ORGAN10 CHEMISTRY. 370 r g an i c C hem i s t riy.Action of Ozone on Hydrocarbons. By L. MAQUENXE (Bull.Soc. Chim. [ 21, 3 7, 298-300) .-Coal-gas,. purified by being passedthrough sulphuric acid and potash, is oxidised by ozone, with forma-tion of formic acid, together with small quantities o€ methaldehydeand a substance which reduces cupropotassic tartrate,. probably me-thylenitan. A small quantity of an amber liquid, which sometimesexplodes violently, is also formed ; it is possibly eit'her oxybenzeneor a nitrogen compound. Nitrogen tetroxide also combines readilywith hydrocarbons. A sensible quantity of nitrobenzene is quicklyformed when benzene mixed with sulphuric acid is exposed to theaction of ozonised air. Pure methane is not affected by ozone, but ifa mixture of methane and oxygen is subjected to the silent discharge,formic acid and methaldehyde are formed.These results confirmBerthelot's view of the experiments of MM. Thenard (Compt. rend.,1873). The products obtained by the action of the silent discharge ona mixture of carbonic anhydride and methane are undoubtedly formedby the oxidation of the latter, and the sugar produced is methylenitan,C7Hl4Os. The same substance is formed by the a.ction of hydrogen oncarbonic oxide38 ABSTRACTS OF CHEMICAL PAPERS.These facts possibly explain the formation of carbohydrates inplants. Methane may occupy an intermediate position between thecarbohydrates and the mixture CO + H2, produced in the chlorophyllcells under the influence of light; by simple oxidation, it yieldsmethylene oxides and sugars ; by polymerisation analogous to thatwhich takes place under the influence of the silent discharge, it yieldsthe complex hydrocarbons and various products so common in thevegetable kingdom.C. H. €3.Dissociation of Trichloromethyl Sulphochloride. By E.NOELTING (Bull. SOC. Chinz. [2], 37, 392--394).-Trichlo~omethyl sul-phochloride, CCl,.SO,Cl, was heated in sealed tubes for eight or tenhours a t a temperature between 170" and 200". A t 170" some un-altered compound remains, but at 200" it is completely decomposedinto sulphurous anhydride, carbon tetrachloride, carbon oxychloride,and thionyl chloride, thus : CCl,.S02C1 = CClp + SO, and CC13.S02C1= coc1, + soc1,. C. H. B.Action of Cupric Hydroxide on Sugars.By J. HABERMANNand M. HONIG (Monatsh,. Chem., 3, 651-667).-By the action ofcupric hydroxide in neutral solution on cane-sugar, inverted sugar,grape-sugar, and fruit-sugar, there were obtained in each case car-bonic anhydride, formic acid, glycollic acid, and a mixture of acidswhose uncrystallisable calcium salts gave an amount of calcium inter-mediate between that required for erythroglucic and glyceric acids.I n the experiments made in alkaline solution (with baryta-water) thesame products were observed, but were obtained in shorter time andin increased amount: in one experiment, in which a solut'ion ofgrape-sugar was heated with soda and copper hydroxide, gluconicacid was obtained. Although the products were the same with eachof these sugars, t,here were great differences in the course of the reac-tions. I n the case of cane-sugar, the reduction commenced only aftersome hours' boiling, apparently not until the sugar had been inverted.With inverted sugar, reduction of the copper oxide commenced shortlyafter the boiling point was reached.With grape-sugar in neutralsolution the reduction was rather slow, whilst in alkaline solution itstarted with the iiitroduction of the copper oxide into the warmliquid. With fruit-sugar the reduction was much quicker than withgrape-sugar.I n conclusion, the authors give reasons for doubting the accuracyof the statements of Reichardt (Annulen, 127, 297), that gum andgummic acid, and of Claus (ibid., 147, 114), that tartronic acid areamongst the products of the oxidation of sugar with copper oxide.A.J. G.Conversion of Maltose into Glucose. By S. J. PHILLIPPS(Bied. Centr., 1882, 710) .-Maltose yields glucose under the influenceof ferments ; artificial gastric juice produces no change. Maltoseappears in the intestinal canal after feeding with starchy matters.Maltose appears in the urine if i t has been previously injected into a,vein ; subcut,aneous injection of maltose results in the conversion of ORGANIC CHEMISTRY e 39portion of it into glucose.the mesenteries contains glucose only.Manufacture of Starch-sugar.After feeding with starch, the blood ofBy F. SOXHLET and A. BEHR(Bied. Ceiztr., 1882, 698 ; compare Abstr., 1882, 1274).-From con-centrated grape-syrup at 30-35", Behr has obtained crystallisedanhydrous grape-sugar by the introduction of st crystal of the same.The sweetness of grape- as compared with that of cane-sugar is1 : 1Q.Action of Ammonia on Propaldehyde.By A. WAAGE (Monatsh.Chem., 3, 693-695).-By the action of ammonia gas on propalde-hyde, cooled by a mixture of ice and salt, a small quantity of a solidproduct, C,H,O,NH,, and an oil were obtained. The oil appears tobe a mixture, and on exposure to an atmosphere contaiuing carbonicacid, long colourless tabular crystals separate, of the formulaCl5HZ9N3 (m. p. 74"), soluble in ether and alcohol, but insbluble inwater. What part the carbonic acid plays in the formation of thesecrystals could not be ascertained.By heating the crude product of this reaction for some days a t200" in sealed tubes, a dark-brown liquid is obtained ; and when thisis distilled, and the fraction 170-210" dissolved in hydrochloric acid,separated fkom resinous and oily matters, and distilled with potash,a colourless base, C9HI3N, is obtained, boiling at 193-195" (corr.),probably parvoline.A. J. G.r-Diethylbutyrolactone. By A. ENMERT and R. FRIEDRICH (Ber.,15, 1851--1852).--From succinic chloride and zinc-ethyl, Wischin(dnndew, 143, 262) obtained ethylene diethyl diketone, which decom-posed on distillation. On repeating his experiments, a body of acidreaction was obtained which boiled at 230-235" without decom-position, and on analysis gave numbers corresponding with a mixtureof nearly equal parts of ydiethylbutyrolactone and ydiethyloxy-butyric acid.The latter was converted into the lactone by standingover solid potassium carbonate ; the liquid then boiled a t 228-2:%3".The barium and calcium salts were prepared, both soluble in alcoholand in water.On attempting to convert the acid into lactone by means of phos-phoric anhydride, a hydrocarbon (C8H1I)% distilled over at 270".E. W. P.E. W. P.J. K. C .Bees' Wax. By E. ZATZEK (Monatsh. Chern., 3, 677-679).-Schalfeef has stated (this Jouriial, 1877, i, 454) that Brodie's ceroticacid is in reality a mixture of acids, into which it may be resolved byfractional precipitation with lead acetate. The author has repeatedthese experiments, but entirely fails to confirm Schalfeef's results.The first fraction which, according to Schalfeef, should contain anacid C3&HS8O2, gave nnmbers perfectly agreeing with those required for(:erotic acid (C27H5402).By 14.CHANLAROFF (Ber., 15, 1987-1989) .-On heating these substancesA.J. G.Action of Thiacetic Acid on Ethyl Thiocyanate40 ABSTRACTS OF CHEMICAL PAPERS.together for 10-1 5 minutes, they combine, forming ethy lic acety ldz'thio-cnrbamnte, CS( SEt) .NHrc ; it crystallises in brilliant yellow needles,melt,ing at 122-123", and is readily soluble in alcohol, ether, and hotvater. On being heated, it decomposes into its original constituents.When boiled with baryta-water, it yields mercaptan and barium thio-cyanate and acetate; with dilute hydrochloric acid, it gives ethylicdithiocarbamate, mercaptan, carbon oxysulphide, acetic acid, andammonium chloride.A. J. G.Azaurolic Acids. By V. MEPER and E. J. CONSTAM (Annalen,214, 328-353).-The ethylnitrolic acid used in the preparation ofethylazaurolic acid is best obtained by the following process :-6 C.C.nitroethane are brought into a vessel containing small pieces of ice,25 C.C. of potash solution (= 6.7 grams KOH) are added, and the mix-ture is shaken until the nitroethane is dissolved. The liquid, havingbeen tra.nsferred to a beaker containing ice, is mixed with 15 C.C. ofsodium nitrite solution (15 C.C. = 8 grams NaN02). Dilute sulphnricacid is now added until the red colour of the mixture changes to paleyellow, when the solution is rendered alkaline by the addition ofrotash.The liquid is three times alternately acidified and made alka-line. It is finally acidified with sulphuric acid, and three times ex-tracted with one-sixth of its volume of ether. The nitrolic acid isdeposited on evaporating the ether.I n order to prepare ethylazaurolic ctcid, 45 grams of 5 per cent.sodium amalgam are added to 2 grams of ethylnitrolic acid, suspendedin 10 C.C. of water. The vessel in which the operatiou is conducted issurrounded by ice and salt, so as to keep the temperature about zero.The alkaline liquid is separated from the metallic mercury and acidifiedwii h dilute snlphuric acid, whereupon ethylazaurolic acid is depositedin needle-shaped crystals, which are purified by recrystallisation fromboiling alcohol.The pure acid forms orange-coloured prisms, sparinglysoluble in water and in ether. It melts a t 142" with detonation, formingleucazone, nitrous oxide, and water. On oxidation with chromic acidmixture, it is converted into acetic and carbonic acids. An ammo-niacal solution of ethylazaurolic acid gives a brown precipitate withsilver nitrate, and yellow precipitates with lead and zinc salts. Ethyl-azaurolic acid is decomposed by warm dilute hydrochloric acid intoethylleucazone and hydroxylamine : to separate these bodies, thehydrochlorides are converted into sulphates by treatment with silversulphate, and on addiag a large quantity of alcohol to a cold concen-trated aqueous solution of the sulphates, hydroxyiamine sulphate isprecipitated, and on evaporating the alcoholic filtrate, ethylleucazonesiilphate is deposited in colourless prisms, melting a t 161.5".Bydouble decomposition with bnryta-water, the sulphate is convertedinto the free base C4K,N30, which crystallises in white needles, meltinga t 158", and soluble in alcohol and in water. The aqueous solutiongives a reddish-brown coloration with ferric chloride. The bariumsalt, (C4H6N,0)2Ba, is a colourless hygroscopic powder. On theaddition of silver nitrate to a solution of leucazone, leucazone silvernitrate, C4H7NS0,AgN03, is deposited as a white crystalline preci-pitate. Ethylleucazone is also produced by the action of stronORGANIC CHEXISTE1Y. 41ammonia or of sodium amalgam on ethyl azaurolic acid.Theconstitution of azaurolic acid may perhaps be represented byCMe(N0) : N.NE.CMe(NOH), or more probably by the formulaCHMe(NO).N : N.CHMe.NO.Propylazaurolic m i d , CsH6N20, prepared from propylnitrolic acid,forms pink crystals, soluble in ether and in alcohol. It melts at 127.5"to a colourless liquid, which does not solidify on cooling.iKethyZa.zauroZic acid has not yet been obtained in the pure state. w. c. w.Acetoacetic Acids. By M. CERESOLE (Ber., 15, 18'71-1878).--These acids were isolated by saponification with potash, and treatmentwikh sulphuric acid. The ethyl salt of the acid required is shaken upwith a slight excess of a 24 per cent. aqueous solution of potash untilthe ether is dissolved. The mixture is then left for 24 hours in thecold, acidified with sulphuric acid, and shaken with ether.Theethereal solution is carefully evaporated and the mixture of the newacid and unchanged salt treated with barium carbonate and water, theacid going into solution as barium salt, whilst the unaltered ethyl saltis removed by ether. The free acid is obtained from the barium saltby treatment with sulphuric acid, shaking with ether, evaporatingthe ethereal solution, and drying over sulphuric acid.Acetoacetic Acid.-The free acid is a hygroscopic and very acidliquid, miscible with water in all proportions, and decomposing rapidlybelow 100" into carbonic anhydride and acetone. The silver andcopper salts are less stable than the barium salt, which is very deli-quescent, but stable in dilute solutious ; on evaporation, i t undergoespartial decomposition into acetone, barium carbonate, and carbonicacid ; on boiling its aqueous solution, it was found that 1 molecule ofcarbonic anhydride was given off for each molecule of barium carbo-nate thrown down, The dried barium salt was analysed volumetricallywith satisfactory results, the admixed barium carbonate being esti-mated and allowed for.By dry distillation, it yields barium carbonateand acetone.Moxometliy lacetoacetic acid, prepared in the same way as acetoaceticacid, is a viscid liquid of similar properties. On boiling, i t decom-poses into carbonic anhydride and ethyl methyl ketone. The bariumsalt is very soluble, and gives no precipitate with silver nitrate ; bydry distillation it yields ethyl methyl ketone.Nitrous acid convertsthe acid into nitrosomethyl acetone, melting a t 74".Dimethy Zacetoacetic acid, dried over sulphuric acid, forms colourlesscrystals of agreeably acid smell, which are however undergoing con-tinual decomposition, and deliquesce a t once in the air. The bariumsalt can also be obtained crystalline, and possesses similar propertiesto those of the other two acids. On dry distillation, it yields the cor-responding ketone.Benaylacetoacetic acid is an acid and aromatic oil, sparingly solublein water, and easily decomposable. Its barium salt is soluble, but notdeliquescent, an d yields benzyl acetone on dry distillation. Concen-trated solutions give a precipitate with silver nitrate. With nitrousacid, nitrosobenzyl-acetone was obtained in white needles melting a42 ABSTRACTS OF CBEMICAL PAPERS.80-81". The barium salts of all the acetoacetic acids give violet orbrown colorations with ferric chloride.The above acids were obtained from the corresponding ethyl salts bysaponification, without any separation of ketone or acid. Their mostprominent characteristic is their instability, and in this they agreewith other ketone acids in which the carbonyl and carboxyl groups areonly separated by one methylene or substituted methylene.Where,however, separation is effected by several methylene groups or by anaromatic residue, the ketone acids appear to be stable, as in the caseof la3vulic or benzoylbenzoic acids.Formation of Saccharin and Lactic Acid from Sugars.ByL. CUISINIER and H. KILIANI (Bied. Centr., 1862, 703--705).-1fmaltose is treated with lime, a solution is obtained which after con-centration yields coloured crystals of the composition C12H20010Ca0 +H20 (14.07 per cent. CaO). This salt has been termed maltate of lime,and is soluble in 100 parts hot water; from it, oxalic acid separates" maltic " acid, C6H100j, which melts a t 95" and resembles saccharin ;a 10 per cent. solution of the crystals has a dextrorotatory power of[a]= = + 63", which is reduced by dilute acids, but raised t o + 73.3"by concentrated acetic acid. I\ilaltic acid is readily soluble in water,glycerol, methyl, and ethyl alcohol, reduces alkaline copper solutions,and does not ferment. The s&lts are laevorotatory, and so is the freeacid when first separated, but after being kept, and more rapidly whenheated with an acid, it changes into a dextrorotatory modification ; itis therefore analogous to saccharin, and the name maltosaccknrin isproposed for1 it, in contradistinction to glucosaccharin.Maltate of lime has also been obtained from lactose.In anothercommunization, it is stated that glucose loses its rotatory power whenin contact with alkalis in the cold, but not its reducing action oncopper solutions j in the presence of alkalis, oxygen is absorbed frornthe air.Kiliani prepares lactic acid from inverted sugar by the followinqprocess: 500 grams of cane-sugar are heated for t,hree hours at 50'in a stoppered flask with 250 C.C.water and 10 of acid (3 partsH,SO, with 4 parts H,O) ; after cooling, 400 C.C. of soda solution(1 NaHO in 1 H,O) are added in small portions, the whole being keptcool, but afterwards the mixture is to be heated to 70" until it onlycolours Fehling's solution green, then sulphuric acid is added in quan-tity equivalent to the soda present, and the freed lactic acid is sepa-rated by 93 per cent. alcohol, and converted into the zinc salt. Saccharinis also formed at. the same time; it is converted by silver oxide andwater into glycollic acid, together with a small quantity of formic andEtcetic acids. E. W. P.J. K. C.pi-Hydroxybutyric Acid. By J. FR~~HLING (Monatsh. Chem., 3,696-704).-Trimethylene glycol (100 parts) mas heated with hydro-bromic acid (70 parts) a t 100" for five hours.The resulting trimethylenehromhydrin, CH,Br. CH,.CH,.OH, forms a colourless liquid distillingbetween 98" and 112" under a pressure of 185" mm. Its sp. gr. at20" is 1.5374. On treatment with potassium cyanide, it gives thORGANIC CHEMISTRT. 43corresponding cyanhydrin, which by the action of moderately concen-trated hydrochloric acid or of potash is converted into yhydroxybutyricw i d , thus completely confirming Saytzeff's formula,CH,(OH) .CH,.COOH,for this acid. A. J. G.Purification of Carbon Bisulphide. By E. OHACH (J. pr. Chem.[2], 26, 281--307).-The author finds that potassium permanganateis without action on pure carbon bisulphide or on the odorous im-purities present in the commercial article, hydric sulphide excepted.Under the influence of daylight the pure bisulphide however yieldssome sulphuretted hydrogen, which is oxidised by permanganate, freesulphur passing into solution.I n the case of impure bisulphide, treat-ment with permanganate causes a rise in the amount of dissolved solidmatters, chiefly sulphur.Effectual purification is obtained by first filtering the bisulphidethrough a dry paper filter to separate water and dirt, distilling fromcalcined lime, treatment of the distillate with about 5 grams per litreof dry powdered permanganate, then with metallic. mercury until allfree sulphur has combined, and lastly with mercuric sulphate. Thebisulphide is then redistilled from calcium chloride, and must be keptin the dark.0. H.Physical Properties of Carbon Oxysulphide. By ILOSVAY( B u l l , Xoc. Cl~irn. [ a ] , 37, 294--296).-Carbon oxysulphide can befreed from carbon bisulphide by passing the gas over a column ofwood charcoal. The mean coefficient of expansion of the gas between0" and 100" at constant volume is 0.0037317 ; at constant pressure,0.003i908. The pressure necessary to liquefy the gas a t differenttemperatures is given in the following table. The critical point is105".Temperature : 0" 3.8" l0.Y 12.0" 17.0" 39.8' 41.2" 630' 69.0" 746" 85.0".Press. in atmos. : 12.5 15.0 1'7.5 19.6 21.5 44.0 45.0 59.0 65.0 '74'0 80.Liquid carbon oxysulphide is colourless, mobile, and highly refrac-tive. It dissolves sulphur, and mixes with alcohol or ether, but notwith water or glycerol.If the pressure is suddenly released, solidflakes are deposited, and persist for some time. These experimentsshow that the physical and chemical properties of carbon oxysulphideare intermediate between those of carbon bisulphide and carbondioxide, and also afford further evidence that the coefficient ofexpansion of an easily liquefiable gas is greater than that of a gasdifficult to liquefy.Carbon oxysulphide, mixed however with mercaptan, carbondioxide, hydrogen sulphide, &c., can be obtained by the action ofsulphuric acid on potassium ethyl-thiocarbonate, C0,SKEt.C. H. B.Dibromosuccinic Acid and Diamidosuccinic Acid. By A.CLAUS (Ber., 15, 1844-1851) .-In t,he preparation of diethyl dibro-mosuccinate by Kekul6's method, after separation of the etherea44 ABSTRACTS OF CHEMICAL PAPERS.salt by adding water and evaporating the solution, a crystalline sub-stance is left, which is the monoethylic salt of dibromo-succinic acid(m.p. 275'). Potassium and sodium ethyl-dibromosuccinates wereformed by mixing alcoholic solutions of the alkalis with the acid, ascrystalline groups, easily soluble in water: the silver salt is a whitecrystalline precipitate. With ammonia, the ammonium salt of di-bromosuccinamic acid is obtained, but an attempt to isolate the acidfailed. Methyldibromosuccinic acid is prepared in the same way asthe ethyl compound. Its sodium and ethyl salts (m. p. 62.5") wereobtained in the usual way.When ethyl dibromosuccinate is treated with sodium and ethylbromide, only diethyl and black products are obtained ; if, however,the sodium is replaced by zinc, the ethyl bromide is not attacked, anddistils over unchanged, while one or two atoms of zinc enter into com-bination with the acid, without removing the bromine, and syrupyliquids are formed containing varying percentages of zinc.Heatedwith ethyl bromide in sealed tubes at above 150", fumaric acid andzinc bromide are the chief products.According to Lehrfeld, the amide of ethyl imidosuccinate is formedby the action of ammonia gas on an alcoholic solution of ethyl dibro-mosuccinate. The author, however, on repeating tho experimezltcould obtain nothing beyond ethyl diamidosuccinate. Lindner, bytreating free dibromosuccinic acid with ammonia, claims to have pre-pared the diamido-acid, which he states is insoluble in water, alcohol,and ether.This body the author was also unable to prepare, and heis of the opinion that Lindner worked with impure materials, andthat the body he describes was perhaps produced from the glass ofthe sealed tube.As regards bromamidosuccinic acid, traces of the diamido-acid arealways formed, whether excess of ammonia or of dibromosuccinic acidbe present. The pure acid can only be obtained by fractional precipi-tation of the silver salt, the middle fractions consisting of pure silverbromamidosuccinate. J. K. C.Geometrical Formulae of Maleic and Fumaric Acids deducedfrom their Products of Oxidation. By J. A. LE BEL (Bull. XOC.Chim.[ 21, 37, 300-302).-By oxidation, fumaric acid yields racemicacid, and maleic acid yields mesotartaric acid. The only suppositionwhich agrees with these and other known properties of the two acidsis that the four hydrogen-atoms are in the same plane as the carbon-atoms and form a rectangle. I n maleic acid, the rectangle is symme-trical about a plane perpendicular to the rectangle and bisecting it.The COOH-groups are a t opposite ends of one side of the rectangle,and the H-atoms at opposite ends of the other side. I n fumaric acid,the rectangle is symmetrical about its central point, the COOH-groupsbeing one a t each end of one diagonal, and the H-atoms one a t eachend of the other diagonal. It follows from these structures thatmaleic acid can yield only mesotartaric acid, whilst fumaric acid canyield only racemic acid.C. H. B.Ethylic Methenyltricarboxylate and Ethylic AcetomalonateORGANIC C€EMISTRY. 45By M. CONRAD and M. GUTHZEIT (Annalen, 214, 31--38).-Eth?jZicrnethenyltrica.rboxylate, CH( COOEt),, prepared by warming a mixtureof ethyl chlorocarbonate, benzene, and e thy1 sodium malonate, crys-tallises in needles or prisms which melt at 29", and boil a t 253". Itssp. gr. at 19" is 1.10 compared with water a t 15". The crystals aresoluble in ether and alcohol. On saponification, i t yields malonic acid.Methenyltricarboxylic acid could not be isolated.Ethylic acetowtalonate described by Ehrlich (Ber., 7,892) decomposeson saponification, forming alcohol, acetone, carbonic and acetic acids.w. c. w.Ethylic Ethenyltricarboxylate. By C. A. BISCHOFF (Annalen,214, 38-44) .-The preparation of the ethylic salt of ethenyltricar-boxylic acid has been described by Pull (Ber., 14, 752). This com-pound is a colourless liquid (b. p. 278") soluble in alcohol and ether.I t s sp. gr. at 17" is 1.1089 compared with water a t 15". It is readilysaponified by a solution of soda, and on decomposing the sodium salt,ethenyltricarboxylic acid, COOH.CHz.CH(COOH), is obtained in pris-matic crystals soluble in alcohol, ether, and water.The acid melts at 159", decomposing into carbonic and succinicacids. Barium tri-ethenylcarboxylate crystallises in white prismssparingly soluble in hot water. The zinc salt contains 2 mols. HzO.It is less soluble in hot than in cold water.w. c. w.Ethylic Monochlorethenyltricarboxglate. By C. A. BTSCHOFF(AnnuZen., 214,44- 53) .