32 ABSTRACTS OF CHEMICAL PAPERS.O r g a n i c C h e m i s t r y .Bromine Substitution Products of Ethane and Ethylene.By R. ANSCH~~TZ (Anmden, 221, 133--157).--The author has carefullyexamined the physical properties of t h e bromine substitution-product8of ethylene and ethane, and many of the results have already appearedin this Journal (Abstr., 1880, 98). The boiling points and specificgravities of the compounds are given in the following table :ORGANIC CHEMlSTRP. 33b.p.CH,.CH2Br . . . . . . 38.4"CH,.CHBr, ...... 110.5CH,Br.CH,Hr , - . . 131 6CHBr,.CI-I,Br.. .. 187-188CBr2.CH,Br ...... 103*5*CHBr,.CHBr, .... 1 1 4 PCH,:CHBr ...... 16.0C Br, CH?. ....... 91.5CHBr: CHBr .... 110.0CBr, : CHBr.. .... 162.5t.15.0"21.521.521.521.521.511.021\*(i17.50.0td- 4.1.41892.083322-1 7672.61 072.93216296291.52862.1 7802.27142.6900From these results it appears that the addition of bromine raisesthe boiling point and increases the sp.gr. of the derivatives ofethane and ethylene. An unsymmetrical bromine-compound hasa lower boiling point and a lower sp. gr. than its symmetricalisorneride. The boiling points of the ethane derivatives are higherthan those of the corresponding ethylene compounds, but the specific w. c. w.Nitro-derivatives of Ethylene. By A. VILLTEHS (Compt. rend.,97, 2.%-260).-When the compound C2(N0,)4Br2,2KH0 (Abstr.,2882, 815) obtained by the combination of potassium hydroxide withtetranitroethylene bromide is treated with dilute acids, it yields nyellowish oily liquid with a penetrating odour.This liquid is pro-bably tetranitroethylene bromide. It may be heated to 100" withoutdetonation, but is very unstable even a t the ordinary temperature.The action of nitric acid on monobrometliylene bromide, and on mono-bromethane yields the same product as the action of nitric acid onethylene bromide. When this compound is treated with sodiumamalgam, or with zinc in presence of dilute alkali, if is reduced withformation of ammonia, hydrobromic acid, and hydrocyanic acid.With ammonium sulphide several products are formed. Tf the potas-sium componnd of tetranitroethylene bromide is mixed with ammoniaand a quantity of water insufficient to dissolve i t , and treated mithhydrogen sulphide for a very short time, the precipitated sulphur ismixed with a compound which dissolves easily on gently warming,and is deposited in crystals on cooling. This compound forms pale-brown crystals of the composition C4K2(N02)4.When heated gently,i t decrepitates a t a temperature below loo", and is converted into apowder without change of constitution. The same molecular changetakes place gradually a t the ordinary temperature. At 200" the com-pound detonates violently, and when treated with even very diluteacids, it is completely decomposed with a violent explosion.gravities are lower.C. H. B.Derivatives of Mannite Hexylene. By L. HEXRY ( C o ~ p t . rentl.,97, 260--263).-He~ylei~e monochlorhyclrin, CGH,,C1.OH, is obtained* Under a pressure of 14 mm.VOTA.XLVI. 34 ABSTRACTS OF CHEMICAL PAPERS.by the action of hypochlorous acid on hexylene or by the action ofhydrochloric acid on hexylene oxide. The product of the first reac-tion boils at about 170", and its sp. gr. = 1.018 a t 11'. As Dornac hasshown, it is the a-derivative, and has the constitution-C€IMe(OH). CHCl.CH,.CH,Me.The product of the second reaction is probably the @derivative, withthe constitution CHMeCl.C'H(OH).CH,.CH,&Ie. It is a slightlyviscous colourless liquid with a peculiar odour, and a very sharpsweetish taste. It is insoluble in water, and boils without decompo-sition under a pressure of 761 mm. ; its sp. gr. at 11" = 1.0143.Hez!/Zene monobromlzydrirz, C6H12Br.0H, obtained by the action ofhydrobromic acid on hexylene oxide, is a colourless slightly viscousliquid, which becomes yellowish after some time.It has a penetrat-ing odour, and a sharp taste, is insoluble in water, and boils at 188-i90" under a pressure of 769 mm. ; its sp. gr. a t 11" = 1.2959. It pro-bably has the constitution Me.CHBr.CH Pr(0H).HezyZene ~ o n i o d h y d r i ? a , C,H,,I.OH, obtained by the action ofhydriodic acid on hexylene oxide, is a colourless liquid which rapidlybecomes brown on exposure to light. It is insoluble in water, aildcannot be distilled.H e x y lene a~:etocl~lorhyd~-in, c6H&l.&o, formed by gently heatingthe monochlorhydrin witJh acetic cliloride, is a colourless liquid, in-soluble in water ; b. p. 188-190" ; its sp. gr.a t 6" = 1.04.R e z y Zene ch loronitrin, CGH12N03Cl, and hexylene d i n i t r i n , C6H,,(N0,),,are formed when hexylene oxide or the monochlorhydrin is added to acooled mixture of nitric and sulphuric acids. They are colourlesscombustible liquids, with a peculiar faint odour, insoluble in andheavier than water. They cannot be distilled.H e x y l e n e dichloride, obtained as a secondary product in the prepara-tion of the monochlorhydrin or by the action oE phosphorus penta-chloride on hexylene oxide, is a colourless mobile liquid, which isnot altered by exposure to light. It has a faint pungent odour and asweetish bitter taste ; its sp. gr. is 1.0527 at 11". It boils a t 162-165"under a pressure of 764 mm., and may be distilled over potash withoutundergoing alteration.~onochZoi.he:c.yler,e, C,HllCl? formed by the action of concentratedalcoholic potash on the dichloride, C6B&12, is a colourless mobileliquid insoluble in water, with a peculiar disagreeable odour, and itsharp taste.It is not altered by expobure to air, and boils a t 182"under a pressure of 768 mm. ; its sp. gr. at 11" = 0.9036; vapour-density 4.02.Heey Zeire ketone, CGHIZO, obtained by the action of sulphuric acidon nionochlorhexylene, is a colourless mobile liquid with an agreeablepungent odour and very sharp taste. It is insoluble in water, andboils a t 125" under a pressure of 753 mm. ; its sp. gr. a t 11" = 0.8343 ;vapour-density 3.45. The ketone is not decomposed by phosphoruspentachloride in the cold.Its constitution will depend on that ofthe monochlor-derivative, which has not yet been determined. c. H. BORQANIC CHEMISTRY. 35Reduction of Potassium Ferricyanide by PotassiumCyanide. By C . L. BLOXAM (Chem. News, 48, 73).-The potassiumcyanide employed contained but little carbonate, but on distilling itwith water hydrocyanic acid and ammonia were found in the distillate,whilst the liquid in the retort contained,-besides cyanide,-potassiumhydroxide, carbonate, and a little formate. When distilled with potas-sium ferricyanide, it yielded it distillate containing hydrocyanic acidand ammonium carbonate, the latter increasing in quantity towardsthe end of the reaction, whilst. the residual liquid, when cool, depositedabundant crystals of potassium ferrocyanide, leaving small quantitiesof potassium cjanate and formate i n the neutral mother-liquor.Theauthor gives the following equation representing this reaction :-K6Fe2C12N,z -+- 2KCN + 2H,O = 2&FeC6N6 + HCN + NHs + CO,.D. A. L.A Polymeride of Trichloracetonitril. By A. WEDDIGE (J. pr.C'hem. [a], 28, 188--189).-By heating ethyl paracyancarbonate(this Journal, 1874, 448) with phosphoric chloride, a thick yellowish-brown oil is obtained, which from its reactions appears to be para-cyancarbonic chloride. By further heating this oil with phosphoricchloride in sealed tubes at 155--160", a substance is obtained Lavingthe composition of trichloracetonitril, but different properties. Itcrystallises in large plates or prisms, melts at 91-92", is insoluble inwater, readily soluble in alcohol, ether, and benzene.By boilingwith alcoholic ammonia, it is converted into a compound of theformula C6H,CI,H4 or c6H3cl,[ NH2I2, crystallising well and melting at165". A chlorinated product of feeble basic properties is obtainedby heating in sealed tubes with aqueous or alcohol& ammonia.A. J. G.Action of Aldehyde on Propyl Glycol. By A. DE GRA;noNfr(Compt. rend., 97, 173).-Equal parts of aldehyde and isopropylglycol are heated together in sealed tubes a t about 160" for two days,and the product is distilled. That portion which boils between 75"and 110" is dried over calcium chloride and fractionated. In this waya colourless, highly refractive liquid of ethereal odour is obtained.Itboils a t about 93", and its sp. gr. is lower than that of water, i n which itis only slightly soluble. The analysis of the liquid and the determina-tion of its rapour-density did not give satisfactory results, but in allprobability it is propyleneacetal, formed by the union of aldehjdeand isopropyl glycol with elimination of water. I n contact withwater it yields aldehyde and isopropyl glycol.Isopropylene oxide has no action on aldehyde in sealed tubes below140", but above this temperature decomposition takes place withformation of volatile and carbonaceous products.Constitution of Natural Fats. By J. A. WANKLYN and W. Fox(Chem. News, 48,49).-The authors suggest that some fats, which donot yield glycerol on saponification, are in all probability ethers ofisoglycerol.Isoglycerol, CH2Me.C( OH),, exists in its ethers, cannot beisolated, and ought to be resolved into CHzMe.COOH + H,O.C. H. B.D. A. L.d 36 ABSTRACTS OF CHEMICAL PAPERS.New Derivatives of Mannitol. By A. GEUTHER (Annalen, 221,59-60) .-The author noticed that a white flocculent precipitate wasgradually separated from a perfectly clear sample of butyric acid;it was filtered off, purified from the adhering acid by heating to170°, and dissolved in water. On evaporating the aqueous solution,a gummy mass of the composition CI2H,,O7 was obtained. As theprocess of lactic and butyric fermentation is always accompanied by apartial conversion of the s u p w into mnnnitol, then this substance isprobably an anhydride of mannitol, C,,H,,O, = 2C,H1406 - 50H2,and is thus a homologue of mannitan, C,H,,O,, and mannide, C6131004.Relation between the Solubility and Rotation of Milk-sugar, and Rate of Transition of its Birotation into NormalRotation. By I?.URECH (Bey., 16, 2270-2271).-When finelydivided milk-sugar is agitated with a quantity of water insufficient todissolve it, a saturated solution is obtained, which exhibits birotation ;but, the solution gradually takes up more milk-sugar as the transitionfrom birotation to normal rotation takes place, showing that thesolubi1it)y is thereby increased. When two saturated solutions areprepared at temperatures differing by about 20") and the warmersolution is allowed to cool down to the temperature of the other, i twill still contain much more milk-sugar than the solution prepared a tthe lower temperature, the greater solubility a t the higher tempera-ture being due not only to the difference of temperature, hut, also tothe more rapid conversion at a raised temperature of the birotatorgsugar into the much more readily soluble sugar of normal rotation.The transition from birotation to normal rotation takes place slowly atatniospheric temperature, so that the rate of change can readily bemeasured by the polariscope and formulated in the same way as therate of inversion of saccharose.A. I(. M.V. H. V.Starch and its Transformations under the Influence ofAcids. By F. SALOMON (J. y ~ . Chenz. [2], 28, 82--158).-Theprincipal conclusions drawn by the author from this lengthy investiga-tion are as follows :-The transformation of starch by dilute sulphuricacid cannot be considered as a splitting up of the rriolecule intodextrin and dextrose, as assumed by Musculus.The products of theaction of sulphuric acid on starch are soluble starch, dextrin, anddextrose; the course of the reaction being that the complex starchmolecule is first converted into the more simple soluble starch, andnext into the still more simple dextrin, the hydrolysis of the latterinto dextrose commencing almost simultaneously. The rate of theconversion is proportional to the quantity of sulphnric acid present.The transformation of starch by organic acids (oxalic, tartaric, andcitric acids) proceeds in the same manner as with inorganic acids,but the action is less vigorous.Soluble starch, i f pure, gives a deep blue coloration with iodine,but if i t is contaminated with dextrin, a reddish-violet, coloration isobtained ; it does not reduce Fehling's solution, and has the specificrotary power [al,j = 211.5" (comp.O'Sullivan, Trans., 1879, 772).There is only evidence for the existence of a single dextrin ; it giveORGANIC CHEMISTRY. 37a brownish-red coloration with iodine, does not reduce Fehling'ssolution, and has the specific rotary power [a> = 216.5".ByW. FOSSEK (Afoi?atsh. Chem., 4, 660-662).-The author's method isbased on the property of the crystalline trimolecular modification ofisobutyraldehyde to change into the ordinary liquid aldehyde, underthe influence of strong snlphuric acid at the heat of the water-bath.The crude isobutyraldehyde was first partly purified by heating it, aspreviously described by the author (Abstr., 1888, 161), with a strongsolution of sodium acetate a t 150".It was then polymerised bymixing it with strong sulphuric acid (1 g. acid to 100 g. aldehyde), orwith hydrochloric acid, the formation of crystals being accelerated bycooling. These crystals were drained on a filter,.washed with water,dried between filter-paper, and preserved for use. To convert them,when required, into liquid isobutyraldehyde, they are fused on thewater-bath, mixed with a few drops of strong sulphuric acid, andheated on the water-bath in a reflux apparatus, whereb7, after aboutan hour's boiling, the whole of the polymeride is converted into liquidisobutyraldehyde, boiling constantly a t 63" (bar.741 mm. a t 0') andhaving a density of 0.8057 at 0" and 0.7898 at 20", referred to watera t the same temperatures. Its vapour, when inhaled, producesnaosea a,nd headache. H. W.A. J. G.Preparation of Isobutyraldehyde free from Acetone.A Derivative of Isobutyraldehyde analogous ts Hydro-benzoin. By W. FOSSEK (Monatsiz. Chem., 4, 663-678).-Theauthor has already shown (Abstr., 1883, 1278) that when the pro-ducts of the action of aqueous potash on isobutyraldehyde are distilledwith steam, a thick yellow oil remains, holding in solution twoisomeric crystalline bodies, C8HI8O2, resembling one another in theirchemical reyctions (which are those of the pinacones), but differing incrystalline form, solubility, and melting point, the more abundant ofthe two crystallising in plates, being moderately soluble in water, andmelting a t 151", whereas the other crystallises in groups of needles,dissolves but very sparingly in water, and melts at 91".The formerwas extracted from the oil by agitation with hot water ; the latterseparated out on adding light petroleum, This higher-meltingbody could not at first be satisfactorily examined, on account of thevery small quantity in which it was obtained; but the author hassince found that it may be prepared mnch more readily by acting onisobutyraldehyde with alcoholic instead of aqueous potash, formingindeed the chief product of the reaction, which likewise yields isobu-tyric acid and a hydroxy-acid to be described further on.The crystalline body melting a t 91" is found by analysis to have thecomposition C6H1802, and its reactions show that it consists of di-iso-propyl-glycol, CHPrp(OH).CHPrfi(OH). It dissolves readily inalcohol and ether, somewhat less readily in water, and separates onquick evaporation of its aqueous solution, as a supernatant oil, which,on contact with a solid body, suddenly solidifies to a cake.By veryslow evaporation, however, a t temperatures near 0", it may be ob-tJained in monoclinic crystals having the axial ratio a : b : c 35 ABSTRACTS OF CHEMICAL PAPERS.0.8223 : 1 : 1.9086, and the angle ac = 97" 30'. Obsrrred faces,m P s , OP, + P, -P.The crystals are flattened by predominance of~ P s . The vapour-density of thecompound is by experiment 67.71-70*03 ; calc. 7300.By oxidation with nitric acid, the glycol yields isobutyric andoxalic acids ; with potassium permanganate i n neutral solution, theisobutyric acid formed in the first instance is further oxidised to aceticand carbonic acids.Di-isopropyl glycol boiled for about two hsurs with a slight excessof acetic chloride, yields an oily diacetate,Treated with an equal weight of a mixture in equal parts of strongsulphuric acid and water, it dissolves in a few minutes, especially ifthe mixture be heated in a refiux apparatus, and there rises to thesurface an oil halving a camphorous odour; and on separating this oilafter boiling with ether for half an hour, washing the etheric solutionwith aqueous sodium carbonate, evaporating off the ether, and dryingthe remaining liquid with calcium chloride, a residue is obtainedwhich may be separated by fractional distillation into two liquids, thesmaller i n quantity smelling like camphor and boiling a t 120-122",whilst the other, which is viscid and nearly colourless, distils a t 260-262".Both these liquids have the composition C,H,,O. They are notaldehydes, and therefore the oxygen contained in them is probably re-lated to the other elements in the same manner as in oxides or inketones.The glycol heated for 6-8 hours in a sealed tube at 140" with tentimes its weight of fuming hydriodic acid, is converted into an iodidewhich, when decomposed by alcoholic potash, yields an octylene,CBHI6, in the form of a colourless mobile liquid, which has a strongodour of petroleum, distils for the most part a t 116-120", and unitesreadily with bromine, forming a very unstable addition-product.Themode of its formation from di-isopropyl glycol shows that it must berepresented by the formula CHPrB : CHPrp.The action of alcoholic potash on isobutyraldehyde gives rise alsoto isobutyric wid and a small quantity of a hydroxy-acid, C8H1,&which forms a white anhydrous crystalline powder, sparingly solublein water and in ether, easily in alcohol; does not volatilise withsteam ; melts a t 92", and distils a t a high temperature : its silver saltis amorphous, and melts at 120".The constitution of this acid hasnot yet been made out.The formation of di-isopropyl glycol and isobutyric acid from iso-butyraldehyde is represented by the equation-Twins occur united by this face.c ~ ~ H ~ ~ o ~ * = c~H~,(oG),o,.3PrWOH + KOH = CHPr~(OH).CHPrS(OH). + P@.COOK.H. W.Action of Carbonic Oxide on Mixtures of Sodium Alcoho-By M. SCRROEDER(Annden, 221, 3&-55).-The researches of Genther and Froelich,Looss and Poetsch (Abstr., 1883, 729) on the action of carbonic oxideQ In the original paper the foi-mula is printed C,,H,O,, which does not agret!either with the rational formula or with the analpis (C = 62.62, H = 9*52).-H. W.lates and Sodium Salts of Organic AcidsOHGASIC CHEMISTRY. 39on sodium alcoholates, have proved that a small quantity of the sodinmsalt of the corresponding carboxyl acid is formed.But in the pre-sence of a considerable quantity of this latter salt, sodium formate isobtained, together with the sodium salts of homologous and isologousacids. The first phase of this reaction may be expressed as follows :-CO + CnH2,+lNaOz + C,,bHz,-,Na02 = HCOONa + C,H,,_,(CnH2,+,)NaO~.The author has studied the same reaction in the case of sodiumphenates and the sodium salts of organic acids belonging to variousseries. When carbonic oxide is passed into a heated mixture ofsodium phenylate and acetate, a hydrogen-atom of the acetic acid isnot replaced by phenyl with formation of phenylacetic acid, butsodium salicylate is obtained in small quantity. This result is pro-bably due to the presence of sodium carbonate in the alcoholatewhich yields the carbonic anhydride.The supposition the authorconfirms experimentally. Similarly in the action of carbonic oxideon sodium ct,hylate and benzoate, the hydrogen of the benzoic acid isnot replaced by an ethyl-group. Conversely, when sodium phenyl-acetate is substituted for sodium benzoate, the sodium salts ofp h eny let b y lace tic, CHE tP h . C 0 OH, and ethenylbut enylph en ylacetic,CPhC,H3.C2HzEt.COOH, acids are formed ; in this respect phenyl-acctic behaves precisely as acetic acid.By the action of carbonic oxide on sodium ethylate and cinnamate,the sodium salts of diethylcinnamic acid, C,H,Et,O,, were formed inone set of experiments, when the mixture was more cornplt~telyexposed to the action of the gas.I n another set, the sodium salt ofdibutyl cinrinmic acid was obtaincd, derived doubtless from thediethylcinnamic acid by the replacement in each ethyl-group of ahydrogen-atom by another ethyl-group.Experiments on the action of carbonic oxide on mixtures of sodiumethylate and potassium oxalate or sodium succinate led to negativeresults, V. H. V.Behaviour of Chromium, Iron, and Aluminium Acetates.By B. REINITZER (Chem. News, 48, 114).