ORGASIC CHENISTRT. 133Organic Chemistry.Some Reactions of Silver Cyanide. By C. L. BLOXAM (Chem.ATeu7s, 50, 155) .-€Iydrocyanic acid is evolved on treating pre-cipitated silver cyanide with concentrated nitric acid ; on boiling, thecyanide is entirely dissolved and silver nitrate crystallises from thecooled solution. If, however, the solution is decanted when onlya portion of the precipitate is dissolved, it deposits minute needlesRS it cools; these crystals, wbich mat together in a remarkablemanner when the solution is stirred, are silver nitrocyanide,AgCN,2AgN03 (Abstr., 1884, 168). The residue left by the nitricacid consists of unattacked cyanide mixed with some of these crystals.This change also takes place slowly in the cold with concentratednitric acid; a boiling mixture of nitric acid, sp.gr. 1.400, with anequal volume of water, appears to be the most suitable for dissolvingsilver cyanide as nitrocyanide.When precipitated silver cyanide is treated with a strong solutinnof sodium carbonate, i t becomes granular, and the granules areobserved to be fringed with minute needles. BJ- boiling the pre-cipitated cyanide with strong solutions of potassium or of sodiumcarbonate, it, dissolves practically without dec?mposition, but isconverted into small prismatic crystals, which are sparingly soluble inthe hot solution of the alkaline carbonate, and are completelydeposited from this solution as it cools.Action of Primary Alcoholic Iodides on Silver Fulminate.By G. CALMELS (Compt. rend., 99, 794-797).-25 grams of driedsilver fulminate were heated with 25 grams of methyl iodide and 40grams of ether in a sealed tube at 50" for 24 hours.The productsare silver iodide, methylcarby lamine, and 6-nitroethylene. Ethyliodide and the higher primary iodoparaffins react in a preciselysimilar CNAg : CAgNO, + 2MeI = 2AgI + CNMe +CH2 CH.NO,. I n this reaction silver fulminate is split u p intotwo parts. I n order if possible to obtain the intermediate com-pounds-100 grams of methyl iodide mixed with 50 grams of ether wereallowed to act on 50 grams of the dried fulminate a t the ordinaryD. A. L.mamner:CNMe : CMe.N02 ; CNEt : CEt.N02131 ABSTRACTS O F CI-IENICAL PAPERS.temperature for four or five days, but the only products obtainedwere a-nitroethylene and rrieth;ylcnrbylamine.EthJl iodide and itshigher homolopes behave in the same way.The nitro-derivatives of the ethylene series are chamcterised bytheir power of existing in two modifications, the &-derivatives formingcolourless liquids soluble in ether and cliloroform, whilst the f!-deriva-tives are yellow resirlous solids insoluble in the same solvents.Fiwm their cl\emical behaviour, it would seem that the former are thetrue nitro-derivatives, whilst the lattcr are oximido-~erivatives.From these results, it follows that silver fulminate contains twodissymmetric:tl groups, each of which contains one atom of silver.One of these groups is silrer cyanide, CNAg, whilst the othercontains the sub-group N/ 1 and the second atom of silver, thelatter being united with the second atom of carbon, which is indirect union with the nitrogen in the first group (this nitrogenacting as a pentad) and thus links the two groups together:-0'0C=N ,Silver fulminate. Mercuric fulminate.It is evident from this formula that the two metallic atoms in thesilver fulminate have diiyerent functions, arid this explains the non-existence of mixed fulminates of the alkali metals.The forniula alsoexplains generally the observed action of the halogens on thefulminates.The fulminates are isocyanides or metallic carbylamines united bynitrogen t o a bivalent residue of a metallic derivative of nitro-methane, the metal attached to the nitro-group being any metal what-ever.This function, which is peculiar to the carbylamines and doesnot appertain to the metallic nitriles (cyanides), may be termed thecnrbazilic function. The relation of the carbazylic type to the alliedtypes is showii by the following formulae :-C i N CH,.CH C : N.Me C : N.HNitrile. Metanitrile. Carbjllamine. Carbazjlic.C . H. B.Gallisin. By C. SCHMITT and J. ROSENHEK (Bey., 17, 2456-2167).--This paper forms a continuation of C. Schmitt and A.Cobenzl's communication on this subject (Abstr., 1884, Wl).Actioii of SuLphzwic Molrochlo~c'de on Gallisin.-When pure dry galli-sin is gradually added to sulphuric: monochloride, SO,Cl.OH, it isdissolved, hydrochloric acid being a t the same time copiously evolved.All lieating must be carefully avoided, as decomposition sets in a tabout 60-70"."'he syrup produced cuuld not be obtaiued in a crysORGANIC CHJ$,RIISTK.T. 135talline state, and as it is decomposed even a t ordinary temperatures itwas poured on to broken ice, and the aqueous solution thus obtainedneutralised with barium carbonate. The barium salt was obtained asa white flocculent precipitate by pouring its solution iuto alcohol ;wheu dried, it forms a white hygroscopic powder which is slowlydecomposed on exposure to the air, quickly a t XO-100'. The corn-position of this substance is C6H,OI8S,Ba2 + 5H20, aud it appears tobe idelltical with Claesson's barium destrosotetrasulphate (Abstr.,1879, 1033). The authors found the rotation of this bariuin salt inaqueous solution to be 52", Claesson obtaining 51" for his compound.If this is really identical with Claesson's compound, the non-crystal-lising of the chloride first formed is probably due to the presence ofimpurities.Action of Bromiize on GaZlisin.-30 grains of gallisin were dissolvedin 1$ litres of water, and heated for about six hours in a well-corkedchampagne bottle in the water-bath, bromine being added at intervals.Altogether i 5 grams of bromine were used.The pressure generatedwas considerable, and the odour of bromoform was perceptible eachtime the bottle was heated. The authors were unable to isolate theunstable brominated compound which is fortlied, andsthe product wastherefore treated with silver oxide. The silver compound was alsovery unstable and was a t once decomposed with sulphuretted hydrogen.The free acid could not be obtained in a c~jstalline or pnre form.Itis dextrorotary, but unlike other acids obtained in a similar manner, itgives a precipitate with lead salts. I f added to a solution of ferricchloride (even in small quantities), it prevents the precipitation offerric hydroxide by arnmouia. It reduces Fehling's and Knapp'ssolutions. When neutralised with calcium, barium, or cadmiumcarbonates, it yields uncrystallisable salts which are precipitated byalcohol. None of the compounds could be obtained in a pure ordefinite state.Dry Distillation of Gallisin with Liti,e.-The distillate separatedinto two layers. The aqueous layer contained acetic acid andacetone; the oily layer boiled a t 82-86" and is probably Fremy'smetacetone.Action ?/' Pancreatic Juice o n Gallisijz.-If gallisin is treated withpancreatic juice and the whole allowed t o rernmn for a considerabletime in a wartn room, the former is converted into a substance caphble9f undergoing alcoholic fermentation with yeast : the quantityconverted is dependent on the length of time during which thepancreatic juice 1s allowed to act, but the authors have not yet beenable to convert the whole of the gallisin into such ferineritablcsubstance .The Specific Rotary Pozvpr oj' Pure Gullisiu, in aqueous solution,increases approximately in proportion to the iucrease in quantity ofthe solvent.Analzjsis of Commercial GI ucose air d Qua,ntitntive Zsstiwzation ofGallisiri therein.-Neubauer states that gallisin does not reduceE'ehling's solution, and this statement has beer1 generally accepted ascorrect. The authors find that gallisin does reduce Fehling's solution,1.01178 grams gullisin requiring 100 C.C.of solution. The author136 ABSTRACTS OF CHEMICAL PAPERS.suggest the following as the best method of estimating pure gallisinand pnre glucose in the commercial article. A solution is made con-taining less than 1 per cent., and is titrated with Fehling's solution.Another solution is made, fermented with yeast, and then titrated.The latter titration gives t,he quantity of gallisin present, and thedifference besween the two, the quantity of pure glucose.L. T. T.Thiovaleraldehyde. By G. A. BARBAGLIA (Ber., 17,2654-2655) .-I n a previous paper (Abstr., 1881,34), the author showed that sulphurreacted with valeraldehyde at about 250" according to the equation4C5HI0O + S, = 2C,Hl0S + 2C5H&.He finds that secondary re-actions also take place which give rise to the formation of : 1, hydrpgensulphide, the quantity of which increases as the temperature is raised ;2, a heavy red-coloured liquid, distilling between 200" and 300°,and having an offensive odour recalling that of onions and putrid eggs,tlie quantity of this substance being greater the larger the amountof sulphur employed ; 3, trithiuvnZeraZdehyde, CH,.CH.CH.CH.CHS,crystallising in bright yellow silky prisms melting at 94.5"; it isiusoluble in water, very readily soluble in ether and alcohol.\s/ yA.K. H.Aldehyde and Ethylidene Derivatives. Value of the Car-bony1 Affinities of Carbon. By R. RUBENCAMP ( A ? l ? d e ? z , 225,267-290) .-The liquid boiling about 15", which Wurtz (Jahresberichf,1856, 597) and Bachmann (Anrzalen, 218, 42) considere'd to bemethyl ethyl acetal, is in reality a, mixture of dimethyl acetal anddiethyl acetal. The author regards the existence of the mixed acetalsas very doubtful.Ethijlidene diacetnte is formed by the action of silver acetate onethylidene acetochlorhydrin diluted with absolute ether ; the pro-perties of this body have been previously described by Franchimont.By a similar reaction, ethylidene dipopionnte, C,H,(C3H,02)2, andother analogous compounds can be prepared. The physical propertiesof these bodies are shown in the followiiig table :-Xp.gr. Index of refractionB. p. (corr.). at 15". at 28-2.Ethylidene diacetate . . . . . . . . 168.4 1.073 1.399,, acetopropionate. . . 178.6 1.044 1.402,, dipropionate. . . . . . 192.2 1.020 1.407,, acetobutyrate . . . . 192% 1.014 1.4065,, dibutyrate.. . . . . . . 215.5 0-9855 1.411, , ace t oval erat e . . . . . 194.1 99 0.99 1 1.408,, divalernte .. .. . . .. 225 0.947 1.414,, propiochlorhydrin . 135 (uncor.) 1.071 -9 7 butyrochlorhydrin . 149 ,, 1.038,, valerochlorhydrin . 162 0-997 --As the cornpound produced by the action of silver propionate onethylidene acetochlorhydrin is identical with the compound obtaineby the action of silver acetate on ethylidene propiochlorhydrin,and in like manner, as the body produced from silver acetate andetbylidene butyrochlorhydrin is identical with that obtained fromsilver butyrate and cthylidene acetochlorhydrin, the author concludesthat both the " carbonyl affinities " are of equal value.w. c. w.Some Reactions of Carbon Bisulphide, and its Solubilityin Water. By G. CHANCEL and F. P A R x E m I E R (Compt. rend., 99,892--894).-When baryta-water is mixed with an aqueous solutionof carbon bisulphide, or with a mixture of carbon bisulphide andwater, very little action takes place a t the ordinary temperature, butif the mixture is heated an abundant precipitate of barium carbonateis formed, and the supernatant liquid becomes yellow. If the mixtureis heated in sealed tnbes a t 100" for some time, the liquid graduallybecomes colourless, and the amount of barium carbonate formed isgreater than that calculated from the equation given by Eerzelius,Experiments made by heating known weights of carbon bisulphidemit8h an excess of a somewhat dilute solution of barium hydroxide at loo", in sealed tubes previously filled with nitrogen, show that underthese conditions the reaction is accIirately represented by the equa-tion CS, + 2BaH20, = BaCOs + BaS2H2 + H,O.If the mixtureis heated in contact with air, the same proportion of barium carbonateis formed, but, it is mixed with a certain quantity of barium sulphateforriied by the oxidation of the hgdrosulphide.The authors have employed this reaction to determine the amountof carbon bisulphide dissolved by water a t different temperatures,with the following results :-Temperature .. . . . . . . . . 34" 15.8" 30.1" 41.0"CS, in grams per litre . . . 2.00 1.81 1.53 1'053CSZ + 6MOH = MzCO3 -t 2M?CS, + 3HzO.The solubility diminishes rapidly above 30", and becomes nil a t theboiling point of the bisulphide. The solution of carbon bisulphidebehaves under changes of temperature in the same way as the solutionof a gas. C. H. B.Normal a-Hydroxyvaleric Acid. By W. JUSLIN (Bey., 17, 2504-2506) .-Hitherto Pinner and Bischoff's trichlororalerolactic acid wasthe only known derivative of tbe above acid. The author has now pre-pared the unsubstituted acid by the action of alkalis on moriobromo-valeric acid, and also by the action of hydrocyanic acid m d hydro-chloric acid on butaldehyde.The valeric acid employed was obtainedby heating propjlmalonic acid. Ethyl a-brontoualerate is a colourlessliquid of pleasant odour. It boils a t 190-192", and has a sp. gr. of1.226 a t 18" compared with water a t 4". This ether was thendigested on the water-bath with a solution of sodium hjdroxide, theproduct evaporated to dryness, treated with sulphuric acid, andextracted with ether. On evaporation, the ether left a- hydyowpulwicacid as a syrup which, in a vacuum, solidified to large tabukir crystals.It is yery deliquescent and melts a t 28-29". The barium salt form135 ABYl11_?CTS O F CHEJIICXL PLIPERS.glistening scaly crystals soluble in water ; the bluish-pcn C>ppey saltis sparingly soluble in water.€Iutaldeh!/de was prepared by the dry distilhtioa of a mixture ofcalcium butyrate and formate, and was converted into its hydrogen.sodium sulpkite coinpou~rl. This substance forms long silky crptnlseasily soluble in water, spnriiigly so in alcohol and insoluble in ether ;it was distilled with a concentrated solution of sodillm hydroxide,and the butaldehyde thus obtained heated with hydrocyanic acidin closed tubes a t 70".Ths nitrile was then boiled with fuming hydro-chloric acid, the excess of the latter acid evaporated off, and theresidue extracted with ether. On evaporating the ethereal solution,an insoluble oil was left, which proved to be the anhydride of thehydroxy-acid. This was reconverted into the acid by boiling withpotash, &c., and the acid thus obtained was found to be identical withthat prepared with a-bromoraleric acid.When kept in a desiccator,the hydroxy-arid is gradually converted into the anhydride.Acetonedicarboxylic Acid. By H. v. PECHMANN (Bey., 17, 2542-2545).-Citric acid is heated with sulphuric acid on the water-bathuntil the carbonic oxide evolved is accompanied by carbonic anhy-dride, and the whole then cooled and water added. Acetoizedica@oxyZicacid, CO( CH2.COOH),, crystallibes out in colourless needles. Thissubstance forms a compound with phenylhydrazine. When heatedalone, it is decomposed into carbonic arihydride and acetone. Themelting point is about 138". The same decomposition takes placewhen the acid is heated with acids or alkalis, or its aqueous solutionis boiled.The elhers of this acid are liquid, and the author is nowinvestigating their substitution products.Amides of Citric Acid and their- Conversion into Pyridine-derivatives. By A.. BEHRMAKX and A. LV. HOFMANN (Bey., 17, 2681-2699) .-Oitramide, C6H504(NHJ3, is readily obtained by the actionof very strong aqueous ammonia on trimethyl citrate a t the ordinarytemperature. If alcoholic ammonia is employed, the action is muchslower and the yield much smaller. It is sparingly soluble in cold,readily in hot water, and insoluble in alcohol and ether ; when heatedabove goo", it begins to turn brown, and at 210-215" it melts to ablack liquid. It yields no acetic derivative when treated either withatcetic chloride or acetic anhydride.If the mother-liquor from tbecitramide is evaporated to a syrup, acidulated with nitric acid, andalcohol and ether then added, citrodiamic acid, C,H,O,(NH,),.OH, sepa-yates; this crystallises in white scales melting a t 158", is readilysoluble in water and almost insoluble in alcohol and ether. Thesilver salt, C,H5O4(NH,),.OAg, forms a crystalline powder sparinglysoluble in water; the lead and other salts are soluble. If thesyrupy mother-liquor from the citramide is treated with ammoniaand silver nitrate, cwgevtic citramorimiate, C6H,0s(NH2) (OAg)?, isprecipitated as a yellowish-white powder. The free acid is extremelysoluble in water, less so in alcohol, and is insoluble in ether and lightpetroleum ; it melts a t 138".A better yield of the citramic acids isobtained by treating citramide with weaker ammonia.L. T. T.L. T. T0% ASIC CHEJJISTRT. 