112",and solidifies at -2". The iodide boils at about 140", and solidifies a t-3". The corresponding hexylene distils between 72" and 74", andforms with bromine a solid compound melting at 169". By oxidationthe alcohol yields acetone and acetic acid. From these facts theauthor infers that the alcohol is dimethyl-isopropyl carbinol.The product of the action of zinc-methyl on a-bromisobutyric bromideis pen tamet hyle thol.Norms1 a-bromohutyric bromide reacts with zinc-methyl to form :Lheptyl alcohol boiling at 138-140", and remaining liquid a t -30".The corresponding chloride boils a t 135-138", and the iodide a t 145-147".The heptylene derived from the alcohol boils a t 92-95', andforms a liquid compound with bromine. By oxidation, the alcoholTields acetone and acetic acid. The author concludes, therefore,that the alcohol is either dimethyl-butyl carbinol or methyl-ethyl-isopropyl carbinol. J. IL.Conversion of Nitrils into Imides. By A. PINNER andF. KLEIN (Deut. Chem. Ges. Ber., 11, 1475--1487).-Action of Hydro-chloric Acid and Alcohol on Eydrocyanic Acid.-When gaseous hydro-chloric acid is passed into a well cooled solution of hydrocyanic acidin absolute alcohol, a series of explosions takes place, ammoniumchloride separates out, and the solution contains a mixture of ethylformate, ethyl chloride, diethyl - glyoxylamide, and ethylic diethyl-glyoxylate.Eth,yZcliethyl ic gZyoxy ltr te, CH( 0 C2H,)2.COOC2H5, boils a t 195-196",The neutral residue was a red mobile oily body.w. sORGANIC CHEMISTRY. 47and is lighter than water. When treated with ammonia, it yieldslarge tabular crystals of d i e t h ~ l - ~ I ~ o x y Z u n t i d e (m. p. 81-82O) and ethylalcohol, C8HI9O4 + NH3 = C6H13N03 + C2H60. If isobutyl alco-hol is substituted for ethyl alcohol in the preceding experiment, nmixture of isobutyl chloride, ammonium chloride, and isobutylicdi-isobutyl-glyoxylate is formed.IsobutyZic di-isobutyl-glyoxylate, CH(OC4Hg),.COOC4Hg, b.p. 250-252", is converted into isobutyl alcohol and di-isobutyl glgoxylamide,m. p. 42-45", by the action of alcoholic ammonia a t 100": C14H2804 + NH, = CloH2,N03 + C4H,,0. The formation of diethyl-glyoxylicacid and of di-isobutyl-glyoxylic acid from hydrocyanic and hydro-chloric acids and alcohol may be represented by the followingequations :-2HCN + 2C2HeO + 2HzO = C,HI,O, + 2NHS2HCN + 2C4H100 + 2HZO = C,&I,,O~ + 2XH3.Neither the imido-ether of formic acid, HC(NH)OC2H5, norGautier's formimido-amide, CH(NH)WHz (Con@. rend., 65, 472),were obtained by this reaction.Action of Hydrochloric Acid n?i t l Alcohol on Cyanogen.-Whencyanogen gas is passed into a solution of hydrochloric acid in ab-solute alcohol, in the proportion of 1 molecule of cj-anogen to2 molecules of hydrochloric acid, the chief product is the hydrochlorideof oximido-ether, which separates out as a white precipitate, leavingin the mother-liquor a mixture of ammonium chloride, ethyl chlo-ride, ethyl formate, and urethane, which owe their origin to a secondaryreaction.The urethane is probably formed by the decomposition ofthe oximido-ether by hydrochloric acid and water, thns : C6HI2N,O2 +2H.20 + HC1= C3H7N02 + CHOLCzH5 + NHdCl.The hydrockloi-icle of ox-i?nido-etl~er, [ C(NH)OC2H5],.2HCI, is adirect addition-product : C2N, + 2CzH60 + 2HC1 = CsH,2N202.2HCl.It is insoluble in alcohol and is decomposed by water, forming ethyloxalate.Aqueous ammonia converts it into oxamide. The free base,obtained by treating the hydrochloride with absolute ether and solidpotash, is deposited from an ethereal solution in long thick colourlessprisms (m. p. 25", b. p. 170"). If isobutyl alcohol is substituted forethyl alcohol, oximido-isobutyl ether and isobutyl urethane are ob-tained.Action qf Hydrochlo& Acid and Alroltol on Propionitri1.-The thickoil which is formed when hydrochloric acid gas is passed into a mix-ture of isobutyl alcohol and propionitril, on decomposition withalcoholic ammonia, yields long prismatic crystals of the hydyochloridrqf propionimidamide or propionanzidine, C2H,C(NH)NH2.HCl.Thehydrochloride is deliquescent', and is very soluble in water and inalcohol, but is insoluble in ether. It melts at 133", and begins to de-compose at 233". Potash solution converts this substamce into an oilyliquid, probably propionimidamide, which decomposes slowly in pw-sexice of moisture, forming ammonia and propionamide.By the action of gaseous hydrochloric acid on a well cooled mixtureof absolute alcohol and acetonitril, a crystalline compound is formed48 ABSTR-4CTS OF CHEMICAL PAPERS.which yields acetimidamide hydrocbloride, on treatment with alcoholicam mon i a.P-nccjd tli h ;llo-etll yl-ef he 1- h y71.0r7i Zwidp, C,,H7 C (N H) OC2H5. H C1, is acrystalline compound, prepared by passing hydrochloric acid gas intoa solution of two parts of @-cynnanaphtllalene in one of alcohol. Tttlecomposes when lieatecl, forming ethyl chloride and the smide of,3naphtiioic acid : C,,H7C(NH)OC2Hj.HCl = C,,H7CONH2 + C2HjCl.The free irriidc-ether is obtained by the action of aqueous ammonia onthe hydrochloride. It is an oily liquid, insoluble in water, but solublein alcoliol, ether.and benzene.Alcoholic ammonia converts the hydrochloride into ,~-nrlyhtl~iinicZo-criwb?e lycZrochZoricZe, Cl,,H,C(NH)NH2.HCl, which crystallises in pearlyneedles (ni. p. 224~--2226'). The ci-ystals are soluble in water andin alcohol, and turn red on exposure to the light.By shaking up the hydrochloride with caustic soda, the free base isobtained in the form of an oily liquid, which crjstallises in a vacuum.P-naph thimido-isoBzit~l-eth er k?yl~ocli loride, Cl,HiC (NH) 0 C,H,.HCI,prepared by passing hydrochloric acid gas into a solution of P-cyano-naphthalene in isobutyl alcohol, melts with deconiposition a t 140°,forming /%naphthamide. /3-11op?~thinlii?o-isobut2/1 ether is depositedfrom a n ethereal solution in long white needles (m. p. 38"), whichdarken on exposure to the light. On boiling with acetic anhydride,~--zic~Iitki,nido-ncetnte, Cl,H,C(NH)OC2HJ0, is formed. This substanceis deposited from a hot alcoholic solution in silky-white needles w. c. w. (m. p. 150-152O).Action of Iodine on Thiocarbamides. By W. RUDKEFF(Deut. Chern. Ges. Rer., 11, 987).-The reaction of diphenylthio-carbamide with iodine results, according to Hofmann, in the forma-tion of phenylthiocarbimide, triphenylguanidine hydriodide, and freesulphur.The author finds, however, that aniline hydriodide is alsoamongst the products of the reaction, which he represents thus :-SCS(NHC,H,), + I 2 = 2CSSCSH5 + CN3H*(CGHj)3.H1+ CGH5NHZ.HI + s.carbaniic acid is represented by Hofniann as follows :-Again, the action of iodine on the ethylamine salt of ethylthio-CS(NH.C,H,)( SNH,.C,H,) + I 2 = CSNCzH5 + C,H,NHz.HI + HI + S.But, according to the author, this equation expresses only the firstphase of the reaction, for the products include also carbon bisnlphideand diethylthiocarbamide, which are the results of secondary actions.5CS(NH.C2H,)(SNH,C2H5) + 31, = 2CSNC2H5 + 2CSz +GC2HsNH2.HI + CS(NHCzH5)Z + 3s.By C.J. MABERY and H. B. HILL (Deut.Chem. Ges. Ber., 11,1329-1352).-When dry neutral lead urate is heatedwith excess of methyl iodide, dimethyluric acid is easily formed, butthe lead salt is not completely decomposed, the product being a mix-ture of the mono- and dimethyl-compounds. A little more than thetheoretical quantity of methyl iodide, diluted with an equal weight ofether, should be used. The decomposition procecds rapidly at lGT,",r i 1 he reaction in its entirety is represented thus :-J. R.Dimethyluric AcidORGANIC CHEMISTRY. 49and is completed in 15 to 20 hours. To prevent formation of themono-compound, potassium urate containing some excess of potas-sium hydroxide, was used for precipitating the lead salt. The productof the reaction was boiled with water, the dissolved lead removed bysulphuretted hydrogen, and the crystals which separated out on cooling,were recrystallised from hot water.Di,,2eth?lZzlricacicEforms small obliqueprisms containing 1 molecule of water. From saturated solutions itsometimes separates at temperatures near 100" in thick prisms, pointedat both ends and anhydrous. The acid fuses only a t a high tempera-ture, with partial decomposition and sublimation. It dissolves in 200parts of boiling and 800 parts of cold water, scarcely at all in alcohol,ether, and glacial acetic acid. I t is easily taken up by concentratedsulpliuric and hydrochloric acids, and on dilution again cr.ystallises out.If the acid be dissolved in a little hot potash-solution arid alcohol beadded, the salt, K2C5( CH3),N4O3.4H20, precipitates in silky needles,very soluble in water, and not quite insoluble in alcohol.A similarsalt, N&C,( CH,),N40s.~H20, less soluhle in alcohol, is obtained byusing soda solution.BaC5(CH3),N4O3.3H2O, obtained by dissolving the acid in baryta-water, separates out on cooling in flat transparent prisms, soluble withdifficulty in cold water, more easily in hot.Ba[C,H(CH3)2N403]2 3H20 is obtaiced by boiling an aqueous solu-tion of the acid with barium carbonate, and precipitating with alcohol.The salts, NaC5H( CH3),N40,.2H20 and KC,H( CH:3)2N403.1+H20, mayhe prepared in a similar manner. By these salts the dimethyluric acidis well characterised as a bibasic acid. Heated a t 170" with concen-trated hydrochloric acid, the acid decomposes into carbon dioxide,ammonia, methylamine, and glycocine, according t o the equation :-CjH2(CH,)zNkO, + 5HzO = 3CO2 + NH3 + 2CHANHz + CZH5N02.The evidence thus obtained proves that the two hydrogen-atoms inthe uric acid, replaceable by metals, are directly combined with twodistiuct nitrogen-atoms.I f these two hydrogen-atoms be replaced bymethyl, then the two remaining hydrogen atoms can be exchanged formetals. This relationship finds a simple explanation only by theassumption that uric acid contains the group NH four times. Thisrequirement is expressed by two only of the various structural formuleNH.CO. C.NHproposed for uric acid, viz., by that of Medicus, I co .EH. C.NH/)I 'coyNH.C- NHN.HC-NHand by that of Fittig, CO< I >CO >CO.w. s.Action of Zinc Chloride on Methyl Alcohol. Hexmethyl-benzene. By LE REL and GREENE (Conzpt. reizd., 87, 26C).-The experiment was conducted in the same way as with butyl alcohol(Bull. Xoc. C'hinz., 1878, 29, 306). The principal products of theaction were marsh-gas, a crystalline body, water, methyl ether, andvarious oils. Traces of methaldelzyde, and of propylene, butylene, andother hydrocarbons were also formed. The crystalline body abovementioned amounts to about 0.5 per cent. of the alcohol employed.VOL. YXXVI. 