-When a current of chlorine is passed throughwarm ethylic ethenyltricarboxylate, the monochlorinated derivative,CC1( COO E t). CH,.COOEt,is produced. This substance is purified by distillation under reducedpressure. It boils at 205-215" under 160 mm. pressure. Continuedboiling with dilute hydrochloric acid splits up the ethereal salt intocarbonic and fumaric acids. On saponification with an aqueous solu-tion of potash, it yields malic acid (m. p. 130-135"), which appears tobe identical with the malic acid which Loydl ( d i d . , 192, 80) obtainedfrom fumaric acid. Treatment with alcoholic potash converts ethylicmonochlorethenyltricarboxylate into ethoxyethenyltricarboxylic acid. w.c. w.Ethereal Salts of Propenyltricarboxylic Acid. By C. A.BISCHOFF (Annalen, 214, 53-58) .-Eth ylic propeny ltricarboxylate,CHMe(CO0Et) .CH(COOEt),, prepared by the action of ethyl a-bro-mnpropionate on an alcoholic solution of the sodium compound ofethyl malonate, is a colourless oil (b. p. 270") miscible with alcoholand ether. Its sp. gr. at 16" is 1.092. Diethylir, monomethyl propenyl-tricarboxy lat e, C 0 OE t. CH (CO OE t) . CHMe. CO OMe, is obtained whenmethylic a-chloropropionate is substituted for ethyl bromopropionatein the above reaction. This liquid boils at 267". It is soluble in alcoholand ether. Its sp. gr. is 1.079 at 15" compared with water at 4".Yropenyltricarbo~~lic acid melts at 146", splitting up into carbonic andpyrotartaric acids and alcohol.The barium salt, Ba,(C6H,0,), issparingly soluble in water. w. c. w46 ABSTRACTS OF CHEMICAL PAPERS.Ethylic Propyl- and Isopropyl-ethenyltricarboxylates. ByG. WALTZ (Armalen, 214, 58-61) .-Ethylic propzJlethenyltricarboxy7-ate, CPr( COOEt),.CH2.COOEt, prepared by the action of sodiumethylate and propyl iodide on ethylic ethenyltricarboxylate, is acolourless oil miscible with ether and alcohol. J t boils a t 280" withpartial decomposition. The free acid,C Pr (C 0 OH) 2. CH,. c) 0 0 H,forms lustrous needles (m. p. 148') soluble in water, ether, andalcohol. A solution of ammonium propylethenyl tricarboxylate gives acrystalline precipitate with barium, silver, and lead salts.Zinc, cal-cium, iron, and copper are precipitated from hot solutions. The acidbegins to decompose at its melting point, yielding carbonic, propyl-succinic, and traces of butyric acids.Theneutral solution gives a white crystalline precipitate with silver andlead salts.Ethylic iso~ropylet?~e~zylt,.ical.boz?/Znte was not obtained in a state ofpurity. The impure compound decomposes a t 180" forming isopropyl-Its sp. gr. a t 13" = 1.052.Propylsuccinic acid, CHPr(COOH).CH,.COOH, melts a t 91".succinic acid (m. p. 114"). w. c. w.Ethylic Isallylenetetracarboxylate. By C. A. BISCHOFF(Annalen, 214, 61-67) .-The preparation and properties of isallylene-tetracarboxylic acid, (COOH.CH,),C(COOH),, and of its ethyl salthave already been described by the author (Abstr., 1881, 156).Thefollowing salts were prepared :-C,TI,Ag40,, somewhat soluble in hotwater: C,H,Pb,Os + H,O and C7H,,Zn208 are crystalline salts. Tbetricurbullyllic acid, obtained by heating issllylenetetracarboxylic acid,is identical with the acid described by Miehle (Annalen, 190, 325). w. c. w.By M. CONRAD and C, Tetrethylic Acetylenetetracarboxylate.A. BISCHOFF (AnnaZen, 214, 68-72).-The ethereal salt,(COOE t),CH. CH( COOE t) 2,formed by the action of ethyl monochloromalonate on ethyl sodiummalonate, crystallises in needles (m. p. 76") soluble in alcohol, ether,and benzene. It boils at 303" with partial decomposition. Whenheated with hydrochloric acid or with alkalis, it splits up into alcohol,carbonic and ethen yltricarboxylic acids.w. c. w.Diethylic Acetylenetetracarboxylate. By M. GUTHZEIT (A%-nalen, 214, 72-75) .-When an alcoholic solution of tetrethylicacetylenetetraca,rboxylate is treated with potash a t 0", the diethyl salt,COOEt.CH(COOH).CH(COOH).COOEt + +H,O,is deposited. This substance forms deliquescent plates soluble inalcohol and ether. It melts a t 132" with decomposition, and at 180"it splits up into carbonic and succinic anhydrides and ethyl succinate.By IT. CONRAD and If.GUTH ZEIT (Amalen, 2 14, 76 -80) .-Te tre thylic dicarbonte tracar-w. c. w.Tetrethylic DicarbontetracarboxylateORGANIC CHEMISTRY. 47boxylate, (COOEt),C : C (COOEt),, prepared by warming an alcoholics~lutiori of sodium ethylate with ethyl chloromalonate, crystallises inmonoclinic plates soluble in ether and in boiling alcohol.It melts at58" and boils at 325-328" with partial decomposition. On saponifyingit with potash solution, the potassium salt, C6H2O8K3, is obtained inmonoclinic prisms, The lead, zinc, and calcium (C608Ca2 + 7H,O)salts are crystalline ; the silver salt, Ag4CsOe, explodes when heated.The free acid is an unstable compound.Action of Potassium Nitrite on Mucobrornic Acid. By H.B. HILL and C. R. SANGER (Ber., l5,1906--1910).-The reaction tookplace in alcoholic solution ; on gently warming it, carbonic anhydridewas given off, and a reddish-yellow potassium salt, K2C3HN307, sepa-rated out in small flat needles. This salt is easily soluble in cold water,sparingly in dilute alcohol.When dry, it explodes on warming orwhen struck, also on moistening it with concentrated mineral acids, Itis decomposed by water at 40", but can be crystallised unchanged fromdilute potash. When heated with strong potash, a new and very un-stable compound is obtained, the composition of which has not yet beendetermined. By the action of bromine on KzC3HN307 suspended incarbon bisulphide, the compound C3HBr,N,0, was produced. It c r ptallises like ammonium chloride, and is easily soluble in carbon bisul-phide, sparingly in cold chloroform. On heating K,C3HN30, withwater or dilute alcohol to 40-60", an evolution of carbonic anhydride,hydrocyanic acid, and nitrous acid takes place, and, on evaporatingthe solution, crystals of the composition KC3H2N04,H20 were ob-tained which lost their water over sulphuric acid.This salt explodeson heating.From sodium nitrite and mucobromic acid, the corresponding sodiumsalt, NazC3HN307, could not be obtained, but, on heating the solutionto 40--CiO0, the compound NaC3H,N04,H,0 was formed and crystal-lised out on cooling. The calcium salt, Ca( C3H,NO4),,4H,O, crystal-lises in sparingly soluble prisms. Salts of barium, lead, copper, andsilver have also been prepared. Attempts to prepare the free acidhave as yet been unsuccessfnl.The action of potassium nitrite on ethyl mucobromate was found todiffer from its action on the free acid, a compound of the formulaAlkylthiosulphuric Acids. By W. SPRING and E. LEGROS (Ber.,15, 1938-1940) .--The sodium salts of ethyl- and methyl-thiosul-phuric acids, prepared by digesting equivalent quantities of' the alco-holic iodides with sodium thiosulphate, have already been described(Ber., 7, 646 and 1162; also Ber., 15, 946).The authors have con-tinued their experiments, and have succeeded in preparing sodiumsalts of propyl-, primary isobutyl-, and amyl-thiosnlphuric acids. Allthree crystallise well, and are soluble in water and in alcohol. Whendecomposed, they yield disulphides of the radicles, sodium sulphateand sulphurous anhydride. Attempts to make alkylthiosulphates con-taining other radicles have been unsuccessful. With allyl and iso-propyl iodides, the authors obtained allyl and isopropyl bisulphides,It decomposes below 100".w. c. w.It is easily soluble in water, sparingly in alcohol.KC6H6llu'O6 being formed. a. K. M48 ABSTRACTS OF CHEMICAL PAPERS.together with sodium suiphate and sulphurous acid. Chloroform,ethylidene dichloride, and some other similarly constituted bodies alsoyielded negative results.The conclusions drawn by the authors are that the only alkyl-thiosulphates which can exist are those in which the nlkyl-group isprimary and saturated, and that they are the more easily formed thesimpler the organic radicle. It also seems that compounds do notexist in which more than one S,O,Na group is joined to one carbon-atom.Propyl bisulphide, ( C3H7),S2 (normal and iso-) , bntyl bisulphide,(CaH,),S2, and amyl bisulphidc, (C5Hll)2S2, which were obtained incourse of the research, are liquids having the characteristic odourand other properties belonging to this class of compounds.Action of Phosphorus Pentachloride on Acid Amides.Part 11.By 0. WALLACH (Annalen, 214, 193--327).-Action of Phos-phorus Pentachloride on the Amides of Monobasic Acids in which oneHydrogen-atom of the NH, group has been replaced by a HydrocarbonRadicle.-The imidochloride, CMeCl : NC6H4Me, obtained by the actionof phosphorus pentachloride on acetoparatoluidide, and the amines de-rived from this compound, have already been described (this Journal,1877, i, 91). Analogous products can be prepared from acetortho-toluide. On carefully heating the imidochloride obtained in this way,a base, C,,H,ClN, (m. p. 52"), is formed.Orthotolylacetnmidie,NHC7H7.CMe : NC7H7, melts a t 69" ; the corresponding para-com-pound melts at 120", and the mixed orthopars-amidine melts a t 142".The imidochloride of benzoylbenzyl sulphamide, CPhCl : NS02Ph(Abstr., 1878, 669) melts a t 80°, and a t a higher temperature decom-poses into benzonitrile and benzenesulphonic chloride, instead of yield-ing a new base. By the action of aniline on the chloride, phenybdplao-phenyl benzamidine, NHPh.CPh NS02Ph, is produced. This amidinecrystallises in plates (m. p. 139"), soluble in alcohol and benzene. Ondistillation it decomposes into diphenylamine, benzonitrile, and phenylsulphide.To ly bu~ho~henylbei~znmidiize, C6H4Me.NH. CPh : NS02Ph, formsmonoclinic crystals (m. p. 145"), soluble in alcohol and benzene.Ondistillation, tolylphenylamine is produced.Benzeneszdphodiphenylamine, PhS02.NPh2, prepared by heating amixture of benzene sulphochloride and diphenylamine at ZOO", crystal-lises in silky needles (m. p. 1 2 4 O ) , soluble in alcohol, ether, and ben-zene. Benzene sulphanilide, PhS02.NHPh, €orms octahedra, whichmelt at 102". It is completely decomposed by heating a t 220" withlead dioxide.The products of the action of phosphorus pentachloride on mono-and tri-chloracetanilide, and on mono-, di-, and tri-chloracetethyl-nmide, have been previously described by Kamenski (Abstr., 1880.The amidine, C4H30.C(NHEt) : NEt, prepared by distilling ethyl-amine pyromucamide, C,H,O.CONHEt, with phosphorus penta-chloride (Abstr., 1881, 714), boils a t 240".It forms a crystallineplatinochloride. When phosphorus pentachloride and formanilide areA. K. M.54.7)ORGANIC CHEXIISTRY. 49brought together, carbonic oxide and hydrochloric acid are evolved,leaving a mixture of phosphorus oxychloride and diphenyl-formami-dine, NHPh.CH : NPh, melting at 137".II. Action of Phosphorus Pentachloride o n those Amides of Mono-basic Acids ~ V L which the Hydrogen of t h e NH,-group has beelk cona-p l e t d y replaced by ITydrocarbon Ihdicles.--No new bases were obtainedby treating acetodidhylamide, MeCONEt, (b. p. '185") or diphenylbcnzamide, PhCONPh, (m. p. 176") with phosphorus pentachloride.Diphen,ylacetamide, MeCONPh, (m. p. lolo), yields a base which wasnot obtained in a state of purity.MeCONMePh,a base is derived which probably has the composition C,,H,,C1N2.Acetopiperidide when treated with phosphorus pentachloride yiddsthe chloride CMeC12.NC5Hlo.The following reaction takes place whenphosphorus pentachloride acts on diethylformamide :-From acetometkyZanilide,HCONEt, + PCI, = POCI, + CHCl,.NEt,, and2CHCl,.NEt, = C,,H,,CNZ + 3HC1.111. Action of Phosphorii 8 Pentachloride onl the A m i d e s of DibasicAcids.-CCanz~horet72ylimidet~yli~~aid~n~, C14H21N20, prepared by heatinget hylsmine camphorde with phosphorus pentachloride (Abstr., 1881,284), is decomposed 'by 'hydrochloric acid a t 200" into ethylaminehydrochloride and camphoric ethylimide.This decomposition may be represented by-co + H,O = C,H,d<CO>NEt + NH,Et.CSH1d.C : NEtI 1CO--NEtCamphor ethylimidethylimidine can be prepared synthetically bytreating the product of the action of phosphoric chloride on cam-phor ethylimide with ethylamine (Abstr., 1881, 28s).IV.Action of Phosphorus Pentachloride oic the Amides of OxnlicAcid.-An account of the substituted oxamides and formamides hasbeen previously published {Ber., 14, 735-751 ; this Journal, Abstr.,1881, 717). Chloroxalethyline and many of its derivatives have alsobeen described (Abstr., 1880, 546-547). By the action of bromineon a solution of chloroxalethyline in chloroform, cl~loroxaZethy linehydrobronzide, c6H,C1N2,HBr, and dibrol-nide, C6H9ClN,,Br2, are pro-duced. The crystals of the hydrobromide are colourless; those ofthe dibromide have a deep red colour.A mixture of bromoclz7or-ozalethy liiie hydrobyomide, C6H8C1BrN2,HBr, and bronaocl~loroxalethyli~aedibronzide, C6H8ClBrN2,Br,, is formed when bromine acts on a solutionof chloroxalethyline dibromide in chloroform. Bromochloroxalethylinedibromide crystallises in red needles or prisms melting at 113". It issoluble in alcohol and ether, and sparingly soluble in chloroform. Thehydrobromide forms bright red monoclinic prisms (m. p. 133"), whichdissolve freely in chloroform. Both the hydrobromide and the dibro-mide are decomposed by hot water, yielding 6 i - ~ ~ z o c l ~ l o r o ~ a l e t l ~ ~ ~ l i ~ C6H8BrC1N2. From this solution, the flee base is obtained by addingVOL. XLIV. 50 ABSTRACTS OF CHEMICAL PAPERS.an alkali to the solution, and extracting the mixture with chloroform.On evaporating the extract, the base remains as an oily liquid, whichslowly solidifies to a crystalline mass.CeH,BrCIN2,HCl,and the nitrate form prisms containing water of crystallisation.ylatir~ochZoride, (C6HBBrCl~,,HCl),,Pt~~~, and the silver saZt,can be recrystallised from alcohol.Chloroxalethyline is decomposed by dilute sulphixric acid a t 240°,with formation of ammonia and ethylamine.On oxidation withchromic acid, ethyloxamide, oxnlic and (probably) ethyloxamic acidsare produced. When a mixture of chloroxalethyline and lime is dis-tilled, pyrroline, ammonium chloride, and para-oxrcZmethy Zine, C,H,N2,are formed.DioxaZetly Zin e, ClzHl9N4, qrepared by the action of sodium on chlor-oxalethyline, is an oily liquid which boils above 300".On distilla-tion with lime, oxalethyline yields pyrroline, hydrocpanic acid, para-oxalmethyline, and animonium chloride. When oxalethyline isheated with dilute sulphuric acid a t 240", it yields ethylamine, andon oxidation with potassium permanganate it splits up into ammonia,acetic and oxalic acids.The derivatives of oxalmethyline and propyline have been pre-viously described (Abstr., 1881, 572).Chloroxalanzyliiie, C12HzlC1N2, prepared by the action of phosphoricchloride on di-amyloxaniide (m. p. l28"), is a liquid boiling a t 267-270". The hydrochloride and platino-chloride are crystalline.Oxalmethyline has been shown to be identical with methy Z-g ZyoaaZine,NH : C<C,">N (Abstr., 1882, SZl), but oxalethyline and oxalpropy-line are not iden tical with propyl- and amyl-glyoxalines.The hydrcchZoricZe,The( CeH, B rCl'N2) 2, AgN03,This base crystallises in silky needles, melting at, 136".It is not miscible with water.CHThe constitutional formulE of these two oxalines is either-CH,.CH, CHMe\---C@ - CH/C H,.CH, CMe,CH : N'NH: C/ \N or NH:C( \N\- CHfl'WH~ or NH:C/ \N. NH: C<w. c. w.Mannitine, a New Alkaloid obtained from Mannitol: By S.FCICHILONE and A. I~ENARO (Gnzzefta, 12, 416-424) .-This base,C6HRKz, is formed by distilling mannite with ammonium chloride, thereaction, which takes place according to the equation, CsH,(OH), +2(NH3,HCl) = 2HC1 + 6H,O + C6H8N2, being analogous to that ofsal-ammoniac on ethyl alcohol, by which Berthelot obtained et>h;pl-amine (-47172.ClLim. Plrys. [ 3 ] , 38, 63), and to that of the samesalt on glycerol, by which Etard obtained glycoline, C,,H,oNORGANIC CHEJIISTRY. 51(Abstr., 1881, 708). The distillate is a red-br<)wn liquid, having astrong but pleasant odour, and containing a few drops of oil, thequantity of which is increased on adding strong potash-ley ; and onagitating the liquid several times with ether, separating the etherealsolution by a tap-funnel, and distilling it, the mannitine remains inthe form of a brown strong-smelling oil soluble in hydrochloric acid,and precipitated therefrom by potash. It was purified by cmvertin?it into hydrochloride, and decomposing that salt with potash, and thengave by analysis 66.77 per cent.C, 6-32 H, and 25.84 N, agreeingnearly with the formula C6H8N2, which requires 66.67 C, 7.40 H, and2.5.93 N. Its vapour-density, determined by V. Meyer’s method, is3.82 (air = l), the formula requiriug 3-74. Mannitine boils withoutalteration at 170” (bar. 760 mm.). It dissolves in alcohol, in ether,and to a perceptible amount in water ; it has a very bitter taste, andexhibits the following reactions : with sodium phosphomolybdute, im-mediate orange-yellow precipitate, soluble in ammonia ; with potassio-nzercuric iodide, reddish-yellow amorphous precipitate ; with iodisedpotassium iodide, reddish-yellow, insoluble in dilute hydrochloric acid ;with mercuric iodide, flesh-coloured precipitate soluble in ammoniumchloride ; with Fruhde’s reagent, indistinct yellow coloration ; withnuric chloride, black precipitate.Benzene Formulae.By A. LADEVBURG (Ber., 15, 1782-1783).-Ac2ording t o Claus, the best expression of the atomic relationship inbenzene is shown by the appended figure.H. W.Clam meets the objection raised by the author, that when theatomic linking only is taken into considerntion, the combinations 1 : 2,1 : 4, and 1 : 6, are equal, by quoting another of his statements, thatthe geometrical relationships of a formula must represent correspond-ing relative attractions of the atoms, and that therefore 1 : 4, as repre-senting a diagonal, cannot be equal to 1 : 2, which expresses a side.To this the author replies that such an assumption necessitates thehypothesis that one of the combining affinities of the caybon-atomis different from the rest, As such a hypothesis is opposed to allknown facts, he considers the above graphic formula untenable.J.K. C.Benzene Formulae. By B. METER (Bey., 15, 1833--1828).--Theso-called “ diagonal ” formula, defended by Claus, has been repre-sented by the author as only allowing the pcssibility of two isomericbisubstitution products : this statement being denied by Claus, theauthor proceecls to explain his reasons. I n the prism formula, t h epositions represented by the two kinds of sides, differ from oneanother in other respects than in their functions as sides of trianglesor quadrilaterals. For example, the two carbon-atoms 1 arid 3, besidese 52 ABSTRACTS OF CHEVICAL PAPERS.being in direct combination, are also bound indirectly through 5,whilst 1 and 4 are indirectly bound by two atoms, 3 and 6 or 5 and 2.--I \ ( 1;In other words, the difference of the positions (1, 3) and (1, 4) isnot a geometrical one only, but expresses also a difference in theatomic linking.On the other hand, in the diagonal formula-4the indirect communication between (1, 2) is exactly -the same asbetween (1, 4), for instance, (1, 6. 3, 2) and C1, 6, 3, 4), &c.To this Claus answers that the diagonal linkings have a, differentvalue from the ordinary or side bonds, but this assumption the authorregai-ds as arbitrary and as introducing a new definition into thescience. The objection to the prism formula', that it does not expressthe well-known tendency of ortho-compounds to form " inner snhy-drides," becomes groundless, .when it is recollected that a similarobjection was raised against the formulae of quinones.Claus considers that it is more than probable that the formula ofnaphthalene is unsymmetrical, as it mould be if represented by thediagonal formula.If such were the case, however, there would existfour isomeric mono-derivatives, whilst, as yet only two have been dis-covered. Molecules like those of benzene and naphthalene, wbichpossess such an extraordinary degree of stability, must exhibit a verystable equilibrium in the position of the various component atoms,and this nould be best attained by a symmetrical structure.Isodurene, Isodurylic Acida, and 'the Third Trimethyl ben-zene. By 0.JACOBSEK (Bey., 15,1853-1858).-Isodurene is obtainedby the action of methyl chloride and aluminium chloride on niesitylerie(b. p. 195"). Dibromisodurene (m. p. 203") is formed from this bytreating it with excess of bromine in presence of iodine : it crystal-lises from hot alcohol in long needles. The dinitro-compound crystal-lises from the same solvent in colourless prisms melting a t 156". Thesulphonic acid was obtained in fine plates, and its barium and sodiumsalts prepared : the corresponding amide (m. p. l l 8 O ) may be obtainedin thin needles from its aqueous solution, by the usual method. Ryfusing sodium isodurenesulphonate with potash, isodurenol is obtainedas a crystalline mass melting a t 108".Isodurylic Acids.-Isodurene is boiled for some time with dilutenitric acid, and after removal of the nitro-compounds the liquid issteam-distilled.From the misture of the three acids, the a-acid maybe separated as crystalline barium salt, the other two acids being leftJ. K. C ORG-WIG CHEMISTRY. 53in the iincrystallisable mother-liquor : in its properties it agrees withBielefeldt's description. The remaining acids are precipitated byhjdrochloric acid, and separated by crystallisation from petroleum.The less soluble, termed /3-isodarylic acid, is obtained in hardshining prisms, melting at; 151': its calcium salt crystallises fromwater in a mass consisting of fine needles. Onrevaporating the petro-leum solution, e/-isodurylic acid (m.p. 84-85') is left behind incrystalline crusts, and may be purified from adhering p-acid by takingadvantage of the greater solubility of its calcium salt. It is preci-pitated from the latter in flakes, and crystallises from alcohol andwater in needles. The barium and potassium salts are uncrystallisable.By the oxidation of isodurenesulphonamide with potassium perman-ganate, sulphaminisodurylic. acids are formed, corresponding to theabove @- and y-acids.The three isodurylic acids were distilled with lime in order to ascer-tain their constitution. a-Isodurylic acid' yields the third trimethyl-benzene called by the author hemellithene .- i t is therefore representedas C6H&Ie3COOH [COOH : Me : Me : Ne = 1 : 3 : 4: 51.From the@-acid [COOH : Me : Me : Me = 1 : 2 : 4 : 61 pure mesitylerie was ob-tained, and pseudocumene from the y-acid, [COOH : Me : Me : Me =1 : 3 : 5 : 61. Hemellithene, C6H,Me, [Me : Me : Me = 1 : 2 : 31, was ob-tained pure from its sulphamide by heating it' with hydrochloric acida t 200". It boils at 168-170". Tribromh'emellithene crystallisesfrom alcohol in fine needles, melting a t 245". ~emeZZithenesuZpho?ticacid crystallises well in six-sided plates, and its amide in short trans-parent prisms, melting a t 196". Coal-tar cumene does not containhemellithene. J. K. C.Action of Aluminium Chloride on the Monohalogen Deriva-tives of Benzene. By 0. v. DUMREICHER (Bey., 15, 1866-1870).-Chlorobenzene is not acted on even when boiled for several dajs withaluminium chloride ; with bromobenzene, however, a lively r e d i o nsets in above loo", hydrochloric and hydrobromic acids are evolved inlarge quantities, and after eight or ten hours a blaok mass is formed.When this is steam-distilled, and the oil fractioned, pure benzene, andtwo dibromobenzenes, para and liquid, together with unaltered bromo-benzene, are obtained, the benzene and dibromobenzene being formedin equal molecular weights.Iodobenzene reacts with aluminium chloride at 80", the liquid be-coming violet from separation of iodine.No hydriodic acid is givenoff, the products of the reaction being benzene and diiodobenzene,with large quantities of iodine. The benzene formed is very large incomparison with the diiodobenzene, and the latter consists chiefly ofthe para-compound.It appears that the hydriodic acid formeddecomposes a t once with iodobenzene into free iodine and 'benzene.The author explains the action of aluminium chloride ou bromo-benzene by the following equations :-(1.) A12C16 + C6H,Br = BrCl + AI,CI,.C6H5.(2.) C6H5Br + BrCl = C6H4Br2 + HCl.(3.) AI,C&,(C&&) + HC1 = Al,Cl, + C6H6. J. K. C54 ABSTRACTS OF CHEJIICAL PAPERS.Metatoluidine. By A. EHRLICH (Ber., 15, 2009--2012).-Thegreater portion of this paper describes improvements in the details ofthe methods for the preparation of metatoluidine proposed by Beil-stein and Kuhlberg and by 0. Widman.~ ~ e t a t o l u y l g l y r o c i n e is obtained as a non-crystalline mass by theaction of 2 mols. metatoluidine in ethereal solution on 1 mol.mono-cliloi~acetic acid. The copper saZt, (CgHloN02)2Cu,2H20, forms brilliantgrass-green plates. Ethy ZmetatoZuy Zg ZZlcoaine, CH, (NH. C7H7). CO OE t(ethyl metatoluylamidoacetate), is obtained by the action of metato-luidine on ethyl chloracetate ; it crystallises in flat plates meltirlg at68", and is readily soluble in alcohol and ether, but only sparingly inhot water. By the action of ammonia in alcoholic solution, it isconverted into the amide of toluylglycocine cry stallising in longspear-shaped needles. A. J. G.37, 390--392).