139Citi*azim'c ncid, C,H,NO, : citrnmide is treated with 4-,5 parts o€sulphuric acid (70-i5 per cent.), the mixture heated at about 130",and the solution poni-ed, after cooling, into '2 to 3 vols. water;the acid then separates as a yellowisli powder. It may also be:obtained by the action of sulphuric acid on the citvarnic acids.Citrazinic acid is very sparingly soluble even in boiling water andirisoluble in other neutral liquids ; boiling concentrated hydrochloricacid dissolves it sparingly, but it is soluble in warm concentratedsulphnric acid, and very readily in alkalis and alkaline carbonates.The solutions of the citrazinates assume a greenish-blue colorationon exposure to the air, the amrnoniacal solution becoming deep bluelike an nmmoniacal copper solution ; the addition of an acid destroysthe colour immediately.When citirtzinic acid is added to a hotneutral solution of potassium or sodium nitrite, a deep blue colora-tion is immediately produced. Citrazinic acid is very stable, andmay be heated to 275" without devomposition; i t carhonises above300" without melting. It may be boiled for hours with thestrongest alkalis without yieldinz a trace of ammonia, but is decom-posed by fusion with alkalis with formation of potassium cyanidp.The alkali salts are very soluble, the barium and calcium saltssparingly so ; the lead salt forms a yellowish, the copper salt a brown,and the silver salt a yellow precipitate.The n / P t h / Z saZt, C6H4&feN0,,forms lustrous scales, which are sparingly soluble in water, alcohol,and ether; the ethyl scrlt, CGH4MeN01, has similar properties. Adiacetyl-deriuatice, CJHS&2NOi, may he obtained by dissolving theacid in boiling acetic anhydride ; it is readily decomposcd by water oralcohol. When cit,razinic acid is boiled with tin aud hydrochloricacid, tricarbnllylic: acid is produced:-C6H5N01 + 2H,O + H, =C6H,06 + NH2. The authors think it very probable t h t citrazinicacid is a dihydroxy-pyridinecarboxylic acid, C,H,( OH),N.COOH.When it is heated with phosphorous pentachloride and oxychlorideat 2.50°, and the product treated witJh boiling water, a dichloro-prridinecarboxylic acid, C,H,Cl2N.C0OH, is obtained, melting a t210" ; this is sparingly soluble in water, moderately in cold, readilyin boiling alcolicll, and extremely soluble in ether ; it is insoluble inhydrochloric acid, but dissolves in warm concentrated sulphuric acid,and readily in all alkaline liquids.The silver salt, CjH,CIIN.COOAg,crystallises from 1)oilin-g water in magriificent; colourless needles. Bythe action of hydriodic acid on the chlorinated acid, a, p?/q*idiw,e-carbolrylic acid is obtained, which melts a t 306", and is identical withSkraup's ypyridinevarboxylic acid (Ber., 12, 233.2) and Weidel'sisonicotinic acid. I t is sparingly soluble in cold, more readily in hotwater, sparingly also in alcohol and ether; the alkali salts alescluble, the silver s a l t insoluble; the copper salt POITUS a bluish-green crystalline precipitate ; the platinochloride,(C,rr,N.C@OH)?.H,PtCl6 + ZHdO,crystallises in thick orange-yellow prisms. If, in the reduction ofrlichloropyridinecarhoxylic acid, as above, phosphorus be added, thecarbox? I-group is reduced to methyl, and pwiipicoZijie is obtained.A. .I(.If1.401 ABSTRACTS OF CHEMlCAL PAPERS.Action of Ethyl Chlorocarbonate on Nitrogenous OrganicCompounds. By E. v. MEYER ( J . pr. Chem., 30, 115-125).-Ethyl chlorocarbonate reacts with cyanethine, forming cyanethineIzydmhlo?-ide and ethyl cyanethiibe carboccylate, thus :ZCgHJT2.NHz + ClCOOEt = CgHJTz(NH,),HCl +C,H13Nz.N€I. GO OE t.This latter compound can be separated from the hydrochloride bytreatment with benzene, which dissolves the ethyl cyanethinecarboxylate.It is an easily fusible solid, boils a t 247", its aqueoussolution has an intensely bitter taste and an alkaline reaction, and bycontinued boiling is resolved into carbonic anhydride, ethyl alcohol,and cyanethine. EthyZ cyanet hine-cai*boxylnte is easily dissolved byacids, and is reprecipitated from these solutions by bases ; its solutionsare precipitated by several metallic salts, such as mercuric chloride,gold chloride, and silver nitrate. This compound may also beregarded as a derivative of ethyl carbnmate, and is, in fact, ethylcyanoconyZ- cnrbanzate, (C,H,,N,)'HN.COOEt. With ammonia it formsc!/nnethiize-cal.bami~e, C,H,,N,.NH.CONH,, and with aniline cyan-Ptl~ine-cal.haniZide, (CgHl3N,)'.NH.CONHPh.This latter compoundcrystallises from alcohol in long, silky needles, melting a t 184", it is avery stable compound, and unaffected by acids or bases. Whenheated in a current of hydrochloric acid gas, it is resolved intocyanethine and phenyl cyanate, thus :-(CgH13N,)'.NH.CONHPh = (C9H13Nz)'NHz + PhNCO.Cy anethine-carba;?ziZiJe is formed also by the direct union of phenylcyanate and cyanethine, a formation analogous to that of methyl-phenylcarbarnide from methylamine and phenyl cyanate.The " ozybase," C9H,,NZ.OH, obtained from cyanethine, reacts withethyl chlorocarbonate, forming a compound similar to that obtainedfrom cyanethine ; it is a liquid which is decomposed by boiling withmineral acids into carbonic anhydride and salts of the " oxybase."Cyanethine heated with acetic oxide a t 170" is converted intoacetylcycrnethiize, ( CgH13N2) .NH%, a crystalline compound melting a t59", and but sparingly soluble in water.Acetnmide, benzarnide, and acetanilide yield no ethyl carboxy-lntes when treated with ethyl chlorocarbonate.Quinoline yields thehydrochloride of ethylquinoline. P. P. B.Cystine. By E. KCLZ ( Z e d . BioZ., 20, 1-lo).-The author found5.33 per cent. H, as the mean of several analyses of pure crystallisedcystine, and consequently assigns the formula C,H6NSO2, insbead ofthe C,H,NSO, give11 by Hoppe-Seyler and others.C,H,NSO, = 5.00HQ=,H,NSOz = 5.78 H.The rotatory power when dissolved in a<mmonia is [ a ] j = - 1 4 2 O ,using a Jellet-Cornu apparatus ; Mauthner found -205-SS" ; thisdifference is, however, accounted for by the fact that Manthnerdissolved his crystals in hydrochloric acid.J. P. LORQSNIC CHEMISTRT. I41Prelparation of Pure Thiophene. By V. MEYBR (Ber., 17, 2641-2643) .-If in extracting thiophene from its mixture with benzenethe proportion of sulphuric acid be diminished, thiophene alone istaken up, and may be recovered in a state of purity by distilling thesulphonic acid. 2000 kilos. coal-bar benzene were treated with100 kilos. sulphuric acid, the product converted into lead salt, andthis distilled with ammonium chloride. The amount of thiopheneobtained was 1944 grams. The acid layer obtained after shaking withsulphuric acid should be a t once diluted with water to prevent car-bonisation.To obtain 100 per cent. thiophene, 400 kilos. benzeneare agitated for two hours with 16 kilos. sulphuric acid, the productconverted into the lead salt, then into the ammonium salt, and t,hissubmitted to distillation. A. K. M.Nitration of Thiophene. By V. MEYER and 0. STADLER (Ber.,17, 2648-2650).-The nitration of thiophene may be effected bypassing air saturated with its vapour through fuming nitric acid,when after some hours the liquid separates into two layers. Onpouring the product into water, a heavy oil separates. The mono-and di-nitrothiophene obtained may be separated either by steam dis.tiilaCion or by fractional distillat'ion. 1Clouzonitrothio~heIze, CaHsS.NOz,more closely resembles paranitrotoluene than nitrobenzene ; it is of apale yellow colour, solidifies in large prisms after fusion, has an odmrlike that of bitter almond oil; it melts at 44", boils a t 224-285"(corr.), and becomes red on exposure to light. It is insoluble inalkalis, and is converted by nitric acid into dinitrothiophene. Nitro-thiophene gives no reaction wit,h isatin and sulphuric acid.Dinifro-thiophene, CdH,S (NO,)?, crystallises from alcohol in yellow scales,moderately soluble in hot water, and is decomposed by alkalis with redcoloration. It melts at 52", is somewhat volatile in steam, and boilsat about 290" without much decomposition. Bfetadinjtrobenzene boilsat 297" (corr.). An isomeric dinitrothiophene is also obtained whichmelts a t 75-76', crystallises in needles, and is somewhat more vola-tile in steam.A. I(. M.Acetothienone and some of its Derivatives. By A. PETER(Bey., 17, 2613-2647).-Acetothze~one, C4H3S.COMe, is best preparedby the action of aluminium chloride on a solution of 10 grams thio-phene (98 per cent. thiophene) and 9.1 gram3 acetic chloride in50 grams light petroleum. When the reaction is ended, the petro-leum is poured off, and the product warmed and poured into water.After purification, acetothiGnone is a colourless oil boiling a t 213.5"(corr.), and remaining liquid at -15"; it has an odour closelyresembling t,hat of acetophenone; its sp. gr. is 1.167 a t 24' When atrace of it is heated with isatin and sulphuric acid, it yields the indo-phenine-blue colour.Thit;nyZ?nethyZacetoziii~e, CaH3S.CMe : NOH,obtained from acetothiiinone and hydroxylamine, forms a whitecrystalline mass, melts a t about 110', and giyes no characteristic reac-tion with isatin and sulphuric acid. Acefotl~i~onepherzyZhlldraz.i~ze,CpH3S.CRfe N.NHPb, is prepared by heating an aqueous solution ofacetothiiinone, phenjlhydrazine hydrochloride, and sodic acetate, andVOL. XLYITI. 142 ABSTRACTS OF CHEMICAL PAPERS.crystalliaes from alcohol in clusters of bright yellow needles meltingat 96". On oxidising acetothihone with alkaline potassium perman-ganate solution, a thiopheuic acid, CdH3S.COOH, is obtained meltingat 124.5" ; it yields the indophenine colour-reaction with isatin andsulphnric acid.Its identity with a- or P-thiophenic acid is not yetestablished. By the nitration of acetothiihone at -go, two isomericmononitro-derivatives are obtained, one crystallising in long yellowfour-sided vitreous prisms melting a t 122*5", the other in smalllustrous scales melting at 86".Decomposition of Benzonitrile by Fuming Sulphuric Acid,By A. PINNER (J. yy. Chem., 30, 125--127).-A reply to Gumpert'sremarks (this vol., p. 52) on the preparation of cyanphenine. Theauthor shows that Gumpert emploved a method different from thatused by Klein and himself (Ber., 11, 764), and cites further experi-ments to show that cyanphenine is obtained on adding benzonitrile toa large excess of sulphuric acid.By W. STAEDEL (Anna7en, 225, 384-388).-The dinitrotoluene melting at 60" which the author obtained fromTiemann's dinitrotoluidine melting a t 168" (Annulen, 217, 205), isshown to have the constitution C6H,kLe(N0,), [Me : NO, : NO, =1 : 2 : 61 by the following facts. On reduction with ammonium sul-phide, the dinitrotoluene yields a nitrotoluidine melting a t 90".Phthalyl orthotoluide melting at.180" forms two isomeric nitro-pro-ducts, which are converted by the action of alcoholic ammonia intonitrotoluidines melting at 90" and 109" respectively. Nitrotohidine(melting at 90') from dinitrotoluene (melting a t 60"), or fromphthalylorthotoluide, can be converted into orthonitrotoluene, and thenitrotoluidine melting at log", from phthalyl orthotoluide, yieldsparanitrotoiuene. The constitution of the following bodies has nowbeen ascertained.A.R. M.P. P. B.Dinitrotoluene.M. p.Trinitrotoluene.. 81" C6H,MeN0,N0,N0, 1 : 2 : 4 : 6Dinitrotoluidine . 168 C,H,h!feNO,NH,NO, 1 : 2 : 4 : 6Dinitrotoluene. . . 60 C6H,MeNo2NO, 1 : 2 : 6Nitrotohidine . . . 90 C6H,&!eNH2No2 1 : 2 : 6>, . . . 109 C6H3MeNH,N02 1 : 2 : 4 w. c. w.Brorno-substitution Derivatives of Orthoxylene. By 0.JACOBSEN (Bey., 17, 2372-2379).-The only halogen derivatives oforthoxylene previously described are those in which substitutionoccurs in the side-chains ; the present paper describes bromine de-rivatives obtained by bromination in the cold in which substitutionoccurs in the benzene-ring.Monobl.omorthoxyZene, C6H3MeMeBr [l : 2 : 41 is obtained by theaction of bromine in presence of iodine cn commercial orthoxylenein the cold, but is contaminated with bromoparaxylerie and bromo-metaxylene.I t s purification is effected by conversion into the sul-phonic acids and crystallisation of the barium salts, when the ortho-derivative separates in large crystals, and is readily separatedmechanically f porn the meta- and para-salts. Monobromoxylene iORGANIC CHEXISTRT. 143regencrated from the barium sulphonate by converting it into thesodium salt and heating this with concentrated hydrochloric acid at200". It is liquid, but solidifies below 0" to a fibrous crystalline mass,melts at-0.2", boils a t 214.5 under 760 mm. pressure, and has a sp. gr. of15" 1.3693 at -0, Heated with ethyl chlorocarbonate and sodium amal-15gam, it is converted into paraxylic acid, showing that the bromine isi n the para-position.Bromorthoxy Zenesulpphonic acid,C6HzBrM'e2.SO:3H + xH20 [Me : Rr : Me : SO,H = 1 : 2 : 4 : 51,is obtained by dissolving bromorthoxylene in weak Nordhausen sul-phuric acid ; it forms a fibrous crystalline mass, very readily solublein water, very sparingly soluble in cold dilute sulphuric acid.Itsconstit,ution is shown by the action of sodium amalgam on the sodiumsalt, when it yields sodium orthoxylene sulphonate [l : 2 : 51, Thehccrium salt, ( CsH2BrMe2.S03)2Ba + 3&0, crystallises in long hardprisms, and is very sparingly soluble in cold water. The sodium salt,CeH8Br.S03Na + 1&H20, crystallises in very long, slender needles, spar-ingly soluble in cold, very readily soluble in hot water.The potassiwnsalf, CpHeBr.SO,K + H20, forms thin glassy prisms, moderatelysoluble in cold water. By fusion with potash, the sulphonic acid issplit up into a variety of products, of which the only one that could beisolated was p-metabromosalicylic acid, and this only in very minutequantity.Bromorthoxyleneszc~honamide, CRH8Rr.SO2NH2, crystallises in longhairlike needles, melts a t 213", is sparingly soluble in water and coldalcohol, moderately soluble in hot alcohol.Broniorthotoluic acid, C,H,MeBr.COOH [Me : COOH : Br = 1 : 2 : 41,is prepared hy boiling bromorthoxylene with dilute nitric acid (1 : 5)in a reflux apparatus. It crystallises in stellate groups of needles,melts a t 174-176", is sparingly soluble in cold, readily soluble in hotwater, soluble in alcohol.The calcium salt cr.ystallises with 2 mols.HzO in small hard prisms. When fused with potash, the acid yieldsparahomometahydroxybenzoic acid.Dibromortho~yZenes.-By the action of bromine on pure bromortho-xylene in presence of iodine, two dibromo-compounds are formed, andcan be separated by crydallisation from alcohol, one only being solidat ordinary temperatures.Solid dibron~orthoxylene, C6H2MeMeBrBr [ 1 : 2 : 4 : 51, is formed inby far the largest quantity ; it crystallises in large rhombic tables orlong needles, is sparingly soluble in cold, readily in hot alcohol andhot glacial acetic acid, melts at 88", sublimes slowly a t a little abovethe melting point in large thin plates, and boils a t 278".Heatedwith methyl iodide and sodium, it yields durene together with somepseudocumene and regenerated orthoxylene.Liquid dibromorthoxylene,C6H2Me2Br2 [Me : Me : Rr : Br=l : 2 : 3(?) : 41,solidifies on cooling to a hard crystalline mass, melts a t + 6-8", boilsat 277", and has a sp. gr. of 1.7842 a t E " The endeavour to deter- 1 5 '1 144 ABSTRACTS OF CHEMICAL PAPERS.mine its constitution by replacing bromine by methyl groups did notlead to satisfactory results ; the action could only be started by re-peated additions of ethyl acetate, but much orthoxylene was thenregenerated ; neither isodurene nor pseudocumene were formed. Itis probable that this compound corresponds with the still unknown[l : 2 : 3 : 41 tetramethylbenzene.All attempts to prepare a pure tribromorthoxylene were unsuccess-ful, although by the action of bromine on solid dibromorthoxylene inpresence of iodine and a little glacial acetic acid a very small quantityof a substance crystallising in needles and melting a t 50-60" wasobtained ; this appeared to he an impure tribromo-derivative.Theend-product of the action of bromine on orthoxylene in the cold istetrabromorthoxylene, C,Me2Br4. I t crystallises in long needles, meltsat 262", and distils unchanged a t a very high temperature, is sparinglysoluble even in boiling alcohol, but is readily soluble in hob benzene.Jlercury diorthoxylena, ~~e~~eC6H,.Hg.C6R*~feMe, is obtained asa bye-product in the action of sodium amalgam and ethyl chloro-Carbonate on bromorthoxy lene.It crystallises in long, slenderneedles, melts a t 150," can be in great part distilled unchanged bycareful heating, and is sparingly soluble in ether and alcohol, readilyin chloroform, carbon bisulphide, benzene, &c.Pure monobromoparaxylene does not solidify a t -15", and boils a t205.5" under 755 mm. pressure. This differs from the figures givenby Jannasch (this Journal, 1874, 465) of + loo f o r the melting point,and 199*5-200*5" for the boiling point, but is in agreement with theearlier statement of Fittig and Jannsscli ( A n o ~ a l e i ~ , 151, 283).1 2 4 1 2Bromopa raxy lenesu Zpho7~ic acid,C6HzMezBr.80,H [Me : Me : BP : S0,H = 1 : 4 : 2 : ?I,crystallises in nacreous plates or flat needles.The sodium salt,C8H,Br.S0,Na + H20, crystallises in long thin prisnis or in rhombicor hexagonal tables. The buriu:rz salt cr~stallises in thin hexagonalplates, or small prisms, and is sparingly soluble i n hot water.B r o ~ ~ o ~ ~ u r a x ~ l e n e s z i l ~ h o n a ~ z i ~ ~ e , C6H2~~e2Br.SOzKH2, crystallises inflat prisms, inelts a t 806", is sparingly soluble in cold, readily solublein hot water. A. J. G.Nitro- and Amido-derivatives of Metaxylene. By E.GREVINGK (Ber., 17, 2422-2431) .