50 ABSTRACTS OF CHEMICAL PAPERS.After purification from a trace of methaldehyde, oily matters, and avolatile chlorine compound, it forms laminae melting a t 150", andboiling a t 259-260" : it does not combine with bromine.I t s analysisleads to the formula c12HE16, and n comparison of the body and its com-pound with picric acid with specimens of hexmethylbenzene and itsOn Dinitroparadibromobenzenes and their Derivatives.By P. T. AUSTEN (Amer. J. Sci. [3). 16, 46). Third Paper.*--P-Dinitro~nrabromophenol, C6Hz(N 02),BrOH.-This compound is pre-pared by treating p-dinitroparadihromobenzene in dilute alcoholicsolution with potassium nitrite, and decomposing the resulting potas-sium salt with hydrochloric acid. It forms, when crystallised fromwater or alcohol, long, flat, very thin, glittering needles, melting at,71" (78" Korner), and volabilising unchanged when gently heated.Exposed to the air it turns red, probably owing to the presence ofammonia.Heated under water, it melts to a yellow oil. Heated withconcentrated sulphuric acid, it evolves nitrous acid, and forms a sul-phonic acid (?). On platinum foil, it burns with a luminous, yellow,smoky flame. When thrown on red-hot foil, it deflagrates. Heatedwith fuming nitric acid, it forms picric acid. It is difficultly solublein boiling water, still less so in boiling dilute hydrochloric andnitric acids ; easily soluble in boiling snlphuric acid ; very easily inhot alcohol, glacial acetic acid, and aniline; less so in carbon bisul-phide.Siher ,@-a initropurnbromophenate, C6H2(N02),BrOAg.-Splendid glit-tering red needles, with brilliant green reflex, difficultly soluble in hotwater, easily in alcohol.When dry, the salt deflagrates on heating ;thrown on a hot surface, it explodes. The potassium salt forms longglittering red needles, with greenish reflex. difficultly soluble in boilingwater. The barium salt, [C6H2(NOz)zBrO]2Ba, forms saffron-yellowneedles, moderately soluble in water and alcohol. Heated in a flask,it explodes, coverinq the sides with carbon. The ammonium saEtforms bright-red silky needles, soluble in boiling water and in alcohol.Volatile at 140" to a red sublimate ; above that temperature it is de-composed, partially recombining on cooling. The cnpper salt is ob-tained by treating with glacial acetic acid the product of the actionof cupric carbonate on the phenol in alcoholic solution, and dilutingwith water until the blue colour changes to brown; the salt thenseparates in short, brown glittering needles, insoluble in water andalcohol, moderately soluble in boilinc acetic acid.None of these saltscontain water of crystallisation, differing in this respect from thesalts of the isomeric dinitrobromophenol obtained by Armstrong (Ber.,6, 649). The formation of P-dinitroparabromophenol affords a con-venient method of separating ,@-dinitroparadibromobenzene from thea- and .y-compounds, which are unaffected by potassium nitrite.picrate, showed the two to be identical. c. w. w.c. w. w.Some Addition-products of Trinitrobenzene and otherNitro-compounds. By E. HEPP (Bull. SOC. Chin%. [2], 30, 4).-A* Compare this Journal, 1876, ii, 406 and 513ORGANIC CHEMISTRY.51solntion of tiinitrnbenzene in benzene deposits large prismatic crystals,which lose their benzene on exposure to the a i r ; they consist of acompound of 1 molecule of each of the constituents, C,H,(NO,), andC6H6. A similar compound with naphthalene forms long white needles,melting a t 152-153", and losing their naphthalene at the ordinarytemperature, or on recrystallisation from alrohol. Anthracene andphenanthrene appear to form similar compounds with trinitrobenzene.The compound with aniline, C,H3(NO,),.C6H,N, crystallises in redneedles melting a t 123-124", and is nearly insoluble in cold alcohol ;it might be used with advantage for the preparation of pure trinitro-benzene free from dinitrobenzene. The analogous compound withdimethylaniline melts a t 106-108".Both compounds are easily de-composed, either by exposure to the air, by washing with alcohol, orby dilute acids.By the action of aniline on an isomeric trinitrobenzene (from parw-dinitrobenzene, m. p. 171"), red needles melting a t 133" were ob-tained. Analysis led t'o the formula C6H3(N02)2NHC6H,, which is thatof a dinitrodiphenylamine. The alcoholic mother-liquors contained adiazo-amidobenzene, produced by the action of nitrous acid on theexcess of aniline.The addition-products of picramide with aniline obtained by theauthor differed from those described by Mertens, in that they lost tbewhole of t4heir base on exposure to the air. Ordinary trinitrotoluene(m. p. 82O) forms compounds exactly similar to those of t'rinitroben-zene.From this similarity between trinitrobenzene, trinitrotoluene, andpicric acid, the author supposes that the N02-groups are similarlysituated ; trinitromesitylene, however, which, according to this hypo-thesis, should form a compound with aniline, has as yet refused todo so.No componnd of aniline with a dinitro-compound has hitherto beenobtained, but compounds of these bodies with hydrocarbons are easilyformed. Ortho- and para-dinitrobenzene form crystallisable compoundswith naphthalene, the para-compound melting at 110-11 5".Action of Aniline on Glyoxylic Acid. By C. BOTTINGER(Deut. Chern. Qes. Ber., 11, 1-559-156l).-The yellow crystalline pre-cipitate, which is formed by slowly adding aniline to dilute glyoxylicacid, is an aniline salt of anilglyoxylic acid, C,aH,4N202.This bodywas also obtained by Frankland and Duppa, by adding aniline oxalateto calcium glyoxylate. It is decomposed by boiling water into aniline,carbon dioxide, and a brittle substance, which splits up on distillationc. w. w.into water, aniline, and carbanilide. w. c. w.Paraxylidine. By W. SCHAUMANN (Deut. Chem. Ges. Ber., 11,1537-1 538) .-Mononitroparaxylene (b. p. 234-237"), prepared fromparaxylene (m. p. 15", b. p. 136"), was reduced by acetic acid andiron filings, and the mixture distilled in a current of steam. Paraxp-lidine sulphate crystallised out on emporating the distillate withsalphuric acid. The free base was obtained by adding excess ofsodium carbonate to a solution of the sulphate, and distilling insteam.e 53 ABSTRACTS OF CHEMICAL PAPERS.Pai*axyZidine is a colourless liquid, which turns yellow on exposuret o the air.I t ssalts crystallise well from acid solutions, but their neutral solutionssplit up on boiling.ParaxylidiTze sukhate [ C6H3( CH3),NH2J2HZSO4, crystallises in colour-less plates. The hydrocldoride, C6H3.( CH3),NH,.HC1 + H,O, formslarge glistening plates, having a faint pink colour. It is more solublethan the sulphate. At 125-130', its water of crystallisation is ex-pelled, and the anhydrous salt sublimes.The xitrate, C6H3( CH3)2NH2.HNOJ, forms pink needle-shaped crys-tals.The ozalate forms thick prisms, having a pink colour. Onheating to 125-130", i t splits up into water and oxaZparaxyZidide[ C,H,( CH,)2NH]2C20,.This body is soluble in alcohol and in ether ;i t sublimes without melting at 125", forming slender silky-white needles.Acetoparazylidide (m. p. 138-139') separates out as a crystallinemass on boiling paraxylidine i n glacial acetic acid. It is converted into?ritracetoparazylide, CsH2( CH3),N0,NH.C2H30, by the action of fumingnitric acid. This nitro-compound is a yellow crystalline powderI t boils at 220-221", and is soluble in hot water.(m.p. 192"). IV. c. w.Oxidation of Sulphamidoxylene. By M. W. ILES and IRAREMSEN (Deut. Clienz. Ges. Ber., 11, 1326-1329).-Jacobsen (ibid.,11, 893) assumed that the authors' sulphaminetoluic acid was not apure product; but as they have obtained the acid crystallised inbeautiful long needles with constant melting point of 254.5-255'(corrwted), they consider his supposition to be unfounded.The oxy-acid obtained was also doubtless pure, and crystsllised in long lustrousneedles, m. p. 174-175", which is a little higher than Tiemann andSchotten found for their orthohomoparoxybenzoic acid. The twoacids are, however, said to be identical. Both contain half a mol. ofwater of crystallisation, both melt a t almost exactly the same tempera-ture, and neither gives any coloration with ferric chloride.If a mixture of the two sulphamidoxylenes be oxidised with thechromic acid mixture until the oil swimming on the solution hascatirely disappeared, a pure sulphaminemetatoluic acid is obtained(rn. p. 254*5-255", corrected).The product was always dissolved iiisqdinm carbonate and the solution evaporated to a small bulk. Oncooling some unaltered amide crystallised out. This was filtered o f f ,t ;ie filtrate diluted, and the acid precipitated by addition of hydro-chloric acid.It is not disputed that Jaoobsen has obtained an acid by oxidisingthe amide melting at 95-96", but the behaviour of this acid withchromic acid mixture must certainly be different from that of thesulphaminetoluic acid. That a mixture of isomeric xylene substitu-tion products can furnish a single compound on oxidation is a factIwetty well settled by other investigators.(1.) Nitroxylene, obtained by the direct action of nitric acid onxylene, yields a ni trotoluic acid.This nitrotoluic acid is ?hot oonverteii by chromic acid into a bibasicacid.After twice recrystallising it was pure.(Beilstein and Kreusler.ORGANIC CHERIISTRT.53(2.) Chlorosylene, obtained direct from xylene, yields a chlortoluicacid. (Vol lrath .)( 3 . ) Bromoxylene, obtained direct from xylene, yields a brointoluicacid. (Fittig, Ahrens, and Nattheides.)Researches are to be carried out as soon as possible to determine theconnection between the nitrotoluic acid (m. p. 203'), the bromotoluicacid (m. p. 205-206"), and the sulphaminemetatoluic acid. It isprobable that all these bodies are similarly constituted.Jncobsen contests the correctness of the conclusion that., because theamide contains a CH3-group in the ortho-position and a second in thepara-position with respect to the sulphamide- group, the productnecessarily furnishes a stable monobasic acid.However, it is wellknown that ortho-compounds behare in a peculiar manner towardschromic acid, and some observations show that they are more stablethan the isomeric compounds of the other groups.An error niade both by the authors and by Jacobsen is now corrected.The acid formed by oxidation of sulphsmiiietoluic acid with potas-sium permanganate is not sulphamineisophthalic acid, but sulpho-Oxidation of Metaxylenesulphamide. By 0. JACOBSEN (Deut.Chenz. Ges. Bey., 11, 1529--1533).