--'YC'hen a solution of chro-mium sulphate or chloride is boiled with excess of sodium acetate, noprecipitate is formed, but if the boiling is conducted for a short timeonly, the solution becomes violet on cooling. The solution thus pre-pared behaves in the following manner in the cold :-Caustic alkalisand barium hydroxide change the colour a t first to olive-green andthen to emerald-green, and in 12 hours the liquid sets to a green jell?.Ammonia produces no immediate effect, but in 48 hours :I violet jellyis formed ; ammonium sulphide and carbonate act in a similar manner.after several days.When the violet chromium acetate solut,ion isboiled with any of these reagents, or with an alkaline or barium car-bonate, a precipitate is produced, immediately or otherwise, accordingto the strength and quantity of the reagent added. Sodium phos-phate does not precipitate the solution. This non-precipitating prc-perty of chromium acetate extends to iron and alumina in solution,for neither by boiling nor by treatment with the above-mentionedreagents can certain quantities of ferric oxide and alumina be de40 ABSTRACTS OF CHEMICAL PAPERS.tected in the presence of chromium acetate. The quantity of theseoxides thus retained is limited if the ferric oxide and alumina arepresent previous to boiling with sodium acetate ; if, however, thesesubstances are added subsequent to sodium acetate treatment, largequantities of iron and alumina can be dissolved.Ammonium sulphidemakes an exception in the case of iron, for it precipitates i t slowlybut completely. If the chromiiim solution and sodium acetate aresimply mixed in the cold, a t first the chromium can be precipitatedby the reagents referred to above ; after a day, however, the solutionacquires the solvent properties it would have done by boiling.D.A. L.Composition of Cocoa-butter. By M. C. TRAUB (Arch. Pharrn.[3], 21, 19-23).-Kingzett has stated (Trans., 1878, 38) that thisbutter contains two new fatty acids, the one apparently an isomerideof lauric acid, the other, called theobromic acid (m. p. 72*8"), andhaving the formula C64H12802. The momalous melting point of suchan acid led the author to make an investigation of cocoa-butter. Bya process of fractional precipitation with magnesium acetahe aftersaponification, an acid was obtained from the first portion of the pre-cipitate, which was not further resolved by precipitation, and afterrecrjstallising from absolute alcohol was proved to be arachic acid( C2,H4,0,). Fractional distillation under diminished pressure (100mm.) confirmed the results obtained by fractional precipitation.Inaddition to arachic acid, oleic, lauric, palmitic, and stearic acids werefound, but no acid isomeric with lauric acid. The author, therefore,cannot confirm the statement that cocoa-butter contains two new fattyacids, and maintains that its physical properties are due to the relativeproportions of arachic, oleic, lauric, palmitic, and stearic acids, whichare present. W. R. D.Carbonyl Iodide, COI,. By S. P. COWARDINS (Chern. NCZC'S, 48,97).-Several experiments were made with a view to prepare t h i ssubstance, but without success. Proportional parts of dry carbonicoxide and iodine in a flask were exposed to direct sunlight. Carbonicoxide and iodine yapour were passed through a tube surrounded byice and salt.Carbonic oxide was passed through heated arsenicpentiodide, and then through the cooled tube, also over red-hot leadiodide. Phosgene gas was passed over potassium iodide and into con-densing tubes. D. A. L.Action of Phosphorus Pentachloride on Succinic Chloride.Ry E. KAUDER (J.PY. Chenz. [Z], 28, 191--192).--By heating onepart of succinic chloride with three parts phosphorus pentachloride insealed tubes at 230", there was obtained, not as was expected thechloride C2H4(CCI3),, but a colourless liquid of sp. gr. 1.694, boiling at199-215", solidifying in large colourless plates at, low temperatures,and having the composition C4C160. If this is heated with sulphuricacid, it is decomposed into a substance of the formula C4Cl,0,,possibly dichloromaleic anhydride, C2C& : (CO), 0.It forms a whitemass, sparingly soluble in water, melts a t 119*5", and sublimes inwhite plates. A. J. GORGANIC CHEMISTRY. 41Tetric Acid and its Homologues. By W. PAU-LOW (Compt.rend., 97, 99-102) .-Ehhylic methylinonobromacetoacetate is slowlydecomposed a t ordinary temperatures and more rapidly when heated,yielding monobromethane and the tetTic acid described by Demarcay.This acid has the composition C5H603, and not C,,H,,O, as stated byDemargay. Ethylic isobutyl-monobromacetoacetate is decomposed ina similar manner when heated, and yields the heptic acid also describedby Demnrgay. This acid has the composition C 61.33, H 7.81, cor-responding with the formnla C8H1203, and not with Demargay'sformula 3(C7Hl,02),H20, which requires carbon 63.63 per cent.,hydrogen 8.08 per cent.The formation of these acids by simpleevolution of monobromethane indicates that they are unsaturatedcompounds, and tetric acid is found to combine readily with twoatoms of bromine. This fact, together with its mode of formation,shows that tetric acid has the formula MeCO.C(COOH) : CHZ, and isin fact acetoacrylic acid, the general formula of its homolcgues beingMeCO.C(COOH) : C,H,,. Its formation is expressed by the equationMeCO.CBrMe.COOEt - C2H,Br = MeCO.C(COOH): CH,. Ethylmonobromacetoacetate, MeCO.CHBr.COOEt, undergoes no similardecomposition. C. H. B.Carboxytartronic Acid. The Constitution of Benzene.By A.K E K C L ~ (Annalen? 221, 230-260).-After referrinq to theresearches of Gruber ( Wien. Acad. Ber., 1879 ; Ber., 12, 514), Barth( Wien. Acad. Ber., 1880 ; Wiener Monatshefte, 1, 869), and Werzig(Wien. Acad. Rer., 1882 ; Wiener Monatshefte, 3, 825), on carbosy-tartronic acid, and their bearing on the constitution of benzene, theauthor describes experiments proving that the so-called carboxjtnr-tronic acid is a dihydroxytartaric or tetrahydroxysuccinic acid. Amixture of racemic and inactive tartaric acid is formed by the actionof zinc and hydrochloric acid on sodium carboxytartronate ; andcarboxytartronic acid is produced as an intermediate product by thespontaiieous decomposition of nitrotartaric acid.The nitrotartaric acid is prepared by adding sulphuric acid to asolution of tartaric acid in 44 times its weight of fuming nitric acid.The crystalline mass is drained by means of a filter-pump, andbrought in small quantities a t a time into a mixture of ice and ether.After washing with ice-cold water, the ethereal solution is evaporatedin a vacunm.A solution of nitrous acid in alcohol is added to anetherial solution of nitrot,artaric acid, and after two or three days theliquid is shaken with ice-cold water. On the addition of sodiumcarbonate to the aqueous solution, sodium carboxytartronate is a t onceprecipitaLed. The sodium salt is decomposed by water a t 6d", withthe formation of carbonic anhydride and sodium tartronate.These experiments show that " sodium carboxytartronate " doesnot possess the coristitution generally ascribed to it, and that carhoxy-tartronic acid is closely related to tartaric acid. The exact composi-tion of the sodium salt has not yet been ascertained, as it loses firstwater, and then water and carbonic acid on drying ; but it is probablyC4Na2OG + 4H@.Since this compound does not contain three carbon-atoms directly united to each other, its formation from pyrocatecho42 ABSTRACTS OF CHEMICAL PBPERS.is no argument against the author's hypotheses on the constitution ofbenzene. w. c. w.Iaonitroso-acids. By A. F~~RTH (Ber., 16, 2180-2182).-0f theisonitroso-derivatives of the acids of the acetic series, only three areat present known, viz., isonitroso-propionic, -butyric, and yvalericacids. The author, following the process proposed by WJGugel, hasobtained, by the action of nitrous acid on ethylpropylacetoacetate,a-ison.itroso-waZeric acid, CH,Me.C Hz. C (N.OH) . C 0 OH. This acidcrystallises in needles which melt at 143" with complete decorr-position; it is soluble in alcohol and benzene, sparingly soluble inwater; its silver salt forms a white precipitate. By the action ofhydrDxylamine hydrochloride on ortho- and para-aldehydo-salicylicacid, the author has obtained the ortho- and para-aldoximesalicglicacids, COOH.C6H3(OH).CH(NOH). Both acids crystallise in smallgolden needles. The former melts at 193", the latter a t 179", and isinore sparingly soluble than its isomeride.Action of Nitrous Acid on Ethyl-glycocine Hydrochloride.By T.CURTIUS (Ber., 16, 2230--2231).-When a concentratedaqueous solution of the hydrochloride of the ethylic ether of glycocineis treated with sodium nitrite, a yellow oil is precipitated and can beextracted with ether. To purify it, it is treated with baryta-water,steam-distilled, dried over calcium chloride, and heated a t 95" on awater-bath. It is a neutral liquid of golden-yellow colour and ofpowerful characteristic odour, miscible in all proportions with etherand alcohol, but almost insoluble in water. It volatilises on ex-posure to air, and when heated t o about 110" is decomposed withviolence and with great evolution of heat. It shows great stability inthe presence of alkalis, but in contact with acids, water, or alcohol,it gives off nitrogen in nearly theoretical amount.With cold con-centrated hydrochloric acid, the decomposition takes place withexplosive violence, etlhyl chloracetate being formed. On boiling i twith water, the products are ethylic glycollate, glycollic acid, alcohol,and nitrogen, whilst with alcohol, ethylic ethylglycollate is produced.These reactions would indicate the body to be ethylic diazoacetate,CH,(N,OH).CQOEt, but analysis shows that its formula is-V. H. V.that is, ethylic diazoacetate minus the elements of a molecule of water.The author is continuing his experiments in the hopes of obtainingdiazo- and diazo-amido-derivatives of the fatty acids. A. K. M.Chemistry of Asparagine. By B. SCHULZE (LandvJ. Tersucl6s.-Stat., 29,2;%-240).--Having occasion to obtain rather large quanti-ties of aspartic acid from asparagine, the author made several experi-ments to ascertain which was the cheapest and best decomposingagent to use.Schlosing's apparatus was used for determining theamount of asparagine converted into ammonium aspartate, and it wasfound that milk o€ lime had no action in thc cold on asparagineuntil after 24 horirs' standingORGANIC CHEMlSTRY. 43Heated wit,h water alone, a t the ordinary pressure, asparagine isbut very slowly decomposed; after 12 hours' boiling only 2 per cent.of the nitrogen was converted into ammonium salt. Under higherpressure the amount decomposed is much greater, and increases slowlywith increase of pressure,The effect of boiling with lime-water or baryta was much morerapid ; when a large excess of baryta was used, one hour was sufficientfor the complete conversion into aspartic acid ; but if the boiling becontinued some hours longer, a further separation of ammonia takesplace, malic acid being formed.Boiling with dilute sulphuric acid in slight excess also effects thecomplete conversion of asparagine into ammonium aspartate.J. K.C.Metaisopropylmethylbenzene. By H. E. ARMSTRONG and A.R. MILLER (Ber. 16, 2748-2750) .-According to Kelbe (AlznaZen,210, 30) metaisocymene yields at least two monosulphonic acids, theRecond of which, the P-acid, he did not thoroughly investigate, but hedescribed the barium salt as being very readily soluble in water, andas cry stallising from a concentrated syrupy solution in small lustrousscales of the composition (C10H13S03)2Ba + HzO.The authors, whogive a full description of the method by which they prepare puremetaisocymene, also find that this hydrocarbon yields two sulphonicacids, which they separate by means of the barium salts, but Kelbe'sdescription is entirely inapplicable to the more soluble modification.Although very soluble, it crystallises very readily in long thin prismsof the composition (CloHl,S0,)2Ba + 9H20. The calcium salt,(C10H13S03)2Ca + 5&H,O, is very similar in appearance to the bariumsalt. The potassium salt, CloH,S03K + 2+H20, crystallises in longwell-formed prisms. A. K. M.Contributions to our Knowledge of Camphor. By H. .E.ARMSTRONG and A.K. MILLER (Bey., 16, 2255--226l).-By the actionof' zinc chloride on camphor, Fittig, Robrich, and Jilke (Arunalen, 145,129) obtained a hydrocarbon, C,,HI4, which they regarded as mostprobably identical with ordinary cymene, together with muchtoluene, xylene, pseudocumene, and Zaurene, the last-mentioned being,according to their analysis, a hydrocarbon of the formula CIIHl,. Bythe same reaction Montgolfier (Ann. Chim. Phys., 1878 [ 5 ] , 14, 87)obtained what he thought to be cymene and an isomeric hydrocarbonboiling a t about 195", from which he prepared a dibromo-derivativemelting at 199"; this isomeric hydrocarbon he assumed to beJannasch's tetramethylbenzene (1 : 2 : 3 : 5), and regarded it asidentical with Fittig's laurene.From the fraction 173-176", sup-posed to be cymene, Fittig, Robrich, and Jilke prepared a sulphonicacid, the barium salt of which contained 10.13 per cent. water,whereas ordinary barium cymenesulphonate contains 8.75 per cent.It would seem that Montgolfier prepared the same salt (with 10.74per cent. water) from the crude distillate boiling at about 195".Pittig's fraction boiling at 188" (Cl,H,o), was assumed to be a di-niethylpropylbenzene, as it yielded a tri bromo-derivative melting a44 ABSTRACTS OF CHEMICAL PAPERS.125", and on oxidation gave monobasic lauroxylic acid, C,H,,O?,melting at 155"The authors heat camphor with twice its weight of zinc chloride ata moderate temperature, until a homogeneous mixture is obtained,and then distil a t as low a temperature as possible.The crudedistillate is extracted with sodium hydroxide solution, then steam-dis-tilled, and the distillate is agitated with dilute sulphuric acid (4 vols.acid to 1 vol. water) to remove the unattacked camphor, and againsteam-distilled. On passing steam into the retort, a second distillateis obtained, consisting of camphorone, CDHIIO, and camphor mixedwith some hydrocarbon, which can be separated by means of sulphuricacid of the above strength, in which the camphorone is soluble; aresidue of zinc chloride mixed with a black carbonaceous mass remainsin the retort. The above-mentioned alkaline extract yields purecarvacrol on addition of an acid.When the mixture of hydrocarbons remaining after treatment ofthe crude distillahe with dilute sulphuric acid, is heated with sulphuricacid, a considerable amount of a saturated hydrocarbon, CIOHZO,remains undissolved, whilst the sulphuric acid solution containsprincipally beuzene hydrocarbons of the formula I=,,H,,, only a verysmall amount of lower and higher homologues being formed, togetherwith a hydrocarbon which has not yet, been isolated, and which iscarbonised by the action of heat on the dilute acid solution. Thechief constituents of the hydrocarbon mixture are a nzethylpropyl-benzene, a dimethylethylbenzene, and a tet?-amethylbenzene ; the pre-sence of ordinary cjmene has as yet not been detected.* Thesulphonic acid of the first-mentioned hydrocarbon yields a verysparingly soluble anhydrous barium salt, a sodium salt containing1 mol.H,O, and an anhydrous potassium salt, the last two crystal-lising in large lustrous plates. The hydrocarbon boils a t 176", isoxidised by dilute nitric acid to metatoluic acid, and is identicalwith the metaisopropylmethylbenzene discovered by Kelbe in rosinspirit. The dimethylethylbenzene (b. p. 189') is probably identicalwith Fittig's laurene; it yields paraxylic acid on oxidation, aricimust therefore have the constitution [Me : Me : Et = 1 : 2 : 41. Ityields two isomeric sulphonic acids. From the chief product there mayhe obtained a barium salt crystallising with 4H,O, and a magnesiumsalt containing about 25 per cent. water, magnesium cymenesul-phonate containing 16.6 per cent. The tetramethylbenzene isiden tical with Jannasch's isodurene, and yields a dibromo-derivativemelting at 2W0, as stated by Jacobsen.The chief products of the action of iodine on camphorare carvacrol,and the saturateu hydrocarbon, C,,H,,.Dimethylethylbenzene andtetramethylbenzene are also formed, but no cymene or meta-cymene.Ordinary cymene appears to be the only benzene hydrocarbonwhich is formed by the action of phosphoric anhydride on camphor,and is also the chief product of the action of phosphorous pentasul-phide, but in the latter case a considerable amount of metaisopropyl-* Subsequent investigation has shown that no cymene is present.-H. E. AORGANIC CHEMlSTRY. 45methylbenzene, and a small quantity of tetrnmethylbenzene are alsoobtained together with traces of higher and lower homologues, and asmall percentage of the hydrocarbon C,,H,,.The hydrocarbon whichcarbonises when its sulphuric acid solution is heated (see above) is alsoformed by the action of phosphorus compounds and of iodine oncamphor.The formation of these different hydrocarbons from camphorcannot well be represented by KekulB's formula, b u t can be to someextent accounted for by the assumption of the following formula,which is a slight moditication of that previously suggested byArmstrong (Rer., 11, 1698 ; 12, 1756).CH, CH CH/\HC CEI:AHC CPr/\H,C CH.CH,I IMeC C.CHMe2I IMeC CHI I IMeHC CMe.COv CH, \c/H Y€Camphor. Cymene. Metacy mene.CMe CHAHC CMeI IMeC CMe/\HC CEt1 1MeC CH\/CMeTetramethylbenzene. Dimethyle thylbenzene.A.K. M.Artificial Formation of Thiophene. By V. MEYER and T.SANDMEYER (Bey., 16, 2176).-I€ ethylene or acetylene is passedthrough boiling sulphur large quantities of carbon, hydrogen sulphide,and carbon bisulphide are foi-med. The last contains a small quantityof an oil which resembles thiophene in all its properties, giving theindophenine reaction with isatin and sulphuric acid, and dyestuffswith beirzoyl cyanide and sulphuric acid, and with phenylglyoxylicand metazophenylglyoxylic acids.The Thiophene Group. By V. MEYER and H. KREIS (Bey., 16,2172-2176 j .-One of the anthors bas recently isolated and describedthiophene, C4H,S (Abstr., 1833, p. 1091), a substance obtained fromcoal-tar benzene ; in the present communication some of its derivativesare described.Z'pJtrabromothiophene, C4Br4S, is formed by the action of bromine inexcess on the residue left in the course of the fractional distillation ofdibromotlhiophene.This substance crgstallises in white glisteningneedles melting at 112", and boiling at 26".Thiophenesulphonic acid, C,H3S.S03H, is obtained as a deliquescentcrystalline mass, of strongly acid reaction, and yielding thiophene ondry distillation. The corresponding acid chloride, C,H,S. SO,Cl, is aheavr golden oil, converted by trituration with ammonium caybonateV. H. V46 ABSTRACTS OF CHEMICAL PAPERS:.into thiophenesdpamide, C4H3S.S0,NH2, which forms delicate whitecrystals melting at 141".ThiopheiLenitriZ, C4H3S.CN, obtained by the distillation of potassiumcyanide and thiophenesulphonates, is an oil boiling a t 190", and smellinglike bitter almonds ; it is readily transformed into the carboxylic acid,C4H3S.COOH, on boiling with alkalis.Thiophenic acid resemblesbenzoic acid in appearance, smell, and manner of sublimation ; it is veryvolatile in vapour of steam, melts a t 118", and boils a t 258". I t s cal-cium salt forms spear-shatped crystais, its silver salt a precipitate,sparingly soluble when dried.The authors briefly note the presence of a sulphur compound boilinga t 110" in the purest toluene of commerce ; they are now engaged ininvestigating it, and the dye-stuffs derived from it, as also those fromthio p hene.Separation of Aniline, Paratoluidine, and Orthotoluidine.Ry LEWY (Dingl. potyt.J., 248, 260).-By decomposing the hydro-chlorides of the bases with sodium phosphate, Lewy obtains thosparingly soluble phosphates of aniline and paratoluidine besides freeorthotoluidine and readily soluble basic orthotoluidine phosphate.By warming the mixture after the decomposition is completed, it ispossible to dissolve the first-named salts ; the resulting supernatantoily layer of orthotoluidine is then decanted, and the aniline and para-toluidine salts are allowed to crystallise out. The mother-liquor con-tains the basic orthotoluidine phosphate. By liberating the bases withsodium hydroxide, the sodium phosphate originally used may berecovered. D. B.V. H. V.Meta-isocymidine. By W.KELBE and C. WARTH (Annalen,221, 157-178) .-Nitrometa-isocymene, CIoH,,NOa, prepared by theaction of strong riitric acid on meta-isocymene (Abstr., 1880, 8'78)is decomposed by boiling, but may be distilled in a current of steam.By the prolonged action of dilute nitric acid (1 of acid to 4 of water),it is converted into r&rotoZuic acid, CGHsMe(NO2).COOH(a), whichis not identical with either of the nitrotoluic acids described byJacobsen (Ber., 14, 2347), and must consequently have the formulaC6H2Me(N02)H. COOH (-0 o r C6HMe (NO,) H2. COOH (8). This acidis deposited from an alcoholic solution in glistening needles (m. p.214"). The b a r i u m salt crystallises in silky needles, freely soluble inalcohol and in water.illeta-isocyirkdine, CloHI3NH2, obtained by reducing nitro-isocymenewith tin and hydrochloric acid, is purified by conversion into thebenzoic-derivative, NHIE.Cl0HI3. This compound crystallises inneedles melting at 165", soluble in alcohol.It is decomposed by alco-holic potash a t 180", yielding meta-isocymidine, a strongly refractiveliquid boiling at 23'L0, freely soluble in alcohol, ether, benzene, andlight petroleum, The platinochloride of meta-isocymidine is unstable.The srdphate, ( C,oH13.NH2),H2S04 forms thin plates, sparingly solublein water and alcohol. The aqueous solution is decomposed by hoil-ing. The oxaZcrte, Cl,H,3.NH2,H.,C20J, is sparingly soluble in waterand alcoholORGANIC CHEMlSTRY. 