摘要:

J O U R N A L S.B. ASHER AROX. C. F. BAKER B.Sc. D. BEXDIX. A. G. BLOXAM. C. I€. BOTRANLEY.LOSDOX HARRISON AND SOX’S PRINTERS IN ORDIR’ARY TO HER XAJESTY ST. MARTIN’S LAXE.J O U R N A L H. E. AEMSTRONQ Ph.D. F.R.S.LONDON 4 ~.MARTIN'S LANE. HARRISON AND SONS PRINTERS IN ORDINARY TO HER MAJESTY,C O N T E N T S.ABSTRACTSiv CONTENTS. TVALTER ( R ).Refractive Indices of Salt Solutions. ,.CARHART (H. S.). Standard Clark Cell .COXTENTS V GAUTIER (11.). Apparatus for Distillation under Reduced Pressure. DOUMER (E‘). Refractire Power of Polritions of Siniple Salts. DOUMERVi CONTENTS.VALENTA (E.).Apparatus for Fractional Dist'illation under Reduced Pressure.CONTENTS. vii ABNEY (W. de W.) and (3 8. EDWARDS. Effect of the Spectruiii on the Haloyd Salts of Silver.viii CONTENTS.WERSHOTEN (F. J.). Electrical Conductivity of Solutions of Cac~rninm Salts ,LSTAXOGLOG (P. L.). Electrolysis of Various Substances. LE BLANCCOKTEKTS.1 3 ToRT3fATN (G.) and C.PAEBERG.Action of Sulphur on Solutions of Metallic Salts.x CONTENTS.SCHERPENBERB (P.A.v.). Behaviour of Bismuth with Sulphur and Sele- nium.CONTENTS.OSXOND (F.). OSMOND (F.). Influence of certain Foreign Metals on the Properties of S tee1.xii CONTEXTS.BETTENDORFF (A.). Earths of the Cerium and Yttrium Groups. PORMANEK (J.). Uranyl Chromate and its Double Salts .xiv CIONTENTS.EELLER (H.F.). Kobellite from Colorado. BELAR (A.). Aurichalcite.COXTEXTS WENJCKOFF (P. N.). Sphmolite Tachjlite froin thc L-ssuri District.VWT (G.).WILL (W.) and J. PINNOW. Meteorite from Carcote Chili .s v i CONTENTS.PENFIELD (s.L.). Spangolite. a New Mineral.WILLIAMS ( 8.H.). HornblendeCONTENTS.xvii PAGE ANSCHUTZ (R.) and W.0.EMERY.Action of Phosphorus Trichloride on Phenol.xviii COXTENTS.PAAL (C.) and M.BUSCH.LADENBURG (A.) and C.HUNDT.FIRBAS (R.). LIEBERMANN (C.). Cinnamylcoca'ine from Coca LeavesCOXTENTS.xix FISCIIER (E.) and F.PASSMORE.Formation of Phenylbydrazides.REISSEET (A.) and XV.KATSER.Action of Phenylhydrazinexx CONTENTS.FOUQUET.Action of Hydrocyanio Acid on Calomel.VARET (R.).Ammoniomercuric Cyanides.CONTENTS. WURX (A.) Benzenylazoximet.heny1carhoxylic Acid and its Deriratires.KOCH (H.). Action of Ethyl Chloracetate on Benzenylamidoxime.BCCHER (E.).Oxidation of Paratolyl Benzylxxii COKTENTS.ANSCHUTZ (R.). Acetyltrichlorophenomalic Acid.HUGOUNENQ (L.). Chlorobenzenes obtained from Aniso’il. MAZZAEA ((3.). DerivativesCON'L'ENTS. xxiii SIEBER (J.). Diethylenedielnine.HECHT (0.). Propylthiocarbamide and some New Thiocarbamides.BAKJMANN (E.)xxiv CONTENTS. PAGE BAMBERGEB (E.). Camphoric Acid. 517 BAMBERQER (E.) and W. LODTER. Action of Carbon BisulphideCONTENTS.ssv PAQE FITTIQ (R.) and R.RIECHELYANN.(Enanthaldehyde and Pyrotartzric Acid.xxvi CONTENTS. IMXENDORP (H.). Carrotene and the Green Colouring Matter of Cldoro- phyll Grnins.CONTENTS. xsvii MASSOL (G.).BUITCHICHIN and ZELIXSEY.BISCHOFE' (C.A.). BISCHOFF (C.A.).BISCHOFF (C.A.) and .4 .xxviii CONTENTS.FITTIG (R.) and H.C.BROWN.EUSSEEOW (R.).Acids obtained by Heating Metahy drazobensoic Acid with Stannous ChlorideCOSTEX’TS.MAGNANINI (G.).Aldol.FASNACHT (A.E.) and C.R .S X S CONTENTS.PAGE G.SCHROETER.Orthocresolbenze'in. 898 .T) OEBNER (0.) and AZINCEE (T.).Hexachlor-tc -dike tohexene. MAZZARA (G.).New Hydroxythymoqiiinone.CIAMICIANxsxii CONTENTS. GIESEL (F.). Methylcocalne.GAZE (R.). Berberine and Hydroberberine.YEO (G.). StabilityCONTESTS. xxxiii PAGE PICTET (A.) and J. FERT. Action of Zinc Chloride on Methylacetanilide.1112 GATTERMANN (L.). Isomerism of Organic Substances coutaining Nitrogen .XXGV CONTENTS.BISCHOFF (C.A.). Azo-colours from a.Naphthylamine Dimethylaniline. BISCHOFF (C.A.) A.SIENBCKI. and H.BRODSKY.Sulplionation ofCOSTEXTS.xxxv PECIIMAKN (H.r.) and F.DAHL.Reduction Producte of 1 2-Diketones.LAYCOCK (W.F.).Isophoronexxxvi COSTEXTS.NEF (J. U.). Constitution of Quinone. HANTZSCH (A.).Stereochemically Isomeric Oximes of Paratolyl Phenyl KetoneCONTENTS. xxxvii NAGNANINI (G.). Conversion of the Homologues of Indole into Quinoline- derivatires. CLAUSxxxviii CONTENTS.MESSINGER (J.) and N.PICKERSOILL.Reduction Products of Iodophenols EEHRMANN (F.) and J.MESSINOER.Action of Hydroxylamine onCONTENTS.XXXlX FISCHER (0.) and E.HEPP.Fluorindine. and Nitroparatoluidine.xl COXTENTS.MARTIN (S.) and R.N.WOLFEXDEN.Physiological Action of the Active Principle of Jequirity.COSTESTS.xli ZUXTZ (N.) and C.LBEIMINN.Respiration in the Horse during Rest and Work.xlii CONTENTS.DIJXSTAN (W.R.).Scatole in the Vegetable Eingdom. DANIEL (L.). Inulin in the Capitula of Composites .COXTENTS.xliii SIEBERT (C.). Constituents of Scopolia atropoi'des.SIEBERT (C.). Constituents of Anisodus luridus.xliv COXTEKTS. HOTTER (E.). Occurrences of Boron in the Vegetable Kingdom and its Physiological Meaning.CONTENTS.REYSEN (I.) and T.V.M.BERTOX.Action of Acids on Benzoic Sulphinide FLUCKIGER (F.A).Estimation of Morpliincxlvi CONTESTS.JENSCH (E.). Estimation of Zinc in Manganiferous Flue Deposits.BRAND (A.).Use of Double Pyrophosphates in the Electrolytic EstimationCOKTENTS. xlvii PAQE 414 414 414 41 5 415 415 416 416 417 417 41’7 418 418 419 419 419 420 420 420 420 421xlviii CONTESTS. MKELLAR (W.G.). Convenient Solution for Use in Titrating Weldon Muds for Manganese Peroxide.CONTENTS.xlix WILLIAMS (E.). Maumene‘s Test foy Essential Oils.GASCH (R.). Estimation of Ferrocyanides in the Bye-products of GasCONTENTS.11 DENAYEB (A.). Analysis of Peptones. and of Pentaglucoses (Pentoses).CONTENTS.11 DENAYEB (A.). Analysis of Peptones. and of Pentaglucoses (Pentoses).L O N D O N :GURNEY & JACKSON 1 PATERNOSTER RCW.LONDON :HARRISON AND SONS PRINTERS IN ORDINARY TO HER MAJESTYC O N T E N T S .ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS :-Genera ILANDOLT (H.). Molecular Refraction.PETERSEN (E.). Heat of Neutralisation of Fluorides.LANDOLT (H.). Exactstances.SEUBE~LT (K.). Physical Constants of Halogen Substitution-products ofBenzene and Toluene .NERXST (W.).Reciprocal Influence on the Solubility of Salts.ROOZEBOOM (H. W. B.). Sudden Changes in the Solubility of Salts canscclby tlie FormationHECHT (W.) 31. CONRAD and C. BL~UCEXER. Determination of AffinityConstants.WALKER (J.). Determination ofHEUPEL (W.). Apparatus f o r limporating by the aid of Heat applied fromabove.XAGNANINI (G.). Emission Spectrum of Aminonia.MAQNANINI (G.). Absorption Spectrum of Nitrosyl Chloride.KALISCHER (G.). Electroniotilc Force of SeleniumKABLUKOFP (I.). Elcctrical conductivity of IIjdrogen Chloride in differentSolvents.GRUNMACH (L.). Electrical conductivityBRABDER (K. A.). Tliermoelectric Currents bctween amalgamated Zinc andZinc Sulphate.JAHN (H ).Electrochemistry andSTOHJIANN (F ) C.KLEEER and H. LASQBEIN. Thermochemistry of illethylAlcohol and solid Methyl Salts.COLSOS (A).EYKMAN (J. F.). Apparatus for making Vapour-density Determinationsunder Reduced Pressurc.WIENS (A.). Specific Volume of someSeries.LUBARSCH (0.). Absorption of Gases by mistures of Alcohol and Water .ETAHDWILEY (H. W.). Determination of Rlolecular Weights of Substances fromthe Boiling Points of their Solutions.PATERNO (E.). Behaviour ofLaw.ANSCHUTZ (R.).Can Raoult’s Method distinguish between Atomic andMolecular Union ?BREDIG (G.). Kinetic Nature of Osmotic Pressure.GALITZINE (B.). Sphere of Action of Molecular Forces.LEHMANN (0). FluidGROQER (M.). New Gas Burners.KLATT (V.) and P. LENARD. Phosphorescence of Copper Bismuth andManganese in the SulphidesDALE (T.P.). Refractive Indiccs of Gases.a dPAGEiv CONTENTS.TVALTER ( R ).Refractive Indices of SaltCARHART (H. S.). Standard Clark Cell.BLOCHMAKN (G. F. R.). Electromotive Forces of Cells containing MixedSalt Solutions .C ~ H S (E.) Spccific Inductive Capacity of Water.UOG~SKI (J. J.). Variations in the Electrical Xesistance of Xtrogcn FLY-oxidePFECFFER (E.). Change in Freshly-pepsred Solutions.BERTHELOT (D.). Electrical Conductii ity ns a means of Investigating theinteraction of Acids of Complex FtunctionBERTHELOT (D .). Electrical Concluctirities and Multiple Affinities ofAspartic Acid.RIMB~CH (E.). Correction of Thermometricside the Heating Medium.COHEN (R.). Experimental Determination of the Ratio of the SpccificHeats in Superheated SteamBERTHELOT and P.PETIT. Animal Heat and the Heat of Formation andCombustion of Urea.,.BAILHACHE and COMMELIN.MULLER-ERZBACH (W.). Dissociation of Salts containing Water and theConstitution of the Combined Watev.REID (E. W.). Osmosis with Living~ I E T E R I C I ((3.). Specific Volume of Aqueous Vapour.BORE (G.). Molecular Constitution of Isomeric SolutionsLE BLANC (nil.). Studies in Chemical Optics with reference to tlic Dissocia-tion Theory. .KOCHLONG (J. H.). Circular Polarisation of certain ‘I‘artmte Solutions .WARBURG (X.). Theory of the Voltaic Cell and of Galranic Polarisation .PE~RCE (B. 0.) andance of Batteries.STREINTZ (F.). Theory of the Secondary Battery.FROMME-4cid.LERNANN (0.).Transfer of Ions in Fused and Solid Silver Iodide .SANKEYLEHMANN (0.). Electroljsis of Mixed Solutions.GORE ((3.). Voltaic Energy of Dissolved Chemical Compounds.TCHERNAY (N. A.). DilatationJOAKXIS. Heat of Formation of Potassammonium and Sodammonium .TANATAR (S.). Thermochemical Data respecting Succinic and IsosuccinicA d s.NALBOT. n e a t of Combustion of Isndibutjlene and Isotributylene .BARUS (C). Relation of Volume Pressure and Temperature in the case ofLiquids .COOKE (J. P.). New Method of Deterinining Gas Densities.LOSSEN (W.). Formuh for Calculating the Molecular Volumes of OrganicEMDEN (R.). Vapour-pressure of AqueousBECKNANN (E.). Determination of the Molecular Weight from Vnpour-pwssure.EYKMAN (J.F.). CryoscopicXEKDEL~EFF (U.). Dissociation of Substances in Solutions.POTILITZIN (A.). Supersaturated Solutions.GORE (G.). Itate of Chemical Change .C0NRL4D (M.) and C. BHUCKNER. Determination of Affinity Coefficients .SPRING (W.). lncrease of Chemical Encrgg a t the Free Surface of LiquidS ttbstances .Ii~crino~n (J.). Chemical Energyv at the Surface of Liquids.XETGERS (J. W.). Isornorphisin.Compounds .PAGE321COXTENTS VGAUTIER (11.). Apparatus for Distillation under Reduced Pressure.,DOUMER (E‘). Refractire Power of Polritions of Siniple Salts .DOUMER (E.). Refractire Power of Solutions of Double Salts.SORET (J L.) and A. A. RILLIET. Absorption of Ultra-violet Rays by Deri-vatives ofGRUNWALD (A.). Spectroscopic Evidence of a New Element occurring i nTellurium and Antimony and also in Copper.BOISBAEDRAN (L.DE). SARRBEKIUS (S.). Conditions of Eq1iilibrinm between Electroljtes.,LEHMAX-N (0.). Electrolytic Crystallisation and Dimorphism of Lead.AMAT (L.). Sodium Phosphite and Pyroplio~pliite.PIGEON (L.). Heat of Formation of P!ntinic Chloride.ALEXBEFF (I?.\ and E. \T-ERNCH. Tl~e~~noehcmical Influence of certainGroups on the Value of thematic Series.PICKERIKG (S. I.). New Form of Mising Calorimeter.PICKEBINGTemperature a Few Degrees.DENIJTH (R.) and V. MEPER. Determination of Vaponr-densities of Sub-stances below their BoilingWSGNEK (G.). Viscosity of Liquids.MEPER (L.). Nature of Osmotic Pressnre.WOYESETARD (A.). Solubility of Saline Mixtnrcs.ETARD (A).Substitution of Salts in Mixed Solutions.GUYE (P.Points.TAX BERCHEM (P.). Equilibrium in Homogcneous Soiutions when Un-equally Heated .LACHOWICZ (B.). Residual Affinity of Inorganic Salts.FLEISCHL v. MARXOW (E.). Production of Monochromatic Light .BENDER (C.). Refractive Indices of XornialWBBNER (R.). Molerular Refraction of the Halogen Salts of Lithium,Sodium and Potassium.,.LE CIIATELIER (H.).Temperatures.STRETXTZ (F.).POINCARB (K.). Batteries with fused Blectrolrtes and the Thernio-electricForces Itt the SurfaceRICHAILZ (F.). Polarisation of Platinum Electrodes in Dilutc SulphuricPASCIXEN (F.). Surface Tension of Polurieccl RiIercnry in different Electro-lytes.MINET (.i.). Electrolysis of Fused dluniinium Oxide and Flnoride .VAN DEVENTER (C.X.) and L. ‘l‘. REICHER. Formation of Salts in BlcoholicSolution .BIQNON (L.). Tliermochemical Properties of Silk.LESC~EUR (H.). Compounds w h i ~ h linre a Tcnsion of Dissociation Equalto theT i V ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ (A). Composition of tlig Vnponr of Mixed Liquids .RAOGLT (F. M.)Acid.KLOBUKOFF N. v.). Influence of Capillarity a i d Diffusion on theAction of Liquids.VAX’T HOFF (J. H.). Nature of Osmotic Pressurc.NAUN ~ N N (A). Stereochemical and Mechanical Views with Refercnce toSingle and IMultiple Union of Atoms and the Clianges of one into theother .VAN DER WAALS (J. D). Molecular Theory of D Substalice forinrd Eroiiitwo different Substances.A Silver-Nercnry CellAcid.PAGE553Vi CONTENTS .VALENTA (E.).ApparatusPressure.BUROEMEISTER (A.).Apparatus for Prepming Gases.HERTZOG (AWALTER (B.). Refractive Indices of Saline Solutions.LOBACH (W.). Anomalous Rotatory Dispersion in Iron Nickel. andCobalt.BARBIER (P.) and L.ROUX.Dispersire Power of Aqueous Solutions .RYDBERG (J.R.). Structure of the Line Spectra of the ElementsLIVEINQ (G.D.) and J.DEWAR.Absorption Spectra of Oxygen .FEOMME (C.).Maximum Polarisation of Platinum Elcctrodes in SulphuricAcid .RICXARZ (F.). Galvanic Polarisation of Platinuni Electrodes in Dilute Sul-phuric Acid with High Current Density.ELSTER (J.) and HFormation of Ozone.KRANNHALS (E.).Electrical Conductivity of some Solutions at Tcmpers-tures between 18" andBERTHELOT (D.). Electrical Conductivity of Phenols and HydroxgbenzoicAcids.PLAXCK (M.).Development of ElcctricitpHOULLEVIQNE (L.). Electrolysis of a Mixture of Two Salts in AqueousSolution.ANDBEWS (T.). ElectrochemicalYLESSNER (P.). Influence of Temperature on the Magnetism of Salts ofMetals of the Iron Group.BERTHELOT andXOUTIER (J.). Combination of Sodium and Potassium with Ammonia .FOGXI (J.). Thermochemistry of Thiosulphates.BEKETOFF (N.). Heatof Combustion of RubidiumOSSIPOFF (I.). Heat of Combustion of Organic Isoniwides.PETERSEN (E.). Neutralisation Phenomena of Aluminium and Beryllium .OSSIPOFF (I.). Heat of Hydration ofCOLLEY (R.). Berthelot's Law of Maximum Work and Spontaneous Endo-tliermic Reactions.EASTERFIELD (T.H.).SCHALL (C.). Determination of Vspour Density.SAKURAI (J.). Molecular Volumes of Aromatic Compounds.NULLER (A.J.).DissociationFatty Acids in Solution.GOLDSTEIN (M.). Rise of Solutions in Capillary Tubes and the GeneralLaw ofRIBALKIN (M.).Chemical Equilibrium between Hydrogen Chloride andLUBATIN (N.). Freezing of Colloi'dal Solutions.WALKER (J.). Solubility and Heat ofROOZEBOOM (H.W.B.). Solution Equilibrium of Thorium Sulphate andits Hydrates.AirHjdrogen in Conjunction with Metals.XOND (L.) and C.LANGER.New Form of Gas BatteryWRIGHT (C .FRAXKLAND (E.). Chemisti*T of Storage Hatterics.s P I m 3 R S (C.L.). Electromotive Force of Afetallic SaltsSriz~sa (W.). Rate of Solution of Carbonates in Acids.Xp1trh.a (W.).SCHNIDT (G.C.). Change of Volume onPICKERIXQ (S.U.).The Nature of Solutions.PICKE~~IXQ ( 8.U.). 'l'he Theory of Osmotic Pressure .WATSON (G.). Precipitation.HILLTEIL (€I.W.). Self-regulating Gas Generator.Rate of SolutionPAGLIANI (S.). Deductions from Van't Hoff's Theory.PAQEG i G845CONTENTS. viiABNEY (W. de W.) and (3 8. EDWARDS. Effect of theHaloyd Salts of Silver.POIXCAR6 (L.). Polarisation of Electrodes.I~ERTHELOTt hroxide.L~ERTHELOT and ANDR~. Heats of Combustion and Formation of Nitro-genous Compounds derived from Albumino‘ids.UERTHELOT and ANDR~. Heats of Combustion ofCompounds in Living Organisms.VIGNON (L.). Thei-mochemistry of Wool and Cotton.CHRISTOXANOS (A. C.). NewWILDERMANN (M.). Boiling Points of Substances are a Function of theirChemical Nature.GORE (G.).SolutioiiRIC~ARDSON (A). Sealing Tubes under Pressure.BRUIIL (J. W.). Concentration of the Sun’s Rays for Chemical Reactions .DOUMER (E.). Refractire PowersSCHUTT (F.). Determination of the Molecular Refraction of Solid Com-pounds in their Solutions.BARBIER (P.) and L.Alcohols of the Fatty Series.GCCKEL (A,). Seat of the Variation of Electromotive Force with Tempcra-ture .GORE (G.). New Method and Departnicnt of Chemical Research .~YARBURG (E.).I’BSCHEN (F.). Surface-tension of Polarised Jlercury.J’HOMSON (J. J.).ORAETZ (L.). Electrical Conductivity of Fused and Solid Salts.EISCHOFF (C. A.) and P. WALDEN. Conductivity of the Substituted Suc-cinic and Glutaric Acids.EERTHELOT (D.). Conductivity of the Ammoniuin and Aniline Salts ofHydroxybenzoic Acids.-. ,NIKET (A.). Electrolysis of FusedWIRTZ (K.). Determination of the Heat of Vaporisation by means of thcSteam Caloriniet er.MATIGNONI~ERTIIELOT. Heat of Transformation of Isomeric Inosites.BISDEL (I<.). Specific Gravity Specific Heat and Heat of Solution of S u p -saturated Salt Solutions.S C ~ A L L (C.). Determination of Vapour-density.G-~LDEEEG (C. 31.).BRUIIL (J. W.). Crystallisation a t a Low Temperature.R~DORFF (F.). Constitution of Solutions.VAX’T HOFF (J. 11.). Solid Solutions and Molecular Weight Deteiminntionof Solid Substances.HECUT (W.) 31. COSXAD and C. BRUCKSER. Determination of AffinityCoeficients.LEPSIUS (B.). dction ofEmployment for Demon stration s.LErsrus ( U.).Lecture Experinlent for the Demonstration of ValencyLOETVEXHEEZ (R.).Molecular Refraction of Nitrates.COSTA (T.). Relation between the Molecular Refracthe Encrgy and theDispersive Yon-cr of Aromatic DcrivatiTes vChains. ,.Pliosphorescence produced by the Contact of Ozone withcertain Watcrs .Fall of Potential a t thc Csthode in Geissler’s Tubes .Laws of Molecular Volumes and of Boiling PointsSMITlI (A. P.).FAHRIG [E.).Tiolet Flame produced by ConiinoiiPAGEloPoviii CONTENTS.WERSHOTEN (F. J.). Electrical Conductivity of Solutions of Cac~rninm Salts,LSTAXOGLOG (P. L.). Electrolysis of Various Substances.LE BLANC (31.). Amalgams .I~EISSERT (A). Melting Points of Organic Compounds.PAGLTANI CS.). Deductions from Van’t Hoff’s Theory.XEICHE~L (L.T.) and C.Cliloride Solutions.DIEFFENRACH (0.). Heat of combustion and Constitution of Organic Com-pounds.LIEBREICII (0.). The “ Dead Space’’ in Chemical Reactions.SPERANSKI. Influence of Glass Surfaces on Velocity of Reaction .RETGERS (J. W.). IsomorphismKUSTER F. W.). Isomorphous Mixtures.BETHMANN (H. G.). Affinity Constants of Organic Acids. ,BARBIER (P-) andBARBIER (P.) and L. ROUX. Uspersire Porn-er of Acids of the AceticSeries.GENDRON.STREINTZ (F.) and (3. hTETJMbNN. Theory of Secondary Batteries .OSTWALD (W.). Electrical Properties of Semi-permeable Walls.PLANCK (31.). Difference of Potential between twoBinary Electrolytes.,NICHOLS (E. L.).Electrical Resistance of the Alloys of Perro-manganeseand Copper .OSTWALD (W.).Conductivity of Distiiled Water.MAGNANIXI (G.). Behaviour of Mannitol towards Boric Acid.SCHUTZENBEROER (P.). Effects of theWITZ (A.). Influence of the Magnetic Field on the Electrical Resistance ofGases.BEBTEELOTBERTHELOT and MATIGXON. Heats of Formation of Sugars. .BERTHELOT and MATIGNON. Heats of Combustion of Sulphur CompouncisBERTHELOT. Stability of Salts alone and inBERTHELOT. Equilibrium and Reciprocal Displacements between VolatileOrganic Bases.WILDERMANN (31.). Boiling Points of Substances areChemical Nature.CHARPY (G.). Determination of the Vapour Pressure of Solutions .ERAUSE (A.) andNERNST (W.). Osmotic Experiment.HORSTMANN (A.). RiYe of Solid Substances in Chemical Equilibrium .MENSCHUTKIN (N.).Affinity CoeKcients ofand of Amines.CHESNEAU (G.). Distribution of Hydrogen Sulphide between the Metals oftwo Dissdved SaltsCOLSON (A.). Berthollet’s Laws.COLSON (A.). Reactions of Organic Bases.NERNSTPACIF1365horganic Chemistry.THIELE (J.). Preparation of Chlorine in a Kipp’s Apparatus. 6THIELE (J.). Automatic Apparatus for EFolving Gases from Liquids.GBERTHELOT. ReciprocalHAUTEFEUILLE (P.) and J. MARGOTTET. Siruultaiieous Synthesis of Waterand Hydrogen Chloride.8LE CIIATELIER (H.) .Oxygen.liVOLHARD (J.). Preparation of Oxygen in a Kipp’s Apparatus .COKTEKTS.1 3ToRT3fATN (G.) and C.PAEBERG.Action of Sulphur on Solutions ofMetallic Salts.THIELE (J.). Preparation of Nitric Oxide.VAuBEL HEMPEL (9 ( .Clilorine from Sodiuni Chloride.DE SCHKJLTEN (A.).Preparation of Crystalline R’ormal Lithium Phosphateand Arsenate.DE SCHTJLTEN (A.).Cadmium Phosphates and Ai-senates.VORTMANN (G.) and C.PADBERQ.Action of Sodium Thiosulphltte onMetallic Salts .XABERY (C.I?.). New Method of Preparing Anhydrous AluminiumChloride.GORQEU (A).AlkaliVORTMANN (G.) and E.MORQULIS .VORTMANN (G.) and 0.BLASBERQ.Cobaltoctamine Salts.VORTMANX (G.) and G.Maaumnaaammonium Salts.RAMMELSBERG (C.). New Case of Isomorphism of Uranium and Thorium .PETERSEN (E.). Fluorine-AKSCHUTZ (R ) and N.P.EVAXS.Vapour-density of Antimony Penta-chloride.KEISBR (E.H.). Atomic Weight of Palladium.JOLY (A.) and M.V~ZES.Ruthenium Potassium Nitrites .EROEL (R.). Hydrochlorides of Chlorides.BLOMSTRAND (C.W.).Iodic Acid Double Salts of Iodic Acid with otherAcidsLUNGE (G.) and T.WIERNIP.Specific Charity of Ammonia Solutions .XEYER (G.). Derivative of Boric and Phosphoric Acids.WARRENBEEETOFF (N.). Combining Energy of Rubidium.CARNEGIE (D.). Potassium Plumbate.Crystalline Hydrated Thallic OxideENGEL (R.). Influence of Hydrogen Chloride onPOLECE (T.).Oxysulphides of Mercury.BAILLE (J.B.) and C.FBRP.GLATZEL (E.). Preparation of Mangancse from Manganese Chloride andDE KONINCE (L.L.). Rednction of Ferric Bromide by Boiling.BESSOX (A.) Phosphonium SulphateMercuricobalt Ammonium Salts .TAMMANN (G.).Hydrogen Peroxide.LESC~CR (H.). Iodic Acid.HARRIS (E.P.). Silicon.Chloride and of Lead ChlorideAluminium AmalgamMagnesium.MOISSAN (H.).Density of Fluorine.TRAUBE (hf.). Autoxidation.BRUNN (0.).JOANNIS (A.). Combination of Potassium and Sodium with Aminonia .FOCK (A.) and I(.KLUSS.Thiosulpliates.LEA (MHITCHCOCK (R.). Action of Light on Silver Chloride.ZOTTA (V.v.). Zinc Hydrosulphide.DEArsenate.MUHLHAUSER (0.). Egyptian Blue.KOSMAW .BRUNNER (H.). Synthesis of Double Sulphides of the Alkali Metals andSORET (L.) and F.ROBINEAU.Pr’ickeloxjdimnine Nitrite.STEIN (G.). DoubleEBEL (F.). Antimonates.the Heavy Metals.PAGB!h213x CONTENTS .SCHERPENBERB (P.A.v.). Behaviour of Bismuth with Sulphur and Sele-nium.MOISSAN (H.). Platinum Tetrafluoride.MOISSAN (H.). Colour and Spectrum of Fluorine.LOEW (0.). Formation ofRAYLEIGH (LORD).Composition of Water.POCK (A.) and K.KLUSS.Thiosulphatcs.BERTHELOT.Preparation of Nitrogen.BESSON.Freezing Points of Arsenic Chloride and Stannic Chloride .MAISCII (HWINKLE (C.).Reduction of Oxygen Compounds by Magnesium .POTILITZIN (A.).Properties of Sodium Perchlorate Supersaturated Solu-tions.LEA (M.C.). Allotropic Silrer.LEA (M.C.). Darkened Silver Chloride not an Oxychloride .FRENCH (A.).Pccdiar Crystalline Alloy of Copper Tin and Lead .WRIGHT (C.R.A.) and C.THOMSON.MUXZINB (L.). Compound of Vanndic Pentoxide with Sulphuric Acid .KLASON (P.).GAVTIER (H.) and G.CHARPY.BECKMANN (E.). MolecularSulphur.ILOWAY (L.). Formation of Ozonc and Nitrogen Oxides during Combus-tion .BESSOX.Combination of Hydrogen Phosphide with Boron Fluoride andSilicon Fluoride.BERTEELOT and P .Derivatives.ROOZEBOOM (H.W.B.).Combination of Alkali Metals with Ammonia .SENDERENSANDERSON (W.S.). Solubility of Calcium Carbonate in Fresh and SeaWater.JOHNSTONE (A.).Silicate.IT-INPLER ((2.). Reduction of Oxygen Compounds by Magnesium .\yYItOUBOFF (a.). CeriumJ OEW (0.). Preparation of V c ~ y Active Platinum-black.~ ~ O I S S A N (H.). Action ofTernary AlloysPrepnration of Chlorine Gas for Laboratory Purposes .Iodine in SoiutionNew Hydrate of Potassium Hydrogen Snlphate .TrIoMs (H.).Zincammonium Compounds.CITABRIB ((2.). Preparation of Carbon Fluorides.CHABRIB ((3.). Vapour-densities of Selenium Chlorides.KICHKOFF.Hytlroxylamine Hydrochloride .CRISNER (L.). Compoiinds of Hydrosylarninc with Metallic Chloridcs .UESSON.Combination of Ammonium and Hydrogen Phosphide with SiliconChloride and Silicon Bromide.JOAXNIS.Conipounds of the Alkali Metals and Ammonia.LET (G.).Blue Flame produced by Common Salt in a Coal Pire .STOLBA (F.). Ammonium Borofluoridc.STAS (J.S.). Silver.KASSNER (G.). Barium Strontium. and Calcium Plumbates.the Magnesium Serics a t High Tempei*atures.FOCR A.and~~AVTEFEUILLE (P.) aiid A.PEEREY.Sodium Beryllium Silicates .~IEYERHOFFXR W.). Saturated Solutions of Compounds of Cupric andPotassium Chlorides.YOLRARD (J.).Crystalline Mercury OxychlorideG (W.) and M.LCCION.Constitution of Manganese Peroxide .PAGE558CONTENTS .OSXOND (F.).OSMOND (F.).Influence of certain Foreign Metals on the Properties ofS tee1.Influence of Foreign Substances 011 Iron and Steel Relationbetween their Atomic Volume and the Allotropic Modificahions ofIron.Action of Sodium Carbonate and Bromine on Solutions ofNickel and Cobalt Salts.MXUNIER (S.).Chrome IronRECOURA (A.). Preparation of Hydrobromic Acid.HAMILTON (R.). Purification of Hydrofluoric Acid.CLNERON (C.A.) andLOEW (0.). Catalytic Formation of Ammonia from Nitrates.GIBSON (J.).L U D E m N a (C.). Prolnnged Action of the Electric DischargeSelenic Acid.ENGEL (R'.). Oxidation of Hypophosphorous Acid by Spongy Platinum .BESSON (A.). Combination of' Hydrogen Phosphide and Aminonis withCAZENEUVE (P.).SCBUTZENBEROER (P.). Condensation of Carbonic Oxide under the I n -BERTHELOT.Condensation of Carbonic Oxide and the Penetrabllity ofBoron Chloride and Silicon Sesquichloridefluence ofGlass by Water.SCHUTZENBERQER (P.).Condensation of Carbonic Oxide.HARPLEY (W .WINKLER (C.). Reduction of Oxides with Magnesium.PREIS (K.). Potassium Silicofluoride.F O ~ HSTOIELAS A (J.). Monocalcium Phosphate.TCEUSS (G.) and H.MORAIIT.Beryllium.FOGII (J.). Lead Thiosulphate..BERTHELOTGEISEEHEIXER (G.) and F.LETEUR.New Form of Ammonium Cliloride .POTILITZIN (A) .FRIEDRICH (I.). Lead Tetrachloridc.KsSSXER (G.). Lead Oxides.POOH (J.). Decomposition of Lead Thiosulphate by Heat.Lead TrithionatePOOH (J.). LendCELEY (V.H.). Conditions of the Reaction between Copper and NitricAcid.DITTEMAGRO (F.). Fluoroxy-salts of Moljbdenum.I'LCHARD (E.).Phosphotrimctatungstic Acid and its Salts.BAILEY (G.H.). AtomicSMITIX (E.17.). Vanadium in Potassium Hydroxide.CLASSEN (A.). Atomic Weight of Bismuth.ASTREAfALLET (J.W.). Rtoinic Weight of Gold.V ~ ~ Z E S (it!!.). Potassium Kitrosoplutinocbloride .C ~ O R E (G.). Rate of Deccmposition of Chlorine-water by Light.BLOUNT (B.).Igniting Point of S d p h ~ ~ i -.HAKKINS (J.D.). Silver Silicate.BRUGELJIANN (G.). Dimorphisin of Barium Oxide A New CatalyticPhcnomenoii .ERUGELRTANN (G.). Characteristics of the Alkaline Earths and of ZincOxide.BURTON (W .WARREN (H.N.). Crystalline Metallic Precipitates.GRIMBEET and B A R R ~ Coimcr Precinitate formed in Ordinarv Water .StrontiumDITTE (A.). Action of Sulpliuric Acid on Aluminium.Atoinic Weight of Magnesium .xiPAGE?08'708'709xii CONTEXTS .BETTENDORFF (A.).Earths of the Cerium andPORMANEK (J.). Uranyl Chromate and its Double Salts.SCHULTZE (B.). Precipitation of Tin from Acid Solutions by Metallic Iron .GATTERMANN (L.) andHydrogen Phosphide.MOISSAN (H.). Carbon Tetrafluoride.STILLMAN (T .SCHNEIDER (E.A.). Relation of the Hydrated Sesquioxides to the Saltsof Iron and Aluminium.GORQEU (A.).Manganese.KLOBB (I1.). Compounds of Ammonia with Metallic Perinanganates .MATTHEY (E.). Liquation ofGEISENHEINER (G.). Iridium Dioxide.HEMPEG (W.).Combustions under a High Pressure.LOEW (0.). FormationNitrogen.TASSEL (E.). Combination of Phosphorus Pentafluoride with NitrogenPeroxide.BESSOK.Interaction of Ammonia and Hydrogen Phosphide with the HaloZclPREIS (K.).Arsenic Compounds.CHABRIB (C.). CarbonBERTHELOT.Reduction of Alkaline Sulphates by Hydrogen and by Carbon .GUNTZ.Silver Subfluoride.OUVRARDANAT (L.). Lead Phosphites and Pyrophosphite.Compounds of Arsenic.CAUSSE (H.). DicalciumFOCK (A. ) and K.KLUSS.Thiosulphates.Ox yclilorides.Mercury.AUGE (E.). Sodium Alum.VOGT (G.). Composition of Clays and Kaolins.ROUSSEAU (G.) .DITTE (A) .Pormation of Crgstallised Metallic Oxychlorides CopperAction of theGORGEU (A.). Manganous Acid.GORQEU (A).Action of Hydrogen Peroxide on Perrnanganic Acid and Per-man ganatSCHNEIDER (E.A.). Relative Basicity of the Hydrated Sesquioxides ofIron and Aluminium.Isomeric Forms ofLACHAUD (A.) and C.LEPIEURE.Double Chromates.COLDRIDGE (W.).Electrical and Chemical Properties of Stannic Chloride .LEVY (L.). ActionFEIEDHEIM (C.) and 31.SzA3iAT6LsIiI.So-called Phosphovanadic Acid andits Salts.ROUSSEAURECOCRA (A.).FRIEDHEIX (C.). Complex Acids.ASTRE (C.). Bismuth Potassium Iodides.JOLYGEISENHEIMER (G.). Iridium Phosphorus Clilorides.GEISENHEIXER (G.).Combination of Iridium Phosphochlorides withArsenic Chloride.ASLANOGLOU (P.L.) Ammonia in Burnt Magnesium.SCHNEIDER (L).Water of Crystallisation.TIVOLI (D.).nate.KRAUSE (A.). Note on the Diamond.FOCK (A.) and I<.K L ~ S S .CLICHE (!I?.). On Copper Oxysulpliides. Potassium TctrathionatePAGEP ~ s c r (I,.). New Amnioniscal Mercury Compounds and a New Reactionfor Mercuramnionium Compounds.PCHRODER (G.).Cobalt and Kickel Oxides.Constitution of the Cobalt Chromium and RhodiumBases.BABANBEFF (A.). Cryoscopic Investigation of Colloids.Composition of some Metallic Sulphidesobtained in the Wet Way and Reactions of the Sulphide ofAu,S,.EAINER (A.). A new Anhydrous Double Chloride of Gold and Potassium .COSSANORLEY (E.W.). Carbon an Impurity in Hydrogen affecting Deteraina-JORGENSEN (S.M.).ANTONY (W.) and A.LTJCCHESI .tions of its Atomic WeightLEDI-c (A.).Air.AHRENS (F.B.). Rhombic Sulphur from Hydrogen Sulphide.NOYES (W.A.).Atomic Weight of Oxygen.UHL (Jp).Action of Sulphurous Anhydride on Metals .EE CHATELIER (H.). Expansion of Silica.KRUSS (G.) and H.MORAHT.Beryllium.ROUSSEAU (G.).Crystallised Basic Cupric Nitrate.WIXKLER (C.). Reduction of Oxygen Compounds by Magnesium .MORSE (H.N.) and HHalogen Cadmium Salts Cadmiiim Sub-hydroxide and Sub-oxicle .VORTMANN (G.) and E.BORSBACH.MercuricobaltammoniL~ln Salts .LEF~VRE (C.). Action of Potassium and SodiumPAGESesquioxides.BERG (A.).Chromiodates.KRUSS (G.) and KOUVRABD (L.).Z’RIEDHEIX ( C.) and W.SC BMITZ.DUYOKT .LEIDIP (E.). Rhodium Nitrites.SEUBERT (K.) and KGEISENHEIMER (G.). Iridium Phospliorus Bromides.Double Phosphates of Tin. Titanium. and CopperArsenovanadic AcidsIllinevalogical Ckemistry .BUCKING (H.). Glaserite from Douglashdl .Busz (K.). AtelesiteQORGETJ (A.). Artificial Preparation of Wollastonite .CHROTJSTCHOFF (K.v.). Anorthite and Enstatite .USSING (N.V.).Minerals from Fiskernas in GreenlandFIRKET (A.). Artificial PayaliteIGELSTROM (L.J.). Native Lead in Siberia.DARAPSKY (L.). Atacamite in Chili..... 1377.1378.1379.1380.1381.1382.1383.1383BLOMSTRA~D (C.W.). 111IQELSCROM (L.J.). Pleonectite. a New Mineral from Sweden. 