--The author denies that the resultsof his experiments agree with those of Remsen (Ber., 11, 1328).Condensation-products of Tertiary Aromatic Bases. By 0.FISCHER (Deut.Chew. Ges. Bey., 11, 950-952).-1t has been shown inprevious papers that dimethylaniline reacts with benzaldehyde audwith furfural to form bodies having the respective formul~ C?,HZ6N?and Cz,Hz4N20. I n the present paper the author describes two newbodies of the same class.Dimethylaniline reacts with chloral in the manner indicatedby the equation C1,C.COH + 5C6H5N(CH3), = 3HC1 + H20 +(C,H,N(CH,)2),C.CHI(C6H,N(CH3),). The product, which must bcregarded as a substituted pentaphenylethane, crystallises in colourlessneedles. It yields by oxidation a blue colouring matter.A mixture of dimethylaniline and bemhydrol, when treated withphosphorus pentoxide, yields din?ethylnmidotri~hen~l~7~etharLe in nearlytheoretical amount. This body is a feeble base.It crystallises fromalcohol in colourless needles, which melt a t 132-133".isophthalic acid. This the authors conclusively prove. w. s.w. c. w.J. R.Cyanoguanidines. By 0. LANDGREBE (Deut. Clzem. Ges. Bey.,11, 973--978).-In a previous paper the author stated that dicyanodi-phenylguanidine reacts with aniline hydrochloride to form a basewhich he called P-clicyanotyiphenylpanidine. He has since found thatthe same base is formed also by the reactions of a-dicyanotriphenyl-guanidine with aniline and toluidine hydrochlorides. The base, unlikethe a-dic-janogiianidines, is not decomposed by boiling with alcoliolicpotash or soda, but when heated a t 100" for some hours in sealed tubes,i t is resolved into aniline, ammonia, oxalic acid, and carbon dioxide.P-Dicynnoditol?Jl~he~iylllutrnitli?2e.--This base is formed by the actionof aniline hydrochloride on dicyanoditolylguanidine. It crystallise34 ABSTRACTS OF CHEMICAL PAPERS.from alcohol and water in yellowish needles, having the formulaC2,H2,N, + $H20.The base dissolved in alcohol is converted by pro-longed boiling with hydrochloric acid into ditolylparabsnic acid. Ityields anorange-yellow amorphous platinum salt, 2(C2,H,,N5,HC1).PtC1,.p- Dicy m o t ritolylguanidin.e.-T h is s u hs tan ce is formed, together withditoly I parabanic acid, on boiling di cyan oditoly lguanidine with hydro-chloric acid. It crystallises irr pale-yellow needles, which melt at284". By prolonged boiling with alcohol and excess of hydrochloricacid it yields ditolylparabanic acid.By W.HEINTZ (Gebiq's Annalen, 193,68--77'L).-By boiling for some time a mixture of acid oxslate ofdiacetonamine, benzaldehyde and alcohol, the oxalate of benzaldi-acetonamine is formed, from which the free base can be obtained bytreatment with potash. The base separates as an oily layer, whichsolidifies on cooling. It dissolves readily in ether, crystallising there-from in large colourless prisms, and is soluble in alcohol, but withdifficulty in water. It melts a t 61*2", and boils a t 2N0, the distillateconsisting of the unaltered substance and another base, which is notvet investigated. Benzaldiacetonamine neutralises acids, forming well-&efined salts ; its formula is C,,H17N0.The nezh-a1 sulplmte, ( C1,H,,N0)2H2SO4, crystallises in small needles,which are easily soluble in hot and in cold water, but very difficultlysoluble in alcohol, and even more so in absolute alcohol.When it isagitated with ether, a portion of the base is removed and the aqueoussolution of the sulphate is rendered acid.The nitrate, CI,Hl,N0.HK03 (dried a t 105"), crystallises from waterin short prisms containing water of crystallisation, which they graduallylose on exposure to air.Neutrul oxulute, ( C,3H17NO)2C20~H2, is insoluble in alcohol and i nether, and soluble with difficulty in water, from which it crystallisesi n prisms. It dissolves more readily in water containing free oxnlicacid; from this solution it separates in crystals, which are un-distinguishable in properties from the neutral oxalate.Theliydrochloride, CrJH17N0.HC1 (dried at lOS"), and the platinum salt,( C13H17N0.HCI),.PtC14, have also been prepared. A. J. C.By B. RATHKE (Deut. C h m . Ges.Ber., 11, 958--962).-The potassium salt of this acid is formed onheating a mixture of aniline and carbon bisulphide with alcoholicpotash: CS, + NH,.C6H5 + KHO = C6H5.HN.C'S.SI( + H20.The same salt is formed, together with diphenylthiocarbamide andpotassium thiocarbonate, on heating an alcoholic solii tion of equalweights of molecule of aniline and potassium xanthate for somehours. The reactions that take place are reprebented thus :-J. R.Benzaldiacetonamine.Phenylthiocarbamic Acid.1. C,H,O.CS.SK + NH,.C,H, = C,H,.KH.CS.SK + C,H,OH.2.C,H,O.CS.SK + e(NHZ.CGH5) = (C,H5NH),CS + CZHSOH +3. CZH5O.CS.SK + KHS = (SK)ZCS + CZHSOH.KHSPotassium ph..nylthiocarbarnate, when pure, forms transparenuRQANIO CHEMISTRY. 55golden-yellow monoclinic crystals, which melt in their water ofcrystallisation below 70". I t dissolves in less than its own weight ofcold water. The solution becomes turbid when heated, owing t o theseparation of diphenylthiocal.bnmide and phenylthiocarbimide. Thisand all the other reactions of' the acid and its salts are explained bythe circumstance that the acid readily breaks up, according to theconditions, in one or other of the ways indicated by the two followingequations :-C6H5.NH.CS.SH = CSN.C6H5 + HzS;C,H,.HN.CS.SH = NH,.CtjH5 + CSZ.The phenylthiocarbimide and aniline thus produced further react toform diphenylthiocarbamide.Potassium phenylthiocarbamate undergoes decomposit,ion in theair.Its solution, when boiled with cupric sulphate, yields cupricsulphide and phenylthiocarhimide. The aqueous solution dissolves alarge quantity of aniline, forming it liquid which, when boiled, givesoff bydrogen sulphide and deposits diphenylthiocarbamide.Free p henylthiocarbamic acid cannot be obtained by acidifying thepotassium salt, because i t breaks up a t once into carbon bisulphideand aniline, as shown above. J. R.Pentabromoresorcin. By R. BENEDIKT (Bed. Chem. Ges. Ber.,11, 1559) .-Aniline acts on pentabromoresorcin, forming tribrom-aniline and tribromoresorcin, 3C,Br5H0, + 2C6H5.NH, + 3C6Br,H30, + '2C6HzBr3.NH,.Under similar conditions phenol forms tribromo-phenol.Tin and hydrochloric acid reduce pentabromoresorcin, first to tribro-moresorcin and then to resorcin. Liebcrmnnn's tribromoresorquinone isreduced to tetrabromodiresorcin, ( OH),HBr,C6.C6Br,H (OH),, whichcrystallises in pink needles. It is reduced by sodium amalgam, form-ing an amorphous body free from bromiue; this yields diphenyl ondistilhition over zinc-dust. w. c. w.Fluorescein-carbonic Acid. By J. SCHREDER (Deut. Chenz. Ges.Ber., 11, 1340-1344) .-Baeyer's beautiful method of forming con-densation-products from phthalic acid and phenols, is founded o u theproperty of phthalic acid to form an auhydride, which afterwardsenters into reaction with hydroxjbenzenes.It was to be assumed a tthe outset that acids with neighbowing carboxyl-groups would con-duct themselves similarly, and in fact this was found the case withoxyphthdic and pyromellitic acid without, in the first case, the oxg-group prejudicing the reaction. It was of interest to see if trimelliticacid, which is a 1 : 2 : 3 derivative (G. Krinos), would behave in asimilar manner. Trimelli tic acid prepared from colophony, was con-verted into the anhydride and fused with resorcin a t 'LOO", and in t h i sway a body very similar to fluorescein was obtained, dieering only byhaving an extra carboxyl-group in its composition, and hence namedtluoresce'in-carbonic acid. The product is a dry red-brown mass ofconchoidal fracture, which may be purified by boiling it with waterand solution and fractional precipitation from alcohol.When dry i56 ABSTRACTS OF CHEMICAL PAPERS.formed a light-yellow amorphous powder.boxylised fluorescein, Cz1H12O7, or C6H3( CO. OH) <Analysis showed a car-CO.(=,H3(0H) >o. ItGO. CGHs( 0 H)is very sparingly soluble in boiling water and glacial-ackc akd, butvery easily in alcohol, ether, and benzene. The barium and calciumsalts were also prepared. The intention was, by boiling it with thecarbonates of barium and calcium, to replace only the hydrogen of thecarboxyl-group by metal, but it was found that both the hydroxylhydrogens were replaced.Bwium Salt.-A blood-red solution was obtained by boiling fluo-resceh-carbonic acid with excess of barium carbonate for a long time.This solution could not be crystallised. The concentrated aqueoussolution was precipitated with alcohol, and the barium salt obtained inthe form of a beautiful orange-red amorphous powder.Calcium Salt.-Brown-red amorphous powder, prepared like thebarium salt. Both salts are very soluble in water, and on evaporationof their solutions are obtained as cantharides-green amorphous masses.The above-named remarkable behaviour of' the two hydroxyl hydro-gens caused the author to investigate Baeyer's fluoresce'in in the samedirection.Baeyer says fluorescein dissolves in lime- and baryta-waterwith a red colour. The author finds that it further decomposes thecarbonates of barium and calcium, furnishing compounds in whichboth hydroxyl-hydrogens are replaced by metal.Although apparentlystronger, fluorescein also, although containing no carhoxyl-group,furnishes these salt-like compounds much more easily than the newbody with the carboxyl-group.Barium, Salt of Fluorescein, CzoHloBaOj + 9H20, prepared like thatof the carboxylised fluorescein, is a carmine-red powder, which afterrecrystallising from water is obtained in beautiful 1eaEy crystals, con-taining 9 mols. of water.Culcium Salt, CZOH,,CaO5 + 4Hz0.-Slender needles. Prepared likethe barium salt.Acetyl-yroduct, C 2 ~ ~ 1 6 0 9 . - ~ ~ ~ o r e s c e ~ n - c c c r b ~ n ~ ~ acid was heated withacetic anhydride (5 parts) for 2-3 hours with inverted condenser,and the product treated with alcohol and left forabout 12 hours.Thesolution, poured off from the brown oily drops which had separated,was treated with water, which precipitated acetyl-products as bright-yellow flocks. No salt of this product could be prepared, fluorescein-carbonic acid being regenerated.Dibromofiworescezn - carbonic Acid.-Fluorescehcarbonic acid sus-pended in glacial acetic acid, dissolves on adding the proper quantityof bromine, and the solution soon solidifies to it crystalline paste.The product, recrystallised from glacial acetic acid, forms beautifulbrick-red needles, soluble in alkaline fluids to yellow solution.Tetrabromo$uorescein,-carbonic Acid.