-Cousecutive nzetacli.1Lits.ometax~le?~e,C6&&fez(N02)2 [bxe : NOz : Me : NO, = 1 : 2 : 3 : 41, is obtainedtogether with the symmetrical dinitrometnxylene melting a t 93" pre-viously described by Fittig ( A n n a l e n , 147,17, and 148,5), by treatingmetaxylene with a mixture of sulphuric and nitric acids a t a tempe-rature of 3-6".It crystailises in plntes, melts a t 82", and is morereadily soluble in alcohol and glacial acetic acid than the other modifi-cation. On nitration, hoth the diuitro-compounds are converted intothe trinitrometaxylene [Me : NO, : Me : NOz : NO, = 1 : 2 : 3 : 4 : 61,melting a t 176", described by Fittig ( h e . cit.).Consc~ci~tive ~netanitroxylt'dinr, C,W,Me,(NH,) .NOZ, is obtained by thereduction of consecutive disitrometaxylene with hydrogen sulphidORGANIC CHEMISTRY. 145in alcoholic ammcmiacal solut'ion. It crystallises in golden-yellowneedles, melts at 78", and is soluble in water, alcohol, and lightpetroleum. The acetyl derivative crystallises in white needles andmelts a t 149".The acetyl derivative prepared from the nitroxylidineof melting point 123", derived freom symmetrical dinitrometaxylene,also crptallises in white needles, but melts at 159-160".Symmetrical metadiamidometaxylene,C6H,Me,(NH2), [Me : Me : NH, : NH2 = 1 : 3 : 4 : 61,is prepared by reduction of tLe corresponding nitroxylidine (meltinga t l23?) with stannous chloride and hydrochloric acid. Afterbeiiig purified by sublimation, it forms snow-white crystals, andmelts at 104". The hydrochloride yields Bismarck brown withsodium nitrate, and a chryso'idine with diazobenzene chloride, showingthe base to be a metadiamine.Consecutice metCLdiamidonaetaxy Zen e,C6H2Me2(NH,), [Me : NH, : Me : NH2 = 1 : 2 : 3 : 4:.The reduction of 1 : 2 : 3 : 4 nitroxglidine cannot be effected bystannous chloride, tin and hydrochloric acid have therefore to be used.The diamine forms fine white crystals, and gives the colour reactionsof a metadiamine.Triumidometaxylerte, C6HMe2(NH,)3 [Me : NH, : Me : NH, : NH, =1 : 2 : 3 : 4 : 61, prepared from the corresponding trinitro-compoundby reduction with stannous chloride and hydrochloric acid, crystallisesin white needles ; its melting point could not be determined ; it doesnot melt up to 140", and suffers complete decomposition between140" and 150".The hydrochloride gives a greenish-brown colorationwith sodium nitrite, and a reddish-black coloration with diazo-benzene chloride.By the nitration of 1 : 3 : 4 metaxylidire, the two nitrometaxyli-clines already mentioned, melting at 78" and 123" respectively,were obtained.By treatment with ethyl nitrite, &c., to eliminatethe amido-group, the nitrometaxylidine of melting point 123" wasconverted into the nitrometaxylene [Me : Me : NO, = 1 : 3 : 41,boiling at 245.5" under 744 mm. pressure, and of sp. gr. 1.135 a t 15",already described by Tawildaroff ( Z e i t . f. Chenz., 1870, 418), andHarmsen (Abstr., 1881, 49); this by reduction with iroc and aceticacid, gave the unsymmetrical metaxylidine described by Hofmann(this Journal, 187i, i, 92) and Schmitz (Abstr., 1879, 156). 1 : 3 : 4aceto-xylide €orms white crystals and melts a t 128".Consecutice nitrometnxylene, C~H&~,.NOZ [Me : NO, : Me = 1 : 2 : 31,is prepared by the action of ethyl nitrite, &c., on the nitroxylidinemelting a t r8".It boils a t 225" under 774 mm. pressure, and has as . gr. of 1.112 a t 15". Reduced with iron and acetic acid, it givest i e consecutive metaxylidine described by Schmitz. 1 : 3 : 2 aceto-xylide crystallises in white needles and melts at 174".Action of Chlorine, Bromine, and Iodine on Sodium Para-cresolate. By C. SCHALL and C. DRALLE (Bas., 17, 2528-2536).-I . Action of ChEorinc.-When chlorine is passed through anhydroussodium paracresolate suspended in carbon bisulphide, the principalA. J. G146 ABSTRACTS OF CHEMICAL PAPERS.product is monochloroparlncresoZ, C6H,MeCl.0H. This compoundyields no sulphonic acid, whilst paracresol yields an ortho-sulphonicacid, so that the chlorine atom is probably in the ortho-position to theOH group.This was proved by treating it with phosphoric chloride,when a dichlorotoluene melting at 200" was formed, which on oxida-tion yielded orthodichlorobenzoic acid. Its constitution is therefore[OH : C1 : Me = 1 : 2 : 41. When the sodium salt of ihis substanceis treated with methyl iodide, i t Fields monochloro~a.mcresZl1 methylether, a colourless, feebly refracting liquid which boils at 213-215",and has a sp. gr. of 1.1493 a t 2.425" compared with water a t the sametemperature. This aniso'il when carefully oxidised with chromic acidyields monochloranisic acid, OMe.C6H,C1.COOH, which crystallises inwhite silky scales melting at 214-215". The barium salt crystalliseswith 3 i mols. H,O : the silver salt forms sparingly soluble scales.11.Action qf Bronziize.-This is similar to that of cblorine. Nono-brornoparacresol is a colourless liquid boiling at 213-214" ; its sp. gr.is 1.5468 a t 24.5". This compound is isomeric with that obtained byVogt and Henninger (Abstr., 1882, 729) by the direct bromination ofparacres0.l. Il.;ronobro?noparacresyl methyl ether boils at 225-227", andhas a sp. gr. of 1.4182 a t 24.5". ikIo?zobronaanisic acid crystallises inneedles melting a t 21.3-214" ; its baliunz salt forms small needles con-taining 3-&H20 : the silver salt is a flocculent amorphous precipitate ;the copper salt crystallises in green plates with 2$ mols. H,O.A small quantity of dibromoparucresql was also formed during theaction of the bromine on sodium paracresolate.This substance formsprisms belonging to the asymmetric system, and isomorphous withthose of dichloroparacresol. Dibromoparacresyl benzoate crystallisesin snow-white needles melting at 91-91-5". The dibromide was alsocoiiverted into the anisoil, but all attempts to oxidise this provedfutile.111. Action of Iodine.-This was similar to that of chlorine andbromine. As the authors were not able to isolate the moniodo-paracresol i t was converted into the methyl ether. Moniodopara-cresyl inethyl ether boils at 237-238". ilfoniodoanisic acid is identicalwith that already described by Griess (Annalen, 117, 54) and byPetzer (AnnadeN, 146, 302), a i d melts a t 234-235'.DiidoparacresoZ forms white plates melting a t 61-61 *5".Diiodo-parawesyl acetate forms white plates melting at 62-62-5". Diiodo-pamcresyl benzoate melts at 129*5-130".Saponification of Halo'id Ethers of the Benzene Series byNeutral Substances. By A. COLSON (Compt. rend., 99, 801-804).-The dibrominated derivatives of the three xylene glycols wereheated with 2 mols. H23 in sealed tubes at loo", and the rate andlimit of saponification were determined by estimating the amount ofacid liberated. The maximum limit of saponification is reached morerapidly than in the case of the corresponding compounds in themethane series, and is the same for all three isomerides, and probablyalso for their homologues. The isomerides are, however, distinguishedby the velocity of saponification, which is highest for the para- andlowest for the meta- derivative.I n the case of the dibrominatedL. T. TORGANIC CHEMISTRY. 147derivatives, the amount of acid liberated is only about 9 per cent. ofthe total acid, but as soon as this proportion is exceeded, the com-pounds rapidly decompose.When the dibrominated derivatives are mixed with an equal weightof ordinary alcohol, and allowed to remain for several days at 30-32",it is found that they are more rapidly attacked by the alcohol thanthe corresponding primary compounds in the methane series. Therate of snponification is highest for the meta- and lowest for the para-derivative, and this also holds good a t 100".If the haloi'd derivatives are heated with 2 molecular proportions ofamyl alcohol in sealed tubes at, loo", it is found that the brominatedderivatives decompose more rapidly than the chlorinated derivatives,whilst in each series decomposition ceases when about the same quan-tity of acid (about 5 per cent.of the total amount) has beenliberated. The meta-derivative is almost completely decomposed,although only a small quantity of acid is set free. This result isexplained by the fornia-ion of (?) bromamyline, CH,Br.C6H+OC5Hll.I t is evident that sitice the haloyd ethers are sensibly attacked byalcohol in the cold, and rapidly a t loo", this solrent should beavoided when working with these compounds.The ethers of the methane series acting on these haloid derivativesof the benzene series yield only one series of compounds, as shown inthe equation-C5H4(CH2Br), + Et,O = C6H4(CH2.0Et), + 2CLH5Rr.C.H. B.Conversion of Phenols into Amines. By K. BUCH (Rer., 17,2634-2641) .-Phenylparatolylamine is formed from phenol and para-toluidine, and from paracresol and aniline, by heating them with anexcess of zinc chloride a t 260-300"; also in very small quantity byheating phenol and paratoluidine with calcium chloride a t 300". Abetter yield is obtained by the action of antimony trichloride on amixture of aniline and paracresol a t 260", diphenylamine being, how-ever, also produced. When paratoluidine and phenol are heated withphosphoric anhydride, ditolylamine is obtained, but no phenyltolyl-amine. Paratoluidirie is produced on heating paracresol with ammo-nio-zinc chloride at or above 300O; ditolyl oxide, (CiH7)20, is alsoformed.This is moderately soluble in alcohol, and crystallises fromit in silky scales, and fram light petroleum in needles; it melts at165" and volatilises a t 100". Ditolyl oxide is also formed whenparacresol or a mixture of paracresol and paratoluidine is heated withzinc chloride. Diphen ylanzine is obtained in small quantity by theaction of calcium chloride at 300" on aniline and phenol. It is alsoproduced by the action of antimony tricbloride on aniline, but a muchbetter yield is obtained when a mixture of aniline and phenol isemployed . A. K. 51.The Action of Cyanogen Chloride on Ortho- and Para.amidopheneto'il. By J. BERLINERBLAU ( J .pr. Chent., 30, 97-115).--By the action of cj-anogen chloride on aniline, cyananilide an148 ABSTRACTS OF CHENICAL PAPERS.diphenylgunnidine are produced (Hofmann) ; its action on ortho- andpara-amidophenetoyl in ethereal solution is now studied and shown tobe similar. Orthoethoxyphen,ylc~janamide, EtO.C,H,.NHCN, formscrystals melting a t 94", almost insoluble in water, and which do notpolymerise on keeping or heating. If heated with hydrochloric acidat 1 2'uo, it does not yield orthoxyphenylcyanamide, but orthnmido-phenol ; when treated in ethereal solution with dry hydrochloric acid,a syrup separates out unsuited for further examination. When treatedwith sodium nlcoholate, the crystalline and stable sodium salt,E t0.c6Hi.NNaCN, separates, which is reconverted into the originalcyanamide by the action of acids : no polymerisation occiurs.Withsilver nitrate, an aqueous solution of this salt gives a curdy pre-cipitate of the siZver salt, Et0.CsH4.NAgCN. The behaviour of thesesalts with ethyl iodide and also with iodine was partially studied.This and the following silver salt are readily decomposed by sul-phuretted hydrogen, but no polymerisation takes place as with silvercyanamide.ParaethoxyphestyIcyanamiae melts at 78" ; only its silver salt couldbe obtained. Once crystals melting a t 160" were obtained: con-taining 1 mol. H,O more ; they are paraethoxypher/ylca~ban~ide,Et0.C6H4.NH.CONH2. This substance can also be prepared bymixing solutions of the hydrochloride of para-amidophenetoil withpotassium cyanate; it is almost insoluble in water; i t is not con-verted into the cyanamide or in any way altered by phosphoric anhy-dride.Treated for a long time with nitrous acid in alcoholic solution,a red precipitate, C9HllN202.N02, separates; if the acid acts for a8hort time only, an intermediate substance is formed insoluble inwater, but decomposing very rapidly.These substituted cyanamides can also be obtained from the corre-sponding thiocarbamid es.Orthoethoxy~henylthiocarbamide.-Orth,zmidophenetoi'l ie evaporatedwith ammonium thiocyanate, and the residue washed with water. Itmelts at 110". Mixed with lead hydroxide and dilute caustic soda,the lead sulphide filtered off, and acetic acid added, the above-described orthoethoxyphenylcjanamide seperates.Paraethoayphenylthiocarbamide was likewise prepared and con-verted into the corresponding cyanamide.A Lakmo'id.By M. C. TRAUB and C. HOCK (Ber., 17, 2615-2617).-W hen a mixture of resorcinol (100 parts), sodium nitrite( 5 parts), and water (5 parts), is gradually heated to l l O o , a briskreaction sets in and the mass assumes a red colour; when ther*eaction becomes less vigorous the heat may be raised to 115-120" ;ammonia is then abundantly evolved whilst the melt becomes reddish-violet, bluish-violet, and finally blue. The product yields a blue solu-tion with water, and on the addition of hydrochloric acid a precipitateis obtained ; this, when dried, forms lustrous reddish-brown grainsinsoluble in chloroform and benzene, but readily soluble in alcohol,acetone, &c., less so in ether and pure water ; these solutions have ared colour which resembles that of many red wines or raspberry-juice,and is changed to blue by the addition of a trace of alkali. Thifi dyea.BORGANIC CHEMISTRY. 149also dissolve^ in boiling concentrated hydrochloric acid, yieldinga bluish-peen solution, and in concentrated sulphuric acid to a deep-blue solution. The absorption-spectrum of the alkaline solutionresembles that of litmus, but the absorption-band is not so strong. Italso resembles litmus in its behaviour on reduction, the alkaline solu-tion being rapidly decolorised by hydrogen sulphide, but the colouris restored on exposure to the air. The authors hope to prove theidentity of this artificial colouring matter with the chief constituent oflitmus.A. K. M.Substitution of the Amido-group in Aromatic Derivatives byChlorine, Bromine, and Cyanogen. By T. SANDMIEYER (Ber., 17,2650-26.53) .-This is it continnation of experiments recently de-scribed (Abstr., 1884, 1311). I n order t o convert mefanitranilineinto metachloronitrobenzene, 4 grams of the former together with7 grams concentrated hydrochloric acid (sp. gr. 1-17'), 100 gramswater, and 20 grams of a 10 per cent. solution of cuprous chloride, areheated nearly to boiling and then a solution of 2.5 grams sodium nitritein 20 grams water is added drop by drop. I n the same way, para-clilorotoluene has been obtained from paratoluidine, orthochlorotoluenefrom orthotoluidine, and orthochlorophenol from orthamidophenol,but in the case of the two ortho-derivatives the yield is small.Para-phenylenediamine and met'aphenylenediamine also yield the corre-sponding dic hlorobenzenes. To obtain bromobenzene from aniline,12.5 grams copper sulphate, 36 grams potassium bromide, 80 gramswater, 11 grams sulphuric acid (sp. gr. l*S), and 20 grams copperturnings are boiled together until the solution is nearly decolorised,9.3 grams aniline added, the whole again heated nearly to boiling, andthen a solution of 7 grams sodium nitrite in 40 grams water graduallydropped in. The product is distilled, washed with soda and water,extracted with ether, dried, and fractioned. The amido-group mayd s o be replaced by cyanogen: 28 grams of a 96 per cent. solution ofpotassium cyanide are added to a hot' solution of 25 grams coppersulphate in 150 grams water, the solution heated to about, go", and asolution of diazobenzene chloride gradually introduced.The whole isthen d i d l e d , the oil extracted with ether, washed with soda solutionand with dilute sulphuric acid, and then fractioned. The amount ofbenzonitrile boiling at 184" obtained is 63 per cent. of the theoreticalamount. A. K. 11.Action of Ethyl Chlorocarbonate on Paranitraniline. ByH. HAGER (Ber., 17, 26'Lri-'Ltj32).