-The introduction of the NO,-group into the halogen-derivatives of the hydrocarbons of the benzene series renders thehalogen more easily displaoeable.Ammonia, for example, has noaction on monochlorobenzene, but yields dinitraniline by its action onmonochlorodinitrobenzene. The chloro- deriva ti ves of the benzeneseries are without action on rosaniline, but the chloronitro-derivativesform substitution-products which give various shades of brown andmaroon. The author has obtained such compounds by acting 011rosaniline with [ 1 : 2 : 41 chlorodinitrobenzene ehlorotrinitrobenzene,and a mixture of chloronitronaphthalenes obtained by treating mono-cliloronnphthalene with a mixture of nitric and sulphuric acids.1 mol. rosaniline is heated with 1 mol. of the chloronitro-derivative,e.g., chlorodinitrobenzene, and some glacial acetic acid in an oil-bath a t180-2200" for five or six hours.When cold, the product is extractedwith very dilute acid to remove unaltered rosaniline, then dried andtreated with benzene to remove excess of the chloride and resinouscompounds. The residue consists of the hydrochloride of the newbase, mixed with carbonaceous products. The hydrochloride and thesulphate are insoluble in water, but soluble in alcohol ; the acetate issoluble both in water and in alcohol. The hydrochloride is extractedfrom the residue by means of alcohol, and the solution mixed withsodium hydroxide, which precipitates the base in the form of a paste.The base is dissolved in dilute acetic acid, and can then be used fordyeing. On silk, it yields a very fast violet garnet colour, approachingmaroon. The dried base forms an amorphous black powder ; the saltsare green, with metallic lustre, but are not crystalline.The new colouring matter formed from chlcrodinitrobenzene is inall probability dinitrophenyl-rosaniline formed in accordance with theequation C20H19N3,H20 + CsH3C1(N0,), = CZoH~,N,.C6H,(NO,),,HCl +H20.Attempts to introduce two or three dinitrophenyl-groups wereunsiiccessful. Any excess of chlorodinitrobenzene always remainedunaltered. No satisfactory results were obtained by heating neutralor alkaline alcoholic solutions in sealed tubes. It is worthy of notethat the introduction of two nit'roxyl-groups changes the colour ofmonophenylrosaniline from violet to maroon.Rosaniline-derivatives. By E. N o E r m N G (BUZZ. XOC. Cl~im.. [2]ORGAXIC CHEMISTRY.55Phenylrosaniline is converted into a sulphonic acid by the action ofDinitrophenylrosaniline is carbonised withoutThe sulphonic acid may, however, beIt formsNitronaphthylrosaniline has a much more violet colour than thestrong sulphuric acid.formation of sulphonic acid.obtained by the action of chlorosulphonic acid S0,HCl.salts which yield colours very similar to those of the original base.nitrophenyl-derivative. C. H. B.Azylines. By E. LIPPNANN and I?. FLEISSNBR (Honatsh. Chenz., 3,705--714).--The authors apply the berm uzylirces to a series of basesobtained by the action of nitric oxide on tertiary amines, and in whichthe tetravalent-group >N-N< is contained in union with benzenenuclei. At present, tertiary azylines of the aromatic series alone havebeen obtained.These compounds are crystalline, and of red colour ;dissolve in hydrochloric acid to fine purple liquids, and in acetic acid t ogreen solutions, from which they are reprecipitated in the amorphousform on adding water. They yield crystalline compounds with thechlorides of platinum, iron, gold, &c. The picrates are crystallineand sparingly soluble. When heated with alcoholic iodides a t loo",the azylines form ammonium compounds. With nitrous acid, nitroso-compount 1s are formed ; as these give Liebennann's colour-reactionwith phenol and sulphuric acid, the tertiary nature of the compoundsis rendered highly probable. If treated with stannous chloride or withhy driodic acid and phosphorus, the azylines yield unstable hydro-corn-pounds, from which crystalline platinochlorides can be prepared.Yiil-zethylu?zili,Leazylitie, NMe2.C6H, : N.N C6H3.NMe2 (m.p. 266'),has been already described. (Abstr., 1881, 161, the formula, C9H,,N-,there ascribed to it being due to an error in analysis). Its formationis represented by the equation 2CBH1,N + ZNO = dH,O + CI6Hl8Ni.On oxidation, i t yields oxalic acid and carbonic anhydride. The picrateis obtained as an alcoholate, CisHl8N4,C6H3(NO2),O 4- C2H60, inbrilliant leaf-green needles.Diethllln?LiLineazyZirLe, C2,H2,N4 (m. p. 170"), forms red needles solublein chloroform and hot alcohol, sparingly soluble in cold alcohol. Thepicrate, C,0H26N4.2[ C6H,(N02)sO], crystallises in yellow needles.Ui~.l.opyla?Lili?Lea~~line, C2iH3iN,, crystallises in red tables of therhombic system, melting at 90".The crystals were measured byScrauf, and gave axial relations a : b : c = 1 : 0.629 : 0.913. Themost important, faces are 101 : 100: 110 : 001.DibutyZ~nill?zeazyZine, C2sH12N4, crystallises in needles melting at1%".Dia~nnyZarLili?zeazyZ,ine, C3,H54N, (m. p. l l S O ) , forms red spear-shapedcrystals, soluble in hot alcohol. It dissolves in concentrated hydro-chloric acid, butl is decomposed on boiiing. A. J. G.Trimethylphosphobenzobetai'ne. By A. MICHAELIS and L.CZIMATIS (Bey., 15, 2018--202O). - Trimethylphosphobenzobeta'ine isobtained as chloride by the oxidation of paratolyltrimethylphospho-nium chloride with potassium permanganate a t a temperature of 55".The chloride forms short, thick, brilliant, colourless prisms of th56 ABSTRACTS OF CHEMICAL PAPERS.formula C6H4(COOH),PMe,Cl ; it is insoluble in ether, soluble in hotalcohol, and very soluble in water.Theplatinochlokle is obtaiiied as a light yellow crystalline precipitate.The free betuzne, C6H4<'pMe~>0,3H,O, is obtained by neutralisationof a solution of the chloride ; it crystallises in rhombohedrons, andeffloresces readily. It does not give salts with bases, but with acids itgives well characterised compounds. The acetate crystallises inslender needles of nacreous lustre, the nitrate in needles. Withexcess of dilute snlphurio acid, it gives an acid salt also crystallisingin needles. On heating the chloride with potash, it is decomposedaccording to the equation-It is decomposed by heat.coC6H4(COOB[).PMe3Cl + KOH = C6H,.COOH + PMe30 + KCI,By the action of potassium permanganate, on the addition-productof ethylene bromide and dimethyltolylphosphine, a compound,C6H4 (c 00 H) .PMeZO,is obtained; it crystallises in colourless prisms of faint acid taste,melts at 243",.and can be ,sublimed with but little decomposition.A. J. G.Formation and Decomposition of Acetanilide. By L. MEYER(Ber., 15, 1977-1978) .-With regard to the formation of acetanilide,the results obtained a t 130" by Steudel in the author's laboratoryagree with those of Menschutkin ; a t 155" a complete reaction nevertakes place., but in the reverse reaction an important difference occurs.According to Menschutkin, the incompleteness of the reaction is duet o the resulting water reacting on the acetanilide and partially decom-posing i t ; but on heating acetanilide with water at 130" for sometime, no traee of an mid reaction could be obtained, so that theincompleteness of the reaction cannot be due to that cause.A. J.(3.Constitution of the Aximido-compounds. By P. GRIESS (Eer.,15, 18Z3--1882).-Under the above definition, the author includesthose bodies which have so far been obtained only by the action ofnitrous acid on aromatic orthodiamido-compounds, the first of whichwas prepared by Hofmann from orthodiamidonitrobenzene. Amongstothers, two have been obtained by the author from 6- and ydiamido-benzoic acids. Two different views of the constitution of thesebodies have been proposed, the one by KeknlB, and the other byLadenburg. According to the former, Hofmam's compound would be,NH.represented by NO,.C N /VN, while Ladenburg assigns the for-5(-N-Nmula N0,.C6H3(NH2)' 11 .'NThe author's investigations, however, lead him to represent thORGANIC CHEMISTRY.57Nabove compound thus : N02.C&&( 1 )NH, and he bases his view on'Nthe following facts :- a- and 6-nitrouramido-benzoic acids,B. 6.COOH (1) (1)N02.CsH3 NH.CO.NH, (3) (4)when heated to boiling with concentrated potash-solution, are bothconverted into p-azimidobenzoic acid with formation of ammonia andcarbonic anhydride.According to RekulB's view, two isomeric acids would be formed ;whilst, if Ladenburg's view were correct, the production of an azimido-benzoic acid would in this case be impossible.When the above fi- and &acids are treated with tin and dilutehydrochloric acid, they: are converted ints the corresponding diamido-acids, which by nitrous acid are converted into the same azimido-uramidobenzoic acid, a fact which only admits of explanation whenthe formula proposed by the author is employed.In the same manner, y-nitrouramidobenzoio acid can be convert'edinto azimido-compounds5 the and s-acids, however, react in atotally different way.Mixed Aromatic Tertiary Phosphines.By L. CZIMATIS (Ber.,15, 2014-2018) .-These compounds were preplared from the homo-logues of phosphenyl chloride by the action of the zinc alkyls.Parndinzethylto7y~hos~hine, C6H4Me.P&fe2, is a colourless liquid ofdisagreeable odour ; it boils a t 210", and does not, solidify a t - 10" ;i t has basic properties, and dissolves in acids ; the chloride yields ajellow flocculent precipitate with platinum chloride. It does notoxidise on exposure to air, but is.converted by mercuric oxide intodirnefI~y1toly~hosphine oxide, C6H4i!de.P1\/Ie0., forming a thick oilyliquid. With mercuric chloride, this yields the double salt,C6H&le.Plk!e20,HgC12,H20,crystallising in slender silky needles, melting a t 156".Methyl iodideuiiites violently with dimethyltolylphosphine, .yielding the phos-phonium iodide, C6H4Me.Ph!fe31 ; it crystallises in colourless needlesmelting at 255", readily soluble in water and hot alcohol, sparingly incold alcohol, insoluble in ether.With mercuric chloride it gives anunstable double salt crystallising in needles. The hydroxide is obtainedby t,he action of silver oxide and water as a strongly basic deliquescentmass ; on treatment with hydrochloric acid and platinum chloride, t,heplatinochloride, ( C6H,D/Ie.PMe3CI)2,PtC14, is obtained in orange-yellowplates melting a t 250".C6H4Me.PMe313,olitained by the action of iodine on the iodide, cryst~tllises in steel-blue rhombs, soluble in alcohol, and sparingly in benzene and ether.Dimethy1to)ylphosphine combines wikh benzyl chloride to an uncrys-(NH, (4) (3)J. K. C.Trimethyltolylphosphonium periodide58 ABSTRACTS OF CHEMICAL PAPERS.talline mass ; the platinochloride, ( C,H,nle.PMe,.C1CiH.I)2,PtC14, meltsat 226".Pu~ad~ethyltol~~hosp7z~ne, CfiH4Me.PEt,, boils at 240", and resemblesthe preceding compound.The methiodid e crystallises in colourlessneedles melting a t 137'" ; the platinochloride in clear yellow plates.Dim ethy ZLy ZyZphosphine, C6H3Me2.PMe2, is a colourless liquid boilinga t 230".DiethyZlryly~~hosphin,e, C,H,Me,.PEt,, is a thickish liquid of faintcolour, boiling a t 260'. The methiodide (m. p. go"), and ethiodide(m. p. 136"), form white crystalline powders, readily soluble in waterand hot alcohol, insoluble in ether. Methyldiethylphosphoniumplatinochloride crystallises in cadmium-yellow rhombic plates, meltingat 202".A comparison of the boiling points of the phosphines shows a riseof 20" for the entry of a methyl-group ifito the aromatic nucleus, whilstthe difference of boiling points of the members of the series is 30".B.p. B. p. Diff.C6H5.PMe, ........ 190" CfiH,Me.PMe, .... 210" 20"C6H5.PEt, ........ 220 C6H4Me.PEt2 .... 240 20B. p. Diff.C6H,Me,.PMe2 .......... 230" 20"C6&jh!fe2.PEt2.. .......... 260 20Dimeth ylphenylphosphine and carbon bisulphide, when mixed inethereal solution, give a compound of the formula C6H,.PMe,,CS,,crystallising in glistening red scales, soluble in carbon bisulphide, in-soluble in ether. It melts in open tubes, with dissociiLtion, at 97" ; inclosed tubes at 101". It has basic: properties, is dissolved by diluteacids, and reprecipitated by soda.( C6H5.PMe?? H C1, C S,) 2, Pt C14,is obtained as an amorphous pale yellow precipitate ; on exposure toair, it loses carbon bisulphide, and is converted into dimethylphos-phonium platinochloride.When the original compound is treated withdry hydrochloric acid or methyl iodide, it is decomposed, carbon bisul-phide being eliminated and phosphonium compounds formed. Waterdecomposes the compound slowly a t ordinary temperatures ; rapidlyon heating.Dimethyltolylphosphine unites with carbon bisulphide, formingclear red plates of the formula C6H4MePMe2,CS2, melting at 110" inan open tube, a t 116" in closed tubes. It closely resembles the pre-ceding compound ; the platinochloride, however, is more stable whenexposed to the air.DimethylxylylphospEiine and carbon bisulphide form the compoundCfiH,Me2.PMe,,CS2 ; it ciytallises in clear red plates, and melts a t115" in open, and a t 121" in closed tubes.Diethylphenylphosphine unites slowly with carbon bisulphide,forming a red crystalline product which could not be obtained in astate of sufficient purity for analysis.Action of Potassium Carbonate on the Chlorides of Benzyland Benzylene.By J. MEUNIER (Bull. Xoc. Chim. [ 2 ] , 38, 159-The platinochloride,A. J. GORGXXlC CHI"M1YTRP. 59160). - By heating ethylene bromide with an aqueous solution ofpotassium carbonate, Zeller and Hufner have obtained glycol directly(this Journal, 1876, ii, 64) ; the author has studied an analogousreaction with benzyl and benzylene chlorides. I n the case of benzylchloride the corresponding or benzylic alcohol mas obtained, but withbenzylene chloride benzaldehyde was formed, the yield being two-thirds of that required by theorj-.By A.LIEBXANN (Ber., 15,1990-1992).-Isobutylphenyl ethyl oxide boils a t 241-242" uncorr. (not234-236", as given in the author's previous communications, Abstr.,1882, 171, 727). By treatment with nitric acid, it yields the ?litm-ether as an oil volatile with water vapour, boiling with decomposi-tion at about 300", and yielding the nmido-ether on reduction. AnlyZ-yhenyl ethy2 om'de boils iat 259-261", and yields mononitro- andamido-compounds like the above.Nitro-derivatives of the Cresols. By E. NOLTING and E. v.SALTS (Ber., 15, 18,58-1865) .-Dinritl.o-~arucl.esoZ.-The ethylic etherof this body is prepared by treating the silver salt suspended in alcoholwith ethyl bromide or iodide; it melts a t 73".The correspondingdiamido-salt, of which only the hydrochloride was prepared, shows thecharacteristic reactions of metadiamides.Dinitro-orthocresol, CGHzMe(N02)2.0H [NO, : NO, = 4 : 61, agreesin all its properties with that obtained by Picard from saffron sub-stitute. The barium salt crystallisesin shining yellow needles, easily.soluble in hot water. The hIdro-chloride of the diamido-compound decomposes in the air, and must beevaporated in a stream of sulphuretted hydrogen.!fii.nitro-cresoZ, obtained from coal-tar cresol, is identical with thatprepared from meta-cresol : it, separates from water in slenderyellowish-white needles melting a t 106".Like picric acid, i t formsmolecular compounds with hydrocarbons. Its composition is repre-sented by the formula-V. H. V.Isobutyl- and Amyl-phenols.A. J. G.The ethylic ether melts at 46".[NOz: OH :NO,: Me: NO, = 1 : 2 : 3 : 4 : 51.The ethyl ether is easily converted into trinitro-toluidine by treat-ment with ammonia ; no separation of a nitro-group occurs as wouldbe the case if two of these groups were in the ortho-position to eachother. The ethylic ether may be prepared by treating the silver saltwith ethyl bromide, and forms thick white needles, melting a t 72".Trinitro-metatoluidine forms small crystals melting a t 126", verysoluble in alcohol and ether, and having weak acid characteristics.Heated with alkaline solutions, it is coovered into trinitro-cresol.J.K. C.Fusion of Orcinol and Gallic Acid with Soda. Bg L. BARTHand J. SCHREDER (Nonutsh. Ckem., 3, 645-650). - Orcinol, whenfused with sodium hydroxide, yields resorcinol (15-16 per cent.),phloroglucol (about 1.5 per cent.), pyrocatechol (1-1.5 per cent.),and a new body, C13H,,0A (about 5 per cent.). This latter is, in allprobability, tetral?,~droz2/di~lienZll?nethane, CHz[ C6H3(OH),]z, it formslong, satiny, snow-white needles, readily soluble in alcohol and ether 60 ABSTRACTS OF CHENICAL PAPERS,it. commences to decompose at 260". It gives no coloration withferric chloride. I n this reaction, it would appear that the methyl-groupis first oxidised, and then split off, so that resorcinol is formed, whichby fiirther oxidation yields phloroglucol : a very large proportion ofthe orcinol however is completely oxidised.The substance, C13H1204,is an intermediate product, and the catechol is due to a secondaryreaction. In accordance with this view, when the heating is continuedfurther, little but phloroglucol is obtained.By the action of fused soda on gallic acid, .phloroglucol is formedin small quantity (0-6-0.8 per cent.) in addition to pyrogallol andhexhydroxydiphenyl (Abstr., 1879, 926).Catechol is acted on by soda a t a high temperature only, and is thencompletely oxidised. Quinol also is but slowly attacked by soda;the products of the reaction have not yet been obtained in the purestate. A. J. G.By H. SCHIFF (Bey., 15, 1841--1844).-Thisbody has already been prepared by Michael from methylqiiinol andacetochlorhydrose ; it was thought advisable to prepare it by anothermethod, and to compare the substances obtained.Equal volumes ofa methyl alcohol solutions of methyl iodide and potassium hydroxide,were gradually added to a solution of arbutin in the same medium,the mixture being boiled after each addition : after concentration andcooling, the methylarbutin. which separated was purified by repeatedcrystallisation from water; it was found to differ in two points fromMichael's preparation : it melted a t 175-176" (168-169" Michael),and contained 1 rnol. H20 instead of half a molecule. Mixed witharbutin (m. p. 187") it melted a t a much lower temperature.Fromconcentrated solutions containing potassium iodide it can be recrys-tallised free from water. It is soluble in water especially wheu hot,and in alcohol, but only sparingly in ether. Commercial arbutin con-tains about 30 per cent. metJiylarbutin, identical with that obtainedby the author. Whether the latter is the same as that prepared byMichael is still open to question.By S. SCHURERT~ (Monatsh. Chel-ra., 3, 680-687).-Di-isobutylquinol (paradi-isobutoxybenzene), CGH,( C4H,0),, isprepared by heating together quinol, potassium isobutyl sulphate, andpotassium hydroxide, in sealed tubes, for 4-5 hours at 150". It formsa colourless leafy crystalline mass of fatty lustre, is insolnble in water,more soluble in benzene and light petroleum, readily solable inalcohol and in hot glacial acetic acid.By theaction of chlorine, it yields chloranil, dichlorodi- isobufylquiiaol, crystal-lisirig in colourless rhombic plates, and tetl.achlorodi-isohut~lzz~~~~~Z,forming long, colourless, interlaced needles, of silky lustre. The onlybromine-derivative obtained was dib,.omodi-isobutylyui7iol, crystallisingin colourless quadratic plates. Tetranitrodi-isob uty Zpuinol cryetallisesin long thin needles, sparingly soluble in water, readily soluble inalcohol, ether, and hot glacial acetic acid.Compounds of Benzo- and Toln-quinol with Amines and ofQuinone with Nitranilines. By A. HEBERAND (Ber., 15, 1973-Methylarbutin.J. K. C.Di-isobutylquinol.It boils a t about 262".A. J. GORGASIC CHEJIISTRT.611!)76) .-Occasionally, in the preparation of quinonedianilide, a com-pound of quinol and aniline, C6H,(OH)2,(C6H5NHz)2, is found in themother-liquor. It forms large micaeous plates, melting a t 89-90",and is readily soluble in hot water and in alcohol. In aqueous solution,i t is readily oxidised to quinonedianilide. It is decomposed when boiledwith benzene, and quinol crystallises out, but the same substance canbe prepared by boiling quinol and aniline in aqueous solution. Thecorresponding paratohidine compound, c6&(oH)z, (C,H,.NH2)z (m. p.95-98") , prepared directly from quinol, resembles the aniline com-pound. Orthotoluidine and naphthylamine compounds could not beobtained in the pure state.Attempts were made to prepare similar compounds with phenol,resorcinol, antl pyrogallol, but without success. With toluquinol, ananiline compound, mystallising in white Eeedles, melting at 82-85',and a paratohidine compound, crystallising in nacreous plates, melt-ing a t go", were obtained.Quinune and Pa?.anitraniZiize.-On mixing hot alcoholic solutions ofthese bodies and cooling, large dark-red crystals (m.p, 115-120')separate, which by heating or by boiling with water are resolved intotheir constituents. The composition of this substance varied in dif-ferent preparations from-C6H407 C:,Ha(NOz) NHz, to 2CsH4OZ73'(NO2. C,H,.NH,).I n acetic acid solution, or by long boiling with alcohol, the course ofthe reaction is different, quinonedinitranilide ,being formed in smallbrown needles, together with a substance of wid nature, crystallisingin red-violet plates, melting at 183".Quinone and O1.t~onitraniZL'ne.-Solutions of these substances, whenmixed, yield large red crystals melting at 94-97"; with excess ofnitraniline, a new body of the formula c 6 ~ , 0 2 , 2 ( N ~ , .c , H ~ . ~ H ? ) , isobtained. When boiled with glacial acetic acid, it yielded the corre-sponding dinitmnilide, crystallising in brownish-red needles. Meta-nitraniline and quinone yield nothing but puinunedinzetan,it~aiziZide,forming yellowish-brown needles.With orthonitraniline toluquinone gives an addition-product (m. p.31") resembling those already described. A. J. G.Compounds of Vanillin with Pyrogallol and with Phloro-glucinol.By C. ETTI (Munatsh. Chem., 3, 637-644).--Singer hasrecently shown (Abstr., 1882, 1122) that the deep red coloration im-parted to pine wood by phloroglucol in presence of hydrochloric acid,is due to a compound formed with the vanillin which is present in thewood. The author has further investigated this compound, and alsothe analogous one of pyrogallol with vanillin.PyroyaZZovaniZZei??, C20H,R08, is prepared by mixing vanillin and pyro-gallol with alcohol and an excess of concentrated hydrochloric acid ;it forms colourless crystals destitute of odour, insoluble in water,sparingly soluble in ether, readily soluble in strong alcohol, By longstanding over sulphuric acid, or by drying at 110", 2 mols. of the sub-stance lose 1 mol. of water, yielding the body C40H30015. Whencrystallised from solutions containing free hydrochloric acid, pyro62 ABSTRACTS OF CHEMICAL PAPERS.gallovanillejin is obtained in fine violet-blue crystals, which containhowever, a trace of hydrochloric acid.PhZoruylZuci~zol.c;.anil Zein, prepared in a manner similar to the above,forms yellowish-white crystals, and behaves towards solvents likep,rro,nallovanillejin.It loses water more readily with formation of thehrownish-red compound, C40H14015. Crystallised from hydrochlorica cicl solutions, the characteristic fiery-red compound is obtained, buta s in the previous case the amount of chlorine contained is too smallto estimate. The formation of these vanilleins is expressed by theequation-COH.CGH3(OH).0Me + 2C6H,(OH), =~H[c~H~(oH)~]~.c6H3(ofT) .OMe + H20,and they must be regarded as derivatives of triphenylmethane.On rubbing together resorcinol with vanillin and hydrochloric acid,a deep bluish-violet coloration is produced ; but the colour vanishesafter a time ; the addition of water causes the precipitation of a whitecrystalline powder. A.J. G.Action of Acetic Chloride on Benzaldehyde in presence ofZinc-dust. By C. PAAL (Ber., 15, 1818--1820).-When acetic chlo-ride is dropped into an ethereal solution of benzaldehgde in whichzinc-dust is suspended, a violent reaction takes place ; zinc chloride isformed, and the ethereal solution, after being washed with water andevaporated, deposits a yellow crystalline mass from which alcoholextracts a substance crystallisirig in white needles of the formulaCeH80,, melting at 125-1 28".Heated with amorphous phosphorusand hgdriodic acid, i t yields dibenzyl, and, when distilled with zinc-dust, i t gives rise to stilbene : these decompositions, however, throwno light on its constitution. A reaction similar to the above occurswhen ethaldehyde is treated with acetic chloride.Orthamidobenzaldehyde. By S. GABRIEL (Bey., 15, 2004-2006).