47Acetic chloride acts readily on dry cymidine, forming acetoineta-isocymidide, NHAc.CloHl,, which crystallises in plates melting a t 118".By tlhe action ofst'rong nitric acid on benzoic isocymidide, the nitro-compound NHBz.CloH,2.N0, is produced.It is deposited from analcoholic solution in yellow needles melting at 177", which are spar-ingly soluble in ether. On oxidation with dilute nitric acid, benzoicisocymidide yields amidometatoluic acid, which melts below 100".Phthalic rnetaisocymidide, C6H4( CO)2N.C,oH13, is deposited from ahot alcoholic solution i n needles, which melt at 145". The nitro-product forms yellow needles melting at 167", soluble in alcohol ande t 11 e r.Il'ltaisocyii~iiay Zcarby Zair~ine, Cl0H,,NC, prepared by the action ofchloroform and alcoholic potash on cymidine, is a colourless liquidhaving a powerful odoiir.It is freely miscible with alcohol, ether,benzene, and light petroleum. It cannot be distilled without decom-position. Ili"TetaisocyminyZcarbamide, C loH13.NH. C ONH2, is obtained byboiling an excess of potassium isocyanate with a feebly acid solution ofcymidine sulphate. It forms lustrous needles melting at 176", solublei n alcohol. By the action of carbonyl chloride on cymidine dissolvedin absolute ether, dimetaisocimynylcarbamide, ( CloH,3NH)2C0, isproduced in colourless needles, freely soluble in alcohol, less solublein ether.~~etaisocynainyZuret7Lane, C,"H13 NH.COOEt, is a colourless crystal-line compound melting at Z9", soluble in alcohol and ether. Dbyminyl-thiocarbamide, ( CloH,,.NH),CS, prepared by the action of carbonbisulphide on cymidine, crystallises in needles melting at 160", solublein alcohol and ether.Neither naetaisoc?/rniizyZethy Zthiocarbnmide, C,,H,,.CSNH.NHEt, normetaisocyminylethylguanidine, CIOH13.C (NH)NH.NHEt, could be ob-tained in a crystalline condition.Nitrophthalylcymidide is decomposed by strong hydrochloric acidat 180", yielding nitroisocymicline, NO2.CloH,,.NH2, an oily liquidmiscible with alcohol and ether.~ ~ e t a i s o c y m i d i n e s u ~ h u n i c acid, CloHl,( NH,) .SO,H, forms thinyellow-coloured needles, very soluble in water.The Larium salt, (NH,.CloH12.S03)zBa, also crystallises in needles,Action of Dichloracetic Acid on Aromatic Amines (11).ByP. J. METER (Ber., 16, 2261-2269) .-The author previously showed(Ber., 16, 926) that the reaction of dichloracetic acid with orthotolui-dine is different from t h a t between dichloracetic acid and paratoluidine,the latter yielding a substituted imesatin.To prepare paratoZy?@ni a-methylimesatin (paramethylisafin-~aratul~limide), C8H4MeN0.NC7H,,dichloracetic acid (1 mol.) is heated with paratoluidine (4 mols.) at100" until a dark-red crystalline mass is formed, which is then treatedwith hot water t o remove the toluidine hydrochloride ; or an aqueousor alcoholic solution of dichloracetic acid may be digested with para-toluidine, or finally dichloracetamide (1 mol.) heated with paratolui-dine (3 mols.). It crybtallises in splendid lustrous gold-colouredneedles and scales. The react:on may be compared with the fcrmationwhich are very soluble in water.w. c. w48 ABSTRACTS OF CHEMICAL PAPERS.of qninoline from aniline and glycerol (Ber., 13, 2086) : 2C7H;.NH, +C2H7C1202 = CI6H,,N,O + 2IIC1 + H,O f H,. Paramethylisatin-paratolylimide melts a t 259", is insoluble in water, dissolves sparinglyin cold, more readily in hot alcohol, and in ether. With concentratedsoda solution, it yields a salt crystallising in red prisms, and which isdecomposed by water. Cold concentrated hydrochloric acid converts itinto paramethylisatin and toluidine ; hot dilute acid or long-continuedheating with soda solution decomposes it in the same way ; it can bereproduced by heating these products with absolute alcohol. Whenpararnethylisatin-paratolylimide is heated for 2 to 3 hours a t 100"with alcoholic ammonia, pwamethy lirn esntin (paramet hy lisa titiin? i d e ) ,C9H,N0.NH, is formed, and can be freed from toluidine and colour-ing-matter by repeated boiling with alcohol.I n its properties, itdiffers from Laurent's imesatin (J. pr. Chem. 25, 457); it has apale yellow colour, is insoluble in cold water and cold alcohol, andvery sparingly in boiling alcohol, from which it crystallises iiiextremely slender silky needles ; it is not converted into paramethyl-isatin by acids or bases, and bears a strong resemblance to Somma-ruga's diimidoisatin (Ar~nnlen, 190, 371; 194, 85 ; Ber., 12, 979).Pnran~efhyliscttin, CeH,MeNO,, obtained as above, is isomeric withthe substance obtained by Baeyer and CEconomides (Ber., 15, 2093)from isatin silver and methyl iodide ; it is odourless, separates fromalcohol or hydrochloric acid in deep red transparent crystals resem-bling chromic anhydride, and from water in lustrous red scales,melting at, 187" ; it is sparingly soluble in cold, more readily in hotwater, readily in hot hydrochloric acid and in alcohol ; with alkalis,it forms a deep violet-coloured solution, yielding methylisatates whenheated OF on long standing.It yields the indophenin-, and withliydroxylamine the ketone-reaction, and forms condensation and sub-stitution-derivatives similar to those of isatiii. Phenylparumethyl-irnesahrz (pnraniethylisatinphe.lzylimida), CeH4MeN0 : NPb, is ob-tained on adding the equivalent quantity of aniline to a concentratedsolution of paramethylisatin in absolute alcohol.It crystallises inthick, yellowish-red, transparent plates or prisms, melts a t 239-240°,is sparingly soluble in water or cold alcohol, more readily in hotalcohol, and in its properties resembles paratolylimide. Metabromo-pnratolylp arnrnefh?y lirnesat i r i (paramethy lisatinin et abro m oparatoly 1 irnide),CeH4MeK0 NC7HeBr, is prepared in the same way as the last corn-pound ; it crystallises from alcohol in transparent brick-red needlesand prisms, melting at, 2 10". Orthoto ly lp~(r,r~yrLethylimesntin (para-nzeth?llisatinorthotolylirnide), CBHQMeN0.NC7H5, isomeric with theabove paratolylimide, crystallises in red transparent prisms, me1 tingat 191". Par.nmethyl~zitroso-oxin~ole, C,H,(NO)NO, is prepared by theaction of liydroxylamine hydrochloride on paramethylisatin (Rer., 16,518).It forms long transparent yellow prisms, is sparingly solublein water, more readily in alcohol, dissolves in potash without decorn-position, and melts a t 225-226". On adding coal-tar benzene to asolution of paramethylisatin in concentrated sulphuric acid, a deepblue coloration is produced, and on agitating with water paramethy I-indqjhenin separates. The numbers obtained on analysis agree onlyapproximately with the formula C1,H,NOS. It forms am indigo-bluORGANIC CHEMlSTRY. 49powder, sparingly soluble in water, alcohol, and acetic acid, morereadily in concentrated sulphuric acid and hot phenol, from which itis reprecipitated by water or alcohol.When treated with zinc andglacial acetic acid, it yields a bright, green substance, which becomesblue again on exposure to the air,Difference in Chemical Behaviour of Aromatic Diamines.By E. LELLMANN (Annalen, 221 1--34).-The isomeric aromaticdiamines, in some cases, present characteristic differences in chemicalbehaviour. Thus for example, Ladenburg has observed that thehydrochlorides of the orthodiamines react with benzaldehyde accord-ing to the equation-C,Hy(NH,),,2HC1 + 2PhCHO = C,H,(NCHPh),,HCl+ 2H20 + HC1,A. K. M.whereas the meta- and para-derivatives are unaltered. Similarly,Hobrecker and Hiibner have shown that ortho-diamines are differen-tiated from the meta- and para-compounds in yielding the so-called.NH.anhydro-bases, C,H \C,H,.Again the reaction of nitrous Y\-,-kacid on the ortho- resembles that on the para-, but differs from thatwhich it exerts on the meta-compounds.The author has studied the reaction of potassium thiocyanate andcyanate, and of the thiocarbimides, on the aromatic diamines, with aview of tracing analogous differences in chemical behaviour.At the outset some remarks are made on the method of pre-paration of ortho- and para-phenylene diamines. It is found that toobtain the former it is best to nitrate benzanilide and not acetanilideas recommended in the text-books ; on the other hand, acetanilide ismore suitable for the preparation of the latter.Action of Thiocyarmtes o n the Diaw&aes.-The diamine thiocyanatesare easily obtained from the hydrochlorides of the diamines and thethiocyanates; but the compounds produced differ in their mode ofdecomposition, the meta- and para- thiocyanate yielding the correspond-ing phenylenedithiocarbamides, C6H4(NHCSNH2),, whilst the ortho-compounds give the corresponding thiocarbamide, C,H,<NH>CS,together with thiocarbamide, CS(NH&.Orthophenylenethiocarbarnide, C6H4 <,,>CIS, obtained by the eva-poration of an aqueous solution of 1 mol.orthophenylenediamine hydro-chloride and 2 mols. potassium thiocyanatc, crystallises in large leaflets,which melt at about 290" with considerable carbonisation.YHNHNH Metapcrrutolylenethiocarbnmide, c6H3Me<NH>cs, from metapara-tolylenediamine and potassium thiocyanate, crystallises in silveryleaflets melting a t 284", and soluble in soda and ammonia, but repre-cipitnted on acidifying the solution.H e t ap h en!/ 1 ened it 1~ iocar b am id e , C 6H (NH C S N H,) ?, cry s t a1 li s e s inmicroscopic leaflets melting a t 215" ; the corresponding para-compoundVOL. XLVI.50 ABSTRACTS OF CHEMICAL PAPERS.in colourless needles melting a t 218", soluble in alkalis, sparinglysoluble in alcohol.The action of potassium cyanate on the diamines is the same for allthree isomerides ; a phenylenedicarbami de is formed.Orthophenylenedithiocarbamide, C6H4(NH.CSNH,),, crystallises inhard needles melting a t 290°, easily soluble in alcohol, sparin8ly inwater, chloroform, or ether. The para-compound crystallises in silveryleaflets and decomposes completely at a high temperature withoutmelting ; khe ?,zeta-compound crystallises in small colourless needlesmelting at 280", soluble in eoncentrated hydrochloric acid, but repre-cipitated on the addition of alkalis,By the action of thzocarbarnides on the dianzines complex thiocarba-mid& of the generic formula C,H,(NH.CSNH.C,H,),, are produced,which in the case of the ortho- and para-compounds are decomposed,when melted, according t o the equation C,H,(NH.CSNH.C,H,), =C,Hy<:E>CS + CS(NH.C,H,),, while the meta-compound is un-changed,Dipheny ZnaetaparatoZy Zenedithiocarbaniide, C,H,Me (NH.CSN HPh), ,from tolylendiamine and phenylthiocarbamide, is a crystalline sub-stance which when heated to 140-150", is decomposed into diphenyl-thiocarbamide subliming in the upper part of the vessel, and rneta-parajtolylenethiocarbamide.Diethyln~ta~al-at~ly~enedith iocarbamide, C6H,Me (NH.CSNHE t)2,from ethylthioearbamide and tolylenediamine forms microscopiccrystals which melt between 149" and 153", and on more protractedheating are decomposed into metaparatolylene- and ethyl-thiocarba-mides. The former is a crystalline substance melting at 284", spar-ingly soluble in water, easily soluble in alcohol and hot soda.DiaZZyZ-meta~aratolylenedithiocarba~~de, CGH,Me(NH.CSNH.C,H,),, fromtolylenediamine and allylthiocarhamide, crystallises in delicate silkyneedles, melting a t 150", sparingly soluble in water, soluble in alcoholand chloroform.The corresponding di~ll.grZmeta~he~~yZene~~tl~i~carbamide,CJI~(NH.CSNH.C,H,),forms an amorphous white powder, which melts at 105", and is notdecomposed when heated.Di~~enylpnraphenyleneclitkiocarbamide,C,H,(NH.CSNHPh),, is a crystalline substance, soluble in hof sodasolution. When heated to 260" it is decomposed partly into para-phenylenethiocarbamide, C~&<NH> NH cs, which crystallises in smallleaflets, melting a t 270".C6H4( NH. C SNH.C3H5;,is a crystalline substance, insoluble in water, sparingly soluble inalcohol. It melts a t 200", with evolution of a gas and emission of asmell resembling diallylthiocarbamide : its decomposition may probablybe expressed by the equation, C6HI(NH.CSNH.C,H5), =DiaZly Ipara~henyllllertei~~io~a~barnide,C6H4<ZE>CS + CS(NH.C,H,),ORGANIC CHEMISTRY, 51The author also made some experiments on the reduction of theorthonitranilides and tolnides of phenylsulphonic acid.When phenyl-sulphonyl chloride is added to orthonitraniline dissolved in benzene,crystals of orthonitraniline hydrochloride separate out. On filteringthese and evaporating the filtrate, phenylsulphorthonitranilide,PhS O,.NH. CGH4.N02,is obtained, This substance is crystalline, moderately soluble inpetroleum, easily soluble in alcohol ; it is reduced by tin and hydro-chloric acid to the corresponding amidoanilide, PhS0,.NH.CfiH4.NH2.This compound crystallises in long colourless needles melting a t168", sparingly soluble in water, readily soluble in alcohol and chloro-form ; its hydrochloride forms large thick crystals.Phenylszilpho-1)2etunitroparntnluide, PhS02.NH.CfiH,Me.N02, obtained together withthe corresponding dinitro-derivative by the action of fuming nitricacid on phenylsulphoparatolnide, crystallises in cubes, which melt a t99". On reduction with tin and hydrochloric acid, it is convertedinto the corresponding arnido-derivative, which crystallises in long,coloui-less needles, melting a t 146*5", sparingly soiiible in water, solublein alcohol.I n a summary, the author remarks that the above observations donot form sufficient material for general conclusions with regard to thereactions of the diamines. To complete the study of these compounds,i t is necessary to compare the decomposition of the isomeric phenylene-diamines with the diamines of the paraffin series.As a step in thisdirection, Hof mann has observed that ethylenediaminethiocyanatewhen melted yields ethylenethiocarbarnide, a decomposition perfectlyanalogous to the decomposition of the corresponding orthodipheriylenecompound. V. H. V.Organic Hydroxylamine Derivatives. By C. SCHRAMM (Ber.,16, 2183--2188).-When a solution of bromacetophenone in aqueousalcohol is heated with an excess of hydroxylamine hydrochloride for12 hours on a water-bath, the alcohol evaporated, and the productextracted with ether, a yellowish oil is obtained which solidifies onstanding. It can be purified by precipitating its solution in soda withdilute sulphnric acid and extracting with ether ; i t then melts a t 162-163".I t s formula is CPh(N.OH).CH,.NH.OH. It dissolvesreadily in alcohol or ether, sparingly in hot water and benzene, and isinsoluble in light petroleum and in cold water. On heating it withconcentrated acids, hydroxylamine is given off. A silver derivatire,C8H,AgN,0,, is obtained by precipitating a solution in concentratedammonia with a concentrated solution of silver nitrate. Dibenzyl-hydroaylamine, (CH2Phj,N.0H, is obtained on heating a solution ofbenzyl chloride (3 grams), hydroxylamine hydrochloride ( 3 grams),and cq-stallised sodium carbonate (6 grams) in aqueous alcohol for halfan hour on a water-bath. On cooling, it separates in long white needleswhich melt a t 1-23', and are decomposed by dist,illation. It is solublein alcohol, ether, and benzene, less soluble in light petroleum, carbonbisulphide, and glacial acetic acid, sparingly in hot water, and insolublein ammonia, soda solution, and hydrochloric acid.A hydrochloride,s 52 ABSTRACTS OF CHEMICAL PAPERS.(C,H,),N.OH,HCl, can be obtained by the action of dry hydrochloricacid gas on its solution in absolute ether.2l/lethyZpropylglyoxh e, CMe (NOH) .C( NOH)Pr, obtained by theaction of hydroxylamine hydrochloride on a, solution of isonitrosopro-pylacetone in aqueous alcohol, forms spiral-like groups of needlesmelting a t 168". Phenylqlyozime, CPh(N.OH).CH : N.OH (m. p.152") is prepared by the action of alkaline hydroxylamine solution ondibromacetophenone, at a gentle heat, acidifying and extracting withether.It can be purified by precipitating the ethereal solutionwith light petroleurn and washing the precipitate with benzene,or by dissolving it in alkali, acidifying and extracting with ether. Thesilver derivative, C8H7AgN202, forms a yellowish-white curdy precipi-tate. On dissolving sodium in absolute alcohol and adding an etherealsoluhion of methylethylglyoxime, the sodium deyivative of the latter,C5HgNaN2O2, is thrown down as a white curdy precipitate. The di-acetyl-derivative of methylglyoxime, CMe(NO&).CH(NOG) is formedwhen a mixture of methylglyoxime with a slight excess of acetic anhy-dride is geiitly boiled until the mass begins to turn brown. The pro-duct is poured into shallow clock-glasses and exposed in a vacuumwhen needles are obtained melting at 51".It crystallises from lightpetroleum in white transparent prisms ; when heated, these explodewith evolution of hydrocyanic acid.The d iacety 1-derivatize of methy lethylg ly yoxims,CMe(NO&?).CEt(NOZ),crpstallises in flat prisms readily soluble in alcohol and in ether,sparingly in hot water. The diacet~jl-derivative of methylbenzyl-glyoxirne forms small white crystals melting a t 80".Hydrazines of Pyroracemic Acid. By E. PISCHER and F. JOUR-DAN ( B e y . , 16, 2241-2245).-Some of the compounds of the hydra-zines with ketones have been described by Reisenegger (Abstr., 1883,798). The reaction is a general one, and holds for the primary andsecondary hpdrazines of the fatty and aromatic series, and f o r allsimple and most of the more complicated ketones and diketones, theketonic acids combining with extreme readiness with the hydrazineseither in neutral or in acid solutions.Pyroracemic acid and phenyl-hydrazine combine with great violence, so that it is advisable to diluteeach substance with five volumes of ether, to cool well and to mixg radu a1 1 y .The phenylhydrazinepyroracernic acid, CSHI0N2O2, separaies as ayellowish crystalline powder which arter being washed with ether andcrystallised from boiling alcohol, forms hard lustrous needles, melt-ing at 169" with evolution of gas ; it is readily soluble in hot alcohol,very sparingly in ether, chloroform, carbon bisulphide, and lightpetroleum, readily in alkalis and alkaline carbonates. The sodiumsalt is sparingly soluble in an excess of concentrated soda solution,with which it can be boiled without decomposition.The formation ofphenylhydrazinepyroracemic acid takes place also in aqueous, aceticacid, and dilute hydrochloric acid solutions, aiid with such readinessthat the reaction can be employed for the detection of pyi*oracemicA. I(. MORGANIC CHEMlSTRY. 53acid (also of phenylglyoxylic acid and levulic acid) in very dilutesolutions. Heated above its melting point, it yields carbonic anhy-dride and ethylidenephenylhydrazine :-PhNzH : CMe.COOH = GO, +l'hNzH : CHMe. It can be boiled with dilute hydrochloric and sul-phuric acids without decomposition, and on boiling with alcoholicsulphuric acid, the ethyZ derivative, PhN,H : CMe.COOEt, is obtainedmelting a t 114-115", and soluble in alcohol, ether, and chloroform.By the action of sodium-amalgam on a cold dilute solution of phenyl-hydrazinepyroracemic acid, pheny1hydrazineprop.ionic acid,PhNzH,.CMeH. COOH,is produced, crystallking from boiling alcohol in white slender needlesmelting a t 152-1.53' with decomposition. It is very sparingly solublein cold alcohol, ether, and water, much more readily iu hot alcohol,also readily soluble in alkalis and in concentrated hydrochloric acid.Mercuric oxide and copper salts are readily reduced by it in alkalinesolution, ammoniacal copper solution reconverting it into phenyl-hydrazinepyroracemic acid.I n order to decide which of the formulae PhNH.N : CMe.COOH orPhN-CMe.COOH is correct, the action of pyroracemic acid onmethylphenylbydrazine was studied.This yields an acid of theformula PhNMe.N: CMe.COOH, the behaviour of which to mineralacids is, however, quite different from that of the acid obtained fromphenyl hydrazine.Metl~ylplaenylhyd~~axinepyro9-ac~mir, acid softens at 70": and melts a t78" ; i t crystallises in yellowish needles readily soluble in alcohol andin ether, sparingly in light petroleum and in water ; it is decomposedby long-continued boiling with water, but is stable in alkaline s o h -t,ions. On warming it with a 10 per cent. solution of hydrochloricacid it becomes red, and then dissolves, the coloiir disappearing as thetemperature is raised, whilst colourless slender needles separate, in-creasiug in quantity on cooling and as the liquid is diluted with water.This new substance, apparently of the formula C,JI,NOz, seems to beformed by the abstraction of ammonia from the methylphenylhydra-zinepyroracemic acid, a considerable quantity of ammonia being foundin the acid liquid.T t is readily soluble in hot alcohol, from which i tcrystallises in colourless needles melting at 206". It can be distilledunchanged, dissolves readily in soda, ammonia, and sodium carbonate,and can be reprecipitated by acids.By E. FISCHER (Ber., 16, 2236-2238) .-In pre-paring diacetonamine from acetone containing aldehyde, Heintz(Annalen, 189, 214) obtained a base CeH,,NO, (vinyldiacetonamine) ;this he afterwards obtained by the action of acetaldehyde on diace-tonnmine oxalate, and he thought it probable that it might be a lowerhomologue of triacetonamine ; this is now confirmed by the author.It is converted into an alkamine by the action of sodium-amalgam,and on heating this with concentrated sulphuric acid, a readily volatilebase is obtained, the properties of which show it to be a homologue oftriacetonine (Abstr., 1883,1155).