-Pal.anitroyhen?Jluretkane (phenyl-en~amnitrourethane), N O,.C,H,.NH.CI)OEt, is prepared by heatingparanitraniline (6 grams) with ethyl chlorocarbonate (6 grams) forabout three hours at 120-130".It is sparingly soluble in water,readily in alcohol, from which it crystallises in long, brown, silkyneedles melting at 129". The mother-liquors contain a very smallquantity of a crystalline compound of metallic lustre which impartsa blue colour to silk. Paramidophenqlurethane, obtained by reducingthe nitro-compound, is sparingly soluble in water, readily in benzene,from which it c~*ystallises in long, brown, transparent prisms meltinga t 71-72' ; with ferric chloride, it yields a green precipitate whic150 ABSTRACTS OF CHEMICAL PAPERS.at once turns black and is readily soluble in alcohol with violetcoloration. It does not yield a carbamide when heated. The hydro-chloride, C,H,,N20,,HC1, forms readily soluble colourless needles ; themercury compound, ( C,H,2N20~,HCl)4,HgC12, crystallises from a hydro-chloric acid solution in long violet needles ; the stannichloride,(C,H,2N202,HCl),,SnC&, forms colourless scales ; the platinochloride,(C,H,,,YZO,),,H,P~C~,, is a light brown precipitate, and is decomposedby boiling with water ; the sulphate, C,H,,N,O,,SO,H,, is readilysoluble and crystallises in concentrically grouped arborescent forms ;t b e oxalate, C9H1',N2O2,C2O4H2, crystallises in violet needles, verysparingly soluble in cold, readily i n hot water Parabeizxoylamido-phenylurethane (phenylenepara.miclobenxoylurethane),NH%.C6H4.NH.C00Et,is obtained on gradually adding a mixture of benzene and benzoicchloride to a cold solution of phenyleneparamidourethace in benzene.It is insoluble in water, sparingly soluble in alcohol, from which i tcrystallises in slender violet needles melting at 230" ; by the action ofnitric acid (sp.gr. 1*53@), a small quantity of a trinitro-derivative isobtained ; this melts at 210" and crystallises from alcohol in slenderyellow needles. When paramidophenylurethane hydrochloride andbenzoic chloride, in molecular proportions, are heated together at140-150°, a substance is obtained which appears to have the formulaN( C,H,.NHB<),.COOEt. It is insoluble in water, very sparinglysoluble in alcohol and glacial acetic acid, and crystallises in slendercolourless needles melting above 360". Orthoparar~initropheny2ure-thane, C,H,(NO,),.XH.COOEt, is obtained by the nitration of para-nitrophenylurethane in the cold.It melts at 110-lll", dissolvessparingly in hot water, more readily in alcohol, from which it crystal-lises in light brown needles. When its a,lcoholic solution is warmedwith potassium hydroxide, ammonia is given off and diorihoparadini-t~ophenylamine (tetranit,.od~henylamin~~, NH( C6HJNB04)2, is produced ;this melts at B O O , is sparingly soluble in alcohol, more readily in glacialacetic acid, crystallises from the former in reddish-brown scales, andfrom the latter in yellow needles and prisms; with caustic alkali,it yields a dark red solution, which gives off ammonia when heated.When orthoparadinitrophenylurethane is submitted to the action ofammonium sulphide, orthamido~ara?l,itrophenyluretl~ane,NH,. C6H3 (NOz) .NH.COOEt,is produced. This is very sparingly soluble in water, readily inalcohol, and crystallises in orange-red needles orl prisms melting at162" ; it is decomposed by dilute acids into alcohol and the carbamide-derivative, N02.C,H,< Na> CO. This is sparingly soluble in water,readily in alcohol, from which it crystauises in colourless needleswhich do not melt at 300" ; it is also readily soluble in cold alkali. Bythe action of tin and hJdrochioric acid on orthoparadinitrophenylure-thane, both nitro-groups are reduced, alcohol is eliminated, and the car-bamide-derivative, CeH3(NH,,IICI)<NH>C0,HCl, is obtained. ThisNHNORQANIC CHEMISTRY. 151is extremely soluble in water, less so in hydrochloric acid, from whichit crystallises in nodular groups of small violet needles.The zincdouble salt, C7H7N30, 2HC1, ZnC12, crystallises from hydrochloric acidin long, dense, graphite-like needles of metallic lustre. The platinicand mercuric: double salts decompose very readily. The picrate,C7H7N,0, C6H3N307, forms gweuish-yellow needles. A. K. M.Oxidation of Paratoluidine. By H. KLINGER and R. PITSCHKE(Ber., 17, 2439-2444) .-The oxidation of paratoluidine has beeninvestigated by Barsilowsky (Abstr., 1879, 237) who used an alkalinesolution of potassium ferricyanide, and by Perkin (Trans., 1880,546),using chromic acid. The same substance, of the empirical formulaC7H,N, was obtained by both observers, but was regarded by Barsi-lowsky as a polymerised azotoluene, whilst Perkin considered thatit was probably a triparatolylenetriamine, ( C7H,),N3H3 ; the authorshave tberefore re-examined the compound.The substance was pre-pared by oxidation of paratoluidine with an alkaline ferricyanidesolution, and its identity with that obtained by the other authorsdetermined hy crystallographic mea,surement. I t melts at 220-225"(216-220", Perkin ; 244---245", Barsilowsky). Its salts can be ob-tained by sha.king a solution of the base in benzene with diluteaqueous acids, as dark violet or iridescent crystalline precipitates ;they are partly decomposed by washing and drying. The hydrochlo-vide, C28H,8N,,:!HCl7 was obtained in a pure state, and then formslustrous, violet plates, readily soluble in water and alcohol with in-tense reddish-violet coloration ; on addition of alkalis, the base isliberated.By the action of stannous chloride followed by tin andhydrochloric acid on a solution of the base in alcohol and hydrochloricacid, it is converted into paratoluidine and a leuco-base, C21H33N3. Asparatoluidine is also formed by the action of hydrochloric acid on thebase, it appears most probable that the latter is an amido-aso-corn-pound of the formula c2,H,7(NHz).N2.C7H7.Parulewcotoluidine, CzIHz3N3, crystallises in thin, white plates, whichvery soon turn red; it melts at 150", is very readily soluble in coldalcohol or in hot water or hot aqueous soda. The hydrochloride,C21H23N3,3HC1 + H20, forms colourless prisms or slender needles.Parurosatoluidine is prepared by oxidation of the leuco-base by acurrent of air, or more conveniently from the hydrochloride by the actionof a strongly alkaline f erricy anide solution.It crystallises in reddish-brown plates having a green lustre, melts at 150", and is decomposedat higher temperatures with formation of ammonia and toluidine. Itis readily soluble in alcohol, ether, and benzene, and dissolves in con-centrat'ed sulphuric acid with purple-red colour. A. J. G.Two Isomeric Isobutylorthamidotoluenes. By J. EFFRONT(Ber., 17, 2317--2351).-The author has already shown trhat anisobutylorthamidotoluene is obtained by heating orthotoluidinehydrochloride with isobutyl alcohol at 300" differing from thatprepared by Erhardt (Inaug. Diss., Zurich, 1882) by heating isobutylalcohol and orthotoluidine with zinc chloride.This latter substanc152 ABSTRACTS Of! CHEMICAL PAPERS.has ths constitution [Me : BUS : NH, = 1 : 3 : 21, whilst the baseobtained by the author is expressed by [Me : Bus: NH, = 1 : 5 : 21.5 . 2 ISOBUTYLORTHAMIDOTOLUENE, CsH,MeBup.NH2 [ 1 : 5 : 21, obtainedas above mentioned, forms a nearly colourless liquid of agreeablearomatic odour, which turns yellow on exposure to light, does notsolidify in a mixture of ice and salt, boils a t 243", and readily distilswith steam. It is nearly insoluble in water, but mixes in every pro-portion with alcohol and ether, and forms well characterised salts.The hydrochZoride, CIlHl7N,HCI, crystallises in long, thin needles. Itis sparingly soluble in cold, readily soluble in hot water.By longboiling of its aqueous solution, the salt suffers dissociation. Thehydrobromide, CllHliNJHBr, crystallises in long needles. The sulphate,(C,,H,7N)2,H,SOa, crystallises in white needles, sparingly soluble incold water. The ozalnte, ( Cl,H17N)2,H2Cz04, crystallises in silveneedles readily soluble in hot water, alcohol, and ether. The acety?derivative, C6H,MeBup.NH&, crystallises in greyish-white plates,melts at 162", is sparingly soluble in hot water, readily soluble inalcohol. The benzoyl-deramtive, C6H3MeBu@.NHE, forms small whiteneedles, melts a t 168", and is sparingly soluble in hot water or coldalcohol.I~obut,ylorthocresol, C6H3NeBuP.0H [l : 5 : 21, prepared by means ofthe diazo reaction from the amine, is a thick, pale-ycllow liquid offaint aromatic odour, sparingly soluble in water, readily soluble inalcohol, ether, and dilute aqueous soda.I.cobuf?llorthiodotolue7le, C6H,hfeBupI [l : 5 : 21, prepared by the actionof hydriodic acid on the crude solution of the diazo-cliloride, formslong white needles, melts at 34-35', and boils at 264-265".Byoxidation with chromic acid, it is completely oxidised ; by heatingwith dilute nitric acid, it is oxidised to nitrotolylisobutyric acid, orby further action it is converted into nitrotolylpropionic acid.NitrotolylisoSutyric acid,C6H,Me(N0,).CH2.CHMe.COOH [Me : NO, : C4H70, = 1 : 2 : 51,cryst'allises in white needles, melts at 139O, can be sublimed, issparingly soluble in cold, readily soluble in boiling water, sparinglysoluble in light petroleum, readily soluble in alcohol and ether.Thesilver salt, C,H,,(N02) .COOAg, crystallises in coloiirless plates, andis readily soluble in hot water.Nit rototy lpropiouic acid, Cti H,Me (NO,). CH,. CH,. C OOH, crystal lisesin thick white needles, meIts between 130-136", and is less solublein boiling water than the preceding acid.Experiments to convert isobu tylorthamidotoluene into the hydro-carbon by the action of ethyl nitrite were not auccessful. It wastherefore converted into the azo-chloride, and this treated withstannous chloride, when a hydrocarbon was obtained agreeing in allparticulars with Kelbe's metaisobutyltoluene (Abstr., 1881, 809).ToZyZpropionic acid, C6H&fe.CH2.CH2.COOH (Me : C3H502 = 1 : 31,is obtained by heating metaisobutyltoluene with excess of nitric acid(sp.gr. 1-15) for five hours a t 180", it crystallises in white needles,melts at 125", and sublimes readily. It is scarcely soluble in cold,sparingly soluble in hot water, readily soluble in alcohol and etherORGANIC CHEXISTRY. 153The silvelr salt, C9H11.COOAg, is crystalline, sparingly soluble incold, readily soluble in hot water. On oxidation, the acid is convertedinto isopht'halic acid.Isobutylorthoformotohide, C,H,MeBup.NH.CHO [I : 5 : 21, is obtainedby heating isobutylorthamidotoluene with formic acid at 250" ; itcrystallises in coiourless tables, melts at 105-106", is sparinglysoluble in hot water, readily soluble in alcohol and ether.I f heatedwith excess of zinc-dust, it is converted into isobutzJlorthotolunit1.ile7C6H3MeBup.CN. This crystallises in long, white needles, melts a t59-60", boils a t 248--249", is readily soluble in alcohol and ether,sparingly soluble in light petroleum, and insoluble in water. IsobutyZ-orthotoluic acid, ~ , H 3 M e ~ u ~ . c o 0 H [l : 5 : 21, is obtained, althoughwith difficulty, by the actiori of alcoholic potash on the nitrile; i t crys-tallises in white needles, melts a t 140", is sparingly soluble in hot water,readily soluble in alcohol and ether. The silver salt forms colourlessplates of the formula C,,H,,.COOAg. By oxidation with dilute nitricacid at 240', it is converted into krimellitic acid, thus showing theparent isobutylorthamidotoluene to have the constitution[Me: Bus :NH2 = 1 : 5 : 21.Di-ortjllotoluisobuty Zthiocarbamide, C S (NH.C,H&f eBup)2, prepared byheating an alcoholic solution of isobutylorthamidotoluene with excessof carbon bisulphide, crystallises in long, thin, silky needles ; melts at184"; is sparingly soluble i n hot alcohol, readily soluble in ether.O~thotoluisobutyltliiocarbinzide, C,H,MeBuP.NCS, is obtained in smallquantity in the preparation of the thiocarbamide, but is best preparedby heating the thiocarbamide with syrupy phosphoric acid. It formslong needles, melts at 46", boils, with partial decomposition, a t275--280", and is sparingly soluble in light petroleum, readilysoluble in alcohol and ether. When heated with metallic copper, ityields isobutylorthotolunitrile.Dimeth~lorthotoluisobutylantine,CBH,MeBu@.NMe, [Me : Bus : NMe, = 1 : 5 : 21,prepared by heating isobutylorthamidotoluene with methyl iodideand decomposing the resulting ammonium iodide by digestion withsilver oxide, forms an oil of aromatic odour, boiling at 250-251".The hydrochloride is white and crystalline.The platinochloride,(N~~eaCl,H,,)z,HzPt~~6, forms a red crystalline mass.3 . 3 ISOBUTYLORTHAMIDOTOLUENE,C6H3&leBu@.NHz [Me : Bup : NH, = 1 : 3 : 21,was prepared according to Erhardt's method (Zoc. cit.) ; his descrip-tion of the properties and derivatives of the base is confirmed by theauthor. Couverted into the diazo-chloride, and treated with zincchloride, it also yields metaisobutyltoluene.As according to theoryonly two isobntylorthamidotoluenes can be derived from metaisobutyl-tolnene, and as the constitution 1 : 5 : 2 has been shown to belong tothe author's base, it follows that Erhardt's base must be the 1 : 3 : 2compound. The following derivatives were prepared by methods simi-lar to those employed for the corresponding derivatives of the 1 : 5 : 154 ABSTRACTS OF CHEMICAL PAPERS.base. Isobutylorthoformotoluide, C,H,MeBufl.NH:.CHO [ = 1 : 3 : 21,crystallises in white tables, melts a t 103-105", is nearly insoluble inwater, readily soluble in ether and alcohol. Issobuty Zorthotolunitrile,C6H,MeBug.CN [1 : 3 : 21, is a colourless oil, can be solidified in afreezing mixture, boils a t 242-244", and is readily soluble in alcoholand ether. IsobutyZorthotoluic acid, C6H,MeBufl.COOH [ 1 : 3 : 21,crystallises i n silvery plates, melts a t 132", is sparingly soluble inhot water, readily soluble in ether and alcohol.The silver salt,C1lH1,.COOAg, crystallises in colourless plates. 07:-o~fhotoluisobutyl-thiocarbamide, CS(NH.C6H3MeBuP),, crystallises in white needles,melts at 175", and is soluble in hot alcohol. Orthotolzcisobutylthio-carbimide, C6H,MeBu@NCS, forms a white crystalline mass, melts a t44", and boils a t 267". It was further converted into the correspond-ing nitrile and 1, 3, 2 isobutylorthotoluic acid. A. J. G.Derivatives of Benzoylpseudocumidine : Constitution ofPseudocumidine and Benzaniline. By E. FROEHLICH (Be?., 17,2673--2681).-1n a previous paper (Abstr., 1884, 1319), the authormentioned the formation of benz~,y~I~thalopseudocumidic acid,CGH,. COOH,as an intermediate product of the action of alcoholic potash on hen-zoylpb thalopseudocumide.J t is insoluble in water, and crystallisesfrom alcohol in colourless microscopic needles melting a t 195" withseparation of water; the substance, dried in a vacuum, contains1 mol. H,O.C,HMe,E.NHZ,is insoliible in water, sparingly soluble in alcohol, ether, and coldglacial acetic acid, and crystallises from the hot acid in large, colonr-less, lustrous needles, melting at 170". Attempts to prepare theisocyanide of benzoylcumiditie were unsuccessful, whilst the carbamideand thiocarbamide could not be obtRined in a crystalline form, butonly as resins.The urethane, C,HMe,Bz.NH.COOEt, crystallises fromdilute alcohol in slender, colourless, silky needles melting a t 105".Dimet hy Z benxo!j lpseud ocuni i d ine met hiodide, C6HMe3E .NMe,,MeI, crys-tallises in magnificent, broad, coloudess prisms which, when placed ina vacuum, lose water and fall to a powder; the substance then meltsa t 187" with decomposition. The author discusses the constitutionof pseudocnmidine, and shows that its formula isThe acetyl-derivative of benzoylpseudocumidine,C6H21fe3.NH, [Me : Me : Me : NH, = 1 : 3 : 4 : 61,the amido-group occupying the same position as the h ydroxyl-groupin pseudocumenol. It is evident from this formula that the benzoyl-group in benzoylpseudocumidine cannot occupy the para-posi tion tothe amido-group, and from the close relationship between benzoyl-pseudocumidine and benzoylaniline, it is also improbable that thislatter substance is a para-derivative, as assumed by Doebner (Awnaleti,210, 266).The author thinks that i t is more probably orthamido-benzophenone. Of the phtl al'c derivatives of the three toluidines,that from parntoluidine alone gives a crystalline benzoyl-compoundORGANIC CHEMISTRY. 155whilst the other two yield resinous products. Phthalorfhotoluide,C,H,MeN CBH40,, obtained by heating together orthotoluidine andpbthalic anhydride, is insoluble in water, sparingly soluble in alcoholand ether, readily in hot glacial acetic acid, from which i t crystallisesin colourless needles melting at 182"; i t is converted into phthnl-orthotoluidic acid when heated with alcoholic potash or ammonia.Phthalometatoluide i s insoluble in water, dissolves sparingly in alcoholand ether, readily in hot glacial acetic acid, and forms sniall colourlessneedles melting a t 153" ; it yields phthalometatoluidic acid whentreated with alcoholic potash o r ammonia.Pht7,aZo~aratoliiide meltsat 204" (according to Michael a t 200°, Ber., 10, 579), and is con-verted by alcoholic ammonia or potash into phthaloparatoluidic acid.When phthaloparatoluide (75 grams) and benzoic chloride (45 grams)are heated at 170--180" for 6 to 8 bours with a little zinc chloride,hydrochloric acid is evolved, and benzoylpTathaloparatoZuide,CsH,MeE.N : C8H1O2,is obtained, accompanied, however, by a second substance not Setisolated.Benzoylphthaloparatoluide melts at 202", is insoluble inwater, sparingly soluble in alcohol and. ether, and readily in hotglacial acetic acid, from which it separates in deiise, well-formed,tetragonal crystals. When heated with alcoholic potash, it is con-verted first into benzoylphthaloparatoluidic acid, and then into ayellow-coloured base. It also yields a yellow base (probably benzoyl-tolnidine) with concentrated sulphuric acid. The second substancementioned above appears to be an isomeric compound, C22H15N03, oflower melting point ; it also yields a yellow base when treated withconcentrated sulphuric acid.Derivatives of Parahydroxydiphenylarnine. By &I. PHILIPand A. CALM (Ber., 17, 2431-24=18).