-The author has already shown, in conjunction with R. Meyer(Abstr., 1882, 188) , that nitrosomethylorthonitrobenzene yields ortho-nitrobenzaldehyde on oxidatlion, and (Abstr., 1882, 1070) that the cor-responding meta-compounds give similar results ; as this appears to bea general reaction for nitrosomethyl compounds, he has applied i t tonitrosomethylorthamidobenzene. The oxidation was effected by adightly insufficient quantity of ferric chloride ; during the reaction,some salicylic aldehyde distils.The contents of the retort are madealkaline and distilled, when o?.tharnidoheizza7del~~ae is obtained as anoil, solidifying to a crystalline mass on cooling ; i t melts a t the tempe-rature of the hand. In an exsiccator over sulphnric acid, i t appears todecompose, the walls being covered with a crystalline deposit, whilstthe other (greater) part of the substance is converted into a yellowbody not meltiiig a t 100".Action of Benzoic Anhydride on Epichlorhydrin. By P.VAX ROXBURGH ( R e c . 7'r.a~. Chim., I, 46--52).*-When these two bodies* Recueil des Travaux Cliimiques des Pap-Bas : par W.A. van Dorp, A. P. N.Franchimont, S. Hoogewertf, E. Xulder, et A. C. Oudemans, Jr. Leide. 1882.J. K. C.A. J. GORGANIC CHEMISTRY. 63in molecular proportion are heated together in sealed tubes at about190" for seven to ten hours, and the product is left a t rest for sometime, the whole concretes to a mass of small crystals soaked in a thickliquid. By solution in ether and spontaneous evaporation, colourlesscrystals (m. p. 70") are obtained containing a small quantity of chlo-rine, and by recrystallising these from alcohol crystals are formed freefrom chlorine, and melting at 74". These crystals have the composi-tion Cl2Hl0O3, or rather C21H2006, and are resolved by saponificationwith alcoholic potash into benzoic acid and glycerol.The compoundis tberefore t r i b e n z o i c i n , formed according to the equationCH,: CHO.CH,Cl + 2BY20 = E C l + O&.CH(CH2.0&)2*;and, as thus prepared, it is identical in its properties with that whichis obtained by heating glycerol with benzoic acid or benzoic anhydride.I t s formation in the manner above described is accompanied by that ofa liquid, which the author regards as probably consisting of a mixtureof mono- and di-benzoicin. H. W.Epichlorhydrin. Tribenzokin..Action of Benzoic Anhydride on Monochloracetone and onPyruvyl Benzoate. By P. VAN ROMBURGH ( R e c . Trav. Chim., 1, 53-54).-Monochloracetone and benzoic anhydride, heated together forthree honrs in a sealed tube a t 180°, formed a black solid substancecontaining benzoic acid, and having a faint odour of benzoic chloride.By heating monochloracetone with potassium benzoate in alcoholicsolution for 12 hours, then filtering and expelling the alcohol by eva-poration, a liquid is obtained which, when distilled a t 245" under apressure of 380 mm., yields a yellow distillate solidifying when sur-rounded by ice; and 011 pressing the solid mass between bibulouspaper to remove oily products, then dissolving it in ether and evapo-rating, p y r u vyl benzoate, CI0H1003 = COMe.CH,.OE, is obtainedin splendid colourless crystals which melt at the heat of tlie hand (25")and have a density of 1.143 at.25'. Their alcoholic solution has noaction on polarised light.Pyruvyl benzoate, like monochloracetone,reduces potxssio-cupric sulphnte, even at ordinary temperatures.Heated with benzoic anhydride i n a sealed tube a t 180", it graduallyblackens and yields a sublimate of benzoic acid.H. W.Synthesis of Cumic Acid. By R,. METER and E. M ~ L L E R (Bey.,15, 1903-1906) .-The authors have repeated their synthesis of cumicacid (Ber., 15, 496) on a larger scale with the view of examining thecause of discrepancy between the melting point ( 1 l O O ) of their syn-thesised acid and that (116") of ordinary cumic acid. The ciwneneW a s prepared by the action of isopropyl bromide on benzene in thepresence of aluminium bromide, then converted into parabromocumene,and this, after careful purification, WRS submitted to the action ofsodium and moist carbonic anhydride.The acid obtained in this waydiffered from that previously prepared in having the correct meltingpoint (116--117"), and it agreed in all respects with ordinary cumicacid. Since both the para-propylbeuzoic acids have now been madesynthetically by similar reactions, there can be no further doubt o64 ABSTRACTS OF CHEMICAL PAPERS.their constitution-cumic acid containing the isopropyl group, and itsisomeride, normal propyl.An attempt to prepare propylbenzoic acid by the action of sodiumamalgam on para-propylbenzene and chlorocarbonic ether did not yieldvery definite results, for although a small quantity of propylbenzoicacid appeared to be formed, the chief product of the reaction was anew bojy of the formula HgJC6H,.C3H;)2 [Hg : C,H, = 1 : 41 (m.p.logo). A. I(. M.Phenylacetic Acid. By S. GABRIEL (Ber., 15,1992-2003).-Bythe action of fuming nitric acid on bromacetamidobenzyl cyanide(m. p. 12 7-129'), acetanzidobromn?iitrobe.lzzyl cyapbide,CsH2(CH2.CN)(N02)(NH&)Br = [l : 3 : 4 : 51,is obtained in slender pale-yellow needles melting a t 190-1 91", andspa,ringly soltible in cold water, more readily in alcohol and glacialacetic acid. When boiled with hydrochloric acid, it yields arnidobromo-nitro$hen,yZace€ic acid,C~H2(N02)(NH2)Br(CHz.COOH) = [3 : 4 : 5 : 13,crystallising in long golden-yellow needles melting a t 191-192", aridsparingly soldble in cold water, readily in hot alcohol, moderatelysoldble in chloroform and benzene. By reduction with tin and hydro-chloric acid, it is reduced to the diarnide-acid,C6H2Br (N13,)2.CH2.000H.This forms groups of long colourless needles, which darken a t 190'and melt with intumescence to a black mass a t 19'Fj--2OO0.Theresults of the reduction show €hat the nitro-group must have enteredthe benzene nucleus a t the 3-position, as in the case of the otherpossibilities [ 2 or 61, an inner anhydride, bromamiao-oxindole,NH2C6HdBr<NH CH2 >CO,would be produced, on reduction.Metanitroparamidophenylacetic acid (m. p. 143.5-144'5") giveson reduction the diamido-acid, c6H3(XH2) (NH,) (CH,.COOH) =[3 : 4 : 13, crystallising with 1 mol. H20 in short hard compact formsshowing numerous faces, sparingly soluble in hot alcohol.By the action of amyl nitrite and hydrochloric acid on the abovemetanitro-acid (m.p. 191-192"), a large yield of a substance givingdiazo-reactions was obtained, buit no formula could be deduced fromits analysis, the fact that it contains chlorine and brominein no simpleratio to one another pointing to a mixture of substances. On gentlyheating it with alcohol, a crystalline mass is obtained which, on beingmixed with soda and distilled with steam, gives an oil solidifying aftera time t o a mass of crystals insoluble in soda, whilst the residue in theretort, after acidification and renewed distillation with steam, yieldscolourless crystals (m. p. 108-109") soluble in water. The results ofanalysis showed these to be a mixture of dihalogen nitrosomethyl-benzenes, C,H3X2.CH2N0 (X, = ClZ or Br, or BrC1). The crystalsinsoluble in soda first obtained (broad flat needles melting a t 65-65.5") gave results agreeing with a mixture of dihalogen benzaldehjde,and on oxidation yielded a mixture of dihalogen cinnamic acids.A.J. GORGANIC CHEMISTRY. 63Action of Sulphuric Acid on Protocatechuic Acid. Bg E.NOELTING and R. BOURCHABT (Bull. 8oc. Chim. [2], 37, 394-397).-1 gram protocatechuic acid is heated with 2 grams of benzoic acid and50 grams of sulphuric acid of 66" B. a t 140-145" for eight hours, andthe product is poured into water, which throws down a deep brownflocculent precipitate ; this is collected, dissolved in dilute soda solu-tion, and precipitated by hydrochloric acid, this treatment beingrepeated several times.The clear brown flocculent substance thusobtained produces with mordants almost the same shades as alizarin,but is distinguished from the latter by the reddish-brown colour of itsalkaline solution and by its a~sorp~ion-spectrurn. The yield is verysmall, whatever the proportion of sulphuric acid, the time of heating,and the temperature. The benzoic acid appears to play no part in thereaction, for, when protocatechuic acid is heated alone at 140-145"with 20-25 times its weight of sulphuric acid, the same product isobtained, although in this case also the yield is very small.The substance thus formed yields an orange-yellow alcoholic solu-tion, which becomes violet with a yellowish fluorescence on addition ofpotash, After some time, the compound is precipitated in red flocks.Alcoholic lend acetate throws down a floccnlent brown precipitate :calcium chloride and ba,riunL chloride produce a violet fluorescence inthe yellow solution, and after some time a precipitate is formed ; ,ferricchloride gives a blackish-brown, ammonia a violet-brown, and alum areddish precipitate.I t s solution in dilute ammonia is brownish-red,approaching violet. In this solution calcium and barium chloridesproduce a brown, lead acetate a reddish-brown, and absolute alcohol aviolet-brown precipitate. Its solution in dilute potash gives, withabsolute alcohol, a reddish precipitate, with alum a reddish-lake, andwith ferric chloride a blackish-green lake. The substance is dissolvedby strong sulphuric acid, with formation of a brownish-violet solutionwhich, when poured into water, yields a yellow solution and a slightprecipitate. It also dissolves in glacial acetic acid, forming an orangesolution.The properties of this substance agree with those of rufiopitbe,CeH,(OH),< c0>CG€12( OH),, obtained by Anderson ( Annalen, 98,51) by the action of concentrated sulphuric aci3 011 opianic acid a t180", and described by Liebermaim and Chonjnacki (Am~alen, 162,321).By analogy from the behavioiir of other hydroxyl-derivativesof benzoic acid, protocatechuic acid ought to form a colouring matteraccording to the equationIt cannot be sublimed without decomposition.coThis reaction is more complicated in the case of opianic acid; butsince in both compounds the hydroxpl-groups occupy the same posi-tions with respect to the carboxgl-groups, it is highly probable thatthey will yield identical condensation-products when acted on bysulphuric acid.C. H. 13.Oxidation-products of Carbon obtained by Electrolysis.By A. MILLOT (Bull. SOC. Chiha. [2), 37, 337-339).--The gas-VOL. XIJV. Gci ABSTRACTS OF CHEMICAL PAPERS.carbon electrodes (Abstr., 1880, 482) are much more rapidly attackedin alkaline solutions than in pure or acidulated water. The dark solu-tion obtained by the electrolysis of a 5 per cent. solution of ammonia,with gas-carbon electrodes becomes acid on evaporation. It containsammonium nitrate and an acid which may be isolated by evaporatingalmost to dryness, heating the precipitated black matter with alcohol,and evaporating the alcoholic solution, when crystals of the ammo-nium salt of the acid, mixed with ammonium nitrate, separate out.The crystals are dissolved in water and mixed with lead nitratewhich produces a crystalline precipitate.This precipitate is sus-pended in water, treated with hydrogen sulphide, the solution filteredfrom lead sulphide and evaporated, when the acid separates out inneedles. I t s composition will be determined when a-sufficient quantityhas been obtained.The black matter precipitated by the addition of an acid to the solu-tion obtained by the electrolysis of a 2 per cent. solution of potassiumhydroxide has the composition 0 37.72 ; C, 58-65 ; H, 3.27 ; N, 0.56.The whole of the nitrogen was evidently not removed from the carbonelectrodes, although the latter were treated withchlorine for 150 hours.The black substance is soluble in boiling water even after being drieda t lc)Oo, bnt is precipitated by ebullition in contact with air.It isinsoluble in alcohol, ether, benzene, and chloroform. When anaqueous solution of the black substance is treated with a current ofair, it absorbs a considerable quantity of nitrogen, which however isagain partially removed by continued passage of the air, the substancea t the same time being oxidised and destroyed.By G. K~RNER ( P l ~ m . J.Trans. [3], 13, 246). - The bark emplojed differs from ordinarycinchona bark, in that its aqueous solution becomes reddish-violet onthe addition of potash, and, moreover, it yields caffeic acid when em-ployed for the manufacture of sulphate of quinine ; ’ the caffeic acid isfound in the mother-liquors as quinine caffeate.The author hasobtained the acid from the bsrk by the following process, the yieldbeing about 0.5 per cent; :--The powdered bark is first extracted withether and then thoroughly with boiling alcohol. The latter extract isevaporated to dryness and the residue treated with 24 times its weightof boiling water and its own weight of potash; the whole is thenboiled for three hours, -supersaturated with dilute sulphuric acid, fil-tered hot, and extracted with ether. This extract is concentrateduntil crystals form. The crystals are well washed with small quantitiesof ether, and are purified by boiling with animal charcoal and recrys-tallising.They form brilliant hard yellowish tables, with 4.8 per cent.water of crystallisation. From acetic acid they separate in crusts ofopaque nodules, which decompose without melting a t 212”, and havetbe formula C,H,O, + +H20, and they give the characteristic reac-tions of caffeic acid. Dimethylcaffeic acid and methylic dimethyl-caffeate were prepared from the acid and identified.The presence of this acid furnishes an additional proof of the re-lationship existing between the coffee and cinchona plants.C. H. B.Caffeic Acid from Cuprea Bark.D. A. LORGANIC CHEJIISTRY. 67Dibromonaphthalene from ,%Naphthol. By P. CANZONERI(Gazzetta,, 12, 424-431) .-When 10 g. of the monobromonaphtholwhich A.J . Smith obtained by the action of bromine on naphthol(this Journal, 1879, Trans., 789) is mixed in a retort with 15 g. phos-phorus tribromide, no action takes place in the cold ; but on graduallyheating the mixture to a temperature above its meltinq point, anaction commences, attended with rapid evolution of hydrogen bromide.This, however, ceases in a few minutes, and if the mixture be thengradually heated, the action mcommences less energetically, the con-tents of the retort at the same time distilling over. This distillation,if carried on to a red heat, yields :-(1) A quantity of unaltered phos-phorous bromide ; (2) an oil having a faint yellow colour ; (3) a thickyellow oil, solidifying in bhe neck of the receiver. In the retort thereremains a considerable quantity of charcoal.The second fraction, which constitutes by far the larger fraction ofthe product, solidifies either at once or after renewed distiIIation (atabout 300") to a mass of hard transparent crystals melting at 67-68'.The substance thus obtained is a dibromonaphthalene, C10H6Br2, a,ndwhen recrystallised from a small quantity of alcohol, forms largemonoclinic prisms, cleaving easily parallel to the base OP, less easilyparallel to MP.It is but slightly refractive, and exhibits only a faintcoloration in polarised light.This dibromonaphthalene does not dissolve in nitric acid of sp. gr.1-40, but funiing nitric acid dissolves it, especially if the mixture begently heated and immediately afterwards cooled.On subsequentlyadding water, a yellow disagreeably-smelling oil separates, which soonsolidifies, and is best purified by dissolving it in a small quantity ofalcohol and precipitating with water, whereupon it separates in yel-lowish-white flocks, apparently made up of slender needles. Thesecrystals, after drying, melted a t 100-105", and gave by analysis 4'7.50per cent. bromine, the formula CI,HsBr2(N02) requiring 48.34. Thesubstance is probably a new nitrodibromonaphthalene isomeric withthat (m. p. 116.5") which Jolin obtained (Bull. SOC. Chim. [2j, 28,515) by the action of nitric acid on the P-dibromonaphthalene, whichmelts a t 81".The third portion of the above-mentioned distillate, the quantity ofwhich was relatively very small, consisted of opaque yellow scalesimpregnated with a yellow oil difficult to separate ; but by crystallisa-tion from dilute acetic acid and afterwards from alcohol, the substancewas obtained in white silvery scales, melting at 55-60", and givingby analysis numbers agreeing nearly with the formula of rnonobromc/-naphthalene, C10H7Br. As only two such compounds are possible, andone of them (a) is liquid, the compound obtained in the manner justdescribed must be the /3-modification which was obtained by Lieber-mann and Palm (Annalen, 183, 267) from p-naphthylamina, anddescribed as crystallising in lamina?, having the same appearance, butmelting a t 68" ; the difference in the melting points perhaps arisingfrom the circumstance that the author's determinations were madewith a very small quantity of material.The formation of this mono-bromonaphthalene may perhaps be ascribed either to the action of thephosphorous bromide on small quantities of @-naphthol contained inf 68 ABSTRACTS OF CHEMICAL PAPERS.the bromonaphthol, or to decomposition of the dibromonaphthalene a tthe high temperature of the reaction.From the perfect agreement in melting point between the dibromo-naphthalene above described and that recently isolated by Guareschi(Abstr., 1882, 734), from Glaser's impure product (melting a t 76"),the autlhor infers the identity of the bodies obtained in these severalways, and thence deduces the constitutional formula of the dibromo-naphthalene in question. This body in fact, having been obtained byGlaser from a-bromonaphthalene, must have one of its bromine-atomsin the a-position, b u t since it is also producible from monobrom-6-naphthol, it must have the other in the @-position, and consequentlymust be an a-/3-dihromonaphthalene.Now of the ten possible dibromo-naphthalenes, four only have the a-@-structure, viz. : [I : 21, [l : 31,[l, 2'1, [l : 3'1. Moreover, A. J. Smith (Zoc. cit.), by oxidising mono-brom-@-naphthol with permanganate, obtained phthalic acid or anhy-dride, and thence inferred that in this brom-p-naphthol the hydroxyl-and the bromine-atom must be found in the same benzene-ring. Thesame conclusion may be extended to the dibromonaplithalene derivedtherefrom : consequently, the two bromine-atoms of this latter cannotbe in the positions 1 : 2' or 1 : 3', and must therefore have the posi-tion 1 : 2 or 1 : 3.Now, Meldola in a recent memoir (Rer., 12, 1962)describes a dibromonaphthalene melting at 64"-obtained by theaction of nitrous acid on dibromonapht hylamine-to which he assignsthe formula [l : 31 ; and since there appears to be no reason for sup-posing that this product is identical with the above-described dibromo-naphthalene melting a t 67-68', the author infers that the latter mustbe represented by t,ie formula [l : 21.Appenclim.-The author has likewise obtained an acetyl-derivativeand a nitroso-derivative of bromo-&naphthol. The former is a densefaintly yellow liquid, decomposed by distillation under ordinarypressures, but passing over undecomposed at about 215" under apressure of 20 mm.By bromine in acetic acid solution, it is con-verted into a brominated derivative, which is resinified by boiling withpotash.The nitross-derivatire sepat-ates from solution in ether in unstablegreen crystals, melting a t 61-65". H. W.Action of Chloroform on Naphthalene in presence ofAluminium Chloride. By M. BONIG and 2'. BERGER (Mo?zmh.Chem., 3, C68-672).-This reaction has been already investigated byScliwartz (Abstr., 1881, 912), who could not obtain any definite pro-ducts frcm it. A pitch-like mass is obtained, from which solventsfail to extract any well-characterised substance. The crude product isdissolved in benzene, filtered, the benzene distilled off, and the residueafter being heated a t 230" for some time to remove unaltered naphtha-lene, is distilled in a vacuum.The distillation begins far above 360°,and wm carried on to redness. By a long series of crystallisations, asubstance was obtained from the distillate, forming plates of a paleyellow colour (m. p. 189-190°, uncorr.), whose formula would appearto be a multiple of C,,H,, ( ClSH8<, 3). It is possible that this hydro-carbon may be identical with Zeidler's synanthrene ( l h ? z a l e ? ~ , 191ORGANIC CHEMISTRY. 69298). Two substances, melting respectively a t 170-175" and at 215",were also obtained and are being investigated.Constitution of Nitronaphthols. By R. WORMS (Bey., 15,lS13--1818).-Two nitronaphthols from a-naphthol are known : inone the nitro-group occupies the para- or a-position; in the other oneof the @-positions, but it is not known which.An anhydro-base froma-naphthol is also known, but the corresponding nitro-compound hasnot been isolated, and it appeared interesting to, compare it with theother known nitro-a-naphthols. For this purpose benz-a-naphthalidewas converted in small quantities into the corresponding nitro-com-pounds. On cooling, the para-compound crystallises out, and the fil-tered liquid is tjhrown into water to precipitate the ortho-compound.It crystallises from alcohol in yellow needles, melting a t 174". Onboiling it with potash and adding an acid, orthonitro-a-naphthol isobtained in yellow cryst,als, melting a t 128". It is identical with the/3-nitro-a-naphthol obtained by Liebermann and Dittler (AnnaZen,183, 228). That the nitro-group occupies the ortho-position withrespect to the hydroxyl is shown by the fact that the correspondingnitrosonaphthol is easily converted into an anhydro-base.To this end,P-nitroso-a-naphthol benzoate was first prepared by treating the cor-responding sodium-nitrosonaphthol with benzoic chloride in the cold.The benzoate (m. p. 162"), purified by crystallisation from chloroform,is treated with tin and hydrochloric acid, when a violent reaction setsA. J. G.n vin, and the anhydro-base, benzenyl-P-amido-a-naphthol, CIoH,/ 'CPE, \N/is obtained in small needles (m. p. 122"), wh,ich may be purified bysublimation.It appeared also of interest to ascertain whether an anhydro-basecould be produced from the a-nitroso-/&naphthol of Stenhouse andGroves (AtinnZen, 189, 153), in .which the nitroso-group and thehydroxyl have been shown to stand relatively in the ortho-position.The same process was used as above, the sodium salt and then thebenzoate (ni.p. 114") being first prepared, and the latier reduced withtin and hydrochloric acid. Renzenyl-a-amido-@-naph tho1 was thusobtained in colourless prisms melting a t 120°, and soluble in waterand alcohol ; it may be purified by sublimatiov.The formation of anhydro-bases in the naphthalene series seemsthus t o be a property of the ortho-position. It is also noteworthy thatorthonitro-a-naphthol can be separated by steam from the solid para-compound, just in the same way as in the case of the two nitrophenolfi.J.I(. C.Indophenol. By M. A. PABST (BUZZ. SOC. Chinz. [2], 38, 160-162) .-Meldola, and Koechlin and Witt have obtained colouringmatters by the action of nitrosodimethyl- or nitrosodiethyl-aniline onphenols or naphthols. One of t,hese substances, indophenol, is manu-factured by the oxidation of sodium a-naphthol a n d amidomethyl-aniline with potassium dichromate or sodium hypochlorite. It givesa blue dye on reduction, like indigo, and can be fixed on fabrics b70 ABSTRACTS OF CHEMICAL PAPERS.stannous oxide. It is more stable than indigo to light and soap, andis less costly, but is destroyed by concentrated mineral acids. Thecolour varies from a violet to a greenish-blue, according to the par-ticular phenol employed.Koechlin, by the action of nitrosodimethylaniline on tannin, gallicacid, and the catechins, obtained a violet dye, galbcyanine ; it formsbeautiful crystalline salts, and can be fixed on cotton by chromiumsesquioxide.These colouring matters are prepared in France by Durand andHuguenin, and it seems probable that from their cheapness andstability they will replace alizarin for violet, and indigo for bluetints.'V. H. V.a-Naphthaquinone-ethylanilide. By L. ELSBACH (Ber., 15,1810--1813).