112Cerium and Yttrium Phosphates in South Noi-way .GRUHN~LEMBERG (J.). Porrcstion of Silicates. 113EYEHMAX (J.). Mineralogy of the French Creek Mines. 113laELsrao&tGRODDECK (A.T.). Tourndine-bearing Copper Ores from Chili.LUZZATTO (G.). Natrolite from Monte Baldo.114T>EXK (H.).E’RIEDTIEIM ( C ).Bleteorites of Alfianello and Concepcion. 115I‘TRSTI.Composition of Roriinaiiinn Rock-salt.EYERMAN (J.). Calamine and Apophyllitc from the United States.113$.JOOREN (H.).The Transcaspisn NaphtLa District.115(:ENTEE (F .xiv CIONTENTS .EELLER (H.F.). Kobellite from Colorado.BELAR (A.). Aurichalcite.MUTHMANN (W.). Messelite. a New Mineral.BONIG (G.A.). Mazapilite. Anhydrite Eleonorite. &c. from XorthAmerica.CEDERSTROM (A.). Pseudobrookite from Havredal. Norway.GOLD~CHMIDT (V.). Chemical-mineralogical Theories.HUSSAK (E.). Artificial Preparation of Wollastonite.HUBBARD (L.L.). Nosean-bearing Ejections from the Laacher See.STEINECEE (V.). Leucitophgre from Persia.PBENDEL (R.). WiluiteBECKER (A.). Two Anal-ses of Mica.WULF (H.).Petrocraphy of South West Africa.MEUNIER (S.). Meteorite from Phu-hong.CLEEVES (J.F.) and J.C.PLATTS.Analysis of Waterwood Colliery.PFEIFFER (E.).Occurrmce of Hydrogen Sulphide and Sulphur in theStassfurt Salt Deposits .HALMBERG (A.). Native Lead from Yajsbeyg. Sweden.UUNZ (a.F.).SCHXEIDER (R.). Artificial Copper-bismuth Glance .BRAND (A.). Metallurgical Products from the Mechernich Lead Works .GLBTZEL (E.). Preparation of Crystallwed Iron Disulphide [Iron Pyrites] .FOULLON (H.I-.). Minerals froin theVOGEL (J.H.). Chemical Composilion of Vesurian.Fluor Spar. Opal. Amber. 2nd DiamondWHEELER'(€€.A.). Plattnerite from Idaho' .CHATARD (T.M.). Urao (Native Soda).FEIT (W.). Kaliborite a new Boron Mineral.JANNETAZ (E.). Pharmacolite fromBECEER (G.F.). Sil;cic Acids.CLARKE (F.W.). New occurrence of Gyrolite.IQELSTROM (LPIOLTI (G ).Cossaite from the Upper Susa ValleyMACHADO (J.).Aegirine.SCHNEIDER (A.). lnesite from Dillcnberg .BRANXER (J.C.) and R.N.BRACKETT .EEMP (J.F.). I'orphyrite Bosses in New Jersey.WHITFIELD ( JMEUNIER (S.). Meteorite from Mighei' Russia.SAEDBERGER (F.v.). New Meteorite from Chili.YEATES (W.S.). PsendomorphsSANDB ERGER (F.r.). Arhenical Pyrites.DE SCHTJLTEN (A) Artificial Formation of Malachite .FLUG (K.). New Variety of AluminiieMACEINTOSH (J.B.). Natirc Iron Sulphatcs from Chili .DARAPSKY (L.). Minerals from Atacama.HAWEINS ( J.I).) andHILLEBRAND (W.F.). 1)escloizite from ?Jew Localities .CHKOUSTCHOFF (K.v.). Art. ificial Rfagnesiit Mica.SCHUSTER (M.) and H.vPOULLON ( t 1.I-.) and V.GOLDSCIIMIDT.Epidote and MuscovitePeridotite from ArkansasHILLEBRAND (W.F.).Ursninite.SJOGREN (A.) and C.H.rlUNDSTRoM.Bnrysite. a New Lead Silicate .GENTH (F. A.). Gadolinite. Cacoclaqite. aid Monazite.HIDDEN (W.E.) and J.B.MACKINTOSH.Yttria and Thoria Minerals fromLlano Co. Texas.BLINK (G.). Rhotlotilite and Heliophyllite from Sweden.SCHNEIDER (A.). Manganese Ores from Ilillenburg.PAQEHOBBS (W.H.). Allanite and Epidotc as Rock Forming Minerals.46COXTEXTSWENJCKOFF (P. N.). Sphmolite Tachjlite froin thc L-ssuri District .VWT (G.).WILLDILLER (J. S.). Native Gold in Calcite.MALLARD (E.). Lussatite a New Form of Silica.HAWKINS (J.UENTH (F. A.). Corundum from Patrick Co. Virginia.GORGEU (A.). Psilomelanes and Wads.FEEDA (G.). Composition of SalineGENTII (F. A.) and S. L. PENF~ELD. Lansfordite and Nesquelionite .BLOMSTRAND (C.W.). 3lonazite from Ural.BLAXE (W. P.). Minerals fisomDANA (E. S.). Barium Sulpliate from Perkins' Mill Quebec .UENTH (F. A.). Jarosite from Utah.SEAMON (W. H.).FREDA (G.). Recent Vesuvian Lams.EAKINS (L. G.). Sew Stone Meteorite.WEINSCHEN'K (E.). MineralSEYFBIEDSBERGER (G.). Mercury Sulphates from a Furnace at IdriaPEARCE (R.). Supposcd New Mineral from Montana.SCHNEIDER (R.). Artificial Silvcr-Bismuth Glance.HANK^ (W.). Sjlvanite and Xagyigite from Nagj-ag.OEBBEKE (K.). Arsenical Pyrites from Wunsiedel.Rocks uEed in the Manuhcture of ChineseHRUSLER. iickel Ore from'Gosenbach.MICHEL-LfiVY and MIJXIER-CIIALMAS. New Forms of Crystallised silica .KRENKER (J. A.). Pseudobrookite from Vesurius .FUNARO (A). Composition of Limestones from the " Montagnola Senese ".Eocrr (A).Occurrence of Celestine and Baryta near Torda.NYIREDI (E.).BOURGEOIS (L.).dite.BROGGER (W. C.) and I€. B ~ C K S T RMURAKOZY (K. T.). Vivianite from the Szentes Artesian Well.Kovd6 (F.). Delvnuxite and Diadochite from Vysocany Bohemia .FLINK (G.) and A. UAXBERG.TCHAJTCHINSKY (M.). Serpentine from Finland.MERHIL (G. P.). Serpentine from Montvillt. New Jersey.CLARKE (F. W.) and (3.DOELTER (C.). Constitution of certain Zeolites.LINDSTROM (G.). Analyses of Idocrase.KIK~CIII (Y.). AnortliiteKALECSINSZKY (A.). Phillipsite from Somosko.KOZIOROFFSKI (K.). Artificial Production of Rock-forming Minerals ,THOULET (J.). Solublility of some substances in Sea-waterCLOWES (If.).Dellosits of Barium Sulpliate from Mine Water.HILLEBRAND (W. F.) and E. S. DANA. Tyrolite from Utah.HIDDEN (W.Carolina. .MASON (W. P.). Manganifcrous Spring Waters.OTTOCLAHKK (F. W.) and E. A. SCHNEIDER. Constitution of Talc .DOLTER (C.). Solubility of Minerals.TRAEBEMALLARD (E.). Tridymite and Clir) stobalite.HAUTEFEUIT~LE (P.) and A. PERREY. Crystallisation of Alumina and otherOxides ,.WILLIAMS (G. H.j. Celestine from Mineral Co. West Virginia.VERNADSKY (W.1. Phosphorites from the Government of Smolensk .BRUS~I (c* J.) and E.BRUHSS (W.) and K. Brsz. Phosphosiderite.Mean Composition of the Celestine Bed of KoppiLnd .s \-PAGE* 573. 711.711.,711P s v iPENFIELD (s.L.). Spangolite. a New Mineral.WILLIAMS ( 8.H.). Hornblende of St.Lawrence Co.NewVERNADSEY (W.). Production of Sillimanite Constitution of Porcelain .CROSS (W.) Phonolites from Colorado.IGELSTROM (L.J.). NewCOHEN (E.). Garnet from the Sout. h African Diamond Fields‘I’RAUBE (H.). Syenites and Hornblende-schists near Glatz in LowerSilesia.BROQQER ( W.C.). Minerals of the Syenite-pegmatite Veins of the SouthNorwegian Augite and Nepheline Spenites.BRIEDEL (C.) andMica.CROSS (W.). Some Secondary Minerals of the Amphibole and PyroxeneGroups .MEUNIER (S.). Mineral Waters of Malaisie and ti Tin Mineral in Processof Formation.DE GRAMONTBEETHELOT and FRIEDEL.Meteoric Iron from Magura Hungary .EAPINS ( L.G.). Meteoric Iron from North Carolina.DELACHARLONNY (P.M.). Normal Aluminium Sulphate.CARNOT (A.).blinerd Waters of Cransac (Aveyron).Os.ganic ChemistryCIAMICIAN (G.) nndLIPP (A.). y-Pentylene 8lpcol and its Anhydride.(;LASER (M.) and T.MORAWSKI.Action of Lead Peroxide on OrganicSubstances inVINCENT (C.) and DELACHANAL.Action of Ammoniacal Cupric Oxide onCarbon-compounds.GUIGXET (C.E.). ActionVINCENT (C.) and DELACHANAL.Sorbite.BOCK (J.). Transformation of Cane-Sugar into Dextrose.BERTHELOT.RaffinoseLOISEAU (D.). Fermentation of Raffinose by Beer-yeast.JONES (E.W.T.). Lactose.BRUSSING (G.v.). Methylhydrazine.KOHLRAUSCH (K.). Action of Methylhydrazine on Dialdehjdes and Di-ketones.CIAMICIAN (G.) and P.SILBER.Derirntires of Dichloromaleimide .B~uMANN (E.) and E.FROXN.Tliioaldehydes.BBUXANNCLAISEN (L.). Introduction of Acid Radiclcs into Ketone Molecules .MABERY (C.F.) and A.W.SMITH.Substituted Acrylic and PropiolicAcidsASSCHUTZ (R.) and A.R.HASLSM.Action of Phosphorus Pentachlorideon Chloralide.Tetrachlorethylidene Trichlorolactate.SCHONBROUT (R.).Derivatives of EthylBUCHKA (K.) and C.SPRAQUE.Ethyl Thiacetoacetate.I?ORMiNEK (J.). 8 Dithioxamide (Cyanogen Dieulphydrate). .XELIPOPP (P.) and Mvatives.VOLHARD (J.). Acetonediacetic or Hydroclielidonic Acid.YEHREND (R.). Alkyl-derivativesHOFFXANN (J.). Alkyl-derivatives of Methyluracil.LEHXANN (M.). Nitrouracil-derivatires.MAQUEXNE.Fiicusol.MAQUENNE.Relation between Sugars and Furfuran-derivatives.CIIABRIB (C.) .Thio-derivatives of KetonesHeleniuni and Oxygen-derivatives in the Benzene SerieePAQRCONTENTS.xviiPAGEANSCHUTZ (R.) andPhenol.Chlorination and Bromination of Aniline.Orthotoluidine,and Paratoluidine.Action of Nascent Nitrous Acid on Various Amines andPhenols.cIAMICIAN (GF.) and PHAFNER (R.) .DENINGPR (A.).NIEMENTOWSKI (5.). Some Nitrated Diaizoamido-compounds.FISCHER (E.). Trinitrohydrazobenzene.WILLGERODT (C.). Symmetrical Nitrophenylhydrazines of theSeries.FISCHER (E.) and F.ACH.Phenylhydrazone.TIEMAEN (F.). Amidoximes and Azoximes.MULLER (H.). Substituted Amidoximes.TIEMANN (F.). Action ofBenzenylamidoxime.WEISE (J.). Paranitrobenzenylamidoxime and Paramethylorthollitro-benzenylamidoxime.SCHUBARTDerivatives.SCHUBART (L.H.). Action of Carbon Bisulphide on the Potaseium-com-ISTRATI.Actionpounds.STRATI.Franceins.ISTRATI.France'in from 1 2 4-trichlorobenzene.ISTRATI.Action of Heat on a Mixture of Sulphuric Acid andDerivatives.MULLER (H.) and H.v.PECHMANN.a-KetoaldehydesBOZARSKI (B.).Isomeric DinitroparatoluicGREENE (W.H.). Acetometanitrobenzoic Anhydride.WOLFF (H.). Phenylallenylamidoxime-derivatives.poundof Parahomobenzenylamidoxime.OPPENHEIMERANSCHUTZ (R. ) and W.0.ENERY.Action of Phosphorus Trichloride onSalicylic Acid.ARBENZ (C.). Constitution of Isoeuxanthone.EHRLICH (E.). Oxidation of Orthocarbosycinnamic Acid.SEMPOTOWSKI (L.). Isomeric Derivatives of EthylbenzeneBROMM (E.). Disulphones and Trisulphones.BRIESS (I?.) and C.DUISBERG.Benzidine and Benzidinesulphonic Acids .HILLRINGHAUS (a.). Derivatives ofRICHTER (E.).Derivatives of the Two Isomeric Naphthenylamidoximes .CAZENEUVE (P.).Acetyl- and Ethyl-derivatives of Camphonitrophenol .CAZENEUVE (P.). Camphonitrophenol Phosphate.HERZIQXNCE (W.H.). Phenylated Indoles.HAIJFF (I!.).B- Naphthy lhy drazine.CAZENEUVE (P.). Camphonitrophenol Benzoate and Phthalate.TAKAHASHI (D.). Scutellarin.ARNAUD.Crystallised Digitalin .ANDERLINI (F.). Dihydropyrroline.ZANETTI (C.U.). Derivatives of Alkylpyrrolines.ANDERLINI (F.). Nitropyrroline-a-carboxylic AcidsMAQNANINI ((3.). Molecular Weights of the Imido-anhydrides of Pyrroline-ANDERLINI (F.). Action of Methyl Iodide on TetramethyldihydropyridineLADENBURG (A.). Synthesis of Oxypyridine and Piperidine Bases .PINNEBACE (F.). Phenylhpdrazonelevulinic Anhydride.carboxylic and Indolecarboxylic Acids.MEYER (E.v.).Hydroxymetadiazines (Hydroxypyrimidines)VOL.LVIII.bxviii COXTENTS .PAAL (C.) and M.BUSCH .LADENBURG (A.) and C.HUNDT .FIRBAS (R.).LIEBERMANN (C.). Cinnamylcoca'ine from Coca LeavesNENCKI (M.v.) and A.ROTSCHY.Hemotoporphyrin and Bilirubin .MALBOT (H.). Purification of Amy1 Iodide.MULLERPOLECE (T.) and K.TnuMatEL.Vinyl Alcohol a constant Constituent ofEthyl Ether.REPORMATZEY (S.). Synthesis of some Glycerols by means of HypoclilorousAcid.THIERFELDEB (H.). IdentityMAQUENNE.Eucalyptus Honey.POHL (J.). Precipitation of Collo'id Carbohydrates by Salts.ZINEEISEN (W.) .SEMBRITZKI (F.). Succinenediamidoxime.BIEDERHANN (J.). Glutarenediamidosime and its Derivatives.HOFPMAXN (C.).Hydroxamic Acids of the Fatty SeriesGABRIEL (S.).Intramolecular chango o€ Allylcarbamides into IsomericBases.HANTZSCH (A.). Conversion ofHANTZSCE (A.). Decomposition-products of Chloranilic Acid.ZELINSKY (N.). Two Isomeric Symmetrical Dimethglglutaric Acids .WISLICENUS (W.). Action of Bromine on Ethyi Osalacetate .Synthesis of Quinazoline-derivatives.Formation of Optically Active TropicBases Contained in the Young Shoots of Solanum Zuberosum .EERSTEIN (W.).Hydrastine.Acids and Opticaliy Active Atropines.SIEQBRIED (M.). Ethylenelactic Acid.Pyridine. and Thiophen-derivativesAUWERS (K.) and V.MEYER.Dicarboxylic Acids CSH,,O.,HJELT (E.). Allylethylsuccinic Acids.EMERY (W.0.). TricarbsllylicRENARD (A.) Phenylthioplien.SUIDA (W.).Derivatires of Ethylhenzene.HJELT (E.). XylylencEYEMAN (J.F.). Ethereal Oil of Betel Leaves.POLECK (T.). Safrole.SKRAUP ( Z.H.). Phloroglucinol.BORNEMANN (E.). Paratoluidine Oxalate.centratedEEHRMANN (F.). Action of Alkalis and Ammonia on Halogen-substitutcdQuinones.HAFNER (R.). ActionGIRATJD (H.). Action of Aluminium Chloride on Dimethylaniline .LASSAR.COHN.Condensation of Phenylenediamines with Butaldehydes .SCHIFF (H.) and A.VANBI.Fluorescent Derivativesammes.Amidoximes and Azoximes.Amidoximes and AzoximesMILLER (J.A.).Anisenyl. Salicenyl. and Methylsalicenyl-amidoxirues .EICHELBAUN (G.).Action of Hydroxylamine on Orthocganobenzyl Cy-anide.ROSENTHAL (E.). Homotei.ephthalenediamidoxime and its Derivatives .BISCHLER (A,.) and S.BmDsnl.Netanitrophenylhydrazinc a i d Parabrom-JANOVSKY (J.V.). Azotoluenes and Azoxytoluenes .TIEMANX (F.).LACHOWICZ (B.). Formation of Benzaldoxime.TIEMANN (F.).SPILEER (A.). Nitrogen-compounds of Salicylic Acid.GOLDBEEXI ((3.). IsophthnlenediamidoximeFBEUXD (M.). Hydrazines.BISCHLER (A.). Orthonitrophenylhydmzine.orthonitropheny lhjdrnzine.PAGBCOXTENTS.xixFISCIIER (E.) and F.PASSMORE.Formation of Phenylbydrazides .REISSEET (A.) and XV.KATSER.Action of Phenylhydrazine 3n theWeselsky's Resorcinol Dyes .Action of Chlorocarbonylamide on Sromatic HydrocarbonsBehariour of Aniline towards Substitution-derivatives ofAction of Aniline on AmidosalicylicAcid.droxy-scids and their Ethyl Salts.BUCHXER (E.).Acetplenedicarboxylates and Phenylhydrazine.HErMANN (K.) and H .NIETZKI (It.) A.DIETZC.and H.NACPLER .HARRIS (E.P.).LIMPRICHT (H.) .LIMPRICHT (H.) and v.RECIIESBERB .in presence of Aluminium ChlorideHydroxgbenzoic Acids a t High Temperatures.PRAQER (B.).Aromatic Substituted PseudothiocarbamidesHINSBERQ (0.). Piaselenoles and Piazothioles.SCHIFF (H.). Constitution of Filicic Acid.EINHORX (A. )hgde.LIPPMANK (E.). Carbothionylic Acids of Resorcinol and Pyrogallol .EINHORN (A) andon Malonic Acid.BOTTIXGER (C.). Benzoyltannin.ETTIPOLIS (A.). Tin Tetraphenyl.HANRIOT (M.) and 0.SAINT.PIERRE .BUCHER (E.).Pnramethjlbenzile and BcnzileparacarboxylicHEIXICHBN (0.). Dibromosulphanilic Acid and its Delsiratives.REULAXD (J.). Derivatires of Diphengline.MAUZELI~S (R.).1 ~'-lodonaphthalenesulphonicKUHAEA (&I.). Spccific Volumes of Camphor and Borneo1.WALLACH (0.) and A.OTTO.Isomeride of Camphor.Oxidation of TriphenylrnethaneWOODRUFF (l'.). Prepaixtion of Alo'in.CLAASEX (E.). Cephalanthin.ARNAUDHANSEN (A).Colouring hhtter of Chlorophyll.CLAUS (A.) and C.GEISLER.Dibromoquinoline.CLAUS (it.) and A.WELTEE.Bromine-derivatives of Quinoline.CLACS (A.) and G .SKRAUP (Z.11.). Gynurin.LIPPMAXN (E.) and F.FLEISSSER.Alkyl-derivatives of 1-Bydroxyquino-linc .BIEDERMANN (J.).Quinolincparanietlieiiylauiidoxime and its Depiratires .DOEBSER (0.) and J.PETERS.a-Cinnamenjlcinchoiiic Acid and ay-Quinol-inedicarboxylic Acid.SRPEP (0.). Hydroquinolinc-deriratives.NIETZKI (R.).The Formation of Aziiies from Orthodiamines and Poly-amines.SODERBAVM (I1.G.) and 0.WIIIXAX- Derivatives of OrthamidobenzoJ1Alcohol.SERAUP (2.H.)STRACHE (H.). Oriclntion-products of Quinoidine.GOLDSCEMIEDT (G.).Action of Potash on Alkyl-derivatkes of Pspaverine .GOLDSCHMIEDT (G.) and II.STHACHE .Acid.GERRARD (.4.W.) and W.H.S~I-MOSS.UlexineHAYCRAFTHOFMEISTER (F.). Preparation of Crptallilie Egg Albumin.SEBELIEN (T.). Peptoile and Similar Substances.C'odci.ne Methiodide.LE BEL (J.A.). Constitution of Petroleum.WAGYEE (G.). DiallSl Tetrcbronide3.h 2PAGExx CONTENTS .FOUQUET.Action of Hydrocyanio Acid on Calomel.VARET (R.).Ammoniomercuric Cyanides .VARET (R.). Interaction of Haloid Salts of Mercury and Zinc.FISCHER (E.) and J.HIBSCIEBEROER.Mannose.TANRET (C.).Sugar from the Qucbbracho.HERLES (F.). Formation of Raffinose.SCHEIBLER (c.)EKSTRAND (b.G.) and R.MAUZELIUS.Molecular Weights of Maltose andof several Inulin-like Substances.SCHUTZELANGE (G.) Lignin.OGLE (J.). Gum Trngacanth.LE BEL (J.A.). Absence of Rotatory Power in Amine Salts.PAAL (C.) and C.HERNAXN.Propargylamine and Derivatives ofamine.BEHAL (A.) and CEIOAP.Action of Heat on Chloral-ammonia .DODGE (F.D.). The Indian Grass Oils.LEVY (S.) F.C.WITTE and A.CURCHODand Tetrachloracetone.AUGER (V.) and A.B~HAL.Preparation of Acetic Chloride and of Chlor-aceticDUVILLIER (M.E.). Action of Triethylamiiie on Ethyl a-Brornobutyratcand Ethyl a-Bromopropionate.HAMONET (J.). Preparation of Alkjl SaltsKLIMENEO (E.). Ethylenelactic Acid from Flesh Extract.ANSCHUTZ (R.).Alkyl Hydrogen Oxalates Dichloroglycollates and Chlor-EMERY (W.0.).Constitution of SuccinicLOV$N (J.M.).Synthesis of Aconitic Acid from AcetylenedicarboxyIicAcid.ULUCKSMANN (G.).Alkaline Solution.GUINOCHET (E.). Isomeride of Tricsrballylic Acid.SWORN (S .MELLINGHOFF (W.). Paracyanobenzyl Chloride and its Derivatives .XEHRMANN (F.). Derivatives of Symmetrical DinitroreRorcinol.KEHRMANN (F.) and W.TIESLER .HERZIU (J.)EYKMAN (J.F.). Constitution of Asarone.ABENIUS (P.W.). Lactones derived from Glycines.SEYEWITZ (A).Metaphenylenecliamine from Resorcinol.MOORE (I.). Condensation-products of Carbodiimides and Orthodiamines .JACOBSON (P.) and V.SCRENCPE.Action ofoxalates Tetralkyl Oxalates.BISCBOFF (C.A.).Substituted Succinic Acids.BIELERHUGOUNENQ (L.).Chloraniso’ils.Derivat. ives of MetadichloroquinoneMAQUENNE.New Sugar with an Aromatic Nucleus .PALMER (A.W.) and C.L.JACKSON.Pentamidobenzene. -Azo-compounds and Hydrazones.BURCHARD (0.). Ethylenephenylhydrazine.UOLDSCHXIDT (H.). Oximes.TIEMANN (F.). Amidoximes and dzoximes .ZIMMEE (H.). Action of Aldehydes on Benzenylamidoxime.STIEGLITZ (J.).Behaviour of Amidoximes towards Diazobenzene-deriva-tives.MINUNNI ((3.). Constitution of Benzhydroxamic Arid.TRIYBLE (H.) and H.J.M.SCHEOETER.Oils of Wintergreen andof BirchPAALPOME BANZ (C.).Methy s ticin.ETTI (C.). Tannins.PAGECONTENTS.WURX (A.) Benzenylazoximet.heny1carhoxylic Acid and its Deriratires .KOCH (H.).Action of Ethyl Chloracetate on Benzenylamidoxime .BCCHER (E.). Oxidation of Paratolyl Benzyl Ketone .KOSTANECPI (S. v.). Azo-colours from Kaphtharesorcinol.TRIMBLE (H.) and H. J. M. SCHROETER. Oil of Camphor.FRAZER (T. R.).FUNARO (A.). SBnkgin from Poly-qala senqqa.PAAL (C.) and N. P. BRAIPOFF. PSr~olinc-derivatives.CIAMICIAX (c.) and c.LIPPMANK (E.) and 3’. FLEISSNER. nerivnt ires of 1-Hydrosyquinoline .CLSUS ( A.) Bromoquinolinesulphonic Acids.CLAUS (A.) andCLAUS (A.) and 0. WURTZ. Sulphonic Acids of 4-Bromoquinoline .CLAUS (A.) and Q-. ZUSCHLAG. 3 1-Bromoquinolinesulplioriic Acid andLIPPMANN (E.) and F. FLEISSNER. H~droxjquinolinesulplionic Acids .ABESIUS (P. W.). Paradiazine-deriratives.BLADIN f J.A.) Dit riazole-deriratires .CLAUS (A.).DURKOPF (E.). Belladonine ~.HARNACK (E.).HAYCRAFT (J. B.) and C. W. DUGGAS. Heat CoagulationYrot c’icls.BOYXOXD. Precipitation of Albumino‘ids from Urine.JAQUETHANTZSCH (A.) and A. WERNER. Arrangement in Space of the Atoms icthe Molecule of Carbon Compounds containing Nitrogen.MABEEY (C. F.) and A.and in Petroleum Residues.CIAMICIAN ((3.). Deriratives of niallyl.ANSCHUTZ (R.).VARET (R.). Action of Ammonia on the Compounds of Mercuric Cyanidewith Metallic Clilorides.KASSNER ((3.). NewKASSNER (G.). Nwv Application of Potassium Ferricpnide.BERTOSI (G.). Ethereal Salts of Nitrous Acid.REFORMATSKY (S.). First OxideCarbinol. .REFORMATSKY (8.). First Oxide of a TctraliFtlric Alcohol from DiallylCarbinol.VOTXOFF (A.).Delirdration of Monoliydric Alcoliols.MAQUENNE. p-Inosit e.RAYMAN (B.)BERTHELOT. Melitose.RAUMER (E. v.). An Unfermentable Dcxtrorotatoiy Constituent of HoneyPARTHEIL (A.). All~ltrimethjl~rnmoninni Compounds.CLAISEN (I,.) and L. MEYEROWITZ. Ketoaldehydes.KXLLER (H. F.).Symmetrical Tetrachlorobroniodiacetjl .MENSCHUTPIN (N.) and M. VASILIEFF. Decomposition of Aceticdride by Water.GABRIEL (S.). y-Amidobut,yric Acid. ,.AUTENBIETHREFORMATSKY (A.). Linole’ic Acid.ANSCHUTZ (R.) and C. BENNERT. Monocubstituted Succinic Acids .ANSCHUTZ (R.). Isomerism of Male’icZELIKSKY (N.). Ethyl Methylenemalorinte and its Polyinerides.LOKG (J. H.). Circular Polarisation of certain Tartrate Solutions .Bases tlerivecl from the Halogen AlkylREICIIWALD (R.).Funiarine.Preparation and Properties of Albumin free from AshxxiPAGECLAIS~N (L:). Conversion of Ethyl Acetoneoxalate int,o SymmetricalHydroxytoliucxxii COKTENTS .ANSCHUTZ (R.). Acetyltrichlorophenomalic Acid.HUGOUNENQ (L.). Chlorobenzenes obtained from Aniso’il.MAZZAEA ((3.). Derivatives of Bromothpiol .KEHRMANN (F.). Isomerism of Halogen Thymoquinones.ANSCHUTZ (R.) F.REUTER. and 0.SCHARPENBERG.Action of Aniline onHINSBERG (0.) andMABEBY (C.F.) and A.H.KRAUSE.Action of Aromatic Amincs on Bromo-propiolic Acid and on Substituted Acrylic Acids .SCHMIDT (C.).Action of Potassium Phthalimide on Halogen Compoundscontaining Oxygen.SCHOPFF (M.). Substitution of thethe Benzene-nucleus.OLIVEBI (V.).Synthetical Hydratropic Acid.OGLIALORO (A.) a dEPDMANN (H.). Derivatives of Benzallevulinic Acid.JACKSON (C.L.) and W.S.ROBINSOF.Action of Ethyl SodiomalonateTribromodinitrobenzene.WISLICENUS (W.) and I(.SPIRO.Action of Aniline on Ethyl Oxalacetateand Ethyl MetliyloxalacetateOTTO (R.). Sulpbone-derivatives.FLIMM (W.). Synthesis of Indigo from Bromacetanilide.ZELINSKY (N.) and M .Cyanide and Symmetrical Diphenplglutaric hcid.BAMBERQER (E.) and L.STBASSEE.Piclitelite.MATTHES (P.) .Benzene.BERNTHSEN (A.). a-N aphthylamine- and a-Naphthol-edisulplionic Acid .%HAL (A.). and V .PHOMINA (E.). Compounds of the Euxanthoilc Series.Phenanthridine.GIESEL (F.). Cinnamylcoca’ine occurrhig in Coca-leaves.ANSCHUTZCitraconic Acid and on Itaconic Acid.SEYEWITZ.Dihydroxydiphenvlamine.KUHLWEIN (A.).FormationSPIEQEL (L.). Constitution of Piclitelite.SCHULTZ ((3.). a-Naphthyl~mine-€-sulphonicDE VARDA (G.). Tertiapy Pyrrolines.PICTET (A.) and H.J.ANKERSYIT .DE BLASI (L.). Brieger’s TyphotoxineHARNACE (E.). Composition of Alhuiiiin.PAWLEWSKY (B.). Paraffin.KOHLERVARET (R.). Action of Cupric Salts on Metallic Cyanides.NIEMILOWICZ (L.).Action of Hydrobromic and Sulphuric Acids on PrimaryAlcohols .GOTTIG (C.). Compound of Calcium Chloride with Normal Propyl AlcoholKLOBUKOFF (N.v.). Cryoscopic Behaviour of the Aqueous Solutions of theSugars obtained Synthetically from ForrnaldehydeFISCHER (E.). Synthesis of Mannose and Levulose.COMBES (C.). Matezite and Matezo-dambose.GIRARD (A.).Rotatory PowerMAQUENNE and C.TANRET.Racemo-inosite.ALLEN (E.W.) and B.TOLLENS.Xylose and Wood-gum fromGABRIEL (S.) and W.E.LAUER.Deriratires of Propylamins.FBEUND (M.) and P.HERRMANN.Xew IIexylamine and aAlcohol.LE BEL (J.A.). Derivatives of Ammonium Chloride.LEVY (S.).Action of Ammonia and Ethylenediamine on Tetrachlorodi-acetpl.PAGECON'L'ENTS. xxiiiSIEBER (J.).HECHT (0.). Propylthiocarbamide and some New Thiocarbamides .BAKJMANN (E.).Thioaldehydes.BAUMANN (E.) and R. CAMPS.AUWERS (K.) and V. MEYER. AnhFdride Formnbion in Acids of the Suc-cinic Series.- .AUWERSglutaric Acid.GUINOCHET (E.).Tricarballylates.DEMETH (R.)HILL (H. B.) and L. L. JACKSON. Chloropyromucic Acids.KEHRMAXS (F.) Dependence of Substitution Phenomena on the Atomicor Molecular Weights of Certain AtomeBENTLEY (W.E.) and W. H. WARREN. Nitro-derivatives of Metabromo-toluene.,.HAFNER (A.). DerivativesJAHODA (It.). Orthonitrobenzyl Sulphide.NENCEI (M. T.). Compounds of Volatile Fatty Acids with Phenols .ZINCKE (T.) and 0.SEIFEET (11.). Beliaviour of Aniline with Substituted HpdroxybenzoicAcids a t a High Temperature.SEIDEL (P.).Formation ofdophenol.TAFEL (J.) and C. ENOCH.LETTS (E. A,) and It. F. BLAKE. Identitywith Tribenzvlphosphine Oxide.KEHRMASX (F.)" and W. TIESLER. Action of Hydrosylamine Hydro-chloride on Paradihydroxyquinones.BEHAL ,4. and 1'. ATJGER. Action of Etlijlmalonic Chloride on Ethyl-benzene.SIEBERMANX (C.).Cocaine.ERLENXETER (E.) Jun.Benzallerulinic Acid.KRAEMERPIKNER (A.). Action of Benzamidine on Ethyl Acetylmalonate.JACKSON (C. L.) and G. D. MOORE. Action of Etltjl Sodiomalonate onTribromotrinitrobenzene.POPPE (0.). Metaqlylmalonic Acid.GOLDSCHIIIDT (El.) and A. MEISSEER. Esperiments to Dctcrmine theConstitution of Tautomeric Compounds .HEBENSTREIT (P.).Sulphoncyammides.NIETZKI (R.) and B. POLLINI. Nitrotoluidinesulphonic Acids.CLATJS (A.) and 0. WELZEL. NormalAUWEES (K.).Paratolylphenylketoxime.POPPE (0.). Formation of Dibenzyl-derivatives.GRAEBE (C.). 'l'he Euxanthone-group .BAMBERGER (E.) and W. LODTER. ac.-Tctrahydro-P-naphthol andSecondary Closed Chain Alcohols.BAMBERGER ($1.) and F. BORDT. ar.-Tetrahydro-a-napllthol .ZAERTLIXG (It.). Derivatives of Nitro-P-naphthaquinone .CLAUS (A) and W.RUFPEL. Di-P-naphthjlketone Oxide.- .BAMBERGER (E.). Decomposition of nc. 1 4'-Tetrahydronaphthylenedi-arnine intoELBS (K.).Honiologues of Anthracene and Anthraquinone.LIEBERXASN (C.) and 0. BEIZGAMI. Truxene- and Trusone-derivatives .ERAEMIER (G.) and A. SPILKEB. Synthesis ofcarbons.CAZENEUVE (P.).Researches on the Constitution of P-Nitrocamphor andof a-Clilorononitrocamphor .CAZENEUTE (P.). New Bases Derived from Camphor. Cainphamines .Formation of Alkyl-derivatives of AmidesPAGExxiv CONTENTS.PAGEBAMBERGEB (E.). Camphoric Acid.BAMBERQER (E.) and W. LODTER. Action of Carbon Bisulphide onMenthol and Borneo1.517HALLER (8.). Activebornyl Phenylcarbamate. 515GINSBERQ (J.). Apiole.518LINTNER (C.EINHORN (A.).Synthesis of Alcohol-acids of the Ppidine Series.520CLAIM (A.) and G. POLLITZ. 2’-Bromoquinoline. 521CLAUS (A.) andCLAUS (A.) and M. POSSELT. 3-ETydroxyquinolinesulphonic Acid.523EOHN (C. A.). First Synthetically prepared Base Isomeric with Quinine.523LELLMANN (E.) and A. DOKNER.GABRIEL (S.) and P. HEYNANN. Preparation of Anhjdro-bases fromAmidomercaptans of the Fatty Series. 524LELLMANN (E.) and A. DONNER.from Toluylenediamine and Bromacetophenone.524ABBNIUS (P. W.). Paradiazine-derivatives. 525HECTOR (D. S.). Derivatives ofROSER (W.). Narcotine.528FREUND (M.) and A. ROSEKBERG. Hjdrastine.FRETJND (M.). Hydrastine.534BRUHNS (G.). Adenine and Hypoxantliine.STILLXARP (H.). Ricin.535GABBIEL (S.). Action of Hot Water on Albuminoyds.BEHREND (R.). The Stereochemistry of Nitrogenous Compound4.575WILLQERODT (C.W.).containing Nitrogen.576CASTHBLAZ andMALBOT (H.). Preparation of Octyl Chloride.577KEUTGEN (C. H.). Action of Sulphur on Glycerol.KKJENY (L.). Benzoyl-derivatives of Carbohydrates &c. 578ANDBEWS (C. W.). Inflcence of Temperature on the Specific Rotstion ofCane-sugar.LEPLAY (H.). BehaTiour of the Hydroxides of Calcium and the Alkalis withSugars.BEYTHIEN (K.) and B. TOLLENS. Compounds of Raffinose with Bases.580BEYTHIEN (K.) and 13. TOLLENS.HOFPMEISTER (W.). Celliilose and its Forms.BEYTHIEN (K.) and B. TOLLENS. Melting Points and Prepnixtion ofOsazones. 581HULLEYAN (T.). EthylMICHAELIS (A.) and B. PHILIPS. Ethyl Thioacetoacetattc.5&2BEYTHIEN (K.) E. PARCUS and B. TOTAESS.Arrangement of the Atoms in Space in CompoundsBehaviourPhenylhydrazine. *.5 & 1Formation of Lactic Acidfrom Raffinose and from Cane-sugar Rctffinose not formedsugarby the Action of Lime or Strontia.582BEYTHIEN (K.) E. PARCUS and B. TOLLENS. Lactic Acids fromMolasses .CSKJM BROWN (A.). New Synt.hesis of Bibasic Acids. 583CBUM BROWN (A.) and J. WALKER. Electrolysis of Potassium H t h TMalonato and Potaesium Ethyl Succinate.583FITTIQ (R.). Lactonic Acids Lactones and Unsaturated A d s. 583FITTIQFITTIQ (R.) and H. E. MILLER. Chloral and Succinic Acid. 58GFITTIG (R.) and A. DRLISLE. Propaldehyde and Succinic Acid.FITTIO (R.) and H. SCHMIDT. Butaldehyde and Succinic Acid.588FITTIG (R.) aEd A. BANNER. Isobutaldehyde and Succinic Acid.589FITTIQ (R.)FITTIQ (R.) and F. FEIST. Valeraldehjde and Pyrotartaric Acid.59CONTENTS.ssvPAQEFITTIQ (R.) and R.RIECHELYANN.(Enanthaldehyde and PyrotartzricAcid .KEISER (E.g.). Synthesis of FumtLric Acid.GUINOCHET (E.). Dibromotricarballylic Acid.DEMUTH (R.) andMULDER (E.).Action of Sodium and Potassium Ethorides on EthylTartrate.KILIANI (H.) and .GGuinochet’s Isomeric Tricarballjlic AcidPreparation of Levulosecarboxylic Acid .FISCHER (E.). Reduction of Acids of the Sugar-group.HILQER (A.) and 0.BVJCHNER .HILLLOSCHMIDT (J.). Stereoclieniical Studies.Constituents of Iceland Moss.HILL (IT.B.) and TV .Acid.MAZZARA (G.). Thymol-derivatives.LEUCKART (R.).PFLUG (L.).Pnraxylidine.BEST (T.T’.). Metlirlortliani.idine.REICHOLDMICHAELIS (A.) and I< GODCHAUX.Action of Tliionyl Chloride on TertiaryAromatic Amines.HEMPEL (A.).FISCHER (0.) and E.HEFP.Paranitrosodiphenylmetaphenylenediamine .GOLDSCHMIDT (H.) and Y.ROSELL.Hydroxpzo- and Amidoazo-coni-pounds.MICHAELIS (A.) and J.R VHL.Inorganic Deriratives of Phenylhydrazine .SMOLKA (A.) and A.FRIEDHEICH.Phenylainmcline and YhenylisocjanicAcid.VILLE (J.).DihSrlroiypliofipliinic Acid and €TSdl.oxyphosphinol~s Acid .SCHWECHTEX (E.). Isomcric Dichlorobenzaldehjtles and Naphthols derivedtherefrom.LIEBERMANN (C.). Tsocinnaniic Acid.FITTIG (R.) :md I?. RODERS.Yhenylparaconic Acid.REBUFATT (0.).ALDRINGEN (I?.). Thiocoumarins and their Gehaviour towards H? droxyl-amine and Phenylhyclrazine.HAtX&fANx (J.). Sitrobrrizil and its IsomericHEILMAXN (E.).X~lalp1i~li:ilide and its Derirutires.CLEVE (P.T.). Derivwt. ix es of 1 3-Dicliloronaphthalene.BABIBEIIGERCLAUSIUS ( A.).2 2’-I)ih~d~oinaphtIialene.HARDEN (A.). ~-Nitroso-~-nnphth~lainine.BAXBERGER (E.)amine.KYM (0.). Aromatic Caybaniide Chlorides.CLEVECLEVE (P.T.). 