-Prepared like the dibromo-pro-duct, only using double the quantity of bromine. d dark-reddishsolution, showing no inclination to crystallise, was obtained.Thebromine-derivative was therefore precipitated with water. It is a darkorange-red amorphous powder, showing colour reactions with alkalisundistinguishable from those with eosin.Red-brown colour with green reflectionORGANIC CHEMISTRY. 57Potassium Salt.--Excess of the acid was treated with potash solu-tion, evaporated, and the concentrated solution treated with alcohol,whereby the salt was obtained in small needles with cantharides lustre.It is undistinguishable from eosin-potassium, and dyes like it. Thereduction of the fluorescein-carbonic acid with sodium-amalgam didnot succeed, for a yellow varnish-like mass easily soluble in alcoholmas obtained. The solution brought in contact with alkalis a t onceoxidises and regenerates the original body.This oxidation takes placepartially, even on evaporating the soliition on the water-bath. w. s.Trinitroso- and Trinitro - phloroglucin. By R. BENEDIKT(Deut. Chem. G'es. Ber., 11, 1374--1378).-The discovery of dinitroso-resorcin by Fitz, and of dinitroso-orcin by Stenhouse and Groves, madethe existence of the corresponding phloroglucin-derivative highlyprobable. On adding a concentrated well-cooled solution of potassiumnitrite to a solution of plrloroglucin in dilute acetic acid covered witha layer of ether, the mixture becomes dark-brown, and after someminutes an acid potassium salt begins to separate. On supersaturatingthe solution with potassium hydroxide, and adding alcohol, the neutralpotassium salt is thrown down in beautiful green needles amountingto about 70 per cent.of the theoretical yield. As this potassium trini-troso-phloroglucin, C,( NO),(OK),, cannot be recrystallised withoutgreat loss, it must be dissolved in water and precipitated with alcohol,to which some potassium hydroxide has been added. It is easily solublein water, with difficulty in dilute potash, quite insoluble in weakalcohol. It may be heated to above 1SO" without decomposition,but explodes a t a high temperature. A drop of sulphuric or nitricacid will also occasion violent explosion. A lead salt of trinitroeo-phloroglucin is obtained by precipitating n dilute solution of the potas-sium salt with lead acetate ; it falls as a yellolv precipitate. Whendried it forms a light cinnamon-brown powder, exploding with vio-lence when heated.Nitroso-phloroglucin can be isolated by cautiousdecomposition of the lead salt mixed with alcohol, by means of sul-phuric acid. On filtering and evaporating the alcoholic solutiongroups of needles are obtained, which are easily soluble in water andalcohol, insoluble in ether.There is a law recogriised already in relation to the number ofnitroso-groups in nitroso-derivatives of the phenols, although thenumber a t present known is so small, viz., that each hydroxyl-groupappears to render easier the admission of a nitroso-group. Into thehydrocarbons (benzene and naphthalene) NO is introduced only withdifficulty and by indirect means.The monhydric phenols, phenol, thymol, and naphthol, take upone NO-group with ease.The dihydric phenols, resorcin and orcin, give dinitroso-derivatives.The trihydric, phloroglucin phenol, yields trinitroso-phloroglucin.Trinitro-ph,ZorogZucin, C,( NOz),( OH), + HzO.-On adding powderedpotassium nitroso-phloroglucin in very small quantities at a time to amixture of nitric acid and sulphuric acid, oxidation takes place a t theordinary temperature, and finally yellow needles of trinitro-phloro-glucin separate out. The mass is then diluted with water, exhauste58 A4BSTRhCTY OF CHEMICAL PAPERS.with ether, and the product recrystallised from boiling water.Thecrystalline form is the hexagonal prisrn modified by combination withthe pyramid and prism of the second order, expressed by the formulacDP,P, OOP,.At 130" it begins tosublime; a t 158" it melts without decomposition, but explodes onfurther heating.It is easily soluble in hot water, alcohol, and ether,and is decomposed bysulphuric acid only a t a hightemperature. Likepicric acid, it possesses great tinctorial power f o r animal matters, butthe tint is richer and more beautiful. Trinitro-phloroglucin gives theisopurpuric acid reaction with potassium cyanide. On reduction withhydrogen sulphide or tin and hydrochloric acid, it appears to form thecompound analogous to picramic acid. On boiling the tin solution i tbecomes decolorised, but no triamido-phloroglucin compound could beobtained.Salts of Tr ;nitro-ph ZowgZucin.-Triaitro-phloroglucin decomposes car-bonates readily, and forms with metals three series of salts containing1, 2, and 3 equivalents of metal.The potassium salts are formed by saturating 2 molecules of thenitro-compound with 1, 2, or 3 molecules of potassium carbonate.Itis necessary to work with a solution as concentrated as possible. Thecompound C6(N02),( OK),, consists of orange-red shining needles oftenan inch long, whilst C6(N02)3(OK)20H is of a deep-yellow colour, andnot so shining as the preceding. The cornpound C6(N02)3( OK) (OH), +H2O forms long, silky, sulphur-yellow needles, losing water at loo",and becoming dull.All three potassium derivatives are sparingly soluble in cold water.The neutral ammonium derivative behaves like the correspondingpotassium compound. The barium compound formed by addingbaryta-water to an aqueous solution of trinitro-p hloroglucin, consistsof microscopically small, sulphur-yellow needles, insoluble in cold orboiling water.Lead acetate gives in an aqueous solution of the acid an amorphous,This body loses its crystalline water a t 100".All are explosive.flocculent precipitate of lead trinitro-phloroglucin. w.s.Aurin. By R. S. DALE and C. SCHORLEMMER (Dezd. Chem. Ges.Uer., 11, 1556).-Aurin is formed, together with formic acid, on heat-ing a mixture of oxalic acid and phenolsulphonic acid or bariumphenolsulphonate, or by gradually adding oxalic acid to a mixture ofsulphuric acid and excess of phenol. Srriall quantities of carbonmonoxide and carbon dioxide are evolved during the process : 3C6H60 + CzHZO, = CigHIAOA + CH2O2 + 2H20.w. c. w.Aurin. By C. ZULKOWSKP (Liebig's Annnlen, 194, 109-144).-The preparation of aurin, and several of the results described in thispaper, have already appeared in the Deut. C'hmi. GM. Ber., 10 and 11,and in this Journal in abstract. Aurin contains 70 per cent. ofpeudorosolic acid. This body separates out as an amorphous resinousmass on treating commercial aurin with sodium bisulphite and dilnt-ing the product with water. On adding strong hydrochloric acid tothe filtrate from the pseudorosolic acid, and heating the mixture tORGANIC CHEMISTRY. 5980", a crystalline precipitate is obtained, which gives off sulphur di-oxide when heated to 130". By carefully crystallising the alcoholicsolution of t h i s residue, the following substances can be obtained, viz.,two homologous rosolic acids, ClgHl1O3 and c2DIi1603 ; lencorosolicacid, C20H1803 ; and a compound having the composition C,nH1606.RosoZic acid, CZOH1603, dissolves in alcohol, forming a reddish-yellowsolution, which changes to carmine on the addition of alkalis.Thealcoholic solution deposits crystals containing 1 molecule of water,which belong to the rnonoclinic or triclinic systems. The crystalsappear dark-red by transmitted, and metallic-green by reflected light.They easily lose their water of crjstallisation a t 100". On boiling thealcoholic solution of rosolic acid with zinc-dust and acetic acid, le'zico-msolic acid, C,,H 180s, is obtained in the form of pale-yellow, anhydrousrliombic crystals.Rosolic acid, C1gH1603, crystallises in anhydrous, rhombic plates,possessing a gnraet-red colour with a bluish lustre. The leuco-pro-duct of this acid has the composition CI9Hl6O3.The compound ~ l , ~ 1 6 0 6 is a derivative of the red roscilic acid,CISHl4O3.It crystallises in violet, needle-shaped crystals, which dis-solve in alcohol, forming a brownish-yellow solution. The alcoholicsolution becomes carmine-coloured on the addition of alkalis ; whenboiled with zinc-dust and acetic acid it yields the leuco-compound cl9HI6o3, identical with the leuco-derivative of red rosolic acid. Theproperties of yseudorosozic acid have been previously described ( Uer.,loc. cit.). w. c . w.Rosolic Acids. By H. CARO and C. GRAEBE (Deut.Cliem. Ges.Ber., 11, 13~8-13jl).-Fom,aat~~t~, of DzozybHnxoi,lie?Lorie f rona Aurin.-Aurin was heated with water a.t 220-'25U0, and a colourless compoundwas thus obtained which appeared to be identical with the dioxydi-Fhrnyl-ketone of Staedel and Gail, and to which the formula co(c6H4.0H)2 is ascribed. The authors have analyscd the dioxy-compound, a i d also its acetyl- and benzoyl-ether, and found nnmbeiswhich exactly correspond with those for dioxybenzophenone and itsether. Complet,e agreement of properties was also found to existbetween the above-named colourless body and that obtained by Baeyer.and Burkhardt by the action of potassium hydrate on yhenol-phtha-lei'n, and which is also dioxybenzoplienone. Besides the coiivertibilityinto aurin, the dioxybenzophenone from either diphenylmethaiie,phthalein, or from aurin exhibits the following colour reactions.Ifsodium amalgam be added to a dilute cold aqueous solution of thedioxybenzophenone, no coloration occurs, but if the alkaline fluidpoured off fkom the sodium stmalgam be heated to boiling, a beantifulred coloration appears, which disappe:trs on cooling, and can be re-produced by again warming. The absorption spectrum of the verydilute red solution shows a strong dark band in the green. On add-ing hydrochloric acid to the colourless rednction fluid, it becomesorange-yellow, and on boiling, an orange-yellow precipitate sepa-rates, which dissolves in soda solution with violet - blue colour,and is decoloriBed by excess of the alkaline solution, This isin entire agreemeit with the observations of Baeyer and Burk60 ABSTRACTS OF CKEMICAL PAPERS.hnrdt.On heating aurin with water, besides dioxybenzophenone andcarbonised decomposi t,ion-products, phenol was formed. The reactionis explained in the following equation, and according to the new aurinformula :-,CJ&' 0(CGH,.OH),C I + H,O = CO(C,H,.OH), + CsH,.OH.Synthesis qf Auriiz from Dioxybenzop7xnone.