-Two parts of a-naphthaquinone are heated in a flaskwith five parts of glacial acetic acid and three parts ethylaniline ; thereaction proceeds by itself when the mixture has begun to boil. Oncooling, the mass is extracted with alcohol, and by repeated crystalli-sations the pure a-naphthaquinone-ethylanilide,is obtained in dark violet needles, melting at 155".When boiled withstrong caustic soda, it is conver.ted into a reduction product and a re-sinous mass. It is a feeble base, and combines readily with acids toform salts, which are easily decomposed.During its formation by the above reaction, a yellowish-green bye-product is formed, which amounts to one-fifth of the yield. Afterboiling it with alcohol and ether, it was analysed, and found to con-tain no nitrogen, numbers being obtained corresponding with theformula C20H1004. Zinc andhydrochloric acid reduce it, forming a green fluorescent solution. I na11 probability, therefore, it appears to be the a-product correspondingwith the p-dinaphthadiquinone discovered by Stenhonse and Groves.J.K. C.Derivatives of Styrolene. By A. BERNTHSEN and F. BENDER(Ber., 15, 1982-1986). -In addition to the method already described(Abstr., 1882, 20l), paramidostyrolene, CsH,(NH,)C,H,, can be pre-pared by heating paranitrocinnamic acid in a paraffin-bath until themass is in quiet fusion. The melting point is difficult to determine ;softening occurs a t 76", complete fusion at 81".Parahydroxystyrolene appears to be obtained in small quantity bydistilling barium paracoumarate mixed with sand, and forms a nearlyc~lourless oil, of phenol-like odour, sparingly soluble in water. Thesolution is precipitated by bromine.Styrolene unites directly with hydrobromic acid, yielding a brom-ethylbenzene. This is a, pale-yellow liquid, of odour resembling thatot benzyl chloride, sp. gr.1.3108 a t 23". When heated, it is decom-posed into hydrobromic acid and styroleue. It is probable that it hasthe constitution CH2Ph.CH2Br.Methylanthraquinone and some of its Derivatives. By E.U~~KNSTEIN (Ber., 15, 1820--182S).--The substance bearing this name,(/3) NXtPh.CloHt,: 0 2 (a),It is soluble only in fuming nitric acid.A. J. GORGANIC CHEMISTRY. 71and sold commercially, was examined for the purpose of identification.After repeated crystallisations from alcohol, it melted at 175-176O,and gat-e on analysis numbers corresponding with the formula ofmethylanthraquinone. Reduced with zinc aud ammonia, and boiledwith xylene, greenish-yellow crystals of rnethylanthracene were ob-tained and analysed.After repeated crystallisation, it melted a t 203".By oxidation wikh chromic acid, anthraquinonecarboxylic acid wasformed, and a dibrominated product was also prepared, melting a t148". Attempts to prepare a definite methylhydroanthranol havehitherto been unsuccessful. J. K. C.New Nitro- and Amido-anthraquinones, and New Methodof Preparing Erythroxyanthraqginone. By H. ROEMER (Ber.,15, 1786--1794).--Nitro- and amido-anthraquinones have been ob-tained by Bottger and Petersen (Ber., 6, 16), and an isomeric amido-compound by von Perger (Bey., 12, 1566). Other experimentershave failed to obtain a nitro-compound by Bottger and Petersen'smethod, and have recommended another, viz., to treat dibromanthra-cene with fuming nitric acid.The author was also forced to haverecourse to this process, but on repeating his experiments could obtainno product of settled composition. Another method was thereforetried, and with success. Anthraquinone dissolved in sulphuric acidwas treated with the requisite quantity of nitric acid ; crystals wereformed, and after two days the whole was poured into a large quantityof water. The white precipitate thus obtained could be separated intothree bodies by crystallisation from alcohol. The body of mediumsolubility attracted attention at once by the beauty and size of itscrystals.The following method was found to give the largest yield:-10 grams of anthraquinone dissolved in sulphuric acid were treated with4.5 grams of nitric acid (sp.gr. 1*48), and left foil two days. The crudeproduct after being washed with water was extracted with ether, theextract distilled until crystals began to form, and after cooling, thefiltered liquid was found to contain the body most soluble in alcohol,whilst the crystals contained the wished-for product, purifiable byrecry stallisation. For larger quantities,. the crude product can besimply extracted by repeated small quantities of hot alcohol : after thesecond extraction the body is obtained almost pure. The pure pro-duct on analysis gave numbers closely agreeing with the formula fornitranthraquinone. That it is not a mixture of anthraquinone andits dinitro-compound is proved by its behaviour with ammonium sul-phide, the latter converting it into a body soluble in cold stronghydrochloric acid, in which anthraquinone is insoluble, even aftertreatment with ammonium sulphide.Nitrmthrayz&mne sublimes in yellow crystals (m.p. 220°), inso-luble in water, sparingly soluble in alcohol, ether, and glacial aceticacid, and crystallising therefrom in brilliant prismatic needles, butmore soluble (with yellow colour) in benzene, chloroform, and con-centrated sulphuric acid. Its solution in the latter becomes red whenheated, and on being thrown into water gives a reddish-violet preci-pitate, which yields a purple solution in alcohol, showing two dar72 ABSTRACTS OF CHEMICAL PAPERS.bands. It thus exhibits decided differences from the body describedby Bottger and Petersen, which become more striking when the amido-compound is examined.Orthami&on.nthra.qrui.1Lone is easily obtained in a pure state by dis-solving the above nitro-compound in alcohol, precipitating withwater, and adding an alkaline solution of stannous oxide.A cleargreen solution is at once obtained, which after twelve hours' standingbecomes reddish-ydlow, and depasits. the amido-compound in beautifulred needles, purified by washing with water. Andysis shows them toconsist of amidoanthraquinone (m. p. 241'). It, sublimes withoutcharring in deep-red needles, insoluble in water, but giving reddish-Fellow solutions with alcohol, ether, benzene, chloroform, glacialacetic, sulphuric, and hjdrochloric acids.From its hot saturatedsolution in the last, the hydrochloride separates out on cooling in whiteneedles. I t s acetyl-compound is obtained by boiling it with aceticanhydride and sodium acetate, and may be separated by adding water.It crystallises from alcohol in mange-red needles melting at 202", or39" lower than Perger's acetyl-compound, exactly the same differencebeing observed between the two * amidoanthraquinones. Perger'sdescription and.results were also confirmed by the anthor, and as hisamidoanthraquinone is a metn-compound, it seemed probable that thebodies obtained by the author belonged to the ortho-series, an assump-tion which was eonfirmed by their conversion into erythro-oxyanthra-quinone in the following way :-The amidonnthraquinone was dis-solved in glaeial acetic acid, a little concentrated snlphuric acid added,and then potassium nitrite until the solution had become yellow.After standing a short time water was added, the mixture boileduntil yellow flakes separated, increasing in quaiitity as the aceticacid evaporated.Crystallisation from alcohol then yields a t onceorange-yellow feathery crystals melting .at 191", and agreeing inevery other characteristic with epythroxyanthraquinone. The nitro-and amido-anthraquinones obtained by the author belong therefore tothe ort h 0- series. J. K. C.Action of Concentrated Sulphuric kcid on Dinitroanthraqui-none. By C. LIEBERMANN and A. HAGEN (Bey., 15,1801-1806).-Bythe action of hot concentrated sulphuric acid on dinitroanthraquinone,a dye-stuff is formed (Be?.., 3, 905), which has not received a thoroughinvestigation. To obtain it, the anthraquinone is heated with 15 timesits weight of sulphuric acid at 2@0', and the cooled *mixture pouredinto water. A brown%precipitate is thrown down,[ dissolving in alkaliswith violet colour,; after being-throwu down again by hydrochloricacid, it is purified by boiling with hryta-water, in which it partlydissolves.The substame is again precipitated by acid from the solu-tion, washed, and transferred in the pasty condition into cold bargta-water. After standing, the filtered liquid is again treated with acid,the precipitate washed, and crystallised repeatedly from alcohol. Onanalysis, numbers were obtained corresponding with the formulaC28H18N207.Ou heating it with hydrochloric acid, a colouring matter is obtainedfree from nitrogen.With nitrous acid, however, it splits up intORGANIC CHE MISTRP. 73erythroxyanthraquinone and purpurosantbin. 'It appears thereforeprobable that the dye-stuff in question consists of a mixture of theamides of these two bodies. The action of sulphuric acid on dinitro-nnthraquinones is first an oxidation, sulp hnrous and phthalic acidsbeing formed : the sulphurous acid then reduces the nitro-groups,forming amides, and this part of the process can be greatly accele-rated by introducing sulphurous anhydride or zinc. The amido-groups are then partially attacked by sulphuric acid and convertedinto hydroxyls. A complicated mixture of substances is thus formed,of which the substance investigated by the authors fornis but a smctllpart. J.I(. C.Derivatives of Arithrol Salts. By C. LIEBERMANN and A. HAGEN(Ber., 15, 1794--1800).--In a former communication (Ber., 15, l427),the authors have given thernameo of ethyl dinitroanthrolate to the bodyobtained by the action of nitric acid on ethyl anthrolate. Furtherexperimmts have, however, shown that this view is not correct, bothit's reduction and oxidation products pointing to another formula.Boiled with glacial acetic acid, tin, and hydrochloric acid, ethyl mon-amidoanthrolate is formed, and, the other half of the nitrogen is foundin solution as ammonia. One only, therefore, of the nitro-groupspossesses the ordinary characteristics of aromatic nitro-groups, andthe other is in reality a nitroso-group, The body in question is there-fore termed by the authors the nitroso-anthrone of ethyl mononitro->CsH,(NO,). fIl3t.nnthrolate, CsH,<rH(NQ) co -\ I By oxidation with boiling acetic and chromic acids, the correspond-ing nitroxyanthraquinone ethylate is obtained in colourless needlesmelting a t 243"; and this when boiled with glacial acetic acid andgranulated tin until the solution becomes red, yields amidoxyanthra-quinone ethylate in red crystals melting a t 182". Contrary to theauthor's expectation, the ethyl-group in t,he above compounds could notbe eliminated by boiling with alkalis or acids, or with alcoholic potash :by fusion with potash, they are, however, decomposed in a more corn-phcat'ed way.The reactions of the hydroxyanthraquinone salts weretherefore studied in order to throw light on this curious behaviour.Ethyl anthrolate was oxidised in acetic acid with excess of chromicacid, hydroxyanthraquinone ethylate being formed (m. p. 1 3 5 O ) , verysoluble in alcohol. This is also proof against all alkaline solutions, andis only gradually attacked by fused potash and converted into alizarin.The ethyl ether of anthraflavol was also found to exhibit this stability,which appears to be characteristic of the hydroxyanthraquinones. Adecomposing agent was, however, found in hot concentrated sulphuricacid. On heating it solution of the ether in this acid to ZOO", it turnsbrown, and on cooling and adding water, hydroxyanthraquinone isthrown down (m.p. 301"). A similar reaction takes place with theethers of anthraflavol. Amidoanthraquinone ethylate was thereforetreated in the same way, and was found to be converted into alizarin-amide, easily recognised by its r( actions.The constitutional formula of the nitroso-anthrone of ethyl nitro-anthrolate is therefore74 ABSTRACTS OF CHEMICAL PAPERS.CJ34<,H~N0)>C,W2<~~~ -co- [NO,: OEt = 1 : 21.J. K. C.Dihydroxyanthracene from a - AnthraquinonedisulphonicAcid (Flavol). By G. SCH~LER (Bw., 15, 1807--1810).-Commercialsodium a-anthraquinonedisulphonate was redaced with zinc-dust andammonia to obtain the sodium salt of flavanthracenedisulphonic acid,which forms yellowish-grey crystals, dissolving in water with intenseblue fluorescence. The thallium and barium salts are whitre andcrystalline, those of silver and lead are yellowish precipitates.Sodiumarzthrosulplio.lzate, C,aH,(OH) .SO,Na, is obtained by fusing the cor-responding disulphonate with potash until the mass has becomethin : when cold, it is treated with acid filtered and alcohol added ;the precipitated salt is recrystallised from water, to which it communi-cates a greenish fluorescence; precipitates are formed with the heavyand earth metals.PZuvoZ, C,4H8(OH)2, is formed when the fusion with potash is con-tinued until the mass becomes intensely black, and gives off a tarryodour. By decomposing the product with acid, and repeatedly re-crystallking the insoluble portion from alcohol, flavol is obtained as abright yellow crystalline powder (m.p. 260-270"), soluble in alkaliswith yellow colour and very fine green fluorescence, Diacetylflavol,prepared in the usual way, crystallises in white plakes, melting a t254-255". The diethylic ether, obtained by saturating an alcoholicsolution of flavol with hydrochloric acid, melts a t 229" after beingpurified by crystallisation from glacial acetic acid.Flavol differs from the other known dihydroxyanthracenes in thestrong fluorescence of its alkaline solutions and in the higher meltingpoints of its salts.Soluble Alizarin Blue. By €3. BRUNCK and C. GRAEBE (Ber., 15,1783-1 786) .-Alizarin blue being but sparingly soluble, and there-fore difficult to fix on the fibre, has not been as extensively appliedas was to be expected from its otherwise valuable properties.Inorder to convert it into a more soluble form, experiments weremade by Brunck, ending in the issue of a patent, from which themethod of obtaining the soluble blue may be briefly extracted asfollows : -Alizarin blue in a fine state of division, and in the form ofa paste containing 10-12 per cent. blue, is stirred up with 25--30percent. of a solution of sodium hydrogen sulphite (sp. gr. 1-25), and themixture left for 8-10 days. lt is then filtered, unchanged blue beingleft behind, and the soluble blue separated from the filtrate in reddish-brown crystals by addition of common salt, or evaporation a t a lowtemperature. The dry powder can be heated to 150" without under-going change, but its aqueous solution begins to decompose at 60", aridon boiling, the blue separates out.In the cold a solution of chromicacetate produces no change, but a t 60-70°, the blue chromium lakeis thrown down. This fact is made use of in printing; the solubleblue and chromic acetnte mixed with starch are printed on the fabric,and the latter steamed for 10 or 20 minutes and then washed.After makirig due allowance €or the sodium chloride present, anJ. K. CORGANIC CHEAWSTRP. 75analysis of the commercial article gave numbers corresponding withthe formula C,,H,N04 + 2HNaS03.Neither alizarin nor the purpurins possess the property of combin-ing with alkaline bisulphites ; quinoline, however, forms very solublecrystalline compounds, whose aqueous solutions decompose in the sameway as those of soluble alizarin blue.It appears therefore probablethat the capacity for combining with biaulphites rests in both cases withthe nitrogen-group. J. K. C.Hydrocarbons of the Formula (C5He)%. By W. A. TILDEN(Chem. News, 46, 120--121).-The author has already suggest,ed(Trans,, 1878, 85-88> that the liquid terpenes and citrenes (CloH16)are not correctly represented as dihydrides of cymene. He now findsthat the hydrocarbons of the formula C5H8 appear to supply importantevidence in connection with this question. The author has furtherexamined isoprene, the most interesting of these hydrocarbons, andobserves that it boils at 35" (not 38"), has the vapour-density for C5H,,that it forms a tetrabromide, C5H8Br4, an oily yellowish liquid- whichcannot be distilled without decomposition, and remains liquid at - 18",and moreover he confirms Bourchardat's statement that when heatedfor some time a t 280" it forms &-isoprene, CIoH,, (b.p. 174-176"),apparently identical with terpilene from turpentine, yielding the samehydrochloride, and being converted by the action of dilute acids intoterpin, CIOHZ2O3, having the same crystalline form as the terpin from tur-pentine. It likewise resembles turpentine in its behaviour with sulphuricacid. Hence it seemed to the author that isoprene might be oht,ainedby depolymerising turpentine. When turpentine is passed through ared-hot iron tube, among the other products a substance is found(b.p. about 37', vap.-den. 35", C5H8 requires 34")) having the samecomposition and some of the properties of isoprene. A litre ofturpentine yields about 20 C.C. of the fraction (37-40"). Rebonl'svalerylene from amylene dibromide, and Hofmann's pipcrylene (Abstr.,1881, 571), are both isomerides of isoprene. Valerylene differs frompiperylene by not forming a tekabromide and from isoprene by form-ing a ketone when digested with mercuric bromide and water ; isopreneis unaffected. Theoretically there are eight compounds of the formulaC5&, all open chains ; of these, three are acetylenes, forming copperand silver derivatives, thus differing from the above isomerides. Asvalerylene is easily converted into a ketone, it would probably be cor-rectly represented as a dimethylallene, either CHMe : C : CHMe orChile, C CH2; and as isoprene does not undergo this change theauthor is inclined to regard it, as P-methyl-crotonylene,-CH, CMe.CH CH,.It would be difficult to explain how such a substance could be poly-merised into a methylpropylbenzene, therefore the author is of opinionthat terpene may be more correctly represented either by the formulaCH, CH.CMe : CH.CH CHP@ or thus:-CH, : CPrp.CH : CH.CMe : CH2.He also feels disposed to look on isoprene as the first term of a seriessomewhat analogous t0 the olefines, COHB, C,,H16, C15H24) &c.Colo76 ABSTRACTS OF CHEMICAL PAPERS.phene from turpentine, seems to be a saturated hydrocarbon of thisform.The absorption spectrum of isoprene a t the ultra-red endhas, according to Abney, the characteristics of that of an aromaticbody. At the other end, according to Hartley, it resembles that ofaustralene, the main constitutent of common turpentine.D. A. L.rend., 89,1117-1120: this Journal, Abstr., 1880, 323).-D. A. L.Note. -Bourchardat has described two bromides of isoprene (Compt.Essence of Sandal1 Wood. By P. CHAPOTEAUT (Bull. XOC. Chim.[2], 37, 303-305) .-!Essence of sandal wood, obtaining by distillingthe wood with water, is a somewhat thick liquid of sp. gr. 0.943 a t15", and boiling between 300" and 340". Tt consists almost entirelyof two oxygenated bodies, the more abundant of which is C,5Hz40 (b. p.300") ; and the other, C&Z,O (b.p. 310"). 'When treated with phos-phoric anhydride essence of sandal wood yields two hydrocarbons,C15H2, (b. p. 248'), and CI5Hz4 (b. p. 260'). Oil of cedar, whenpuritied from oxygen compounds, has the composition C15H22, and boilsa t the same temperature as the hydroc~rbon from essence of sandalwood. The two products are probably identical. The hydrocarbon,C15H2,, is either isomeric or idelltical with oil of copaiba.When slowly distilled, essence of sandal wood yields products boilingbelow 250" and above 350°, together with water arid hydrogen, but thedecomposition is not complete. If the essence is heated in sealedtubes a t 310", it splits up in accordance with the equations 4Cl5H,O=C2,H3,0 $- C&6203 + 2H2, and GOH,,O3 = C4,H6,OZ + &O.Thecompound, C,o€€300, boils at 240°, and when treated with phosphoricanhydride yields a cymene boiling a t 175-180'. The product,C10H6203, is a thick liquid, boiling at about 340", and the third body,C,oH,,Oz boils at 350", and has the consistence of honey. The essence,C15H260, apparently splits up in a similar manner.When heated a t 150" under pressure for seven or eight hours withhalf its weight of glacial acetic acid, essence of sandal wood yields twoproducts, CMH4,0 (b. p. 280-285"), formedfrom 2C!,H,,O b3 loss ofH,O, and C,,H,,O, (b. p. 298"), the acetate derived from the bodyC,,H,,O. With hydrochloric acid a t 125", essence of sandal woodyields a hydrochloride boiling at about 275", but the reaction is morecomplex than with acetic acid.The cornpound, CI5Hz6O, has thereforethe properties of an alcohol ; the compound C1,H,,O has the propertiesof an aldehyde, and is probably the aldehyde of Cl5HZ6O.C. H. B.Synthesis of Salicin and of Anhydrosalicylic Glucoside.By A. MICHAEL (Ber., 16, 1928--1925).-Bg the action of sodiumamalgam on helicin obtained from salicin, Lisenko succeeded in reform-ing the latter body. The author has repeated this with artificial helicinprepared by the action of acetochlorhydrose on potassium salicylate,and has obtained salicin identical in properties with natural salicin.In an attempt to make the glucoside of salicylic acid, the action ofacetochlorhydrose (2 mols.) on disodium salicylate (1 mol.) inalcoholic solution was tried. The sodium chloride, which separatedout after several days, was filtered off, and by the spontaneous evaporaORGANIC CHEMISTRY.77tion of the filtrate, a body of the formula C2,H3,015 was obtained,crystallising in needles. A portion of the same substance also sepa-rated with the sodium chloride. This new compound melted a t 184-185"; it is almost insoluble in water and cold alcohol, moderatelysoluble in hot alcohol. It is insoluble in cold ammonia, but dissolvesgradually in cold soda. Boiling it with alkalis or acids decomposes itinto salicylic acid and dextrose. When heated with acetiLanhydrideand sodium acetate, it forms an acetyl-derivative, C26H2201,Ac,, meltingat 110-111". A. K. M.Santonous and Isosantonous Acids. By C. CANNIZZARO andG. CARNELUTTI (Gazzetta, 12, 393-41 6).- I. SANTONOUS ACID,C1,H2,0,.-This acid, containing 2 atoms of hydrogen more thansantonic acid, is prepared by heating santonin in a reflux apparatuswith hydriodic acid (b. p. 127") and amorphous pbosphorus. Onfiltering the resulting liquid through asbestos, and digesting the solidmass on the filter with cold aqueous sodium carbonate, the santonousacid dissolves, and on acidifying with hydrochloric acid and leavingthe liquid to cool. separates iii needle-shaped crystals, which may bepurified by repeating this treatment several times, and finally crpetal-lising from ether. The acid thus purified crystallises in white needles,melts at 178-179", and resolidifies on cooling. Under a barometricpressure of 5 mm, it distils unaltered at 200-260" ; under ordinarypressure, i t is partly decomposed by distillation.It is very soluble inabsolute alcohol and in ether, slightly in cold water, and crystallisesfrom a boiling aqueous solution on cooling. Its solutions are opticallydextrogyrate, a character by which it is most readily distinguishedfrom isosantonous acid, which is optically inactive. It dissolves at theordinary temperature in aqueous solutions of the alkaline carbonates,and of the earthy-alkaline hydroxides. Its alkali salts are verysoluble in water and in alcohol, slightly also in a mixture of alcoholand ether.-The sodium salt, C15H19Na03, crystallises in very smallneedles ; the silver salt, obtained by precipitation, blackens veryquickly even in the dark.-The barium salt, Ba(C15H190J)2, is solublein water, and on evaporation in a vacuum separates in efflorescentcrystals ; on the other hand a cold saturated aqueous solution whenheated deposits a salt which is not efflorescent, although it containswater of crystallisation; it is also much more soluble than the saltdeposited a t higher temperatures.E t h y l santonite, C17H2403 = C15H1903.C2H,, prepared in the usualway, and purified by repeated crystallisation from ether, forms whitecrystals, soluble in alcohol and ether, melting a t 116-117".Its solu-tions are dextrogyrate.-Methy I santonite, prepared in like manner, iswhite, very soluble i n ether, and melts a t 81--84°.-BthyZic sodium-santowite, C15H1,Na03.Et, obtained by boiling under pressure a solu-tion of ethyl santonite in absolute ether with sodium, separates as awhite powder, and is instantly resolved by cold water into ethyl santo-nite and sodium hy droxide.-Bthylic bei~zoyZ-sa,ntonite, C2,H,,O3 =C,,H,,EO,Et, formed byv heating ethyl santonite with benzoyl chlo-ride in a reflux apparatus, is a white crystalline body, very soluble inether, melting at 78". By boiling with alcoholic potash it is resolve78 ABSTRACTS OF CHEJIICAL PAPERS.into benzoic and santonous acids.