1 l’-Cl~loi~~naplit~halenesulphonic Acid.I(ONIG (K.). ~ - I ~ y t l r o x y ~LUCAS (L.). Hydrides of Anthracene and Phenanthrene.SACHSE (H.). Deriwtires of Dianthryl.WOY (E.FHALLER (A.) and MIXGVIN.HydroxgcampliocarboxSlic Acid from Campho-GBOENEWOLD (E.).ANDERLINI (F.). Drriratircs of Cantharidin.BLANCHARD (R.). C‘olnnring Matter from DiapfomusCarrotene.HEICEE (C.).Parn&idodiplienplamine.MOHR (P.). Action of AridireKUHN (€3.) and E.LAHDAV.P-DinaphthSlcarbamide Chloride.carboxjlic Acid.Alclin fi-orn Barbados Curacao andxxvi CONTENTS.IMXENDORP (H.). Carrotene and the Green Colouring Matter of Cldoro-phyll Grnins.MACCHIATIAKDEBLINI (F.). Pyi-oglutamic Acid.REISSERT (A.).Pyridine- and Pyrroline-derivatives from Anilidopyro-tartaric Acid.GROOS (A.). Compounds of Pyridine and Mercury Salts.BORSBACH (E.j. Metallic Quinolides and Double Salts of Quinoline .PELLIZZARI (G.). Compounds ofHESSE (0.). Morphine from Papaver ~hceas.EINHOEN (A.) and A. MARQUARDT. Dextrococitine.LIEBERMANN (C.) and F.Synthesis of Coca'ine.SCHMIDT (E.) and \I-. KERSTEIN. Berberis Alkaloids.SELLE (F.). Alkaloi'dsHILGER (A.).Taxine the Alkalo%l of the Yew Tree.LINTNER (C. J.). Diastatic Ferment of Ungerminated Wheat.METER (V.).Gum (P. A.). Chemical Constitution of Carbon Compounds and the Signand Variations of their Rotatory Power.BISCHOFF (C. A.). LimitationaLtoms. ,.MESLANS. Fluoroform.PATERNORaoult's Jfethod.,.OTTO (R.) and J. TROGER. Products of the Action of Propionitrile onChlorides ofOTTO (R.). Molecular Weight of the Solid a-Dichloropropionitrilc .PAREXTI (C.). Coloration of Organic Substances by Thiocjnnic Acid .WALLER (E.).Purification of Alcohol .Pom (0.). Etherificatioii by Uranium Salts.CHOUPOTSKT (A) and N. MAEIUTZA. Action of Clilorine on Tetra-methrleiic.MARIUTZA (N.). Action of Acids on Methjl Isopropenjl Carbinol .MARKOWNIKOFF.Derivatives of Heptametliylene.DOUBINEVITCH (W.). Pentatomic Alcohol and Unsaturated GlycerolDiallyl Carbinol.GRIMAUX (E.) and C. CLOEZ. Derivatires of Erytlirol.MEUNIER (J.).LOEW (0.). Formation of Volatile Fatty Acids from Dextrose.BIQINELLI (I?.). Action of E t h ~ l Acetoacetate 011 Dextrose in PresenceAlcoliolrc Aniinonia.ERWIQ (E.) and W. KOEKIGS. Pentacetyllerulose ,.LINDET (L.). Estraction ofRafinoqe from Saccharose.ALECIIIN (A.). Melezitose.MANGIN (L.).brane.CURTICS (T.) and R. JAY. Prepm*i~tion of Hydrazine from Aldehyde-ammonia .RDFIEMANX (S.). Constitution of Cicrazinamide.MELIKOFF (P.) and P E T K E ~ ~ O - I ~ RFatty Series.BUCHXER (E.). Action of Methyl Diazoacetate on the Ethereal Saits ofUnsaturated AcidsSULC (0.).Uolecular Weights of some Acids of the Oleic Series .ASCRAN (0.).HENRY (L.). Glvcollic Nitrile Direct Smthesis of Glrcollic Acid .CLOEZ (C.) IIyciroxytetric A ~ ~ C I.".".PAGEG,io'730'732CONTENTS. xsviiMASSOL (G.) .BUITCHICHIN and ZELIXSEY .BISCHOFE'BISCHOFF (C.A.) .BISCHOFF (C.A.) and .4.T.KOHLBERG .BISCHOFF (C.A) ancl E.VOIT .BISCHOFF (C .BISCHOFF (C.A.) and N.MINTZ .Potassium Hydrogen Malonate. Quadromalonate. and Quadr-oxalate.Symmetrical Diethyisuccinic and Methyl-Theory of Anhydride Formation in the Case of Acidsof the Succinic Series.PreparationAcids from Ethyl Malonate.Methylsuccinic. Ethylsuccinic.and Unapnimetrical Dimethylsuccinic Acids.The Two SymmetricalAcids.Relation of the Two Symmetrical Di-Symmetrical Ethylmetliylsuccinic Tri-metliFlsuccinic Symmetrical and Unsymetrical DiethylsuccinicEthyldiillethylsuccinic Acids.BISCHOFF (C.A.) ancl N.MINTZ.Anhydride Fornlation and IiitraniolecularChange of SubstitutedGERREZ (D.).Rotatory Power of Compounds of Malic Acid with NormalLithium and Magnesium Moljbdates.BISCROFF (C.A.) andof Eth? 1 Ethen~ltricarboxylate.BISCHOFF (C.A.) and.I. KUHLBEEG.Attempts to Prepare Alkyl-sub-stitutedDCVILLIRR (E.). Preparation of Betaines.WEISS (J.). a- and P-HomobetaYnes.MAYER (F.).EYKNAN (J.IT.). Conversion of Allylbenzene- into Propenylbnnzene-d erirat ires.G-~TTERMAXS (L.) andTHURSAU . 11 (G.). Preparation of Aromatic Thiocranates.ECEENROTII (11.) and J.RUCKEL.Diphenyl Carbonate.WENDER (V.)MAZZAR 4 (G.).Constitution of Bromonitrothymol Dinitrothymd Dinitr-amidocpene Dinitrocjmene and the Isomeric Chloro- nnd Bromo-thymoqninones.ZIXCPE (T.) and F.XUSTER.Action of Chlorine on Catcchol and Orth-HEHRMAKN (B.).Quinoncimides and Ainidoquinones.MARINO-ZI-co (F.). A HigherPICTET (A.1. Properties of Several Snilides.LEUCKART (R.). Syntheses by Means of Phenjl Cyanate.KLIXGEIL (13.) andbenzenes.KIETZKI (R.) and 1%.MAECPLER.Resorcinol and Orcinol ColouringMattcrs .FISCHER (0.) and E.HEPP.Inclalines.LETTS (E.A.) mid R.P.BLAKE .BIGIXELLI (P.). Action of Ethyl dcetoacctate 011 Cinnamaldehyde .CLAUS (A.). Aromatic Alkyl Ketones.FITTIG (R.) and J .JACKSON (C.L.) and G.I).MOORE.Action of Ethyl Sodacetoacetate onTribromodinitrobenzene.AKSHUTZaconanil and Pyrsnilpj roinlactone.I~ISCHOFF (C.A.) and N.MIIITZ.Be-qlsuccinic Acid and its Hon~ologuesBITTIGethylsuccinic Acids.methplsuccinic Acids to Pyrocinchonic Acid.Amido-compounds .amidophenol.Bcnzaldehjde and Pyrotartaric AcidPAGE'743'748'761$68xxviii CONTENTS .FITTIG (R.) and H.C.BROWNEUSSEEOW (R.).Acids obtained by Heating Metahy drazobensoic Acidwith Stannous Chloride.CARRARA (G.).Sulphonic DerivativesOTTO (R.) and A.ROSSING.MICHAEL (A.). Replacement of the Sodium in Ethyl Sodiophenylsulphone-acetate by Alkyls.ROSSING (A.). Analogy of Ketonic Acids to Sulphonecarboxylic Acids .STRASSMANN (H.). Indazole-derivatives.TAUBEE (E.). Some New Diphenyl-derivatives .REDZKO (‘7.).Derivatives of St. ilbene and Isostilbene.LEUCKART (R.). Action of Ammonium Formate on Ketoncs.ZINCKE (T.) and T .its Decomposition Products Orthotrichloracrylbenzoic Acid andPh thallylch loracetic Acid.CLAUS (A.).Dichloro-a-naphthaquinone Dichloride .ZINCPE (T.) and C.CAMPBELL.Azimido-compounds.ABEGG (R.). Amidochrysene.KOURILOFF (W.).FLAVITZKY (F.). Dextrorotatorj Terpene from Pinzrs cemhra.JUNBFLEISCH (E.). Camphoric Acids.HALLER (A.). Camphorates of theCAZENETJYE (P.). Phenolsulphonic Acids from Camphor.MASSUTE (F.). Constituents of Quassia amara and Picraena excelsa .Action of Acids on Litmus .KUHLINB (0.). Preparation and Properties of certain Pyrrolidone-deriva-tives.EDINGER (A.) .the Alkalo’ids.DURKOPF (E.) and H.GOTTSCH.Pyridine-derivatives from PropaldehydeBORSBACH (E.).ActionBTJCHKA (K.) and C.SPRAGUE.Action of Phenylhydrazine on Ethyl Thio-acetoacetate.SalicylaldehydePreparation of SulphonesMARSH (J.E.).and Propaldehyde-ammonia.BALBTANO (L.). Brominated Derivatives of 1-Phenylpyrazole.BALBIAHO (L.).BALBIANO (L.). Two Pyrazolebenzoic Acids.FISCHER (0.) and E.HEPP.Oxidation of Orthophenylenediamine .DEHOPF (H.). Nitro- andline.LELLMANN (E.) and W.0.MULLER.y.Conicei’ne Conyrine andConiine.LIEBERMANN (C.) and F.GIESEL.Bye-products from the Spthesis ofCocai’neMOISSAN (H.) and E.LANDRIN.Aricine.ANDEER (J.). Action of Rssorcinol on Egg Albumin.NETJNEISTER (R.). Reactions of Albumoses and Peptones.STADELMANN (X.).Protei’nchrome and Proteinchromogen.BRANDL (J.) and L.PFEIFPER .KUHNE (W.) and R.H.CHITTENDEN.Neurokeratin.BERTHELOT.The Marsh Gas Fermentation.DUNSTAN (W.R.). Double Cyanides of Zinc and 3lercui.y.SMOLKA (A.) and A.FRIEDREICH.Ammeline.FARRINGTON (T.). Mixtures of Alcohol and Water.PICKERINB (S.U.). The supposed Hydrates of Alcohol.DEMUTH (R.)JAEHNE (0.). Ethereal Salts of Phosphorous Acid.LONG (J.H.) and C.E.LINEBARBER.American Fuse1 OilRIRSCIX (P.). Derivatives of fl-Bromopropylamine.Tribromopropyl Alcohol and Tribromopropionic Acid.NIEMILOWICZ (L.).PAQBSO?COSTEX’TS .MAGNANINI (G.).Aldol.FASNACHT (A.E.) and C.R.LINDSEY .WENDER (V.). Conversion of Ethyl Acrylate into 8-Alanine.MELIKOFF (P.) and Pand Tiglic Acids.BENEDIKT (R.).Sclitnidt’s Process for the Conversion of Oleic Acid intoOSSIYOFF (I.).MAGNANINI (G.). Action of Aininonia on Dehydrodiacetyllevulinic Acid .ENKE (E.). Ethereal Salts of Alkyloxyquartenylic Acids.FITTIG (R.). Action of Sodium and Sodium EthosideBITTIG (R.) and H.RASCH.Valerolactone.FITTIQ (R.) and H.DUBOIS.Caprolactone.Action of Xethylamine on Ethyl Maleateand Fumarate.CIAMICIAN (G.) and C.ZATTI.EulyteFITTIG (R.) and A.SCHMIDT.Ethyl Prop?lparaconate.FITTIG (R.) and S.LEVY.Ethyl Terpenylate.FITTIG (R.) and J.KRAENCKER.Ethyl Tsobutjlparaconatc.BAEYER (A.) and H.RCPE.Recluction-products of Dicliloroniuconic Acid .QUTR ZEITDecahydrated Lead Acetate .Solid Fatty Acids.BREDT (J.). Acctyllevulinic Acid.Lactone Acids and on Lactones.KORNEB (G.) and A.MENOZZI .Acids and of Compounds containing Closed CarbonFITTIQ (R.).Action of Ammonia on Lactones.FITTIG (R.) and H.RASCH.y-Hydroxyraleramide.BARINGERPATEIN (G.). Sulphines.LADEXBURG (A.). Benzene Forniule.HAND (A.).YETRICOU.New Method of Chlorinating Aromatic Compounds.Action of Fuming Nitric Acid on Hexaclilorobenzene.STAHL (J.). Ethylxjlenes.Action of Sulphuric Acid on Tribroniophenol.XAZZARA (G.) and E.VIGHI.Thymol-deriratives.Constitution of Deriratives ofand Tliymol.WEKDER (V.). Trisubstituted-derivatives of Benzene.KEMPFF (K.). ActionGRUSEAQEN (H.). Action of Methjlene Chloride on Para- and Ortho-tolui-dine.PITTIG (R.) andISTRATI.Conrersion of Paraclichlorobetizene into Metadichlorobenzene .ISTRATI .GEORGESCO .XAZZARA (G.) .-4 NDREOCCI (A.).Action of Phenylhydrazine on Acetylurethane.FITTIG (R.) and Lcorresponding Primary Amines.ALEXBEFF (P.). Azocuniic Chloride.NEIJMANN (A.). Substituted PlithalimidesFITTIG (R.) and L.J.MORRIS.Action of Halogen Acids on Phenylbutjro-lactone.CLAISEN (L.) Preparation of Cinnamic Acid and its Homologues .EDELEANO (L.) and BUDISHTEANO.Preparation of Unsaturated AromaticAcids.NICOTERA (L.). Synthesis of Thymolcinnaluic Acid.ARBENZ (C.).Phenylsalicylic Acid.FITTIQ (R.) andFITTIQ (R.) and P.XDERS.Phenylitaconic Acid.BBTTINQEB ((3.). Eew Reaction of Tannin.ZATTI (C.). Nitro-derivatires of the Indoles.KAISER (J.1. Dbhenrl-deriratives.xxivPAGES X S CONTENTSPAGEG.SCHROETER.Orthocresolbenze'in. 898EILOART (A).Chlorine Compoundsof Tolane.899FORTE (0.). Naphthylanlidoacetic Acid.900PHOMINA (E.).phenylcneDOEBNER (0.). Coinpounds of Benzotrichloride with Phenols. 901BAMBERGER (E.) and C.BURGDORF.Amidochrysene.902NICOLAYSRN (C.).GTTCCI (P.). Santoninoxime and its Derivatives.902GRASSI-CRISTALDI (G.). Santoninphenjlliydrazoiie.903DE REP PAILHADE (J.). AlcoholicMACFARLAXE (W.W.) and P.S.CLARKSOX.Action of Chlorine onHzmatoxylin and Logwood Extract.Action of Ethyl and" Propyl Iodides on Potassiuma- and P-Naphthylphenylene Ketone O d e and Metliplcli-MAGNANINI (G.). Molecular Weights of P~n.oline-deriratires.306ZANETTI (CPyrroline. 907FISCHER (0.) and E.HEPP.Induline Group.EINHORN (A) and A.MARQUARDT.Dextrococafne.913ABEL (J.J.).bilirubin.SEUBERT (K.) and W.POLLARD .MolecuIar Weights of Cholic Acid Cholcstcrin and Hjdro-Vapour Density and Melting Point ofCyanogen Iodide.HAGELBERG (L.).Thiocyano- and SelenocJ.uno-clcrivatires. 9-10throl on Alkali Alkyloxides. 950SEUMLER (F.W.).WILLGERODT (C.). Stereochemistry of Nitrogen Compouiiils. 951GAYON (U.) and EBERG (A.). Chloramylamines.922GALEWSKY (P.).tion Products of Hydrocarbons.Action of Ammonia on Di- and Tri-Halogen Substitu-JBRGBNSEN (S.M.). Constitution of the Cobalt Bases. 953JORQENSEN (S.M.). MetallicANGELI (A.). Diinethylethylenediamine. 954 .ESCRWEILRR (W.). Formaldehyde. 554ORNDORFF (W .SPRING (W.j and E.TART.a-Dichloropropaldehyde.955XREER (P.C.). Action of Sodium on Acetone.VLADESCO.Products of the Distillation of Wood.956DTTVILLIER (E.).Action of Ethyl Iodide on Amido-Acids. 956DUVILLIEROTTO (R.) Ethoxpacrylic Acid from n-Dichloropropionic Acid. 957OTTO (R.) and G.HOMT .HENDRIXSON (W.S.). So-called Dihydroxymaleic Acid .Cliloride Ethylacetone-chloroform. 959a-Dichloro-Substitution Products of Dimethyl-succinic Acid.WILLGERODT (C.) and S.SCHIFF.Acetonechloroform Chlorisobutyric( 3 1 ~ ~ 0 ~ (H.B.) and C.F.KAHNWEILERSCHUTZENBERGER (P.).Condensation of Benzene and Acetylene underAcid.959the InfluenceFITTICA (F.). The Second Monobrombenzene.962f ( i j ~ ~ (B.) and M.SIEBERT.Preparation ofVINCENT (C.). Action of Lead Oxide on Toluene.96%LESPIEATJ (R.).Nitration of Propylbenzrne.OTTO (R.).Behavionr of Sodiophenylmercaptidc with Isobutyleiie Brom-~ATTERMANN (L.) and R.EHRHARDT and H.MAISCH.Synthesis ofide.Eetoncs from Phenol Etliers by Friedel and Crafft's Jletliod.96;ZINCEE (T.).Hexachlor-tc -dike tohexene.MAZZARA (G.)CIAMICIAN (G.) and P.SILBER. Safrole.OIAMICIAN ((3.) and P. SILBEB. Eugenol.NIETZKI (R.)quinone Ether.KROBER (T.). Derivatives of Ortho- and Para-tolubenzylamine.BISTRZYCKI (A.). Action ofHANTZSCH (A.) nnd A. WERNER. Stereochemically Isomeric KitrogenGATTERMANN (L.) W. HAUSSKNECHT A. CANTZLER and R. XHRHARDT.Diazo-compounds.HIWSBERG (0.). Piazothioles and Piaselenoles.TAPEL (J.) and C. ENOCH.GATTERMANN (L.) and A. Rosso~nxo. Blodification of the Chloroform-amide SynthesisHARTMANN (A,).Action of Carbonyl Chloride on Orthodiamines .GOLDENRING (A.). Derivatives of ‘I‘riinethSlenecliaiiiine.GUNTHER (H. K.). Derivatires of ParacynnobenzTl Chloride .MILLER (W. v.) and G. ROIIDE. Etard’s Renctioii.MILLER (W. v.) and G. RO~DE. Hydrocinnamic Aldehyde.CLAUS (A.). AlkylBOTTIKGER (C.). Dipyrogallopropionic Acid.JACKSON (C. L.) and W. 1). RANCROFT. Tetrabromodinitrobenzene .JACKSON (C. L.).Compounds preparcd fromNEF (J. U.). Tautomeric Compounds.LIMPRICHT (H.). Hydrazobenzeneclisulplionio Acid.STUPFER (E.). Decomposition of Sulphones .LAVES (E.). Oxidation of Phenyl Trithioformate.ZATTI (C.) and A. BEERATIXI. Acetgl-deriratire of Indoles.GRAEBE (C.). Benzilorthoc~rboxylic Acid .ZINCKE (T.). Azo-derivatives of Phenyl-,3 naphtliylaruine.MATTHES (P.).Azo-derivatives of Secondarv /I-Naphthplamines .EYM (0.)./3-Dinaphthylcarbamide Clilorqde and P-Tetranaplit~ylcarb-amide .EEBOM (A.). Action of Hydriodic Acid on 1 4’-Nitronaphthalenesnlphon-amide.MARSH (J. D:). damphoric Acids .KILIANI (H.). Composition of Digitonin.SCHALL (C.) and C. DRALLE. Brazilin.WIJSXAN (IT.D extrinase.REINITZER (F.). Kature of Gum Fermeiit,.DENXSTEDT (M.). Action of Acetone on Pproline.ANGELI (A.). Condensation-products of a-Acetylpyrroline with Benzile .TAFEL (J.) and A. NEUGBEAUER. Dimethylpyrrolidine andhexane.DUEKOPF (E.) and H. GOTTSC~. Pjridine-derivatives from Propaldehgdeand Propaldehyde-ammonia.DUREOPP (E.) and A. GOTTSCH. A New Lutidine.LELLMANN (E.) and M. BUTTKEB.Piperidine Bases.LELLMANN (E.)MXRCKWALD (W.). Quinoline Ring Bormation Constitution of Benzene .LELLXANN (E.) and H. BOYE. Colouring Matter from Tetrshydro-COMEY (A. M.). Etlianediquinol-yline.DOEBNER (0.) and 5. PETERS. Formation of a- and /3-Phenylenepjricline-ketonecarboxylic Acids.BALBIANO (L.). Synthesis of Pyrazole.EIN~ORN (*4.). Reaction between Cocai’ne and Atronine.Compounds.Formation of Alkyl-derkatives ofquinoline.PAGECOSTESTS. sxsxsxii CONTENTS.GIESEL (F.). Methylcocalne.GAZE (R.). BerberineYEO (G.). Stability of Oxyhremoglobin.ARAKI (T.). Methsemoglobin and Sulphur Methscmoglobiii.RITHKE (B.). Melamine.BAMBERGER (E.). Synthesis of Ammeline and Cyanuric Acid .AUWERS (H.) and v. MEYER.ASCHAN (0.). Constitution of Dibromhydrin.ASCHAN (0.).Atomic Rearrangement ofPARCUS (E.) and B. TOLLENS. Multi-rotation of Sngars .SCHEIBLER (C.) and H. NITTELMEIER. Melitriose and NelibioseWOHL (A.). Carbohydrates.Stereochemistry of Ethane-derirativ 'es .PAGE.1011.1011.1012.1012.1082.1082.1083.1083.1084.1084FLOURENS (G.). Products of tlie Saccliarification of ilniylaceous Substancesby Acids.WILLGERODT (C.).GeometricallyLAUER (W. E.). Derivatives of Propylamine.INCE (W. H.). Action of Amines on Diketopentamethylene.HANTZSCII (A.). Breaking the PentamethyleneKRAUT (K.) W. ESCHWEILER and G. GROSSMAN. Formaldehyde .BAUMASN (E.). Action of Hydrogen Sulphide on Aldehydcs.B$HAL and CHOAP. Chloralimide and itsHANTZSCII (A). The so-called Cyanoacetone.HANTZSCII (A.).Cyanoacetone.MULLER (I€.). Chloro-substitution-products ofREFORXATZKY (S.). Action of Bromine on Trimethylacetic Acid .PETERS (T.). Action of Alcohols on Ethyl Acetoacetate.PETERS (T.). Behaviour of EtherealAcids with Ammonia.REISSR (E.). Decomposition-products of the Sodium Salts of tlie Chloro-lactic Acids .BISCHOFF (C. A.). Brominnted Pyrotartaric Acids.AUWERS (I(.) and L. L. JACKSON. Determination of the Structure ofAliphatic Acids.BISCHOFF (C. A.). Trimetliylsuccinic Acid and Dimethjlglutsric Acid.PAAL (C.) and T. HOFFMANX. ?-Ketone Acids.BISCHOFF (C. A.). Synthesis ofPropenyltricarboxylate.REISSEBT (A.). Citraconanil and Pyranilpyroi'nlactone.FITTIG (R.) and G. PARKER. Condensation ofoxylic Acids.GERNEZ (D.).Combination of Malic Acid with Normal Potassium andSodium Tungstates .BISCHOFF (C. A.) and A. HAESDORFER. Distilhtion-products of Citrates .BISCHOFF (C. A.) and A. TIGERSTEDT. Action of Ethyl a-Bromisobutyrateon Ethjl Propylmalonate and Isopropylmalonate .HECHT (0.). Dialkylcyanothiocarbamides.BIELER (K.) and B. TOLLENS. Fucusol.HEBRMANN (F.). Configuration ofcule.CLAUS (A.) and IF. BUESTERT. Chlorine Substitutioli-products of Meta-xjlene.AMME ME EL ICE (H.). Action of Sulphuric Acid on Iodometaxylene .GARZINO (L.).Metadichloroplienol and Metadibromophenol.GABZINO (L.).Chlorodibromo- andversion into Q.uinones.ZINCKE (T.) and 0. KEGEL. Action of Bromine on Phloroglucinol .SPITZER (A.).GRIMAUX (E.). Homofluoresce'in.POYERABZ (C.). Phenol contained in Sassafras Oil..CONTESTS. xxxiiiPAGEPICTET (A.) andGATTERMANN (L.). Isomerism of Organic Substances coutaining Nitrogen.1112BISCHOFF (C. A.) and 0. NASTVOGEL.Acid.SCH~PFF (M.). Orthonitrodiphenylamine. 1113NIETZKI (R.) and 0. ERNST. 1114BISTRZPCKI (A.) and F. ULFFERS. Diacetylorthodiamines.SANDMEYER(T.). Diazobenzene a Correction.1115LELLMANN (E.) and H. BOPE.Diazo-salt arid a Phenol Residue.WILLQERODT (C.) .nium Sulphide. 1116FEHRLIN (H. C.). Isomeric Hydrazones of Orthonitroplien~lglyoxylic Acid 1117WILLGERODT (C.).GATTERMANN (L.) and A. RITSCHKE. Azoxyphenol Ethers.1119CIAMICIAN (G.) and C. U. ZANETTI. l’henylsuccinazone. 1120NORDENSKJOLD (0.). Cyanogen AdditiveBECKMANN (E.). Isomerism of the Aldoximes.1121BEHREND (R.) and E.KONIG. 1122SCHIFF (H.). Mercurobenzamide.ROTHSCHII~D (F. W.). Derivatives of Amidocinnamic Acid. 1123ASCHAN (0.). Oxanilic Acid.1124SCHIFF (H.)RATHEE (B.) and R. OPPENHEIM. Triphenylguanylthiocarbamide andDicyanodiamide. 1125VOLTYER (L.). Action of Hydroxylamine and itscarbimides. 1126EICHENGRUN (A.) and A. EINHORN. Paraniethox~dili~droxydihydro-quinoline and a New Case of StereochemicalGRANDE (E.). Pheneto’ilphtlialoylic Acid. 1128ERDMANN (H.). /3- and 8-Benzallevulinic Acid.1139GABRIEL (S.).BOETTINGER (C.). Oxidation of Gallic Acid Tannin and Oak-tannin. 1130BAEYER (A.) and J. HERB. Reduction-products of Terephthalic Acid.1130BISCHOFF (C. A.) and A.Benzyldimethylsuccinic Acid.1134TILLMANNS (H.).Anhydride of the Diphenylsuccinic Acids. 1135ALEXANDER (H.). Phenylmalic Acids.PARKER (H. C.). Diparatoluylene Sulphoside.1136OTTO (R.) and A. ROSSINQ. Displacement of the Sodium in Ethyl Sodio-phenylsulphonacetal by Alkgl-radiclesLANDSBERG (L.). Displacement of the Amido-group by the Sulplionic Group 1137TRAUBE (W.). AromaticSulphonamic Acids.1137MILLER (W. v.) and G.LIEBERMANN (C.) and F. HABBR. Bidioxymethyleneindigo. 1140BRUCKNER ((2.). Condensation of Dichlorether with Cresols. 1140BAEYER (A.) and R. L ~BUDDEBERG (M.). Displacement of tahe Methylene Hydrogen-atoms inDeoxybenzoh and Benzyl Cyanide Synthesis of Substituted Quin-olinc?.EPHRAIM (J.). Ilerivatives of Deoxybenzo’in.1143HOFPMANN (E.). Isomeric Cuminildioximes.1143AUWERS (IC.) and V.MEYER (V.).Molecular Weight of the Desaurina.1144BACH (C.). Benzjloxanthranol.1144BISCHOFFof Hydrocarbons obtained from Carminic Acid. 1145BAMBERGER (E.) and M. KITSCHELT. Reduction of Naphthalene an$Anthracene.ZINCEE (T.) and L. SCEMUXK. Action of Clilorine on Quinonoximes.1146Anilides and Toluidides of TartaricDerivatives of Diphenylamine and Phenazine.Intramolecular Transformation between aReduction ofA Dimolecular Isomeride of Benzaldoxime .Uenzylmethylsuccinic Acid andVOL. LVIII. XXGV CONTENTS .BISCHOFF (C.A.). Azo-colours from a.Naphthylamine Dimethylaniline.BISCHOFF (C.A.) A.SIENBCKI.Aniline and Naphthylamine with Potassium Hydrogen Sulphate .SEMMLEB (F.W.). Nutmeg Oil and Mace Oil.and a-Hydroxynaphthoic AcidTOBIAS (G.).Diazosulphonic Acids.WINZER (H.). Ethyl Camphorylmalonate.CAZENEUVE (P.). Amethylcamphophenolsu'lphone .JASSOY (A.).Peucedanin.JASSOY (A.). Ostruthiii.BISCHOPF (C.A.) and 0.NASTVOGEL.Distillation of Rosin in a Vacuum .HANTZSCH (A.). Formation of Pjrroline-derivatives.CIAMICIANine-derivatires.AWELI (A.). Action of Ethyl Oxalate on Pyrrpl Methyl Ketonc .GARDKER (J .STRACIHE (H.). Pyridineorthocarboxylic Acids.PANAJOTOW (G.). Orthoparadimethylquinoline-a-ald~liyde.SCHWARZE (R.). Polymerisation of Nitriles Cynnalkines.NASTVOGEL (0.). a-Aniliclol>ropioiiic Acid and a- Anilidobntyric Acid .NASTVOGEL (0.). Isomerism of the DiPhenyl-ay-dimetl~~ I-@-diketopiper-azines.NASTVOGEL (0.). Diphenyl-ay-diethyl-~8-diketopiperaziiic~.BISCHOFF (C.A.) and 0.NASTVOQEL.Diplieiiylkctopipcrazine and Di-BISCHOPF (C.A.) and 0.KASTTOQEL .BISCHOFF (C.A.) and 0.NASTYOQEL.Action of Cliloracetic Acid andOxalic Acid on Ethyleneparaclitolyldianiinc and Etliylenc-n-clinsphth3 1-diamine.BISCHOPF (C.A.) and 0.WASTVOGEL.Action of Acetic Anhydride on theAnilides. Toluidides.and Kaphthalides of Mnlic Acid.BISCHOFFBISCIIOFF (C.A) and 0.NASTVOQEL.Attempts to Prcprt Closed Chains.BALBIANO (L.). Derivatives of 1-Phenylppzole.HANTZSCH (A.). Diazothiazoles and their Decompositions.BLADIN (J.A.). Oxidation of Phcnylmetllyltriazoleci~r~ox~lic Acid .Compounds of Tertiary Amines with Acetic Acidphenyl-@-diketopiperazine.Oxalic Acid on Ethyleneorthoditolyldimnine.Tetra- and Tri-ketopiperazines.containing 2 Xitrogen-atoms and 2.3. and G Carbon-atomsTHOMS (H.). Ethosycaffe'iiie.HESSE (0.). Quinine. Cinchonine. and theirPASCHKIS (H.) and A.SMITA.Lobeline.CONINCE (0.DE).Ptoma'ines.Bromo-derivatires of Pseudobutylene.LADENBURG (A.). Conrersioii of Tropidinc into Tropinc.SCHMIDT (E.and I?.). AlkylhydrastinesPAVORSKY (A.) and C.DEBOUT.The Geometrical Isomerism of theXRAFPT (F.) and L.GROSJEAX .PAT ERN^ (E.) and A.PEBATONERFATORSKY (A.). Dimethylacetylene and its Tetrabromidcs.SMOLKA (A.). Constitution of the Derivatives of Cpnamide.UBTTIG (C.). Crystallisation of Sodium HydroxidePECHMANN (H.T.). Oxidation of 6-Methyletlijlet2iyle~ie Gljcol.FISHER (E.) and F.PASSMORE.Sugars Richer in Carbon. fromNASINI (R.) and A.SCAU.The Sulphines and the Different Vnlencies ofSulphur.REAFFT (F.).Xjristic Aldehyde.Hcxadecylene Bromide Derivatives .The two Diiodides of Acetylene .GABRIEL (S.).y-Chlorobutjronitrile .FISCHER (G.). Syntheses in the Sugar Group.PAGECOSTEXTS.xxxvPECIIMAKN (H.r.) and F.DAHL.Reduction ProducteLAYCOCK (W.F.).Isophorone.BUNQE (N.). Electrolysis of Fatty Acids.MARIE (T.). Oxidation of Cerotic Acid by Nitric Acid.NOEEDLINGER (H.). Decamethylenedicarboxylic Acid.HANTZSCH (A.). Halord Derivatives of EthylPIUTTI (A.). Ethyl Oximidosnccinates.~ E N T S C H E L (W.). Diacctamide.TANATAR (S.). Action of Alcoholic Potash on Bromosuccinic Acid .BEHREND (R.) and P.EBNERT.Condensation of Carbamide with EthylAcetoacetate.BEHREND (R.) and P.ERNERT.Diazouracilcarboxylic Acid and its Deriva-tives.OLIVERIand of Furfuraldehyde.CIAMICIAN (G.).Conversion of Pyrroline into Tetramethylenediamine .ANGELI (A.). Action of Ethyl OxalateBALBIANO (L.).The Pgrazole Group.Derivatives of Trimethylenephenyl-diamine.&rACNAIR (D .ZIEQLER (J.H.). Synthesis of Tetraphenylthioplien.CLAUS (A.) and G.RUNSCHKE.The Orientation of 4 6-Dichlorometa-xylene andROCH (E.).Dibromo- and Dichloro-xylenes and their Transformations byUHLHORN (E.). Laurenes.UHLHORN (E.). Propylxylenes .DAY (A.W.) and S.GABBIEL.Orthocyinobenzyl Chloride.MEYER (E.T.). Benzoyl Derivatives of Acetonitrile.KRAFFT (F.) and Gt.KOEKIG.Tricyanidee.BUDDBUS (W.). Action of Benzoic Chloride on Sodium Cyanamide in thePresenceSODERBATJN (H.(3.).Orthamidobenzyl Alcohol.ERRERA (G.). Action of Chromyl Dichloride on Cymenc.Z f Samicloplienol.SODERBATX (H.G.) and 0.WIDMAN.Phenylortliobcnzylenediamine andSaratolylorthobenzylenediamine .WILLQERODT (C.) and B.HEBMASN.Derivatives of Oi-thoparadinitro-phenplphen ylhy drazine.STAHEL (R.).DerivativesGOLDSCHNIDT (H.). Isomeric Oximes.HANTZSCE (A.). Thc Stereochemical Isoinerism of Asymmetrical 3lon-osimes.AUWERS (K.) and T‘. MEYER.Isomeric Hydroximes of Unsymm-tricalKetones and the Configuration of Hydroxylamine.WERNER (A.). A second Benzolnosimc .HOCHHEIM (P.). Arnidosimes.KEBMANN (F.). Constitution of Eurbodine Induline and Allied Dyes .WERNER (A.). Two Stereochemically Isomeric Derivativesoxime.GABRIEL (S.) and T.HEYNAKX.Oxazolines.CULMANN (J.).Tetraphenyltetracarbazone.MICHAELIS (A.). Thiophenylmethylpyrazolone.MICHAELIS (A.) and J.RABIKEBSON .CARRICKBeuzaldeliyde.QCHYEEQAXS.Vanillin from Rosa cnninn.NOAH (G.). Deriratiresmeans of Sulphuric Acid.COMSTOCK (W.J.). Alkylation of Foriiinnilidc.AromaticPAGExxxvi COSTEXTS.NEF (J. U.). Constitution of Quinone.HANTZSCH (A.).Stereochemically Isomeric Oximes of Paratolyl PhenylKetone .DOEBNER (0.). Formation of Racemic Acid by the Oxidation of Unsatu-rated Acids.EANTZSCH (A.).Ketone and Phenylglyoxylict Acid.BOTTINQER (C.). Gallic Acid Tannin and Oak-tannin. .BAEYER (A. v.). ConstitutionAcid.CLAUS (A.). The Constitution of Benzene.DOEBNEE (0.). Symmetrical Alkylisophthalic Acids.KNEBEL (W.).Derivatives of Yhenyl Salicylate (Salol). .BISCHOFF (C. A.) and A. HAUSDORPER.BISCHOFF (C. A.) and A. HAUSDORPER. Derivatives of Orthotolylglycin .KULZ (E.). Compounds of Glycuronic Acid.JACKSON (C. L.) and G.Acid.EBBERA ((3.). Nitrocymenesulphonic Acids.CABBARA (G.). FormationMonochloride. .KRAFFT (F.). Dibenzamide.FBANKE (E.) .ANGELI (A.). Diphenylacetylenediureine and some of its Derivatives .BERTRAM (A.). Monophenylthiocarbamide and Imidothiocarbaminates .ZIEGLEB (J. H.). Preparation of Aromatic Sulphides and of ThionanthoneZATTI (C.)ZATTI (C.) and A. FERRATINI. Nitrosoindole.ZATTI (C.) and A. FERRATINI.CIAMICIAN (G.) and P. SILBER. Constitution of Apiole andSENEOWSKI (M.). Trimethylphcnylmethane.BECHHOLD (J.).Carbazoledisulphonic Acid.SCHIFF (H.) and A. VANNI. Benzidine .WALDEN (P.) and A. KEBNBAUM.BAMBERGER (E.). Contributions to the Theory of Six-membered “ Rings ”BAMBERGIER (E.) and F. LENBFELD. Characteristics of the HydrogenationProcess .SCHMIDT (M.). Action of Sulphucous Anhydride on Nitroso-compounds .GBOGJEAN (L.). aa-Dithionaphthol.EYM (0.). Thio-deriratives of Aromatic Aniines.WITT (0. N.). Cyanamines a New Group of Dyes.HAUSDORFER (A.). Constitution of Diphenyl- and Phenylnaphthylamine-Blue.BISCHOFF (C. A.) and A. HAUSDORFEB. Derivatives of a- and &Xsphtliyl-glycin.PATE EN^EUHN (B.) and W. LANDAU. p-Dinaphthylcarbaniide Chloride and PTetra-KBAFFT (F.). Dinaphthyl Sulplides and Dinaphthylsulphones.BAMBERQEE ((3.) and C.BURQDORF. Chrysene.WAGNER ((3.). Camphene Glycol and a Tetrahydric Alcohol from LimoneneWALLACH (0.). Terpenes and Ethereal Oils.WALLACH (0.). Pinepe .WALLACH (0.). So-called Massoyene.PIESZCZEK (E.). Constituents of the Bark of Nerium oleander.KOHLER (0.). MyrrhSCHNEIDER (A.). Damascenine from NigelEa damascena.BECEURTS (H.). Ferrocyanides of the Allialoi’ds.BAMBERGER (E.) and F. LENQPELD. Reduction-productsCLAUS (A.) and A. WELTER. Rromo-derivatives of Quinolinc.Synthesis of /3-Tndolecarboxylic Acid .Isomerism in the Stilbene-group .naphthylcarbamide.PAGBCONTENTS. xxxviiNAGNANINI (G.). Conversion of the Homologues of Indole into Quinoline-derivatires.CLAUS (A,) and H.quinoline and Parahydroxyquinoline.KYRITZ (G.M.). Acid Deriratires of Orthamidoquinoline. MILLER (W. r.). Regularities inOTTO (R.) and G. HOLST. Action of Phenylhydrazine on Pyrocinchonic,a-Dichloro-symmetrical-dimethylsuccinic and a-Dicliloro-propionic An-hydrides and on Pyrocinchonic Chloride.LELLVANN (E.). Coniceynes.BECKURTS (H.).Strychnine.BECKURTS (H.). Brucine.BISCHOFFBISCHOFF (C. A.). Stereochemical Studies in the Piperazine-group .BISCROFF (a. A.) and C. TRAPESONZJANZ. Diphenylpiperazine.BISCHOFF (C. A.) and A. HAPSDOBFER. Diphenyl-ay-azine.BISCHOPF (C. A,) and A. HAFSDOBFER. Ortho- and Para-ditolylpiperazinesand /3-Dinaphthylpipenzine .HEIM (M.). Hydrastine a Correction.LADENBUEQ (A.). Conversion of Tropidine into Tropine.VILLARD. Hydrates ofSACHSE (H.).Geometrical Isomerides of the Hexamethylene Derivatives .QRUD’HOMME. Nitroprussides.B’REUSD (N.) and F. LENZE. Tertiary ButylcarbinolSELL. Amy1 Alcohol in Brandy from different parts of the German EnipireMOUBGUES (L.). Mannitol Hexachlorhydrin.MEUNIER (J.). Conversion of GlucoseVINCENT (C.) and DELACHANAL. Hydrogenation of Sorbin and Oxidationof Sorbite.FISCHER (E.). Optical IsomeridesSaccharic Acid.BUNTHER (A.) and B. TOLLENS. Fucose an Isomeride of Rhamnose .LADENBURQ (A.)of @-Picoline. ,.GRIMALDI (S.). Methylnonylplienylhydrazone.COMBES (A.). Derivatives ofKRAUT (K.). Formation of Glycocine from Chloracetic Acid.HAL LEE^ (A). Alkyl Dicyanacetates.GERARD (E.). New AcidPIOTROWSKI (S.). Addition of Chlorine and of Halogen Acids to Oleiicand Elddic Acids.MASSOL (G.).SKRAUP ( Z.H.).Conversion of bfaleiic Acid into Pumaric Acid.BUCHKER (E.) and €I. WITTEB. Symmetrical TrimethjlenetricarboxylicAcid.FISCIIER (E.). Acids of the Sugar Group.BOUTROUX (L.).Hgdroxygluconic Acid.MALYSESTIXI (F.) and L. SESTINI.LINDET (L.). Presence of Furfuraldehyde in Commercial Alcohols .FRIEDBURG (L. H.).Preparation of Thiophen.BIDET (A.). Alteration of Compounds of the Benzene Series when exposedto Air and Light.FRIEDBURGVarious Substances in Solution in Carbon Bisulphide ,.VILLABD. Hydrates of Gases.MASSOL (G.). Lithium Malonates .Ammoniacal Fermentation of Uric AcidBAUK (A.). Artificial Musk.LEPETIT (R.). Action of Nitrogen Iodide on some Orgmic SubstancesPAGExxxviiiMESSINGER (J.) and N.PICKERSOILL.Reduction Products of IodophenolsEEHRMANN (F.) and J.MESSINOER.Action of Hydroxylamine on Nitroso-phenols.EEBZIG (J.) and S.ZEIGEL.Desmotropy in Phenols.ZOLKOWSKI (E.) and K.PETERS.Orcei'n.SPITZER (A.).Tetramethylphloroglucinol.FREUND (N.) and P.IMMERWAHE.Reduction of Nitriles.HERZ (R.). TriphenylarnineIJELLMANN (E.) and F.MACK.Dinitrodimethylamidodiphenylamine .ELAUBER (A.). Xylylhydrazine.GOLDSCHMIDT (H.) and H .GOLDSCHMIDT (H.). Oximes.BEHREND (R.) and E.EONIG.Two different Xodifications of Parsnitro-benzylisobenzaldoxime .GRESSLY (0.) and M.NENCKI.Constitution of CarbonlylorthamidophenolCOMSTOCK (W.J.) and F.KLEEBEBB.Silver Formanilide.PASL (C.)GLUCKSYANN (C.). Oxidation of Ketones by Potassium Permanganat e inAlkaline Solution.LIEBERUANN ((3.).Isocinnamic andHECHT (J.L.). Dichlorosalicylic Acid.DITTRICH (E.). Action of Picric Chloride on Ethyl Sodacetoacetate .PUROOTTI (A.). OrganicRENARD (A.). Phenyldikhienyl.FISCHER (E.) and J.MEYER.liethylation of Indoles.STAEDELFREUND (M.) and P.RENSE.Reduction of Xitriles.MELLJN (E.).Triphenylbenzene.CLAUS (A.). Constitution of Naphthalene.LOEWE (E.). Constitution of Dinitro-P-naphthol.LIEBERMANN (C.). Theory OPFRIEDBURG (L.H.). Formation of Anthraquinone.Rotatory Power of Camphor when Dissolved in Various Oilsphenone.BACH (C.). Benzyloxanthrttnol.GOLDMANN (F.). Mesoanthramine.LBQER (E.). Combination ofANDRES (H.). Russian Oil of Peppermint.DENNSTEDT (M.).Conversion of Pyrroline into its Homologues.AKDERLINI (I?.). DerivativesKRUQER (M.). Betai'nes of Pyridine Bases.CHABOT (P.).ZANETTI (C.U.). Tertiary Pyrroline Derivatives.ANDERLIKI (F.). Action of Methyl Iodide on Pentamethvldihydropyridine .LADENBURG (A.). The Second P-Picoline and the Constitution of Pjridinearid Benzene.KOENIGS (W.).Formation of Lepidine Derivatives from Chinine andCinchine.BUSCH (A.) andMATZDORFF (A.). a-Picolylethylnlkine and its Derivatives.PRAUSKITZ (G.). Methylethylpyridylalkine.SCHUFTAN (E.). Metanitro.a.stilbazole its Reduction Products and Anid-ELEINidenepyridylalk ine.BUTTER (F.). Hydroxy-a-stilbazole and its Derivatives.MAQUENNE.Derivatives ofFREUND (M.) and F.KUII.Constitution of Carbizines.GABRIEL (S.) and R.JANSEN.Quinazolines.PAAL (C.) and 3'.KRECPE.Diliydroquinazolines.FISCHER (0.) and E.HEPP.Osidetioii Products of Orthoiliamines andOrthoamidophenols .PAQECONTENTS.XXXlXFISCHER (0.) and E.HEPP.Fluorindine.and Nitroparatoluidine.ALEXANDER (H.). Attempts to Synthesise Conhydrine.TAFEL (J.). Strychnine.AHRENS (F.B.).LIEBERNANPI’ (C.).Oxidation of Ecgonine.BOHB (C.). Compounds of Heemoglobin with Oxygen.LEICESTER (J.) .Ph y s io 1 og ical CA einis try .ROSEKTHAL (J.). Calorimetric Investigations on Foods.JOLIX (S.). Conditions of Absorption ofTBAUBE-MENQARIN (M.). Gases in the Swimming Bladder of Fishes .ELLENBERGER and HOFMEISTER.Digestion in the Pig.GXUENHAGEN (A.) and KBOHN .COPPOLA (F.). Origin of Urea in the Animal Economy.HORBACZEWSKI iJ.).Origin of Uric Acid in Mammals.MOLINARI (A.).KATJFFXASN.Diastatic Ferment of the Liver.LAPICQUE (L.). Quantity of Iron in the Spleen and Liver of YoungAn in1DASTRE (A.). Physiological r61e of Lactose.ZEINITZER (F.). Physiology of the Tannins.WINTER (J.).Reducing Substance in Urine.KIRK (R.). Uroleucic Acid and Alcaptonuria.MESTER (B.) .BUNGE ((3.). Respiration of EntozoTc Worms.BERTHELOT .BEETHELOT and P.PETIT.Animal Heat.STUTZEB (A.). Artificial Digestion of ?roteids.GIHSBERG (S.). Absorption of Sugar from the Small Intestines.REID (E .ILOSVAY (L.). Detection of Xitroua Acid in Saliva.ASHDOWN (H.H.). Reducing Substnnccs in Urine.SCHTTLTZECABLES (P.). Is Potassium Ferrocjaiiide Poisonous?.RINGER (S.).Influence of Inorgrnic Salts on Developinent.h’oil~ PATON (D.). HumanKNIERIM (W.). Yuliw of Commercial Foods.BLYTH (A.W.). Sutritirc Value of Wheat-meal.OELKEES (L.).uhile performing work.SPALLANZSHI (P.). Volatile Fatty Acids of Butter.CORN (R.).ROBIN (A.). Determination of Potassium Hydrogen Tartrate in Urine .GAUBE .COHN (R.). Benzamide in Urine after Administration of Benzaldehjde .Behayiour of Tjrosine Ethyl Ether inHeat dcvclopecl by the Action of Oxygen 011 the Blood .SCHTJLZE (E.). Effcct o€ Feeding on the Secretion of Amidic Substances .BLEIBTREU (L.). Nitrogenous ConstituentsGIBBS (W.) and H.A.HAKE .SMITH (F.). Respiration in the Horse during Rest and Work.HUNTER (W.). Method ofGABRIEL (S.). Mutritire Value of Different Albuminoids.Action 01’ related Compounds on AnimalsLAXGLEY (J.IS.).Iiifiueiice of Nicotine and Atropine onHAIG (A.). Influence of Sodium Phosphate on the Excretion of UricAcid.TITALTER (TPAGExl COXTENTS .MARTIN (S.) and R.N.WOLFEXDEN.Physiological Action of the ActivePrinciple of Jequirity.MABTIN (S.). Toxic Action of the Albumose from Jequirity Seeds .WEST (S.). Acetonuria and Diabetic Coma.MOTT (FROBEBTS (W.). Pfeiffer's Test for Latent Gout.ROLLESTON (H.D.). Temperature in Nerves.LEAWEISKE (H.) and E.FLECHSIC).Saving effect on Albumin o i Organic Acidsin Vegetable Foods.ULBBICIIT.Amount of Substances Yielding Oil of Mustard in VariousFoods tind their Action in the Animal Body.NENCEI (L.).Gases.CHABRIE (C.) and L.LAPICQUE.Physiological Action of Selenious Acid .GORDONROBERTS (W.). Uric Acid.RAUDXITZ (R.W.).Digestibility of Boiled Milk.HOPPE-SEYLEB (F.). Oxidation in the Blood.MACMUNN (CMOHB (P.). Fat of Bone-marrow.NILSON (L.F.). Aniount of Nitrogen in Cows' MilkSTOBCH (V.). Changes inHydrochloric Acid on the Digestible Albumin of FoddersIRVIR-E (R.) and S.T.WOODHEAD .JAFFE (IT.) and R.COHNSecretion of Calcium Carbonate byAnimals.Ethyl Carbamate in the Alcoholic Extract ofNormal UrineDifferences between Arterial and Venous Blood in DifferentBlood Veesels.Permeabiliby of the Red Corpusclestheir Isotonic Coefficients.CUSBROT (L.). Blood of the ApIj&x?.PBAFSNITZ (W.). Formation and Fate of Gl;~ogen.Absorption of Direrent Fats from the Alimeutary CanalBehayiour of Sulphur in the Organism :sulphuric Acid in the UrineComposition of the Milk of theBottle-nose Whale.Physiological Action and Opticalstances.Action of Related Clieniical Compound3 onAuimals.LEZB (R.).Living Motors and the Theory of Heat.XRUQER (F.).