-It was thought probablethat aurin might be formed from dioxybenzophenone and phenol. Thisdid not succeed directly, but it was successful through the mediu'm ofphosphorus trichloride. Dioxybenzophenone was heated for a shorttime with phosphorus trichloride, the excess evaporated off on thewater-bath, and, after cooling, phenol and some concentrated sulphuricacid added.An evolution of hydrochloric acid begins even in thecold, and the mass becomes yellowish-red. By heating on the water-bath or a t 140" the reaction is completed after a short time, and onadding water, aurin separates out. Chlorinated bye-products arcformed at the same time. The relations manifested by the de-composition and synthesis of aurin to dioxybenzophenone, which, ac-cording to the researches of Stadel and Beck most probably containsboth hydroxyl groups in the para-position, indicate that in aurin bothhydroxyl groups, and in rosaniline both amido groups, are also in thepara-position. That the third oxygen atom in aurin and the imidogroup in rosaniline most likely take the ortho-position, the formationof rosaniline from orthotoluidine, and a rosolic acid from salicylicaldehyde testify.The latter compound, according to the results ofLiebermann and Schwarz, is probably ident'ical with aurin. The violetbody formed from iodo-dimethaniline (Weber) is against this theory,however, as here one must assume that all three nitrogen atoms are inthe same position.Formation of it Colouring Matter from Jfonozybenzopheitone a dPhenol.-The oxybenzophenone of Dobner and Stackmann was heatedwith phosphorus trichloride, and then with phenol and sulphuricacid. On treahment with water, a resin separated out, which in appear-ance resembles crude corallin. This resin contains a colouringmatter, and its properties place it in the group of the rosolic acids.By solution in soda and precipitation with sulphurous acid, it is puri-fied, and then forms an orange-red powder which fuses under water tloa red-brown resin with green lustre.It dissolves in alkalis with aless intense violet-red than phenol-phthalein. The solutions graduallydecolorise. With alkaline hydrogen sulphites it forms colourless solu-tions, and it combines with hydrocyanic acid like rosolic acid. Theauthors believe from these observations that this compound is a rosolicC,H,acid, (C6H,)(C,H,.0H)C< I It is considered very probable that0Dobner and Stackmann had this substance in their hands when theyacted with phenol upon benzotrichloride, and that it was actually con-tained in the red-brown resin which they describe in their paper asthe product of the reaction.On repeating their experiments theORQANIO CHEMISTRY. 61authors obtained a coloaring matter on treatment with hydrogensodium sulphite, the properties of which agree with those of theReduction of Acetophenone. By K. BUCHKA (Deut. Chem Ges.Ber., 11, 1550--1551).-By the action of sodium amalgam on aceto-phenone, Emmerling and Engler obtained a pinacofie boiling a t 202",and a secondary ethyl benzene alcohol, whilst the author by the samereaction obtained only pinacone. The author considers that the lowboiling point of the pinacone is probably due to its splitting up intoequal molecules of acetophenone and the secondary alcohol.compound from oxybenzophenone. w. s.w. c. w.A Sulphuretted Derivative of Acetophenone.By C. ENGLER( D e d . Chem. Ges. Ber., 11, 930).-Acetophe1ione reacts with ammo-ninm sulphide and hydrogen sulphide in alcoholic solution to form abody which the author regards as thiacetop7~eitone or a polymeride of it.This substance crystallises from alcohol in colourless or yellowishlamina, which are insoluble in water, but soluble in ether, chloroform,and benzene. It melts a t 119.5", and sublimes in feathery crystalsexhibiting a bluish iridescence. J. R.Sulphuretted Derivatives of Benzophenone. By C. ENGLER(Deut. Chem. Ges. Ber., 11, 922-926).-1. When alcoholic solutionsof benzophenone and ammonium sulphide are mixed together andsaturated with hydrogen sulphide, the following reactions takeplace slowly: C6&.CO.C6& + H2S = C6H5.CS.C6H5 + H20; andThe product is a solid substance crystallising from alcohol in snow-white needles, which melt a t 151".It is identical with the bodywhich A. Behr (Ber., v, 970) obtained by the action of alcoholic potas-sium sulphydrate on benzophenone chloride.2. The mother-liquors of the above substance, as prepared byBehr's reaction, Field by further treatment a.nother body which crys-talliees in small white needles (m. p. 146.5"), and has the compositionof thiobenxopheizoiie, C6H5.C S .C6H5.Both these compounds, when cautiously oxidised with chromicacid, yield benzophenone and no intermediate product.3. Benzhydrol reacts with phosphorus pentasulphide to form thecrystalline compound melting a t 151" described above, and an oily body,which by treatment with mercuric oxide or chloride yields the corn-pound [ ( C6H5),CH.S]&.Dibromo-metaxylene-sulphonic Acid. B y 0. JACORSEN andE. WEINBERG (Deut. C'llem. Ges. Her., 11, 1534--1536).-~d~rorno-Inetax2/lene-sul~~~oizic acid, C6HBr2( CH,),SO,H, separates out in smallanhydrous scales when water is added to a solution of dibromo-meta-xj-lene (m. p. 72") in fuming sulphuric acid. The crystals melt a t16J", and are soluble in hot, sparingly soluble in cold water. Thebcxriim salt [ C6HBr,( CH:3)zS03]2Ba, is sparingly soluble in water.CGHBrZ( CH,),SO,PU'a + 2Hz0 forms colourless pearly scales, soluble in2(C6H,.CS.CeH5) + HZS = (C,H5),CH.Sz.CH(CtjH,)z + S.J. RG2 ABSTRACTS OF CHEMICAL PAPERS.hot, and almost insoluble in cold water.The acid chloride,C,HBr,( CH,),SO,Cl, crystallises in coloiirless rhombic plates, whichmelt a t 107". The amide, CsHBrz(CH3)zS0zNH2, forms woollyneedles, insoluble in absolute alcohol ; they melt a t 220', and begin todecompose a t 230".A mixture of 6-metaxglene-sulphamide (m. p. 96') and monobromo-8-metaxylene-sulphamide (m. p. 161") is formed by treating the pro-duct, of the action of sodium-amalgam on sodium dibromo-metn-xylene-sulphonate with phosphorus pentachloride and ammonia. Themonobromo-metaxylene-sulphamide crystallises from dilute alcohol o rfrom hot water in long flexiblc needles. The relation between dibromo-metaxylene-sulphonic acid and the allied xylene derivatives is shownby the following formulse :-B-Metaxylene-sulphonic acid.Monobromo-t9-xylene-su!phonic acid.C,H3(CH,) (SOBH) (CH3) (1 : 2 : 3). C6Hs(CH3) (S03H) (CH3\Br(l : 2 : 3 : 6).M.p. of amide.. 9 6 O . 161".Dibromo-j3-metaxplene-sulphonic mid.C,H(C&) (SOBH) (CH,) (Br2(l : 2 : 3 : 4 : 6).M.p. of amide . . 220".a-Metaxylene-sulphonic acid. Monobromo-a-xylene-sulphonic acid.C6H3(CH3)(S0,H)CH3.(1 : 3 : 4). C6H2(C&)(S0,H)(CH,)Br.(1 : 3 : 4 : 6).M.p. of amide . . 137". 194". w. c. w.Oxidation of Ditolylparabanic Acid. By 0. LANDGREBE(Deut. Chew?. Ges. Ber., 11, 978).--By the oxidation of ditolylpnrabanicacid, Nz( CO) ( Czoz) ( C~H*.CH,)Z, with potassium permanganate, theauthor has obtained an acid agreeing in composition with the formulaN2( CO) (C,O,) ( C,H,.COOH)z.The potassium salt of this acid dis-solves easily in water, sparingly in alcohol, and gives crystalline pre-cipitates with salts of the alkaline earths and heavy metals.J. R.Parachlorobenzyl Chloride and Bromide. By C. L. JACK-SON and A. W. FIELD (Deut. flhern. Ges. Ber., 11, 904).-The sub-stance described as parachlorobenzyl chloride has hitherto beenprepared from the chlorotoluene obtained by the direct action of chlo-rine 011 toluene in the cold. But this last product has been shown byHiibner and Majert ( B e y . , 6, 790) to be a mixture of ortho- and para-chlorotoluene. The authors have therefore prepared paraehlorobenzylchloride from pure parachlorotoluene, and find that it is not a liquid,as was formerly thought, but a solid substance.It crystnllises inwhite brilliant needles or prisms, having a pleasant aromatic odonr.It melts a t 29", and volatilises a t common temperatures. The vapouracts violently on the mucous membranes. Ether, benzene, carbon bi-sulphide, acetic acid, and warm alcohol dissolve i t easily. It is in-soluble in water, and when boiled therewith, it is resolved into para-chlorobenzyl alcohol and hydrogen chloride.Puracl~lorobenzyl bromide, C6&C1.CH2Br, similarly prepared, melts a t48-5", and resembles the chIoride in propcrtiea. J. RORGANIC CHEMISTRY. 63Vapour-density of Indigo. By E. v. SOMMARUGA ( n e d . Chein.Ges. Rer., 11, 1355--1356).-After his investigation on the action ofammonia on isatin, whereby he was led to the conclusion that thisbody possessed the formula C16H10N204, the author determined thevapour-density of indigo by Hnbermann's modification of Dumas'method.As a mean of nine determinations he obtained the number9.45, whilst the formula C16H10N,02 requires 9.06. Isatin is totallyAction of Ammonia on Isatin. (11.) By E. v. SOMMARUGA(Liebig's Annlrlen, 194, 85--108).-The author has proved quantita-tively that the action of ammonia on isatin under pressure may berepresented by the following equations :-decomposed before it can be vaporised. w. s.1. C16H,"N,Or + 2NH3= 2H20 + C16H12N4Oz.Isatin. isat in-diamide.2. 4'ClfiH10NzOr 4- 7NH3 7HzO + CI~H,*N~O, -+ 3C16Hi,N302.Isatin. Oxjdiimido- Desnxyimido-Derivatives of Diamido-isatin.-In addition to the salts, which havebeen previously described (Amalen, 190, 367-4384?), the author ob-tained the chromate, C16H12N40z.HzCr0d, as an orange-coloured powder,by boiling a solution of the sulphate wit'h potassium dichromate.Bythe action of sodium-amalgam on diamido-isatin, the sodium salt ofdihydro-isatinamide is obtained in long colourless crystals, which aresparingly soluble in cold water: C,6H,2N402 + HzO + H, = NH, +Cl8Hl3NJO3. The potassium salt resembles that of sodium. The freebase is deposited from an alcoholic solution in colourless needles(m. p. 2 1 3 O ) , which are sparingly soluble i n ether and in water, Di-amido-isatin is not acted on by zinc and sulphuric acid, and is withdifficulty re:?uced by tin and hydrochloric acid.Ox diimid 0- diamido-isatin, c I6H ,1N60 8.-The sul p h at e and nitrateof this base are crystalline salts. Their solutions are fluorescent. Thenitroso-compound has not yet been obtained in a state of purity.Dianaido-hydridic acid, CI6Hl"N2(OH)?