\/NHA.I(. B!.Diacetonamine54 ABSTRACTS OF CHEMICAL PAPERS.Other aldehydes, both of the fatty and aromatic series, yield baseswith diacetonamine, and in this way numerous homologues of hydroxy-piperidine and piperidine can be obtained. Benzdiacefonarnine,C13H17N0, is prepared by boiling a solution of acid diacetonamineoxalate (1 part) in alcohol (3 parts) with bitter almond oil (1 part)for about ten hours; the product is filtered hot, and the oxalateformed is washed with hot alcohol.By the action of potash the freebase is obtained as an oil, which solidifies on standing ; it crystallisesfrom hot light petroleum in splendid colourless plates, melts a t 62-63", dissolves very readily in alcohol and in ether, sparingly in water ;the o x a l d e (Cl,H,7NO),C,H,04, forms white scales, very sparinglysoluble in alcohol and in water, readily in hydrochloric and oxslicacids. On adding gold chloride t o the hydrochloric acid solution, theaurochloride is precipitated as a yellow oil, which solidifies to mag-nificent gold-coloured needles. By the action of sodium-amalgam onan acidulated solution of benzdiacetonamine, the latter is partially con-ver ted into benzdiacetona Zkamine, C 13H19N0.The hydrochloride,C1,H,,NO,HC1, forms small hard crystals, readily soluble in water,sparingly in alcohol. On decomposing it with an alkali, the base isprecipitated as a thick colourless oil, Sulphuric acid acts on this baseor the hydrochloride in the same way as on triacetonalkamine, withformation of a new base, which is volatile in steam, has an odourresembling that of piperidine, and yields a sparingly soluble hydro-bromide.From these reactions, it is assumed that benzdiacetonamine has aconstitution similar to that of triacetonamine, its formation beingthus expressed :-H,C.CO.CH, H,C . CO . CH,PhCHO + I = l I + H,O.H2N.CMe2 PhCH.NH.CMe,The author intends to try the reaction with other aldehydes, withAction of Phosphorus Trisulphide on Phenols.By A.GEUTHER ( A n n a l e n , 221, 55- 59).-Kekul6 and Szuch ( J a h e s b e r . ,1868,628) have isolated from the products of the reaction of phosphoruspentasulphide on phenol, besides phenyl mermptm and sulphide,a small quantity of benzene. As the formation of this hydrocarboncan only arise from the reduction of the phenol, it is probable thatthe samples of pentasulphide contained some trisulphide as an impu-rity. In order to confirm this suggestion, the author has studied theaction of phosphorus trisulphide on phenol. On submitting the crudeproduct of the reaction to fractional distillation, it was separated intotwo portions, the one boiling below loo", the other above 280".The former was principally benzene, together with traces of phenylmercaptan and sulphide, the latter triphenylphosphate.The reactionsof phosphorus trisulphide and pentasulphide on phenol may probablybe expressed by the following equations :-(1) 8PhOH + P,S, =2Ph3PO, + SH,S + 2C6H6, and (2) 8PhOH + P,S5 = 2Ph,P04 +3H2S + 2PhSH.ethyl acetoacetate, and with pyroracemic and other ketonic acids.A. K. MORGANIC CHEMISTRY. 55As an analogous case, it is shown that, creeol is similarly reduced totoluene by phosphorus trisulphide ; the other products of the reaction,.which were not minutely examined by the author, are probably tolylmercaptan and tolylphosphate. V. H. V.A Fourth Monobromophenol. By A. FITTICA ( J .pr. Chenz. [a], 28, 176--188).-10 grams of phenol are dissolved in 10 gramsabsolute alcohol, 3 grams of amorphous phosphorus added, and17 grams of bromine allowed to flow in through a capillary tube ; thevessel is surrounded with cold water ; the temperature of the mixturemust not rise above 20". The product is shaken with water, withdilute sodium carbonate, again with water, dried and aistilled. Thefraction 235-240" repeatedly redistilled, finally yields the newmonobromophenol as a liquid boiling at 236-238", and not soli-difying a t 10-12". The pure substance cannot be distilled withoutdecomposition. No further description of its properties is given.The boiling and melting points of ortho-, meta-, and para-bromophenolare-Ortho. Meta.Para.Melting point . . . . (Liquid) 32-33' 64"Boiling point.. . . . . 194-195" 236-236.5 238By nitration in glacial acetic acid solution, a crystalline compoundmelting a t 60-65", and of the formulaC6H3Br ( N02).0H, CsH,Br (NO,) ,OH,is obtained. This on further nitration yields a bromdinitrophenol,C,H,Br(NO,),.OH, crystallisiiig in yellow prisms, and melting a t108-110". The same product is obtained on boiling with baryta-water, together with a substance melting at 68-70', and crystal-lising in stellate groups of yel1o.w needles, to which the authorassigns the formula 2C6H3Br(NOz) .0J3,C6H,Br(N02)z.0H.A. J. G.Action of Phenol on Ketonic Acids. By C. BOTTINGER (Ber.,16, 2071-2075).--Uy the action of phenol on pjroracemic acid in pre-sence of sulphuric acid, a condensation-product of the compositionC15H140a,H,0 is obtained.This substance, which the author proposesto name diphenylyropionic acid, forms a horny mass (m. p- 268"),soluble in acetone, insoluble in water, benzene, and chloroform. It, isa monobasic acid, and a soluLion of its ammonium salt gives precipibakswith salts of barium, calcium, lead, and silver.Dibroi,zopheno~ropionic acid is a pale golden amorphous and eIectricpowder, insoluble in water and alcohol ; on heating this with concen-trated hydrochloric acid at 230" in a sealed tube, it gives off bromineand carbonic anhydride, and is converted into a black substance.AcetyZdi23hennpro~ionir, acid is an amorphous yellowish substance,soluble in acetone, insoluble in chloroform ; its barium salt forms aninsoluble amorphous precipitate36 ABSTRACTS OF CHEMICAL PAPERS.Acetylclibromophenopropioizic acid is colonred a t first violet, and thendissolved by ammonia; it forms sparingly soluble barium salt.V.H. V.Derivatives of Thymol. By H. KOBEK (Ber., 16, 2096-2105).-Pnrathyrnotk aldehyde, C6H2MePP( OH).CHO (Me : OH : Pr : CHO= 1 : 3 : 4 : 6) obtained by heating thymol with chloroform andsoda, crystallises in long white glistening needles melting a t 133",sparingly soluble in water, soluble in alcohol and ether. It dissolvesin ammonia and sodium carbonate to form a golden-coloured solution.The author was unable to obtain a crystalline compound of the sub-stance with sodium hydrogen sulphite ; but its other general propertiescharacterise i t as an aldehyde.C6H,MePra( OH) .CHNPh,prepared by heating parathymotic aldehyde and aniline in molecularproportions, crystallises in golden needles melting at 142", insolublein water, soluble in alcohol and ether; i t is decomposed by boilingwitb water or dilute acids into the aldehyde and aniline.Pa7-athymotic alcohol, CGK2MePra( OH).CH,.OH, obtained by thereduction of the aldehyle with sodium-amalgam and water, forms agreyish amorphous powder, which melts gradually a t 120-130" ; itis insoluble in water, soluble in alcohol and ether.2IethyQ??arathymotic aldehyde, C6H,MePrcL( OMe) .CHO, preparedfrom parathymotic aldehyde, methyl iodide, and alcohol, is a goldenoil boiling a t 270", insoluble in water, soluble in alcohol and ether;it dissolves with difficulty in a solution of sodium hydrogen sulphite.Its anilide crjstallises in clear transparent tablets (m. p.SO"), inso-luble in water, r e a d i l ~ soluble in other menstrua. On oxidation withpotassium permanganate, it is converted into the correspondingcarbozyZic acid, c6H2MePr( OMe).COOH, which crystallises in longwhite silky needles melting at 137" ; a solution of this acid gives nocoloration with ferric chloride, and precipitates more or less sparinglysoluble, with salts of calcium, silver, copper, zinc, and lead.In order to determine the constitution of the compounds, and tocompare the parathymotic acid corresponding with the above-men-tioned aldehjde with the thymotic acid described by Kolbe andLautemann (AimaZem, 115, 205), the author prepared both acids, andstudied tlieir reactions.The former can be best obtained by heatingthymol with carbon tetrachloride and soda ; it crystallises in leafletsmelting a t 157" ; the latter by the joint action of sodium and carbonicanhydride on thymol melts at 123" and gives a deep blue colorationwith ferric chloride. This reaction, characteristic of those aromaticacids in which the hydroxyl is in the ortho-position to the carboxylgroup, taken in connection with the method of preparation, showsthat the tbjmotic acid of Kolbe and Lautemann is the ortho-acid,possessing the constituiionC6H,MePP(OH),COOH [Me : COOH : OH: Pro! = 1 : 2 : 3 : 41.On the other hand, the method of preparation of the author's acid,I t s anilids derivativeORGANIC CHEMlSTRY.57together with the absence of any reaction with ferric chloride, pointprobably t o its constitution as expressible by the formulaC,H,MePr(OH).COOH [Me: OH: Pr : COOK = 1 : 3: 4: 61.Thymodiuldehyde, C6H,MePr( OH) (CHO),, obtained in the course ofthe preparation of paratbymotic aldehyde, forms golden compactneedles melting at 80"; it gives a cherry-red coloration with ferricchloride; on boiling with sodium acetate and acetic anhvdride it isconverted into tl/,ymoparacryZic acid, C$H,MePr(OH) .CH : CH.COOH,which forms microscopic crystals melting a t 280'. The methyl deri-vative of the latter crystallises in golden needles melting at 141",sparingly soluble in water, soluble in alcohol and ether.Both acids givesparingly soluble calcium, barium, and copper salts ; their silver salts,however, differ, that of the former crystallises from water, that of thelatter dissolves in hot water, forming a resinous mass.V. H. V.A New Glycerol. By A. COLSON (Conyt. re%& 97, 177-179).-The aromaiic tribromhydrin, C,H,( CH,Br),, previously de-scribed (Abstr., 1883, 734), can be ohtained in crystals by pro-longed refrigeration, and the crystals, after recrystallisation fromalcohol, melt at 94.3". The tribromhydrin is decomposed by water,yielding mesitylene glycerol, C,H,( CH,OH),. To obtain t h i s com-pound, the crude product of the action of bromine on mesitylene isboiled for several hours with 25-30 parts of water and an excess oflead carbonate, the liquid filtered, and concentrated by evaporationin a vacuum.The crude product is mixed with a small quantity ofsilver oxide, then treated with hydrogen sulpbide in order to removelead, and the solution filtered and concentrated. The viscous liquidthus obtained is purified by successive treatment with ether, alcohol,and chloroform, and is finally concentrated in a vacuum. Mesityleneglycerol is a viscous liquid with a bitter taste ; if is insoluble in etherand in chloroform,, but is very soluble in alcohol and in water. Whentreated with hgdrobromic acid, it yields the original tribromhydvin.Hydrochloric acid forms a colourless oily liquid, which is in all pro-bability the triclilorliydrin : the same compound is obtained by theaction of chlorine on the vapoor of mesitylene ; it boils a t 170-180"i u a vacuum, and s t 277-284" with partial decomposition, underatmospheric pressure.It is decomposed by water with formation ofthe glycerol. acetic acid also combines with mesitylene gljcerol,forming a compound which is only slightly soluble in water.If the product of the saponification of the crude tribromhydrin istreated with ordinary ether after evaporation of the water, the etherdissolves a substance which separates o u t in crystals on evaporation.When purified by repeated crystallisation from water, this sub-stance forms nacreous plates which melt a t 126". They are tastelessand inodorous, soluble in 55 parts of boiling water, but only slightlysoluble in cold water, still less soluble in ether, but very soliible inalcohol.They have the composition, CgHg(OH),Br ; when boiled withwater and potassium carbonate, this compound is not decomposed ;and when treated with hydrobromic acid it yields a tribromide which,after recrystallisation from alcohol, melts a t 81-82". The compoun53 ABSTRACT8 OF CHEMICAL PAPERS.is therefore not a derivative of mesitylene glycerol, but is a mono-bromo-glycol, C6H2BrMe( CH,.OH), and its dibromohydrin,C,H,BrMe( CH2Br),,(m. p. 81-82'), is isomeric with mesitylene glycerol tribromhydrin.C. H. B.Quinone Derivatives. By R. WIETSKI (Bey., 16, 2092-2096) .-The author has &own that by passing nitrous acid into an etherealsolution of quinol, a dinitrohydroxyquinone, C,(OH),(NO,),O,, ornitranilic acid, is formed ; the same substance may also be obtainedeither by the action of fuming nitric acid on dinitroquinol, or by thenitration of diacetylquinol : all these methods of preparation, how-ever, are very unsatisfactory.In the present communication a detailedaccount is given of an improved process, which consists in acting ondiacetylquinol with nitrosnlphuric acid in the cold, and precipitatingthe characteristic sparingly soluble potassium nitranilate from an ice-cold solution of the crude product. The corresponding acid, which isvery unstable, may be obtained from this derivative. The potassium-derivative is converted by a, strongly acid solution of stannous chlorideinto nitramidotetrhydroxybenzene, C,(OH),( NH,) .NOa, which crystal-lises in needles, having a violet iridescence, insoluble in alcohol,ether, and benzene.Potassium nitranilate is further converted bystannous chloride, with an excess of kin, into a substance crystallisingin delicate iridescent green leaflets, resembling quinhydrol in appeal.-ance. This compound is probably a diimido-derivative of dihjdroxy-,NHquinone, C6(OH),0r/ 1 , and analogous to diimidonaphthol: a"I3view which receives some support from the similarity of phenomenaobservable in the preparation of these two substances,Action of Orthonitrobenzaldehyde on Acetaldehyde. BgA. BAEYER and V. DREWSEN (BRT., 16, 2205-2208).-1n a previouscommunication (Abstr., 1883, 341) the authors mentioned the forma-tion of a condensation-product by the action of alkalis on a solutionof orthonitrobenzaldehyde in acetaldehyde.It is prepared bygradually adding a 2 per ccnt. solmtion of sodium hydroxide to asolution of orthonitrobenzaldehyde in freshly prepared aldehyde keptcool with ice, until an alkaline reaction remains for a t least fiveminutes. The acetaldehyde is expelled by a current of air, thecrystalline product dried on a porous tile and crystallised from ether.It forms moderately large colourless monoclinic prisms, readily solublein alcohol and chloroform ; it softens a t 120" and melts at 125" withevolution of aldehyde vapour. Its formula, C9H9N01, C2H40, corre-sponds with that of a compound of orthonitrophenyllactic aldehydewith aldehyde.On passing a current of air through its solntion at4C-50", as long as the odour of aldehyde is perceptible, a non-crystallisable product ifi obtained (probably orthonitrophenyZZacticaldehyde), combining with acid sulphites and reddening rosanilinesulphite. Like the condensation-product, it yields indigo withaqueous alkalis. Orthonitro-~-~hen.yllactic acid,V. H. V.NO,.CGH,.CH( OH).CH,.COOHOltUANIC CHEMISTRY. 59(m. p. 126') is obtained on warnling a solution of the condensation-product in dilute alcohol with an excess of freshly precipitated silveroxide, until the addition of alkali no longer produces indigo ; the pro-duct is boiled with hydrochloric acid, filtered, and extracted withether, and the acid purified by means of the barium salt,.It crystal-lises in short well-formed prisms, readily soluble in water, alcohol,and ether, and is identica1 with the acid obtained by Einhorn from theaddition-product of orth onitrocinnamic acid with hy drobr omi c acid(see p. 66). Orthoizitrocinnamic aldehyde, N 0,.C,H4.CH : CH.CHO,is obtained on boiling the condensatiowproduct with acetic anhydrideuntil indigo ceases to be formed by the addition of soda solution. Itforms colourless needles melting at 127", readily soluble in boilingwater, very sparingly in cold water, readily in chloroform, less so inalcohol and ether. It forms a crystalline compound with hydrogen-sodium sulphite, reacts with rosaniliiie snlphite, reduces ammoniacalsilver solution with formation of orthonitwcinnamic acid, and on reduc-tion readily yields quinoline.From the above, it is seen that the con-densation of orthonitrobenzaldehyde with aldehyde takes place in thesame way as with acetone, the resulting ortl10nitro-/3-phenyllacticaldehyde, N02.Cs&.CH(OH).CH,.COH, forming, however, an un-stable compound with acetaldehyde.Benzoylacetone. By E. FTSCHER and H. KUZEL (Ber., 16, 2239-2241).--On boiling ethyl benzoylacetomcetate with 4 parts of 25 percent. sulphnric acid, carbonic anhydride, alcohol, acetic acid, andacetophenone are produced as stated by Bonn6 ( A n n u l e n , 187, 1).The authors find that a small quantity of benzoic acid and about4 per cent. of berhzoylucetone are also produced, the formation of thelatter corresponding with the production of nitrocinnamylacetonefrom ethyl nitrocinnamylacetoacetate (Abstr., 1883, 587).To isolatethe benzoylacetone, the oil is dissolved in ether, agitated with dilutesoda solution, which dissolves the benzoic acid and the benzoglacetone;the solution is then acidified, extracted with ether, and the residuefrom the evaporation of the latter dissolved in cold dilute sodasolution, from which the benzoylacetone is precipitated by carbonicanhydride as a colourless oil, which crystallises on cooling. It maybe obtained in larger quantity by boiling ethyl benzoylacetoacetatefor some hours with 7-8 parts water.A. E. M.Benzoylacetone,CH& . C 0.CH3,melts at 58", distils unchanged, is voIatiIe in steam, and has an agree-able penetrating odour.It dissolves sparingly in cold water, morereadily in hot water, very readily in alcohol and in ether. The alkalisdissolve it readily, sodic cnrbonate less so, whilst it is insoluble in theacid carbonates. The sodium salt of benzoylacetone is precipitated inthe form of Fellowish scales on adding concentrated alkali t o its solu-tion in dilute soda ; the silver salt, CIOHS02Ag, obtained on adding anexcess of silver nitrate to an ammoiiacal solution of benzoylacetone,forms a white crystalline precipitate, almost insoluble in water.Benzoylacetone gives an intense red coloration with ferric chloride.It is decomposed by boiling alkali with formation of acetophenoneGO ABSTRACTS OF CHEMICAL PAPERS.When warmed with phenylhydrazine, the two combine forming aslightly coloured oily product insoluble in alkali.Orthonitrobenxoylacetone is obtained in the same way from ethylorthonitrobenzoylacetoacetate, and likewise combines with phenyl-hydrazine, forming a compound of the formula-NO,.C,H,. C .CH2.CMeII IIPhNZH, N,H,PhThe hehaviour of benzoylacetone with alkalis shows that the hydrogenof the methylene-group can be substituted by metals, which is notthe case with the hydrazine-derivatives in which the oxygen of theCO-groups is replaced by nitrogen.Anthroxanaldehyde and Anthroxanic Acid. By A. SCHIL-LINGER and S. WLEGGEL (Ber., 16, 2322--2236).-When a solution oforthonitrophenyl hydroxyacrylic acid in an equal weight of glacialacetic acid is heated on a water-bath as long as carbonic anhydride isevolved, and then diluted with water, neutralised with chalk, andsteam-distilled, A distillate is obtained from which ether extractsunthroxnnaldehyde mixed with anthranil ; the latter is removed byboiling with light petroleum, from which solvent anthroxanaldehydeorystaliises in long yellowish needles of a slightly aromatic andpenetrating odour ; it dissolves readily in boiling water, and volatiliseseasily in steam.It melts at 72.5", and can be sublimed withoutdecomposition. Its formula, C8H5N02, shows it to be isomeric withisatin. An intense reddish-violet coloration is produced on addingzinc-dust to its solution in very dilute ammonia and warming. Whenan aqueous solution, containing also anthranil, is boiled with ferroussulphate, slender red silky ueedles separate, which, after crystallisationfrom chloroform, contain no iron; this substance melts above 21.5"with decomposition ; it has basic properties.Anthroxanaldehyde dis-solves readily in concentrated hydrogen-sodium sulphite, and pro-duce a red coloration with rosaniline sulphite. When it is warmedwith aniline, an oil is obtained which solidifies t o large fan-shaped crystals, melting a t about 40". Anthrozaaic acid, CeH5NOs, isprepared by adding tbe calculated quanbhy of a 4 per cent. perman-ganate solution to a cold solution of the aldehyde in very dilute soda,filtering and slightly acidifying. The solution is warmed with animalcharcoal, filtered, and dilute sulphuric acid added, when anthroxanicm i d separates in delicate white needles.It is moderately soluble inhot water, almost insoluble in cold water, readily in acetone, moresparingly in glacial acetic acid, and still less readily in benzene andother solvents. It melts a t 190-191" with decomposition. Onwarming its solution in dilute ammonia with ferrous sulphate, filter-ing and acidulating, isatin is obtained.A. I(. M.C .COOHThe authors assign to this acid the constitution C H ' I ' 04\N/ 3,CO.C.COOHanalogous to isstogenic acid, CsH1' / I , which it resembles"-ORGANIC CHEMlSTRY. 61in its behaviour to feeble reducing agents. Unsuccessful attemptswere made to decompose it into carbonic anhydride and anthroxane,C8H/ I ' 0 , which, if capable of existing, would be isomeric witha.nbhrani1.Possibly anthrosane becomes converted into the latter inthe same way as isatogen into isatin.CH\&/A. K. 51.Constitution of Anthranil. By P. FRIEDLANDER and S. WLE~~GEL(Ber., 16, 2227-2229) .