-A continnation of Calm'sresearches on this subject (Abst,r., 1884, 592).Para7z~droaydi~hen?/Z-amine hydrobronzide, CI2HlINO,HBr, prepared by the action of hyd1.o-bromic acid on a solution of the base in anhydrous benzene, crystallisesin pale rose-colonred needles, and is very unstable.~~tros~arahydrozyphenylanzine, OH.C6H4.NPh.N0, is prepared byadding sodium nitrite to a well-cooled solution of the base in hydro-chloric acid. It forms yellow crystalline plates, or needles, or redtables, melts at 95", and is readily soluble in benzene, alcohol, ether,glacial acetic acid, and light petroleum. It behaves as a nitrosamine,giving Liebermann's reaction.M e t h y l ~ n r a m e t h ~ y d ~ ~ ~ i e ~ ~ 7 a ~ ~ n e , OMe.C6H4.NMePh, is preparedby heating parahydroxydiphenylamine (1 mol.) with methyl iodide(2 mols.), potash (2 mols.), and a little methyl alcohol for two hours at120-130". It forms a pale yellow oil of violet-like odour, and boils a t313".It behaves like atertiary amine, and yields a green colouring matter when heated withzinc chloride and benzotrichloride.Eth y lparaet hox,ydiphen ylamine, OEt. C&Tu'PhEt, resembles themethyl- compound, and boils a t 31 8-320".Paraisobutox?/cl~lLenyZamiil.e, 0Bup.COHJTHPh. Although preparedA. K. M.It rapidly turns brown on exposure to air136 ABSTRACTS OE' CHENICAL PAPERS.in a manner similar to the compounds just described, only thehydroxylic hydrogen is replaced by isobutyl in this compound. Itforms pale yellow quadratic plateg, melts a t 68", and is readily solublein benzene, alcohol, ether, and light petroleum.For my 1 par ah y dr oxy d ipheyzy lamin e, 0 H.C6H4. N P h. CO 33, prepared byheating the base with sodium formate and excess of formic acid,cryatallises in white needles, melts a t 1 7 8 O , is soluble in ether, hotbenzene, and glacial acetic acid, readily soluble in hot alcohol.Diacetylparaoxydiphenylamine, OZ.CsH,.NPhAZ, prepared in asimilar manner to the formyl-compound, forms large colourless prismsterminated by pyramids, apparently of the rhornbic system, melts a tl20", and is readily soluble in hot benzene, alcohol, ether, and glacialacetic acid.L)ibensoy~paraoxydiphenytamine, oE.c6&.NPhE, prepared byheating the base with benzoic chloride, forms pale yellow, compact,prismatic crystals, melts a t 175", is sparingly soluble in cold, solublein hot alcohol, more readily soluble in glacial acetic acid, benzene,and ether.On nitration, it is converted into a didro-compound,C,,H,,N0,(K02)2, forming a pale yellow, crystalline mass, whichmelts a t 194-195", is readily soluble in hot glacial acetic acid,moderately soluble in ether and hot benzene, very sparingly solublein alcohol. It gives a red coloration with concentrated aqueous soda orpotash ; addition of hydrochloric acid to the alkaline solution causesthe formation of a reddish-brown flocculent precipitate.A. J. G.Action of Carbon Bisulphide on Metaphenylenediarnine.By P. Guccr (Ber., 17, 2656--2658).-When an alcoholic solution ofmetaphenylenediamine is heated with carbon bisulphide, the solutionbecomes red, and hydrogen sulphide is abundantly evolved ; thiscontinues for about eight hours, and as it ceases thin, red prismaticcrystals make their appearance.These are insoluble in water, alcohol,ether, carbon bisulphide and benzene, hut dissolve very readily inammonia, witli orange-yellow coloration, and separate out again onheating tlie solution t o 50-60". From the results obtained on analysis,this substance appears to be a thiocarbol.~ylpIienyle~ze~~aminethiocar-tonate, c,H4<,,>sc.s2c. When the mother-liquor from thesecrystals is warmed, hydrogen sulphide is again evolved, and ayellow amorphous substance gradually separates, which is insolublein water, alcohol, et'her, carbon bisulphide, benzene, and coldammonia.Its formula appears to be CZ0HmN6S2, so that it may bederived either From 1 mol. C,H4(N: CS), and 2 mols. phenylene-diamine, or from 3 mols. phenylenediamine and 2 mols. carbonbisulphide, in which latter case it wouid be a dithioccnrbo?ayZtr~ph(~n~Z-enedianz ine, NH,. C,H,.NH. S C. NH. C6&. NH. S C. NEE. C6&. NH2. Onpouring the mother-liquor from this into water, a third substance,CI2H1 3N,S,, is obtained as an abundant orange-yellow amorphousprecipitate, extremely soluble in alcohol.NHA. K. 141ORGANIC CHEMISTRY. 157Mixed Azo-compounds. By E. BAMBERGER (Ber., 17, 2415-2422>.-Ethyl orthonitrophenylazoacetoacetate,C6H4 ( NOz). Nz . C H E . C 0 OE t ,is prepared by dissolving 3 grams orthonitraniline in hydrochloricacid, cooling with a mixture of ice and salt, and adding a diluteaqueous solution of 1.5 grams of sodium nitrite ; after remaining for1 2 hours, the mixture is largely diluted with water, neutralisedwith soda, and a dilute solution of, ethyl acetoacetate (2.9 grams) andpotash (1.3 grams) added drop by drop.After adding a few dropsof soda, the mixture is allowed to remain for a day in a warmplace, when the new praduot separates as a hard crystalline crust. Itis obtained on recrystallisation in lustrous golden-yellow plates, meltsa t 92-93", is readily soluble in alcohol, ether, glacial acetic acid, andchloroform, and also soluble in hot water.0 r f h o nit ropheny Zazoacetoacetic acid, C,H,( NO,) .Nz.CH hc. C 0 OH, isprepared by heat;ing the ethyl salt on the water-bath with potash for1-2 minutes, the potash salt which separates then being decomposedby hydrochloric acid.' It crystallises in lustrous golden-brown platesresembling mosaic g d d ; when heated, it blackens a t 183" and meltsat 185" with evolution SF carbonic anhydride ; it is readily soluble inglacial acetic acid,.glycerol, and hot alcohol, sparingly soluble in etherand cold alcohol. The ammonium salt forms golden-yelluw needles,the lead salt ayellow .pwder, the copper salt is obtained in greenflocks,and the bm-ium salt crystallises in tufts of yellow needles.Orthonitropl~snyZnzouct:to~~e, C,H4( N02).N, CH,.COMe, is obtainedby heating the acid (best mixed with glycerol), by heating either thefree acid or the ethyl salt with potash or, best, as follows : an alcoholicsolution of orthonitraniline is treated with the nitrogen oxidesevolved by the action of nitric acid on arsenious anhydde, the pro-duct of the reaction is poured into water, filtered, and the filtratemixed with ethyl acetoacetate and potash, and tbe whole digested for15 minutes a t 40" The mixture of nitrophenylazoacetone and a littleethylic nitrophenylazoacetoacetate which is then precipitated, isheated for a few minutes with alcoholic potash and poured into a largevolume of water, when the ketone separates in voluminous yellowflocks and can be purified by crystallisation.It crjstallises in long,silky, sulphur-yellow needles, melts a t 123-124", and is soluble inall the ordinary solvents? but is insoluble in alkalis.Orthoarnidoazoacetic acid, C6H4(NH,).N,.CHG.COOH, obtained bythe reduction of the nitro-acid with ferrous siilphate and ammonia,crystallises in satiny orange-red tables, melts with decomposition atl57", is very readily soluble in gtacial acetic acid and chloroform,moderately soluble in ether, somewhat soluble in water. It is veryunstable.The corresponding members of the toluidine series were prepared bysimilar methods from metanitroparatoluidine.Metanitroto Z~Ziual.aaznaeetoacetic acid, C6H.3e( NO,). N?. C H Z . C 0 0 €3,crystallises in long yellow needles, melts a t licj", is readily soluble inglacial acetic acid, alcohol, and glycerol. It is converted into thocorresponding ketone by the action of heat or of alkalis.VOL.XLVI1:. 158 ABSTRACTS OF CHEMICAL PAPERS.MetanitrotoZy Ilparaazoacetone, C6H,Me(N0.L).N,.CH,,COMe, crystal-Metamidoparaazoacetoacefic acid, C,H3Me (NH,) .N2. CHZ. C 0 OH,lises in lustrous orange-red prisms and melts a t 134-1 34.5".forms brick-red needles and melts at 162". A. J. G.Action of Acetic Anhydride on Benzamidine. By A. PINNER(BcT., 17, 2511-2516).-The author has reinvestigated the bodyC,,H,,N,, described by himself and Klein (Abstr., 1878,491; 1883,1099;and 1884, 1324) in order to determine whether this or C9H,N, is its trueformula. If its composition were C9H8N2, it must have the constitu-tion C61-f,.C<N>cMe, and should then yield a carboxylic acid onoxidation : but neither permangsnate nor chromic acid has any actionon it.When bromine is added to a solution of the substance inchloroform, deep yellow needles are deposited which appear to be abromine additive product. This compound is, however, very unstable,and the analytical results obtained agree as well for C,H,N,Br, asfor C,,H,,N,Br,. When dissolved i n fuming nitric acid, the oiiginalsubstance yields a compound which gives numbers correspondingfairly well with the formula C,dH,(N02)aN,. The most conclusiveproof of the correctness of the formula C1,H1,N3, however, is theformation of a mmosdphonic acid, CIdH,,N3. SO,H, by dissolving theoriginal substance in fuming sulphuric acid. This acid crystallises innodules with $H,O, and loses its water of crystallisation a t 140", butis then partially decomposed. It forms a crystalline sodiu,m saZZRolulde in water ; the barium saZt crystallises with 1OH,O in glisteningscales, very spwingly soluble in water.When fused with potash, theacid yields parahydroxybenzoic acid. When heated a t 100" withconcentrated hydrochloric acid, the original substance deposits a com-pound in shining scales, which is decomposed on the addition ofwater into the previously described hydrochloride. When heatedwith twenty times its weight of hydrochloric acid in closed tubes atlOO", the original substance is decomposed into benzoic acid andammonium chloride.From these results, there can be no doubt that, the substancc isdibsnzimidine, NH : CPh.N CPh.NH,.The author also attempted to determine the molecular weight ofcganphenine by preparing its sulphonic acid.The acid obtained con-tained one S03H-group t o every seven carbon-atoms, and thus gaveno clue to the molecular weight.NL. T. T.Action of Ethyl Acetoacetate on the Amidines. By A.PIKNER (Ber., 17, 2519--2520).-Ethyl acetoacetate reacts extremelyreadily with the amidines, water and alcohol being eliminated.X . C < ~ ~ , + Me.CO.CH,.COOEt = R.C<E>C4H60 + H,O+ EtOH.The compounds formed have basic properties. and their constitution iORCIANIO 0HE;IIISTRY. 159N co- probably R.C<": CMe>CH2. By means of phosphoric chloride,&c., they may be converted into derivatives of the nucleus,Benzamidine and ethyl acetoacetate thus yield a compound,CllH,ON20,which crystallises in prisms melting a t 215.5-216", and is sparinglysoluble in ether.It dissolves easily in acids, and yields a sparinglysoluble pl atinochlorid el ( C,,H1oNZO) Z,H2Pt GI6 + H20. When heatedwith phosphoric chloride, the compound C11HlnN20 yields a substanceof the formula CllH9NZCl, melting a t 71". This body is soluble inether, insoluble in water, and crystallises in rhombic plates. Theconstitution of the chloride is probably CPheNi CMe> CH.Acetamidine when similarly treated yields a compound, C6H8N20,which forms long silky needles soluble in water, sparingly so in ether.The amidines also react easily with the cyanates and isothio-cyanates. The author is now investigating these reactions.N CCI-L. T.T.So-called Phthalylacetarnide. By W. ROSER (Ber., 17, 2623-2625)..-This compound is an acid, and therefore cannot have the con-stitution implied by the name which was given to it by Gabriel. Theauthor suggests t)he name plithalimidylacetic acid. The calcium saltcontains + mol. H20, and forms a white crystalline precipitate, almostinsoluble in water ; the barium salt is readily soluble in hot water andcrystallises in small prisms containing 2 mols. HzO ; the silver salt,C IoH603NAg, is insoluble and amorphous. When phthalimidylaceticacid is boiled with alkalis, ammonia is liberated and acetuphenone-carboxylic acid produced. Of the two formulz for phthalimidylaceticacid, GO< G$>C.CH2.COOH, and CO< kE4>C CH.COOH, thefirst is considered the more probable, for if the second formula werecorrect, the compound CO<&;>C : CH.COOH should be formedby the action of methylamine on phthalylacetic acid ; this, however,is not the case.Gabriel's phtbalylpropionamide is probably phthalimidylpropionicacid.By the action of sodium-amalgam on phthalimidylacetic acid inalkaline solution, a dark violet-coloured liquid is obtained whichyields an almost black precipitate on the addition of hydrochloric acid.By H.KOLBE (J. pr. Chem.,30, 124--125).--k former communication (this vol., p. 58) con-tains an account of the preparation of isatoic acid from isatin ; thisacid when boiled with concentrated hydrochloric acid is resolved intocarbonic anhydride and anthranilic acid.This decomposit'ion offers aconvenient method of preparing anthranilic acid.CH C HC HA. K. M.Preparation of Anthranilic Acid.P. P. B.'m160 ABSTRACTS OF OHEMICAL PAPERS.Betaines. By R. SILBERSTEIN (Rer., 17, 2660-2665) .-Whenphenxlbetalns hydrochloride is heated a t about lOO", it splits up intodimethylaniline, carbonic anhydride, and methyl chloride. Onheating ethylic phenylbetayne chloride, or a mixture of ethyl chlor-acetate and dimethylsniline at a temperature not exceeding 130°, thefollowing reactions take place :and NPhMe.CH,.COOEt + 2HC1= NPhMe.CH,.COOH,HCl + EtC1.The phenylmeth~Zg7ycocine h ydrochzoride, NPhMe.CH2.COOH,HC1, ob-tained, forms colourless prisms readily soluble in water, less so inalcohol, and very sparingly in cold concentrated hydrochloric acid.Itis decomposed by continued heating with water with evolution of car-bonic anhydride and formation of dimethyl aniline hydrochloride. Whena mixture of dimethylaniline (1 mol.) and chloracetamide (1 mol.)is digested in alcohol, and the solution, after concentration, precipi-tated with ether,.plier~?llbetnzneamide chloride, NPhMe,CI.CH2.CONH,,is obtained. This, heated to 110-120", yields methyl chloride andphenl~/~neth?~lgZycocineu~~~~~e, NPhMe.CH,.CONH,, which is sparinglyfioluble in cold, moderately in hot water and in alcohol, from which Itcryshliises in silky prisms or scales melting a t 163" ; it sublimeswhen carefully heated, but, on distillation, is decomposed into ammonia,dimethylaniline, and other products ; when boiled with alkalis, ityields pheny lmet h ylgl ycocine.Pheny lmet hy lgl y cocinearnide hy dyo-chloride forms colourless prisms, readily soluble in water, moresparingly in alcohol. Phenylmethylglycocineamide is also producedwhen methylaniline and chloracetamide are heated together, and thehot aqueous solution precipitated by ammonia.Whm dichloracetic acid is heated with dimethylaniline, it appa-rently breaks up into carbonic anhydride and dichloromethane, whilsttrichloracetic acid yields chloroform and carbonic anhydride. I n thelatter reaction, an intermediake product can be obtained (probablyNPhMe,Cl.CCl,. COOH).Diethylaniline and methyldiphenylamine when heated with chlor-acetamide yield neither ethylic nor methylic chloride.The abovereaction with trichloracetic acid, however, may be effected not onlyby means of dimethylaniline, but also by diethylaniline, methyldi-phenylamine, quinoline, and pyridine.NPhMe2C1.CH2.COOEt = NPhMe.CH,.COOEt -t MeCl,A. I(. M.Action of Benzaldehyde on Nitromethane and Nitro-ethane.Ry B. PRIEBS (A?/naZen, 225, 319-364).-The preparation of phenyl-witroethlylene, CHPh : CHNO,, by the action of nitromethane on benz-aldehyde in t'he presence of zinc chloride has been previouslydescribed by the author (Abstr., 1884, 313). The formation of thiscompound may serve as a reaction for the detection of nitromethane.For this purpose the dilute solution, supposed to contain nitro-methane, is mixed with sodium hydroxide, and well shaken with anexcess of benzaldehSde.The unaltered benzaldehyde is removed byextraction with ether, and a current of air is passed through thesolution to expel the last traces of ether. On adding dilute sulphuriORGANIC CHEMISTRY. 