-EthyZic ethyLanton,ite, C,,H,,O, =CI5H1,EtO3.Et, obtained by heating ethylic sodium-santonite withethyl iodide under pressure, crystnllises in long needles, melts a t 31 -32", dissolves in alcohol, and very easily in ether.--Etlz?~Z-sa~ito~ousacid, C17H,,03 = CI5H,,( C2H5)03, obtained by boiling ethylic ethyl-santonite with alcoholic potash, crystallises in long slender needles,melts between 115.5" and 116", and exhibits strong acid properties.It is reconverted into the ethylic ether by passing hydrogen chloridethrough its alcoholic solution.The preceding facts show that san-tonous acid contains, in addition to acid hydroxyl-groups, an alcoholicor phenolic hydroxyl.ISOSANTONOUS ACID, C15H,o03.-When a mixture of santonous acid(1 pt.) and barium hydroxide (3 pts.) is heated t o n temperature abovethe melting point of lead, a fused yellowish mass is obtained ; and onexhausting this mass with hot water, and passing carbonic anhydrideinto the filtered solution, barium carbonate is precipitated together witha, phenol ; and on again filtering and treating-the filtrate with hydro-chloric acid, isosantonous acid is precipitated in larger or smallerquantity, according to the time for which the heating with baryta hasbeen prolonged.The acid is purified by dissolving it in alcohol, pre-cipitating with hot water, pressing the precipitate between cloth, andwashing with water, till the liquid passes through clear. This treat-ment is repeated several times, and the prodact finally crystallisedfrom ether. Isosantonons acid crystallises in laminae, different in'appearance from those of santonous acid, me3ts a t 153-155", andresolidifies on cooling. It distih unaltered a t 150-160" under a pres-sure of 4 mm. ; under ordinary pressure, it partly distils, partly decorn-poses like santonons acid.It is soluble in alcohol and in ether, verysparingly in cold-water, and separates from a boiling aqueous soluticnas it cools in shining plates.Theethy Zic ether, C17H203, prepared by passing hydrogen chloride throughthe alcoholic solution of the acid, forms white crystals melting a t 125".In this ether, as in ethyl santonite, an atom of hydrogen may bereplaced by benzoyl, sodium, or potassium, or by ethyl, whereby a seriesof derivatives is obtained isomeric wit'h the corresponding santonites,but differing therefrom in melting point and other characters, especiallyby the absence of rotatory power.The following table exhibits a comparative view of the meltingpoints of the two isomeric acids and their ethereal derivatives :-Santonous acid, C,5H200s Isosantonous acid,178".154".Ethylic santonite, CI5Hl9O3. E t E thylic isosantonite,117". 125'.The solutions are optically inactive.Isosantonous acid is a strong acid, and is easily etherified.Ethylic benzoylsantonite, C16HlA&03.Et Ethylic benzoylisosantonite,78". 91".Ethylic eth y lsnntonite, C15H18Et O,.E t31". 54O.Ethylsantonous acid, CI5Hl8EtO3.H Ethylisosantonous acid,116". 143".E th ylic e thylisosantoniteORGXSIC CHEXISTRY. 79These two isomeric acids further yield the same products of decom-position, vie., dimethyl-naphthol and dimethyl-naphthalene.DIMETHYL-NAPHTHOL, ClzH120 = CloH7Me,.0H.-This is the phenolobtained, as already observed, together with isosantonous acid, byheating santonous acid with barium hydroxide.It is also formed,together with dimethyl-naphthalene, by distilling santonous acid withzinc-powder, and may be separated by agitating the distilhte withpotash-ley, and extracting with ether the portion not dissolved by thealkali. The impure phenol, prepared in either way, may be purifiedby dksolving it in alcohol, precipitating with hot water, washing theprecipitate on a cloth filter, and repeating this treatment till the pro-duct presents a homogeneous appearance. Dimethyl-naphthol thuspurified crystallises in shining needles, melts without alteration a t135-136", sublimes under ordinary pressure a t loo", and may beboiled and distiJled under reduced pressure. It is very soluble inether, soluble also in alcohol, very sparingly soluble in cold water, andseparates ou cooling from its solution in boiling water in very smallneedles.It dissolves in aqueous baryta, soda, and potash, and is pre-cipitated by excess of the latter in a crystalline form.Afethylic dinaethylnayhtho late, prepared by heating the phenol underpressure with methyl alcohol and methyl iodide, crystallises in hardwhite prisms, melts at 68", is volatile, and dissolves in ethyl alcohol,methyl alcohol, and more abundantly in ether.-The ethylic ether is aviscid liquid, the solution of which in chloroform gives with brominea crystalline prodtuct which melts at 90".Acety I-dimethy Zn~plLthol, Cl,Hl4O2 = C1?H11.GO, ppepared by boilingthe phenol with fused sodium acetate and excess of acetic anhydride,crystallises after purification in white scales melting ,at 77-78".Dimethyl -naphthol, oxidised in acetic acid solution with chromic acid,yields yellowish rhombic plates, and a very small quantity of white,apparently rhomboNa1 prisms, both of which melt between 104" and105".The yellow crystals gave by analysis numbers agreeing nearlywith the formula C1,Hl20,.-This substance when treated with potashblackens without dissolving. Heated with hydriodic acid and redphosphorus, it is reconverted into dimethylnaphthol.DIMETBYL-NAPHTHALENE, Cl,H,, = C10H6Me2 may be prepared byheating dimethyl-naphthol with 10 parts of zinc-powder, and passingthe resulting vapour through a column of the same powder heated tolow redness, whereupon a yellow liquid distils over, from which potashdissolves out unaltered dimethyl-naphthol.The whole is then dis-tilled with steam, and the watery distillate, holding an oil in suspen-sion, is mixed with potash and shaken with ether, which dissolves outthe dimethyl-naphthalene, tlogether with a small quantity of naphtha-lene. The ether having been evaporated off, the remaining oil isboiled several times with sodium in a reflux apparatus till the globulesof the metal remain bright, and is then distilled in a Sprengel vacuumat the heat of a salt-bath. By careful fractionation in this manner, itis possible to separate small quantities of naphthalene, but the removalof the last traces is very difficult.Dimethyl-naphthalene purified in this manner as completely a81) ABSTRACTS O F CHE3IICAL PAPERS.possible, boils at 262-264" under a pressure of 751 mm., has a densityof 1.0283 a t 0", and 1.10199 a t 1 2 O , and a vapour-density = 77.8"(H. = l), the calculated density being 78.I t unites with picric acid,forming a very characteristic compound, which may be obtained bymixing the two bodies in hot concentrated alcoholic solution, andcrystallises on cooling in long orange-yellow needles melting a t 139".Dimethyl-naphthalene also forms a characteristic tribromo-derivative,C12HHSBr3, which crystallises in white needles melting at 228".The dimethyl-naphthalene obtained as above from diniethyl-naphthol,may also be prepared by the action of inethyl iodide on GLaser'sdibromonaphthalene melting at 81" (Annalen, 135, 49) ; and finally,together with the above-mentioned dimethyl-naphthol, and a smallquantity of xylene, by distilling santonous acid over zinc-powder in anatmosphere of hydrogen.S a n t o nin, C15H1803 (from wormseed), distilled with zinc-powder ina stream of hydrogen, yields the same dimethyl-naphthalene, togetherwith propylene and a dimethyl-naphthol, apparently identical with thatwhich is obtained by the decomposition of santonons acid.Theauthors have not been able to confirm the statement of Saint-Martin( C o q ~ t . rend., 75, 1120), according to which santonin distilled withzinc-powder yields a compound, which he calls santonal, partly liquid,partly crystalline, and having the composition C3,,H1802.Psoromic Acid, a New Acid extracted from Psoromacrassum.By G. SPKA (Gazzetta, 12, 431--43S).-This lichengrows in a few localities in Sicily, and the small quantity with whichthe author's experiments were made was gathered near Dahlia, provinceof Caltanisetta. By exhaustion with ether in a percolator, i t yieldeda yellow substmanee (A') crystallising in needles from the ether on cool-ing, and a brown residue (B), which remained in considerable quantityon distilling off the solvent.The crystallised body is soluble in warm alcohol, et'her, chloroform,and acetic acid, and recrystallises from these solvents more or less oncooling, but benzene, unless employed in large excess, dissolves onlya part of it, leaving a nearly white crystalline residue.The consti-tuent soluble in benzene was purified by repeated crystallisation fromthat liquid ; the insoluble portion by crystallisation from alcohol andrepeated washing with cold alcohol.The yellow substance crystallised from benzene is usn ic acid,C,eH1808, melting at 195-197", and yielding a sodium salt,H. W.which crystallises from warm water in stellate groups of needles.The white substance only slightly soluble in benzene crystallises fromalcohol in silky needles, dissolves in the solvents above mentioned,and t o a slight amount in water, to which it imparts a faint acidreaction. It dissolves also in alkalis and dkaline carbonates, and insulphuric, nitric, and hydrochloric acids, melts with decomposition a t263-264", and begins to sublime, but resolidifies a t a high teKpera-ture, about 215".Dried at loo0 it gave by analysis 60*23--60.2!4 percent. carbon, and 3.71-3.97 hydrogen, leading t o the formula CzoH,,09ORGANIC CHEMISTRY. 81which requires 60.30 carbon and 3.51 hydrogen. Its silver salt, obtainedby precipitation, forms white flocks, which alter on exposure to light.The analysis of this salt leads to the formula CZOH15Ag010, Ahowingthat the corresponding acid (psoromic acid) has the compositionC2,H,,0,,, and that the compound C2,H,,09 extracted from the lichenas above described, is not the acid but the anhydride. The acid itsel€has not been obtained in the free state.Psoromic anhydride boiled with aniline is converted into a crystallineyellow substance, which when further heated does not melt, but decom-poses, yielding a carbonaceous residue, and a liquid having a charac-teristic acetic odour, probably psoromic anilide. The anhydride heat'edwith water in sealed tubes a t 240°, jields a yellow-brown liquid and abrown residue, which, as well as the residue left on evaporating thesolution, exhibits the characters of an acid, and gives with ferricchloride a dark green coloration, not produced by psoromic acid.The brown residue B, left 011 evaporating the ether nsed for theextraction, yields to benzene a small quantity of a resinous substance,together with psoromic acid.The lichen, after exhaustion with ether, yields to boiling alcohol asubstance having the characters of a wax.This the author reservesfor further examination.H. YY.Laws of Variation of the Specific Rotatory Power of Alka-loids under the Influence of Acids: By A. C. OUDEMANS, J u n .(Bec. Il'rav. Chim., 1, 18--4O).-The author records and tabulates alarge number of observations relating to the influence of acids, orgacicand inorganic, on the mon-acid bases quinamine and conquinnniine,and on the biacid bases quinine, yuinidine, cinchonine, and cinchoni-dine, both in aqueous and in alcoholic solution,-and deduces fromthese observations the following general conclusions :-1. The specific rotatory power of the mon-acid bases, as mani-fested in the aqueous solut'ions of their normal salts, is the same forall the salts, and is independent of the chemical character of the acidwith which the base is united.Small differences occasionally ob-served are due to partial and unequal decomposition of these saltsunder the influence of water, and to the varying influence of thedegree of conceiitration on the different salts.2. As long as the normal salt is not decomposed by water, thisspecific rotatory power coincides with the maximum value, the smalldifferences sometimes observed arising from partial decomposition.3. Biacid bases form two series of salts, in each of which series thebase exhibits a distinct specific rotatory power, the value of which isusually much smaller in the basic: than in the normal salts.4. The real specific rotatory power of the biacid bases in the formof mormal saZts and in aqueous solution is probably the same for allthe salts, and independent of the chemical nature of the acid withwhich the base is combined ; but in consequence of partial decomposi-tion and of the unequal influence of concentration on the various salts,the specific rotatory power cannot show itself with its true value.6.The real specific rotatory power of the biacid bases in the formof9 VOL. XLIV82 ABSTRACTS OF CHEMICAL PAPERS.basic salts is probably the same for all the s a h , the differences betweenthe observed values being due to partial decomposition, and for themost part to the unequal influence of concent,ration on the differentsalts. El. W.Action of Nascent Hydrogen on Pgrroline. By G. L. CIAMICIANand M. DENX'STEDT (Ber., 15, 1831-1832).-An acetic acid solutionof pyrroline is heated with zinc-dust for some days, the excess of pyrroldistilled off with steam, the zinc removed by sulphnretted hydrogen,and the acetic replaced by hydrochloric acid.The solution is thentreated with potash and steam-distilled, the distillate treated withhydrochloric acid and evaporated t o dryness on a water-bath, redis-solved, and steam-distilled with potash. The firsti portions of the dis-tillate richest in the base are mixed with solid potash, whereby thebase is separated as an oil, and, after drying over fresh potash isagain distilled. It boils a t 90--91", and is a colourless liquid havingtt strongly alkaline reaction and ammoniacal odour ; it is very solublein water, from which it is not easily separated.The plat'inochloridealone was analysed, as the free base could not be obtained in a suffi-ciently dry state. The former is a yellow precipitate almost insolublein cold water. Analysis of this compound leads to the formula C,H,Nfor the free base. J. I(. C.Synthesis of Pyridine Derivatives from Ethyl Acetoacetateand Aldehydammonia. By A. HANTZSGH (Annulen, 215,l-82).-Bietlayl hydroco7lidine~icarto~~late, CaMes( COOEt),H,N, is prepared bywarming a mixture of 52 grams of ethyl acetoacetate and 13.5 gramsof aldehydammonia for five minutes, and then adding an equal bulkof dilute hydrochloric acid to the mixture. After extracting thecrude product with dilute hydrochloric acid and with w:Lter, it isrecrystallised from boiling alcohol.Diethyl hydrocollidinecarboxylatecrystalhes in monoclinic or triclinic plates or needles (m. p. 131")freely soluble in chloroform and hot alcohol. It begidins to boil at 3 1 5 O ,but rapidly decomposes a t this temperature. This ethereal salt' resiststhe action of aqueous solutions of potash, but is completely decom-posed by alcoholic potash. By the action of warm fuming hydro-chloric acid, it is split up, yielding acetone, ethyl chloride, ammoniumchloride, and aldehyde, CI,Hz,04N + 3H20 + 3HC1 = 2C02 +2CZH5Cl + 2C3HeO + CZH4O + NH,Cl.Ethyl dibromhydrocolli~inedicarboxylate dibronzidle,C,H,BI.~(COOE~)~H,N,B~,,formed by the action of bromine diluted with carbon Fisulphide on thepreviously-mentioned ethylic salt, crystallises in thick prisms (m.p. 88")of a yellow d o u r . The substance dissolves freely in hot alcohol.By the action of strong nitric acid, it, is converted into ethyZ dibromo-co7Zidinedicnl.boxylate d i b r o i d e , C,H,Br,( COOEt),NBr,, which crystal-lises in white needles (m. p. 102") soluble in ether and in alcohol.When chlorine is passed into a solution of ethyl hydrocollidinecar-boxylate in chloroform, the hepta-derivative, C8H4C15( COOEt),Cl,NORGANIC CHENISTRY. 83is produced. This substance crystallises in needles (m. p. 150')sparingly soluble in hot alcohol.E t h y l coll.idiiLedicarBoxylate, C,NMe,(COOEt),, is best prepared bythe action of nitrous acid on a mixture of equal weights of alcoholand ethyl hydrocollidinedicarboxylate. When the reaction is complete,the excess of alcohol is removed by evaporation, and a dilute solutionof sodium carbonate is added to the residue, which causes the ethylcollidinedicarboxylate to separate out in the form of a heavy oil boilingat 310".It combinesreadily with acids. The hydrochloride, C14Hg04N,HC1, is deliquescent.The platinochloride, ( C14H,g0,N)zH,,PtC16, forms pink-coloured tri-clinic plates melting a t 184", insoluble in alcohol and ether, but solublein water. The nitrate crystallises in vitreous needles which melt at 92'and decompose at 122'. The hlydriodide crystallises in plates, solublein water and in hot alcohol. Itf melts at 170" with decomposition.By the action of an alcoholic solution of iodine, this salt is convertedinto the triodide, C14H190LNHI,13. The methiodide, C14H1904N,McI,crystallises in white needles soluble in alcohol and water.Althoughit is precipitated from its aqueous solution by soda, i b has a stronglyacid reaction. The crystals melt a t 138" and decompose at 160".Ethyl collidinedicarboxylate is not attacked by strong hydrochloricacid or by ammonia a t 150°, but it is easily saponified by alcoholicpotash. From the potassium salt, 1 ead collidinedicarboxylate and thefree acid can be prepared. Colli~inedi.carboxylic acid, C3Me3( COOH),,forms needle-shaped crjstals, sparingly soluble in alcohol, ether, andcold water. The salts which this acid forms with the alkalis andalkaline earths are very soluble in water and do not crystallise well ;C,HgN(C00)2Ba .+ 3H20 is more solubie in water than the calciumsalt C6H,N(C00)zCa + H20, which crystallises in needles.Thesilver salt, C6H9N(COOAg)2, is an amorphous body insoluble in water.The pale-green precipitate, obtained by the addition of potassiumcollidinedicarboxylate to a solution of copper sulphate, has the com-position 2C6H,N(CO),0 + 3CuO + 11H20. On boiling the mixturea pale-blue salt is produced which has the composition C8HgN(CO),0-t 3CuO.The hydrochloride of collidinedicarboxylic acid, CloHllOaNHC1 +2H,O, a:d the platinochloride, ( C,,Hl104N),,H2PtCI,, are crystalline.On heating potassium collidinedicarboxylate with lime, 6-coZlidine,or /3-trimethylpyridine, C6NMe3H2, is obtained. The following tableshows the most marked points of difference between a- and 6-colli-dine :-This ethylic salt has the sp.gr. 1.087 a t 15'84 ABSTRACTS OF CHEJlICAL PAPERS.a Gollidine.3. p. 178', sp. gr. 0.953.~~Solubility ..............Exposure to a i r . . ........The addition of CrO, giresMn, Co, and Fe salts ....C,HiiN,HAuCI,. .........AgN03 ................p-Collidine.B. p. 1'71', sp. gr. 0.917 at 15".Very slightly solublein water.No change.Does not melt underwater.Red oil.No precipitate.No precipitate.-- I- ---More soluble in cold than hotTurns brown.Melts under water; the dryRed crystalline precipitate ofSlow precipitation of hydr-White crystalline precipitatewater.salt melts at. 112'.(C*HllN) 2H2Cr207.oxides.soluble in hot water.An ethereal solution of ethyl hydrocollidinedicarboxylate absorbshydrochloric acid gas, forming ethyl collidinedicarboxylate and otherproducts.Dilute hydrochloric acid decomposes ethyl dihydrocolli-dinedicarhoxylate at loo", yielding ethyl chloride, carbonic anhydride,and ethyl dihydl.~ol1idinemonocarboxyln.te, CeHllNH.COOEt, as acolourless oil. On treating the alcoholic solution of this ethylic saltwith nitrous acid, it yelds ethyl colIidinemonocarboxylate,C,NHMe,,COOEt.The platinochloride, (CllH,,0,N)2,H2PtC16, cryshllises in prismsmelting at 194", soluble in water. By the action of dilute hydrochloricacid on ethyl dihydrocollidinedicarboxylate at 125", a mixture of di-hydrocollidine, tetrnhydrodicollidine, a ketone, C8HI20, and anotherbody of the composition C8HI4O2, is obtained.On distilling the crudeproduct in a current of steam, the two bases are found in the residue.Dihyd roc011 idine, ChHI3N, is a strongly alkaline liquid, boiling a t175-180", and having a penetrating odour. It dissolves in coldwater, but is reprecipitated on heating the solution. The pZati9zo-chloride, (C,H,,N)z,H,PtC1,, and the hydriodide, CsH,,N,HI, are crys-tzlline. Dihydrocollidine readily precipitates the hydroxides of mag-nesium, iron, manganese, and nickel from solutions of their salts,and forms a crystalline compound with methyl iodide. It is notoxidised by nitrous acid. Tetrah7JIJroajcoIZidine7 C,,H,,N,, boils at 255-260". The hydriodide, ClcH&N2,HI, is very soluble in water andalcohol. The ylatiriochZoride, C16H2,Nz,H2PtCIc, crystallises withdifficulty.The ketone, C,H,,O, is a mobile liquid having a pleasant odour andboiling at 208".It combines directly with bromine to form the tetra-bromide CsH12Brr0, an oily liquid. By the action of bromine on t h i scompound a crystalline substance is obtained of the compositionChH,Br,O or C8H6Br40, melting at 138".0% id atiorz-products of Collid ined icarboxy lic Acid .-Potassium colli-dineciicarboxylate is converted into the lutidinedicarboxylate by boil-ing i t with the theoretical amount of potassium permanganate solutionfor two hours. From the potassium salt, the lead salt and the freORGANIC CHEMISTRT. 85acid are prepared. Lutidinetricnrboxyzic acid, C,H,O,N + 2H20,resembles collidinedicarboxylic acid.It crystallises in rhombohedrons,which lose their water of crystallisation a t 120" and melt a t 212" withdecomposition. The neutral potassium salt of this acid is deliquescent ;the ammonia salt is very soluble in water : (C,,H,06N),Ba3 + 8H20forms hygroscopic needles ; (C10H606N)2Ca3 + 8H,O is gelatinous ;(Cl,,H60,N)2Mg3 + 10H20 is also amorphous and freely soluble.CloH6O6NAg3 and the lead and mercurous salts are insoluble orsparingly soluble. Lut idine, C5MezH3N, obtained by heating a mix-ture of potassium lutidinetricarboxylate and lime, boils a t 154'.By the prolonged act ion of potassium pernianganate on potassiumcollidinedicarboxjlat e, the potassium salts of picolinetetracarboxylicacid and py ridinepeiit~acarboxylic acid are produced.To obtain pico-linetetracarboxylic acid, strong nitric acid is added to a solution of thecrude potassium salt, which precipitates an acid salt of the compositionC5NMe(COOH),(COOK)2 + 4H,O. The concentrated solution of thissalt is decomposed by strong sulphuric acid, and the free acid extractedwith ether. Pyridinepentacarboxylic acid is obtained by a similarprocess. PicoZi?ietetracarbole?lZic acid, C5NMe(COOH)4 + 2Hz0, crys-tallises in prisms which lose their water of crystallisation at 120", andmelt with decomposition a t 199". The acid dissolves freely in water.I t s salts do not crystallise well. The dipotassium salt forms largerhombic plates ; the mono-potassium salt, C5NMe(COOH)3.COOK +2H20, crystallises in needles.C5NMe( C,04Ca), + 4H,O is sparinglysoluble.Pyri~~ne~entacarboz2/Zic acid, C,N(COOH), + 2H,O, dissolves freelyin water, formiiig a strongly acid solution. The crystals lose theirMrater of crystallisation a t 120", and decompose without melting a t220". It is a powerful acid, resembling oxalic acid in its property offorming acid and double salts. The following pyridinepentacarboxyl-ntes were prepared:--C,,H4010NK + 3 or 2H,O, shining needles.C10H3010NK2 + 4 or 3$H20, cubes. C,N(COOK),, crystalline powder,freely soluble in water. (C;,oOloN)2Ba5 + l l H z O is deposited as acrystalline powder when barium chloride is added to the free acid.(C,0010N)2Ca5 + 12H20, sparingly soluble non-crystalline powder.Clo0,,NH3Ca + iHtr,O, sparingly soluble crystalline powder.C16010NCa,.NH4 + 5H,O is deposited as an amorphous precipitatewhen pyridinepentacarboxylic acid is added to an ammoniacal solut,ionof calcium chloride.The ammonium in this salt can be replaced bypotassium or sodium. Acid potassium osalate also forms a double saltwith potassium pyridinepentacarboxylate, viz., C,,O,,NH,K + C204HK + 5&0. Pyridine, C5H5N, obtained by the action of lime on potas-Picoline, C6NMeH,, boils at 135".sium pyridinepentacarboxylate, boils at 120". w. c. w.Dipyridyl Derivatives. By Z. H. SKRAUP and G. VORTMAN~(il.Zbii,atsh. Chem., 3, 570--602).