-From the close relationship of anthranil toanthroxanic acid (see last Abstract) an attempt was made to preparethe latter by heating anthranil with ethyl chlorocarbonate at 120-140". Of the three possible formulae for anthranil-co ,C.OHC6H4 11 9 'NcIjH4( IN NH'the first alone could yield anthroxnnic acid, the second an isomericanthra,nilcarboxylic acid, whilst the third could not yield a carboxylicacid.The product of the reaction was an acid (anthranilcarboxylic acid)isomeric with anthroxanic acid, but possessing different properties.It dissolves sparingly in the usual solvents, most readily in acetoneand in ether, and crystallises from hot water in slender needles melt-ing a t about 230" with evolution of carbonic anhydride, but anthranilis not re-formed.The presence of a carboxyl-group is proved by itssolubility in dilute ammonia and in a,lkaline carbonates, mineral acidsreprecipitating it unchanged. It dissolves in a one per cent. soda solu-tion, showing a blue fluorescence which soon disappears, and on thenacidifying with acetic acid and extracting with ether, the equivalentquantity of anthranilic acid is obtained. This change probably takesplace thus :--.coC6H4' -1 + HZO = COOH.CsH4.NH.COOH\N.COOHAnthranilcarboxylic acid is decomposed by hot concentrated sodasolutlion, with formation of anthranilic acid and of a high-melting acid,probably a derivative o€ diphenylcarbamide.On gently heating a mixture of dry anthranil with benzoic chloride,an abundant evolution of hydrochloric acid takes place, whilst benzoyl-alzthaanil, C6H4' I , is formed.The product crystallises oncooling, a,nd can be purified by recrjstallisation from dry benzenewith the addition of light petroleum. It forms long white needlesreadily soluble in the ordinary solvents, insoluble in water and lightpetroleum ; it melts at 122-123", and distils above 360" nea,rly un-changed. Like anthranil, it readily takes up the elements of waterCO'N.COP62 ABSTRACTS OF CHEMICAL PAPERS.with formation of bemoylanthranilic acid, COOH.C6H1.NH.COPh ;the change being effected by solution in hot dilute alkalis or by crys-tallisation from dilute alcohol, when the melting point is raised from123" to 180-181".The benzoylanthranilic acid obtained is identicalwith the acid obtained from nrithranilic acid and benzoic chloride(AnnuZen, 205, 130). It yields sparingly soluble barium aud calciumsalts, and a nearly insoluble stable silver salt, C,,H,,NO,Ag.These results prove that anthranil is represented by the second ofthe above formulae, and that it is the lactam of anthranilic acid.A. K. M.Action of Hydroxylamine on Diketones. By H. GOLDSCHMIDT(Bey., 16,2176-2180).-The author and V. Meyer have isolated anddescribed a diphenylglyoxime (m. p. 237"), C14H12N202, obtained bythe action of hydroxylamine on benzil.Under other conditions, theauthor has obtained an isomeride which in contradistinction to thefirst named substance may be called P-diphenylglyoxime ; it differsfrom its isomeride in its melting point (2OC;"), its appearance, and itsgiaeater solubi1it.y in water arid alcohol. The a-glyoxime may be con-verted into the @-isomeride by heating to 180".On heating phenanthraqui none with alcohol and hydroxylaminehydrochloride, a monisonitroso - derivative of phensnthraquinone,Cla &NO2, is formed.This substance crystallises in small golden needles melting a t 158O,soluble in alcohol; it dissolves i n soda to form a green, and in sul-phuric acid to form a red solution. It is converted by hydroxylaminehydrochloride into a dioximide derivative of phenanthraquinone, ofC6H4.C : N,possible constitution, I 1 )0, which crystallises in goldenC6Hd.C Nneedles melting a t 181", insoluble in soda.When anthraquinone isheated with alcohol and hydroxylamine hydrochloride, in a flask fittedwith an inverted condenser, no reaction takes place.I n order to obtain the monisonitroso-derivatire of anthraquinone,it is necessary to heat the reacting substances in a sealed tubeat 180",when the compound separates out as a pale red powder, soluble inalcohol, to form a red solution. I t sublinies a t 2OO", volatilising com-pletely, without melting. Its constitution may be expressed by theformula, c6H,<~~~H>C6H~. V. El. V.Derivatives of Benzil. By B. S. BURTON (Ber., 16, 2232-2233).-With the view to obtain diphmyltartaric acid, the author has madeexperiments on the saponification of Zinin's nitril of diphenyltart aricacid, CI,H,,O2(CHN),, obtained by the action of anhydrous hydro-cjanic acid on an alcoholic solution of benzil (Annnleiz, 34, 189).Thefinely powdered nitrile is introduced into a large excess of glacialacetic acid saturated a t 0" with hydrobromic acid, and frequentlyagitated. After some weeks, the unaltered substance is separated, andthe clear liquid yields monoclinic crystals of a vitreous lustre. Onadding ammonium carbonate to the filtrate, a white precipitate,CONH,.CPh(OH) .CPh(OH.).CONHZ, is produced, insoluble in colORGANIC CHEMlSTRY. 63water, but which can be crystallised from dilute alcohol ; it crystallisesfrom hot water in small needles.It softens gradually on heating,begins to darken at 150", becoming completely liquid a t 230". I t sbasic properties are very feeble, as it crystallises unchanged from hotconcentrated hydrochloric acid, although it yields a crystalline hydro-bromide. It has no acid properties, is not dissolved by sodium carbo-nate solution, but is soluble in soda solution with decomposition. Onboiling it with hydrochloric acid, acid substances are obtained stillcontaining nitrogen. The above mentioned monoclinic crystals con-sist of the hydrobromide of the amide ; this melts a t 185" with evolu-tion of hydrobromic acid. Sodium carbonate conrerts it into theamide. A. K. M.Benzoylacetic Acid.By A. BAEBER and W. H. PERKIN, Jun.(Rer., 16, 2128--2133).-One of the authors has recently shown thatethyl phenylpropiolate is converted by sulphuric acid into ethylbenzoylacet.ate, thus : PhC C.COOEt + H20 = COPh.CH,.COOEt(see Abstr., 1882, 336). The latter is a colourless oil resemblingethyl acetoacetate in odour ; when quickly heated, it distils with slightdecomposition between 268-270" ; it is coloured by ferric chloride.On boiling with water or acids, it is decomposed according to theequation, CH&.COOE% + H20 = PlaCOlle + CO, + EtOH. Inorder to prepare benzoylacetic acid, a solution of the alkyl salt insoda is left a t rest ; after filtration, the solution is cooled with iceand carefully acidified, and then exhausted with ether. The acidis obtained from the ethereal extract as a hardcrystalline mass, whichmelts a t 85-90" with evolution of earhonic anhydride ; it is solublein alcohol and ether, and its solution is coloured violet by ferricchloride.EfhyZbenzoyZacetic acid, CHEtE.COOH, is obtained as an ethylsalt by the joint action of sodium and ethyl iodide on ethyl benzoyl-acetate; on subsequent saponification of this salt, the pure acid isobtained. This latter melts a t 112-115", and is generally contami-Iliited by benzoic acid.On boiling the ethyl salt with alcoholic potash,like ethyl acetoacetate, it yields either a mixture of acids, or a ketone,according to the concentration of the alkali, thus :-(1.) CHEt(COPh).COOEt -+ 2KOH = PhCOOR + CHJWCOOK + EtOH, or(2.) CHEt(COPh).COOEt -+ 2KOH = COPh.CH,Et + EtOH + I(zc03.Diethy Zbenzoic acid, CEt&.COOH, obtained by a repetition of theprocess used for the acid above, forms a colourless, crystalline massmelting a t 128-130° ; when heated with alc-oholic potash, it yieldsdiethylacetophenone, boiling a t 230", thus :-CEtz(COPh).COOH + 2KOH = COPh.CHEt,, + &co3.AZZy Zbenxoylacetic acid, CHE(C,H,) .COOH, prepared by the actionof ally1 iodide on the ethyl salt of sodium benzoylacetic acid, isisomeric with benzoyltetramethylenecarboxylic acid from trimethy-lene bromide and ethyl henzoylacetate. The former exists 3s a colour64 ABSTRACTS OF CHEMICAL PAPERS.less crystalline mass melting at 122-125", soluble in all menstruaexcept water ; when its ethyl salt is heated with alcoholic potash, ityields allylacetophenone (b.p. 235O), thus :-CI-E(COPh) (C,H,).COOEt + 2KOH = COPh.CH,(C,H,) + K2CO3 + EtOH.Ethy7nitrosobenzoyZacetate, CO Ph.CNOH.COOEt;, formed by theaction of nitrous acid on ethyl benzoglacetate, crystallises in longneedles melting a t 121", which dissolve in alkalis to form a goldensolution. On long standing in contact with soda, it is converted intoan acid, COPh.CH (OH) .COOH, crystall ising in small prisms.Dibenzoylacetic acid, CHE,.COOB, obtained by the action of benzoicchloride on ethyl sodium beneoylacetate, and subsequent saponification,crystallises in needles melting at log", sparingly soluble in alcohol.This substance on protracted heating with water is converted intodibenzoylmethane with evoliitiou of carbonic anhydride, thus :-CHE2.COOH = CH&2 + ( 3 0 2 .This latter compound crystallises in large tables belonging to therhombic system, which melt a t 81" and boil a t 200".By the combinedaction of sodium and benzoic chloride it is converted into trihenzoylmethniie, CHI%,, which crystallises in small needles (m. p. 224O), andsublimes wiChout decomposition. V. H. V.Action of Ethylene Bromide on Ethyl Aceto- and Benzoyl-Acetates. By W. H. PERKIN, Jun. (Bey., 16, 2136--214O).-By thecombined action of ethylene bromide and sodium on ethyl acetoace-fate, the ethyl salt of acetyl trimethyleme carboxylic acid is formedaccording to the equations : I. CHGNa.COOEt + CH&r.CH,Rr =CHiG(C2H4Br).COOEt + NaBr ; and 11. C%Na(C2€€,Br).C0OEt =CH?1 )CZ.COOEt + NaBr.CH2This substance is a colourless oil boiling a t 193--1c35", aud yields thecorresponding acid as a thick oil on saponification and subsequentlyacidifying the alkali salt.The silver salt crystallises in characteristicwarty masses.CH2,Similarly, bemoyl trimethylene carboxylic acid, 1 CE.COOH,may be obtained ; it crystallises in the monoclinic system, and meltsa t 148" with evolution of carbonic anhydride. Its silver salt forms awhite flocculent precipitate, the ethyl saltl a colourless oil boiling at 280-28:Y'. Benzoyl trimethylene carboxylic acid when heated to 200"yields benzoyl trimethylene with evolution of carbonic anhydride,thug 1 \C%.COOH = I 'CHB; + GO,.CH2'CH, CH2/ CH,' CH,The author is engaged ill investigating homologues of the sub-stances above described. v.H. vORGANIC CHEMISTRY. 65Phenylhydroxyacetimidoether and Amidine. By C. BEYEE(J. pr. Chem. [2], 28, 190--191).-Benzaldehyde cyanhydrin is dis-solved in ether, 1 mol. proportion of alcohol added, and a stream ofdry hydrochloric acid passed into the liquid. The resulting hydro-chloride, CHPh(OH).C(OEt) : NH,HCl, crystallises in needles, melts at121", and on treatment with otash and ether, yields phenyZhydroxy-imidoether, CHPh( OH.) .C( 08t) : NH, crystallising in fine needlesand melting at 71-72". On strongly heating the hydrochloride, it isresolved into ethyl chloride and mandelamide ; on treatment withwater, it yields ethyZ mandelate, CHPh(OH).COOEt, as a heavycolourless liquid of faint jasmine-like odour, boiling at 253-255", andsolidifying to a crystalline mass in a freezing mixture.By the action of alcoholic ammonia on the imidoether hydrochloride,the corresponding p henylhydroxyamidine hydrochloride,CHPh(OH).C(NH,) NH,HCI,was obtained crystallised in fine prisms, melting a t 213-214".Thefree amidine could only be obtained in an impure state, and thenformed stellate groups of needles having a strongly alkaline reactionand melting a t 110". A. J. G.Derivatives of Orthonitrocinnamic Acid. By A. EINHORN( Ber., 16, 2208-2216). - Orthonitrophenyl-P-bromopropionic acid,N02.C6H4.CHBr.CH,,COOH, is prepared by heating orthonitrocinna-mic acid (10 grams) with a solution'of hydrobromic acid in glacialacetic acid (100 grams) saturated at 0".The mixture is heated in asealed tube for about half an hour on zt water-bath, and frequentlyshaken until the nitro-acid is dissolved. The product is purified byboiling i t with benzene and recrystallising from chloroform ; it formspale yellow monoclinic crystals melting at 139-140", with decompo-sition, I t dissolves readily in the ordinary solvents, but is onlysparingly soluble in benzene. It dissolves to a small extent in warmwater, decomposition however taking place with formation of indoxyl.Boiling concentrated sulphuric acid is almost without action on it,whilst alkalis very readily decompose it. On treating the powderedacid with an excess of cold sodium carbonate solution, a clear solutionis obtained, which soon assumes a bright red colour, whilst aprecipi-tate forms which the author assumes to be the lactone of orthonitro-phenyl-&lactic acid, N02.C6H4. CH<-ol> GO.The filtrate containssmall quantities of orthonitrocinnamic acid, orthonitrophenyl-p-lacticacid, and orthonitrostyrene. The lactone is readily soluble in chloro-form, acetone, benzene, and glacial acetic acid, sparingly in ether andin absolute alcohol, whilst alkalis convert it into the correspondinghydroxy-acid. It is converted into orthonitrostyrene and carbonicanhydride by boiling with water, some indoxyl, indigo, and probablyalso orthonitrophengl-P-lactic acid being simultaneously produced.Indigo is also formed when it is boiled with glacial acetic acid oracetic anhydride.By the action of zinc-dust and hydrochloric acidon a solution of the nitro-lactone in glacial acetic acid, hydrocarbo-CHVOL. XLVI. 66 ABSTRACTS OF CHEIIICAL PAPERS.styril is formed, and not the expected amido-lactone. When finelypowdered orthonitrophenyl-6-bromopropionic acid is added to a hotsolution of sodium carbonate and the product steam distilled, an oil isobtained solidifying in a freezing mixture to a white crystalline mass,which melts a t about 12-13.5." When orthonitrostyrene, CsH,N02,is heated with concentrated sulphuric acid, it assumes a blue colour.On adding a solution of bromine in chloroform to nitrostyrene alsodissolved in chloroform, the liquid being kept cool with ice, orthonitro-styrene dibrornide, N02.C6H4.CHBr.CH,Br, is obtained, melting a t 52"and volatile in steam.Besides nitrostyrene (10 per cent.), ortho-nitrocinnamic acid (16 per cent.), and orthonitrophenyl-p-lactic acid(42 per cent.), are formed in the above reaction, and the latter com-pound can also be obtained by warming the lactone with baryta-water. The purified acid, No2.C6H~.CH(OH).CHE-r,.COOH, is readilysoluble in alcohol and in water, crystallising from the latter in six-sided monoclinic prisms, melting at 126". When heated with dilutesulphuric acid a t 190", it yields orthonitrocinnamic acid ; with con-centrated sulphuric acid it yields indo'in. The methyl derivative meltsat 51"; the barium salt, (C,HsNO6),Ba + 2H20, crystallises inneedles. A direct comparison of this acid, with that obtained byBaeyer and Drewson (p.59), shows that the two are identical.A. I(. M.Substituted Coumarins. By H. v. PECHMANN and C. DUISBERG(Ber., 16, 2119- 2128).-The ethyl salts of aceto- and benzoyl-aceticacids react witlh the phenols in presence of a dehydrating agent toform substituted coumarina or hydroxycoumarins. T hns, for example,phenol and ethyl acetoacetate, in presence of strong sulphuric acid,yield methylcoumarin, thus :C,H,.OH + MeCO.CH,.COOEt = C6H4< CMe:CH>CO 0 + H,O+ EtOH.In this communicat'ion a description is given of the preparation andproperties of various substituted coumarins obtained by means of thisgeneral method.p-2Methyz.umbelZiferone, O H . C , H , < ~ ~ ~ -- ' 'H,>co, from resorcinoland ethyl acetowletsate, crystallises in prisms or needles melting at185", insoluble in water, soluble in alcohol and in ammonia and causticalkalis.Its solutions are of a pale yellow colour, and display a cha-racteristic blue fluorescence. When heated with potash, it yieldsresacetophenone and also resorcinol, and in this connection the authormentions that traces of resorcinol can be detected by the fluorescenceformed on adding ethyl acetoacetate and sulphuric acid to the sus-pected solution. The resacetophenone, C,H,(OH),.CO&fe, is identicalwith the substance obtained by Nencki and Sieber from resorcinoland acetic acid. The acetyZ and benzoyZ derivatives of @-methyl-umbelliferone crgstallise in needles, soluble in alcohol, sparinglysoluble in water and ether; the former melts a t 150°, the latterat 160."The methyl-ether of p-methylumbell~ferone is a crystalline substancORGANIC CHEMISTRY.67(m. p. 159"), resembling in all its properties the correspondinghydroxyl-compound mentioned above ; when heated with potash, it isconverted into a carboxyl-acid, C6H,(0Me) (OH) .C%fe : CH.COOH,crystallising in four-sided tables, which melt at 140" with evolution ofcarbonic anhydride, and are insoluble in water, easily soluble in alco-hol. Dimethyl-B-resorcyZirJ acid, C6H,(OMe)2.COOH, obtained byfurther methylntion and subsequent oxidation of the above-mentionedmethyl-ether, crystallises in white needles (m. p. 108").and ethyl benzoylacetate, crystallises in colourless leaflets melting at244" ; up-dimethylumbeltiferone, C6H3(OH)< ''Ie ' c M 6 > ~ ~ , fromresorcinol and etbyl dimethylacetoacetate in colourless needles melt-ing at 256" ; /3-wwthyZcowmarin from phenol and ethyl acetoacetatein colourless needles ; meta-toluene-B-metla y lcoumarin,from paracresol and ethyl acetoacetate in large refracting needles ;dihydroxymethy lcoumarin, C6&( OH)z< ':>CO, in colourlessneedles (m.p. 235").exception of the last named, display a well-marked blue fluorescence.The sohtions of a11 these substances, with theV. H. V.Bsculetin. By W. WILL (Bey., 16, 2106-2119).-The author,associated with Tiemann, has shown that dimethylaesculetin resemblesin many points methplumbelliferone and coumarin (Abstr., 1882, 199).As the.former has been recognised to be a monhydroxyl-derivativeof coumarin, it becomes exceedingly probable that aesculetin is adihydroxyl-derivative. In order to obtain further evidence in supportof this conjecture, the author has repeated with aesculetin Perkin'sresearches on coumarin (this Journal, Trans., 1881, 409), and provesthat the former undergoes transformation precisely similar t o thelatter, yielding isomeric a,- and /l-aesculetic acids, related to oneanother as the a- and @-ortlhomethoxyphenylacrylic acids.Monethy Zcesculetin, gg>c6H2<cH-' ' z > C o , is obtained, togetherwith the di-derivative, by heating aesculetin with solid potash andethyl iodide in alcoholic solution ; the two prodncts may be separatedby ether which dissolves the di-derivative.Monethylaesculetin formsmore or less colourless crystals (m. p. 143"), soluble in dilute alkalis ;its solutions give a blue fluorescence. Diethylcesculetin,crystallises in glistening leaflets (m. p. log"), sparingly soluble inwater, readily soluble in ether and benzene. It dissolves in hot soda,forming a red solution, from which the sodium compound separatesf 68 ABSTRACTS OF CHEMTCAL PAPERS.out on evaporation.there is formed the ethyl salt of P-triethylcesculetic acid,If the residue be digested with ethyl iodide,C6H2(OEt),.CH : CH.COOEt.This substance crystallises in glistening tablets melting a t 75", boilingat 360", insoluble in water, readily soluble in dilute acids andalkalis ; on saponification it is converted into @-triethyltesculetic acid,C,H,(OEt),.CH : CH.COOH.This acid forms colourless glistening prisms melting at 144" ; a solu-tion of its ammonium salt gives precipitates with salts of lead, mercury,copper, and silver. If in the preparation of the ethyl salt of P-tri-ethylaesculetic acid an excess of ethyl iodide be avoided, and the timeof heating be not more than 4-5 hours, the ethyZ salt of the isomerica-acid is produced.It forms thick golden prisms melting at 51", boil-ing a t 230", insoluble in water, soluble in alcohol and ether ; whenheated to its boiling point it is transformed into the isomeric @-corn-pound. a-Triethylcescwletic acid can be obtained by the saponificationof the corresponding ethyl salt ; it is a crystalline substance meltingat 102", and a solution of its ammonium salt gives precipitates withsalts of lead, zinc, cop,per, and mercury.When heated to its boilingpoint or with hydrochloric acid, it is converted into the isomeric &acid.On reduction with sodium-amalgam, both the a- and P-triethyltesculeticacids yield the same triethoxyp henylpropionic acid,which crystallises in leaflets melting a t 77" ; it solution of its ammo-nium salt gives precipitates with salts of lead, silver, mercury, andcopper. a- and P-trietiiyla3sculetic acids are converted by oxidationwith alkaline permanganate in the cold into the game triethoxybenzal-dehyde, C6&,(OEt),.CHO, forming colourless crystals melting a t 95",insoluble in water, soluble in alcohol and ether.It has all the cha-racteristic properties of an aldehyde. If the oxidation of the triethyl-aesculetic acid be effected a t 60" instead of the aldehyde, friethoxybenzoicacid, C6HZ(OEt),.C00H, is obtained : this substance crystallises indelicate needles melting at 134O, and solution of its ammonium saltgives precipitates with salts of lead, mercury, and silver. On dis-tilling the potassium salt of this acid with potash, it is convertedinto a substance crystallising in needles melting a t 57", which givesthe characteristic phloroglucol reaction with ferric chloride. Fromwant of material the anthor was unable t o examine the compoundmore fully.a-DimetiiyZumbelZic acid, c6H3(oMe)*cH : CH.COOH, obtained byheating 1 mol. methylumbelliferone with 1 mol.of sodium dissolvedin methyl alcohol, and 1 mol. methyl iodide, crystallises in colourlessneedles melting at 138", soluble in alcohol, ether, and benzene. Onboiling with hydrochloric acid, it is converted into the more stableisomeric compound.Both a- and /3-dimethylumbellic acids when reduced by sodium-amalgam yield the same dimethoxyprqionk acid,C,H:,(OEt),.CH,.CH,.COOH,C5H3(OMe),.CH3[,.CH,.COOHORGANIC CHEMlSTRY. 