( NHZ),, is obtained in granu-lar crystals by boiling the base with sodium-amalgam and neutralisingthe product with sulphuric acid. This acid melts a t 215-217", withpartial decomposition. It is oxidised by a mixture of sulphuric acidand potassium dichromate, forming diimido-hydrindin-carbonic acid,Cl6H1,N4O4, which crystallises from hot water in colourless glisteningneedles.Deoxyimido-isatin is not reduced by sodium amalgam, but is con-verted into the sodium salt of oxya?izido-7Lydr.oi.s.atin. The samechange takes place on boiling amido-isatin with alkalis, C,,HI,N,0, +HzO = Cl6HI3N,O3.On adding sulphuric acid to the sodium .salt,oxyamido-hydro-isatin sepxrates out as a yellow flocculent precipitate,which is soluble in hot water, in alkalis, and in acids.According to the author, the existence of the above compoundsshows that the molecules of isstin and of indigo contain 16 atomsof carbon. The following formuh are proposed €or these bodies andtheir derivatives :-diamido-isatin. isatin64 ABSTRACTS O F CHEMICAL PAPERS.Indigo-white.On Diphenol.Isatin. Diamido-is Itin.B.y L. BARTH and J. SCHREDER (Deut. Chew,.Ges. Ber., 11, 1332---1339).-By the action of fused potash on phenol,salicylic acid, oxybeczoic acid, and diphenol, C,,H,,02, are formed.The latter body began to crystallise after standing for some weeks,and was distilled in a vacuum : the greater portion passed over undera pressure of about 150 mm.between 310-330", and became a hardcrystalline mass, in which two different crystalline forms were easilyperceptible, viz., long thin needles and scales. This was dissolved in alarge quantity of boiling water, and the very dilute solution (whichdid not become turbid on cooling) was partly precipitated with leadacetate, the dark brown flocks removed, and the filtrate completelyprecipitated with lead acetate ; and the bulky white precipitatedecomposed with hydrogen snlphide. The solution exhausted withether yielded, after evaporation, an oil which solidified. This was care-fully crystallised from boiling water.The crystals obtained were mostclearly of two different forms. No method of separation by meansof solvents or precipitants, could be discovered, but by fractionalcrystallisation from water, a separation could be effected, althoughwith much trouble. The body crystallking in needles was thus ob-tained in some considerable quantity ; but only enough of the scalybody to enable the authors t o study its chemical characteristics. Thebulk remained behind, a, mixture defying further separation. Theneedle-shaped body was found to be the most soluble in water, butcrystallised out first owing to its preponderating quantity.The less soluble substance crystallises in small glittering scales. Bothhave the same formula, C12H1002,and are isomeric diphenols.The needle-shaped compound was designated a-diphenol, the other ,tI-diphenol.a-Diphewol, Cl,Hlo02.-Soluble in water, and easily so in alcohol,ether. chloroform, benzene, &c. Its aqueous solution gives with ferricchloride a pure cornflower-blue coloration, remaining unaltered fora week. Addition of sodium carbonate destroys the colour, andon heating, a red-brown precipitate separates, which however doesnot consist of ferric oxide. In water the diphenol melt,s below 100" ;heated alone it melts at 123". It crystallises anhydrous, and thORGANIC C€IEMISTHY. G5vnpour-density by Victor Meyer's method was found to be 6-40 ; caJ-culated 6.44. By distillation with zinc-dust it gave a very richyield of diphenyl (over 70 per cent.).Heated for some hours a tiSO", with potash and methyl iodide and some methyl alcohol insealed tubes, it yielded dianisoil.a-ni~heizol-sul~~honic acid, Cl2H8(HSO3),O,. a-Diphenol warmedwith sulphuric acid in a platinum dish until the vapours of the acidbegan to be given off , and the mass became reddish-brown, solidified oncooling to a granular crystalline mass. It dissolved very easily in coldwater. Treatment with lead or barium carbonates in the ordinaryway to remove excess of sulphuric acid is inadmissible, since thesulpho-acid itself forms almost insoluble salts with these metals. Itis best to add approximately calculated quantities of lead carbunate,and after separating the traces of dissolved lend by hydrogen sul-phide, to concentrate to a syrups consistence.I n the exsiccator thesyrupy solution solidities to a light grey crystalline mass. The acidis extremely soluble in water. At 110" it is decomposed, turningbrown, and becoming a varnish like and very hygroscopic mass. Thisdecomposition takes place in the air a t 100" after long drying.Analysis showed that the body was a disulpho-acid, C,2H8(HS03)202.The sodium salt, Cl2H,Na2S2Os + 2H,O, obtained by exactlysaturating the sulphoacid with sodium carbonate, separates in finestellate groups of needles. The water of crystallisation is driven offat 200".Sodium determinations made on crystals obtained by further con-centration of the mother-liquor gave a smaller amount of sodium. Thisobservation &as made in the case of the other salts, and indicates thata portion of the sulpho-group becomes split up on concentrating theaqueous solution. The potassium salt crystallises likewise in needleswith one molecule of water. The barium salt is obtained as a crys-talline precipitate, by decomposing the potassium or sodium salt wif hbarium chloride.The crystallisation-water could not be exactly esti-mated.Diyyrocntechin, C1?H1004.-If the potassium salt of the disulpho-acidbe heated with excess of potash, the fused mass gradually becomesyellow, and on acidifying liberates sulphurous oxide freely. Theether extract obtained in the usual way yields a brownish crystallinemass, consisting of fine interlaced needles, which easily decompose incontact with the air.It was only by sublimation in a stream ofhydrogen, that a small quantity was obtained as a colourless crystal-line sublimate ; the greater portion was, however, decomposed, remain-ing behind as a blackish-brown syrup. The melting point of tlie sub-limate was 84". I t s aqueous solution gave a bright green colourreaction with ferric chloride, which on addition of very little dilutesodium carbonate solution becomes dark blue, on further additionviolet, and finally red. This reaction is the same as that of pyro-catechin, only the first green coloration is brighter. The namedipyrocatechin was chosen in order to recall its formula and tlieanalogous colour reactions.The colour of the unsublimed product which was analysed, wasthe same (with ferric chloride and sodium carbonate), oiily theVOL.XSSVL. 66 ABSTRACTS OF CHEMICAL PAPERS.green had a shade of brown in it. The reaction is so delicate, thatmere traces can be detected. The blue and violet shades are especiallyintense.In water it israther sparingly soluble, and does not fuse therein sooner than thea-diphenol. The aqueous solution gives a bright green colour withferric chloride. After some time the clear solution becomes turbid,and green flocks separate, leaving the solution colourless. With othersolvents it behaves just like the a-diphenol. On distilling with zinc-dust, diphenyl is obtained abundantly. It melts a t 190", is anhydrous,and its vnpour-density (Victor Meyer's method) was found to be 6-39 for6.44 (calculated). Just as with a-diphenol, a dianisoil was obtainedfrom the /3-diphenol.This dianiso'il solidified in a short time after dis-tillation, forming a crystalline mass. Under the microscope octahedrawere readily distinguished. The boiling point could not be estimatedas the quantity was too small. The authors have proved qualitativelythat a number of interesting derivatives may be obtained from both thediphenols, if only a good method of separating these isomerides couldbe discovered.Dlp72en~Zbenzene.-The residue left on distilling the crude diphenolunder diminished pressure was distilled at a higher temperature. Adark yellow mass resembling rosin was obtained, whilst some carbonremained in the retort. The distillate was repeatedly boiled up withwater, whereby some a- and e-diphenol were separated.The exhaustedresidue of dark brown colour was mixed with zinc-dust and distilledin a stream of hydrogen, to ascertain if i t still contained diphcnol o rperhaps a higher condensed product. The product was a yellowish-brown semi-solid mass smelling of diphenyl, and yielding diphenyl asa sublimate on warming on the water-bath and passing a stream ofhydrogen over it : the dark residue, when distilled, furnished a yellowishoil which crystallised on cooling. This body was almost entirely solublein boiling alcohol, which deposited i t on cooling in white crystallineflocks (m. p. = 206"). Vapour density (Victor Meyer) = 7-70 ; cal-culated for Cl,H14 = 7.94. Thus the body is a diphenylbenzene, andjudging from its melting point, is the so-called paradiphenylbenzene,obtained by G.Schulz as a bye-product in the preparation of diphenylfrom benzene.Now although i t is possible that this diphenylbenzene is a secondaryproduct arising from the diphenyl, yet regarding the properties ofthe mother-substance, it seems probable that it is rather formedby reduction from a more highly condensed phenol, triphenol forexample.Of the numerous possible isomerides of diphenol four are known : (1.)That obtained by Griess from tetrazodipheuyl, later by Lincke fromphenylparasulphonic acid. (2.) That obtained by Engelhardt and Lats-chinoff from diphenyldisulphonic acid, and afterwards more closely in-vestigated by Dobner, and ( 3 ) and (4), those described by the authors.These bodies are sharply distinguished by their melting points (l),mclts a t 156-158" ; ( 2 ) 269-270" ; (3) 123", and (4) at 190".Heat-ing with zinc-dust does not decompose No. 1, whilst Nos. 2, 3, and 4yield diphenyl almost quantitatively. The colorations with ferricP-Diphenol, when pure, forms small glittex-ing scalesORGANIC CHEMISTRY. 67chloride and the lead acetate reactions are not stated in the case ofthe first-named.As regards constitution, the diphenol of Griess and Linke may bestbe named paradiphenol. As regards that investigated by Dobner (2),both hydroxyls are contained in one benzene-group, and so the namediphenol does not seem suitable, in so far as i t would express that twophenol molecules have united, with loss of H2, to form one molecule.a- and P-diphenol might perhaps be designated ortiio- and rneta-dipheid,in so far as, in their preparation, salicylic acid is formed in pre-dominating proportion, and oxybenzoic acid in smaller quantity,whilst paraoxybenzoic acid is never observed.It is by 110 means im-possible that an ortho-meta-diphenol is likewise produced. It is nott o be denied that the mechanism of the reactions in all three cases isvery similar, since by fusing phenol with potash the removal of hydro-gen at the ortho- and meta-position is effected, and by fusing thephenolparasnlphonic acid, the removal of HSO, at the para-position ;and in all cases the two phenol residues unite to form diphenols.Action of Potash on Tetranitrodiphenyl-carbamide.By S.31. LOSANITCH (Dez6t. Ciieni. Ges. Ber., 11, 1539--1542).