~ ~ A M B U R O E R (HL~PINE (R.).ARNSCHINK (L.).PRESCH (W.).FRANKLAND (P.F.) and F.J.HAMBLY .BLAKE (J.).GIBI~S (W.) and H.A.li.4RE .Presence in ChjleMARCET (W.). Hmnau Respinition.SMITH (F.). Chernisb*y of the UrineHALLIBURTON (W.D.). Prote'ids of Liver and Kidney CellsBAAS (H.K.L.). Decomposition of Ethereal Salts in the AlimentaryCaual.COPEMAX (S.M.) and C.S.SEEBRINGTON.The Proportion of Blood toSCHAFER (E.A.). I s Free Hamoglobin present iMANASSE (P.).Lecithin and Cholesterin in Red Blood Corpuscles .Body Weight.Splenic Vein 2.HUNTER (W.). Pernicious Anseniis.DELEPINE (S.). Cystin in the Urine.PAVLOFP (C.). Phjsiological Action of Hyoseine Hydrochloride. GIBBS (W.)PA QECOSTESTS.xliZUXTZ (N.) and C.LBEIMINN.Respiration in the Horse during Rest andWork.MINKOWSKI (0.). Absorption of Fat.LEPIXE (R.) and BAREAL .THUMUMEL (K.). Cattle Marrow.SCRUTT (F.). Pigments of Peridinin.HALLIBURTON (W.D.). Pathological Effusions.PATON (DLEA (A.S.) and W.L.DICKINSON.Action of Rennin and Fibrin FermentRINGEX (S.) and H.SAINSBUBY.Influence ofREXD (E.W.). Osmosis with Living and Dead Membranes.MOTT (F.W.). Pernicious Anemia.DELCPINE (S.). h’ormal Storage of Iron in the Liver.STOCKMANX (R.) and D.B.DOTT.Physiological Action ofits Derivatives.ZANQLEY (J.3.) and W.L.DICEIWOS.Physiological Actionand Nicotine.GRANDIS (V.).Inflnence of Muscular Work Hunger and Temperature 011the ExhalationHERQENHAHN (E.).Glycogen in tlie Liver and Muscles.KULZ (E.). Formation of Glycogen in Muscle with an Artificial Circula-tion.KWLZ (E.) and A.E.WBIQHT.Phloridziii Diabetes .POPOFF (M.).STUTZER (A.).NIEBL~NG (H.). Artificial Digestion of Agricultural Feeding Stuffs .~CHROEDER (W.v.). Formation of Carbamide in the Dogfish .LETELLIER (A.). Colouring Matter of Purpurn ltrpillus.ABEL (J.J.). Animal Melanins and Bemosiderin.BLAKE (J.). PhysiologicalDestruction of Glucose by Blood and ChyleInfluence of Cooking on the Digestion of Beef and FishEffect of “Saccharin” on the Digestion of Albumino’idsChemistry of VegetablePETRI (R.J.).Reduction of Nitrates by the Cholera Bacteria.KRAMEE (E.). Mucous Fermentation.NENCKINENCEI (M.v.) and N.SIEBER.Gases Evolved during the Putrefaction ofSerum Albumin.NENCKI (M.v.) and N.SIEBER.Formation of Paralactic Acid during theFermentation of Sugar.XUNTZ (A.). Function of Ammonium Salts in the Nutrition of HigherPlants.CHODAT (R.)VILLE ((3.). Influence of the Composition of tlie Soil on the PhysicalProperties of Plants.B Ap y ocyanicus.JUUELLE (H.). Relation between the assimilation and transpiration pro-duced by ChlorophyllMANGIN (L.).KOHL.Formation of Calcium Oxalate in Plants.WEHMEE (C.).Calcium Oxalate in the leaves of Alnus glutinosa,carpus racemosa aud Cratregusoxyacantha.Decomposition of Albumin by Anerobic Ferments .BRBAL (E.). Fixation of Nitrogen by Leguminose.NANGIN (L.). Pectic Compounds in Plants.SCHLOESTNG (T. jun.). The Atmosphere in Soils.Influence of Acids on the Evolution of Gasee by PlantsPAGE’isxlii CONTENTS .DIJXSTAN (W.R.). Scatole in the Vegetable Eingdom.DANIELGOESSMANN (C.A.). Analpis of White Soja Beans.EQUERTZ (C.Q.) and L.F.NILSON.MoorlandROMMIEB (A.). Influence of Yeast on the Bouquet of Wines.LIKDET (L.). Influence of Carbonic Anhydride on the Products of Fer-mentation .XELLNEB (0.). P.MORI and M.NAGAOEA.Inverting Ferment.SCHLOESINGI- (T.). Nitrification of Ammonia.SCHLOESIKGSCHULZE (E.).Formation of Cane-sugar in Etiolated Plant Shoots .BOEORNY (T.). Living Vegetable Protoplasin.SCHULZE (E.) E.STEIGER,SCUULZE (E.) and E.STEIGER.Non-nitrogenous Reserve Substances of theARNAUD.Carrotene in Leaves.DUNSTANWine Statistics of Germany.VOELCEER (J.A.). Experiments on Ensilage.MUNTZ (A.). Ammonia and the Nutrition of Plants.MAERCPER (M.). Effect of Manuring with Ammonium Sulphate and withSodium Nitrate .HORNBERGER (R.). Aniount of Mineral Matter and Manurial Value of theCupules of theBeech from different soils.LOEW (0.) and TDilute Alkaline Silver Solutions.VAN ITALLIE (L.). Occurrence of Iodine in Fucus cesiculosus and Chondruscrisps.DUNSTAN (W.R.) and A.E.CHASTON.Chemical constituents of Scopoliacarniolica.WILEY (H.W.).Analyses of the Seed of CaZycaitthus gZaucus.ARATA (P.N.) and F.CANZONERI.Bark of Quinafebrifugus).ARATA (P.N.) and P.CANZONERI.True Winter Bark .ILOSVAY (L.). Xitrous Acid in the Atmosphere.DEHERAIN (P.P.). Causes of the Exhaustion of Arable Soil by CroppingwithoutGILBEBT (J.H.). Experiments at Rothamsted on the Growth of Potatoes .HEIDEN (E.).Experiments with Farm-yard Manure.KERRY (R.).CEdema.SELITREKNY (L.). Decomposition of Gelatin by Anaerobic Ferments .BERTHELOT.FormationHECEEL (E.). Utilisation and Transformations of Alkaloids during theGermination of Seeds.MAXWELL (W.). Sugar-yielding Insoluble CarbohydratesREUTER (L.).PICHARD.Nitrogen in the Soil.Nitrification.Fixation of AtmosphericKELLNER (0.) and J.SOWANO.Preparation of Silage .KELLNEB (0.).Digestibility of Rice Straw.GESSARD (C.).Chromogenic Function of Bacillus pyoeyaaicus.GREEN (J.B.).BECHI (E.). Boric Acid in Plants.MANQIN (L.). Intercellular Matter.MOLISCHSTELLWAAU (A.). Composition of Fats of Fodders.EXVERLIKU (A.) and G.LOUES.Corllposition and Digestibility of theProtei'ds of variousSeeds of L u p i w s luteus.Constituents of Urtica wens U.dioi'cn,Kitrogen.Root Excretion and their Influence on Organic VrltteySTOCKBBIDQE (E.). Lupulin.PAffECOXTENTS.xliiiSIEBERT (C.). Constituents of Scopolia atropoi'des.SIEBERT (C.). Constituents of Anisodus luridus.HATTENSAUR (G.).CEATIN (A.) Chemistry of Truffles. STONE (W.E.). Composition of Cultivated Stlawberries.BRBALROMMIER (A.).Effect of Copper Salts on Elliptical Yeast.LAWES (Sir J.B.) and J.H.GILBERT .PBTERMANNACTON (E.H.).RICCIARDI (L.). Diffusion of Alumina in Plants.WILEY (H.W.) and WBUSGEN (M.). Function of Tannin in Plants.HOOPER (D.). Tannin in Indian and Ceylon Teas.DEHERAINCHATIN (A.). Chemistry of the Truffle.SCHLOESSINQ (T.). Absorption of Ammonia from the Air by VegetableSoils.BERTHELOT.Vegetable Soils and Atmospheric Nitrogen.SCHLOESSING ('l'.). Vegetable Soils and Atmospheric Nitrogen.VAN BEUMELEN (J.M.). Compositionof the Zuider Zee.VAN BEMMELEN (J.X.). Composition of the Volcanic Soils ofFRANKLAND (P.F.) and J.J.Fox.Fermentation of Mannitol andGlycerol.BRUNTON (T.L.) and A.MACFADTEN.Ferment Action of Bacteria .WILLE (X.).Gases containcd in the Bladders of Fucus vesiculoszts andOzothellia'CUPKE (R.). R61e of Potassium ir?.Plants.MAXWELL (W.). Soluble Carbohydrates in Seeds of Legumes.GIACOSAFRANK (B.). The Fungus SSmbiosis of the Leguminostz.DURIN (E.). RBle of Sugar and its Development during the growth of theBeetroot .ACTON (E.H.). Assimilation of Carbon from Organic Compounds by GreenPlants.SERSO.Nitiic AcidSTONE (W.E.). Carbohydrate in Peach Gum.STONE W.E.). Carbohydratcs of the Sweet Potato.XOHLRAUSCH (0.) and li.STROHNER.Experiments with Beet-root .SCHMITTER (A.G.). Sonrcc of Kitrogen of Plants.PAGNOULROMMIER (A.). Prcparation of Wine Yeasts.LISOSSIER (G.) and G.ROUX.Alcoholic Fermentation and Conversion ofAlcohol into AldehydeJACQUEYIN (G.).The " Bouquet " of Fermented Liquids.WINOGRADSKI.The Nitrifying Organism.GIUNTI (M.).LOEW (0.). Elaboration of Nitrates in the Plant.ACQEA (G.). Calcium Oxalate Crystals.JORISSEN andPLASTA (A.v.). Nitrogenous Constituents of the Tubercles of StnchysBAESSLER (P.). Yields and Composition of a Variety of Red Clorer .MUNTZ (A.).MUNTZMUN~Z (A.). Green Manures as Suppliers of Nitrogen.KUHXE (W.). Silicic Acid as a Culture Medium for Organisms.The FixationAssimilation of Carbon by Green PlantsXalang and the Clay Soil of Relnbang.tubertyern.Decomposition of Hocks and Formation of Arable SoilsPAQExliv COXTEKTS.HOTTER (E.). Occurrences ofPhysiological Meaning.VAN BEMIJIELEN (J. 31.).WOLL (F. W.). Loss of Nitrogen in Acid Fodders .VAN BEMMELEN (J.31.). Composition of Soils.VAN BEMIUELEN (J. 31.). Causes of Fertility of the Forest-land of Deli(Sumatra) andERAUSE (H. v.). The Loss of Nitrogen during the Fermentation of Nitro-genous Organic Matters and tlie Means for it,s Prevention.DE BLASI (L.)LEONE (l'.). Reduction of Nitrates by Micro-organisms.XERRF (8.) and S. FRANKEL. Action of the Bncillus of Malignant (Edemaon Carbo11,vdratcs .SOSTEGNI (L.) and A. SAKXINO. Formation of Hydrogen Sulphide duringthe Alcoholic Fermentation.JACQVEMIN (G.)- Production of EtherealSIGMUHD (W.). Fat-decomposing Ferments in Plants.MACH (13.) atid K. PORTELE. Fermentation and Composition of CranberryJuice.~CEITJLZE (E.). Cliemical Composition of Vegetable Cell-membraiics .SCEULZE (E.).Cholesterin in Plants.LEHMANN and MORI. Poison ofI t i A Y c e (A.). Combustibility of Tobacco.DEHERAIN (P. P.). Exhaustion of Cultivated but Unmanurcdage Waters.HEBCRT (A.). Composition of Straw.Composition of the Ash of Tobacco Leaves .Ana 1 y t ica 1 Chemistry.HEMPEL (W.). Estimotion of Phosphorus in Phosphor-tin.QTOCKLISA (J.).POLENSKE (X.1. Rapid Method of Estimating Arsenic.HAUSIIOFER (K.). behaviour of Silicates when Fused with Pliospliates .SCHETLIE (B.). Technical Analysis of CommercialMAYER (F.). Qualitative Analysis of the Ammonium Sulphidc Precipitate .BEILSTEIN (F.) and T. GROSSET. Analysis of Aluminium Sulphate .BEISHARUT (C.). Estimation of Chromium andWAHLBERG (E.). Volumetric Estimation of Chromium in Iron and Steel .HATJSHOFER (K.).Microscopical Test for Tantalum and Niobium .WALLER (X.). Hardness of Water .HAZEN (A). Estimation of Chlorine in Water.WARDEX (R. B.). Dynamical Theory of Albuminoi'd -4mmonia.KXOBLACCH (0.). Estimation ofHALPHEN ((3.). Absorption of Bromine by Fatty Acids.WILLIAXS (R.). Estimation of Citric Acid in Lemon-juice.XISCHER (B.). Impurities inJEAN (F.). Oil Testing.BISHOP (W.). Oil of Sesame.AMAGAT (E. H.) and F. JEAN.MUTER (J.) and L. DE KONJEQH. Analysis of Fats and Oils.RICHMOND (H. D.). Extraction of FatPARSONS (C. L.). Volumetric Estimation of Fat in Milk.FABEB (H.). Condensed Milk and tlie Estimation of Casei'n and Lact-albumin .JOENSTONE (W.). Estimation of Soluble and Insoluble Fatty Acids inButter.RICHMOND (H.D.).Butter.GLADDIXG (T. S.). Examination of Lard for Adulteration.Optical ExaminationPAQECONTENTS .REYSEN (I.) and T.V.M.BERTOX.Action of Acids on Benzoic SulphinideFLUCKIGER (F.A).Estimation of Morpliinc in OpiumJOHNSTONE (W.). Analysis of Pepper and the Occurrence of Piperidinetherein.GOELDNER (M.). DetectionOWEN ( F.A.). Eetimation of Indigotin for Commercial Purposes .REINHABDT (C.). Filter Holder for Drying and Weighing.and AnalysisLUNGE ((3.). Estimation of Sulphur in Burnt Pyrites.DUNYTAN ( W.R.) and T.S.DYMOND.EstimationREIS (M.A.v.). Estimation of Arsenic in Iron.RACINE. Carbonic Oxide Detector.PUCHS (F.). Improvenient in the Method of Estimating Carbonic AnhydrideCRAIG ((3.).Estimation of Silica and Analysis of Siliceous Naterials .ISBERT and VENATOR.AnalysisDE KONINGH (L.).Chromium and Barium in Foods.WARREN (X.H.). Magnesium as a Reagent.VOIQT (A.). Volumetric Estimation of Zinc.JAHODA (R.). Standardisation of l’ermanganate.LECHARTIER (G.). Incineration of VegetableTEILLICH (H.). Estimation of Carbonic Acid in Potable Waters containingMagnesium.VITALI (D.).DetectionBBUNNER (H.). Reaction of Sodium Nitroprusside with Alkaline andby Volume.Water Analysis.NELSON (F.E.). Standard Sclution for Clark’s Soap-test.Alkaline Earthy Hydroxides.GRUNWALD (H.).EOLDAINI (E.). Copper Sclution for the Estimatim of Glucose.DATIES (R.H.). Iodine Absorption of Essential Oils.SNOWCRIPPS (R.A.). Reactions of Essential Oils.M ~ R K (F.X.).Testing for Fixed Oils .GROGER (M.). Estimation of Neutral Fats.KURNLENZ (F.A.). Bottle for Washing and Absorbing GasesKUPPFERSCHLAEGER.Detection ofVITALI (D.). Action of Sulphuric Acid on the Haloid Salts of the AlkalisBURTON (W.M.). Estimation of Sulphur in Organic Compounds .BEHEEND (P.)tures.PRUNIER .MAISSEN (P.) and E.ROSSI.Estimation of Nitrogen in AmmoniumDEVARDA (A.). Jodlbauer’s Modification of Kjeldahl’s Method for the Esti-Quantity of Nitric Oxide produced in the CombustionFormation of Tetra-WILLIAMS (R.). Rcact?ons of Essentialin Presence of some Metallic Salts.PRUNIER (L.). Simultaneous Estimation of Sulphur and Carbon .Action of Sulphides on Chloral and Chloroform.sium Phosphate.mation of NitrogenILOSVAY (L.).Detection of Nitrous Acid in Saliva.of Nitrogenous Organic Compounds with Copper Oxide.hydrated Ferric PhosphateLASNE (H.). Analysis of Natural Phosphates.MOERCK (F.) Estimation of Hypophosphites.KLINGEMANN (F.).ABTH (G.). Estimation of Phosphoric Acid in Slags .DOBBIN (L.). Detection and Estimation of Alkaline Hydroxides in Presenceof Alkaline Carbonates.GOEBEL (H.). Volumetric Estimation of Sodium Carbonate and HvdroxidexlvPAGEin C&nmercial Caustic Soda.29xlvi CONTESTS .JENSCHBRAND (A.).Use of Double Pyrophosphates in the Electrolytic Estimationand Separation of Metals.XASTLE (J .WALKER (J.). Analysis of Organic Substlrnces containing Copper .REINHARDT (C.).Estimation of Iron by means of Potassium Yerrnangandein Hydrochloric Acid Solutions .ZALESKI (S.S.). Macro- and Micro-chemical Iron Reactions.LAPICQUE (L.).Estimation of Iron in Blood.LECRENIER (A.).REINHARDT (C.). Volumetric Estimation of Chromium in Chrome IronOre.ALLEN (A.H.).MUCK (F.). Estimation of Alkalis in Water.BENEDIKT (R.) and A.GEUSSNER.Estimation of Methoxyl.MORAWSEILEWKOWITSC~I (J.).Estimation of Glycerol in Crude Glycerol.WILLIAMS (R.). Examination of Commercial Carbolic Acid and of Disin-fectant Powders made therefrom .GERRARD (A.W.).Percentage Glucosometer.JIJSGFLEISCH (E.) and L.GRINBERT.dnalysis of Sugars.EREYER (T.). Estimation of RafTinose in Raw Sugar.BENECKE (F.). Detection of Rye-meal in Wheat-meal and Bran .LANGE ((3.). EstimationBOESSXECK (P.).Valuation of Wine Lees.POTT (R.). The Fokker-Salkowski Method of Estimating Uric Acid inXormal and Pathological UrinesCRAWLEY (J.'I'.). Simplified Fat Extraction Apparatiis.KUHN (M.). Estimationof Fat in Sour Milk.STOKES (ASALVATORI (S.). Examination of Butter.TAFFE (H.). Rapid Method for the Analysis of Tallow.HORWITZ (H.). AnalysisHAZURA (K.). Examination of Commercial Ole'in for Linolei'c Acid .BAESSLEB (P.). Estimation of Fat in Poppy Cake.BOCKAIRY.EstimationSNOW (H.W.).HIESCHSOHN (E.).Detection of Ordinary Turpentine in Venice TurpentinePFLUGER (E.) and L.BLEIBTREU.LORESZ (N.v.). Analysis of Argol.Rapid Estimation of Fat in MilkIodine Absorption as a Teat for EssentialEstimation of UreaGIRAIJD (H.). Analysis of Methylanilines.STARK (A.C.).Test for Antipyrin.FAWSSETT (T.). Estimation of Cinchona AlkaloYds.MARE (V.D.).PAUL (B.H.) and A .BLUNT (T.I?.).BROCINER (A.L.). Reactions of the Alkaloids.MONNET .Estimation of Alkalo'ids inCinnamvlcocdine in Coca Leaves .Assay of Emetine in Ipecacuanha WineColouring Matter of Wines.HERZ (J.). Detection of AlkanaHONIG (M.). Valuation of Indigo.PETEOWITSCR (M.). Lime in Tanning Materials.BOYMOND .RUFFLE (J.). Modified '' Orsat" Apparatus.BLOCHXANN (R.). The Concentration of lteagents.AURIOL (E.) and DSTEAD (J.E.). Gas Sampling and Testing Apparatus.YOUNGER (W.). Estimation of Chlorine and Hydrogen Chloride in Gases .PETTERSSOX (0.)MULLER (M.). Estimation of Free Oxygen in Water.LUNGE ((3.1.Estimation of Sulnhur in Pvritcs.EstimationPAUECOKTENTS. xlviiPAQEBAILEY (G. H.). Estimation and Occurrence of Sulphur in Coal .SETLIK (B.).ANDEEWS (L. W.). Volumetric Estimation of Combined SulphuricNIEBLING (R.). Kjeldhal’s Method of Estimating Nitrogen.MULLER (J. A.). Estimation of Nitric Acid by Diphenylamine.LUNGE (G.). Detection of TracesBOEMAIW (K.). #otz’s Method of Estimating Phosphorus in Iron .REITMAIR (0.). “ Citrate ” Method of Phosphoric Acid Estimation .CHATARD (T. 31.).MULLERREITNAIR (0.). Estimation of Calcium in Presence of Phosphoric Acid,Iron Aluminium and Manganese.MINOR (W.). Estimation of ZincALT (H.) and J. SCHULZE.ALT (H.). Precipitation of Manganese as Peroxide.BELL (5. C.). Estimation of Iron inGLASER (E.). Estimation of Ferric Oxide and Alumina in PhosphaticManures.LUNGE (G.).ZIEGLER (A).SETLIE; (B.).Analysis of Wolframite and Scheelite.LECRESIER (A.). Electrolytic Estimation of Antimony.L E m r EHAGER (H.; Detection of Ceresin Ozocerite and Paraffin in Bees-wax .AIGNAS (A). Adulteration of French Essence of Tcrebentliene .BEXEDIKT (R.) and A. GRUSSXER. AnalysisGILBERT (H.). Examineldon of Oil of Cassia.COLASANTI (G.). New Reaction of Thiocpnic Acid.STAVELY (W.HEHFER (0.). Estimation of Glycerol in Soap Lyes and in Crude GlycerolTOERRISG (H. r.).BORA-TRAGER (A.). Polariscopic Estimation of Sugar in Sweet WinesRAUMER (E. T.). Unfermentable Dextrorotatory Constituent of Honey .GANS (R.). Estimation of Potassium Hydrogen Tartrate and of TartaricJOLLES (A.).EstiEation of Tartaric Acid in VinegarPERRON. Adulteration of Milk.PATTINSOS (J.). Testing Lard for Cotton-xed Oil and Beef Stearin .GILBERT (I3ROTTGER (H.). Examination of Wax.REVERDIX (F.) and C. DE LA HARPE. Analysis of Xcthylanilines .KISSLIXG (R.).Q-ANNTE~ (F.). Estimation of Tannin by Permanganate.ROOS (L.) CUSSON and GIRAL-D. Volumetric Estimation of Tannins inWines.REIKITZGR (F.). Estimation of Lupulin in Hops.CBIPPS (R. A.). Diastasic Power of Extract of Malt.WELZELADAMS (M. A.). New form of Air-bath.LE ROT (G. A.). Detection of Free Chlorine in Hydrochloric Acid .SYMONS (17. H.). Detection of Sodium in Lithium Carbonate.ELLIS (a. E. R.) Estimation of Copper by Titration with PotassiumCyanide.JOHXSON (F.). Precipitation of Copper as Thiocpanate.STEAD (6.E.). Estimation of Minute Quantities of Aluminium in Iron andSteel.Estimation of Sulphuric Acid in Fuming Sulphuric AcidEstimation of Water and Carbonic Acid in Salts .Separation of Zinc from NickelHIEPE (C.). Application of Hydrogen PeroxidePrecipitation of Alumina and Ferric Oxide by AmmoniaTEED (F. L.). Clarke’s Soap Test.ALT (H.). Estimation of ThiocyanatesEstimation of Glycerol in Wine and BeerWERNER. Detection of Sugar in Urine.and Mslic Acids in Wine .xlviii CONTESTS.MKELLAR (W. G.). Convenient Solution for Use in Titrating Weldon Mudsfor Manganese Peroxide.BLUNT (T. P.).LUNQE ((3.). Tho Q-asvolumeter. .KN~~PLXR (0.). New Extraction Apparatus.MANN (C.).DONATH (E.).Detection of Nitrogen in Organic Compounds.DENIQES (G.). Phosphorus Trichloride and Oxychloride.SCHLAGDENHAUFFEN. Magnesia in Sodium and Hydrogenphates.SXITH (E. F.) and L. I(. FNANKEL. Electrolytic Separations.PEBRON.HOLTIIOF (C.). Estimation of Copper by converting the Sulphide intoOxide.ETARD (A.) andVOLHABD (J.). Estimation of Mercury.HILGER (A.) and H. HAAS. Separation and Estimation of Tin andTitanium.FEIEDHEIY (C.). Separat.io3 of Vanadic and Tungstic Acids.VIGNON (L.). Water Analysis.,.RAULIN (J.) EstimationBURTON (W. M.). Xstimation of Petroleum in Turpentine.BORNTRAGER (H.).Impurities in Commercial Alcohol.PLUQGE (P. C.). Mercury NitrateGROBERT (J. v.). Estimation of the Mineral Matter in Sugar.GODEFFROY (R.) and M.COULON.BAYEAC. Estimation of Uric Acid in Urine bybromite.DAVENPORT (B. F.). Milk Analysis.FOEESTER (0.).JEAN (F.). New Apparatus for the Analysis of Oils.NEUMANN (S.). Estimation of Quinine in Quinine Tannate.TBCHIRSCH. EstimationLux (F.). New Gas Balance.MCCULLUCH (N.) Volumetric Estimation of Bromine in the Presence ofChlorine and IodineLEBEAU (P.). Estimation of Free Halogens and of Iodides in Presence ofChlorides and Bromides.GAWALOWSKI (A.). VolumetricPRESCII (W.). Detection of Thiosulphuric Acid in Urine.PEEIS (K.).CHAPPELLE. Estimation of Total Phosphorus in Urine.HIBSCEWALD (J.).cosmic Salt.JOHNSTONE (A.).WEQSCHEIDEE (R.). Impurities in Commercial Barium Carbonate .FRESENIUS (R.).STAHL (W.).Estimation of Zinc in Blende containing Manganese .GORE (G.). Sensitive Test for Impurities in Mercury.FARTHBII (A). Volumetric EstimationFRESENIIJS (R.) and E. HINTZ. Analysis of Cliroine-iron Ore.JOHNSTONE (A.). Detection of Tin in Minerals. .BEILSTEIN (F.)TATE ((3.). Estimation of Minute Quantities of Gold.SMITH (E. F.) and H. F. RELLER. Electrolytic Estimation of Palladium .RIDEAL (S.).JOHNSON (A. E.). Colorimetric Estimation of Nitrates in Potable Waters .VAN BEMMELEN (J. M.). Estimation of Water Humus Sulphur &c. inS o i l sKWASNIK (W.). Eetimation of Ash in Food and Dmps.Estimation of Wood Fibre in PaperEstimation of Phosphoric Acid in the Presence ofDetection of Metallic Silver in tlie Presence of LeadColorimetric Estimation of Nitrates in Potable Waters .PAGEG64CONTENTS.xlixWILLIAMS (E.).Maumene‘s Test foy EssentialGASCH (R.). Estimation of Ferrocyanides in the Bye-products of GasWorks.EASSNER ((3.). VolumetricVIZERN (M.). Assay of Commercial Glycerol.HIBSCHL (J.A.). Value of the Phenylhydrazine Test for Sugar .GUTTMANN (P.).FOXMANEK (J.). Estimation of Inverted Sugar.VIGNON (L.). Estimation of Acetone in Methyl Alcohol and in the Liquidsused for MethylatingARACHEQUEBNE ((3.). Estimation of Acetone as Iodoform.LEZS.Estimation of Fat in Milk.BON~ZYNSKISQUIBB (E.R.). Valuation of Crude Coca’ine from PeruMEZQER (K.). Cocai’ne Chromate.SCHOEN ((3.A.). EstimationLEONE and DENABO.Detection of Blood Stains.BEIN (8.). Detection of the Colouring Matter of the Yolk of EggB F f N (S.).Exact Method for the Estimation of Egg Substaiice.GWCH ( F.A.) and F.W .of Alkaline Chlorides and Iodides.BLUM (L.). Estimation of Sulphur in Iron.AT SINWILSON (J.H.). Test for Nitrous Compounds in Sulphuric Acid .KI;OBUEOW (IS.). Use of the lnduction Spark for Detecting Traces ofArsenic .C.IYBY (R.C.). Estimation of Arsenic.WIDMEB (J.). Estimation of Carbon inMACKINTOSH (J.B.). Estimation of Graphite in Minerale.W~BOBQH (J.). Volumetric Estimation of Carbon in Iron.FBESENIUS (R.).FESSENDEN (R.A.). Volumetric Analysis of Copper.BBUGNATELLI (E).Detection of Mercury in Organic Liquids.THRESH (JMILKOWSKI (2.v.). Estimation of Starch in Grain.LENZ (W.). Discrimination of Jute Fibres from those of Flax and HempWATTB (F.).Milk Analysis.TERBEIL (A.). Melting and Solidifying Points of Fats and their Mixtwes .LEONEPATTERSON (H.J.).OUENEZ.Volumetric Estimation of Tannin.OBEBMULLER.Reaction of Cholesterin .HAZEN (A.). Estimation of Ammonia in Sand and Sewage .HAZEN (A.) and H.W.CLARK.Effect of ‘Temperature on the iessle;Test .SPIEQEL (L.). Estimation of Nitric Acid.QILBEXT (J.P.). Estimation of Silica in Silicates by Fusion with AlkalineCarbonatesBUBGHABDT (C.A.).PETTEESSON (0.) and A.SMITT.Estimation of Free and Combined Carbonin Iron and Steel.SMITH (E.F.). Electrolysis of Metallic Phosphates.DE ROODE (R.). Combustion with Lead Chromate.YVON .NOERDLINQER (H.). Analysis of Fats.DOTT (D.B.). Estimation of Urea.BUCHAN (A.). Ruffle’s Method of Eetimating Ammonia.Estimation of Fat in Feeding S t d sRENARD (A.). Estimation of the Indigo inBOYER (E.). Estimation of Nitric Acid.BOAM (F.W.). Estimation of Arsenic.Soda or PotashVOL LVIII.(IPAORSMITH (E.F.) and L.I(.FRANKEL.HAAS (H.). Separation of Titanium and TinBOURCART (R.) Titrstion of Alcohol with Chromic Acid.CAZENEIJVE (P.) and L.DUCRER.Raisin Wines and their -Richness inOST (H.).&fOHI. ER (E.). Detection of Benzoic Acid in Foods.ROSENBACH (0.).BAMBEBOER (M.). Analysip of Resins and Balsams.GNEZDA (J.). A Cyanogen Reaction of Protei‘ds.SIDERSKY (D.).DENIQPS ((3.). Characteristic Reaction of Hydrogen Peroxide.STORTENBEKER (W.). EstimationGOOCH (F.A.) and P.E.BROWKING.Estimation of Iodine in HaloydSalts.JANNASCH (P.). Estimation of Sulphur in Inorganic Sulphides.KUHN (B.) and 0.SAEGER .HALDANE (J.S.) and M.SPETTERSSOK (0.). Estimation of Carbonic Anhydride.Electrolytic SeparationsNitrogen.Occurrence andApparatus for Drying Substances in a Partial VacuumEstimation of Arsenic by Marsh’s Methodonic Anhydride in Air.KLEMP ((3.). Valuation of Zinc-dust.BLUM (L.). Volumetric Estimation of Zinc.CODA (I).).PLATZ (B.). Estimation of Zinc in Iron Ores.RIBAN (J.). Estimation of Zinc in presence of Iron and Manganese .THIELE (J.). Detection and Estimation of Antimony and Arsenic .FBEYDL (J.).Loss of Pr’itrogen in some Analyse? by Will and Varrentrapp’sMethod .MORPURGO (J.). Detection of Nitrobenzene.PHESENIUS (W.). Examination and Valuation of Spirituous Liquors .LECLEHC (A.). Estimation of Starch inCHTSWE X. (L.). Test for Aldehyde.AIQNAN (A.). Adulteration of Linseed Oil.CLAASENTANIQUTI (K.). Analysis of Urine.WETZEL (A.). Detection of Carbonic Oxide Hsemoglobin.RICHTER (E.). Reactions ofVAN XUYS (T.C.) and R.E.LYONS.Estimation of Albumin in Urine .HENTSCHEL (W.).MEYER (E.v.).SMITH (E.F.).ApparatusSalts.A Source of Error in the Estimation of Sulphuric Acid .Oxidation ofCHABLTON (T.). Blowpipe Test for MercuryLOOF (Q.). Reactions for Arsenic.HOLVERSCHEIT (R.).MACH (E.) and K.PORTELE.Detection and Estimation of Lactic andCAMBBEB (W.). Quantitative Estimation of Uric Acid in Human Urine .LANQKOPP (0.). TheHINSDALE (S.J.). Colorimetric Method for Estimating Tannin in Barks .HINBDALE (S.J.). Colorimetric Method for Estimating Morphine in Opiumration of Vanadic AcidButyric Acids in Wine3.WARREN (T.T P.B.). Examination of Oils Fats &cMOULLADE (A.). Estimation of Tannin by Means of Iodine.Preparations.LOOF (G.),RITSERT (E.). Teeting Acetanilide.KINZEL (W.). Estimation of Pyridine Bases in Gas-liquor.REICHL (C.),BBUYLANTB ((3.).New Reactions of Albumins.CONTENTS.11DENAYEB (A.). Analysis of Peptones.and of Pentaglucoses (Pentoses). GUNTHER (A.) and B.TOLLENS.Quantitative Estimation of FurfuraldehydeLOTIBOND (J .Tintometer.BIZBTHELOT. ANDR~. and MATICINON.Oxidation of the Sulphur in CarbonCOHEN (J .ttnd Steel.REINHARDT (C.). Rapid Grttvimetric Estimation of Sulphur in Iron andSteel .ODDY (R.W.) and J.B.COHEN.Use forBORSTEH (0.). Kjeldahl’s Method for the Estimation of Nitric and TotalVOFLTMANN (G.). EstimationMESSINQER (J.). Wet Method for the Estimation of Carbon in OrganicSubstances.GRANT (J. )LUNQE ((3.). Gas-Volumetric Analyses of Potassium Permanganate,Compounds.ARCHBUTT (L.). Estimation of Sulphur in Iron andComparison of the MethodsEstimating Organic Nitrogen.Nitrogen.Sulphites.Bleaching Powder and Manganese DioxideVOETMANN ((3.). Volumetric Estimation of Manganese.HOPE (J.). Estimtttion of Cobalt and Nickel.BOTER (E.) Estimation of Ash in Sugars.MOHLER (E.). Detection of Impurities in Alcohol.KOHK (C.A.). Test for Glycerol.SCHCLZE (E.). Isocholesterin.SAUPE (M.). Estimation of the Fatty Acids in Soap.MEDICUSZIECILER (A.). Analysis of Ferro-Aluminium and Aluminium Steel .BALLARIO and REVELLI.Estimation of the Mineral Constituents of COW’SMilkMESSINQER (J.) and G.VORTMANN .BENEDIET (R.) and M.BAMBERCIEB .KOSSEL (A.) and K.OBERMULLER.New Method of SaponificationVolumetric Estimation of PhenolsQuantitative Reaction of LigninVULPIUS ((3.). Analysis of Diuretin.PATTERSON (T.L.). Estimation of ColouringAbsorption Spectra.PBOCTEB (H.R.). Gantler’s Method of Estimating Tannin.KO”+ (J.). ExaminationHEB~RT (A.). Analysis of Straw.HORN (F.M.). Analysis of Bootblacking.