69which forms a white crystalline powder melting at 105" ; its ammoniumsalts give precipitates with salts of silver, lead, and mercury. a-Di-methylumbellic acid is converted by oxidation into a dimethoxy-benzoic acid, C6H3(OMe),.COOH-, identical with the @-dimethyl-resorcylic acid, C6H3(OMe)2.COOH [COOH : OMe : OMe = 1 : 2 : 4.1,obtained by the oxidation of t'he corresponding aldehyde.Bromine acts readily on dietliylsesculetin dissolved in carbon bisul-phide to form monobrorndiethylssculetin, CI3Hl3O4Br, a crystallinesubstance melting at 1 6 9 O , and converted on boiling with concentratedalcoholic potash into diethoxycournarilic acid, CI3HI4O5, which crystal-lises in delicate transparent needles melting at 195".On reduction withsodium-amalgam, it is converted into a substance probably homologouswith hydrocoumarilic acid. V. H. V.Benzylsulphonic Acid. By G. MOHE (Annalert, 22 1, 215-229).--Nitrobenzylsulp~ohorzic acid, C6H4(N02). CH,. SO&, prepared by themethod described by Biihler (Anniclen, 154, 50 ; Ber., 5, SSS), yieldsa chloride which is decomposed by heat into sulphurous oxide, andparanitrobenxyl chloride (m.p. 71.5" j mixed with a small quantity ofthe ortho-compound. On reducing an ammoniacal solution of thenitrobenzylsulphonic acid with sulphuretted hydrogen, paramido-benzykulphonic acid, C6H4( NH2). CH,. SO3€€, is deposited in colonrlessneedles. The mother-liquor: contains a mixture of the para- andortho-compounds. The para-acid is sparingly soluble in cold water ;100 grams of the solution at 11" contain 0.097 gram acid. The saltsare crystalline, and freely soluble in water. The diaao-compound,CH/-- \N, is prepared by passing nibrous acid into the amido-acid suspended in water. As soon as an evolution of nitrogen isobserved, the mixture is filtered. On adding alcohol to the filtrate,the diazo-compound is obtained in colourless microscopic crystals.When boiled with water it is decomposed, yielding parabydroxybenzyl-sulphonic acid, C6H4( OH).CH2.S03H, which crystallises in deliquescentneedles, freely soluble in alcohol..The solution of the acid or of itssalts gives with ferric chloride a blue coloration, which is destroyedby alcohol. The potassium and the barium salts crystallise in prismssoluble in water. The former contains, 0-5, and the latter 7.5 mols.H,O.By the action of hydrobromic acid on the diazo-compound, para-bromobenzylsulpphonic acid, C6HIBr. CH2. S03H, is obtained as a syrupyliquid. The barium salt, (C6H4Br.CH2.S0&Ba + 1+H20, formscolourless plates, soluble in water. The chZoride (m.p. 107") is solublein benzene and ether.The d iazo-compound is decomposed by absolute alcohol underpressure, yielding paraethoxy lbenzylsulphonic acid,N4'CH2S03'C,K,(OEf) .CH2. SOJXThe barium salt of this acid crystallises with 2 mols. E,O.PuruzobenzyZdisu$ honic acid, CGH, (CH,. S 0,H) .N2 .C6H&H2. S O,H70 ABSTRACTS OF CHEMICAL PAPERS.prepared by the oxidation of amidobenxylsulphonic acid with potassiumpermanganate, forms the following salts : C&&2N2S2061(2 + liHzO,orange-coloured plates, soluble in water ; C14H12N2S206Ba + l&HzO,yellow needles, sparingly soluble ; C1JL2NZSz06Ag~,H20, yellow needles,soluble in hot water. The chloride forms crystalline leaves meltinga t 149", soluble in beneene.Nitrobenzylsulphonic acid is converted into the dinitro-acid by theaction of a mixture of strong sulphuric and nitric acids.The anhy-drous potassium salt, and the lead and barium salts containing 4 mols.HzO, are soluble in water. Amidonitrobenzylsu~ho~ic acid is sparinglysoluble in cold water. The potassium salt forms purpl6 anhydrouscrystals, and the barium salt, [ C6H3(NH2) (NO2) CH2SO3I2Ba,2H2O,yellow needles or plates.Diamidobenzylsulphonic acid, C6H3(NHJ2.CH2.S0,H, crystallises incolourless needles, soluble in acids or alkalis. The ammoniacal solu-tion gives, with silver nitrate, a white precipit'ate which rapidly turnsblack. w. c. w.Parabromotoluenedisulphonic Acid. By 0. KORNATZKI (AnnaZen,221,191-~02).-Para~romotoluenedisulphonic acid, prepared by pass-ing snlphuric anhydride into it solution of bromotoluene in sulphuricacid, forms a deliquescent crystalline mass.The potassturn salt, C,H,Br( SOJK), + H,O, crystallises in colour-less needles or rhombic prisms, which dissolve freely in cold water.The barium salt, C7H5BrSzOsBa + 5H20, forms colourless prisms,needles, or plates, soluble in hot water, and the lead salt, C7H5BrS206Pb + 2H20, crystallises in colourless needles, which dissolve easily inwater.The chloride, C7H,Br( SOpCI)2, is deposited from an etherealsolution in colmrless rhombic plates melting at 99". The amideis sparingly soluble in water and alcohol.Parabromotolzienedisulphonic acid is slowly attacked by strong nitricacid with the formation of sulphuric,:dibromonitrotoluenesulphonic,nitrotoluenedisulphonic, and bromodisulphobenzoic acids.Potassium parabromodisulphobenzoate, C6HzBr(COOK) (S03K)2 +HzO, forms colourless plates, soluble in water.The barium saltcrystallises in plates containing 12 mols. HeO. The chloride is depo-sited from an ethereal solution in rhombic plates melting a t 151". Theamicle crystallises in prisms soluble in ammonia and in warm water.It melts above 250".Potassium dibrornonitrotoluenesubhonate, C7H4Brz.(.NO)2S03K +H20, is soluble in alcohol and water, The barium salt forms thinplates, containing 3+ mols. H,O.P0tnssiu.m nitro to luenedisulp honate, C7H,N02 ( S 0,K) 2, crystallises inthin needles, soluble in warm water. The amidotoluenedisu~honic acid,obtained by the action of ammonium sulphide on this salt, is notidentical with either of the amido-acids described by Pechmann(Alznalen, 173, 217), or Lorenz (ibid., 172, 188).It forms yellowneedles or prisms, which dissolve freely in water. The toluenedisul-phonic acid, which is formed by the reduction of sodium parabromo-t oluenedisulphonate, is not identical with any of the toluenedisul-phonic acids described by Blomstrand and Haknnsson (Ber,, 5, l084),It melts above 260"ORGANIC (IHEMlSTRY. 71Claesson and Berg (ibid., 13, 1170), or Senhofer (AnnaZen, 164, 126).It yields an anhydrous potassium salt, and a barium salt,C ~ H ~ ( S O ~ ) Z B ~ + 4HzO,both of which are very soluble in water. The chloride crystallises inprisms melting at 86*5", soluble in ether and light petroleum, and theamide forms colourless needles which melt above 260".w. c . w.Azotoluenedisulphonic Acids. By 0. KORNATZKI (Annalen, 2 21,179-191) .-The author finds that the only satisfactory generalmethod of preparing azotoluenesulphonic acids is by the oxidation ofthe potassium salt of the amido-acids.Ort hazoto ZuenediparasuZphonic acid, and parazotoluenediorthosulpiioninacid, which Neale (Annulen, 203, 73) prepared by reduciug the corre-sponding nitrotoluenesulphonic acids with zinc-dust and potash solu-tion, are also formed by the action of potassium permanganate onort hamidotolueneparasulphonic acid (described by Hayduck, Arznalen,172, 2C4), and on paramidotolueneorthosulphonic acid.Parazotoluenedimetasul~lio~zic acid, obtained by a similar reactionfrom the corresponding amido-acid (ibid., 173, 195) yields a bariumsalt, C1&,zBaN2S206 + 3H20, which forms small red crystals,sparingly soluble in water.Orthuzotoluensdimetasul~honic acid crystallises in plates of a redcolour, which dissolve freely in alcohol or water.The potassium salt,C14H12K2N2S206, also forms beautiful red-coloured plates, soluble inwarm water. The barium salt, C14H,2BaN2S206 + H,O, formssparingly soluble microscopic plates, which effloresce on exposure tothe air. The calcium salt crystallises in microscopic needles contain-ing 3 mols. H,O. The lead salt, Cl4H1,PbN2S2o6 + H20, is depositedfrom a solution in hot nitric acid, in needles which effloresce inthe air. The chloride, CIiH,,N,( S02Cl),, crystallises in dark redneedles melting at 218", soluble in benzene.The amide,C,Hl2N2( SO,NH,),,forms rhombic plates which melt a t 250°, and are soluble in ammonia.Dibromoparamidotolueneorthosulphonic acid, described by Jenssen(ibid., 172, 234) is slowly converted into dibromazotoluerLeaisulrphonicacid by oxidation with potassium permanganate. The azo-acidcrystallises in glistening red plates which dissolve freely in water.The potassium salt, C14H,oKI(,Br,N,S206 + 4H20, forms six-sidedplates, soluble in hot, water. The orange-coioured barium salt,C,4H,oBaBr,N2S206 + 5H20, and the red calcium salt,ClaHloCaBr,N,Sz06 + 44Hz0,forms microscopic plates, sparingly soluble in hot water. The leadsalt is deposited from hot dilute nitric acid in beautiful rhombicprisms containing 5 mols.H20. The chloride, C14HloBr2Nz( SO,Cl),,crystallises from benzene in pale red prisms melting a t 226'. Theanzicle melts at 260"72 ABSTRACTS OF CHEMICAL PAPERS.Tetrabrornorthoazotoluenedi23arasulponic ucid, prepared from Hay-duck's dibromamidotoluenesi~lphonic acid (ibid., 172, 211), formsglistening red plates, which dissolve easily in water and alcohol.The potassium salt forms microscopic plates, containing 2 mols. HzO.It, is sparingly soluble. The barium salt, C14H,BaBr4N2S,06 + 9H20,crystnllises in six-sided plates, which are sparingly soluble in hotwater. The calcium salt, CIIH8CaBr4NzSz06 + 8110, and the leadsalt, C,,H,PbBr,N,S,O, + 9H,O, form red-coloured plates. ThechZoride, C1*H8Br4N2( SO,Cl),, is deposited from benzene in dark redplates, which melt at 243" with decomposition.A hydrazo-acid is not produeed by the action of stannous chlorideon the potassinm salt, w. c.w.Amidobenzenernetasnlphonarnide. By F. HYRBENETH (Annalei,,221, 204-208) .-The preparation of nmidobenzenemetasu lph,onan? ide,C6H4(NH2).S02NH2 (m. p. 142O), has been previously described(Annden, 172, 72). The oxalate, nitrate, and hydrochloride arecrystalline. When nitrous acid is passed int#o a mixture of absolutealcohol and the sulphonamide, am orange-coloured diazo-compound isproduced. I f nitric acid is substituted for alcohol, either an orange-coloured powder soluble in water, or a yellow crystalline compound,will be obtained. The orange-coloured substance has the compositionC6H4(S02NHz).N,,N03. It is decomposed by boiling with water oralcohol, yielding nitrogen and benzenesulphonamide (m.p. 156").The yellow crystalline compoundNHZSOz.C,jH4.N2.NH.C6H4. SOZNH?,previously mentioned, is insoluble in water. It melts a t 183" withdecomposition. It is decomposed by hydrochloric acid, yieldingchlorobenzenesulphonamide fm. p. 148"), which was first prepared byKieselinsky (Annalen, 180, 110).2[C6H4(NH,).SO2NK,] + RNO, =NH,SOz.CJ€,.NH.N,. CJ&. SOzNHz.The conditions which determine khe formation of either of the twocompounds have not yet been ascertained. w. c. w.Orthamidotolueneparasulphonamide. By W. PAYSAN (Annalen.,221, 210-215) .-The amide of orthamidotolueneparasulphonic acid,NHz.C611,Me.SOzNHz, prepared by the action of sulphuretted hydrogenon an ammoniacal solution of orthonitrotolueneparasulphonamide(m. p. 12so), crystallises in four-sided prisms melting at 175", whichare sparingly soluble in cold water o r alcohol. It forms a series ofcrystalline salts.The diazo-compound, NHzSO2.CsH,Me.N,.NHC6H,~~e.SO2NH2, isobtained as a pale-yellow powder, when niti-ons acid is passed into amixture of the sulphonamide and alcohol. It detonates feebly whenheated, and is also easily decomposed by dilute acids, e.g., by hydro-chloricacid, i t is split up into nitrogen, amidotoluenesnlphonamidehydro-chloride and or thochloro t olueneparasulphonamide, C6H3Me C1. SOZNHORGANIC CHEMlSTRY. 73(m. p. 135"). The latter compound crystallises in white needles orplates, whichare sparingly soluble in water.By the action of hydm-chloric acid at 150", it is converted into orthochlorotolueneparasnl-phonic acid. The acid exists as an oily liquid. I t s potassium and bariumsalts do not contain water of crystallisation. The chloride is also anoily liquid. When nitrous acid is passed into orthamidotolueneparasul-phonamide, made into a paste with nitric acid, an exceedingly unstablecolourless diazo-compound is produced, which is decomposed by boilingalcohol, yielding the ethyloxidetoluenesulphonic acid described byHayduck (Annalen, 172, 215). w. c. w.Paramidotolueneorthosulphonamide. By A. HEFFTER ( A n n a Zen,2 21,208-210) .-Paramidotolueneorth osulp honam ide,is obtained by the action of sulphuretted hydrogen on a warmam moniacal solution of paranitro toluenesulphonamide ( A n n a Zen, 17 2,233).It crystallises in silky needles or plates which melt at 164", anddissolve in alcohol or warm water. It forms a crystalline nitrate,oxalate, and hydrochloride. When nitrous acid is passed into analcoholic solution of the snlphonamide, a yellow amorphous compoundis produced, which is decomposed by hot absolute alcohol, yielding theamide of tolueneorthosulphonic acid (m. p. 154"), which has beendescribed by Claesson aod Wallin (Bey., 12,1850). A diazo-derivativeof amidotoluenesulphonamide could not be isolated. ParachZorotoZuene-orthosdphonamide (m. p. 138") is produced when nitrous acid acts onthe sulphonamide in presence of hydrochloric acid.The S02-group inparamidotoluenesulphonamide is not eliminated by oxidation with potas-sium permanganate ; but the amide of azotoluenedisulphonic acid(m. p. 270"), described by Neale (Annalelz, 203, 52), is formed. w. c. w.Compounds of the Indigo-group. By A. BAEYER (Ber., 16,2188-2.204) .-Part IV.-The author has finally est>ablished theposition of the hydrogen-atom (external to the benzene-ring) in indigo,showing that tlhe latter is an imido-body, produced by the union oftwo indogen-groups. In the conversion of isatin and indoxyl intomembers of the true indigo-group, an isomeric change takes place,pseudoisatin and pseudoindoxyl existing however only in corn bination :co coNHCBH4< $OH, ca,( >GO,Isatin. Pseudoisatin.co\ COHNH NHC6H4( >CH, C6H4( /CHZ.Indoxyl.Pseudoindoxyl.For the stability of pseudoisatin it is sufEcient to replace thehydrogen of the NH-group by a monad radicle, whilst in the case o74 ABSTRACTS OF CHEMICAL PAPERS.pseudoindoxyl, a dyad-group must replace both hydrogen-atoms of thegroup CH,.Action qf Nitrous Acid on Indoxyl and Indoayl-compounds.-On treat-ing a solution of indoxyl with sodium nitrite and then acidifying,slender yellowish needles separate which, from their similarity to thenitrosamine of ethylindoxyl (obt'ained in the same way), and fromtheir behaviour to hydrochloric acid, must be the nitrosamine of indo%$,.C(OH>. \ I \CH. By the action of indoxyl on dinzobenzene hydro-C"'(N(ON)/chloride .in 'dilute aqueous solution, ,phenylazoindoxy Z, Cl4HI1NO3,separates in very sparingly soluble red needles; it is moderatelysoluble in alcohol, from which it crystallises in thick orange-colouredprisms of yellowish-green metallic lustre; it melts a t 236Owith decom-position, and dissolves in warm soda solution, from which it is repre-cipitat,ed by carbonic anhydride. Zinc-dust decolorises the alkalinesolution, and on exposure to air indigo is formed. Isonitrosopseudo-**indoayl ( pseudoisatin-a-oxime), C6H4< :E >CNOH, was previouslydescribed as nitrosoindoxyl (Alostr., 1882, l l O Z ) , but an examinationof its ethers shows that it is an isonitroso-derivative. The first ether,pseudoisatin-d-ethyZoxim.e, is obtained on heating an alcoholic solutionof pseudoisatoxime with ethyl iodide and sodium ethylate (1 mol.).It yields isatin on reduction and oxidation, showing that the ethyl-group does not replace the imido-hydrogen ; neither can it be derived.COH,from a nitrosoindoxyl of the formula C6H/ \C.NO, for it can\-NH-/be boiled with concentrated hydrochloric acid without undergoingchange ; nor from CsH,< >CHNO, as such a compound, containingethyl attached to the a-carbon atom, would not be so readily convertedinto isatin.I t s formula must therefore be C6H,<NH>CNOEt,and that of the parent-substance the one given above. This ethyl-derivative is a weak acid, dissolves in alcoholic potash with a violetcolour, and in alcoholic sodium ethylate with a blue colour.To pre-pare the second ether (ethylpseudoisatin-a-ethyloxirne) an alcoholic soh-t ion of pseudoisatosime, mixed with ethyl iodide and sodium ethylate(1 mol.), is boiled until the sodium salt first formed is completely dis-solved, when a quantity (1 mol.) of sodium ethylate aud ethyl iodide isadded, and the boiling continued for about half an hour ; the alcohol isremoved by distillation, the product dissolved in ether, and washed withdilute soda solution. It is readily soluble in alcohol and in ether, spar-ingly in hot water, from which it crystallises in yellow needles meltingat 99" ; it is neither attacked by alkalis nor by boiling hydrochloric acid.Its formula is C6Ha<NEt>CNOEt. Isatoxime and its two ethers,pseudoisatoxime and its first, ether, all yield isatin on reduction andsubsequent oxidation, whilst the second ether of pseudoisatoxime(containing ethyl attached to nitrogen) yields ethylpseudoisatin,NHcocORGANIC CHEMlSTRY.75C6H4<$it >CO. This crystallises in large blood-red plates meltinga t 95", is readily soluble in hot wat,er and i n alcohol, less so in ether.It dissolves in alkalis with a yellow colour and formation of ethyl-isatates. Acetylpseudoisatin behaves in a similar manner, being a tonce converted into an acetylisatate. On acidulating a solution ofan ethylisatate, ethylpseudoisatin is a t once precipitated, whilstacetylisatic acid is perfectly stable. Barium ethylisatate-obtained by dissolving ethylpseudoisatin in warm baryta-water, crys-tallises in silky yellow needles; the silver salt forms flat yellowneedles, moderately soluble in water.Ethylpseudoisatin yields anindopheiiin with coal-tar benzene and sulphuric acid, which forms ablue solution with ether (distinction from isatin). Ethylpseudoisatin,even when heated with concentrated hydrochloric acid for seven hoursat 150-160c, is in great part unattacked, whilst ethylisatin is saponifiedby cold dilute alkalis. By the action of a solution of hydroxylaminehydrochloride and sodium carbonate in dilute alcohol, ethy Zpsezdo-isatin-p-ozirne, C6H4<-NEt->C0, is obtained crgstallising inyellow four-sided prisms (m. p. 160-162"). On reduction and sub-sequent oxidation, it yields ethylpseudoisatin ; it does not yield indigowith ammonium sulphide.Action of Aldehydes and Ketonic Acids on IndoxyL-On treating anaqueous solution of indoxyl with aldehyde, or with benzaldehyde, andthen acidulating with hydrochloric acid, an extremely unstable yellowprecipitate is obtained, whilst paranitrobenzaldehyde, terephthalicaldehyde, anthroxanaldehyde, and pyroracemic acid, when treated inthe same way, yield very stable red precipitates.On cautiously heatinga mixture of dry indoxylic acid (7 parts) and benzaldehyde (10 parts)carbonic anhydride is evolved ; this ceases as soon as the temperatureis raised to 120". When the action is completed, the excem of benz-aldehyde is removed by steam-dist illation, and the residue crystallisedfirst from alcohol and then from ether. The indogenide of benanldehydethus obtained crystallises in long, flat, orange-yellow needles, meltingat 175-176".It dissolves readily in alcohol and chloroform, moresparingly in ether, with which i t forms a fluorescent solution ; it isdissolved by concentrated sulphuric and hydrochloric acids, but isreprecipitated on adding water; it is iiisoluble in aqueous, butsoluble in alcoholic alkalis. Its formation from indoxyl and benz-aldehyde takes place thus: CsH,NO + C7H60 = C15Hl,N0 + H,O,similar t o the action of nitrous acid on indoxyl, and from the similarityof both products and their behaviour with sodium ethylate, it isevident that they are similarly constituted, and that the formula ofC(N0H)rinthe indogenide of benzaldehyde is C,H,<;g>C : CHPh.It yieldsR blue solution with sodium ethylate, showing the indigo-spectrum,the blue colour disappearing on the addition of alcohol. The indo-genide of paranitrobenzaldeh?lde, Cl5Hl0N2O3, is prepared by adding asolution of paranitrobenzaldehyde in glacial acetic acid to an aqueou76 ABSTRACTS OF CHEMICAL PAPERS.solution of indoxyl acidulated with hydrochloric acid, and thentreating the precipitate several times with boiling water, and recrystal-lising it from acetone. It forms small red needles melting a t 273".The indogenide of pyroracemic acid, C6H4<NH>C co CMe.COOH, isobtained by adding concentrated hydrochloric acid to an aqueoussolution of indoxyl and pyroracemic acid, and can be purified bypassing a current of air through its solution in ammonia, filtering andprecipitating with hydrochloric acid ; it crystallises in red needles, andmelts a t 197".It, is readily soluble in acetone and in alcohol, is astrong acid, forms brownish-red solutions with the alkalis andalkaline carbonates, and a blue solution with sulphuric acid. It isreduced by ammonia and zinc-dust, forming a colourless solution,which becomes yellow on exposure to air, and yields a yellow flocculentprecipitate on the addition of an acid.Action of lsatin and Ethylpseudoisatin on Idoxyl.