-When asolution of diphenylguanidine or carbanilide in cold concentrated nitricacid, is heated until red fumes are no longer evolved, and the liquid isallowed to cool, tetranitrodiphenylcarbamide is deposited in paleyellow needle-shaped crystals, which are blue or green by reflectedlight. On boiling tetranitrodiphenylcarbamide with alcoholic potash,i t is slowly converted into tetranitrodiphenyl-potassium-carbamide,C0.[NKC6H3(N0,)e]?, a glistening green crystalline powder, whichexplodes on heating. This compound is converted into dinitraniline byboiling with water. CO[NKC&(N02)2]2 -I- 2H20 = 2CsH3(N0,)2.NH2+ K2COJ. Acids convert the potassium compound into tetranitrodiphe-nylcarbamide, small quantities of dinitraniline a d carbon dioxide beingalso formed.CO[NKC&&(No2)& 4- H80, = CO[NH.C~H3.(N02)2]2 + KS04.Tetrani trodiphenylcarbamide forms a yellow crystalline compoundwith calcium, and a red unstable compound with ammonium.Naphthyl-phosphorus and Napthyl-arsenic Compounds.By W. KELBE (Deut. Ghem. Ges. Be.., 11, 1499--1503).--To preparelln~7ithyZ-~hosplioroi~s acid, C,,H,.POH( OH), a mixture of mercurydinaphthyl and excess of phosphorous chloride is heated in sealedtubes a t 200" for five days; the phosphorous chloride is distilled off;and the residual oily liquid, consisting of impure naphthylphos-phorous chloride, is poured into water: PCl2CI,H, + 2H20 = 2HC1 +C,,H,.POH(OH).The liquid is boiled to expel the hydrochloricacid, and is mixed with a slight excess of sodium carbonate. Thesolution is now filtered, and the acid precipitated by the addition ofhydrochloric acid. The precipitate is washed with cold and recrys-tdlised from hot water. During this operation, oily drops of dinaphthyl-phosphinic acid remain undissolved. Naph t hyl phosphorous aci clcryatallises in small white needles, which are soluble in alcohol and inhot water, but are insoluble in hydrochloric acid, and only sparinglyw. s.w. c. w.f Cis ABSTRACTS OF CHEMICAL PAPERS.soluble in ether and in cold water. The dry acid melts a t 125--126",but when boiled in water, it melts before dissolving. Silver nitrate isreduced by this acid.Diet h y lnaph t h?y Zpl~osp7~in e, C ,H7.P ( C,H,) ?, i s prepared by tb e actionof crude naphthylphosphorous chloride diluted with benzene on nwell cooled mixture of zinc-eth3-1 and benzene. PC12C,,H7 t Zn(C2Hj)2= ZnCI, + CloH7.P(C2H5),. The benzene is distilled off from thecrude product, and the residue dissolved in hydrochloric acid. Sodais added to the solution, and the phosphine is extracted from the pre-cipitate with ether. It is a yellow oily liquid, boiling with pvrtialdecomposition above SGO", and possessing a most repulsive odour.Diethylnaphthylphosphine ah.wrbs hydrochloric acid gas, formingtirst a solid, and then a liquid compound.Trietl/ylnapkt 1yZplj osphoniznn iodide, CI0H7. P ( CZH5),I, formed bythe direct addition of ethyl iodide to diethylnaphthylphosphine,crystallises from an aqueous solution i n colourless plates (m.p. 209").Dinaphtkylphosp7inic mid, PO (OH) (C1,,Hi)2.-The formation of thisacid has been already mentioned. The oily drops solidify, forming awhite crystalline mass, m. p. 208-204", soluble in alcohol.Nqlz thy Zarsinic acid, C loHz A s 0 (OH)?.- Mercury- d i naph thy1 isreadily acted on by arsenious chloride, thus, 2AsC13 + Hg(CloH7), =HgCI, + 2C,,H2AsC12. The compound is separated from the mercuricchloride by extraction with benzene. The oily liyuid left after dis-tilling off the benzene unites with a molecule of chlorine to formC,oH7AsC14, which is decomposed by water into hydrochloric andnaphthylnrsinic acids: CloH7AsCl, + 3H20 = 4HC1+ CloH7As0. (OH),.The acid forms needle-shaped crystals (m.p. 197"). Analogous anti- w. c. w. mony compounds have not been obtained.Metabenzdioxyanthrsquinone. Ry E. SCHUNCK and H. ROE-VER (Deut. Chem. Ges. Ber., 11, 969-973).-A substance thus namedby the authors, and isomeric with alizarin, is formed, together withanthraflavic acid and a third product t o be described hereafter, by theaction of sulpburic acid on oxybenzoic acid. It crystallises fromnlcohol, in which i t is easily soluble, in yellow anhydrous needles,which melt at 291-293', and burn with a bright flame. It is solublealso in acetic acid, benzene, ether, and chloroform, but not in wateror carbon bisulphide. Sulphuric acid dissolves it, forming a brownish-yellow solutJion, which exhibits no absorption-bands. Potash, soda, andammonia dissolve i t with deep-yellow eolour. Its barium derivativecrystallises in long red needles.The calcium derivative is nearly in-soluble. The substance combines with acetic anhydride to form thecompound, C1,H6(C,H30),04, which crystallises in tufts of yellowneedles melting a t 199". Metabenzdioxyanthraquinone, when heatedwith potash, yields purpnrin.Tetraphenylethane. By C. ENGLER ( D e d . Chew. GRS. Ber.,21, 926 -93O).-'I'efraphenylethane has hitherto been prepared (1) byreducing benzophenone with zinc-dust ; (2) by the action of hydriodicacid and phosphorus on benzpinacone; (:3) by the action of hydro-ahioric and zinc on benzhydrol in acetic solution; and (4) by t h eJ. RORGANIC CHEMISTRY.6action of hydriodic acid and phosphorus on benzpinacolin. Thauthor describes the two following new methods of preparation, thcformer of which is suitable for preparing the body in large quantities.1. The sulphuretted derivative of benzophenone melling a t 1.51'described by the author in a former paper (p. 61) (which may easily beobtained in any quantity) is dissolved to saturation in boiling alcohol.and the solution is boiled for some hours with an excess of copperprecipitated from cupric sulphate by zinc. Cupric sulphide is therebyformed, and the whole ot the benzophenone-compound is convertedinto tetraphenylethane, which is deposited from the tiltered liquid, asit cools, in small acicular crystals, generally quite pure. The yield isabout 94 per cent.of the tlieoretical amount. Or the benzophenone-compound may be heated with copper in the dry state, and the result-ing tetraphenylethane sublimed in a wide-necked retort.2. Benzophenone chloride (diphenyl-chloromethane), (C,H,),CHCl,obtained by passing dry hydrogen c!iloride into benzhydroi kept cool, isdissolved in benzene and boiled for Eome hours with sodium. The liquidon cooling, or after evaporation, deposits crystals of tetraphenylethane.I t dissolvesmore freely in etber and benzene, and very easily in carbon bisulphideand chloroform, from which last it is deposited in large crystals, onslow evaporation of the solution. With benzene it forms a crystallinecompound, c26HtJI?2.c6H6, which is deposited from its solution in thatliquid in well-formed transparent tables, turning opaque in the air.A szdphonic acid of tetraphenylethane is formed on gently warmingit with eight times its weight of concentrated sulphuric acid.Thebarium salt, (C26H:16(SOJ)4Ba2, is vcry soluble. The free acid is solublein water and alcohol, but scarcely in ether or chloroform. Whenfused with potash, it yields a phenol having the composition of tetru-It !jclroxyl-tetraphenyl et hane, and crystallising in la,minz, which me1 t a t248".A nitro-con?pound, C26H18(NO,)4, crystallising from aniline in smallneedles, is obtained by treating tetraphenylethane with nitric acid inthe cold. By the action of tin and hydrochloric acid, i t yields anxmido-compound, the hydrochloride of which crystallises from water,and forms a crystallisable double salt with stannic chloride.Tetraphenylethane is but sparingly soluble in alcol~ol.J.R.Camphor. By F. WREDEN (Deut. Chem. Ges. Bey., 11, 989).-On heating ordinary camphor at 190" with hydrochloric acid of sp. gr.1-03 it is converted into an isomeric liquid modification, of sp. gr.0.913. The liquid boils a t 187-193", and does not solidify at - 17".It absorbs oxygen from the air, especially in snnshine, and gives nosilver mirror with ammoniacal silver nitrate. J. R.Reduction-products of Elerni-resin with Zinc-dust. ByG. CIAMICIAN (Deut. Cliem. Ges. Bw., 11, 1344--1348).-This is acontinuatiou of a. previous investigation, undertaken to determinewhether the different terpene-resins on reduction with zinc-dust,furnish similar products. The above resin was chosen because itcould easily be obtained quite pure and crystallised.The productsobtained were toluene, meta- and para-ethylmethyl- benzene and ethyl7 0 ABSTRACTS OF CHEMICAL PAPERS.naphthalene. Those obtained previously from abietic acid and fromcolophony were toluene, e thyl me thyl- benzene, naphthalene, met hg 1 -naphthalene, and methylanthracene. Elemi-resin and abietic acid bothyield toluene and ethylmethyl-benzene. Naphthalene and methy1-anthracene are not obtainable from elemi-resin, or a t least in scarcelyperceptible traces, and instead of the met8hylnaphthalcne of the abieticacid, ethylnaphthalene is obtained from elemi-resin. In both casestoluene, ethylmethyl-benzene, and methyl- ‘or ethyl-naphthalene, occurin far preponderating quantity, and it may therefore be inferred thatthe chemical constitution of these two substances is very similar.Splitting up of Cyclarnin into Glucose and Mannite.ByS. DE LUCA (Coiizpt. rend., 87, 297--’299).-The author shows thatcyclamin, either coagulated or in aquems solution, when left to itselffor several months, splits up into two distinct substances, namely,gIucose and crystallised mannite. Cyclamin must, therefore, be re-garded as a glucoside, from which not only glucose, but also mannite,may be obtained. R. R.New Synthesis of Glycocyamine. By M. NENCKI and N.SIEBER (J. p r . Chem. [Z], 17, 477--480).-Glycocyamine is producedby the action of glycocine upon guanidine carbonate, in accordance withthe equation 2C,H5NO2 + (CN3H6),COs = 2C3H,N302 + (NH&C03.The aqueous solution of the two substances is boiled down to a smallbulk, the glycocyamine is precipitated by addition of much water,and purified by repeating the same process three or four times.Theglycocyamine obtained is identical with that of Strecker (Conzpt. r e d . ,52, 1212). The authors find that glycocyamine is soluble in 627 partsof water at 14.5”.I n the reaction of glycocine with guanidine carbonate, a substanceis also produced which is possibly a double salt of the formulaC,H~No,.(CN,H,),CO,.H,O. This substance separates in large clearrhombic tables from the warm saturated solution obtained by boilingdown the original mixed liquids.Theauthors reserve the account of the compounds produced in this way fora future paper.Action of Iodic Acid, LLSulphomolybdic Acid,” and FerricChloride on Morphine and other Substances.