ISSN:0368-1769    

DOI:10.1039/CA89058FP001

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c C h e m i s t r y . Preparation of Chlorine in a Kipp's Apparatus. By J. THIELE (A?znden, 253, 239--'L42) .-Chlorine may be conveniently prepared in a Kipp's apparatus by the action of hydrochloric acid on bleaching powder. By means of a handpress, tbe bleaching; powder is compressed i n to a hard cake ; this is broken into small lumps and used in this f o r in. w. c. w. Automatic Apparatus for Evolving Gases from Liquids. By J. THIELE (AnnuZen, 253, 242-246).-A convenient apparatus f o r preparing hydrogen chloride from commercial hydrochloric acid or sulphurous anhydride from a concentrated solution of sodium hydrogen sulphite may he made from R three-necked Wo1fl"s bottle. This is provided with-(1) a delivery tube fitted with a stop-cock; (2) a small stoppered separating funnel with the stem drawn out to a fine point; and (3) a safety funnel with some mercury in the bend and a loose plug of cotton wool in the funnel.The Wolff's bottle is half filled with the solution of sodium hydrogen sulphite, for example, and the sulphuric acid is slowly introduced through the separating funnel. w. c. w. Reciprocal Displacement of Oxygen and the Halogens. By BRRTHELOT (Compt. rewd., 109,546-548 and 590--597).-'l'he author summarises his previous work on the reciprocal displacement of oxjgen and chlorine and describes some later results. Pure concentrated fuming hydrochloric acid is not decomposed by oxygen in presence of sunlight, but if some maiiganous chloride is present the liquid acquires it deep-brown colour, the atmosphere i n the flask becomes cliarged with chlorine, and the liquid has bleaching properties.Oxygen is absorbed and hydrochlorides of manganese perchloride are iormed. If the liberated chlorine is removed and hydrogen chloride and oxygen are introduced into the flask, a further quantity of chlorine is set free, and this process may be repeated several times. The decomposition ceases when the hydrates of the hydrochloric acid contain the maximum amount of wat,er ; dilute non-fuming hydrochloric acid is not decomposed even after long ex- p osure in presence of manganese chloride. Ferric chloride behaves i n the same manner as mariganous chloride, but the phenomena are very much less distinct. The heat of formation of dissolved hydrobromic acid is almost iden- tical with that of water, and hence i n presence of water, but under these coiiditions only, reciprocal decomposition may take place, In pre- sence of excess of water, oxygen readily decomposes hydrogen bromide under the influence of light.Similar decomposition takes place a t the ordinary temperatnre in the case of it fuming solution of hydrobromic acid, that is, hydrates of the free acid not saturated with water, but is arrested almost immediately by the formation of hydrogen perbrom-INORGANIC CHEMISTRY. 7 ide, HBr3; HBr conc. soh. + Br2 gas = HBr, diss. develop +9*2 Cals., the total heat of formation, +43.5 Cals., being greater than the heat of formation of water. Oxygen does not decompose dilute hydrobromic acid, that is, the saturated hydrates of the acid, nor a solution of potassium bromide acidified with hydrochloric acid .The formation of hydrogen perbromide explains the decomposition of water by bromine, but this change is limited by the dissociation of the perbromide in presence of water. Dilute solutions of hydriodic acid are readily decomposed by oxygen under the influence of light at the ordinary temperature, the change corresponding with the liberation of 15.9 Cals. for each atom of gaseous iodine. The heats of formation of dissolved potassium iodide and hydroxide arc practically the same, and slight variations in the conditions serve to turn the reaction in one direction or the other. The combination of iodine with potassium iodide in concentrat'ed solution to form potassium triiodide liberates f5.0 Cals.for each atom of gaseous iodine ; the action of iodine on dissolved potassium hydroxide with formation of hypoiodite or iodate liberates +4*1 Cals. and + 5.4 Cals. respectively for each atom of gaseous iodine. l t follows that oxygen will not displace iodine from potassium iodide except under conditions in which potassium triiodide is stable, that is, in very con- centrated solutions. Experiment showed that dilute solutions of potassium iodide remain quite colourless when exposed to light for a long time in presence of pure air ; very concentrated solutions soon become orange and the colour deepens with prolonged exposure. The liquid then gives a blue coloration with starch and has an alkaline reaction; if, however, it is diluted, it rapidly becomes colourless, owing to dissociation of the potassium triiodide and the action of the liberated iodine on the potassium hydroxide which has been formed.It is well known that even dilute potassium iodide solutions become yellow when exposed to ordinary air. This is due to the fact that the carbonic anhydride of the air takes part in the reaction. Carbonic acid does not displace hydriodic acid, but the simultaneous action of oxygen and carbonic anhydride on a dilute solution of potassium iodide produces potassium hydrogen carbonate and free iodine. the change being accompanied by the liberation of +13.5 Cals. for each atom of gaseous iodine. The colour of the liquid becomes deeper if the quantity of carbonic anhydride in the atmosphere above it is increased.The action of the oxygen is still greater in presence of acetic or hydrochloric acid, but in these cases the result is in part due to the displacement of some hydriodic acid. Acetic acid liberates verylittle hydriodic acid, but the action of the oxygen depends on the successive liberation of small quantities. Hydrochloric acid liberates more hydriodic acid and in this case the action of the oxygen is more marked. In presence of a large excess of air, a solution of potassium iodide acidified with hydrochloric acid is completely decomposed by the action of light in a few days. If manganous chloride is added to a highly concentrated solution of8 ABSTRACTS OF CHEMICAL PAPERS. potassium iodide and the mixture exposed to light, a higher oxide of manganese is precipitated and iodine is liberated ; dilute solutions show the same phenomena in a lower degree.All the reciprocal displacements of oxygen and the halogens under the influence of light are in agreement with the thermochemical determinations. C. H. B. Simultaneous Synthesis of Water and Hydrogen Chloride. By P. HAUTEFEUILLE and J. MARGOTTET (Oowpt. rend., 109, 641-644). --Mixtures which contained oxygen and hydrogen in the proportion required to form water, with varying proportions of chlorine ; and mixtures of hydrogen and chlorine in the proportions to form hydrogen chloride, with varying quantities of oxygen, were exploded by means of a spark, and the residual chlorine was determined by means of standard sodium arsenite. If p represents the total hydrogen which enters into combination, and p' the quantity which combines with oxygen, v - p' gives the ratio of the hydrogen converted into W water to thb hydrogen which forms hydrogen chloride.This ratio is independent of the initial pressure, and of the nature of the spark. It is always less than unity if the proportion of chlorine is more than half the volume of the hydrogen, and it varies with every alteration in the proportion of chlorine. When the volume of chlorine present is double the volume of the hydrogen, the quantity bf water formed becomes inappreciable. It is evident that the results do not agree with Bunsen's law. With equal volumes of hydrogen and chlorine and varying propor- tions of oxygen, the 'ratio is always less than unity and does not vary greatly when the ratio of oxygen to hydrogen varies from 0.25 to 3.With equal volumes of the three gases the change is re- presented by the equation 5C1, + 5H2 -t 502 = 8HC1 + H,O + C1, 402. C. H. B. P Equilibrium between Hydrogen, Chlorine, and Oxygen. By H. LE CHATELIER (Cornpt. rend., 109, 664--667).-The author dis- cusses'the results of Hautefeuille and Margottet (preceding Abstract) from the point of view of his own laws of chemical equilibrium. The agreement between the observed and calculated numbers is very close. He points out that the degree of moisture of the gases, which is very important, is not specified. The fornlula shows that a reduction of initial pressure should be accompanied by a reduction in the propor- tion of water formed, and the fact that this is not observed indicates that' the chlorine is pai*tially dissociated.The varying effects of chlorine and oxygen depend solely on their relative volumes and not on their chemical properties. C. H. B. Preparation of Oxygen in a Kipp's Apparatus. By J . VOLHARD (AnnaZen, 253, 246--24H).-Small quantities of oxygen can be con- veniently prepared in a, Kipp's apparatus by the action of hydrogcbitINORGANIC CHEXISTRT . 9 peroxide on bleaching powder. quantity to neutralise the lime in the bleaching powder. Nitric acid is added in sufficient The oxygen contains a small quantit,y of chlorine. w. c. w. Action of Sulphur on Solutions of Metallic Salts. By G. VORTMANN and C. PADBERG (Ber., 22,2642-2644).--The authors find that with many proto-salts when their aqueous solutions are boiled with flowers of sulphur, about half the metal present is precipitated as sul- phide, the remainder being oxidised to the per-salt.When a strongly acid solution of stannous chloride WRS employed, no stannous sulphide was precipitated, but hydrogen sulphide was evolved, and the whole of the tin oxidised to stannic chloride. With an aqueous solution of stannous chloride, and with an acid solution of' cuprous chloride, laather less than half the tin was Precipitated as sulphide, a littie being oxidised in the same manner as with the strongly acid solution of tin. With mercurous nitrate, almost exactly halt of the mercury was precipitated as sulphide. Solutions of manganese, iron, nickel, zinc, and cadmium sulphates, and acid solutions of bismuth and antinionious chlorides, and of arsenious and arsenic acids, are not altered wlien boiled with sulphur.L. T. 'l'. Preparation of Nitric Oxide. By J. THIELE (Annulen, 253, 246) .--Nitric oxide is prepared in the apparatus previously described (t,his vol., p. 6) by adding a strong solution of sodium nitiite to a solution of ferrous chloride or sulphate in hydrochloric acid. I f the sodium nitrite contains carbonate, i t may be removed by precipit,at,ion with calcium chloride. w. c. w. Phosphonium Sulphate. By A. BESSON ( C O V Z ~ ~ . Tend., 109, 644-645) .-When hFdrogen phosphide is passed into sulplinric acid a t the ordinary temperatxre, there is considerable development of heat, sulphur separates, and sulphurous acid is formed. If the acid is previously cooled by means of ice and salt, the gas is somewhat largely nbaorhed, and the liquid remains limpid.After a time, how- ever, it begins to decompose in the manner indicated, the temperature rises, and deconiposition becomes very rapid. If the acid is cooled to -20" or -25" by the rapid evaporation of methyl chloride, a syrupy liquid is obtained, from which a white, crystalline, highly deliquescent, solid separates; this seems to be phosphonium sulphate. When thrown into water at the ordinary temperature, it dissolves w i t h a strident noise, and hydrogen phosphide is evolved, but the sulphuilic acid is not reduced. When exposed to air a t the ordinary tempera- ture, the phosphorus is oxidised to phosphoric, phosphorous, and hypo- phosphorous acids, whilst the sulphuric acid is reduced to sulphurous acid and sulphui., with a small quantity ot' hydrogen sulphide.The crystals may be dissolved in dilute sulptiuric acid, and if t'he solution is electrolysed a t -25" or -40" with a mercury cathode, there is only a very slight intumescence of the mercury, and hence, if phos- phonium amalgam exists, it is very unstable even at the freezing point of niercury. Tlie solution bas a high resistance, and ii' the10 ABSTRACTS OF CHEMICAL PAPERS. current is too strong the compound is decomposed with great rapidity in the manner already described. Hydrogen phosphide has no action 011 nitric acid at -23". Behaviour of Sodium Thiosulphate towards Acids and Metallic Salts. By W. VAUBEL ( B e y . , 22, 2703-27@4).-A reply to Vortman (Abstr., 1889, 1107) upholding the author's previous news C.H. B. (ibid., p. 943). Direct Production of Crystalline Sodium Carbonate and Chlorine from Sodium Chloride. By W. HEMPEL (Bey., 22, 2475--2478).-1n the electrolysis of metallic chlorides, which give readily soluble decomposition-products, the latter are further decom- posed as soon as the quantity produced reaches a certain limit. When, however, the compound produced is only sparingly soluble, this secondary decomposition does not take place, and the whole strength of the current is utilised. Potassium chloride and sodium chloride, f o r example, can be converted into the corresponding chlorate ; calcium chloride and magnesium chloride can be decomposed into chlorine and a solid hydroxide, by employing a diaphragm.Marx (D. R.-P., No. 46318) has shown that alkaline chlorides can be directly converted into clilorine and an alkaline hydrogen car- bonate, by passing carbonic anhydride through the solution during electrolysis, metal aud liquid diaphra,%ms being employed. The author, who has been engaged independently in making similar experiments, describes, with the aid of diagrams, an apparatus in which sodium chloride can be directly converted into chlorine and crystalline carbonate. The cathode is a perforated ircn disc, the anode a per€orated carbon disc, the perforations being about 4mm. in diameter, and bored in an upward direction to allow the gas to escape freely. A disc of ordinary asbestos-paper, placed immediately between the carbon and iron discs, serves as a diaphragm.The three discs are placed in the centre of a vessel made of porcelain and glass, which is thus divided into two chambers, each of which is provided with a conducting tube, in one case for carbonic anhydride, in the other for chlorine. If sodium chloride is added from time to time t'nrouph a suitable aperture, and the water which is removed with the crystalline carbonate is replaced, the apparatus can be worked continuously, sodium carbona,te m d almost chemically pure chlorine being obtained. A tension of 3.2 volts is required for decoruposing the sodium chloride, and a tension of 2.5 volts to overcome the polarisation current ; but the latter has only a slight tension when both electrodes are made of carbon. With a current of 1.73 amp&res 0.93 gram of chlorine per hour was produced, so that if a dynamo were employed it should give 64.5 grams of chlorine and 259.8 grams of Na2C0, + lOH,O per horse-power-hour.F. S. I(. Preparation of Crystalline Normal Lithium Phosphate and Arsenate. By A. DE SCHULTEN (Hull. 8oc. Chim. [3], 1, 479-480). -Fused lithium chloride dissolves the amorphous, normal phosphate, and on cooling and washing the melt, rhomboidal, tabular crystals ofINORQ ANIC CHE YIISTR Y 11 normal lithium phosphate, which have a sp. gr. 2.41 at 15", and are infusible at a white heat, are obtained. The normal arseiiate is similarly prepared ; it corresponds with the phosphate physically, and is of sp. gr. 3.07 a t 15". T. G. N. Cadmium Phosphates and Arsenates. By A. DE SCHULTEX (Rz;ZZ.Xoc. Chim. [3], 1, 473--4i9).-The normal orthophosphate, Cd,( POa),, falls as a voluminous, amorphous precipitate when normal sodium phosphate is added to the solution of a cadmium salt. Hydrogen disodium phosphake throws down from a, hot solution of cadmium chloride or sulphate an amorphous precipitate which quickJr becomes crystalline. After purification by dissolution in phosphoric acid and cautious reprecipitation by alkaline hydroxides, i t forms small, prisnintic hexagons of sp. gr. 3-98 at 15", having the composition H2Cd5(P04)d + 4H20 ; these, when dissolved in cold phosphoric acid (sp. gr. 1.1), are reprecipitated unaitered on warming or on heating 111 sealed tubes to 250", butr redissolve on cooling ; as thus produced, tlieir sp. gr. is 4.12 a t l5O.This phosphate loses its water at a red heat, and fuses at a white heat ; it is probably tbe compouiid described by S tromeyer as the noriiial phosphate. Monocadmium phosphate, H,C'd(P@,), + 2H,O, crystallises out after slow evaporation of a saturated solution of the previous salt in cold dilute phosphoric acid a t the normal temperature. It exists as large clino-rhombic prisms of sp. gr. 2742 a t 15", which lose their water of crystallisation at lOO", and are decomposed by water to form a flocculent phosphate, H?Cd5(P04), + 4H20. Cadmium ch1orapatite.-Normal cadmium orthophosphate and the second phosphate described above dissolve in fused cadmium chloride, aiid on slowly cooling the melt, long, hexagonal prisms of the salt, 3Cd,(P04),,CdC12, of sp. gr. 5.46 at 15", separate.A cadmium loromapatite, 3Cd3( PO4),,CdBr2, may be similarly pre- pared, but is a1 ways contaminated with cadmium pprophosphate, from which it may be separated by cold, dilute nitric acid, which dissolves only the bronrapatite ; the cadmium pyrophosphate, Cd2PZO7, exists as flattened oblique lamella: of sp, gr. 4.965 at 15". Cadmium arsenates.--When the amorphous powder, H2Cd5( As04)4 + 4H20, which is precipitated on the addition of hydrogen disodium arsenate to the solution of a cadmium salt, is dissolved to saturation in a cold solution of arsenic acid of sp. gr. 1.3, and, subjected to heat, crystals of the salt HCdAsO, + H,O, having a sp. gr. of 4.164 a t 15" are deposited. Monocadmium arsenate, H4Cd(As04)2 + 2H20, crystallises out when a saturated solution of the compound H2Cd,(P04)4 + 4H20, in arsenic acid solution (sp.gr. 1.3), is allowed to evaporate at the ordinary temperature. It forms large, clino-rhombic prisms of sp. gr. 3.241 at 15", which are isomorphous with those of the corresponding phosphate. At 70-80", they lose their water of hydration, and are partly decomposed; with excess of water, they form a flocculent substance, H,Cd5(As0,)r + 4H20. Cadmium chlorarsenioapatite, 3Cd:,(AsO4),,CdCI2, is produced by fusiiig either normal ammonium arsenate or the salt HzCd,(As04), +12 ABSTRACTS OF CHEMICAL PAPERS. 4H20, with excess of cadmium chloride. Its sp. gr. is 5.865 at Is", and its physical properties correspond with those of the chlor- apatite. Cadmium bromaraenioapatite, 3Cd3(AsOl).?,CdBr,, is similarly pre- pared, and exists as long yellow prisms of sp.p. 6.017. Cadmium pyroarseriate, CdrAsoO,, is prepared by f'using a mixture of cadmium bromide (22 parts) with potassium bromide (5 parts), and adding to the fused mass iiormal ammonium arsenate (9 parts) ; after washing the melt, the colourless crystals of the pyroarsenate are separated from the yellow brorliarsenioapatite Ins treatment with dilutJe nitric acid, which dissolves the latter compound only. This pyroarsenate forms crystals of sp. gr. .5*474 at 15", corresponding in physical properties with the pyrophosphate. T. G. N. Action of Sodium Thiosulphate on Metallic Salts. By G. VO~WXANN and c. PADBERG (Bw., 22, 2637 --2641).-The authors have extended Vortmann's work on copper salts (Abstr., 1898, 787) to ot,hcr metallic salts.When a concentrated solution of sodium thiosulphate is added to a strong solution o i lead acetate until thc lead thiosulphate first precipi- tated has been just redissolved, and alcohol is then added, an oily liquid separates, which when rubbed with absolute alcohol solidifies to a crystalline mass of the formula PbY20,JSa,Sz03 + 12H,O. Thallious sulphate under similar treatment yields small needles of the formula T1,S20,,2Na,SL0, + 8H,O. When molecular proportions of cadmium sulphate and barium thiosulphate are rubbed together with a little water, the insoluble barium sulphate formed filtered off, and alcohol added to the filtrate, cadmium thiosulphate, CdS,O, + 2H,O, separates as an oil, which gradually solidifies to a yellowish-white, crystalline mass.When equal molecular proportions of sodium thiosulphate and cadmium nitrate in aqueous solution are mixed together and alcohol added, yellowish-white needles of the formula 2CdE,O3,NalS20, + 7H20 are formed. If a large excess of the thiosulphate is used, the compound CdS20,,3Na,S,03 + 9H,O separate., as an oil. This gradually solidifies to sinall, yellow scales, which lose 4 mols. H,O over sul- phuric acid. On mixiiig strong solutions of zinc iodide and sodium thiosulphate and adding alcohol, an oil separates, wliicli after long exposure over sulphuric acid solidities tci a gum-like mass of t h e formula 2ZnS,03,3Na2S,0, + 1 OH20. I t is deliquescent, and decomposes gradually with formation of zinc sulphide. Ferrous tliiosulphate, PeS20, + 5Hy0, forms green crystals easily soluble in water.A double salt, FeS2O3,3Na2S2O3 + HH,O, was ob- tained by precipitating a mixed solution of ferrous iodide and sodium thiosulphate with alcohol. It forms bright-green crystals, soluble in w a t 61'. Rlanganese t,hiosulphate, MnS,O, + 5H20, is crystalline but un- stable. A pale, rose-coloured double salt, hlnS20,,2N%S,0, + 16H20, was obtained. The cobalt double salt, CoS,0j,3NaLSLOj + 15H20, forms a Iilue,INORGANIC CHEMISTRY. 13 gum-like mass, soluble in water. No corresponding nickel salt could be prepared, though a crystalline salt, NiS203,6NH3,3H20, was obtained. L. T. T. New Method of Preparing Anhydrous Aluminium Chloride. By C. F. MABERY (Ber., 22, 2658).-The author finds that dry hydrogen chloride extracts the whole of the aluminium from an alloy of copper and aluminium without attacking the copper.The reaction is most energetic a little below a red heat. The alloys containing 15 to 40 per cent. of alaminium are hest powdered, .mixed with powdered charcoal (to prevent the fusion of the remaining copper), put into a graphite retort, and when heated just below R red heat a current of hydrogen chloride is passed through. The aluminium chloride distils over, and may be condensed in suitable vessels, the liberated hydrogen passing on. L. T. T. Alkali Aluminium Silicates. By A. GOEGEU Zeit. Kryst. Min., 15, 646, from BdZ. SOG. fran. win., 10, 278).-On melting kaolin with alkali haloid salts in the presence of moist air, silicates are formed, having the composition AlR'SiO,.B.7 melting kaolin with potassium carbonate or caustic potash at a dull-red heat, an amorphous salt, A1KSi04, is obtained, whilst a t a more intense heat octahedra are obtained, having the composition Al2K2Sio6, o r else a more basic silicate also cr.ystallising in the regular sjstem. The sodium-corn- ponnds prepared in a similar way are alm~~ys basic, and form doubly refracting crystals. B. H. B. Mercuricobaltarnmonium Salts. By G. VVRTMANN arid E. MORGULIS (Rer., 22, 2644--2648).-When solntions of the mercuric double salts of cobaltammonium chlorides are treated with potash or soda, rsd precipitates are formed, which appear to be cobalt-ammo- nium chlorides, in which part of the hydrogen is replaced by varying proportions of the univalent radicles (HgCl) or (HgOH).A solution of the salt CO~(NJH,)~~C~,,~H~C~,, or a mixture of one part by weight of lut,eocobalt chloride and three parts of mercuric chloride, when treated with 6 mols. of soda yields the salt ; or with excess of soda, the salt Co,N12Hz8(HgOH)8C16. Both compounds are bright-red, and decompose quickly when moist, slowly when dry. Equal weights of luteocobalt chloride and mercuric chloride with excess of soda yield a slightly more stable, red salt, Co2N12H3,( Hg0H),CI6. Pirrl7ureocobaZtdecamin~ salts.-1 mol. of purpureocobalt chloride, 6 niols. of mercuric chloride, and 6 mols. of soda yield a dark-red, flocculent salt, Co2Nl,H,2(HgC1),(H~oH),C16 ; with excess of ~ o d a , the salt CO,N,,H~~(H~OH)~CI~ is formed. RoseocohaZtdecamine saZts.-1 mol.of roseocobalt chloride, 6 mols. of mercuric chloride, and 6 mols. of soda yield a violet-red precipitate, Co2NlOHZ4( HgOH)&I, ; with excess of soda, a salt, Luteocobalt salts. coz"JL( HgOH)6C14( OH)*, is formed. Both salts are very unstable.14 ABSTRACTS OF CHEMICAL PAPERS. Pur~ureocobaltoctaminu snlts.-l mol. of purpureocobaltoctamine chloride, 6 mols. of mercuric chloride, and 6 mols. of soda yield the d t , Co2N6Hl6(HgCl),( HgOH )&16 ; with excess of soda, the salt Co,N,H,, (HgOH),Cl, is formed. Equal weights of the cobalt and mercuric salts with excess of soda yield the salt Co,N,Hls(HgOH),Cl,(OH),. Roseocobultoctamine salts.-Under like conditions as with the pur- pureo-salts, the three salts, CO,NBH~~(H~CI),(H~OH)~C~~, Co2N8HM( HgOH)SCh, and CO~N~H,~(H~OH)EC~,(OH),, are formed.All three are rio:et-recl, and decompose at ordinary atmospheric temperature, as do also the corresponding purpureo-compounds. L. T. T. Cobaltoctamine Salts. By G. VORTMANN and 0. BLASBERG (Be,.., 22, 2648-2655) .-When cobalt nitrate, sulphate, or chloride is dis- solved in a small quantity of water and added to a mixture of ammonia and ammonium carbonate, violet-red solutions are formed. If these are oxidised by a current of air, decamine salts are formed, but on evaporation these are decomposed, octamine salts crystallising o u t . The following salts are described :- CO,(NH,)~~(NO~>~(CO~)~,~H,O ...... Crystalline. Co,(NH3) SO,) ,C 03,4H ,O ......... Crystalline. ~ o , ( N H , ) , ( ~ ~ ~ ) , C ~ ~ ~ ~ H ~ O ..........Long, thinneedles. CO,(NH,)~SO,(CO~),,~H,O. ......... Dark red, prismatic Co,(NH3),CI,C0,,2 H-0. ............ Crgstalline. Co2( NH3) (X O&( CO,) 2,H20 ........ Cherry red crystals. crystals. CV? (NH,),Cl,( CO3)2,H,O ........... 9 7 CO,(NH~),(NO~)~(SO~)~,~H,O ....... 7 , CO,( NH3) 8 (“0,),,2H,O. ............ CO,( NH,),(N03),C14,4H?O. .......... 7 7 C‘O~(NH,),(NO~)J~,~H~O ........... 9 7 Co,( NH,) ,Br2( SO,) ............... 99 Co2(NH3),1,(SO4),. ................ 9, 1 , CO~(NH,)~I,CI~,~H,O .............. Brown scales. Co2(NH3),(OH)2C1,,2H20 .......... Dark green powder. CO~(NH~),(OH),C~,,~H~C~, ......... C O ~ ( N H ~ ) ~ ( OH),CI,,PtCI,,H?O ...... L. T. T. Action of Sulphurous Acid on Cobaltammonium Salts. By G. VORTMANN and G. MAGDEBURG (Ber., 22, 2630--2637).-The authors have obtained the following compounds :- CO,(NH,),(SO,A~)~,~OH~O ........Yellowish-brown needles. Co,(NH3),( S03)6Ba377H20 ........... Golden-yellow scales. C O ~ ( N H ~ ) , ( S ~ ~ ) , B ~ ~ A ~ , , ~ H , G . ...... Golden-yellow scales. Co2(NH,),(S03),Co~vi7~6H,0 ........ Orange crystals. Co2( NH3),( So3)6c02v’,~4H,0 ........ Orangc crystals.ISORQANIC CHERIISTRY. 15 C O ~ ( NH3),( SO3),(NH3) ,,Co.,"'.SH,O . . CO,(NH,),(SO,),(SO~A~),,~H.?~. .... CO~(NH~)~SO~[SO~)~CO~",~~H~O ..... Coz(NH3) (NH3),( SO3)?C1?,4H:.?O . . . C ~ ~ ~ ~ H , > ~ , ( s o , ~ a ) ~ , ~ H ~ o .......... *Co2(NH,) lo( S03)6C02Vi,8H,0 ......... Coz( NH,) S03)zC12. ............... CO~(NH,),,(SO,),,~H,O. ............ CO~(NH,)~~(SO,)~C~~,~H,O .......... Orange powder. Yellowish- bro w n needles .Yellow crystalline powder. Dark brown crystals. Light brown crystals. Brom.nish-yellow powder. Brown crystalline powder. Yellow needles. The authors consider that these salts show the exist.ence of f o u r series of salts. New case of Isomorphism of Uranium and Thorium. By C . RANMELSBERG (Zeit. K~yst. Nifl., 15, 640-641 ; from Sitzber. preuss. Akad. Wiss., 1886, 603).-The author shows that the thorium sulphate described by Nordenskiijld and others, and the uranium sul- phate hitherto regarded as rhombic, have a similar composition, namely :- (SO,)zTh + 9H,O, (so*),u -k 9H2.0. The crystals of the latter are only seemingly rhombic in conse- quence of twin-formation ; in reality they are monosymmetric, like the thorium sulphate. The axial ratios of the two minerals are: uranium sulphate, a : b : c = 0.597 : 1 : 0.6555, /3 = 82" 11'; thorium sulphate, a : b : c = 0.598 : 1 : 0.658, /3 = 81" 30'.Fluorine-compounds of Vanadium and its Analogues. By E. PETERSEN ( J . p. Chenz. [a], 40, 271-296 ; compare Abstr., 188:4, 107).-The following double salts of vanadium oxyfluorides and potassium fluoride have been obtained :- 2KF,VOF3: a white, crystalline precipitate, is obtained by adding a solution of potassium fluoride to one of vanadic acid in hydrofluoric acid ; when dried over sulphuric acid, it becomes reddish-brown, and has the above formula. 4KF.VF,,VOF3 separates as a white precipitate from the mother- liquor of the above salt. HB',3KF,2VOF3 crystallises from a hot solution of either of the preceding salts in hydrofluoric acid in beautiful, colourless prisms, which lose very little weight at 100".3KF,VOF3,V0,F is the white, crystalline residue left when the precipitate obtained by adding a solution of vanadium pentoxide in hydrofluoric acid to a solution of potassium fluoride is treated with water at the ordinary temperature; if hot water is used and the solution is poured into a hot solution of potassium fluoride, a crystal- line precipitate is obtained, cf uncertain composition, but approaching * Probably Kunzc.l's penttlmineclicobaltic sulphite. B. H. B.1 li ABSTRACTS OF OHENICAL P-1PERS. the formula 4KE',VOF3,V02F ; or if the first-mentioned precipitate is heated with water for some minutes, a salt having nearly the coin- position VOF,,VO,F is obtained. 2KP,VO,F separates from a warm solution of vanadium pentoxide in hydrofluoric acid when i t is nearly neutralised with potassium hydroxide.It crystallises in yellow, six-sided, truncated prisms. When reci*ystallised from water, it yields the salt 3KF,2V02F. 3HF.9NH4F,5VOY3, obtained by adding ammonium fluoride in slight excess to the solution of vanadium pentoxide in hydrofluoric acid, crystdlises in larqe, colourless, four-sided prisms. SNH,F',VO,F cryst allises from a solution of vanadium pentoxide in hpdrofluoric acid wheii it is nearly neutralised with ammonia. The crystallography of the salt is given. HF,7NH4F,4V02F separates in white crystals from the solution of the last-nxmed salt in warm water. 