-The formationof indirubin from indoxyl and isatin may be compared to the abovereactions, in which case indirubin must be regarded as the indogenideof isatin, thus :-Pseudoindoxyl. Isatin.co C(OW\= CeH4( >C C' ,N + H,O.NH '-(&H4Indirnbin.When a hot aqueous solution of indoxyl is poured into a hotsolution of ethylisatin mixed with one-fourth its volume of con-centrated hydrochloric acid, a violet-coloured liquid is obtained, whichyields crystals of the 8-indogenide of ethylpseudoisatin.It crystallisesfrom boiling alcohol in needles of a coppery lustre, sparingly solublein acetone, more readily in chloroform. It melts at 197-l%", and at,higher temperatures volatilises in yellowish-red vapours. Thepowdered substance is violet, its concentrated solution in chloroformred, and its dilute solution pink, showing a broad band in the middleof the spectrum. It is reduced by zinc-dust and alkalis, yields abrown solution with concentrated sulphuric acid, which changes toviolet when heatcd, and behaves like indigo.From the fact that inthe reduction of ethylpseudoisatin, the CO-group next to the benzenenucleus is the one attacked, and also in the reaction with hydroxyl-amine, it may be assumed that this is also the case in the condensation-product with indoxyl. Its formula is therefore-C6H4<gg>C : C<zgi>NEt,and it is possible that indimbin has a corresponding constitution.Diethy Zindigo.-Assuming the probability of indigo being an indigo-body, the author attempted to convert ethyl- and benzyl-amidoacetoORGANIC CHEMlSTRY. 77phenone into ethyl- and benzyl-indigo, but without success. By thereduction of the second ether of pseudoisatin-a-oxime by alcoholicammonium sulphide, diethylindigo can be obtained, in which ethyl isattached to the nitrogen, and which still possesses the properties ofindigo.It crystallises in blue needles with coppery lustre, it is dis-tinguished from indigo by its moderate solubility in alcohol; but isinore sparingly s o h ble in acetone, chloroform, aniline, ether, andcarbon bisulphide. Its solutions are of a pure blue colour, and givean absorption-spectrum very like that of indigo. It forms a greenish-hlue solution with concentrated sulphuric acid, which changes to blueon warming (from formation of a sulphonic acid). When heated, ityields purple vapours, condensing in the form of thick blue prisms.With alkalis and zinc-dust, it yields a reduction-compound, and onoxidation, ethylpseudoisatin, proving that the ethyl in diethylindigo isunited with nitrogen.In the same way that diethylindigo is obtainedfrom ethylpseudoisatin-a-ethyloxime, indigo can be obtained frompseiidoisatin-a-oxime, and also by the action of ammonium sulphideon isatin chloride and on +ethylisatin, but from the formula of thesethree indigo-producing substances it will be seen that by their reduc-tion and the splitting of€ of hydroxylamine, hydrochloric acid, andalcohol respectively, each is capable of yielding an indogen-group orindoxyl.The constitution of indigo can be adduced from the following con-siderations :-1. Indigo contains the imido-group ; 2. From its forma-$ion from diphengldiacetylene, the carbon-atoms must be arrangedthus: Ph.C.C.C.C.Ph; 3.It can only be obtainedfrom such compoundsin which the carbon-atom next to the benzene nucleus is also unitedto oxygen; 4. Its formation arid properties show that it is closelyrelated to indirubin and to the indogenide of ethylpseudoisatin ;5 . This last substanee is formed by the union of the a-carbon-atom ofpseudoindoxyl with the 6-carbon-atom of pseudoisatin. Indigo musttherefore be the a-indogenide of pseudoisatin, although from thewant of activity of the a-oxygen-atom in isatin it cannot be directlyobtained from indoxyl and isatin.co C6H4<NH>CHZ + co<:g 6 1 >NEtPseudoindoxyl. E thylpseudoisatin.CO co = CJL<NH>C : C<C6H,>NEt + K O -Indogenide of ethylpseudoisatin.co co C~H~<NH>C& CO<NH>C~J%Pseudoindoxyl.Pseudoisatin.co co = c6H1<,H>c : C<NH>c6H4 + HZO.Indigo.The half molecule (CsH5NO) of indigo is called by the aniho78 ABSTRACTS OF CHEMICAL PAPERS.indogen, and compounds in which this dyad-group replaces anoxygen-atom, indogenides. The indogenides are of a yellow to bluish-red colour, and some of them yield blue salts showing the indigo-spectrum. A. K. M.Chemical Constitution of Acetylisatin and AcetylisaticAcid. By H. KOLBE (J. pr. Chem. [2], 28, 79-82).-The authorobjects to the formulae assigned by Baeper to isatin and its deriva-tives ; he regards isatin as having the constitution C,H,N.CO.COH(the nitrogen-atom acting as a monovalent element, and replacingone of the hydrogen-atoms in phenyl), and represents the conversionof acetylisatin into sodium acetylisatinate by the equation-CGH4N.C0.COAc + NaOH = C6H4(NH&).C0.COONa.A. J.G.Quinisatin. By A. BAEYER and B. HOMOLKA (Rer., 16, 2216-2221).-Baeyer obtained isatin from oxindole by converting the latterinto a nitroso-derivative, then into the amido-derivative which yieldsisatin on oxidation. The authors have obtained the isatin of quino-line in the same way from yhydroxycarbostyril (Abstr., 1883, 197).To prepare nitroso-nphydroxycarbostyril, CSH6N203, y-hydroxycar-bostyril is dissolved in dilute soda solution, a slight excess of sodiumnitrite added, and the mixture gradually poured into cold dilute sul-phuric acid. The precipitate is washed with water, dried and c r ptallised from alcohol, when it is obtained in small orange-colouredprisms, sparingly soluble in water, cold alcohol, ether, benzene andchloroform, readily in glacial acetic acid and in hot alcohol.It meltsat 208" with decomposition. Alkaline carbonate and ammonia dis-solve it, forming a green solution, whilst the fixed alkalis yieldreddish-brown solutions. On boiling it with concentrated hydro-chloric acid, it decomposes into isatin and hydroxylamine. Promits resemblance to isatoxime, the authors consider the following con-stitution probable,CO.C(N.OH)By the action of zinc-dust on its solution in glacial acetic acid,acetyldihydroxytetrahydro~u~nol~ne, CIlHJ'J 0 3 , is obtained, crystallisingin long colourless silky needles. When exposed to the air in a moiststate, it is rapidly oxidised to a violet-red product, from which theoriginal substance can be obtained by reduction. Acetyldihydroxy-tetrahydroquinole is very sparingly soluble in cold water, alcohol andether, moderately in glacial acetic acid, especially on warming ; it dis-solves in alkali to a violet solution or in excess of the lattler to a bluesolution, acids reprecipihating it in reddish coloured flocks whichgradually become white.On reducing nitroso-7-hydroxycarbostyril by means of a saturatedsolution of stannous chloride in concentrated hydrochloric acid, andsubsequently decomposing the tin salt with hydrogen snlphide, a com-pound of the formula, C9H7N03, is obtained, which is probablyC(OH)->ORGANIC CHEMlSTRY.79long colourless nsedles, very sparingly soluble in water, ether andbenzene, readily ia alcohol.Heated to 260", it becomes converted intoa brown substance infusible at 310". With dilute alkalis it yield8 ablue solution, which becomes decolorised on exposure to the air withformation of a violet precipitate. On adding soda to its solution inalcohol and ether, a deep blue flocculent gelatinous precipitate is pro-duced. When finely powdered 6-y-dihydroxycarbostyril is treatedwith a solution of ferric chloride in hydrochloric acid a t 70-80", areddish-yellow liquid is obtained from which quinisatic acid,NH,. C,jHd. CO. C 0. C 0 OH,crystallises out on cooling. It is moderately soluble in cold water,very readily in hot, water, from which it crystallises in pale straw-coloured prisms.The alkali salts are nearly colourless and readilysoluble ; the silver salt forms a yellowish-green unstable precipitate.On reducing a solution in glacial acetic acid with zinc-dust, and ex-posing the filtrate to the air, an indigo-blue coloured precipitate isformed, insoluble in water, ether, and chloroform, but soluble inalcohol, the supernatant liquid assuming a green coloration. Bothcolours are destroyed by acids, but reproduced on adding an alkali.On heating crystallised quinisatic acid for a short time a t 120-125"water is given off, and the red anhydride, quinisutin, CsH,NO,,formed : this readily combines with water forming quinisatic acid.I t darkens in colour above 185", melting between 255" and 260".Sodasolution dissolves it to a reddish-yellow solution, which is rapidlydecolorised. It forms compounds with aniline and benzene, whichare soluble in alkalis, but reprecipitated by carbonic anhydride,showing that quinisatin is not a carboxylic acid. Its formula is pro- c0.co co.cobably either C,H/ 1 or CGHd'NH.CO <N k(OH)* A. K. AT.So-called Pyrocressol. By H. SCHWARTZ (Ber., 16, 2141-2145).-In this paper the author mentions that the results of vapour-densitydetermination of the so-called pyrocressol were not in accordance withthose obtained in the combustion analyses : the latter correspondedwith a formula CZ8H2,O2, the former to C,,Hl4O (comp. Rer., 16,1056). Both have been repeated, and the latter formula confirmed ;pyrocressol, therefore, may have the constitution of a ditolyl or dibenzylketone, CGH4Me.C0.C6H4Me or CH,Ph.CO.CH,Ph, although its pro-perties are not in accordance with either of these substances.Similarly,it is shown that the a-pyrocressol oxide obtained by the oxidation ofpyrocressol with chromic acid has the empirical formula C,,H,,O, ; itforms a tetranitro-derivative, C15H8(NOz)40,, crystallising in goldenneedles, and a tetrabrom-derivative C16H8Br402, crystallising in longwhite leaflets melting at 215".Derivatives of a- and p-Naphthol. By E FRIEDL~NDER (Bey.,16, 2075--2092).-The monohydroxy-phenols readily react with theV. H. V80 ABSTRACTS OF CHEMICAL PAPERS.monamines yielding the dismines with elimination of water ; the bestdehydrating agent for effecting this change is calcium chloride, andfrom the author's experiments it foliows that the gqeatest yield is ob-tained when 1 mol.of the phenol and 2 mols. of the amine are heatedwith 1 mol. of calcium chloride. I n this communication, the variouscompounds obtained by the action of aniline and the three toluidineson a- and &naphthols are described.Phenyl-6-naphthyzamine, CloH7.NHPh, crystallises in white needlesmelting a t 108" ; phenyl-a-nap hthy lamine in white leaflets melting at60".Paratolyl-13-naphthy lamine, CloHT.NH.C7H7, forms white glisteningleaflets melting at 108" ; its acetyl and benzoyl-derivatives crystallisein needles ; with excess of bromine a tetrabrom-compound is obtained,which forms glistening needles melting at 168".Paratolyl-oc-naphthyl-amine forms white prisms melting a t 79" ; orthotolyl-a-naphthylamineglisteniug needles melting a t 95'. Orthotolyl-p-naph thy lamine crystal-lises from petroleum in white leaflets melting a t 96" ; its picrate inreddish- brown needles, and its benaoy Z-derivative in leaflets.All the above-mentioned amines give colour-reactions with nitricand chromic acids ; when heated with hydrochloric acid they are re-converted into the corresponding phenol and the hydrochloride of theamine. V. H. V.Naphthalene-derivatives. 111. By F. GRAEFF (Ber., 16, 2246-2255).-The action of nitric acid on naphthonitril takes place intwo stages, nitronaphthonitril being first formed, and the CN-groupsubsequently converted into COOH, so that it is possible to stop theaction after the first phase, and obtain nitronaphthonitril.For theiiitrntion of the a-compound (20 grams) a mixture of 50 C.C. fumingnitric acid, sp. gr. 1.48, with 200 C.C. nitric acid, sp. gr. 1.3, is recom-mended, whilst for the @compound 150 C.C. of the stronger acid to100 C.C. of the weaker acid are employed. a-Naphthonitril yieldsthree mononitro-derivatives, the chief product melting at 205" as pre-viously stated (Abstr., 1881, 882). Another more scluble nitronaph-thonitril melts at 152-153", whilst the third compound, which hasnot yet been obtained pure, melts between 100" and 130". A mono-nitro-derivative melting a t 172-173" is readily obtained fromP-naphthonitril, but the chief product melts between 95" and 120'.Nitro-a-naphthonitriz, CloH6N0,.CN (m.p. 152-153"), is morereadily soluble in boiling water than its isomeride melting a t '205",very sparingly in light petroleum, more readily in carbon bisulphide,moderately in alcohol and glacial acetic acid, and very readily inbenzene and in chlorofwm. It crystallises in yellowish colouredneedles from alcohol, ether, and glacial acetic acid, and in lustrousscales from light petroleum. Nitro-6-naphthonitril (m. p. 172-173") is very sparingly soluble in hot light petroleum, and sparinglyin alcohol and glacial acetic acid, from which it separates either insingle long crystals of golden lustre or in fern-like clusters; it ismoderately soluble in ether and carbon bisulphide, more readily inbenzene, and extremely soluble in chloroform. It may be obtained inlarge nearly white needles of great purity by sublimation.These nitroORGANIC CHEMlSTRY. 81naphthonitrils are saponified by heating them with Concentratedhydrochloric acid for five hours at 150-160".Nitro-a-naphthoic aedd (m. p. 241-242") obtained from the nitro-naphthonitril melting a t 205", is moderately soluble in hot alcoholand glacial acetic acid, less so in ether and chloroform, still momsparingly in benzene and carbon bisulphide, and very sparingiy inlight petroleum and in water. It crystallises from spirit in flat, con-centrically-grouped needles, and sublimes in the form of splendidlustrous scales.The potassium salt, C~oHfiNOz.GOOK + HzO, forms hard yellowishcoloured crystals of a vitreous lustre, On boiling the acid with anexcess of barium, carbonate,is obtained.The silver salt forms a yellowish amorphous precipi take sparinglysoluble in water ; the lead snZt resembles the silver salt, and separatesfrom its solution in boiling water in small wart-like forms ; the coppersalt is sparingly soluble in water, from which it separates in smallbluish-green crystals ; the methy Z-derivative forms small yellowneedles melting at 109-llO", and readily soluble in alcohol; theethyl-derivative is much more sparingly soluble in alcohol, and crys-tallises in long, slender, well-formed needles melting at 93" ; theisopropy Z-derivative forms lustrous crystals melting at 101*5", andsparingly soluble in alcohol.Nityo-a-naphthoic acid melting a t 255" dissolves readily in mostsolvents, and sublimes in long colourless needles.For want ofmaterial it has not been further examined.Nityo-8-napJrthoic acid melts at 295", and in most of its propertiesresembles the acid melting atl 241-242". It is insoluble in water,sparingly soluble in ether, light petroleum, benzene, chloroform andcarbon bisulphide, moderately in hot alcohol and glacial acetic acid ;it sublimes in small nearly colourless needles. The potassium saZt,CloH6NOz.COOK + H20, forms small clusters of lustrous needles veryreadily soluble in water. OR boiling the acid with barium carbonate,two salts are obtained, a more sparingly soluble acid salt,6 [ (C ,,H,NO,. C 0 O)2Ba], C: &LN 0 2 . C 0 OH + 24H20,crystallising in sniall lustrous scales; and a more sohble norntal saltalso crystallising in scales.The methyl-derivative is sparingly solublein alcohol, from which it crystallises inclusters of large bright yellowneedles, melting at 112" ; the ethyZ-derivative is readily soluble inalcohol, and crystallises in large well-formed dark yellow needlesmelting at 109" ; the isopropyZ-derivative forms long silky needlesmelting at 75-76', and readily soluble in alcohol. This acid appearsto be the same as that obtained by Ekstrand (Ber., 12, 1395) from/3-naphthoic acid, but which melted a t 280" owing to the presence ofimpurities. A. K. &I.Reduction of Dichlorophenanthrone. By B. LACHOWICZ (J. pr.C'hern. [2], 28, 168-1 75)-The preparation and properties of di-chlorphenanthrone (phenanthrenedichloroketone) have already beensparingly soluble basic salt,5 [ (CloHfiNOz.C00)2Ba],Ba0 + 10H20,VOL.XIrVI. 82 ABSTRACTS OF CHEMICAL PAPERS.described by the author (Abstr., 1883, 666). The formation ofresinous bye-products is minimised by adding excess of benzene tothe phenanthraquinone before running in the phosphoric chloride.Nitric acid readily converts it into the nitro-derivatives of anthra-quinone.Monochlorphennnthrone, C14H90Cl, is obtained by the reduction ofdichlorophenanthrone with iron and acetic acid ; it crystallises inlarge yellow prisms, melts at 122-123", is readily soluble in alcohol,ether, benzene, light petroleum, &c. It dissolves without decomposi-tion in alkalis, and is not decomposed by long boiling with alcoholicammonia. By heating with nitric acid of sp.gr. 1.3 i t yields nitro-pliennnthroqirinone, C14H,N04, crystallising in orange-yellow plates,melting a t 281-282", and soluble in glacial acetic acid and nitricacid.Phenanthrone, C,aHloO, is obtained by the long-continued action ofnascent hydrogen on dichloranthrone, best by gradually a,dding ironfilings to a solution of dichloranthrone in glacial acetic acid heated to1CO-110". Too strong heating leads to the formation of resinousproducts. It crystallises in brilliant brownish-red tables, melts a t148-149", resembles the monochloro-derivative in solubilities, andlike it, is not decomposed by aqueous alkalis.The authors consider that phenanthrone has the structural formulaCeH.i.CH21 - - I - , whilst the isomeric compound obtained by Japp andC,H,.COStreat'feild from et8hy1 phenanthroxyleneisocrotonate (Trans., 1883,33) may probably be represented by I I ',O.CsH,.CHc 6 ~ 4 . c H/ A. J. G.Coloured Essential Oils. By K. HOCK (Arch. Pharnz. [ 3 ] , 21,17-18) .-The essential oils of chamomile, wormwood, and mille-folium, although differing in colour, were found by the author tohave the same absorption-spectrum, namely, three bands in the redand orange. When these oils were submitted to fractional distillation,in each case the portion which distilled a t 260" was deep blue, andyielded the same absorption-bands with great distinctness. The blueoils obtained from Matricaria chaworni2la, Perula sunzbul, Nectnndyapuchury, Inula lielenium, Pogostervlon patschuly, also by the dry dis-tillation of galbanum, guaiacum, and asafcetida resins, as well asa blue product from oil of valerian, gave the same characteristicabsorption-spectrum. From these results, the author concludes thatall these blue oils contain the same colouring-matter, azulene, whichin some cases is present in the plant from which the oil is obtained,in others, is produced by the action of water on some constituent ofthe plant during distillation, and sometimes is formed by destructivedistillation.I n the case of those essential oils from which the blueportion was obtained by distillation, an oil oxidised by keeping appearedto yield a larger quantity of the blue product than the same quantityof the fresh oil.W. R. DORGANIC CHEMlSTRY. 83Destructive Distillation of Colophony. By A. RENARD (Compt.rend., 97, 111-1 12).-When colophony is introduced into an eartheu-warc retort heated to dull redness it is decomposed, and yields a largequantity of combustible gas rich in hydrogen, and a black, somewhatfluid tar, mixed with a small quantity of water. The t a r when dis-tilled a t a temperature rising to 300' yields a resin which solidifieson cooling, and a liquid which cont.ains benzene and its homologues,a small quantity of naphthalene, and other oils which hare not beenstudied. The residue from the distillation of this liquid is mixedwith the resin, and the mixture distilled as far as possible.A residueof coke is left, arid an oil was obtained which becomes semi-solid oncooling. This oil contains two isomeric hydrocarbons, cozophanthrenes,which bave the following composition :-White.T---A--- 7 Yellow.Carbon .......... 93.02 93.20 93.20Hydrogen.. ...... 7.18 7.01 6.71The yellow colophanthrene is very sIightly soluble in alcohol, fromwhich it separates in yellow crystals with a greenish fluorescence. Itboils at about 360°, and by repeated crystallisation from alcohol itappears to be converted into the white isomeride. The white colo-phanthrene is much more soluble in alcohol, from which it is depositedin brilliant white cryst,als, with a violet fluorescence. It melts a t about87", boils a t about 340", and by repeated distillation is partially con-verted into the yellow isomeride.It also acquires an orange-yellowtint when exposed to light. Both hydrocarbons begin to decomposeat the boiling point of sulphur (440'). Wheu oxidised by chromicacid in acetic acid solution, they both yield carbonic anhydride and adiketone, which yields a sulphonic acid. The potassium salt of thisacid when heated in a seaIed tube at about 170" with a concentratedsolution of potassium hydroxide is converted into a deep violet snb-stance ; this dissolves in water, and is decomposed by hydrochloricacid, yielding a colouring-matter, which imparts to cotton mordantedwith alumina a shade similar to that given by alizarin.Extraction of Colouring-matters by a Solution of Borax,By R. PALM (Chenz.News, 48, 114).-For the extraction of alizarinand purpurin from ga,rancin, the author digests the garancin with acold saturated borax solution until a deep blood-red solution is ob-tained ; this is filtered, and precipitated with sulphuric, hydrochloric,or acetic acid. The precipitate is boiled with a saturated solution ofalum, filtered, and cooled ; the alizarin and purpurin then depositedare filtered off, and a further quantity of the colouring-matter is pre-cipitated from the filtrate on adding sulphuric acid. The author alsoemploys borax solution for the extraction of santalin from sanderswood, and violet colouring-matter not identical with carmine fromcoc b ineal.C. H. B.D. A. L84 ABSTRACTS OF CHEMICAL PAPERS.Cochineal Dye-stuffs.By H. F~RTH (Ber., 16, 2169-2171).