(Phurm. ,I.Trans. [ 3 ] , 9, 70) .-Morphine hydrochloride dissolved in water, strikesa transitory blue with starch and iodic acid. With grape juice andstarch, iodic acid produces no blue ; but a dirty blue is observed withthe alcoholic extract of the dried juice. Orange-juice, with starch andiodic acid, gives instantly a blue colour. Saliva also produces a brightblue; but a mixture of orange juice and saliva produces a violetcolour. This reaction resembles that of morphine, but there is no alte-ration of the colour, the blue not being produced. With sulpho-molybdic acid, morphine gives a purple colour, which rapidly disap-pears, tnhe liquid becoming brown, and finally blue.With grape juiceno coloration appears for nearly half -an-hour. Fresh orange juiceremains unaltered, but with the dried juice, a faint blue is visible inw. s.Guanidine carbonate reacts with amido-acids in general.M. M. P. MORGANIC CHEMISTRY. 71ten minutes. The same result is obtained with saliva. When salivaand orange juice are mixed, coloration ensues only after the lapse ofhalf-an-hour. Ferric chloride produces a bluish-green with morphine,whereas a red is produced with dry or wet saliva; but no result isobtained with orange juice and saliva. A wine-red tint is perceptiblewith the twelve-thousandth of a grain of meconic acid in presence offerric chloride.E. w. P.Remarks on Rice’s Articles on the Cinchona Alkaloids.By 0. HESSE (Deut. Chew Ges. Ber., 11, 1549-1560).Substitutes for Quinine. BJ 0. HESSE (Dmt. Chent. Ges. Ber.,11, 1546--1549).-Dita bark (the bark of Alstonia scholtzris or Echitesschobnris) contains two alkaloids, ditamiize and echitamine. Gruppe’sextract of dita bark, ditaine, acts like curare ; this is probably due tothe echitamine.The bark of Aistonin spectabilis, which is also used as a febrifuge,contains the alkaloid alstonnmine.‘I’he bark of Crossopteryx Kotschyan,a (syn. Crossopteryx febrifiqa) con-tains 0.018 per cent. of the alkaloid crossopterine, but does not containquinine.Itis precipitated from the hydrochloric acid solution by ammonia, soda,platinum chloride, and by the double iodide of potassium and mer-Cinchonine and Cinchonidine.By Z . H. SKRAUP (Deut. Chem.Ges. Ber., 11, 1516--1519).-The results of numerous analyses of cin-chonine and its salts are given in support of the author’s view, thatthe composition of cinchonine is C19HT2N20, and not C,,H?,N,O. Cin-chonine generally contains small quantities of the compound C,,H,,N,O(the hydrocinchonine of Willm and Caventou), to which the namecinckotine is given by the author. The two bases may be separatedby fractional crystallisation of the mixed sulphates or tartrates. Cin-chotirie sulphate crystallises in prisms containing 11$-12 moleculesof water. I t is slowly attacked by potassium permanganate in thecold. Dihydrodicinchonine sulphate is easily distinguished from thepreceding compound by forming long slender crystals, containing2 molecules of water, and by being readily attacked by potassiumpermanganate.Cinchonine is oxidised by potassium permanganate, forming formicacid and cinchotenine.Cinchonidine has the same composition as cinchonine, vix., CI9H,,N2O,and is considered by the author to be probably identical with homo-cinchonidine.On oxidation, cinchonidine yield6 formic acid and alaevo-rotatory body (m. p. 25S0), which is an isomeride of cinch6tenine.Remarks on the preceding Paper. By 0. HESSE (Deut. Chem.Ges. Ber., 11, 1520--1521).-The author publishes the results ofseveral analases in favour of the formula, CmH2iN20, for cinchonine,Crossopterine is soluble in alcohol, ether, and hydrochloric acid.cury.w. c. w.I t is proposed to call this substance cinchotenidine.Tv. c. w72 ABSTRACTS OF CHEMICAL PAPERS.and gives a, test for distinguishing cinchonidine sulphate from homo-cinchonidine sulphate, viz. : 1 part of the substance is dissolved in 50parts of warm water, and left at rest for two honrs. Cinchonidinesulphate crystallises out in long brilliant prisms, whilst homocin-chonidine sulphate forms groups of delicate dull-white prisms. Thistest cannot be used in presence of appreciable quantities of quinine. w. c. w.A New Organic Base in Animal Organisms. By P.SCHREINER (Liebig's Annalen, 194, 68--84).-Charcot and Robinand numerous other observers have remarked the occurrence of apeculiar crystalline body in the secretions and in certain organsof the animal organism.The crystals, which appear to be especiallyplentiful in patients suffering from bronchial asthma, or from leuco-cythemia, were supposed by Friedrich and Huber to be tyrosine.Harting believed them to be calcium phosphate, Bottcher albumi-noid bodies, and Salkowski and Forster regarded them as mucouscompounds. The author lias shown that this body is the phos-phate of an organic base. The crystals form 5.237 per cent. of thesolid constituents of human semen, and can be easily obtained byboiling the fresh fluid with alcohol, treating the precipitate, after i lhas been dried a t 100". with warm water, containing a few drops ofammonia, and evaporating the alkaline solution.The crystals alsoseparate out on the surface of pathological preparations which arepreserved in alcohol. After purification by recrystallisat ion from hotwater containing a small quantity of ammonia, the crystals (prismsand double pyramids) are colourless and brittle. They are insolublein ether, chloroform, alcohol, and in cold water, but they dissolvereadily in dilute acids, in solutions of caustic alkalis and alkaline car-bonates.The salt contains two atoms of nitrogen to one of phosphorus ; i tloses 3 mols. of water a t loo", melts a t 170°, and decomposes at ahigher temperature, givinp off ammonia. By precipitating the phos-phoric acid with baryta-water, the free base is obtained as a colourless,inodorous crystalline mass, having a bitter taste. It is soluble inalcohol, insoluble in ether, and its solution immediately formsa crystalline compound on the addition of phosphoric acid. Thebase has been extracted from the liver, spleen, lungs, and blood ofcattle, and from the liver, spleen, blood and marrow of men who hadsuffered from leucocythEmia, by boiliiig with water containing aceticacid. Lead acetate was added to the solution, tbe excess of lead re-moved from the filtrate by means of sulphuretted hydrogen, and thebase pyecipitated by phosphotungstic acid. The free base, obtainedby boiling the phosphotungstate with baryta, forms it crystalline com-pound with hydrochloric acid, C2H5N.HCl. On the addition of platinumchloride to the hydrochloride, large prismatic crystals slowly sepa-rate out. Gold chloride precipitates the compound C2H5N.HC1.AuCl3,which crystallises in golden plates, soluble in ether, alcohol, and inwater. The characteristic odour of fresh human semen is observed,when an aqueous solution of the gold salt is treated with metallicmagnesium. w. c. wORGASIC CHENISTRY. 73Lotur Bark. By 0. HESSE (Deut. Cliem. Ges. Ber., 11, 1542-1546 j .-Lotur bark, the bark of S'ynqdocos mcemosn, contains threealkaloids, viz. : Zoturioze, 0.24 per cent. ; colloturine, 0.02 ; and lotzwidiw,0.06 per cent, The alkaloi'ds are extracted from the bark by hot alco-hol, and are converted into acetates. Loturine and colloturine areprecipitated from the neutral solution by the addition of potassiumthiocyanate, leaving the lot uridine in solution. The crystalline preci-pitate is decomposed by soda, and the alkaloids are extracted withether and recrystallised from alcohol. The efflorescent crystals ofloturine are separated mechanically from the non-efflorescent crystalsof colloturine.Lotzmhe is soluble in alcohol, ether, chloroform, and acetone, but isinsoluble in water, ammonia, and caustic soda. It gives no colora-tion with ferric chloride, strong sulphuric or nitric acids, or even onthe addition of bleaching powder and ammonia. Loturine melts a t 234',and sublimes, forming colourless prisms. The fluorescence exhibitedby a solution of loturine in dilute acids is more intense than thatof quinine sulphate. Loturine fornis well-crystallised salts. Thehydrochloride, which crystallises in white prisms soluble in alcoholand in water, fornis double salts with the chlorides of platinum, gold,and mercury. The hydriodide forms a crystalline double salt withmercuric iodide. The nitrate, thiocjanate, acetate, chromate, andpicrate arc crystalline compounds. The taunate and phosphotungstateare amorphous powders.Colloturine is deposited from alcohol in prisms terminat>ing inpyramids, which sublime a t 234". The solution of the alkaloid indilute sulphuric or hydrochloric acid is fluorescent. Gold chlo-ride produces a yellow amorphous precipitate in the solution of thehy dr oc h 1 (ride.5oturicZine.-The filtrate from the thiocjanates of loturine and collo-turine is rendered alkaline by ammonia, and the loturine extracted withether. Loturidine is a yellowish-brown amorphous body yieldingamorphous salts. It dissolves in strong nitric and sulphuric acidsforming yellow solutions. The solution iu dilute acids is fluorescent.Winckler's calyornine was not a simple substance, but a mixture ofthe acetates of these three alkaloids. w. c. w.Amyrin and Icacin. By 0. HESSE (Liebig's Anna!en, 192, 179-182).-The author compares the analyses of these two substances, andis inclined to regard icacin and amyrin as hydroxyl-compounds, viz. :CJ7H7,.0H and C,,H7s(OH)2 respectively. No new experimental dataare given. M. M. P. MI.By BOUSSINGAULT(Compt. rend., 87, 277--28l).--.The author has recently analysedthe juice of the cow-tree (Brosiwum galactodendron) which is used inSouth America as an article of diet. The results show that thisvegetable milk, in its general composition, has much resemblance tothat of the cow, inasmuch as it contains a fatty substance, saccharinematters, casein, albumin, and phosphates. The proportions of thesesubstances in the juice of Brosimum gulactodendron are, however, suchComposition of the Milk of the Cow-tree74 ABSTRACTS OF CHEMICAL PAPERS.Juice of B. Galactodendrow.Saccharine substances .... 2.8Case'in, albumin, phosphates,&c. .................. 4.0T a x and saponifiable matter 35.2Cream.Butter .............. 34.3Milk sugar .......... 4.0Casein and phosphates 3.5Water .............. 38.2Water .................. 58.0100.0 - I --100.0The fatty substances in the vegetable milk, according to C. Bernard,are capable of being split up into fatty acids and glycerin.R. R