161acid, a crystalline precipitate of phenylnitroethylene indicates thepresence of nitromethane. Phenylnitroethylene is identical withSimon's nitrostyrene (AnnaZen, 31, 269). It may therefore be pre-pared by the action of nitric acid, or better, of nitrous anhydride on itcold ethereal solution of styrene. Phenylni troethane yields benzoicacid on oxidation. With nitrous acid, it exhibits the nitrolic acidreaction. At 85", sulphuric acid (diluted with one-third its volume ofwater) decomposes phenylnitroethane into hydroxylamine, benzalde-hyde, and carbonic oxide, and strong hydrochloric acid splits it upinto phenylchloracetic acid and hydroxylamine. On exposure to thelight, phenylnitroethylene undergoes a gradual transformation intoisophenylnitroethylene, which is deposited from alcohol in rhombicneedles or plates melting between 172" and 180".PhenyZrLitroethy Zenedibromide, CHBrPh.CHBr.N02, prepared by adding bromine to nsolution of pheuylnitroethylcne In carbon bisulphide, crystallisesin the monoclinic system, namely, in a combination of OP withcmP . cmP00 and Po0 ; ,B = 83" 54'; a : b : c = 1.2568 : 1 : 1.3960. Thecrjstals dissolve freely in chloroform, benzene, and carbon bisulphide,and are decomposed, by boiling with alcohol, into hydrobromic acidand phenylbromonitroethylene, CBrPh : CHNO,.'l'he latter com-pound is more easily prepared by the action of soda instea,d of alcohol.It crystallises in iridescent golden needles 01' plates which melta t 67".When chlorine is passed into a solution of phenylnitroethylenedissolved in chloroform, the dicldoride, CHClPh.CHC1 NO2, is ob-tained as a thick syrup, which crystallises with difficulty; thecrystals melt a t 30". Phen yZchZoronitroeth?yZene, CClPh : CHN02, isdeposited from light petroleum in golden piates or needles which melta t 48".On nitration, phenylnitroethylene yields two isomeric nitro-pro-ducts ; if the acid is cooled in a freezing mixture, the para-derivativeis mainly formed, but a t a temperature of 25" a considerable quantityof the ortho-derivative is prodnced.Parnnr'trophenyZ.r~itroet1~ y Zene, N02.C,H4.CH 1 CH.N02, has been pre-viously prepared by Priedlander and Miihly (Bsr., 16, 848), fromparanitrvcinnamic acid.It unites with bromine, forming a dibromidemelting a t 102"; this crjstallises in colourless plates, soluble inbenzene and in glacial acetic acid. The orthonitro-compound is muchmore soluble in alcohol and other solvents than the para-derivativeIt forms needle-shaped crystals melting a t 106", which turn brown onexposure to the light. The dibromide also crystallises in needlesmelting a t 9U", which dissolve freely in chloroform, beczene, and inhot acetic acid.CMe.N02, is prepared by the actionof zinc chloride on a mixture of benzaldehyde and nitroethane.Theyield is by no means so good as in the case of phenylnitroethylene, asbenzamide and resinous bye-products are also formed. Pheny initro-propylene resembles the ethylene compound in many of its prnperties.It readily crystallises in rhombic prisms which melt a t 64". It-yieldsbenzoic acid on oxidation, and is decomposed by boiling alkalis intobetzaldehjde and ni troet'hnne. The dibromide, CHBrPh.CBrMe.NOz,Phen yZnitrop*opyZene, CHP162 ABSTRACTS OF CHEMICAL PAPERS.forms transparent prisms which melt between 77" and 78.5". This com-pound is not decomposed by alkalis.YuI.aniti-~hen,~lnitro;uro~ylene forms yellow needle-shaped crystalswhich melt at 114". The orthonitro-product forms pale yellow plateswhich are much more soluble in alcohol than the para-compound.The crystals melt a t 76".w. c. w.Paracarvacrotic Aldehyde. By E. NORDMANN (Rer. 17, 2632-2634) .--This aldehyde is obtained from carvaurol together with somesecondary products, by means of the chloroform reaction. It crystal-lises in white, flat, silky scales, melts a t 96", is insoluble in cold,sparingly soluble in hot water, readily in alcohol, ether, benzene, andchloroform, also in dilute sulphuric acid with greenish-yellow colora-tion. It gives no characteristic colour with ferric chloride, and fromthis it is concluded that the group COH has taken up the para- andnot the: ortho-position in reference to the hydroxgl group. Theformula ofpuracarvncrotic aldehyde is thereforeC6H,MePr(OH).COH [Me : OH : Pr : COH = 1 : 2 : 4 : 51.Like parathymotic aldehyde (Abstr., 1884, 56), it does not combinewith the hydrogen alkaline sulphites, but yields crystalline compoundswith aniline and phenylhydrazine.Action of Bromacetophenone on Amides. By F.0. BL~MLEIN(Ber., 17, 2.578-2581) .-On heating bromacetophenone with amides,there are formed neither the amides of acetophenone, nor isoindolesderived from them by the abstraction of a molecule of water, but sub-stances which differ from the latter class in containing about 2 percent. less carbon than that required by theory.Thus, if bromacetophenone be heated with acetamide, there isformed a basic substance crystallising in long needles ; this melts a t45", boils a t 241--'242O, and is easily soluble in alcohol and ether.Its hydrochloride forms a white crystalline powder.The corresponding compound obtained with formamide forms a,crystalline mass, and the benzamide compound forms crystals whichmelt at 103" and boil a t 339".It is proposed to investigate moreclosely the constitution of these substances.(Dingl. polgt. J., 254,23l.)-Onheating diphenyl carbonate with sodium phenate, basic sodium silicyl-ate is produced, in addition to phenol and diphenyl ether. (ChemischeFubrik u.f' Actien, formerly E. Schering, Berlin.) To prepare sa,li-cylic acid, 50 kilos. of diphenyl carbonate is heated with 54 of sodiumphenate €or 6 hours a t 160-170", with constant agitation ; the salicylicacid being subsequently extracted from the saline product.Brominated Phthalic Acids. By F.0. BLi?JlLEIN (Bey., 17,A. K. M.V. H. V.Preparation of Salicylic Acid.D. B.2485-2497).-When a-naphthol is treated with excess of bromine, acompound is formed containing six bromine-atoms in the molecule.This is very unstable and is probably a dibromo-additive product oftetrabromonaphthol, C,oH3Br4.0H,Br2, or a tetrabromo-additive proORGANIC CHEMISTRY. 163duct of Biedermann's dibromo-a-naphthol (Ber., 6, 1119). Theauthor has not further investigated this compound, but has studiedthe bromination of a-naphthol in the presence of aluminium bromide.In this way, the-author obtained a pentabromo-z-naphthol, C10HBB~*5.0H,which melts a t 238-239", crystallises in pale straw-coloured needles,and is almost insoluble in alcohol and ether, and only sparingly solublein boiling benzene, xylene, or cumene.The yield was about 90 percent. of the theoretical. This compound dissolves in alkalis to formmetallic compounds : CloH,Br,.ONa crystallises i n long needles, solublein alcohol and water: C,,H,Br,.OK in small colourless needlessparingly soluble in water.When oxidised with dilute nitric mid (one part C,,H,Br,.OH to 10parts acid of sp. gr. 1-15) a t loo", pentabromo-or-naphthol yields tetra-brorno-a-napJu%quinone, CloH2Br4.a. This compound crystallises ingolden-yellow scales which melt a t 265" to a dark liquid. It can besublimed with care, and is soluble in glacial acetic acid and inbenzene, sparingly so in alcohol and ether. It is isomeric with the tetra-bromo-@-naphthaquinone obtained by Fleasa (Inaug.Bissert., Zurich,1884). If the oxidation of the pentabromonaphthol with dilute nitricacid is carried out at 150°, instead of a t loo", and the action con-tinued f o r about 18 hours, dibromopkthalic acid, C6H,Br,( COOH),,is formed ; under similar circumstances Flessa's pmtnbromo-6-naphthol yielded tribromophthalic acid. Dibromophthalic acidcrystallises in long aggregated needles which are easily soluble inalcohol, ether, and boiling water, sparingly in petroleum. It melts a t206", and is converted into the anhydride. Dibromophthalic anhydride,obtained by sublimation of the acid, crystdiscs in long colourlessneedles melting at 208". It is easily soluble in alcohol, spariugly soin ether and water.The salts of dibromophthalic acid, except thoseof the alkalis, are sparingly soluble, and contain no water of crystal-lisation. The calcium salt is deposited as an amorphous precipitate,which becomes crystalline on standing ; the barium salt is similar tothe calcium ; the s i h e r salt forms a flocculent precipitate soluble inmuch boiling water, and crystallises from this solution in smallcolourless plates. When the anhydride is fused with resorcinol, abrominated fluoresce'in appears to be formed. This compound issoluble in alkalis and in alcohol to a red solution with an intensegreen fluorescence.Action of Bromine on Ortkoxy lene in Presence of Alunainiurn.--Inthis way, a tetrabromo-xylene, C6BrlMe2, was obtained, in which thebromination took place entirely in the benzene nucleus. This com-pound crystallises in colourless silky needles, melts a t 2541-255", anddistils without decomposition a t 374-375O.It is easily soluble inbenzene and xylene, almost insoluble in alcohol and ether. Tetra-bromo-xylene is not acted on by dilute nitric acid (sp. gr. 1-15> belowabout 250-2SU0, and then the oxidation is only partial. Nitric acidof sp, gr. 1.20 effects the Oxidation at 180-200", but the productconsists of a mixture of tetrt~bronzophthalic and tribromomononitro-phthalic acids, the complete separation of which could not be effected.If 5 grams of tetra,bromo-xylene are heated a t 170" with 50 C.C. ofnitric acid of sp. gr. 1.15 and about 10 grams of bromine, tstrabromo164 ABSTRACTS OF CHEMICAL PAPERS.phthabic acid is alone produced. This crystallises in small needles, verysparinglg soluble in the usual solvents.At 266" it melts and is con-verted into the anhydride. Tetmbronzophthalic anh.ydride, obtained bysublimation of the acid, forms small glistening needles which melt a t258-259", and are almost insoluble in the usual solvents. Thealkaline tetrabromophfhaZates are easily soluble, the salts of the otlhermetals sparingly soluble or insoluble. The bariunz and calcium saZfsform white crystalline powders. When fused with resorcinol, tetra-bromophthalic acid yields a brominated fluorescejin isomeric witheosin. This compound is soluble in alkalis to a dark red solutionshowing intense green fluorescence.From the above results, it is clear that in the pentabromonaphtholformed by the action of bromine on a-naphthol in the presence ofaluminium bromide, the three hydrogen-atoms of the nucleus con-taining the hydroxyl have d l been replaced by bromine, but theposition of the remaining two bromine-atoms in the other nucleus isuncertain.In the tetrabromo-xylene all the bromine-atoms are in thebenzene-ring. L. T. T.Constitution of Phthalylacetic Acid, By S. GABRIEL (Ber., 17,2521-2527) .-When phthalylacetic acid is distilled in a vacuum,carbonic acid i s evolved, and the distillate comprises a yellowish-whitesemi-solid mass. If a current of steam is driven through this mass,the distillate deposits small shining rhombic prisms, which melt a t58-60', have an odour resembling that of phthalide, and are solublein water.On keeping, however, they gradually polymerise to a yellowvitreous and odourless mass. Some of this polymerised body is alwaysformed in the retort when the white substance is distilled with steam.It is partly reconverted into the original volatile compound by distil-lation in a vacuum. The frehhly prepared volatile compound has thecomposition C9H602, and its constitution must therefore be either-C=CHa(a) C6H,<Eg>cH2, or ( 6 ) c6H4' >o This compound can 'coalso be obtained from the resinous bye-products obtained duringthe preparation of. phthhlylacetic acid. When treated with bromine,this compound absorbs Br2, yielding a crystalline substance, C9H,Rr2O2,melting a t 98-99'.The original volatile substance must thereforebe methylenephth~alide, and have the formula ( b ) , and the bromoderiva-tive must be methybenepkthalide bromide, c6H /CBr.CH2Rr0 qco/When gently warmed with potash, methylenephthalide is convertedinto acetophenon ecarboaylic acid ; probably according to the equationsIf the dibromide is boiled with water, it gives up hydrobromic aciORGANIC CHEMISTRY. 165and yields a methylenephthalicle oxide, C9H603. This crystalline com-pound melts at 144-146", and is identical with that previouslyobtained from acetophenonecarboxylic acid ( Abstr. 1878, 734).P11 thalylbromacetic acid, when similarly treated, yields a com-pound which is identical with bromomethyZe?ze~hthaZyZ, previouslyobtained by bromination of aceto piienonecarboxylic acid (Zoc.cit.).The name of this comDound should therefore be changed to bromo->o. C:CkiBr methyZeneph,thaZide, and its formula would be C,H4<- co-The compouiid previously described as benzylidenephthalyl alsoforms a crystalline dibronzide melbing a t 146", and should therefore becalled benzylidenepht~ialide; its formula is C6H4<<-cO ->O. Thedibromide, when boiled with alcohol, is converted into the crystallinecompound CI5Hl0O2Br.OEt, which melts at 149".C'CHPhL. T. T.Phthalyl Derivatives ; Conversion of Ketonic Acids intoLactones. By W. ROSER (Bey., 17, 2t;19-2622).-When ethylene-benzoylorthocarboxylic acid is dissolved in about 15 parts of concen-trated sulphuric acid, and the solution allowed to remain for sometime in the cold, slender yellow needles of ethinediphtbalyl separate :C O OH.C6H4. C 0. C Hz. C H?. C 0. CsH4. C O O H - 2 HZO =CO<??>C CH.CH: C<?Z>CO.When a solution of benzoylacetorthoc,arlooxylic acid in concentratedsulphuric acid is precipitated with water, phthalylacetic acid isobtained, as observed by Gabriel (Bw., 17, 2526), but this acid meltsabove 260" according to the author, and a t about 276" decomposeswith evolution of gas. By similar treatment, acetophenoneortho-carboxylic acid Tields a compound melting a t 213-215", insoluble inwater and cold alkalis, sparingly soluble in alcohol, and readily inacetic acid, from which it crystallises in colourless scales. It isperhaps a polymeride of Gabriel's phthalidimethylene, C9H6O2.Itmay be concluded from these experiment,s that acids containing thegroup :CH.CO.C,H,.CoOH [l : 21 are converted into lactones byconcentrated sulphuric acid. When et hylenebenzoylort hocarboxylicacid is heated with 10 parts concentrated hydrochloric acid in a sealedtube, the product washed with water and extracted with boilingalcohol, a residue of ethinediphthalyl remains, whilst the alcoholicsolution contains the anhydride CpH4<&~c~H~~Co>0. This is in-soluble i n water and cold alcohol, but crystallises from hot alcohol inslender silky needles melting at, 230-231'. It agrees in its pro-perties with the compcund obtained by Gabriel by heating the di-ketonic acid. A. I(. M.C O C H COReduction of Phthalimide and Phthalide. By C.GRAEBE (Bey.,17, 2598-2600) .-By the action of tin and hydrochloric acid,phthalimide is converted into a base of the composit'ion C,H,NO, whic166 ABSTRACTS OF CHEMICAL PAPERS.crystallises in needles melting a t 150", and boiling at, 337"; it issoluble in alcohol and ether, sparingly solixble in water. From itsready formation, and its reconversion into phihalide, one of *hefollowing forrriula can be assigned to it :the former of which the author considers the more probable, andassigns to it the name yhthuIzdhe. With sodium nitrite, i t forms itnitroso-derivative, C,H,<C(:;~Y?>O, which crystalliscs in goldenneedles melting a t 1X0, sparingly soluble in water, readily soluble inhot alcohol ; on heating it with soda, i t is converted into the mon-hy d roxy l-deri vative of meth y lbenzoic acid, OH.CH2. C,H,. C 0 0%.Phthalimide is converted into phthalide by treatment with tin andhydrochloric acid, and t'he addition of sodium nitrite to the product.The nitroso-derivative separates out, and phthalide is obtained on pre-cipitating its alkaline solution w,ith acid. Through the intermediateformation of this substance, phthalic acid may be converted intoorthoxy lene. V. H. V.Constitution of the Benzenetetracarboxylic Acids. By 0.JACOBSEN (Bey., 17, 2516--2518).--In order to determine the con-stitution of the three benzenetetracarboxylic acids, the author preparedtwo of them by the oxidation of durene, C,H,Me,. [l : 2 : 4 : 51, andisodurene [l : 2 : 3 : 51.Dureiie was first boiled with di1ut.e nitric acid,arid thus converted into a mixture of durylic and cumidic acids,and this mixture was then oxidised with permanganate. The tetra-basic acid thus obtained proved to be pyromellitic acid. By similartreatment', isodurene yielded mellophanic acid. The constitution ofthe three isomeric acids, therefore, must he :-Pyromellitic acid,C,H,(COOH), [I : 2 : 4 : 51 ; mellophanic acid, [1 : 2 : 3 : 51 ; andphrenitic acid, [l : 2 : 3 : 41. L. T. T.Action of Sulphuric Acid on AcetophenoneorthocarboxylicAcid. By S. GABRIEL (Ber., 17, 2665-26681.- When concentratedsulphuric acid (1 5 grams) is added to acetophenoneorthocarboq-licacid (1 gram), an amber-coloured solution is obtained; this is allowedt o remain for 24-48 hours arid then poured into water, when a brownresinous substance (A) separates.The filtrate yields a furtherseparation of a fine white powder (B) on standing. The substance Aforms (after purification) dense, yellow, pointed crystals melting a t215-216*5", sparingly soluble in alcohol, insoluble in alkali and inammonia. When it is heated a t 150-160"with hydroxylamine hydrochloride and alcohol, it yields an oximido-derivative, ClsH1203 : NOH.The second substance (B) is readily soluble in alcohol, glacialacetic acid, and in fixed and volatile alkali, from which it can be pre-cipitated by the addition of an acid; it melts at 132-135". Itsformula, C18H1,05, indicates that it is formed by the abstraction of oneIts formula is CleH1,04ORUANIC CHEMISTRY.167mol. H,O from 2 mols. acetophenoneorthocarboxylic acid. Thissubstance is a monolnasic acid (diacetophenor~ecarbozy Zic acid), asshown by the composition of the silver salt, C,8H,305Ag, and thebarium salt, (C18H,305)2Ea. When it is heated f o r some time aboveits melting point, it is converted into the compound ClsH,,Oi.A. K. M.Preparation of Isatin. (DingZ. polyt. .J., 254, 232.)