--By acting on carmine with sulphuric acid, Liebermann and v. Dorphave obtained a brown amorphous dye-stuff , ruficoccine, C,6H&67which on distillation with zinc-dust is converted into an anthracene-like hydrocarbon of composition C16H12 (Annalen, 163, 97). Theauthor has succeeded in obtaining this hydrocarbon not only fromcoccinine, a quinone derivative of carmine, but also directly fromcarmine. This hydrocarbon, which condenses in small green-goldleaflets when coccinine or carmine are distilled with zinc-dust, meltsat 1%", and is soluble in ether, alcohol, and benzene. By heatingacetic chloride and coccinine in sealed tubes a t loo", an acetyl-deriva-tive is obtained, which forms small golden crystals insoluble in water,soluble in alcohol ; i t cannot be sublimed without decomposition.Ascoccinine yields a c16 hydrocarbon on distillation, the compositionCI4H1?O5, assigned to it by Hlasiwetz and Grabowsky, must be alteredto C16H1406, and its acetyl-compound will then be a tetra-derivative,C ~ ~ H ~ O O ~ A C ~ . Coccinine is thus a tetrahydroxy-qninone, C1,H,oO,(OH),,which formula is in accordance with its quinone-like characteristics.V. H. V.Preparation of Diquinoline. By .R. C. TRESSIDER (Chern. News,48, 31).-Quinoline hydrochloride is heated with an equal weight ofzinc chloride a t 350" for five or six hours, the flask being fitted witha reflux arrangement. Soda is added to t'he product until the zinchydroxide first precipitated is redissolved, the mixture is steam dis-tilled to remove any unchanged quinoline, and the residue which isblack and solid is well washed with water, boiled with a large quantityof alcohol, and filtered hot.The filtrate is decolorised with animalcharcoal, and again filtered hot, : on cooling, diquinoline separatesout, and is recrystallised from alcohol. The yield is not large.D. A. L.Hydroxycinchonic Acid. By W. KOXIGS and G. KORNER (Ber.,16, 2152-2160) .-By fusing cinchoriic acid with potash, one of theauthors has obtained a hydroxycinchonic acid, CgH,N(OH).COOH(Abstr., 1879, 472) ; this acid is converted into a chloro-derivative,C,H,ClN.COOH, by phosphorus pentachloride, and by heating withhydriodic acid and phosphorus into the amorphous hydroquinoline,(C9H,N),.This last reaction shows that the hydroxyl-group is notin the benzene, but in the pyridirie nucleus ; and in the present com-munication this supposition is confirmed, and it is further shown thathydroxycinchonic acid is a carboxyl-derivative of carbostyril.The authors were unable to obtain a hydroxyquinoline by distillinghydroxycinchoiiic acid with bases; but on heating its silver salt,C,H,(OH) .COOAg, in a current of carbonic anhydride, a sublimatewas formed crystallising in needles, and having the characteristicproperties of carbos tyril.Chlorocinchonic acid, when heated with sodium alcoholate, yieldsethoxycinchonic acid, C,H,N(OEt).COOH, which crystallises in hairyneedles melting a t 145", soluble in hot water, alcohol, and dilute mineraORGANIC CHEMISTRY.85acids; its siZver and lead salts are sparingly soluble precipitates, ofwhich the former is an acid salt of compositionCgH,N (OEt) , CO OAg,CgH,N (OE t) . COOH ;its platinochloride, [ C9H5N (OEt) ,C00E],.H2Pt C16, is crystalline.When ethoxycinchonic acid is heated to a temperature slightlyabove its melting point, it is transformed into the isomeric ethyl saltof hydroxycinchonic acid, C,H,N(OH) .COOEt, also obtained by theaction of ethyl iodide on silver hydroxycinchonate. This salt crystal-lises in needles melting a t 206", and, unlike its isomeride, is insolublein dilute acids or alkalis. The intermolecular change of the ethoxy-acidinto the ethyl salt of the hydroxy-acid probably prevents the elimina-tion of carbonic anhydride from the acid, when it is heated with lime.When the silver hydrogen salt is heated in a current of carbonic anhy-dride, ethylcarbostyril and the ethyl salt of ethoxycinchonic acid areproduced.The latter substance, which can also be prepared from ethyliodide and the silver salt, crystallises in fine needles melting at 86".From these researches it follows tbat hydroxy- and ethoxy-cinchonicacids are derived from carbostyril, and as cinchonic acid is convertedinto pgridine tricarboxylic acid by oxidation with potassium yerman-ganate, the carboxyl-group is in the pyridene nucleus.In cinchonic and hydroxycinchonic acids, the N-atom and the carbonto which the COOH-group is united, are probably in the para-positionto one another, The authors have also succeeded in converting quino-linic, or pyrididinecarboxylic acid, into hydroxyquinolinic acid bymelting the former with potash.The relations of these acids isevident from the following formulae : -CH CHCO0H.C CH CO0H.C (i CHCO0H.C \NH C.OHCooH.C 'iC*The latter forms colourless crystals melting at 254' of strongly markedacid properties; its aqueous solution gives a deep red colorationwith ferric chloride, and voluminous precipitates with copper, lead,and silver salts. Its hydrogen barium salt crystallises in tufts ofneedles ; its hydrogen silver salt, when heated in a current of carbonicanhydride yields a compound haying all the characteristic propertiesof oxypyride, C5H5N0.Oxidation of Morphine. By L.BARTH and H. WE~DEL (Monatsh.Chem., 4, 70&-703).-The action of most oxidising agents on mor-phine does not yield very definite results ; potassium permanganntehowever in slightly alkaline solution acts on it somewhat moreenergetically, yielding as chief product a light-brownish uncrystallis-able acid syrup, which forms amorphous salts, and when mixed withcupric acetate, remains clear at first, but becomes turbid on boiling,depositing a blue-green flocculent precipitate, which redissolves oncooling. This result is like that which is obtained by similar treat-V. H. V86 ABSTRACTS OF CHEMICAL PAPERS.ment of cinchomeronic and pyridine-tricarboxylic acids. Morphinesubjected to dry distillation with lime yields a basic oil having a,decided odour of pyridine.Arsenic acid acts but slowly on mor-phine even in sealed tubes, yielding a base which appears t o containone methyl-group less and one hydroxyl-group less than morphine ;the action is however variable and so are the products. Whenmorphine is heated with potassium hydroxide till the surface of themelt begins to glow, and the product, after cooling, is acidulated,brown-black non-ni trogenous flocks are deposited, and a solution isobtained from which ether extracts a considerable quantity of sub-stance ; and on expelling the ether, digesting the residue with. water,precipitating the filtrate with lead acetate, decomposing the precipi-tate with hydrogen sulphide, evaporating, and repeatedly crystallisingthe residue, a product is obtained, consisting of protocatechuic acid.The filtrate freed from lead and evaporated yields more protocate-chuic acid, together with another acid which crystallises in prisms,and gives no colour-reaction with iron salts.When the melting with potash was conducted in 8 silver retort, andthe vapours were received in dilute hydrochloric acid, methylaminewas obtained, together with n small quantity of another base.The absence of aromatic compounds amongst the products formedby oxidising morphine with permanganate, and the non-occurrence ofderivatives of pyridine (or quinoline) in the oxidation of this alkalo'idwith caustic alkali, seem t o show that the mode of combination ofthe aromatic and of the pyridine- (or quinoline-) groups in it, is dif-ferent from that which exists in narcotine, which, it is well known, iseasily resolved into its two principal constituents.H. W.Constitution of Quinine and Quinidine. By Z. H. SKRAUP(Monatsh. Chem., 4, 695-699) .-The author has already shown(Abstr., 1882, 279) that these two alkaloids, when oxidised bychromic acid, yield carbonic anhydride and quininic acid, CllH9N03,which latter, when heated with hydrochloric acid, gives methylchloride and xanthoqninic acid, CloH7N03, resolvable by heat intoCO, and a hydroxyquinoline, C9H,N0 = CgH6(OH)NO2; further thatquininic acid is converted by oxidation with permanganate into apyridine-tricarboxylic acid, C,H,N(COOH),, identical with that whichis obtained from cinchoninic acid : hence it, is probable that quininicacid is a, derivative of quinoline, and that its methyl-group is situatedin the benzene-residue of the quinoline-molecule ; hence also it maybe inferred that the hydroxyquinoline obtained from xanthoquinicacid has its hydroxyl-group situated in the benzene residue.Accord-ing to existing views there should be only four hydroxyquinolinesthus constituted. Three are already known, and the main object ofthe present investigation is to ascertain whether the hydroxy-quinoline obtained in the manner just mentioned is identical witheither of these three, or consists of the hitherto unknown fourthmodification.Xanthoquiiiic acid is for the most part resolved at 310" into car-bonic anhydride and a hydroxyquinoline, which when purified byconversion into platinochloride, &c., crpstallises from absolute alcohoORGANIC CHEMlSTRY. 87in slender white prisms, soluble in alcohol without coloration, thesolution however acquiring, on addition of water, a faint yellowcolour, which disappears on further addition of alcohol.Thisbehaviour dis tingnishes the hydroxyquinoline in question from themeta-moditication, the alcoholic solution of which exhibits a splendidgreen fluorescence. From the ortho-modification it is distinguishedby giving, on addition of ferric chloride to its alcoholic solution, nota green, but a reddish coloration. With para-hydroxyquinoline onthe other hand it agrees very nearly in its melting point (194"), andfurther in the yellow coloration of its alcoholic solution by ferricchloride ; in giving with picric acid slender yellow prisms meltinga t 235-235.5" ; with cupric acetate, first a fine blue-green colour,then gradually violet prisms which dissolve iu boiling alcohol with afine lea€-green colour, and remain unaltered on evaporation.This hydroxyquinoline dissolves readily when gently heated withfour times its weight of strong nitric acid, and the solution,when quicklycooled and cautiously diluted with cold water, deposits orange-redcrystals, easily soluble in hot water, the solution slowly mixed withpotash-lye, depositing yellowish prisms, which, after recrystallisationfrom dilute alcohol, melt, like nitro-p-hydroxyquinoline, at 140-141".The alcoholic solution, mixed with cupric acetate, first turns brightgreen, and then deposits a copper-brown precipitate, or if a trace ofalkali be added, a green precipitate. The barium salt of the nitro-compound forms orange-red needles, slightly soluble in cold, muchmore freely in boiling water,Cinchoninic, quininic, and xenthoyainic acids may be representedby the following constitutional formulae :-COOH COOH COOHCinchonic acid.Qnininic acid. Xanthoquinic acid.H. W.Cinchonamine. By ARNAUD (Compt. r e d . , 97, 174-1 76, Seealso Abstr., 1882, p. 229) .-Cinchonamine, C19H24N,0, exists inRem,ijia piwdiana, but is not contained in B. pedunculata, which con-tains quinine. To extract cinchonamine, the finely powdered bark isexhausted with very dilute snlphuric acid, the solution filtered, boiled,and precipitated with milk of lime. The precipitate is dried onporous tiles, and digested with boiling ether.The ethereal solutionis decanted from iindissolved resinous substances, &c., washed withdilute hydrochloric acid, which removes the cinchonamine, and theacid solution of cinchonamine hydrochloride is evaporated to crystal-lisation. The hydrochloride is dissolved in boiling dilute acid,filtered through animal charcoal, and recrystallised. The free base isobtained by adding ammonia to a solution of the hydrochloride, andcrystallking the alkaloid from boiling ether. An alcoholic solutionof the alkaloid is dextrogyrate, its rotatory power at 97" bein88 ABSTRACTS OF CHEMICAL PAPERS.[.ID = 123.2". According to Dr.Laborde, cinchonamine is highlypoisonous, even in very small doses.The salts of cinchonamine generally crgstaliise readily, aud are butslightly soluble in water, especially in presence of free acid. Theydissolve in hot alcohol, from which they crystallise on cooling. Thehydrochioride crystallises from an acid solution in thin, brilliant,anhydrous, pismatic lamellae, very slightly soluble in acidulatedwater. From. a neutral aqueous solution, the salt crystallises inopaque flattened prisms containing 1 mol. HzO. These crystalseffloresce, and are much more solttble in water than the anhydroussalt. This property of the hydrochloride to crystallise in an anhy-drous condition from acid solutions furnishes a method of separatingcinchonamine from all the alkalo'ids with which it is associated inR.purdiana. The hyilrobrowaide forms brilliant, slender, anhydrousneedles, slightly soluble in cold water, much more soluble in hotwater. The kydriadide crystallises in micaceous plates, almost insol u-ble in cold water. The nitrnte is only slightly soluble in cold alcohol,but is much more solubae in hot alcohol, from which it crystallises inIiard, thick, short prisms. This salt is slightly soluble in pure water,but is insoluble in acidulated water, and is precipitated on addingnitric acid to even a dilute aqueous solution of any cinchonaminesalt. The precipitate is at first flocculent, lout, on standing, it rapidlybecomes crystalline, the crystals being small prisms, which polariselight.At 15", 100 parts of alcohol of 94" dissolve 0'825 part of thesalt; 100 parts of water at the same temperature dissolve 0.2 part ofsalt. Asolution of the salt in water containing 1 mol. H,S04 has a rofiatorypower a t 15" [all, = + 43.5; at 25" [a]= = + 42.2, The formatecrystallises with difficulty. The acetate is very soluble in water, fromwhich it is deposited as a resinous mass on evaporation. By spon-taneous evaporation of the aqueous solution the salt is obtained indeliquescent crystalline concretions. The oeaZcnte does not crystallisefrom an aqueous solution, but is deposited in a resinous form. Thetartrate forms a crystalline powder consisting of small hexagonalprisms which polarise light. 100 psrts of water a t 15" dissolve 1.150parts of the salt.The maZate forms brilliant nacreous plates, veryslightly soluble in cold water, but somewhat soluble in boiling water.The crystals retain 1 mol. H,O at 120°, but melt and become anhy-drous at 160". 100 parts of water at 15" dissolve 1 part of malate.The citrate is deposited from a boiling solution on cooling as a resin-ous mass, which gradually becomes crystalline, forming concretionscomposed of brilliant prisms which polarise light. 100 parts of waterat 16" dissolve 1.950 parts of the citrate.Conversion of Brucine into Strychnine. By HANRIOT (Compt.i*eizd., 97, 267-268) .--The author has repeated Sonnenschein'sexperiments (Ber., 8, 212), and finds that strychnine is not producedby the action of nitric acid on pure brucine. Sonnenschein's experi-ments were probably made with impure brucine. Brncine has thepower of completely masking the ordinary reaction for strychnine(with sulphuric acid and dichromate), even when the latter is presentThe suZp23hute can be purified by crystallisation from alcohol.C. H. BORGANIC CHEMISTRY. 89to the extent of 50 per cent. It is evident therefore that the presenceof strychnine in many samples of brucine may easily have been over-looked, and this will probably account for the confusion which existsas to the physiological action of brucine. Morphine, quinine, methylalcohol, and many other substances also have the property of maskingthe strychnine reaction.Products of the Bacterial Fermentation of AlburninoYds.By A. GADTIER and A. ETARD (C'ompt. rend., 97, 263-267. Seealso Abstr., 1882, 1115 ; and 1883, 100 and 224.)-The authors havepreviously shown that the putrefaction of albumino'ids results in theformation of leucines, glucoprotejins, nitrogenous and nsn-nitrogen-ous acids, phenol, skatole, indole, tyrosine, trimethylamine, ammonia,and ptomai'nes. Whatever the variety of the ferment and the sourceof the putrefying flesh, the principal ptomaines formed are constantin properties and composition.The liquid and solid putrid matter is distilled in a vacuum a t a lowtemperature. The distillate (A) contains ammonium carbonate,phenol, skatole, trimethylamine, and volatile fatty acids ; the residueis treated successively with ether and alcohol. The ethereal solution(B) contains ptomajines and a fatty acid, and holds in suspension verylight, brilliant, white nacreous plates. The alcoholic solution (C)contains fatty acids and crystallisable nitrogenous compounds. Theresidue insoluble in ether and alcohol is boiled with very dilute hydro-chloric acid out of contact with air, the solution evaporated andtreated with alcohol (D).The ethereal solution (R) when distilled leaves a brown oil, fromwhich a large quantity of fatty acid crystallises out. The mother-liquor is acidified with sulphuric acid, saturated with potash, andagitated with ether, which dissolves the ptomaines. A solution ofthe ptomajines from beef treated in the cold with platinum tetra-chloride, care being taken to avoid an excess, yields a precipitate ofthe coniposition (C,H3N)2,H2PtC16. It is the platinochloride of ahydrocollidine, identical with the base previously obtained from fish(Zoc. cit.). The mother-liquor from this platinochloride containsanother platinochloride, which forms yellowish crystals of the com-position C, 28'73; H, 5.8; N, 7.19; Pt, 27-99. It is partiallydecomposed at 100" with development of the hawthorn-like odour ofits alkalo'id.The brilliant plates held in suspension by the ethereal solutionconsist of the calcium salt of amido-stearic acid, C,,H3,(NH,)0,. Thisis almost insoluble in all solvents, but is dissolved slightly by alcohol,When treated with hydrochloric acid, it yields amido-stearic acid,which is insoluble in water, only slightly soluble in cold alcohol,but readily in hot alcohol, from which it crystallises in aggregatedneedles on cooling. It melts at 63", and when heated a t about 140"it loses 1 mol. of water, and yields the anhydride, C,,H,,NO. Theamido-stearic acid is obtained from beef: the nacreous plates obtainedfrom putrid fish are soluble in alcohol and in potash, but are insolublein water and acids. By treatment with inorganic acids they yield anacid of the composition, CsH,,N,03. When they are fused withC. H. B90 ABSTRACTS O F CHEMICAL PAPERS.potassium hydroxide, ammonia is given off, and a mixture of alkalinecaprylate, caproate, and acetate is formed.The alcoholic solution (C) contains the greater part of the leucinesand leucoproteins. After evaporation, the residue is treated withinorganic acids, the aqueous liquid separated from the liberated fattyacids, concentrated by evaporation, and treated with alcohol, whichdissolves out leucines and leucelnes, particularly those containing C,and Cc. The principal compound thus obtained from putrid fish formswhite rhombcidal lamellae, somewhat soluble in water, and somewhateasily sublimed ; it has the composition CllH26N2065 and appears tobe the hydroxide of the glucoprotein, CllHz2NzO4, obtained bySchutzenberger from the products of the decomposition of albumi-nolds by baryta. It has the general properties of amido-acids, anddissolves in dilute alkalis ; when fused with potassium hydroxide, ityields hydrogen, ammonia, and potassium carbonate, butyrat,e, andvalerate, a portion splitting up a t the same time into the correspond-ing leucines and leuceines. When distilled at about 280', it yields anamylamine boiling a t 92-93', which is probably formed together withamido-valeric acid in accordance with the equation CllHz6N2D6 =CsHlsN + C,H,NOz + GO, + 2H20. C. H. B.Albumin, Nuclein, and Plastin. By E. ZACHARIAS (Bid Cmtr.,1883,405-407).-The principal portions of the nitrogenous substancesof plant cells, insoluble in alcohol, consist of albumin, nuclein, andplastin, the two latter are attacked but slightly, or not a t all, by thegastric juices ; on the contrary, they readily dissolve albumin, Plas-tin is insoluble in very dilute solutions of alkalis, nuclein is easilysoluble in these menstrua; plastin and nuclein are the soluble andinsoluble nucleins of other authors. The supposition of Schimpersthat the substance from which starch is produced is similar to albumin,at least to a great degree, the author believes he has confirmed byresearches on the leaves of Tradascantia virginea and orchis.Albumin diminishes and plastin increases in the protoplasm of thecells examined ; according to Hartig's reaction: sections soaked ina dilute solut'ion of potassium ferrocyanide, and then transferred tg avery dilute solution of ferric chloride, show the nucleus deep blue,whilst in the ducts no trace of a blue colour is visible. When por-tions of the epidermis of the leaves of those plants are so treated, thestarch material becomes intensely blue, the cell protoplasm remainscolourless, or is coloured only in points. The nuclei show a bluecoloration, as also the nucleoli ; the plastin is colourless or very slightlycoloured.The author does not think that the chemical constitution of thenuclei and nucleoli can be ascertained from these reactions, but theyare aids to that kuowledge. J. F