--In this paper, the authors show thatthe reaction which takes place in the synthesis of quinoline, hithertoapplied only to mono-substitu ted derivatives of benzene and phenol(Abstr., 1881, 919; also this vol., p.89), may be extended to thediamidobenzenes, and in particular they describe the results ob-tained by heating a mixture of m-diamido- and in-diaitro-benzen56 ABSTRACTS O F CHEMICAL PAPERS.with sulphuric acid and glycerol. The diamidobenzene-which wasemployed in the form of stannochloride-was prepared by the actionof tin and hydrochloric acid on nt-nitraniline; and the solutionobtained by treating this stannochloride with glycerol and sulphuricacid-after being freed from separated resin and rendered alkaline--was shaken up with alcoholic ether. The ethereal liquid was thenexhausted with hydrochloric acid ; the solution of the new base thusobtained was evaporated ; and the hydrochloride which crystallisedout from it after addition of alcohol was converted by potassiumdichromate into a sparingly soluble chromate (foreign matters beingat the same time destroyed by oxidation); this chromate, heatedwith ammonia, yielded the base in the form of a hydrate, which whenleft over sulphuric acid, or mvJre quickly when heated a t lOO", gave offits water, leaving the anhydrous base, which was purified by distil-lation.The base thus obtained is regarded by the authors, for reasons to beexplained further on, as formed by the attachment of .two pyridine-rings to a benzene-ring, in the manner represented by the right-handfigure below, and may be called phenanthroline, from the analogyof its struc$ure to that of phenanthrene.Phenanthrene.Phenanthroline.Pure phenanthroline forms a white crystalline mass made up of four-sided plates. It has L faint odour when cold, becoming stronger onheating, and resembling that of naphthaquinoline.It melts a t 78-78*S0, remains liquid for some time after cooling, but then solidifiesinstantaneously on being tonched with a solid body. It is somewhathygroscopic, the clear crystals when exposed to the air becomingcovered with a white opaque coating, and ultimately falling to powder.When the fused substance is covered with a very thin film of waterand rubbed with a glass rod, it is completely converted into thehydrate, which is thus obtained as a perfectly dry mass. Phenanthro-line is nearly insoluble in cold, more easily soluble in boiling water,dissolves in all proportions in alcohol, but is nearly insoluble in ether,benzene, and light petlrolenm ; dilute acids dissolve it readily.Theaqueoiis solution is nearly neutral when cold, but has a distinct alka-line reaction a t the boiling heat. The pure base may be distilled with-out decomposition, and boils a t a temperature much above 360". Itvolatilises to a slight extent with the vapour of water. The hydratedcompound, C12H8N2,2H20, crystallises in long soft needles, which donot effloresce on exposure to .the air, but give off their water oversulphuric acid, and melt in a capillary tube a t 65.5".Phenanthroline in most of its salts appears as a mon-acid base, andit is only with a great excess of acid and very strong solutions thatnormal salts can be obtained in which it is bi-acid.The basic hydi.0-chloride, C,2H8N2,HC1 + H20, separates from alcoholic solution, evenpresence of excess of acid, in long white prisms, easily soluble iORGANIC CHEMISTRY. 87water, sparingly in a'rcohol. The normal salt, C12H8N2,2HC1 + 2H20,separates in small prisms on cooling from a warm solution of the basein a small quantity of strong hydrochloric acid. It is veryunstable,and is decomposed by water. The pZatinochZoride, C,H8Nz,HzP tCl4 +H,O, forms small reddish-yellow prisms, sparingly soluble in alcohol.The chromate, (CI2H8N2),Cr20,, forms golden-yellow needles, slightlysoluble in cold water. The picrate, Cl,H6NZ,C6H2(NO2)3.OH, crystallisesin light-yellow prisms, very silghtly soluble in alcohol, melting at238-240".The sdpkate is sparingly soluble in alcohol ; the tartruteboth in alcohol and in water.A nzethiodide. ClZH8N2,McI + H20, obtained by heating phenan-throline a t 100" with methyl alcohol and excess of methyl iodide,crystaJlises in broad prisms, dissolves easily in water, sparingly inalcohol, and gives off its water of crystallisation with great facility.I t s aqueous solution turns red on addition of potash-lye, and depositsa non-solidifying oil.BROMIDES.-on adding bromine to a hot concentrated alcoholicsolution of phenanthroline, an octobromkcle, C12HeN, Br8, separates inred crystals melting a t 1 76-178". The dibromide, CIzH8N2,Br2, sepa-rates on adding bromine-water to an aqueous solution of phenan-throline hydrochloride, as a light yellow crystalline precipitate meltingat 149"; heated for a short time with a small quantity of alcohol,it is converted into dark-red crystals which have the composition(C1zH6Nz)zBr3, or C12H8N2,Br2 + CIZH8N2,HBr, melting at 178", andgiving off bromine when heated with water.By prolonged boiling withalcohol, the dibromide is converted firs& into orange-red slender needles,then into thick yellow prisms, and finally into nearly colourless needles,consisting of phenanthroline hydrobromide, Cl2H6N,H Br + +H20,melting a t 278-280". When, on the other hand, phenanthroline isheated at 120-130" with excess of bromine and water, it yields a,brownish-yellow bromine-compound, which dissolves in glacial aceticacid, and separates therehorn in non-crystalline Crusts, and appears tobe a mixture of CI2H,Br2N2 and ClZH5Br3N2.HYDRIDES.- By redaction with tin and hydrochloric acid, phenan-throline is converted into an amorphous compound purifiable by dis-tillation, and probably consisting of a mixture of tetra- and octo-hydrideof phenanthroline, C12H,N2,H4 and Cl2H8N2,H8.Dipyridyl-carboxylic Acids.-Phenan throline is readily oxidisedby potassium permanganate in very dilute solution ( 5 : lUOU), yjeldingas chief product-together with a small quantity of quinolinic orpyridine-dicarboxylic acid-an acid, C12HRNP04, or C,,H,N,( COOH)?,called p h e n a n t h r o l i n i c or dipyridyl-di carboxylic acid, whichmay be isolated by nearly neutralising the concentrated filtrate withnitric acid, adding the calculated quantihy of silver nitrate, and pre-cipitating the resulting silver salt of phenanthrolinic acid by furthercautious addition of nitric acid.This silver salt decomposed byhydrogen sulp hide, yields the phenanthrolinic acid in large triclinictablets, having the axes a : b : c = 0-5909 : 1 : 0.9773, and exhibitingthe faces wP&, OP, mP:, m:P, P', 'P, ,P, P,. They contain crystal-water, have a slightly acid taste, dissolve sparingly in cold, morefreely in boiling water, easily in alcohol, very sparingly in ether an88 ABSTRACTS OF CHEMICAL PAPERS.in benzene. They give off their water a t loo", melt with evolution ofcarbonic anhydride a t 217", give a blood-red to yellow-red colorationwith ferroas sulphate, a yellowish gradually crystallising precipitatewith ferric chloride and sodium carbonate, no precipitate with bro-mine- water.Phenanthrolinic acid forms salts both with bases and with acids.The norinnl potassizm saZt is extremely deliquescent, and remains onevaporating its aqueous solution, as a vitreous mass, which becomescr.yst alline when left, in contact with alcohol.The acid potnssiurn s d t ,Cl,H7N20~K,1~Hz0, may be crystnllised in like manner. The calciumsaZt, ClzH6N2O4Ca,3H2O, forms transparent shimmering laminae ; theBicrium salt, C,2H6N,04Ba,l&H,07 very sparingly soluble granules ; thecopper salt, Cl2H6NzO4Cu,3H2O, nearly insoluble greenish-blue granules ;the normal silver salt forms microscopic lamintt? ; the acid silvey salt,C,,H7N204,Ag,4H20, is a precipitate composed of stellate groups ofneedles.The hydrocldoride, C,,H,N204,2HCI, prepared with stronghydrochloric acid, forms transparent prisms. The pJatimchZor;de,( Cl~H8Nz0,,HCi),,PtC14 4- 6H20, separates gradually in large thickyf~llow prisms, and the mother-liquor when left to evaporate yields thesalt CJ€I,N,Oi,HzPtCl, in orange-red tablets.Dipyridyl-monocarboxylic acid,ClIHsN202 = CJI,N2(COOH),is obtained by heating phenanthrolinic acid to its melting point, andcrystallises in delicate white needles containing 2H20, which they giveoff at 100". The dehydrated acid cakes together a t 17Y", melts a t182*5-184", solidifying to a vitreous mass on cooling, and is butslightly decomposed by distillation. It dissolves with difficulty in coldwater and alcohol, easily with the aid of heat; gives no colorationwith ferrous sulphate, yellow-brown with ferric chloride ; a light-bluecrystalline precipitate with cupric acetate, and with silver nitrate awhite precipitate soluble in excess of the acid and of the precipitant;with bromine-water a cinnabar-red precipitate.The culciwn sult,(C,,H,N202),Ca,2H20, forms long shining easily soluble needles, whichgive off their water a t 2.20" ; the silver salt, C,,H,N,02Ag,$H20, is adense precipitate, which becomes crystalline on standing.A d i p y r i d y I, CIoH8N2, is obtained by distilling calcium dipyridyl-monocarboxylate with quicklime, and passes over as a colourless oil,boiling a t 149.5". Its picmte, CloH8N,,C6H,(N02)3.0H, forms smalldull-yellow needles, slightly soluble in cold water, melting a t 149.5" ;ar,d its plntinochloride, CioHBNO, H2PtCl, + +HzO, is a light-yellowprecipitate, very slightly soluble in water and in hydrochloric acid.This dipyridyl, which differs distinctly from, Anderson's dipyridine,and from the isodipyridine of Cahours and Etard, is related to pyri-dine in the same manner that diphenyl is related to benzene.Theformation of dipyridyl-dicarboxylic acid has led the authors to assignto phenanthroline the constitutional formula above given (p. 86),analogous to that of phenanthrene. H. W.Quinoline from Cinchonine. By 0. DE COKIXCK (BUZZ. XocORGANIC CHEJIISTRY. 89Chim. [2], 37, 208-209 ; see this vol., 414).-The hydrochloric acidsolution of the fraction of crude quinoline boilin? between 226-231"is repeatedly treated with ether, which removes a small quantit'y of aneutral compound having a strong odour, and boiling a t about 220".The purified base is then distilled.It is a t first colourless, but darkenssomewhat rapidly, even when protected fwm air and light ; sp. gr. at 0"= 1,1055 ; at 11.5, 1.0965 ; b. p. 236-237" at] 775 mm. The quinolineobtained by adding potash to crystallised quinoline tartrate, also boilsa t 236-237" under the same pressure. Quinoline obtained by synthesisboils at 228" (Skraup and Koenigs), or 232" (Baeyer and others).Quinoline hydrochloride forms white; deliquescent crystals, which emitan odour of quinoline, and melt a t 93-94" to a colourless liquid.Thehydrochloride is very soluble in warm, slightly less soluble in coldwater, Eoluble in all proportions in absolute alcohol and chloroform,only slightly soluble in cold, but very soluble in hot ether or ben-zene. C. H. B.The Quinoline of Coal-tar and of the Cinchona Alkaloyds,and its Oxidation by Potassium Permanganate. By S. HOOGE-WERFF and W. A. v. DORP (Bee. 'Ikav. Chim., 1, 1-17 and 107-131).-After a historical sketch of the discussion as to the identity orisomerism of the bases C9H7N, obtained from the cinchona alkaloYds(quinoline), and from caal-tar (leucoline), the authors describe themethods which they adopted for purifying the bases obtained fromthese two sources, and give as the mean results of their analysesof both bases C = 835.58 per cent., H = 5.8.The boiling pointsfound were for quinoline 238%" to 239*25O, and for leucoline'239.25" to 240.25" (thermometer wholly in vapour). Moreover,both yield the same hydrate, 2CgH7N,3Hz0, platinochloride,(C9H,N),,HZPtCI, + 2H@,dichromate, (CgH7N) ,H2Cr2O7, and argentonitrate. By oxidation withpotassium permanganste in alkaline solution, both bases yield, asprincipal products, carbonic anhydride and q ci noleic ac id, C7H5N03,according to the equation C9H7K + O9 = C7H,N04 + 2C0, + H20,together with very smsll quantities of oxalic acid and ammonia. Theidentity of the bases from the two sources may therefore be regardedas established, and the name " leucoline" may be dropped.The quinoleic acid may be separated from the products by neutra-lising with nitric acid, removing the crystals of potassium nitratewhich separate on concentration, then precipitating with calciumnitrate, treating the concentrated filtrate with lead nitrate, decom-posing the resulting precipitate with hydrogen sulphide, and con-centrating the solution filtered therefrom.Quinoleic acid is thendeposited in small honey-yellow monocliiiic crystals, having the axesa : b : c = 0.5418 : 1 : 0.6075 and /il = 64" 54'. Observed faces, KIP,PA, mP&, and a pyramidal face not determined. Cleavage, parallelto the clinopinacold.Quinoleic acid is but slightly soluble in cold, rather more so in hotwater, very slightly soluble in alcohol, insoluble in benzene, and isremoved from its aqueous solution by ether.It is but very slightl90 ABSTRACTS OF CHEMTCAL PAPERS.attacked by pot,assium permangnnate in alkaline solution, easily inacid solution. When heated to loo", it gives off CO, and leavesn i c o t i c acid, C6'H,N02. Heated in capillary tubes, it begins to turnbrown a t 175", and melts a t 228-230", but if rapidly lieat'ed it meltsat about 180", giving off gas and resolidifying, after which it meltsa t 228".A cold moderately dilute aqueous solution of this acid exhibits thefollowing reactions. With-Heatjed with lime, it yields an oil smelling of pyridine.CaCl, : gelatinous pp., graduallyBaC1, : gelatinous pp.ZnSOa : pp. of microscopic needlesafter a few hours.MnSO,: like the last, but smallercrystals.Co(NO,), : like the last ; pp.rose-coloured.NiSOa and HgCl,: no pp.Peso4 : orange colour ; yellow-brown crystalline pp. after sometime.becoming crystalline.Fe2CI, : yellow - brown, amor-phous.CuSOl: light - blue, apparentlyamorphous, nearly insoluble inwater and acetic acid, even atboiling heat.Hg(N03),: white pp. ; micro-scopic needles.Pt(C2H30,), ; like t'he last.AgN03 : shining needles of acidsalt (infra).Quinoleic acid is a pyridine-dicarboxylic acid,C5H3N (CO OH) (C ;OH).1 2It is therefore bibasic. The acid potassizcm saZt, C7HaN01R,2H,0,forms limpid triclinic crystals, which give off their water at 100". The?iorvnal barium sali, C7B,NO4Ba, obtained by adding a soluble bariumsalt to a cold solution of the acid neutralised with ammonia, crgstal-lises sometimes with 16, sometimes with 2$ mols.H20, part of whichgoes off a t loo", the last semi-molecule only at 260". The normalsiher salt, C7H3N04Ag2, is obtained by adding silver nitrate to a coldneutralised solution of the acid, as a gelatinous precipitate whichbecomes granular or crystalline on standing.is obt,ained by adding a hot aqueous solution of the acid to an acidsolution of silver nitrate diluted with boiling water, and separates oncooling in concentric groups of shining needles. Sometimes, how-ever, a hyper-acid salt, C7H4N04A g,C7H5NO4, is deposited under theseconditions, in concentric groups of small needles.Quinoleic acid, when heated a t 120-140° and upwards, gives off waterand carbonic anhydride, and is converted into nicotic acid, CsH5N02= C7H,N04 - C02.The same result is obtained by heating quinoleicacid with acetic acid. The nicotic acid thus produced agrees incharacter with that which is obtained by other methods. Its calciumsalt, (CBH,N02),Ca, forms monoclinic cryst,als; a : b : c = 1.5372 : 1 :0.6293. = 62.50. Observed faces, COP, PA. H. W.The acid salt,CTH,NO,Ag + &O,Nitro- and Amido-bromoquinoline. By W. LA COSTE (Bey., 15,191 8--1922).-Bromoquinoline (prepared from parabromaniline) iORGANIC CHEMISTRY. 9.1added gradually to a mixture of two parts sulphuric acid and onepart fuming nitric acid, the whole being cooled if necessary. Onpouring the product into water and neutralising with sodium carbo-nate, nitrobromoquinoline is precipitated, and can be purified bycrystallisation from alcohol.I t forms long Fellowish-white needles,which melt a t 133". It dissolves readily in ether and in boilingalcohol, and is slightly soluble in boiling water, from which it crys-tallises in long thin colourless needles. With platinum chloride, nitro-bromoquiioline gives a bright-yellow crystalline precipitate,[ C,H6NBr(NO2) ,HCl],,Pt C1,.Bromoquinoline, obtained by the bromination of qninoline, also yieldsa nitro-compound which melts at 133". It crystallises from hotalcohol in short yellowish needles, grouped together in nodules. I tgives a yellow granular precipitate with platinum chloride.For the reduction of nitro- to amido-bromoyuinoline, it is best toheat it in alcoholic solution with an acid (HC1) solution of stannouschloride. The double salt which crystallises out on cooling is dissolvedin water, and treated with dilute soda-solution, when amidobromo-quinoline separates in flocks, and may be crystallised from boilingwater.It forms long almost colourless needles, containing 1 mol.H,O, which it loses over sulphuric acid. It melts (anhydrous) a t164O.1 Amidobromoquinoline is a weak base, which forms salts withacids. The nitrate, C9H,NBr(NH2),HN0,, forms gold-coloured groupsof needles ; it explodes on heating. The hydrochloride crystallises invery soluble red prisms, which contain water of crystallisation ; it formsa platinochloride. Acetn?nidohromoquiizoZi?ze, CgH,NBr.NH.COllIe,crystallises in colourless plates melting at 104-10.5".By 0.FISCHER (Ber., 15, 1979-1981) .-Quinoline yields two isomeric monosulphonic acids, of which theortho-acid, as previously described (Abstr., 1882, SSS), yields thehydroxyquinoline of melting point 75-76'. The meta-acid crystal-lises in long thin colourless needles, and is more readily soluble inwater than the ortho-acid; it is best separated by the difference ofsolubility of the calcium salts, the meta-salt being the more soluble.The best yield of the meta-acid is obtained by conducting the reactionat. 140-150', the yield being then 10-15 per cent.Netahydroxyquinoline forms colourless silky needles, melting a t about230', i t is readily soluble in alcohol and benzene, sparingly in water,ether, and light petroleum.With ferric chloride, it yields no colora-tion in the cold, but on heating a faint red tilit appears. The platino-chloride forms brownish-yellow prisms.Metametho~~pitinoline, prepared in a similar manner to the ortho-compound (Zoc. cit.), is a limpid oil, boiling with partial decompositiona t 275' under 720 mm. pressure. The platinochloride crystallises inlong brownish-yellow prisms ; the picrate crystallises in tufts of thinneedles, both salts are sparingly soluble in water. The oxalate formssilk7 needles, readily soluble in water.On distilling sodium quinolinorthosulphonate with potassiumcyanide, the distillate was found to contain a mixture of ortho- andA. R. M.Hydroxyquinoline92 ABSTRACTS OF CHEMICAL PAPERS.heta-cyanoqninolines, the latter being in excess, intra-molecularchange having occurred. A.J. G.Synthetic Researches in the Quinoline Series. By Z. H.SKRAUP (Jfonatsh. Chem., 3, 531-569) .-HYDROXYQUINOLINES,These bases (ortho, meta, and para, according to the relative positionsof the N-atoms and the OH-group) are formed by heating a mixtureof an amidophenol (or better its hydrochloride) and the correspondingnitrophenol, with sulphuric acid and glycerol, according to the equationC,H,(NH2).OH + C,H,Os = C,H,NOH + 3Hz0 + H2. The amido-phenols used for the purpose must be pure, as even small quantities offoreign substances greatly diminish the yield of hydroxyqninoline.Ortho-hydroxyquinoline is but very slightly soluble in water,easily soluble in absolute alcohol, less soluble in aqueous alcohol.From water and from dilute alcohol, it separates in anhydrous brittleprisms, from absolute alcohol in more compact crystals.Ether dis-solves it with difficulty, warm benzene in all proportions. The solu-tions in nearly absolute alcohol and in benzene are colourless; theformer becomes deep yellow on addition of a small quantity of water,colourless agaiu when mixed with a large quantity of alcohol. Thesolutions in acids and alkalis are yellow.o-H:y droxy y uinoline quickly becomes reddish on exposure to sun-shine; it has a peculiar phenolic odour and burning taste; sublimesvery easily bot'h from its solutions and in the solid state, softens at i2",melts a t 73-74", and usually solidifies a t 53-55'.Under a pressureof 752 mm. it boils at 258.2" (cow.). The impure substance decom-poses on distillation, the pure substance scarcely a t all. The dilutealcoholic solution is coloured blackish-green by ferric chloride, thecolour becoming darker on addition of sodium carbonate, whichultimately throws down a dingy brownish-green flocculent precipitate.The coloration is prevented by the presence of free hydrochloric acidbut not by acetic acid. Ferrous sulphnte forms a dark brown-red pre-cipitate soluble in acetic acid with silver nitrate. The solution ofthis hydroxy quinoline in potash gives a yellow flocculent precipitatebecoming crystalline on standing ; with mercuric chloride an orange-yellow crystalline precipitate ; with lead nitrate a light yellow floccu-lent precipitate, and with barium chloride a white pulverulent pre-cipitate.The acid su@hate, CgH7N0,H,S04, crystallises in light yellowprisms containing 2 mol. H20, 1 mol. of which is given off over sul-phuric acid. The hydrochlode, CgH7N0,HC1 + H,O, forms yellowprisms easily soluble in water and in alcohol; the jdatinockloride,(CgH7N0,HCl)2PtC14 + 2H20, forms long golden-yellow sparinglysoluble needles ; the picrate, C9H7N0, C6H2(N02)3.0H, crystallises inyellow prisms very slightly soluble in cold alcohol, caking together a t170" and melting a t 203-204". A characteristic copper-compound,(CgHENO)lCu, is precipitated as a siskin-yellow powder on addingcupric acetate to an alcoholic solution of the hydroxyquinoline.The acetyl-corn pound, CIIHgNO = C9H,BEN0, prepared by boilORGANIC CHEMISTRY.93ing the hydroxyquinoline with acetic anhydride and sodium acetate, isa nearly colourless oil which remains fluid a t - Z O O , boils at about280°, is gradually decomposed by exposure t o the air, more quicklyby bases, with separation of o-hydrosyquinoline ; it dissolves readily inhydrochloric acid, and the solution mixed with platinic chloride formsthe salt (Cg€€6&N0,HCl)2PtC14 + 2H20, which separates in tufts ofsmall yellow needles.Nitro-com P O unds.-Strong nitric acid converts o-hydroxyquino-line into a mixture of the mono- and dinit1.o-derivatives, C9H6(NOz)0and C9H,(N0,),0, the latter greatly predominating. The mixturedissolves in hot dilute potash-ley, forming a deep yellow solution,which on cooling deposits a potassium derivative in slender yellowneedles.The alcoholic solution is coloured deep garnet-red by ferricchloride.Bromine-co mpound, C9H5BrzN0.-This compound separates ondropping bromine (1 mol.) into an alcoholic solution of o-hydroxy-quinoline, as a mass of needles, and may be obtained by recrystallisa-tion from alcohol or benzene in white britt'le prisms. It appears to beconverted into a bromine addition-product by excess of bromine,o-Methoxyquinoline or o-Quinanisoil, CIOHQNO = CgH6NOMe,is prepared, not from the hydroxyquinoline, but directly by treating itmixture of o-miidanisoil and o-nitranisoll with glycerol and sulphuricacid. It is a nearly colourless oil, which boils at, 265-268", turnsbrown on exposure to the air and forms a platinochloride-CIoHgNO,HzPtCI6 + 2Hz0,which crystallises in short reddish-yellow prisms.Hydro-o-hy droxyquinoline, CQHIINO, previously obtained byBedall u.Fischer (Ber., 11, 1368), is prepared by the action of tin andhydrochloric acid on the hydroxyquinoline. The aqueous solution ofits hpdrochloride gives a blood-red colour with ferric chloride, and isdistinguished from that of the para-derivative by not emitting theodour of yuinone when boiled.Para-hydroxyquino1ine.-This base, prepared like the o-compound,is best purified by reci-ystallisation of its hydrochloride. The free basecrystallises from alcohol in small brittle prisms, melts a t 1 9 3 O , boilsabove 360", dissolves Fery sparingly in water and ether, still less inbenzene and in chloroform, more freely in alcohol, easily in acids andalkalis.Ferric chloride colours the alcoholic solution faintly yellow ;ferrous sulphate produces no coloration. The alkaline solution giveswith silver nitrate a yellowish gelatinous precipitate ; with mercuricchloride a light yellow, with lead nitrate a nearly white precipitate,with barium nitrate none ; with cupric acetate, after neutralisationwith ammonia, a green precipitate.The hydrochloride, C9H,N0,HCl -!