2Nbp0,,3KF,5H,0 is obtained by melting niobium pentoxide (1 part) with potassium fluoride (3 25 parts) and treating the melt with water, when the salt remains undissolved as a crystalline powder.Nb20,,KF,3H,0 is a prismatic, crystalline powder, obtained by fusinq niobium pentoxide (1 part) with potassium fluoride (1*.3-1*5 parts). The author reviews the work already done on the vanadium double fluorides, and concludes his paper with the followinq directions for extracting vanadic acid from the finery slag of Taberg:--.300 grams of the finely-powdered slag is mixed with 400 C.C. of hydro- chloric acid (sp. gr. 1.18) and shaken. After 24 hours, water is added to make the bulk up to 1i litres, and the whole filtered through linen. Iron is then addpd, and, after the evolution of hydrogen has ceased, sodium acetate until the liquid is reddish-brown; finally, acetic acid and sodi nm phosphate are added until all iron, chromium, aluminium, and vanadium are precipitated as phosphates.The precipitate is mixed with sodium carbonate (0.5 part) and heated on an iron plate for i-2 hour ; the mass is treated with water, hydrochloric acid nddecl to nearly neutralise the solution, which is then heated, filtered, and made acid with acetic acid ; solid ammonium chloride is now added, when a red, crystalline ammonium vanadate, (NH&0,2V2O5,4H20, separat,es ; this is heated and the residual vanadium oxide treated with hot nitric acid at 110-120", and converted into ammonium mets- vanadate by evaporating off the nitric acid, dissolving in ammonia, and cr~+stallising ; pure vanadic acid is obtained from this salt by igniting and repeating the nitric acid treatment.Vapour-density of Antimony Pentachloride. By R. ANSCH~TZ A. G. B. and N. P. EVANS (Annnlen, 253,95--105).-By means of a modification of La Coste's apparatus, the authors have attempted to determine the density of the vapour of antimony pentachloride under reduced pressure. As antimony trichloride boils at 143-144" under 70 mm. pressure and antimony pentachloride boils a t 102-103" under 68 mm. pressure, the determinations were made under 58 mm. pressure a t a temperature of 218". The mean of four determinations gave the \ d u e 10, the theoretical density being 10.33. It was impossible toIKORGANIC CHENISTRY. 17 exclude all traces of moisture from the apparatus and avoid the formation of minute quantities of the monohydrate of antimony penta- chloride.w. c. FV. Atomic Weight of Palladium. By E. H. KEISER (Amer. Chew. ,J., 11, 398--403).-Attempts were at first made to use the double chlorides of palladium with ammonium and with sodium, but they had to be abandoned, a s these compounds contain water, from which i t is almost impossible to completely free them ; moreover, the dried salts are very hygroscopic, and absorb water rapidly while being weighed. Finally, the yellow, cry stadline palladiodiammonium chloride, PdN,H6C12, was used ; this is formed whenever hydrochloric acid is added to a solution of palladium chloride in excess of ammonia ; it is R stable compound, and can be obtained very pure. It contains no water of crystallisation, c:m be dried completely, and is not hygro- bcopic.When heated in a current of pure hydrogen, the colour changes from yellow to black, hydrogen being absorbed, and metallic palladium and ammonium chloride formed. On raising the tempera- ture, the ammonium chloride volatilises, and spongy palladium is left behind ; this is cooled below a red heat in a current of hydrogen, and then the hydrogen is displaced by air; in this way the occlusion of hydisogen is prevented. The weight of palladium obtained from a known weight of the chloride is thus ascertained, and from this the atomic weight of palladium is calculated, assuming N = 14.01, H = 1, C1 = 35.37. Two series of experiments were made; the palladammonium chloride used in the second scries was prepared from the metallic ptiliadium obtained in the first.The results give a s mean value Pd = 106.35:- Atomic weight. r----h.---- - Series. Experimenta. Mean. Maximum. Minimum. I. 11 106.352 106.459 106-292 11. 8 106.350 106.455 106.286 C. F. B. Ruthenium Potassium Nitrites. By A. JOLY and M. VEZES (Compt. rend., 109, 667-670 ; compare Abstr., 1889, p. 352).-If ruthenium chloride is added to a boiling solution of potassium nitrite until the precipitate which forms a t first is redissolved, and the liquid is concentrated and allowed to cool, it deposits dichroic, orange-red, monoclinic prisms of 90" 10'. They are very soluble in water, can be purified by repeated recrystallisation without under- going a1 teration, and have the composition RuZOL( N,0,)a,4KN0, or When the potassium nitrite is in excess, and prolonged ebullition is avoided, a pale-yellow, crystalline precipitate is obtained of the composition $uz02, (N203),,8KN02 or Ru?O,( NO)2,N,03,8KN0,.Sepa- ration of the ruthenium is never complete, and the mother-liquor, OIL concentration, yields crystals of the first compound. The second salt is converted into the first by prolonged ebullition with wat8er, and the reverse change is effected by the addition of potassium nitrite. A t a voc. LVIII. C RU~O,(NO),,(N?O~),,~KNO~.I S ABSTRACTS OF CHEMICAL PAPERS. low temperature, the second salt crystallises with 2 mols. H,O. Other double nitrites seem to be formed, but are relativelyvery unstable. If the double nitrites are heated with ammonium chloride and hydrochloric acid, only part of the nitrogen is evolved and one atom of the nitrogen remeins i u combination with each atom of ruthenium.The solution wh '11 concentmtc.d yields the potassium ruthenium nitrosochloride previous1 y described (Zoc. cit.). No compound was obtained corresponding with that to which Claus attributes the formula Ru(N0,),,3KNO2. C. H. B.ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h e m i s t r y .Preparation of Chlorine in a Kipp's Apparatus. By J. THIELE(A?znden, 253, 239--'L42) .-Chlorine may be conveniently preparedin a Kipp's apparatus by the action of hydrochloric acid on bleachingpowder. By means of a handpress, tbe bleaching; powder is compressedi n to a hard cake ; this is broken into small lumps and used in thisf o r in. w.c. w.Automatic Apparatus for Evolving Gases from Liquids. ByJ. THIELE (AnnuZen, 253, 242-246).-A convenient apparatus f o rpreparing hydrogen chloride from commercial hydrochloric acid orsulphurous anhydride from a concentrated solution of sodium hydrogensulphite may he made from R three-necked Wo1fl"s bottle. This isprovided with-(1) a delivery tube fitted with a stop-cock; (2) asmall stoppered separating funnel with the stem drawn out toa fine point; and (3) a safety funnel with some mercury in thebend and a loose plug of cotton wool in the funnel. The Wolff'sbottle is half filled with the solution of sodium hydrogen sulphite, forexample, and the sulphuric acid is slowly introduced through theseparating funnel. w. c. w.Reciprocal Displacement of Oxygen and the Halogens.ByBRRTHELOT (Compt. rewd., 109,546-548 and 590--597).-'l'he authorsummarises his previous work on the reciprocal displacement ofoxjgen and chlorine and describes some later results.Pure concentrated fuming hydrochloric acid is not decomposed byoxygen in presence of sunlight, but if some maiiganous chloride ispresent the liquid acquires it deep-brown colour, the atmosphere i nthe flask becomes cliarged with chlorine, and the liquid has bleachingproperties. Oxygen is absorbed and hydrochlorides of manganeseperchloride are iormed. If the liberated chlorine is removed andhydrogen chloride and oxygen are introduced into the flask, a furtherquantity of chlorine is set free, and this process may be repeatedseveral times. The decomposition ceases when the hydrates of thehydrochloric acid contain the maximum amount of wat,er ; dilutenon-fuming hydrochloric acid is not decomposed even after long ex-p osure in presence of manganese chloride.Ferric chloride behavesi n the same manner as mariganous chloride, but the phenomena arevery much less distinct.The heat of formation of dissolved hydrobromic acid is almost iden-tical with that of water, and hence i n presence of water, but underthese coiiditions only, reciprocal decomposition may take place, In pre-sence of excess of water, oxygen readily decomposes hydrogen bromideunder the influence of light. Similar decomposition takes place a t theordinary temperatnre in the case of it fuming solution of hydrobromicacid, that is, hydrates of the free acid not saturated with water, but isarrested almost immediately by the formation of hydrogen perbromINORGANIC CHEMISTRY.7ide, HBr3; HBr conc. soh. + Br2 gas = HBr, diss. develop+9*2 Cals., the total heat of formation, +43.5 Cals., being greaterthan the heat of formation of water. Oxygen does not decomposedilute hydrobromic acid, that is, the saturated hydrates of the acid,nor a solution of potassium bromide acidified with hydrochloricacid .The formation of hydrogen perbromide explains the decompositionof water by bromine, but this change is limited by the dissociation ofthe perbromide in presence of water.Dilute solutions of hydriodic acid are readily decomposed byoxygen under the influence of light at the ordinary temperature, thechange corresponding with the liberation of 15.9 Cals.for each atomof gaseous iodine.The heats of formation of dissolved potassium iodide and hydroxidearc practically the same, and slight variations in the conditions serveto turn the reaction in one direction or the other. The combinationof iodine with potassium iodide in concentrat'ed solution to formpotassium triiodide liberates f5.0 Cals. for each atom of gaseousiodine ; the action of iodine on dissolved potassium hydroxide withformation of hypoiodite or iodate liberates +4*1 Cals. and + 5.4Cals. respectively for each atom of gaseous iodine. l t follows thatoxygen will not displace iodine from potassium iodide except underconditions in which potassium triiodide is stable, that is, in very con-centrated solutions.Experiment showed that dilute solutions ofpotassium iodide remain quite colourless when exposed to light fora long time in presence of pure air ; very concentrated solutions soonbecome orange and the colour deepens with prolonged exposure. Theliquid then gives a blue coloration with starch and has an alkalinereaction; if, however, it is diluted, it rapidly becomes colourless,owing to dissociation of the potassium triiodide and the action ofthe liberated iodine on the potassium hydroxide which has beenformed.It is well known that even dilute potassium iodide solutions becomeyellow when exposed to ordinary air. This is due to the fact that thecarbonic anhydride of the air takes part in the reaction.Carbonicacid does not displace hydriodic acid, but the simultaneous action ofoxygen and carbonic anhydride on a dilute solution of potassiumiodide produces potassium hydrogen carbonate and free iodine. thechange being accompanied by the liberation of +13.5 Cals. for eachatom of gaseous iodine. The colour of the liquid becomes deeper ifthe quantity of carbonic anhydride in the atmosphere above it isincreased. The action of the oxygen is still greater in presence ofacetic or hydrochloric acid, but in these cases the result is in part dueto the displacement of some hydriodic acid. Acetic acid liberatesverylittle hydriodic acid, but the action of the oxygen depends on thesuccessive liberation of small quantities.Hydrochloric acid liberatesmore hydriodic acid and in this case the action of the oxygen is moremarked. In presence of a large excess of air, a solution of potassiumiodide acidified with hydrochloric acid is completely decomposed bythe action of light in a few days.If manganous chloride is added to a highly concentrated solution o8 ABSTRACTS OF CHEMICAL PAPERS.potassium iodide and the mixture exposed to light, a higher oxide ofmanganese is precipitated and iodine is liberated ; dilute solutionsshow the same phenomena in a lower degree.All the reciprocal displacements of oxygen and the halogens underthe influence of light are in agreement with the thermochemicaldeterminations. C. H. B.Simultaneous Synthesis of Water and Hydrogen Chloride.By P.HAUTEFEUILLE and J. MARGOTTET (Oowpt. rend., 109, 641-644).--Mixtures which contained oxygen and hydrogen in the proportionrequired to form water, with varying proportions of chlorine ; andmixtures of hydrogen and chlorine in the proportions to form hydrogenchloride, with varying quantities of oxygen, were exploded by meansof a spark, and the residual chlorine was determined by means ofstandard sodium arsenite. If p represents the total hydrogen whichenters into combination, and p' the quantity which combines withoxygen, v - p' gives the ratio of the hydrogen converted intoWwater to thb hydrogen which forms hydrogen chloride. This ratio isindependent of the initial pressure, and of the nature of the spark.It is always less than unity if the proportion of chlorine is more thanhalf the volume of the hydrogen, and it varies with every alterationin the proportion of chlorine. When the volume of chlorine presentis double the volume of the hydrogen, the quantity bf water formedbecomes inappreciable.It is evident that the results do not agreewith Bunsen's law.With equal volumes of hydrogen and chlorine and varying propor-tions of oxygen, the 'ratio is always less than unity and doesnot vary greatly when the ratio of oxygen to hydrogen varies from0.25 to 3. With equal volumes of the three gases the change is re-presented by the equation 5C1, + 5H2 -t 502 = 8HC1 + H,O + C1,402. C. H. B.PEquilibrium between Hydrogen, Chlorine, and Oxygen. ByH. LE CHATELIER (Cornpt. rend., 109, 664--667).-The author dis-cusses'the results of Hautefeuille and Margottet (preceding Abstract)from the point of view of his own laws of chemical equilibrium.Theagreement between the observed and calculated numbers is very close.He points out that the degree of moisture of the gases, which is veryimportant, is not specified. The fornlula shows that a reduction ofinitial pressure should be accompanied by a reduction in the propor-tion of water formed, and the fact that this is not observed indicatesthat' the chlorine is pai*tially dissociated. The varying effects ofchlorine and oxygen depend solely on their relative volumes and noton their chemical properties. C. H. B.Preparation of Oxygen in a Kipp's Apparatus. By J . VOLHARD(AnnaZen, 253, 246--24H).-Small quantities of oxygen can be con-veniently prepared in a, Kipp's apparatus by the action of hydrogcbiINORGANIC CHEXISTRT .9peroxide on bleaching powder.quantity to neutralise the lime in the bleaching powder.Nitric acid is added in sufficientThe oxygencontains a small quantit,y of chlorine. w. c. w.Action of Sulphur on Solutions of Metallic Salts. By G.VORTMANN and C. PADBERG (Ber., 22,2642-2644).--The authors findthat with many proto-salts when their aqueous solutions are boiled withflowers of sulphur, about half the metal present is precipitated as sul-phide, the remainder being oxidised to the per-salt. When a stronglyacid solution of stannous chloride WRS employed, no stannous sulphidewas precipitated, but hydrogen sulphide was evolved, and the wholeof the tin oxidised to stannic chloride. With an aqueous solution ofstannous chloride, and with an acid solution of' cuprous chloride,laather less than half the tin was Precipitated as sulphide, a littiebeing oxidised in the same manner as with the strongly acid solutionof tin.With mercurous nitrate, almost exactly halt of the mercurywas precipitated as sulphide.Solutions of manganese, iron, nickel, zinc, and cadmium sulphates,and acid solutions of bismuth and antinionious chlorides, and ofarsenious and arsenic acids, are not altered wlien boiled with sulphur.L. T. 'l'.Preparation of Nitric Oxide. By J. THIELE (Annulen, 253,246) .--Nitric oxide is prepared in the apparatus previously described(t,his vol., p.6) by adding a strong solution of sodium nitiite to asolution of ferrous chloride or sulphate in hydrochloric acid. I f thesodium nitrite contains carbonate, i t may be removed by precipit,at,ionwith calcium chloride. w. c. w.Phosphonium Sulphate. By A. BESSON ( C O V Z ~ ~ . Tend., 109,644-645) .-When hFdrogen phosphide is passed into sulplinric acida t the ordinary temperatxre, there is considerable development ofheat, sulphur separates, and sulphurous acid is formed. If the acid ispreviously cooled by means of ice and salt, the gas is somewhatlargely nbaorhed, and the liquid remains limpid. After a time, how-ever, it begins to decompose in the manner indicated, the temperaturerises, and deconiposition becomes very rapid. If the acid is cooled to-20" or -25" by the rapid evaporation of methyl chloride, a syrupyliquid is obtained, from which a white, crystalline, highly deliquescent,solid separates; this seems to be phosphonium sulphate.Whenthrown into water at the ordinary temperature, it dissolves w i t h astrident noise, and hydrogen phosphide is evolved, but the sulphuilicacid is not reduced. When exposed to air a t the ordinary tempera-ture, the phosphorus is oxidised to phosphoric, phosphorous, and hypo-phosphorous acids, whilst the sulphuric acid is reduced to sulphurousacid and sulphui., with a small quantity ot' hydrogen sulphide. Thecrystals may be dissolved in dilute sulptiuric acid, and if t'he solutionis electrolysed a t -25" or -40" with a mercury cathode, there isonly a very slight intumescence of the mercury, and hence, if phos-phonium amalgam exists, it is very unstable even at the freezingpoint of niercury.Tlie solution bas a high resistance, and ii' th10 ABSTRACTS OF CHEMICAL PAPERS.current is too strong the compound is decomposed with great rapidityin the manner already described.Hydrogen phosphide has no action 011 nitric acid at -23".Behaviour of Sodium Thiosulphate towards Acids andMetallic Salts. By W. VAUBEL ( B e y . , 22, 2703-27@4).-A replyto Vortman (Abstr., 1889, 1107) upholding the author's previous newsC. H. B.(ibid., p. 943).Direct Production of Crystalline Sodium Carbonate andChlorine from Sodium Chloride. By W. HEMPEL (Bey., 22,2475--2478).-1n the electrolysis of metallic chlorides, which givereadily soluble decomposition-products, the latter are further decom-posed as soon as the quantity produced reaches a certain limit.When,however, the compound produced is only sparingly soluble, thissecondary decomposition does not take place, and the whole strengthof the current is utilised. Potassium chloride and sodium chloride,f o r example, can be converted into the corresponding chlorate ; calciumchloride and magnesium chloride can be decomposed into chlorineand a solid hydroxide, by employing a diaphragm.Marx (D. R.-P., No. 46318) has shown that alkaline chlorides canbe directly converted into clilorine and an alkaline hydrogen car-bonate, by passing carbonic anhydride through the solution duringelectrolysis, metal aud liquid diaphra,%ms being employed.The author, who has been engaged independently in making similarexperiments, describes, with the aid of diagrams, an apparatus inwhich sodium chloride can be directly converted into chlorine andcrystalline carbonate.The cathode is a perforated ircn disc, theanode a per€orated carbon disc, the perforations being about 4mm. indiameter, and bored in an upward direction to allow the gas to escapefreely. A disc of ordinary asbestos-paper, placed immediately betweenthe carbon and iron discs, serves as a diaphragm. The three discsare placed in the centre of a vessel made of porcelain and glass, whichis thus divided into two chambers, each of which is provided with aconducting tube, in one case for carbonic anhydride, in the other forchlorine. If sodium chloride is added from time to time t'nrouph asuitable aperture, and the water which is removed with the crystallinecarbonate is replaced, the apparatus can be worked continuously,sodium carbona,te m d almost chemically pure chlorine being obtained.A tension of 3.2 volts is required for decoruposing the sodiumchloride, and a tension of 2.5 volts to overcome the polarisationcurrent ; but the latter has only a slight tension when both electrodesare made of carbon.With a current of 1.73 amp&res 0.93 gram ofchlorine per hour was produced, so that if a dynamo were employedit should give 64.5 grams of chlorine and 259.8 grams of Na2C0, +lOH,O per horse-power-hour. F. S. I(.Preparation of Crystalline Normal Lithium Phosphate andArsenate. By A.DE SCHULTEN (Hull. 8oc. Chim. [3], 1, 479-480).-Fused lithium chloride dissolves the amorphous, normal phosphate,and on cooling and washing the melt, rhomboidal, tabular crystals oINORQ ANIC CHE YIISTR Y 11normal lithium phosphate, which have a sp. gr. 2.41 at 15", and areinfusible at a white heat, are obtained.The normal arseiiate is similarly prepared ; it corresponds with thephosphate physically, and is of sp. gr. 3.07 a t 15". T. G. N.Cadmium Phosphates and Arsenates. By A. DE SCHULTEX(Rz;ZZ. Xoc. Chim. [3], 1, 473--4i9).-The normal orthophosphate,Cd,( POa),, falls as a voluminous, amorphous precipitate when normalsodium phosphate is added to the solution of a cadmium salt.Hydrogen disodium phosphake throws down from a, hot solution ofcadmium chloride or sulphate an amorphous precipitate which quickJrbecomes crystalline.After purification by dissolution in phosphoricacid and cautious reprecipitation by alkaline hydroxides, i t forms small,prisnintic hexagons of sp. gr. 3-98 at 15", having the compositionH2Cd5(P04)d + 4H20 ; these, when dissolved in cold phosphoric acid(sp. gr. 1.1), are reprecipitated unaitered on warming or on heating111 sealed tubes to 250", butr redissolve on cooling ; as thus produced,tlieir sp. gr. is 4.12 a t l5O. This phosphate loses its water at a red heat,and fuses at a white heat ; it is probably tbe compouiid described byS tromeyer as the noriiial phosphate.Monocadmium phosphate, H,C'd(P@,), + 2H,O, crystallises outafter slow evaporation of a saturated solution of the previous salt incold dilute phosphoric acid a t the normal temperature.It exists aslarge clino-rhombic prisms of sp. gr. 2742 a t 15", which lose theirwater of crystallisation at lOO", and are decomposed by water toform a flocculent phosphate, H?Cd5(P04), + 4H20.Cadmium ch1orapatite.-Normal cadmium orthophosphate and thesecond phosphate described above dissolve in fused cadmium chloride,aiid on slowly cooling the melt, long, hexagonal prisms of the salt,3Cd,(P04),,CdC12, of sp. gr. 5.46 at 15", separate.A cadmium loromapatite, 3Cd3( PO4),,CdBr2, may be similarly pre-pared, but is a1 ways contaminated with cadmium pprophosphate, fromwhich it may be separated by cold, dilute nitric acid, which dissolvesonly the bronrapatite ; the cadmium pyrophosphate, Cd2PZO7, exists asflattened oblique lamella: of sp, gr.4.965 at 15".Cadmium arsenates.--When the amorphous powder, H2Cd5( As04)4 + 4H20, which is precipitated on the addition of hydrogen disodiumarsenate to the solution of a cadmium salt, is dissolved to saturationin a cold solution of arsenic acid of sp. gr. 1.3, and, subjected toheat, crystals of the salt HCdAsO, + H,O, having a sp. gr. of 4.164a t 15" are deposited.Monocadmium arsenate, H4Cd(As04)2 + 2H20, crystallises outwhen a saturated solution of the compound H2Cd,(P04)4 + 4H20, inarsenic acid solution (sp. gr. 1.3), is allowed to evaporate at theordinary temperature. It forms large, clino-rhombic prisms of sp.gr.3.241 at 15", which are isomorphous with those of the correspondingphosphate. At 70-80", they lose their water of hydration, and arepartly decomposed; with excess of water, they form a flocculentsubstance, H,Cd5(As0,)r + 4H20.Cadmium chlorarsenioapatite, 3Cd:,(AsO4),,CdCI2, is produced byfusiiig either normal ammonium arsenate or the salt HzCd,(As04), 12 ABSTRACTS OF CHEMICAL PAPERS.4H20, with excess of cadmium chloride. Its sp. gr. is 5.865 at Is",and its physical properties correspond with those of the chlor-apatite.Cadmium bromaraenioapatite, 3Cd3(AsOl).?,CdBr,, is similarly pre-pared, and exists as long yellow prisms of sp. p. 6.017.Cadmium pyroarseriate, CdrAsoO,, is prepared by f'using a mixtureof cadmium bromide (22 parts) with potassium bromide (5 parts),and adding to the fused mass iiormal ammonium arsenate (9 parts) ;after washing the melt, the colourless crystals of the pyroarsenateare separated from the yellow brorliarsenioapatite Ins treatment withdilutJe nitric acid, which dissolves the latter compound only.Thispyroarsenate forms crystals of sp. gr. .5*474 at 15", corresponding inphysical properties with the pyrophosphate. T. G. N.Action of Sodium Thiosulphate on Metallic Salts. By G.VO~WXANN and c. PADBERG (Bw., 22, 2637 --2641).-The authorshave extended Vortmann's work on copper salts (Abstr., 1898, 787)to ot,hcr metallic salts.When a concentrated solution of sodium thiosulphate is added to astrong solution o i lead acetate until thc lead thiosulphate first precipi-tated has been just redissolved, and alcohol is then added, an oilyliquid separates, which when rubbed with absolute alcohol solidifiesto a crystalline mass of the formula PbY20,JSa,Sz03 + 12H,O.Thallious sulphate under similar treatment yields small needles ofthe formula T1,S20,,2Na,SL0, + 8H,O.When molecular proportions of cadmium sulphate and bariumthiosulphate are rubbed together with a little water, the insolublebarium sulphate formed filtered off, and alcohol added to the filtrate,cadmium thiosulphate, CdS,O, + 2H,O, separates as an oil, whichgradually solidifies to a yellowish-white, crystalline mass.Whenequal molecular proportions of sodium thiosulphate and cadmiumnitrate in aqueous solution are mixed together and alcohol added,yellowish-white needles of the formula 2CdE,O3,NalS20, + 7H20 areformed.If a large excess of the thiosulphate is used, the compoundCdS20,,3Na,S,03 + 9H,O separate., as an oil. This graduallysolidifies to sinall, yellow scales, which lose 4 mols. H,O over sul-phuric acid.On mixiiig strong solutions of zinc iodide and sodium thiosulphateand adding alcohol, an oil separates, wliicli after long exposure oversulphuric acid solidities tci a gum-like mass of t h e formula2ZnS,03,3Na2S,0, + 1 OH20. I t is deliquescent, and decomposesgradually with formation of zinc sulphide.Ferrous tliiosulphate, PeS20, + 5Hy0, forms green crystals easilysoluble in water. A double salt, FeS2O3,3Na2S2O3 + HH,O, was ob-tained by precipitating a mixed solution of ferrous iodide and sodiumthiosulphate with alcohol.It forms bright-green crystals, soluble inw a t 61'.Rlanganese t,hiosulphate, MnS,O, + 5H20, is crystalline but un-stable. A pale, rose-coloured double salt, hlnS20,,2N%S,0, + 16H20,was obtained.The cobalt double salt, CoS,0j,3NaLSLOj + 15H20, forms a IilueINORGANIC CHEMISTRY. 13gum-like mass, soluble in water. No corresponding nickel salt couldbe prepared, though a crystalline salt, NiS203,6NH3,3H20, wasobtained. L. T. T.New Method of Preparing Anhydrous Aluminium Chloride.By C. F. MABERY (Ber., 22, 2658).-The author finds that dryhydrogen chloride extracts the whole of the aluminium froman alloy of copper and aluminium without attacking the copper.The reaction is most energetic a little below a red heat.The alloyscontaining 15 to 40 per cent. of alaminium are hest powdered, .mixedwith powdered charcoal (to prevent the fusion of the remainingcopper), put into a graphite retort, and when heated just below Rred heat a current of hydrogen chloride is passed through. Thealuminium chloride distils over, and may be condensed in suitablevessels, the liberated hydrogen passing on. L. T. T.Alkali Aluminium Silicates. By A. GOEGEU Zeit. Kryst. Min.,15, 646, from BdZ. SOG. fran. win., 10, 278).-On melting kaolin withalkali haloid salts in the presence of moist air, silicates are formed,having the composition AlR'SiO,. B.7 melting kaolin with potassiumcarbonate or caustic potash at a dull-red heat, an amorphous salt,A1KSi04, is obtained, whilst a t a more intense heat octahedra areobtained, having the composition Al2K2Sio6, o r else a more basicsilicate also cr.ystallising in the regular sjstem.The sodium-corn-ponnds prepared in a similar way are alm~~ys basic, and form doublyrefracting crystals. B. H. B.Mercuricobaltarnmonium Salts. By G. VVRTMANN arid E.MORGULIS (Rer., 22, 2644--2648).-When solntions of the mercuricdouble salts of cobaltammonium chlorides are treated with potashor soda, rsd precipitates are formed, which appear to be cobalt-ammo-nium chlorides, in which part of the hydrogen is replaced by varyingproportions of the univalent radicles (HgCl) or (HgOH).A solution of the salt CO~(NJH,)~~C~,,~H~C~,, ora mixture of one part by weight of lut,eocobalt chloride and threeparts of mercuric chloride, when treated with 6 mols. of soda yieldsthe salt ; or with excess of soda, thesalt Co,N12Hz8(HgOH)8C16. Both compounds are bright-red, anddecompose quickly when moist, slowly when dry.Equal weights ofluteocobalt chloride and mercuric chloride with excess of soda yielda slightly more stable, red salt, Co2N12H3,( Hg0H),CI6.Pirrl7ureocobaZtdecamin~ salts.-1 mol. of purpureocobalt chloride,6 niols. of mercuric chloride, and 6 mols. of soda yield a dark-red,flocculent salt, Co2Nl,H,2(HgC1),(H~oH),C16 ; with excess of ~ o d a ,the salt CO,N,,H~~(H~OH)~CI~ is formed.RoseocohaZtdecamine saZts.-1 mol. of roseocobalt chloride, 6 mols.of mercuric chloride, and 6 mols.of soda yield a violet-red precipitate,Co2NlOHZ4( HgOH)&I, ; with excess of soda, a salt,Luteocobalt salts.coz"JL( HgOH)6C14( OH)*,is formed. Both salts are very unstable14 ABSTRACTS OF CHEMICAL PAPERS.Pur~ureocobaltoctaminu snlts.-l mol. of purpureocobaltoctaminechloride, 6 mols. of mercuric chloride, and 6 mols. of soda yield thed t , Co2N6Hl6(HgCl),( HgOH )&16 ; with excess of soda, the saltCo,N,H,, (HgOH),Cl, is formed.Equal weights of the cobalt and mercuric salts with excess of sodayield the salt Co,N,Hls(HgOH),Cl,(OH),.Roseocobultoctamine salts.-Under like conditions as with the pur-pureo-salts, the three salts, CO,NBH~~(H~CI),(H~OH)~C~~,Co2N8HM( HgOH)SCh,and CO~N~H,~(H~OH)EC~,(OH),, are formed. All three are rio:et-recl,and decompose at ordinary atmospheric temperature, as do also thecorresponding purpureo-compounds.L. T. T.Cobaltoctamine Salts. By G. VORTMANN and 0. BLASBERG (Be,..,22, 2648-2655) .