-The pre-paisation of this substance forms the subject of a patent taken out, bythe FarJ,enfabriken, late F. Bayer and Co. Instead of convertingthe products of the reaction of dichloracetic acid with aromaticamines directly into isatin, it is proposed to subject them to a processof oxidation, it having been found that during the reaction and thesubsequent process of purification oxidation by atmospheric oxygentakes place, and that the yield of imesatin, o r substituted imesntins,depends on the exteiit of this oxidation process. D.B.Methylated Indoles. By A. LTPP (Ber., 17, 2507-2511).-O~thomethylumidoclzlorosfyrene, CHCl : CH.C6H4.NHDle, was preparedby treating an alcoholic solution of amidochlorostyrene with the cal-culated quantity of methyl iodide. It is heavier than water, is easilysoluble in alcohol and ether, very sparingly so in water. I t is liquidat ordinary temperatures, may be distilled with steam, but not alone.It dissolves in hydrochloric acid to form a hydrochloride whichcrystallkes in small needles. When heated with sodium ethylate at1;3%--140", orthomethylamidochlorostyrene yields the same methyl-indole which Fischer and Hess obtained from methylphenyihydrazine-pyroracernic acid (Abstr., 1884, 1180).This reaction proves thecorrectness of the formula proposed for this body by Fischer andHew, as its formation must take place according to the equations-(I.) NHMe.C6H,.CH : CHC1 + NaOEt =NHMc.C6H4.CH CH.OEf; + NaCl.(11.) NHMe.C6H,.CH : CH.OEt = C6H4<~cH>CH 1 Me + Et.OH.Baeyer and Jackson's met,hylketole has the formulaso that skatole, the remaining methylindole containing the methylgroup in the side-chain, must be represented by the formulaL. T. T.Tolane Tetrachloride. By L. GATTERMANN (Ber., 17, 2601).-Schupphaus recently referred to a compound obtained by the action ofchlorine on boiling toluene (Abstr., 1884, 52), and it wits thoughtprobable that this might be a new dichlortolnene.The author finds,however, that the substance in question is tolane tetrachloride,CPhCI,.C2i1PC2, which was obtained in the same way by Liebermannand Homeyer (Abstr., 1880, 259). A. I(. M168 ABSTRBOTS OF CHEMICAL PAPERS.A New Method of Preparing Secondary Arnidoazo-deriva-tives. By R. HENRIQUES (Bey., 17, 2668--2673).--EthyI-lu-na~ht~c?ll-anline may be prepared from P-naphthylamine, and forms ZL thick oilwhich boils without decomposition, and does not solidify in a freezingmixture ; its hjydroc?dol-ide, C,,H,,N,HCl, is sparingly soluble in cold,moderately in hot water, crystallises in scales, melts a t 235", anddistils with but slight separation of hydrochloric acid.It forms anitrosamine, CI,H,,N,O, which melts at 49", and yields a yellowcoloration with concentrated sulphuric acid, When nitrosoethyl-naphthylamine and aniline are heated together in solution in glacialacetic acid, a violent reaction sets in, and a deep red liquid is obtainedwhich is kept boiling for some time; this deposits benzazoethyl-P-.nuphthyZamine, PhN2.C,,H6.NHEt, on cooling. The same compoundis also obtained from diazobenaene and ethylnaphthylamine. It formsred needles melting at 102-103°, is insoluble in water, but yieldsorange-red solutions with alcohol and other solvents. With concen-trated acids, it gives bluish-violet salts which are decomposed bywater. It yields a nitrosamine which forms rubj-coloured crystalsmelting a t 97"; when this is treated with aniline in glacial aceticacid, the nitroso-group is removed and the amidoazo-compound re-produced.Nitrosoethylnaphthylamiiie reacts with ortho- and para- toluidinein the same way as with aniline, the compounds obtained meltingrespectively a t 1'32" and 112-113".With amidoazobenzene, it formsazoZ,enze.rreazoethyl-~-naphtkylamine, PhNZ.C6H4.N,.C,,H6.NHEt, which,for comparison, has also been prepared from diazoazobeneene andethylnaphthylamine. It forms small cherry-red crystals, melts at141-142", and gives a deep blue colour with sulphuric acid. Thereaction with diamines is apparently less simple ; metaphenylene-diamine and toliiylenediamine give brownish-red dye-stuffs with thenitrosamine, whilst paraphenylenediamine gives no colour reaction.Methy lamine and phenylhydrazine do not react with nitrosoethyl-naphthylamine.Experiments in which the nitrosamine was treatedwith aminesulphonic acids yielded negative results ; no combinationoccurs i n glacial acetic acid solution, but if hydrochloric acid isadded colouring matters are formed.Streiff '8 nitrosophenyl-6-naphthylamine (AnnnZen, 209,157), whensubmitted to the above reaction with aniline, yields benzeneazophenyl-P-nnphthylamine, C'L2H17N3, corresponding with the ethyl-compound.It forms compact dark-red needles of metallic lustre, melting a t128-129" ; the mother-liquor contains phenylnaphthplamine, thisreformation of the amine constituting the chief reaction in the caseof the other nitrosamines which the author has examined.Nitroso-ethyl-a-naphthylamine and aniline yield, for instance, amidoazoben-zene, ethylnaphthylamine, and a little benzene~znethyZ-oc-na~l~t??yla~~n~,C,,H,,N, ; this is a stronger base than the @-compound, forms large,bright-red, transparent crystals, melting a t 58-59") and yields saltscr-jstallising readily in violet needles ; it gives a bluish-violet colourwith salphuric acid, Nit,rosodiphenjlamine and aniline (see alsoBer., 10, 1309) yield diphenylamine as the chief product, also amido-azobenze-ue and a small quantity of phenylamidoazobenzene, SimilaORGANIC CHEMlSTRY. 169results are obtained from nitrosomethylaniline and aniline. I n theaction of aniline on the nitrosamines of more complex substances,such as carbazole and tetrahydroquinoline, the NO group is eliminatedand the amine is reproduced.Nitrosonaphthol and its Derivatives.By 31, ILINSKI (Ber., 17,2581-2593).-a-Nitroso-/3-naphthol is best' prepared from /3-naphtholby the process suggested by Stenhouse and Groves (comp. Trans., 1884,294) ; in addition to its properties described by former workers, theanttior finds that it is volatile in a current of steam when pure, but ifimpure it forms resinous matters.Its potassium-derivative, C,oH,NO,K, crptallises in metallic, glisten-ing leaflets, soluble in water. Its n~nmo?az'u~n salt, crystallising in thesame form, is stable only in an atmosphere of ammonia ; on boilinga solution of the ammonium salt, t,he corresponding amido-deriva-tive, is formed.I t s silvw salt forms a red-brown powder, insolublein water and alcohol ; the siZwr-nnimonium salt crystallises in deli-cate green needles, and the hydrogen-siZver salt forms a microscopiccrystalline preciptiate. By the action of methyl iodide on the normalsilver salt, there is obtained the methyl ether of a-nitroso-P-naphthol,C,,H,NO2Me, which crystallises in long prismatic needles melting a t75", dissolving in concentrated sulphuric acid with formation of a redcolour.a-Kitroso-a-72.ap7LthoZ is best prepared from a-naphthol, together withits isomeride p-nitroso-a-naphthol, by the process of Sterihouse andGroves mentioned above : the two compounds are then separated bytlie difference of their solubility in dilute soda solution. The resultanta-nitroso-a-naphthol melts with decomposition a t 190".Its salts arecomparatirely unstable, and even on agitation with ether are recon-verted into the original substance. The potassium, sodium, calcium,barium, and magnesium salts are readily soluble in water. On tjheaddition of silver nitrate to a solution of the last-named salt there isprecipitated a red- brown resin, which on purification and subsequenttreatment with methyl iodide can be converted into tbs methyl etherof a-nitroso-2-naphthol, which crys tallises in needles, melting probablyat about 100". It is readily soluble in alcohol, ether, and benzene,but insoluble in water. ~~-Nitroso-P-naphthol and lJ-nitroso-a-naphtholdiffer in their reaction with cobalt chloride ; the formela yields a cobalt-derivative, containing no chlorine and unaltered by acids, alkalis,oxidising and reducing reagents, whilst the latter yields no such com-pound.By the action of ammonia on a-nitroso-P-naphthol a substance ofthe formula C,,H,N,O is formed ; this was ccnsidered to be a nitroso-amidonaphthalene, CloH6N0.NH2, but is more probably a quinon-oximine.V. H. V.A. K. M.a- and p-Hydrojuglone. By F. MYLIUS (Bey., 17, 2411-2414).-The earlier writers on the subject all regard juglone as occurring readyformed in the p e e n shell of the walnut, the author, however, findsthat this view is incorrect, and that it is formed by the oxidation oftwo isomeric crystalline bodies, a- and P-hydrojuglone, standing i170 ABSTRACTS OF CHEXICAL PAPERS.the same relation to it as that of the dihydroxybenzenes to quinone.Those substances occur i n all the green parts of the walnut tree, butthe shells of the ripe nuts do not contain even a trace of hydrqjuglones.No account of the method of preparation is given.a-HydrojugZone, CloH,03, forms colourless plates, melts a t 168 -1 70",is soluble in about 203 parts of water a t 25", is readily soluble inalcohol and ether, insoluble in chloroform; i t is readily soluble inalkalis with yellow colour, turning quickly to red on exposure to air.Ferric chloride or bromine-water oxidises it to juglone.On reducingjuglone, a-hydrojuglone is alone formed.Acett!l-a-hyd?.o~ziglorze, CloH,03Ac3 formed by digestion of a-hydro-juglone with acetic anhydride, melts a t 124".A solution of a-hydro-juglone or of juglone in organic bases yields nitrogenous componndsof juglone by oxidation in air. Of these compounds that with di-methglaniline, C,oHS03,NMe2Ph, is very readily prepared ; it crystal-lises in lustrous red tlables, and by treatment with hydrochloric acidis converted into a hydroxyjuglone of the formula C,H,O,.OH, havingthe charactem of a strong acid.p- HydrojugZorze crystallises in colourless plates, melts a t 97", issoluble in about 900 parts of water at 25", is sparingly soluble inalcohol and ether, readily soluble in chloroform ; it is readily solublein alkalis with yellow colour, which changes to red on exposure toair. It @ves a blood-red coloration with ferric chloride, and isconverted into a brominated product by bromine-water.It occurs inmuch smaller quantity tban its isomeride.On fusion with potash, both hydrojuglones yield phenol, salicylicacid, and metahydroxybenzoic acid.The author had independently arrived a t the same conclusion asBernthsen (Abstr., 1884, 1365) as to juglone having the formulaC,,,H60,. He further confirms Bernthsen's view that juglone is a hydr-oxynaphthaquinine, by showing that a-hydrojuglone also yields naph-thalene when distilled with zinc-dust. A. J. G.A Sulphoxide of Naphthalene. By A. G. EESTRAND (Ber., 17,2601-2694). Whilst preparing naphthonitrile by disbilling a mix-ture of potassium a- and P-naph thalene sulphonates with potassiumferrocyanide, the author observed the formation of secondary sub-stances which crptallise from the highest fraction of the crude nitrile.Two compounds may be separated by crystallisation from alcohol, oneof which is obtained in very small quantity and forms scales melt-ing a t 148" ; the other crystallises in long needles, melts a t 1 Ll", a,nddissolves very readily in carbon bisulphide, ether, benzene, warmglacial acetic acid, and alcohol.Its formula appears to be C,,H,SO.It is insoluble in acids and alkalis, and is not acted on by acetic anhy-dride ; it readily yields a bromine-derivative, and this crystallises incolourless needles melting a t 182", is rery readily soluble in carbonbisulphide, and very sparingly in alcohol and glacial acetic acid.Thecompound C,oH20S0 is probably napkthylenedinuphthy lsulphoxide,When its solution in glacial acetic acid is heated with potassium di-CioH6 : SO(CioH,),ORGANIC CHEMISTRY. 171chromate, dinup h t h y 7szclp h oxide, SO ( C is produced, and crystal-lises in prisms melting a t 162'. By the action of nitric acid (sp. gr.1.21) on naphthylenedinaphthylsulphoxide a t 130--140", a diviitro-naphthyl sulphide, S(C,H,.NO,),, is obtained, crystallising in smallgolden yellow prisms melting a t 230-231'. It is insoluble in alkalis,almost insoluble in alcohol and carbon bisulphide, and very sparinglysoluble in glacial acetic acid.Derivatives of the Isomeric Dinaphthols. By E. OSTERMATERand J. ROSENHEK (Rer., 17, 2453--2455).-The authors descrikeseveral derivatives of Dianin's a- and P-dinaphthols.a-DinuphthyZ diethy2 ether, EtO.CIoH6.CloH6.OEt, was prepared byacting on a-dinaphthol with alcoholic potash and ethyl iodide.Itcrystallises in white pearly scales melting a t 211", and is easily solublein hot benzene, sparingly so in ether or alcohol, insoluble in water.a-Dinaphthyl dimethyl ether, ( C,oH,.0Me)2, crystalhes in glisteningplates melting a t 251".@-Dinaphthyl diethyl ether, (C,,H6.0Et),.ci~ystallises in needles whichmelt a t go", and are soluble in alcohol and benzene. p-Dinaphthyldimethyl ether cryst'allises in double pyramids, soluble in benzeze,insoluble in alcohol ; it melts a t 190".The authors were unable to isolate the potassium or sodium com-pounds of a- or g-dinaphthol.These compounds are very nilstable,and in all attempts at purification were either partly or wholly recon-verted into the dinaphthol. Schaeffer's experiences wit,h a- and@naphthol were similar.A. K. M.L. T. T.Ethereal Oils. By 0. WALLACH (Annnlen, 225, 314--318).-Thechief constituent8 of oil of cajeput is identical with cyneol. The ter-penes contained in oil of bergamot and oil of eucalyptus are distinctfrom cynene. Oil of lemon yields a small precipitate with bromine,and a large quantity of the crystalline tetrabromide is obtained fromOZeum corticis aurantiorum. This compound closely resembles cynenetetrabi*omide, but differs from it in its melting point (104"). w. c. w.Oleum Cpe. By 0. WALLACR and W. BRASS (Annalen, 225,291-314) .-After referring to the researches of Volckel (Annalen,87,312), Kraut (Jalwesber., 1862, 460), and Faust and Homeyer (thisJournal, 1875,375)on this subject, the authors describe the experimentsby which they succeeded in isolating cpeoE, CIOH180, and cynene, CloH,6,from the crude oil.The separation depends on the fact that cpneolforms an unstable crystalline compound, ( C~oE180)2,HCl, when it istreated with the hydrochloric acid gas. This substance is decomposedby water into hydrochloric acid and cyneol. It is decomposed also whenheated in sealed tubes, yielding cynene, water, and hydrochloric acid.Pure cyneol boils at 176-177", and has no action on polarisedlight. It is oxidised to oxalic acid bynitric acid sp. gr. 1-15.Cyneol also forms an unstable crystallinecompound with hydrobromic acid, and with hydriodic acid it yieldsthe iodide C10H1812, which crystallises in transparent rhombic plates.The iodide is decomposed by heat into cpene and hydriodic acid.Its sp. gr. is 0.92297 at 16"172 ABSTRACTS OF CHEMICAL PAPERS.Ry slowly dropping bromine into a well-cooled mixture o i lightpetroleum and cyneol or rectified oZmm cynce, an additive product,C,oHIs0,Br2, is obtained, which crystallises in red prisms. If thecrystals are placed in a sealed tube and kept in a cool place, theyslowly decompose, forming a colourless liquid, which in the courseof time deposits a crystalline mass. By reciytallisation from chI(,ro-form, cynene tetrabromide, CloH16Br4, is obtained in rhombic cryat&melting at 125.5".Cyneol diiodide is formed when iodine acts on cyneol diluted withlight petroleum. It is deposited from its ethereal solution in longneedle-shaped crystals, which are more stable than those of thebromide.Cyneol is not acted on by metallic sodium, nor by sodium ethylateand ethyl iodide ; neither does it enter into reaction with hydroxyl-amine or phenylhpdrazine, nor yet with phosphorus pen tachlorideor benzoic chloride a t the ordinary temperature.These negative re-mits indicate that the oxygen in cyneol is not present in the form ofhydroxyl.Pure cynene is best prepared by warming a mixture of the iodide,C,,HlET2 (3 parts), with aniline (4 parts), amd distilling the product ina current of steam.The hydrocarbon boils at 181-182". Its sp. gr.is 0.85384 at 1~'. Pure cynene has a characteristic odour of lemons.When bromine is added to a well-cooled mixture of cynene and alco-hol or ether, crystals of the tetrabromide are deposited. Cynene isconverted into cymene by strong sulphuric acid or by phosphorusAction of the Halogen Acids;on Wormseed Oil. 11. ByC. HELL and A. RITTER (Ber., 17, cLG09-2614).