- HzO, is colourless when pure, verysoluble in water, sparingly in absolute alcohol, insoluble in ether, veryslightly soluble in strong hydrochloric acid, and in a saturated solutionof sodium chloride ; it gives off its crystal-water easily at 100".ThepZati~ochloride, ( CQH,N0,HC1)2,PtC14 + 2H20, is a reddish-yellow crys-talline precipitate. A copper-puinoZinelacetate, (CzHE-I,N02)zCu,2C2H40z,separates gradually from an alcoholic solution of p-hydroxyquinolin94 ABSTRACTS OF CHEMICAL PAPERS.mixed with a dilute solution of cupric acetate, in groups of acutewedge-shaped crystals nearly black by reflected, amethyst-blue bytransmitted light.Nitro-p-hydroxyquinoline is obtained as a nitrate-CsH6(NO2)NO,HNO3 + EL),on adding y-hydroxyquinoline to 4-5 parts strong nitric acid, warm-ing the liquid till the whole is dissolved, and diluting the red-brownsolution with water. The salt then separates in orange-red acuteprisms which become whitish at 100".It dissolves easily on heatingwith a small quantity of water, less easily in a largez. quantity, easilyin alcohol. By dissolving it in sodium carbonate and acidulating withacetic acid, the free nitrohydroxyquinoline, CgH6(N02)N0, is obtainedin small yellow needles, insoluble in water, sparingly in cold, easily inhot alcohol, easily also in acids and alkalis. It melts at 139-140", andsublimes when cautiously heated. Its alcoholic solution is colouredreddish by ferric chloride, gives st yellow-brown precipitate withcupric acetate, and orange-yellow with silver nitrate. Its potassiumsalt forms yellowish-brown brittle needles ; the barium salt, orange-yellow needles slightly soluble in cold water.Brcmo-p-hydroxy yuino l i n e , C9H6BrN0, is obtained on slowlyadding bromine to an alcoholic solution of p-hydroxyquinoline, as ahydrobromide, CgH6BrN0,HBr, which separates in reddish-yellow heavygranules.This salt dissolves sparingly in absolute, easily in hotaqueous alcohol, and with partial decomposition in a large quantity ofhot water. Its dilute alcoholic solution, when treated with sodiumcarbonate, deposits the free bromhydroxyquinoline, C9H6BrN0, innearly colourless needles, easily soluble in hot dilute alcohol, meltinga t 184-185". With silver nitrate, on addition of ammonia, it givesa yellowish flocculent precipitate ; with cupric acetate, after neutrali-sation, an olive-green precipitate.The a c e t y 1-c o m p o u n d, C9H6ZN0, prepared like the correspond-ing ortho-compound, is a light yellow scentless oil, boiling a t 298",easily soluble in alcohol and ether, soluble also in hot water.Whencooled to -20", i t remained liquid for nearly half an hour, but beganto crystallise soon after its removal from the freezing mixture. Thewhite crystals thus obtained melted between 36" and 38" to a colour-less liquid which solidified only in contact with the solid substance.The yZntinochZoride, (C,1H,NO,,HCl),,PtG11, is a yellow crystalline pre-cipitate. The benzoyl-compound, C9H6EN0, prepared by boilingthe hydroxyquinoline with benaoic chloride, crgstallises from glacialacetic acid in white slender needles, nearly insoluble in water, alcohol,et,her, and hydrochloric acid, slightly soluble in alkalis, and melting a tp-Quinani so'il, CgHsN.OMe, prepared like the ortho-compound,is a non-solidify ing-oil.This hydrochloride crystallises in long whiteprisms, deliquescing in water, moderately soluble in alcohol, sparinglyin ether alcohol. The pZatiizocliZor.icle, (CgH6N.0Me,~C11),,EJtCld + H,O,crystallises in acute orange-red prisms, easily soluble in hot water.Hydro-p-hydroxyquinoline, C,H,,NO, has been obtained as ahydrochloride, though not quite pure, by the action of tin and hydro-230--231"ORGAXIC CHEJIISTRY. 95ahloric acid on p - hydroxyquinoline. The hydrochloride is easilysoluble in water and separates by evaporation over sulphuric acid, infeathery groups of large white prisms,. afterwards in small whiteneedles. The free base is coloured reddish-violet by ferric chloride,becoming brownish on boiling, and emitting a strong odour ofquinone.Meta-hydroxyquino1ine.-This base is most readily purified byfractional precipitation of the acid oxalate.It crystallises fromabsolute alcohol in prisms, from dilute alcohol and from ether inneedles, from chloroform, and by spontaneous evaporation of itsaqueous solution, mostly in grariular aggregates. It melts, withpartial blackening, a t 235--238", sublimes undecomposed when quicklyheated, and boils with rapid decomposition a t a higher temperaturethan the para-compound. It is inodorous and nearly tasteless,slightly soluble in water, much less soluble in alcohol than p-hydroxy-quinoline, more soluble in chloroform, moderately in cjther solvents.Its soli~tions in alkalis and acids have a deep yellow colour, so long a8any of the undissolved substance is present, but they become colourlesswhen Dhe whole is dissolved.It dissolves readily in caustic potashand barytn, sparingly in ammonia. All the solutions, especiallythe dilute alcoholic, have a distinct green fluorescence. Ferric chlorideadded to the dilutic alcoholic solution, produces a, fine brown-redcolour, becoming lighter on addition of sodium carbonate ; ferroussulphate produces no reaction. The meta-compound withstands theaction of potassium dichromate m o ~ e completely than its isomerides,which are thereby oxidised.The liydrochZorid~, C9H,N0,HC1 + 1+H20, crystallises in prisms,colourless when quite pure, but mostly light yellow, freely soluble inwater, very sparingly in alcohol ; the platinochloride-(CgH,KO,HC1)2,PtC14 + 2H20,in orange-yellow needles ; the picrate, in light yellow needles meltingwith decomposition a t 244-245".( C9H6NO)2Cu,2C2H402,is obtained in violet crystals when an alcoholic solution of hydroxy-quinoline mixed with an equivalent quantity of cupric acetate and asmall quantity of acetic acid, is left to evaporate.N i t r o-m-h y d r o xy q u i n o line, C,H,(NO,)NO, is obtained on addingm-hydroxyquinoline to fuming nitric acid, precipitating with water,and recrystallising the yellow granules thereby thrown down from hotwater, in ello ow shining laminae which melt with evolution of gas a t255", and unite with acids, forming salts which are decomposed bywater.Bromine-compound.-On adding bromine-water to the hydro-chloride of m-hydroxyquinoline, a bromide of bromhydrox pquinolineis obtained, which when boiled with alcohol, is converted into a,hydrobromide, CgH6BrN0,BrH.A benzoyl-derivative is obtained in the same manner as thecorresponding para-compound in the form of an oil which slowlyThe copper-cornpound96 ABSTRACTS OF CHEMICAL PAPERS.solidifies, melting at 88-89", and yields a platinochloride having thecomposition (C,H,~N0,HC1),,PtC14.Hydro-m- hy droxyquino1ine.-The hydrochloride of this base isobtained in colourless well-defined prisms by heating a solution of332- h ydroxyquinoline in hydrochloric acid with excess of metallic tin,precipitating the excess of tin with hydrogen sulphide, and evaporating.When heated with ferric chloride, it first turns light yellow, thenbrown-red, and gives off an odour slightly resembling that of quinone.Quinoline-derivatives.By A. RHOUSSOPOULOS (Ber., 15, 2006-2009).-By the union of quinoline with ethyl monochloracetate, a com-pound, C,sH14N0,C1 = C,H,N(C; H2.COOF: t) C1, is obtained, crystallisingin stellatle groups of white needles. It is extraordinarily soluble inwater, readily soluble in alcohol, insoluble in ether. The platino-chloride, C,,H,,NO,CI,,PtCI,, crystallises in small thin needles. Thecompound, C,sH14N0,CI, treated with freshly precipitated silver oxide,yields quinoline-betainne, according to the equation-H. W.C,H,N(C,H,O,Et)Cl + AgOH + H,O = AgCl +EtOH + CgH7NCzHzOz,HzO.Quinoline-betajine forms short, thick crystals, readily soluble in waterand alcohol.It begins to decompose at 168", and fuses at 171".Hydrochloric acid converts i t into the hydrochloride, which uniteswith plat'inum chloride, yielding stellate groups of orange-colouredneedles of the formula (ClIH9N02,HC1),,PtC&.Bromoquinolinesulphonic Acids. By W. LA COSTE (Bey., 15,1910-1918) .-Bromoquinoline, prepared as previously described bythe author (Abstr., 1882, 978), was gradually added to five times itsweight, of warmed fuming sulphuric acid, and the product when coldwas mixed with a considerable quantity of water and well stirred ; theheavy crystalline precipitate consisted of two isomeric bromoquinoline-sillphonic acids, which can be easily separated by means of theirpotassium salts.The acid from the less soluble potassium salt iscalled by the author a-, and that from t h e more readily soluble salt,G-bromocyuiiiolinesulphonic acid.The a-acid crystallises from boiling water in short thin anhydrousneedles, sparingly soluble in cold water and in alcohol. The potas-siunc salt, CgH5KBr.S03K, forms shortt prisms, which decrepitat'e onheating. The b a ~ i u n ~ salt, (CgH,NBr.S03),Ba, is a sparingly solublecrystalline precipitate. The magnesiunz salt, (CgH,NBr.8O3),Mg +10H20, forms colourless plates, which lose their water at 120". Thezinc salt, (CgH,NBr.SO,),Zn + 4H20, slender needles, which losetheir water at 120" F. The manganese salt, (CgH6NBr.SOs),Mn +4H20, forms short greenish-yellow needles ; and the d v e r salt,C9H5NBr.S0,Ag, anhydrous needles.6-Bromoquinolinesulphonic acid crystallises in short] needles with1 mol.H20, which it loses at 150-160". It is sparingly soluble in coldwater, although considerably more soluble than the a-acid. The potas-sizlrn salt, C,H,Br.SO,K + l+H,O, crystallises in plates of moderate size,which are easily soluble in water. The barium salt, (CSH6NBr.SO3),BaA. J. GORGANIC CHEMlSTRY. 97+ 2R20, forms crystalline groups of needles; the magnesium salt,(C,H,NBr.SO,>,Mg + 9H,O, small needles, and the zizzc salt,( C9H5NBr.SO3),Zn + 9H,O, large transparent six-sided plates, easilysoluble in hot water. The inctngaiiese salt, (CgH5NBr.S03),Mn + 6H,O,crystallises in colourless plates, easily soluble in hot water, and thesilver salt, CgH5NBr.S0,Ag, forms colourless needles.The a- and /I-acidsboth form crystallisable salts with aniline.By TANRET (,J. Pharm. Chim. [5], 5, 591--595).-Thesalts of caffeine which it is generally supposed to form, are here shownfor the most part not to exist. Owing to its weak basic properties andneutral reaction, it does not neutralise the smallest trace of acid, andeven relatively concentrated solutions of it do not give a precipitatewith potassium-mercuric iodide.Acetic, valeric,lactic, and citric acids merely dissolve it, and on cooling the solution,pure caffeine separates out. Caffeine crystallised from valeric acidretains the odour of the acid, which, however, may be removed bywashing, so that the substance sold for cafleine valerate is only thebase, whilst caffeine citrate is a mixture of caffeine and the acid.Todissolve one equivalent of caffeine, three equivalents of citric acid arerequired, which is the inverse of the proportion which would berequired for the formation of the citrate.With mineral acids, however, caffeine does form salts, the sul-phate being cryst8allised with difficulty, whilst the hydrochloride andhydrobromide crystallise well. They are, however, decomposed bywater into caffeine, which is precipitated, and the free acid ; the hydro-chloride decomposes even on exposure to the air. Such compounds,as well as its solutions in organic acids, are useless for hypodermicinjections.It appeared, however, that the compound which exists in coffee,chlorogenate of potassium and caffeine might be used for this purpose ;bat the difficulty of preparing it in large quantities, its instability,and sparing solubility in water, prohibit its use. It was found, how-ever, that caffeine forms with benzoate, cinnamate, and salicylate ofsodium, compounds similar to the natural compound, and very solublein water.They are prepared by treating caffeine with its equivalentof the sodium salt, dissolved in a small quantity of water. One equi-valent of sodium cinnamate dissolves one equivalent of caffeine,yielding a compound containing 58.9 per cent. caffeine. The doublebenzoate contains 48.5 per cent., and the salicylate 61 per cent.These compounds are not stable, however, being readily decomposedby chloroform.100 parts of water dissolve 2 parts of the benzoateand cinnamate, and 3 parts of the salicylate.Similar compounds have been obtained with sodium acetate, lactate,citrate, sulphate. and chloride.By means of these compounds, caffeine may be used for hypodermici 11 j ec t ions.Hydrocinchonidine. By 0. HESSE (Anna?%, 114, 1-17).-Hydrocinchonidine, ClgHz4Kz0, is contained in considerdble quantitiesVOL. XLIV. hA. K. M.Caffeine.Caffeine does not form salts with the organic acids.L. T. 0’s98 ABSTRACTS OF CHEMICAL PAPERS.in the aqueous mother-liquor from the preparation of homocinchonidinesulphate. The alkalo'ids are precipitated from this solution by ammo-nia and recrystallised from alcohol.The crystalline mass is dissolvedin hydrochloric acid, and by fractional precipitation with sodium tar-trate the homocinchonidine is separated from the hydrocinchonidinetartrate ; the latter is contained in the last precipitate. The tartrateis converted into the neutral chloride : this is purified by recrystallisa-tion from water, and then decomposed by ammonia, when it yields purehydrocinchonidine. The pure alkaloid melts at 230" (uncorr.), anddoes not decolorise potassium permanganate immediately. The sul-phuric acid solution is not fluorescent. Hydrocinchonidine is depositedfrom an alcoholic solution in six-sided plates or prisms, which are inso-luble in boiling chloroform, and but sparingly soluble in ether or inwater.It is scarcely attacked by strong hydrochloric acid at 160".The following salts were prepared :-C19H,4N,0,HC1 + 2H,O, shortsix-sided prisms, soluble in water and in alcohol. ( C,,H,,N,O),,H,PtCI,, + 3H20, yellow amorphous precipitate. C19Hz,N20,H,PtC16, orange-coloured six-sided plates. The thiocyannte and the neutral oxalnteform anhydrous needles. The salicy Zate does not crystallise. Thequinate crystallises in anhydrous needles, soluble in water. The tar-trate, (C,H24N20)2,C4H606 + 2H20, is sparingly soluble in cold water.The crystals of the thiostdplznte containing 1 mol. H,O dissolve in117 parts of water at 10". C19Hz4N20,HzS0, + 4H20, is deposited inlustrous prisms! sparingly soluble in cold water. ( C,,H?4NzO)2,HzSOa + 7H,O, dissolves freely in alcohol and hot water.At 10" one partof the sulphate requires 57 parts of water for solution. The phenolsubhate, ( C19H,4N,0),S0,,CsH60 4- 5H&, forms whiteprisms, sparinglysoluble in cold water. The acetic derivative, CI9H,,AcN2O, is a hygro-scopic amorphous powder, soluble in alcohol, ether, acetone, andchloroform.Amorphous hydrocinchonidine is formed when the acid sulphnte ofthis base is heated a t 160" with hydrochloric acid, and is precipitatedin the form of a resin on the addition of soda to the aqueous solutionof the crude product. It is easilysoluble in ether, alcohol, chloroform, and acids. Hydrocinchonidinedeviates the ray of polarised light to the left much more powerfully inan acid than in a neutral solution. w. c. w.The pure base melts below 100".Xeronic and Pyrocinchonic Acids.By W. ROSER (Bey., 15,2012-2014).-In a previous communication (Abstr., 1882, 1114) theauthor has shown that pyrocinchonic acid is probably dimethylfumaricacid, and stated his belief that xeronic acid is the homologous diethyl-fumaric acid. In accordance with this view, he now finds that calciumxeronate yields propionic acid when oxidissd.By beating pyrocinchonic acid with hydriodic acid, an acid, CGH,,O,,is obtained, which from its reactions is probably identical with theunsymmetrical dimethylsuccinic acid of Pinner (Ber., 15, 582). Asacetic acid is obtained by the oxidation of pyrocinchonic acid (2 mols.),pointing t o a symmetrical constitution, intermolecular change musthave occurred in one or other of these reactions.A.J. GORGANIC CHEMISTRY. 99Strychnine. By A. GOLDSCHMIDT (Ber., l5,1977).-A preliminarynotice that the author has obtained indole by fusing strychnine withcaustic potash. A. J. G.Distillation of Strychnine with Zinc. By S. SCICHILONE and0. MAGNAWMI (Gazzetta, 12, 444-448) .-By heating strychnine withzinc-powder in small glass retorts to a temperature near the meltingpoint of the glass, a distillate is obtained, separable by treatment withether and fractional distillation, into two portions, boiling respectivelyat 165-180" and 230-300". In a second distillation the first ofthese fractions yielded n light yellow fragrant oil boiling at 173", andthe second yielded two yellow liquids, one boiling at 240-250", theother at about 292", and crystallising in a mixture of snow and salt.The liquid boiling at 173" gave by analysis numbers agreeing withthe formula C7H9N, which was confirmed by its vapour-density, deter-mined by Meyer's method (exp.3.89 ; calc. 3-70) ; and from the odourof this base and the pyridic nature of strychnine, the authors inferthat it is a lutidine, distinguishing it as ylutidine (a-lutidine boilsat 145", P-lutidine at 163-168"). This base is insoluble, or nearly so,in water, soluble in alcohol and ether, aud smells somewhat likeliquorice. The other two liquids, which were obtained in very smallquantity only, are also nitrogenous compounds, and the second, whichboils at about 292", solidifies in a mixture of snow and salt, whereasthe first remains liquid.The behaviour of the three bases with the usual tests for alkaloids,is shown in the following table:-Sodium phospho-molybdate.Potassio - mercuricIodised potassiumMercuric chloride.iodide.iodide.Auric chloride . . . .FrGhde's reagent..Picric acid . . . . . .Platinic chloride . ,y-Lutidine @. p.1'73').Dark-yellow preci-pitate soluble inNH, with faintblue colour.Yellow amorphousprecipitate.Crimson precipitateinsoluble in dilutehy$irochloric acid.White curdy preci-pitate soluble inNH,Cl.Dirty white preci-pitate.Faint red colour. -Liquid,b. p. 240-250'.White precipitatesoluble in ammo-nia withoutcoloration.Dirty yellow preci-pitate.White precipitatesoluble in N,H4Cl.Brown precipitate.Yellow amorphousReddish piecipitate.precipitate.Liquid,b. p. about 292".Light Fellow preci-pitate soluble inammonia, withoutcoloration.Red-brown precipi-tate.White precipitatesoluble in NH,Cl.Brown precipitate.Yellow amorphousRed-brown precipi-precipitate.tate.H. W.h 100 ABSTRACTS OF CHEMICAL PAPERS.Action of Dehydrating Agents on Lupinine. By G. BAUMERT(Annulen, 214, 361-376) .-Anhydrolupinine, C,,H3JY,O, and diun-hydrolupinine, C21H36N2, are formed by the action of phosphoric anhy -dride or of fuming hydrochloric acid at 200" on lupinine, C,,H,,N,O,.Anhydrolupinine is an oily liquid insoluble in water. It turns brownon exposure t o the air, and begins to decompose at 150". The platino-chloride, C21H99N20,H2PtC16, forms quadratic plates, soluble in waterand in alcohol. Dianhydrolupinine is an oily liquid (b. p. 220°), whichrapidly absorbs oxygen from the air. It yields a platinochloride,C2&6N2,H2PtC16 crystallking in dark red needles.Oxylupinine, C21H40N205, prepared by the action of phosphoric anhy-dride on lupinine hydrochloride at 175", is an unstable oily liquid.The platinochloride C,,H4,N205,H2PtC16, forms orange-coloured plates,insoluble in water and alcohol. This salt is decomposed by pro-longed boiling with water. If the mixture of phosphoric anhydrideand lupinine hydrochloride is heated at 185-190" for five hours,hydrochloric acid is evolved, and anhydrolupinine is produced.Colouring Matter (Ruberine) and Alkaloid (Agarythrine) inAgaricus Ruber. By T. L. PHIPSON (Chem. News, 46, 199).-Ruberine is insoluble in water and in alcohol; it is rose-red by re-flected, bright blue by transmitted light, and gives two wide and darkabsorption-bands in the green. As it is soluble in water, a heavyfall of rain washes it out from the head of the fungus. Frequentlythe upper surface of A. Tuber is eaten through by slugs, which, how-ever, do not penetrate deep. A yellowish-white alkaloyd (agarythrine)is extracted by ether from the fungus itself, after removal of the skin.It has a bitter taste at first, which changes to a burning sensation,resembling that produced by aconitine; the chloride is soluble inwater, but the sulphate, although insoluble in water, is soluble inalcohol. Nitric acid solutions become red. Bleaching powder pro-duces also s red coloration with agarythrine, but the colour is soonbleached. When the solution is shaken up with ether, it is oxidised bythe air to a red colouring matter; this is probably the cause of thered colour OE the surface of the fungus, the alkalo'id being oxidised bythe air in presence of light.Bases formed by Putrefaction. By A. GAUTIER and A. ~ T A R D(BUZZ. Xoc. Chirn. [2], 37,305-307).-The authors have extracted fromputrid animal mattler two liquid alkaloids, which have a strongly alka-line reaction, attack tissues in the same manner as potash, saturatestrong acids, and appear to absorb carbonic anhydride from t,he atmo-sphere with formation of crystalline carbonates. One of these alka-loYds boils at about 210°, and is a colourless, syrupy, bitter, and verycaustic liquid; its sp. gr. at 0" is 1.0296. Its hydrochloride formsslender needles, somewhat stable when pure, but rapidly reddenedby excess of acid. It is very soluble, and has a cery bitter taste. Theplatinochloride is also stable, and crystallises well. It is precipitatedimmediately from moderately concentrated solutions, dissolves onheating, but separates out again on cooling in slightly curved needles.The aiirochloride is very unstable, and rapidly deposits metallic gold.w. c. w.E. W. PORGANIC CHEMISTRY. 101The various salts of this base rapidly reduce ferric chloride to theferrous state.The second alkalojid boils at a higher temperature, but decomposeson boiling into ammonia and products which have a carbolic odour, andare only slightly soluble in ether.These alkalo'ids appear to be accompanied in the putrid matter byother more complex and more unstable basic compounds. When thecrude ethereal solution of the alkaloids is evaporated to dryness, andthe residue treated with potash, zt strong odour of carbylamine is givenoff. The carbylamines are doubtless produced by the action of thepotash on the complex basic compounds.Formation of Alkaloids from Normal Human Fluids. ByA. GAUTIER (Bied. Centr., 1882, 710).-If saliva be evaporated and theresidue dried for some hours, it will act as a poison on birds ; this sub-stance, like the ptomaines, turns potassium ferricyanide and ferrichlo-ride blue. An easily oxidisable alkaloid, which combines and formscrystalline compounds with gold and platinum chloride, has been pre-pared from urine.Urorosei'n. By M. NENCKI and N. SrEBER (J. pr. Chem. [2], 26,333-336).-The urine of a diabetic patient was found to becomebright pink on the addition of pure hydrochloric acid. The colouringmatter is extremely unstable. It dissolves in amylic alcohol, and thesolution shows a characteristic absorption-band between the lines Dand E, the maximum of intensity corresponding to 557 millionthmillimetres wave-length. 0. H.Behaviour of Unorganised Ferments at High Temperatures.By F. HUPPE (Bied. Centr., 1882, 718).-Pepsin, when dry and heatedt o 100", is not injured, but at 170" its power is diminished, althoughnot entirely destroyed.Pancreatinstill dissolves albumin, even after being heated to 160" ; the tempera-ture at which all are killed is about 160-170".C. H. B.E. W. P.Malt diastase is not affected by a temperature of 100".E. W. P.The Temperature most Favourable to the Action of Inver-tin. By A. MAYER, W. HAGEMANN, and W. HEUBACH (Bied. Centr.,1882, 706).--In a previous communication, it has been shown that pre-cipitation by alcohol destroys the fermenting power of invertin, andfurther experiments have not resulted in the discovery of any methodfor the separation of this ferment in the pure state. The temperatureat which action is most intense is about 30", but if an acid be present,then the temperature may be raised to boiling ; with various prepara-tions the temperature may be different, ranging from 31-2 48".Influence of Invertin on the Fermentation of Cane-sugar.By E. BAUER (Bied. Oentr., 1882, 707).-It is generally stated that thefermentation of cane-sugar induced by invertin proceeds with equalrapidity, whether it is previously inverted before the ferment is intro-duced or not ; such a supposition is incorrect, as nnkss the sugar beE. W. P102 ABSTRACTS OF CHEMICAL PAPERS.previously inverted, the fermentation will proceed but slowly, althoughthe complete change does finally take place, and the time occupied islonger. E. W. P