-When cobalt nitrate, sulphate, or chloride is dis-solved in a small quantity of water and added to a mixture of ammoniaand ammonium carbonate, violet-red solutions are formed. If theseare oxidised by a current of air, decamine salts are formed, but onevaporation these are decomposed, octamine salts crystallising o u t .The following salts are described :-CO,(NH,)~~(NO~>~(CO~)~,~H,O ...... Crystalline.Co,(NH3) SO,) ,C 03,4H ,O ......... Crystalline.~ o , ( N H , ) , ( ~ ~ ~ ) , C ~ ~ ~ ~ H ~ O .......... Long, thinneedles.CO,(NH,)~SO,(CO~),,~H,O. .........Dark red, prismaticCo,(NH3),CI,C0,,2 H-0. ............ Crgstalline.Co2( NH3) (X O&( CO,) 2,H20 ........ Cherry red crystals.crystals.CV? (NH,),Cl,( CO3)2,H,O ........... 9 7CO,(NH~),(NO~)~(SO~)~,~H,O ....... 7 ,CO,( NH3) 8 (“0,),,2H,O. ............CO,( NH,),(N03),C14,4H?O. .......... 7 7C‘O~(NH,),(NO~)J~,~H~O ........... 9 7Co,( NH,) ,Br2( SO,) ............... 99Co2(NH3),1,(SO4),. ................ 9,1 ,CO~(NH,)~I,CI~,~H,O .............. Brown scales.Co2(NH3),(OH)2C1,,2H20 .......... Dark green powder.CO~(NH~),(OH),C~,,~H~C~, .........C O ~ ( N H ~ ) ~ ( OH),CI,,PtCI,,H?O ......L. T. T.Action of Sulphurous Acid on Cobaltammonium Salts. ByG. VORTMANN and G. MAGDEBURG (Ber., 22, 2630--2637).-Theauthors have obtained the following compounds :-CO,(NH,),(SO,A~)~,~OH~O ........Yellowish-brown needles.Co,(NH3),( S03)6Ba377H20 ........... Golden-yellow scales.C O ~ ( N H ~ ) , ( S ~ ~ ) , B ~ ~ A ~ , , ~ H , G . ...... Golden-yellow scales.Co2(NH,),(S03),Co~vi7~6H,0 ........ Orange crystals.Co2( NH3),( So3)6c02v’,~4H,0 ........ Orangc crystalsISORQANIC CHERIISTRY. 15C O ~ ( NH3),( SO3),(NH3) ,,Co.,"'.SH,O . .CO,(NH,),(SO,),(SO~A~),,~H.?~. ....CO~(NH~)~SO~[SO~)~CO~",~~H~O .....Coz(NH3) (NH3),( SO3)?C1?,4H:.?O . . .C ~ ~ ~ ~ H , > ~ , ( s o , ~ a ) ~ , ~ H ~ o ..........*Co2(NH,) lo( S03)6C02Vi,8H,0 .........Coz( NH,) S03)zC12. ............... CO~(NH,),,(SO,),,~H,O. ............CO~(NH,)~~(SO,)~C~~,~H,O ..........Orange powder.Yellowish- bro w n needles .Yellow crystalline powder.Dark brown crystals.Light brown crystals.Brom.nish-yellow powder.Brown crystalline powder.Yellow needles.The authors consider that these salts show the exist.ence of f o u rseries of salts.New case of Isomorphism of Uranium and Thorium.ByC . RANMELSBERG (Zeit. K~yst. Nifl., 15, 640-641 ; from Sitzber.preuss. Akad. Wiss., 1886, 603).-The author shows that the thoriumsulphate described by Nordenskiijld and others, and the uranium sul-phate hitherto regarded as rhombic, have a similar composition,namely :-(SO,)zTh + 9H,O, (so*),u -k 9H2.0.The crystals of the latter are only seemingly rhombic in conse-quence of twin-formation ; in reality they are monosymmetric, likethe thorium sulphate.The axial ratios of the two minerals are:uranium sulphate, a : b : c = 0.597 : 1 : 0.6555, /3 = 82" 11'; thoriumsulphate, a : b : c = 0.598 : 1 : 0.658, /3 = 81" 30'.Fluorine-compounds of Vanadium and its Analogues. ByE. PETERSEN ( J . p. Chenz. [a], 40, 271-296 ; compare Abstr., 188:4,107).-The following double salts of vanadium oxyfluorides andpotassium fluoride have been obtained :-2KF,VOF3: a white, crystalline precipitate, is obtained by adding asolution of potassium fluoride to one of vanadic acid in hydrofluoricacid ; when dried over sulphuric acid, it becomes reddish-brown, andhas the above formula.4KF.VF,,VOF3 separates as a white precipitate from the mother-liquor of the above salt.HB',3KF,2VOF3 crystallises from a hot solution of either of thepreceding salts in hydrofluoric acid in beautiful, colourless prisms,which lose very little weight at 100".3KF,VOF3,V0,F is the white, crystalline residue left when theprecipitate obtained by adding a solution of vanadium pentoxide inhydrofluoric acid to a solution of potassium fluoride is treated withwater at the ordinary temperature; if hot water is used and thesolution is poured into a hot solution of potassium fluoride, a crystal-line precipitate is obtained, cf uncertain composition, but approaching* Probably Kunzc.l's penttlmineclicobaltic sulphite.B.H. B1 li ABSTRACTS OF OHENICAL P-1PERS.the formula 4KE',VOF3,V02F ; or if the first-mentioned precipitate isheated with water for some minutes, a salt having nearly the coin-position VOF,,VO,F is obtained.2KP,VO,F separates from a warm solution of vanadium pentoxidein hydrofluoric acid when i t is nearly neutralised with potassiumhydroxide. It crystallises in yellow, six-sided, truncated prisms.When reci*ystallised from water, it yields the salt 3KF,2V02F.3HF.9NH4F,5VOY3, obtained by adding ammonium fluoride inslight excess to the solution of vanadium pentoxide in hydrofluoricacid, crystdlises in larqe, colourless, four-sided prisms.SNH,F',VO,F cryst allises from a solution of vanadium pentoxide inhpdrofluoric acid wheii it is nearly neutralised with ammonia.Thecrystallography of the salt is given.HF,7NH4F,4V02F separates in white crystals from the solutionof the last-nxmed salt in warm water.2Nbp0,,3KF,5H,0 is obtained by melting niobium pentoxide (1 part)with potassium fluoride (3 25 parts) and treating the melt with water,when the salt remains undissolved as a crystalline powder.Nb20,,KF,3H,0 is a prismatic, crystalline powder, obtained byfusinq niobium pentoxide (1 part) with potassium fluoride (1*.3-1*5parts).The author reviews the work already done on the vanadium doublefluorides, and concludes his paper with the followinq directionsfor extracting vanadic acid from the finery slag of Taberg:--.300grams of the finely-powdered slag is mixed with 400 C.C.of hydro-chloric acid (sp. gr. 1.18) and shaken. After 24 hours, water is addedto make the bulk up to 1i litres, and the whole filtered through linen.Iron is then addpd, and, after the evolution of hydrogen has ceased,sodium acetate until the liquid is reddish-brown; finally, acetic acid andsodi nm phosphate are added until all iron, chromium, aluminium, andvanadium are precipitated as phosphates.The precipitate is mixedwith sodium carbonate (0.5 part) and heated on an iron plate for i-2 hour ; the mass is treated with water, hydrochloric acid nddeclto nearly neutralise the solution, which is then heated, filtered, andmade acid with acetic acid ; solid ammonium chloride is now added,when a red, crystalline ammonium vanadate, (NH&0,2V2O5,4H20,separat,es ; this is heated and the residual vanadium oxide treated withhot nitric acid at 110-120", and converted into ammonium mets-vanadate by evaporating off the nitric acid, dissolving in ammonia, andcr~+stallising ; pure vanadic acid is obtained from this salt by ignitingand repeating the nitric acid treatment.Vapour-density of Antimony Pentachloride.By R. ANSCH~TZA. G. B.and N. P. EVANS (Annnlen, 253,95--105).-By means of a modificationof La Coste's apparatus, the authors have attempted to determine thedensity of the vapour of antimony pentachloride under reducedpressure. As antimony trichloride boils at 143-144" under 70 mm.pressure and antimony pentachloride boils a t 102-103" under 68 mm.pressure, the determinations were made under 58 mm. pressure a t atemperature of 218". The mean of four determinations gave the\ d u e 10, the theoretical density being 10.33. It was impossible tIKORGANIC CHENISTRY.17exclude all traces of moisture from the apparatus and avoid theformation of minute quantities of the monohydrate of antimony penta-chloride. w. c. FV.Atomic Weight of Palladium. By E. H. KEISER (Amer. Chew.,J., 11, 398--403).-Attempts were at first made to use the doublechlorides of palladium with ammonium and with sodium, but theyhad to be abandoned, a s these compounds contain water, from whichi t is almost impossible to completely free them ; moreover, thedried salts are very hygroscopic, and absorb water rapidly whilebeing weighed.Finally, the yellow, cry stadline palladiodiammonium chloride,PdN,H6C12, was used ; this is formed whenever hydrochloric acid isadded to a solution of palladium chloride in excess of ammonia ; it isR stable compound, and can be obtained very pure. It contains nowater of crystallisation, c:m be dried completely, and is not hygro-bcopic. When heated in a current of pure hydrogen, the colourchanges from yellow to black, hydrogen being absorbed, and metallicpalladium and ammonium chloride formed. On raising the tempera-ture, the ammonium chloride volatilises, and spongy palladium is leftbehind ; this is cooled below a red heat in a current of hydrogen, andthen the hydrogen is displaced by air; in this way the occlusion ofhydisogen is prevented. The weight of palladium obtained from aknown weight of the chloride is thus ascertained, and from this theatomic weight of palladium is calculated, assuming N = 14.01,H = 1, C1 = 35.37. Two series of experiments were made; thepalladammonium chloride used in the second scries was preparedfrom the metallic ptiliadium obtained in the first. The results givea s mean value Pd = 106.35:-Atomic weight.r----h.---- - Series. Experimenta. Mean. Maximum. Minimum.I. 11 106.352 106.459 106-29211. 8 106.350 106.455 106.286C. F. B.Ruthenium Potassium Nitrites. By A. JOLY and M. VEZES(Compt. rend., 109, 667-670 ; compare Abstr., 1889, p. 352).-Ifruthenium chloride is added to a boiling solution of potassiumnitrite until the precipitate which forms a t first is redissolved, andthe liquid is concentrated and allowed to cool, it deposits dichroic,orange-red, monoclinic prisms of 90" 10'. They are very soluble inwater, can be purified by repeated recrystallisation without under-going a1 teration, and have the composition RuZOL( N,0,)a,4KN0, orWhen the potassium nitrite is in excess, and prolonged ebullition isavoided, a pale-yellow, crystalline precipitate is obtained of thecomposition $uz02, (N203),,8KN02 or Ru?O,( NO)2,N,03,8KN0,. Sepa-ration of the ruthenium is never complete, and the mother-liquor, OILconcentration, yields crystals of the first compound. The second saltis converted into the first by prolonged ebullition with wat8er, and thereverse change is effected by the addition of potassium nitrite. A t avoc. LVIII. CRU~O,(NO),,(N?O~),,~KNO~I S ABSTRACTS OF CHEMICAL PAPERS.low temperature, the second salt crystallises with 2 mols. H,O. Otherdouble nitrites seem to be formed, but are relativelyvery unstable.If the double nitrites are heated with ammonium chloride andhydrochloric acid, only part of the nitrogen is evolved and one atomof the nitrogen remeins i u combination with each atom of ruthenium.The solution wh '11 concentmtc.d yields the potassium rutheniumnitrosochloride previous1 y described (Zoc. cit.).No compound was obtained corresponding with that to whichClaus attributes the formula Ru(N0,),,3KNO2. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8905800006

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

I S ABSTRACTS OF CHERLICAL PAPERS. M i n e r a l o g i c a l Chemistry. Glaserite from Douglashall. By H. B~~CKING (Zeit. Kryst. illin., 15,561--575).-1n the astrakanite (bloedite) of Douglashall, crystals of potassium sodium sulphate have recently been found. The crystals vary from 5 to 20 mm. in length. They have a hardness of 2$ to 3, and a sp. gr. of 2.6-50 to 2.656, the differences being due to small inclusions of rock-salt. The crystals belong to the hexagonal system, the axial rat,io being a : c = 1 : 1.2879. These samples of crystals, easily soluble in water, gave on analysis the following results :- K2S04. N+S04. MgSO,. NaC1. Insol. H20 and loss. Total. I. 66.5 22.0 - 10.1 0.4 1.0 100.0 11. 67.3 18.2 - 21.6 - 2.9 100.0 111. 58-7 19.5 3.4 14.4 0.1 3.9 100.0 The author also gives crystallographical descriptions of bloedite, Atelestite from Schneeberg, in Saxony.By K. Busz (Zeit. R r y s t . Min,., 15, 625-627).-A specimen of this rare mineral from the Neuhilfe mine, at Schneebei-g, gave on analysis results corre- sponding with the formula As2O5,3Bi2O3,2Hz0. The axial ratio was calculated by G. v. Rath to be a : b : c = 0.869 : 1 : 1.822, p = 110" 30'; whilst the author finds that it is kainite, and boracite from the same locality. B. H. B. a : b : c = 0.92974 : 1 : 1.51227. /3 = 110" 23'. The hardness is 3$, and the sp. gr. 6.4. B. H. B. Artificial Preparation of Wollastonite. By -4. GORGEG (Zeit. K r y s t . iiin., 15, 646; from Bull. SOC. fmn. win., 10, 271).-One equivalent of CaC12 melted with one equivalent of precipitated silica, in the presence of steam, gives CaSiOj, whilst two equivalents of the former give Can,SiO,, which, however, cannot be isolated in distii;ct crptals. With a larger excess of calcium chloride, the compound Ca,C12SiOs is obhinqd in rhombic crystals and pseudo-MINERALOGICAL CHEMISTRY.19 hexagonal tablets, whose composition is probably Ca2C12Si03. If 1 gram of Si02, 15-grams of CaCl,, and 3 grams of NaCl are melted for half an hour in a current of moist air there is obtained, besides small quantities of the chlorides mentioned above and of tridymite, long prisms of wollastonite exhibiting the optical properties of the natural mineral. B. H. B. Anorthite and Enstatite. By K. v. CHROUSTSCHOFF (Zeit. I h y ~ t . &fin., 15, 649; from BulZ. Xoc.j?an. rnin., 10, 329).-The olivine inclusions in the basalt of Wingendorf, in Silesia, contain anorthite (I) and almost colourless enstatite (11). Both minerals were isolated and analgsed with the following results :- SiO,. A120,. Fe,O,. FeO. MgO. OaO. Na,O. K20. Ignition. Total. I. 44-68 35.32 0.41 - 1.13 17.45 1.33 0.45 0.33 101.10 11. 56.96 0.79 - 3.21 33.65 4.32 traces 0.26 99.09 B. H. B. Minerals from Fiskernas, in Greenland. By N. V. USSIN (Zeit. Kryst. Mim, 15, 396-615) .-1. Sapphirim.--The sapphirine- bearing rock belongs to the crystalline schist series. The sapphirine occurs in blue, tabular crystals, with distinct pleochroism. The axial ratio is calculated to be a : b : c = 0.65 : 1 : 0.93 . /3 = 79" 30'. The hardness of sapphirine is 7+, and its sp. gr.is 3.486. Analysis gave the following results :- Si02. A1203. Fe203. FeO. MgO. Ignition. Total. 12-83 65.29 0.93 0-65 19.78 0.31 99.79 Formula : Mg5A112Si2027. 2. KorrLerupine.-This was described as a new mineral by Lorenzen. No crystallographical and optical examination has hitherto been made. The mineral belongs to the rhombic system, the axial ratio being a : b = 0.854 : 1. It is perhaps identical with the prisniatine of Sauer. 3. Gedrite.-This mineral is found at Fiskernas in colonrless grains or short prisms, having a hardness OF 5.5 and a sp. gr. of 3.100. Analysis gave the following results :- Its formula is MgA1,SiOs. SiO,. A120,. Fe203. FeO. MgO. Na,O. H20. Total. 46.18 21-78 0.44 2-77 25.05 2-30 1-37 99.89 Formula : (NaE),Si03,6MgSi0,,2A1,0,. This variety of gedrite differs from all other rhombic amphiboles by its high percentage of alumina.4. Paqasite.-This monosymmetric hornblende o6cnrs in small, transparent grains, having a sp. gr. of 3.064, and giving on anal-+- 46.79 15.36 0.69 2-38 13-11 20-17 2*1:3 100*C;3 SiO,. A1,0,. Cr203. PeO. CeO. MgO. Ignition. Total. B. H. B. c 220 ARSTHACTS OF CEEMICAL PAPERS. Artificial Fayalite. By A. FIRKET (Zeit. Kryst. Min., 15, 6.52-6rj3; from Ann. Xoc. gebl. Belg., 14, 196).-A slag from the OugrBe ironworks analysed by the author gave the following results :- SiOz. FeO. Fe,O,. MnO. S. I?. Total. 28.00 62 00 9.30 0.97 0.14 0.50 100.91 The hardness is 6, and the sp. gr. 4.812. B. H. B.I S ABSTRACTS OF CHERLICAL PAPERS.M i n e r a l o g i c a l Chemistry.Glaserite from Douglashall.By H. B~~CKING (Zeit. Kryst. illin.,15,561--575).-1n the astrakanite (bloedite) of Douglashall, crystalsof potassium sodium sulphate have recently been found. Thecrystals vary from 5 to 20 mm. in length. They have a hardness of2$ to 3, and a sp. gr. of 2.6-50 to 2.656, the differences being due tosmall inclusions of rock-salt. The crystals belong to the hexagonalsystem, the axial rat,io being a : c = 1 : 1.2879. These samples ofcrystals, easily soluble in water, gave on analysis the followingresults :-K2S04. N+S04. MgSO,. NaC1. Insol. H20 and loss. Total.I. 66.5 22.0 - 10.1 0.4 1.0 100.011. 67.3 18.2 - 21.6 - 2.9 100.0111. 58-7 19.5 3.4 14.4 0.1 3.9 100.0The author also gives crystallographical descriptions of bloedite,Atelestite from Schneeberg, in Saxony.By K. Busz (Zeit.R r y s t . Min,., 15, 625-627).-A specimen of this rare mineral fromthe Neuhilfe mine, at Schneebei-g, gave on analysis results corre-sponding with the formula As2O5,3Bi2O3,2Hz0. The axial ratio wascalculated by G. v. Rath to be a : b : c = 0.869 : 1 : 1.822, p =110" 30'; whilst the author finds that it iskainite, and boracite from the same locality. B. H. B.a : b : c = 0.92974 : 1 : 1.51227. /3 = 110" 23'.The hardness is 3$, and the sp. gr. 6.4. B. H. B.Artificial Preparation of Wollastonite. By -4. GORGEG (Zeit.K r y s t . iiin., 15, 646; from Bull. SOC. fmn. win., 10, 271).-Oneequivalent of CaC12 melted with one equivalent of precipitatedsilica, in the presence of steam, gives CaSiOj, whilst two equivalentsof the former give Can,SiO,, which, however, cannot be isolated indistii;ct crptals. With a larger excess of calcium chloride, thecompound Ca,C12SiOs is obhinqd in rhombic crystals and pseudoMINERALOGICAL CHEMISTRY.19hexagonal tablets, whose composition is probably Ca2C12Si03. If1 gram of Si02, 15-grams of CaCl,, and 3 grams of NaCl are meltedfor half an hour in a current of moist air there is obtained, besidessmall quantities of the chlorides mentioned above and of tridymite,long prisms of wollastonite exhibiting the optical properties of thenatural mineral. B. H. B.Anorthite and Enstatite. By K. v. CHROUSTSCHOFF (Zeit. I h y ~ t .&fin., 15, 649; from BulZ. Xoc. j?an. rnin., 10, 329).-The olivineinclusions in the basalt of Wingendorf, in Silesia, contain anorthite(I) and almost colourless enstatite (11).Both minerals were isolatedand analgsed with the following results :-SiO,. A120,. Fe,O,. FeO. MgO. OaO. Na,O. K20. Ignition. Total.I. 44-68 35.32 0.41 - 1.13 17.45 1.33 0.45 0.33 101.1011. 56.96 0.79 - 3.21 33.65 4.32 traces 0.26 99.09B. H. B.Minerals from Fiskernas, in Greenland. By N. V. USSIN(Zeit. Kryst. Mim, 15, 396-615) .-1. Sapphirim.--The sapphirine-bearing rock belongs to the crystalline schist series. The sapphirineoccurs in blue, tabular crystals, with distinct pleochroism. The axialratio is calculated to be a : b : c = 0.65 : 1 : 0.93 . /3 = 79" 30'. Thehardness of sapphirine is 7+, and its sp. gr. is 3.486. Analysis gavethe following results :-Si02.A1203. Fe203. FeO. MgO. Ignition. Total.12-83 65.29 0.93 0-65 19.78 0.31 99.79Formula : Mg5A112Si2027.2. KorrLerupine.-This was described as a new mineral by Lorenzen.No crystallographical and optical examination has hitherto beenmade. The mineral belongs to the rhombic system, the axial ratiobeing a : b = 0.854 : 1. It is perhapsidentical with the prisniatine of Sauer.3. Gedrite.-This mineral is found at Fiskernas in colonrlessgrains or short prisms, having a hardness OF 5.5 and a sp. gr. of 3.100.Analysis gave the following results :-Its formula is MgA1,SiOs.SiO,. A120,. Fe203. FeO. MgO. Na,O. H20. Total.46.18 21-78 0.44 2-77 25.05 2-30 1-37 99.89Formula : (NaE),Si03,6MgSi0,,2A1,0,. This variety of gedritediffers from all other rhombic amphiboles by its high percentage ofalumina.4. Paqasite.-This monosymmetric hornblende o6cnrs in small,transparent grains, having a sp. gr. of 3.064, and giving onanal-+-46.79 15.36 0.69 2-38 13-11 20-17 2*1:3 100*C;3SiO,. A1,0,. Cr203. PeO. CeO. MgO. Ignition. Total.B. H. B.c 20 ARSTHACTS OF CEEMICAL PAPERS.Artificial Fayalite. By A. FIRKET (Zeit. Kryst. Min., 15,6.52-6rj3; from Ann. Xoc. gebl. Belg., 14, 196).-A slag from theOugrBe ironworks analysed by the author gave the followingresults :-SiOz. FeO. Fe,O,. MnO. S. I?. Total.28.00 62 00 9.30 0.97 0.14 0.50 100.91The hardness is 6, and the sp. gr. 4.812. B. H. B

ISSN:0368-1769    

DOI:10.1039/CA8905800018

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

20 ARSTHACTS OF CEEMICAL PAPERS. Organic Chemistry. Tetrabromides of Diallyl. By G. CIAMICIAR and F. ANDERLINI (Bey. 22 2497-!2500).-A small quantity of an oily bromide C6H1,,Br1 is formed in preparing diallyl tetrabromide (m. p. 63") by treating the hydrocarbon with bromine ; when the crude product is crystallised from alcohol the liquid bromide remains in solution. It boils at 135-140" (about 8 mm.) with slight decomposition and its molecular weight determined by Raoult's method in benzene solu- tion was found to be 325 as the average of two experiments. ?-Pen tyleneglycol and its An'hydride (Tetrahydromethyl- furfuran). By A. LIPP (Bey. 22 2567-2573).-y-PentylenegIycol (Freer and Perkin Trans. 1887 836) mixes in all proportions with water alcohol and chloroibrm is rather sparingly soluble in ether in presence of moisture and is insoluble in light petroleum.At -18" it is quite viscid. It boils at 219-220" (under 713mm. pressure) and does not decompose at 236". Sp. gr. = 1.0003 a t 0" (water at 0" = 1). When heated with 35-40 per cent. hydrobromic acid for one hour at loo" the anhydride is formed ; this boils at 77-7.9" ; sp. gr. = 0.8748 a t 0" (water a t 0" = 1). It !is not changed when heated with water a t 200-210". y-Penty Zene dihrornide CHBrMe.CH2*CH2*CHzBr is obtained by heating the glycol or the anhydride with 3 to 4 parts of fuming hydro- bromic acid for three hours at 100". I t boils at 200-202'with partial decomposition is insoluble in water readily soluble in alcohol ether chloroform and carbon bisulphide. Action of Lead Peroxide on Organic Substances in Alkaline Solution.By M. GLASER and T. MORAWSKI (Jfonatsh. 10 57%- 584).-When a mixture of glycerol (2 grams) sodium or potassium hydroxide (5-10 grams) and lead peroxide ('25 grams) contained in water (100 c.c.) is gently heated a vigorous evolution of hydrogen occurs sodium or potassium formato being simultaneously formed according to the equation C3Hs03 + 3 0 = H2 + SH*COOH. About 97 per cent. of the theoret cal quantity of formic acid is produced. Under somewhat similar circumstances ethylene glycol also yieIds hydrogen and formic acid (yield about 60 per cent.) G2H6Oz + 2 0 = F. S. K. Ammonia is also withaut action on it at 200". N. 3. &I.ORQANIC CHEMISTRY. 22 H + 2CH,O2. peroxide with polyhydric alcohols in alkaline solution. The,authors intend to study the behaviour of lend G.T. 31. Action of Ammoniacal Cupric Oxide on Carbon Compounds. By C. VINCEPT and DELACHAXAL (Conzpt. rend. 109 615 -616).- Pure sorbite is completely precipitated by ammoniacal cupric oxide and hence cannot be separated from mmnilol by means of this reagent (compare Guignet Abstr. 1889 1133). Action of Cuprammonium Sulphate on Sorbite. By C. E. GUIGNET (Coiiipt. rend. 109,645).-Cupr,zmmonium sulphate un- doubtedly precipitates sorbite (preceding abstract) but it precipi- tates mannitol more rapidly and by fractional precipit,ation the author has been able repeatedly to separate pure mannitol from liquids which also contained sorbite. C. H. l3. C. H. B. Sorbite. By C. VINCEXT and DELACHANAL (Conipt.rend. 109 676-679).-Sorbtte exists in the fruit of all the wsaceSe and espe- cially in pears cherries arid plnms which contain 0.7 to 0 8 per cent. When heated with concentrated hydriodic acid it yields /3-hexyl iodide which boils at 16'7" undera pressure of 753 min. ; when heated with alcoholic potash i t yields /3-hexylene boiling a t 68.5 under a pressure of 735 mm. and acetic and butyric acids when oxidised. 90 C.C. of water and 35 grams of red phosphorus were gradually mixcd with 150 grams of iodine in a capacious retort 60 grams of crystallised sorbite was added and the mixture gently heated. An energetic reaction took place and /3- hexyl iodide was obtained in almost theoretical quantity no resinous products being formed. Mannitol yields the same /3- hexyl iodide when treated wit,h hydriodic acid.When heated with acetic anhydride and a small quantity of zinc chloride sorbite yields a hexacetate C6H,(OAc) which is obtained as a very thick colourless syrup on washing the crude product with water dissolving in ether and evaporating the filtered ethereal solu- tions. It follows from these results that the constitution of anhydrous sorbite is c6&( OH),. C. H. B Transformation of Cane Sugar .*into Dextrose. By J. BOCK (Che:;i. Cedr. 1889 ii 30 from Oster-ungar. xeit. Zucker. h i d . L w d w . 18 194) .-Cherries which had been preserved by heating with a hot concentrated solution of cane-sugar and which had kept perfectly sound during the winter were allowed to remain for four or five days in a loosely covered dish when it was found that they were coatedwith a white crystalline mass which after separation and recrystallisation proved to be dextrose.Levulose was not found. The exact circums tames under which this change took place could not be determined. J. W. L. Raffinose. By BERTHELOT (Conzpt. r e d . 109 548-550).-The ordinary crystals of raflinose are generally regarde.1 as having the28 ABSTRACTS OF UHEMXCAL PAPERS. composition C,,H,,016 + 5H20 but rafliriose from cotton seed sepa- rates from dilute alcohol in the form of a syrup which gradually solidifies to lamellar crystals which contain 6 mols. H,O and are different from the ordinary crystals. The rotatory power of their solution is however the same as that of a solution of the ordinar;)- crystals. The aut,hor confirms Tollens' observat'ion that good beer yeast fer- nients raffinose completely but that weak yeast ferments only about one-third even after 48 hours zlthough during the same time it will completely ferment eaccharose and glucose.I t seems most probable tlint uiider these conditions raffinose splits up into glucose which ferments and either a saccharose which has a sinall reducing power like lactose or a mixture of two glucoses only one of which has reducing power. C. H. B. By D. LOISEAU (C'ompt. 1-e7atZ. 109 614-615).-111 a sealed paper dated March 5th' 1888 the author described the following results Raffinose is com- pletely fermented by low bcer yeast but with high beer yeast only about one-third of the total possible alcohol is formed whilst the solution has a reducing power equivalent to that of a quantity of glucose equivalent t o the amount of raEnose which has been fey- mented.It is probable that 2 mols. of raffinose are converted into 1 mol. of laevogyrnte glucose which always ferments and twice the quaiitity of a dextrogyrate compoiind which is not fermented by high yeast. Prolonged contact with acids converts this compound into glucose which is completely fermented by both forms of yeast. This difference in behaviour wit,h raflinose may be used as a means of distinguishing between high and low yeast (compare Berthelot preceding abstract). C. H. B. Lactose. By E. W. T. JOKES (Analyst 14 81-83).-Having obtained some very pure crystallised lactose the author has redeter- mined the specific rotatory power and cupric reduction.For a solu- tion of 5 grams of the crystals C,,H2,0 + H,O in 100 c.c. pi.('- pared hot and of sp. gr. 1018.6 at 15*5" the values obtained are :- Fermentation of Rafhose by Beer Yeast. For C,2H,,01,. 60.5" 54.6 CUO x 0.5723 = C1ZHZZO1I. CuO x 0.6024 = ClzH2z0,1 + H20. The determinations were made by O'Sullivan's method the cuprous oxide being converted iuto cupric oxide by careful ignition and weighed. Lactose is not affected optically or in reducing power by heating with citric acid whilst cane sugar is completely inverted. The cryst,als do not lose their water by 24 11oui*s' heating in a water-oven bnt if dissolved in water and re-dried the anhydrous sugar is obtained in a few hours. 31. J. S.ORGANIC CHEMISTRY. 23 Methylhydrazine.By G. v. BR~~NING (Annalen 253 5-14).- I n order to prepare methylhydrazine nitrosomethylcarbamide NO-NMe-CONH is first obtained by adding the theoretical quantity of solid sodium nitrite to a solution of methylcarbamide nitrate mixed wif h powdered ice. Not more tban 50 grams of methylcarbamide nitrate should be used in each operation. The nitroso-compound forms small yellow crystalline plates and melts at 123-124" with decomposition. It is soluble in hot water alcohol and ether. The aqueous solution is decomposed by prolonged boiling. Methylhydrazine is prepared by adding zinc-dust (4 parts) in small quantities to the nitroso-compound suspended in water (6 parts) and acetic acid ( 2 i parts) ; the tempe- rature of the mixture must be kept between 5" and 15" and the operation lasts two to three hours.The product is filtered; the filtrate acidified with hydrochloric acid concentrated and the thick liquid boiled with 3 pwts of strong hydrochloric acid for 12 hours in a flask provided with a reflux condenser in order to decompose the carbamide; the well-cooled liquid is then mixed with an excess of sodium hydroxide and distilled in a current of steam the distilla- tion being stopped as soon as the distillate ceases to reduce l-'ehling's solution. The distillate consists of an aqueous solution of methyl- hydraziiie ammonia and methylamine. The latter compounds are removed by boiling the solution briskly for eight hours in a flask with a reflux condenser. The methylhydrazine is converted into the acid sulphate which is deposited on the addition of absolute alcohol to the concentrated solution. The free base is obtained by decomposing a concentrated solution of the sulphate with sodium hydroxide.The last traces of water are removed by treating the base with barium oxide in sealed tubes at 100". Methylhydrazine NHMe*NH2 is a colourless mobile liquid fuming in damp air. It boils a t 87" (745 mm.) and is miscible in all. proportions with water alcohol and ether. It strongly red iices Fehling's solution at the ordinary temperature and attacks cork caoutchouc and the skin. The acid s d p h u t e N,HJfe,H2SO4 forms long white needles. It melts a t 139.5" and decomposes a t 182". Unlike the normal sulphate it is insoluble in alcohol. The hydrochloride is precipitated from its alcoholic solution by ether.The picrate is deposited from alcohol in yellow needle-shaped crystals and melts a t 162" with decomposition. Methylseinicarbazide NH,*CO*N2H,Me prepared by the action of potassium cyannte on methylhydrazine sulphate. crystallises in prismatic plates and melts at 113". It is freely soluble in water and alcohol. 