-l'he action of hydro-chloric acid has been described (Abstr., 1884, 1363). When hydro-bromic acid acts on wormseed oil in the cold, a crystalline substanceis obtained, and is apparently the additive product CloH,,O,HBr,corresponding with the hydrochloric acid additive product previouslydescribed (Zoc. cit.). It is, however, much less stable than the lattercompound, and rapidly deliquesces and becomes brown on exposure tothe air.It melts between 33" and 35". A cynejie dihydrobrornide,C,,H,,Br,, may also be obtained, correspmding with the dihydro-chloride. This crystallises in white silky scales, melts at 64O, and isdecomposed by heat into cynene and hydrobromic acid, as also whenboiled with water or dilute alkalis. By the action of hydriodic acidon wormseed oil in the cold, crystals may likewise be obtained, butthe compound is so unstable that, it could not be isolated. Theflirther action of hydriodic acid yields cynene dihp?riodidR, C,,H,,I,,which crystallises in short white needles melting at 76-77', and iseven less stable than the dihydrobromide. It, can be kept for three orfour days only, even in the dark, and in a sealed tube.When heatedwith zinc-d ust aiid water, dihyclrocynene, C1OHIEr is obtained, boilinga t 166-167'. This is a colourless strorigly refracting oil, resemblingcynene in its odour. It may also be obtained from the dihydrochloride.On comparing the properties of the dihydrochlorides, bromides, andiodides of the terpenes with those of the uorrespmding cynene-pentasulphide. w. c. w0 RGANIC CHEMISTRY. 173derivatives, striking resemblances are observed. The dihydrochlo-rides of many of the terpenes melt, for instance, at nearly the sametemperature as cynene dihydrochloride. Further experiments are,however, necessary to decide whether these terpenes are identical orisomeric with cynene.By J. KACHLER and F.V.SPITZER (Ber., 17, 2400-2401).-The authors regard the compound,CIOHt602, recently described by Goldschmidt and Ziirrer (A bstr.,1884, 1364) under the name of campholenic acid, as identical with thesubstance termed by them hydroxycamphor, formed by the- action ofsodium amalgam on ,B-dibromocamphor. They consider the constitu-tion of this substance to be still unsettled, and will continue theirresearches on it. A. J. G.A. K. M.The so-called Campholenic Acid.Coal-tar Quinoline. By M. C. TRAUD and C. SCHARGES (Ber., 17,2618-2619).--In preparing qninophthalone from coal-tar quinoline, ared resinous substance is also produced which, however, is not formedwhen pure quinaldine or a mixture containing only quinoline andquinaldine is employed. When coal-tar quinoline (b.p. 2.35") isheated with a little phosphorus pentoxide, it assumes a more or lessintense reddish coloration, and on dissolving the product in water oralcohol, the solution obtained shows a splendid yellowish-greenfluorescence. Neither Skraup's quinoline nor pure quinaldine yield thisreaction. The fractions of coal-tar quinoline distilling below 200"behave like pure qninoline and quinaldine, whilst the portion distillingbelow 230" yields a feeble reaction.The above is a convenient method of recognising coal-tar quinoline.The reaction indicates the mesence of a third substance besidesquinoline and quinaldine, and this the authors are trying to isolate.A. K. M.x-Diquinoline from Azobenzene. By A. CLAUS and P.STEGELITZ (Her., 17, 2380--2383).-By heating a mixture of 20 gramsazobenzene, 80 grams glyceroI, 30 grams concentrated sulphuric acid,a.nd 20 grams Nordhausen sulphuric acid, for two days on the wuter-bath, there are obtained a-diquinoline (2 grams) and benzidinesulpbate (6 grams).By dissolving a-diquinoline in fuming nitric acid, heating on thewater- bath, and precipitating with water, nearly colourless, slenderneedles are obtained.These decompose without fmion a t 260", do notyield compounds with acids, and appear t o consist of a mixture ofnitration products. A. J. G.Synthesis of a-Diquinoline. By E. OSTERMAYER and W.HENRICHSEN (Ber., 17, 2444-2451).-This base was originally ob-tained by Weidel (Abstr., 1882, 69) by the action of sodium onquinoline at 192".The authors find that it can also be prepared frombenzidine by Skraup's reaction. For this purpose, benzidine sulphate(50 grams), nitrobenzene (25 grams), snlphnric acid (100 grams), andglycerol are slowly heated in a reflux apparatus, care being taken thatthe reaction does not become unmanageable. The yield of diquinolkeVOL. XLVIII. %174 ABSTRACTS OF CHEMICAL PAPERS.is very good (about 33 per cent. of the benzidine sulphate employed),but its purification is rendered difficult by tar-like products simul-taneously formed ; by substituting para- or ortho-nitrophenol forthe nitrobenzene, however, there is obtained not only a much largeryield (about 72 per cent. of the benzidine sulphate), but from theabsence of the tar-like products the purification is very easily effected.The aurochloride,C,,H12N2,HAuC14 + 2H20, crystallises i n very slender needles and isvery sparingly soluble.The sfannichloride, Cl8HI2N2,H2SnCl4, crys-tallises in colourless needles. The methiodide, C1BHT2N2(MeI)2, wasprepared by heating diquinoline with methyl iodide and methylalcohol in sealed tubes a t 120". Acompound with methyl chloride of like composition was also obtained.Weidel had described the methiodide as containing only 1 mol. ofmethyl iodide (Zoc. cit.).Diquinoline n i t r a t e is nearly insoluble in water.It crystallises in yellow needles.The compound with methyl s u b h a t e ,CI,H12J%(MeSOaH)2 + 2&0,prepared by heating diquinoline, methyl alcohol, and sulphuric acid insealed tubes at 180°, crystallises in colourless needles.Its diluteaqueous solution shows a bluish-violet fluorescence and gives a blood-red coloration with alkalis.Diquinoline unites directly with bromine to form two additive corn-pounds : an orange-yellow, apparently crystalline substance of theformula C,,H,,N,Rr,. and a pale yellow tetrabromide, C,,Hl2N2Br4.Both compounds are very unstable ; when boiled with water, they aredecomposed, diquinolirie being in part regenerated. By heating withhydrochloric acid a t 180-200 O , mono byom odiquiq? ol ine, C,,HllBrN2,IS formed amongst other products. It crystallises in tufts of needles,melts a t 150-155°, and is readily soluble in cold alcohol. Di-quinoliiLechli,riodide hydrochloride, C,sH12N2C121,,2HCl, is prepared byprecipitating an aqueous solution of diquinoline hydrochloride with asolution of iodine chloride.DiqiiinoZirLedisulp~~n~c acid, C,sHI2N2( S03H),, is prepared by theaction of nitrophenol, glycerol, and sulphuric acid on benzidinedisul-phonic acid ; it crystallists in colourless plates or needles, is sparinglysoluble in water, insoluble in alcohol, and has a very bitter taste. Thepotassium salt has the formula C18H12N,(S0,K), + H20.It isprobably identical with the disulphonic acid prepared directly fromdiquinoline by Weidel. A. J. G.Formation of Pyridine Derivatives. 11. CondensationProducts from Malic Acid. By H. v. PECHMANN and W. WELSH(Bar., 17, 2334-2395) .-In a previous eomrnunication, v. Pechmannhas shown that by the action of sulphuric acid on malic acid, formicacid and coumalinic acid are formed (Abstr., 1884,1124). The presentpaper deals with the derivatives of coumalinic acid.By the action of ammonia or ammonium carbonate on coumalinicacid 1 : 4 hgdroxynicotic acid is formed.The reaction proceeds morereadily if ethyl coumalinate is employed instead of the free acid. Thischange is most probably represented by the equationORQANIC CHEMISTRY. 175c(cOOH) ' CH>O + NH, = COOH.CH CH.C(COOH) CH.NH, <CH: CH-GO= H20 + COOH.C<cH:cH>C.OH. CH-NFor although the intermediate coumalamic acid could not be isolated,yet the analogous methyl coumalanilidate has been obtained. Thehydroxynicotic acid obtained is identical with Koniqs and Geigy'sh~droxypyritiineclarboxylic acid (Abstr., 1884, 1195) ; if heatedwlth phosphoric chloride it is converted into chloronicotic acid,C5H,NC1.COOH.This crystallises in shining plates, nielts withdecomposition a t 199', is readily soluble in water, ether, alcohol, andglacial acetic acid, sparingly soluble in chloroform and benzene. Theaqueous solution gives a pale-green precipitate with cupric acetate.By reduction with tin and hydrochloric acid, it is converted intonicotic acid. As the chlorine-atom in cb-loronico tic acid exhibitsproperties shown by Friedlander and Ostermaier to be characteristicfor the chlorine-atom occupying the position next to the nitrogen-atom, it follows that from its formation from hydroxyquinolinic acid,and from the known constitution of nicotic acid, that this hydroxy-nicotic acid must, have the constitut'ion [N : €30 : COOH = 1 : 2 : 51.Monomethy1 coumalairilidate, (C,H,NPh)(COOH>.COr>Me, is pre-pared by the action of aniline on methyl coumalinate.It erptallisesin citron-yellow needles, melts with decomposition at 140", is readilysoluble in hot alcohol, chloroform, and benzene, sparingly soluble inether, insoluble in water, and behaves as a free acid. It readilysuffers decomposition by the action of water, acids, or alkalis.Phenox?/nicotic a c i d , C,H,N(OPh).CfiOH [OPh : COOH = 1 : 4J7is prepared by boiling methyl coumalanilidate for a few minutes withsoda, &c. J t crystallises in lustrous white needles, melts a t 275-%0',can be sublimed by careful heating, is soluble in hot water, alcohol,and glacial acetic acid, nearly insoluble in ether, chloroform, andbenzene. By heating it with concentrated hydrochloric acid at 200°,a crystalline substance, probably p henoxypyridine, is obtained, whilstcarbonic anhydride is evolved.Metholrynicofic acid, C,H,N(OMe) .COOH + H,O, is obtained eitherby the direct methylation of hydroxynicotic acid or by condensationfrom coumalinic acid and methylamine.It crystallises in flat needlesof satiny lustre, melts a t 237-4238", is nearly insoluble in cold, butvery readily soluble in hot water, soluble in alcohol, ether, and glacialacetic acid, insoluble in chloroform and benzene. It has scarcely anybasic properties. A. J. G.Synthesis of Pyridine Derivatives.111. Coumalinic Acid.By H. v. PECHMANN (Ber., 17, 2396-2399) .-Bro?nocoi~n.raZi?zic crcid,C5H2BrO2.COOH, is prepared by heating a mixture of finely powderedcoumalinic acid (10 parts), glacial acetic acid (30 parts), and bromine(12 parts), with a little iodine, on the water-bath. It crjstallises i ncolourless, lustrous needles, melts a t 176", can be sublimed in smallportions, is readily soluble in alcohol, ether, glacial acetic acid, andchloroform, more sparingly soluble in benzene, insoluble in lightn 176 ABSTRAOTS UP CHEMICAL PAPERS.petroleum. It is nearly insoluble in cold, moderately soluble in hotwater, t'he solution soon decomposing, if boiled, with copious evolutionof carbonic anhydride and formation of a substance volatile in steam,and of very penetrating odour.Like coumalinic acid, it is convertedby alkalis into an acid yielding yellow salts. Ammonia gas passedinto an alcoholic or ethereal solution of the acid causes the pre-cipitation of a colourless crystalline salt. MethyZ bromocoumalinczte,C5H,Br02.COOMe, crystallises in prismatic needles, melts at 134", canbe distilled unaltered, is insoluble in water, sparingly soluble in ether,more readily soluble in alcohol and benzene.Bromhplrozynicofic acid, OH.C5H2NBr.COOH [OH : COOH = 1 : 41,is obtained as met'hyl salt by slowly adding finely powdered metliylbromocoumalinate t o two parts of concentrated ammonia, and sepamtesafter some time in crystals. The free acid is dimorphous, crystallisirigin long slender needles, or in strongly refractive rhombic tables.IGmelts a t 296", is sparingly soluble in boiling water, nearly insolubiein ether, alcohol, and glacial acetic acid. On boiling its aqueoussolution with cupric acetate, a green precipitate is formed. The methylsalt, OH.C5H,NBr.COOMe, cr.ystallises in colonrless, flexible, asbestos-like needles, melts a t 221-222", and is soluble in water, alcohol, andglacial acetic acid, only when heated.MrthyZ bron~ophe?iozynicotate, OPh.C5H2N Br.COOMe, is formed bythe action of aniline on an alcoholic solution of methyl broinoconmali-nate, there being no formation of the intermediate coumanalidate as inthe case of the non-brominated acid (preceding Abstract). T t crystallisesin lustrous white needles, melts at 183*5", can be distilled unaltered,is insoluble in water, soluble in alcohol, ether, and chloroform. Itsodour is peculiar, recalling that of rotten fruit. It is readily saponifiedb j heating i t with alcoholic soda.Oxidation of Piperidine. By C. SCHOTTEN (Ber., 17, 2544-2547) .-Benzoylpiperidine was suspended in water and oxidised withpotassium permanganate. Benzoylhomopiperidic acid, Ph.CO.C,H',,O,X,thus obtained crystallises in needles melting a t 94" to a clear liquid,and volatilises completely a t higher temperatures. It is moderatelysoluble in the usual reagents. It is easily soluble in ammonia oralkaline carbonates, and with these neutral solutions the heavy metalsgive insoluble precipitates. The acid decomposes slowly when boiledwith water, more rapidly with mineral acids. Heated in closed tubeswith concentrated hydrochloric acid at 100-110", it splits u p intobenzoic acid, and the hydrochloride of a nitrogenous acid. Honzopiperidicacid hydrochloride, C5H1102N,HC1, crrstallises in hygroscopic rhombicplates or prisms. These crystals are doubly refracting. The platino-chloride crystallises in easily soluble plates.By C. SCHOTTEN andJ. BAUX (Bey., 17, 2548--2551).-Benzoylconine was oxidised withperrnanganate in a similar way to that employed by Schotten withbenzoylpiperidine (przceding Abstract). Benzoylhomoconic acid,COPh.C8H,,02N, t h u s obtained, crystallises in prisms or needleswhich melt a t 142-143" to a clear liquid, and volatilises if moreA. J. G.L. T. T.A New Oxidation-product of ConineORGANIC CEEJIISTRY. 1'77strongly heated. It is very sparingly soluble in ether, easily inalcohol or ethyl acetat.e. When boiled with water, slight decomposi-tion takes place. It dissolTes readily in dilute ammonia or in alkalinecarbonates, and forms insoluble salts with most of the heavy metals :the silver salt is an amorphous powder. When heated with hydro-chloric acid in closed tubes a t lOO", this acid is decomposed intobenzoic acid and a nit,rogenous acid now under investdgation.Prom the stability of conine towards oxidising agents, the authorsare inclined to think that it contains the isopropyl group, and not thenormal one. L. T. T.Parabuxinidine, a Fourth Alkaloid from the Box Tree,Buxus Sempervirens. By G. A. BARBAGLIA (Ber., 17, 2655-2656).-The leaves and twigs of the box tree are extracted in the usualway, and the extract treated as previously described (Gazzetta, 1883,249). The product is dissolved in alcohol, nentralised with analcoholic solution of oxalic acid, the white precipitate boiled withwater, dissolved in dilute aqueons oxalic acid, sodium carbonate addedin slight excess, and the liquid extracted with ether. Parabuzinidinecrystallises from the ethereal solution in thin, colourless, transparent,microscopic prisms. It is insoluble in water, but very readily soluble inalcohol ; with oxalic acid, the alcoholic solution gives a heavy whiteprecipitate insoluble in water and alcohol. The dkaloi'd containsnitrogen, melts readily, has a rery bitter tastc, and burns with asmoky flame. A. K. M.Lupinidine from Lupinus Luteus. By G. BAUMERT (Anralm,225, 365--384).-1n order to separate lupinine from lupinidine, theauthor takes advantage of the fact that lupinine sulphate dissolvesfreely in absolute alcohol, but the acid sulphate of lupinidine is onlysparingly soluble in this solvent. The lupinine was further purifiedby Baeyer's process (Landw. Versuchs- Stat., 14, 161). Lupinidilzeplatinochloride is thrown down as an amorphous precipitate when analcoholic solution of lupinidine hydrochloride is added to an aqueoussolution of platinum chloride. This precipitate is somewhat suluble,but is redeposited from its solution i n a Tariety of different crystallineforms, all of which belong to the rhombic system. The crystals m every sliyhtly soluble in alcohol or hot water.Lirpinidine h ydrochlorida forms rhombic prisms which are veryhygroscopic. The aimchloride is unstable. The ucid suZphatP,C,HI5N,H,SO4, dissolves freely in water, but, is insoluble in absolutealcohol. The hydriodide, C8H,,N,HI, is precipitated on mixing con-centrated solutions of potassium iodide and the hydrochloride, Theprecipitate dissolves in alcohol ;md hot water, and the aqueous solu-tion deposits colourless plates containing h mol. H,O. The free baseis a thick oil, heavier than water, and has a bitter taste. It iseasily at'tacked by oxygen, especially in presence of acids, or potash,or soda. w. c. w.Albumin of the Splenic Fever Bacilla. By M. NENCKI (Be)..,17, 2605--2ti09$.-Nencki and Schaffer ( J . pr. Cliem., 20, 443178 ABSTRACTS OF CHEMlOAL PAPERS.showed that albumino'id substances formed the chief component (morethan 84 per cent.) of dried bacteria which had been generated in agelatin medium. Of these albuminoids, mycoprote'in formed morethan 90 per cent. The albumin obtained from the splenic fever.bacillus is found to contain only traces of mycoprote'in, whilst thechief component resembles in its chemical behaviour vegetable caseinand mucous substances. It is readily soluble in alkalis, but quiteinsoluble in water, acetic and dilute mineral acids. I n compositionsit, also appears to differ from mycoprote'in, but, like the latter, con-tains no sulphur. It is named by the author nnthra,zp-otezn.A. K. M