1Clethylphenylthiosemicarbazide NHPh.CS*N,H2Me is formed by the action of phenylthiocarbimide on an aqueous solution of methylhydrazine. This compound is soluble in water and alcohol and melts at 143"; the aqueous solution is decomposed by mineral acids. Dibenzoy Zmethylhydrazine N,HMeBz is freely soluble in alcohol and in dilute alkalis ; it melts at 143" and crystallises in colourless needles. Metlylpicraxide N,H,Me*C,H,(NO,) is formed when an alcoholic solution of picryl chloride is added to a solution of the base.It crystallises in yellow plates melts a t 171" with decomposit]ion and is freelv soluble in alcohol and ether. OxnZyZd inaethyZhydraci?ze N,H,Me*C,O,*N,H,Me melts at 221" but The oxalate is soluble in warm alcohol.2 4 Al3STHACTS OF CHEMICAL PAPERY. it begins to sublime about 160". It is soluble in alcohol and reduces Fehling's solution when gently warmed. The nitroso-derivative crystallises in plates and melts at 147" with decomposition. Action of Methylhydrazine on Dialdehydes and Diketones. By K. KOHLRAUSCH (A.nii.aZen 253 15-24).-Methylphenylhydr- azine yeacts with berizile a t loo" yielding b e n z i Z e m e t h y l ~ h e ~ ~ ~ ~ Z h ~ d ~ r a x o ~ ~ e COPh.CPIi:K*NMel,h a crystalline substance freely soluble in alcohol ether and light petroleum.It melts a t 5.5-56" and is completely decomposed a t 200" ; it is also decomposed by strong hydrochloric acid a t the ordinary temperature. Benzilemethylphenyiosuzone C,Ph,(N*NMePh) is formed when a mixture of benzile (1 mol.) and methylphenylhydrazine ('2; niols.) is heated a t 120" ; the crude product is treated with hot dilute sulphuric acid to remove the excess of base and the red crystalline mass which is deposited when the mixture cools is purified by recrystallisation from alcohol. The pure substance forlns yellow needles soluble in ether arid acetone melts a t 1 7 ~ - 1 8 ~ " and is decomposed a t 220' ; it is not readily attacked by strong hydiw hloric acid. Olyoxulrtteti~ylp;pherLyl.,scizolze C,H2(N*NMePh) is deposited as a yellow pi-ecipttat,e when an aqueous solution of glyoxal is added to nil acetic acid solution of niethylpheiiylhydrazine.It melts a t 217-218" and is completely decomposed a t 250". This osazone does uot give a characteristic coloration with ferric chloride. i s freely soluble in ether.. It melts a t 103-104" and begins to decom- pose a t 2 10'. 1'.2'.3'-MethylplienylacetylilLclole is formed when methylpheiiylhydrazone is fused with zinc chloride. The indole melts a t 136" arid dissolves freelyin glacial acetic acid. It is decom- posed by strong hydrochloric acid a t loo" yielding Degen's 1'.2-methylplie1rylindole (Abstr. 1887 149). Acet!jlu,:etonem~t~~~ZplisiLylh~drazirL~ CHi?Ac.CMe:N*NePh is a yeliow oil which can be distilled in a vacuum without decomposition.The compound formed by the action of niethylphenylhydrazine on an excess of acetonylacetone could not be isolated as it undergoes spon tsrieous decomposition losing a molecule of water and changing into the methylphenylamidodimethylpyrroline described by Knorr (Abstr. 1887 276). a c e t o n y l i c e t o . r L e m ~ t ~ ~ y l ~ ~ ~ e n ~ I l ~ ~ ~ i y d r a % o n e C2H4( CMe:NMePh) is deposited in the form of an oil which slowly crystallises when an aqueous solution of acet,onylacetone is added to excess of metliyl- phenyl hydrazine dissolved in acetic acid. The crystals melt at 143-144!" and dissolve in alcohol ether benzene and light petroleum. The diliydrazone dissolves also in hydrochloric acid ; when this solu- tioii is heated the preceding pyrroline-compound appears to be formed.w. c. w. w. c. w. Be 7 b zoy 1 ace t o ? A e rn e 1 IL y lp h my 1 hg d r az 011 e C H A c * C P h N * N Me P h Derivatives of Dichloromaleimide. By G. CIAMICIAN and p. SICBEE (Ber. 22 fL490-2497).-Chlorar1ilidomaleimide (m. p. 195-196") is decomposed when heated a.bore its melting- point; it is soluble in ether and hot alcohol but only sparingly in boiling water.ORGANIC CEEMISTRP. 25 It dissolves in hot dilute sulphuric acid,.yielding a colourless solution and in alcoholic solutions dimethylanilme produces a reddish-brown coloration. Chloramidomaleinzide C,C102(NH,) :NH is obtained in sinall quantity when dichloromaleirnide is he8 ted under pressure with excess of alcoholic ammonia.It ci~ystallises from water in golden needles melts a t 280" and is soluble in alcohol and ether but insoluble in benzene. It dissolves in alkalis with a yellow coloration but the solution becomes colourless on heating. Dich ZoromuZewnic acid COOH-C,Cl,-CO-NH + H20 prepared by heating dichloromaleiniide (8 grams) with ammonia (80 c.c.) in sealed tubes separates from water in crystalline aggregates melts a t 175" with decomposition and is soluble in ether alcohol and warm water but insoluble in benzene. The silver salt CaHC1,N0,Ag2 crystallises in colourless needles and explodes when heated. An orange-red compound CuH,,N,O or C,,H,,N,O2 separates in crystals when dichloromaleimide is heated with phenylhydrazine in alcoholic solution. This substance crystallises from boiling acetone or glacial acetic acid in orange-red needles melts at 269-271" with decomposition and is only sparingly soluble i n most ordinary solvents.It dissolves in concentrated sulphuric acid with an intense red coloration and on adding water an orange-red flocculent substance is precipitated. P. S. K. BJ- E. BAUMANN and E. F n o m ( B e y . 22,2600- 26~9).-P-Trithioaldel~yde (Klinper Abstr. 1879 780) is formed when hydrogen sulphide is passed through a mixture of aldehyde (1 part) with alcohol previously saturated with hydrogen chloride (3 parts) ; crystals soon separate and the whole becomes solid. The product is washed with water and crystallised from alcohol from which it separates in Iong needles melting a t 125-126". A small amount of a-trithioaldehyde melting a t 101-102" is also formed as well as a few crystals of a substance melting a t 76" possibly Marck- wald's y-derivative (Abstr.1886 865). a-Trithioaldehyde is obtained as the chief product when eqiral parts of aldehyde water and strong hydrochloric acid are used. It crlstal- lises from acetone ill splendid prisms an inch long. The /%compound is also formed. p-'l'hiobenzaldehyde and ythiobenzaldehyde are formed when hydro- gen sulphide is passed through a mixture of benzaldeb yde and alcoholic hydrogen chloride. The product is boiled with benzene until almost all is dissolved; on cooling the @compound separates in crystals having the ComposiLion sc7H6s + c6H6 (not C7H,S 4- CsHc Klinger) ; this gives up all the benzene a t ItjO" and a portion when kept a t the ordinary temperature for a long time.y-T~~iobenzuZdehy~e C7H6S crystallises from Senzene in small pointed needles melting a t 166-167". The crystals contain no benzene of crystallisation. When the solution in benzene is treated with iodine the whole solidifies after some time being converted into the p-derivative. When a - or P-trithioaldehyds is oxidised with potassium perman- Thioaldehydes.26 ABSTRACTS OF CHEXICAL PAPERS. ganate they both give as end-product a trisdphone C6Rl2S3O6 together with products containing less oxygen (compare Guareschi Abstr. 1884 294). This forms slender needles softens at 340" becoming yellow and sublimes a t a higher temperature without melt- ing. It is almost insoluble in water very sparingly soluble in alcohol ether chloroform and benzene more soluble in hot acetic acid; it also dissolves readily in strong nitric or sulphuric acid but is pre- cipitated by water.Alkalis dissolve it readily and it can be crystal- lised from ammonia and alkaline carbonates. The constitution of trithioaldehyde sulphone is S02<CHMe.SO:>CHMe. CHMe* S 0 When an alcoholic alkaline solution of the substance is treated with methyl iodide the compound CgH18S3O6 melting at 302" is formed. I n a similar manner ethyl- allyl- and benzyl-groups may be added. N. H. M. Thio-derivatives of Ketones. By E. BAUMANN and E. FROMX ( B e r . 22 2.592-2599 ; compare Abstr. 1889 852).-Thioacetone CSMe is formed as a readily volatile oil in the preparation of tri- thioacetone and tetrathioacetone (Zoc. cit.) but was not isolated owing to it's instability and the difficulty of separating it from trithioacetone.It is also produced together with ethyl sulpliide and other sulphur- derivatives when acetone-ethylmercaptole CMe,(SEt) is heated above 160". Owing to the very unpleasant odour of the compound which is stronger tIhan that of any other known substance the smallest traces of it being sufficient to infect whole districts the study of the compound was not continued. Trithioacetone is decomposed by strong nitric acid with explosive violence. A further examination of the sulphone obtained by oxidising tri- thioacetone with potassium permanganate (loo. cit.) showed that this could be separated by crystallisation from alcohol inho two substances. The more sparingly soluble compound triacetnnetrisulphone C9H,,S306 crystallises from glacial acetic acid in slender needles which melt at.302" (uncorr.) and sublime readily. The more readily soluble com- pound CsHl8SsO4 is probably tritlzioacetonedisu~lio~e ; it melts at 208". Acetonetrisulphone is not changed by acids and alkalis; it dis- solves in strong acids and is precipitated by water unchanged. Boiling fuming nitric acid has no action on it. Its constitution is probably CMe2<S02,.CMe:>S02. The compound CgHl,S304 dissolves in bromine pielding an unstable bromine-derivative which readily decomposes with evolution of hy- drogen bromide. When gently heated with fuming nitric acid the compound is oxidised with formation of much sulphuric acid. Probably the substance has the constitution S<C&e:,so:>CMe2.SO *CMe CMe -SO N. H. M. The Introduction of Acid Radicles into Ketone Molecules. By L. CLAISEN (BUZZ. Xoc. Chin&. [S] 1 496-510 ; compare Abstr.,ORGANIC CHEMISTRY. 27 1888 666 671 676 and 1889 5S4 619 850).-B re'sume' of the author's already published work on this subject concluding with a discussion as to the theory of the reactions. Substituted Acrylic and Propiolic Acids. By C. F. MARERY and A. W. S w r H (Ber. 22 2659-2660) .-When a,!%dichloracrylic acid is dissolved in carbon bisulphidc and chlorine passed through the solution whilst it is exposed to sunlight tetrachloroproyiolzic acid C,HCl,-COOH gradually crystallisea out. It forms large rhombic prisms is soluble in carbon bisulphide chloroform and water and melts a t 76". Its barium salt crystallises in prisms ; its ca1ciu.m salt in needles; its potassium salt in plates.Its silver salt is very un- stable When ap-dichloracrylic acid is heated with hydrobromic acid in closed tubes a t 110-120" bromodichloI.opro~ionic acid is formed. It is soluble in water and boiling carbon bisulpliide ci-ystallises in prisms and melts at 75-76'. When an aqueous solution of bromopropiolic acid is mixed with hypochlorous acid and left. in the dark chlorobro.ulzhydroxyacrzJlic acid C,(OH)ClBr.COOH is formed. It is easily soluble in boiling wa.ter is crystalline and melts a t 104-105". I t s silaer salt is soluble in nitric acid and is very unstable in aqueous solution. T. G. N. L. T. T. Action of Phosphorus Pentachloride on Chloralide.Tetra- chlorethylidene Trichlorolactate. By R. ANSCH~TZ and A. R. HASLAM (Annalen 253 121-131).-The compound of the composi- tion C,HC1,O3 which the authors obtained by the action of phos- phorus pentachloride on chloralide (Abstr. 1887 9151 proves to be the tetrachlorethylidene trichlorolactate. It boils a t 276" without decomposition. Nethyl and ethyl alcohol act on this compound at the ordinary temperature yielding hydrogen chloride and the ethyl or methyl salts of trichloracetic and trichlorolactic acids. Normal propyl and isobutyl alcohols act less energetically than ethyl alcohol. Normalpropyl trichlorolactcrte boils at 115-11 7" under 12 mm. pressure and at 248-250" under the ordinary atmospheric pressure. Its sp. gr. a t 20° compared with water a t 4" is 1.51628.Isobutyl tri- chZorolactate boils at 111-i12" under 12 mm. pressnre and at 236-238" under the normal atmospheric pressure. I t s sp. gr. at 20" is 1.53216. The chloride is slowly decomposed by water yielding trichloracetic and trichlorolactic acids. These results indicate that the constitution of the chloride is represented by the formula CC;l,*y (OH) coo- >CC1.CCl,. " w. c. w. Derivatives of Ethyl Acetoacetate. By R. SCH~~NBRODT (AwnaZea 253 168-205).-Ethyl monochlor~~cetoacetate is formed by passing chlorine into ethyl cupracetoacetate suspended in chloro- form until the green colour of the compound changes to grey. By t h e prolonged action of chlorine a dichloro-substit'ution-product is obtained. Analogous resalts are produced when bromine is used instead of chlorine ; the sthylic salts of mono- and di-bromacetoacetic28 ABSTRACTS OF CHEMICAL PAPERS. acid have been described by Duisberg (Annalen 213 152 and 143).E t h y l iodacetoacetate prepared by the action of iodine on ethyl cupr- acetoacetate is a yellow oil miscible with ether and alcohol. The alcoholic solution gives a blood-red coloration with ferric chloride. The compound is unstable. I t decomposes at 25" in a vacuum and its sp. gr. at 1P" is 1.7053 compared with water at the same temperature. It is converted into ethyl monochloracetoacetate by the action of silver chloride but with silver cyanide it yields hydrogen cyanide and ethyl succinosuccinate. The product of the action of silver nitrite on ethyl iodacetoacetnte is a yellvw oil probably ethyl nitroacetoacetate.This substance gives an intense blood-red coloration with ferric chloride and strong snlphuric acid. It does noC yield an amido-com- pound on reduction with tin and hydrochloric acid nor does it form a solid compou'nd with hydroxylamine. It combines with phenylhydr- azine yieldingphenylmethylisonitrosopyrnzolone [ 1 3 4 51 described by Knorr (AWr. 1887,602). The same compound is formed by the action of phenylhydrazine on the ethylic salt of monochlor- brom- or iod-acetate. The reaction may be represented as follows CsFi,C103 Bender (Abstr. 1888 53) has shown that in the ethereal solution phenylhydrazine and ethyl monochloracetoacetate yield the ethylic salt of p-phenyl azocrotonate. The author confirms the accuracy of this observation.Ethyl sodacetoacetate reacts with ethyl iodacetoacetate yielding ethyl diwetosuccinate. Metallic silver eliminates the iodine from ethyl iodacetoacetate and forms the ethyl diacetofumarate described by Just (Abstr. 1886 141). Ethyl thiacetoacetate first prepared by Buchka (Abshr. 188.5 1200) is formed by boiling sulphur in a solu- tion of ethyl cupracetoacetate in benzene. I n the presence of alcohol phosphorus acts on ethyl cupracetoacetate forming ethyl acetoacetate and triethyl phosphite. Arsenic trichloride is reduced by the copper compound arsenic being liberated and ethyl mnochlorncetoacetate formed. Ethyl cupracetoacetate is not attacked by cyanogen. but nitro- gen peroxide acts on it with formation of the nitro-compound which is produced by the action of silvei.nitrite on ethyl iodoacetoacetate. Attempts to displace a hydrogematom by copper in ethyl mrth- ace toacetate were unsuccessful. w. c. w. + SNHPh*NHZ = CloHgN302 + 2NHzPh + NHdC1 + C,H,*OH. Ethyl Thiacetoacetate. By I(. BUCHKA and C. SPRAGUE (Bey. 22 2.541-2556 ; compare Ruchka Abstr. 1885 1200 ; Delisle Abstr. 1887 915 ; and Schonbrodt preceding abstract) .-Ethyl thi- acetoacetate is best prepared by Delisle's method; 100 grams of ethyl acetoacetate yield 60-70 grams of pure ethyl thiacetoacetate. Molecular weight determiiiations by Raoult's method in glacial acetic acid solution showd that the molecular formnla was C,,H,,O,S. It melts at about 76" b u t the melting point observed depends to a considerable extent on tlie rapidity of heating and on other conditions.The sodium-derivative C,,H,,O,SN& is formed when ethyl thiaceto- acet,ate is treated with sodium in ethereal solution. When ethyl thiacetoacetate is treated with phenylhydrazine hydrogen sulphide is evolved and phenylmethylpyrazolonsketv-ORGANIC CHEMISTRY. 29 phenyl hydrazon e ( pheny lme thyl p yrazolonenzobenzei~e) melting at 156O identical with the compound obtained by K n o x (Abstr. 1887 601) is formed together with a yellow substance which is insoluble in all ordinary neutral solvents. The compound obtained by Schon- brodt (Zoc. cit.) by treating ethyl chloro- bronio- or iodo-acetoacetate with phenylhydrazine is not phenylrnethylisonitrosopyrazolone as stated by him but is identical with the phenylmethylpyrazolone- ketophenylhydrazone referred to above.The yellow compound which is obtained together with phenyl- methg1pyrazoloncketophenylhydrazone (see above) when ethyl thi- acetoacetate is treated with phenylhydrazine is decomposed when heated but without melting ; it dissolves in alkalis and is reprecipi- tated on adding acids. It seems to have the composition C,,H,N,Sc) ; when heated with phenplhydraeine it is converted into phenyl- methyl pyrazoloneketophenyl hydrazone with evolution of hydrogen sulphide small quantities of di-phenylmethylpyrazolone being also formed. Para f olylmethy Ipyrazoloneketoparatolylhydrazone is formed w'hen et'hyl thiacetoacetate is Created wiGth qaratalylhydr- azine ; it crystallises from chlorofrom in orange needles melting a t 216-217". When excess of the hydrazine is employed in the above reaction a compound free from sul i)hur and probably corresponding with di-phenylmethylpyrazolone is also obtained. If only a small quan- tity of the hydrazine is used a sulphur compound which is only soluble in alkalis is formed ; .this substance is converted into tolyl- methylpyrazoloneketotolylhydraaone (im.p. 216-21 7") when heated with paratolylhydrazine and when heated with phenylhydmzine it yields a compound. probably tol.ylmethy1pyrazoloneketophenylhydr- azone which crystnllises i n rcd needles melting a t 1.86". E thyl %hiacetoacetate combines with a-naphthylhydrazine yielding similar compounds. I?. S. K. Dithioxamide (Cyanogen DimLphydrate). By J. FORM~NEK (Ber. 22 2655-26569. When a saturated solution of cupric sul- phate is treatod with ammonia untiltthe precipitate first formed is just redissolved potassium cyanide added in quantity just sufficient to discharge the blue colonr and then a rapid stream of hydrogen chloride passed through the solu+ion the latter becomes first yellow and then red; and if it is kept well cooled small red crystals of the formula NH,-CS*CS*NH gradually separate out.L. T. T. Hydroxycitraconic Acid and its Derivatives. By P. MELIKOFF and M. FELDMANN (Annalen 253,87-95 j.-In dilute solutions hypo- uhlorous acid unites with cibraconic acid to form chlorocitramalic acid which has been described by Morawski (this Journ. 1875 142) and by Gottlieb (Annalen 160,101 j. The acid prepared by Gottlieb's process melts a t 139". It is converted into Morawski's hydroxycitra- conic acid by the addition of potessium hydroxide in alcoholic solution.30 ABSTRACTS OF CHEMTCAL PAPERS.The precipitate of pot,assium chloride and hydroxycitrctconate i s washed with alcohol and ether. It is khen dissolved i n water the hydroxy-acid liberated by sulphuric acid and extracted with ether. The acid melts a t 162" as stated by Scherks (Abstr. 1885,513). The ethyl salt C,EI,O(COOEt) has the sp. gr. of 1.1376 at 0" and 1.1167 at 22" compared with water at the same temperatures. Hydroxycitraconic acid dissolves in strong hydrochloric acid a t 0" ; and ether extracts from this solution a monochlorinated hydroxy-acid CUOH*CH( OH)*CClMe*COOH crystallising in rhombic plates which is an isomeride of the acid formed by the union of hypochlorons acid and citraconic acid COOH.CMe(OH)*CHCl*COOH.This acid melts a t 162" and forms unstable salts. The compound which is formed by the addition of hydrobromic acid to hydroxycitraconic acid has already been described by Scherks (Zoc. cit.). Hydroxycit,raconic acid is a glycidic acid as it is converted into amidocitramalic acid by the action of alcoholic ammonia at 100". The amido-acid forms short prisms which seem to belong to the monoclinic system; it reddens litmus and decomposes carbonates. 100 C.C. of water at 18" dissolve 31 grams of the acid. It is almost insoluble in hot alcohol. The calcium and barium salts are amorphous. The hjdrochloride OH.CsH,( NH,) (COOH),,HCI forms transparent prisms soluble in water and alcohol. It melts a t 100" with decomposition.w. c . w. Acetonediacetic or Hydrochelidonic Acid. By J. VOLHARD (AnnuZen 253,206-236) .-The dilsctone of discetic acid is prepared by maintaining succinic acid in a state of slow ebullition for six hours. When a small quantity of the contents of the retort no longer solidifies on cooling but remains as a greasy mass the operation is complete. The crude product is repeatedly extracted with boiling chloroform ; on cooling succinic anhydride is deposited in crystals and the lactone remains in solution. The chloroform is removed by distillation the residue dissolved in water and the lactone is ngaiii extracted from this aqueous solution by chloroforni. The lactone forms transp3rent rhombic prisms u b c = 0.3649 1 0.9816 freely soluble in chloroform acetone ether alcohol benzene and ethyl acetate.It melts a t 75" and boils between 200 and 205"under 15 mm. pressure. The lactone dissolves in alkalis and in strong hydrochloric or hydrobromic acid yielding acetonediacetic acid CO( CH,*CH,*COOH) which is identical with the hgdrochelidoiiic acid of Liebenand Haitinger ( Monatsh. 5 353) and with Marckmald's propiondicarboxylic acid (Abstr. 1888 678) The acid forms rhombic plates soluble in hot water and in alcohol. It melts a t 143O and decomposes at a higher temperature. The normal salts of the alkali metals are very soluble in water and do not cr-j-st:~llise well. The acid potassium sodium and ammonium salts are anhydrous. The barium salt crjstallises with 2 and with 2; mols. H,O. The manganese salt C,H,MnO + fLH,O forms pale pink needles.The zinc and cadmium salts crjstallise in six-sided plates containing 2 mols. H20. The silver salt C7H8Ag?03 is crjstalline and insoluble inORUANIC CHEMXSTRY. 31 water. The dimethyl salt melts at 56' and boils with decomposition at 276-277" (uncorr.). The sp. gr. of the diethyl salt is 1.0862 at 13". Acetic chloride acetic anhydride and phosphoric anhydride convert the acid into the lactone. The phenylhgdrazide of acetonediacetic acid melts at 107 -108". The phenylhydrazide of the dimethyl salt melts a t 88-90' and dissolves in ether benzene and hot alcohol. The corresponding diethyl compound melts at 67". The oximeof the acid crystallises in prisms and melts with decomposition at 129". The oximes of the dimethyl and diethyl salts form needles and melt at 52" and 38' respectively. w.c. w. Alkyl-derivatives of Methyluracil and Nitrourscil. BJ- R. BEHREKD (Annalen 253,65-68).-Ethyl bromide does not react w i t h free methyluracil but it acts on potassium methylurscil forming mono- methyluracil and dimethyluracil. I t is probable that monethylmethyl- uracil is first formed. A portion of the monethylmethyluracil reacts with potassium methyluracil formingpotassium monethylmethyluracil. This is attacked by ethyl bromide yielding diethylmethyluracil. In a previous communication the author stated that methyl iodide acts on potassium methyluracil yielding trimethyluracil and the dihydride of methyluracil ; he now finds that the supposed dihydride is identical with the dimethyluracil described by Hoffmann (next Abstract).w. c. w. Alkyl-derivatives of Methyluracil. By J. HOFFMANN (Annalen 253 68-77).-Ethyl methyluracil and diethylmethyluracil are formed by the action of ethyl bromide or iodide (3 mols.) on potassium methyluracil (1 mol.) in sealed tubes at 150; the excess of ethyl bromide or iodide is removed from the crude product by distillation the residue is dissolved in water and the aqueous solution treated with chloroform. The chloroform extract is then dried and distilled and the residue dissolved in boiling alcohol ; on cooling crystals of ethyl- methyluracil are deposited. The mother-liquor contains monethyl- arid diethyl-methyluracil. The former is deposited as a crystalline crust but the diethyl-derivative can only be isolated by dropping a crystal of diethylmethyluracil into the mother-liquor when crystallisation takes place.fithylmethyZuraci1 is deposited from ethyl bromide in prisms and from alcohol in needles. It is freely soluble in chloroform and in ethyl bromide and is much more soluble in hot than in cold alcohol. A crystalline silver salt C,H,E tAgN20z is obtained when silver nitrate is added in sufficient quantity to produce a permanent turbidity t o a solution of ethylmethyluracil in a 10 per cent. solution of potassium hydr0xid.e. Diethylnaetl/y Zz~racil crystallises in rhombic plates and melts at 52-53" dissolves freely in chloroform alcohol ether and water and is decomposed by potassium hydroxide at the ordinary temperature with liberation of ethylamine. Methjl bromide acts on potassium methyluracil at 140" forming dimethyluracil and tri- methyluracil. !Z'~*imethylz~raciZ melts at lo>" crystallises in rbombic plates and is freely soluble in chloroform alcohol and water arid sparingly soluble i n ether. Di~niethyluracii is insoluble in ether but can32 ABSTRACTS OF CHEMICAL PAPERS.be reerystallised from hot alcohol. Methyluracil di-iodide C,H,N,O,I is formed by the action of iodine dissolved in strong hydriodic acid on methyluracil. It is an unstable compound dissolvinq with decompo- sition in water alcohol and chloroform. The di-iodide furms deep Nitrouracil-derivatives. By M. LEHMANN (Annalen 253 77-87).-Meth~lZnifrozcracil C,H,N30 + H20 is formed by the action of methyl iodide on potassium nitrolnracil in sealed tubes a t 140". It crystallises in long needles and is soluble in hot water.100 C.C. of water a t 20" dissolve 0.714 gram and 100 C.C. of alcohol a t 17" dissolve 0.115 gram of the substance. It is less soluble in ether chlorofsm benzene and methyl iodide than in water. The potassium silver and barium salts are crystalline; the silver and barium salts me almost insoluble in cold water. Methylisobarbitiiric acid C5H6N203 is deposited in crystals when methplnitrouracil is rediiced by tin and hydrochloric acid ; the mother-liquor contains methylamidoucacil in small quantiky. A neu,tral solution of methyl- amidouracil hydrochloride turns red on the addition of potassium cyanate ; the d o u r is destroyed by hydrochioric acid and methylhy- droxyxanthine C6H8N403 is deposited a s a yellow crystalline powder.100 C.C. of water a t 16" dissolve .0*16 gram of rnethylhydroxyxan- thine. Methylnitrouracil i s decomposed by baryta-water a t 160-1 70" with liberation of methylamine ; dimethylnitrouracil under similar treatment yields dimethylamine. Dimethylnitrouracil melts at 154.5" and is deposited from hot water in needles eontairling 9 mol. H20. It does not unite with bases to form salts. The constitntion of methyl- and dimethyl-nitrouracil can be represented by the formulae C o < ~ ~ e - ~ ~ NH'cH >C*NO and C O < ~ ~ ~ ~ ~ > C . S O . Methyhitro- methyluracil prepared by the action of methyl iodide on potassium nitromethyluracil crystallises in needles and melts a t 149". It unites with bases forming c r p t a lline salts. E t h y7nit rouracil C,H,N304 + H,O forms silky needles and melts at 194.5 ; it is de- posited from alcohol in anhydrous crystals and is soluble in hot water ether chloroform benzene and ethyl bromide.The potassium and silver salts crystalhe in needles. Ethylisobarbituric acid C,H,N,O melts at 250" but begins to decompose at 230". It is soluble m hot but almost insoluble in cold violet crystals. w. c. w. water. Ethylhdroz yxanthine crystallises in prisms which turn pink on exposure to the air. Etl~lllrnethy Znitrouracil CO<N~e.CO>C.N02 NFtCH crystallises from hot water in needles containing 1 mol. H,O. The crystals effloresce ; it melts at 109". itl;.thyleth~lnit,.ouracil CO<NEt.Co >C*SO melts at 73" and crystallises in rhonibohedra containing 1 mol. H20.The substance becomes anhydrous a t go' and remains liquid a t the ordinary temperature but solidifies on the addition of water. NMe-CH I t is freely soluble in alcohol and ether. w. c. w.ORGANIC CHEMISTRY. 33 FUCUSO~. By MAQUENNE (Compt. rend. 109 571-573).-Dried Fucus vesiculosus was heated in an oil-bath at 160" with 4.5 parts of sulphuric acid of 20" B and the product after neutralisntion was distilled and fractionated. Small quantities of water and acetone were obtained together with two fractions boiling a t 162-163" and 185-187" respectively. The fraction 162-163" consists of pure fur- furaldehyde the fraction 185 - 187" is methyIfurf.~raldehyde a liquid of sp. gr. 1.105 at 15". With ammonia it yields a crystalline product closely resembling furfuramide ; its hydrazone is an oily liquid ; with silver oxide i t yields methylpyromucic acid melting at 108-109". When treated with hydriodic acid it resinifies but does not carbonise and does not become green ; the product yields iodo- form when mixed with potassium hydroxide.With acetic anhydride in presence of fused sodium acetate it yields methylfurfuracrylic acid melting a t 157" and crystallising from boiling water or alcohol in small white needles which retain aboilt Q mol. H20. If methylfur- furaldehyde is heated with strong hydrochloric acid it becomes green a reaction which Stenhouse observed with fucusol. The following reaction serves to detect methylfurfuraldehyde in presence of a large proportion of furfuraldehyde. One drop of the liquid is dissolved i n 5-6 C.C.of alcohol of 90" and 1 C.C. of sulphuric acid of 60" is added slowly without agitation; a green coloration appears at the junction of the two liquids. The coloration persists even after agitation if the methylfurfuraldehyde is abundant but changes to grey if furfur- aldehyde is in excess. The reaction is similai- to that given by heptine (or its oxidation-products) from perseitol. This methylfurfuraldehyde is identical with that obtained by Hill from wood tar. Fucnsol is not a distinct compound as Stenhouse supposed but is a mixture of furfuraldehyde with about. 10 per cent. of methylfurfur- aldehyde. C. H. B. Relation between Sugars and Furfuran-derivatives. By MAQUENNE (Compt. rend. 109 603-606) .-Methylfnrfnraldehyde from Fucus (preceding Abstr.) yields acetic acid on oxidation and hence contains a terminal methyl-group and is one of the three isomerides which contain the methyl-group in the position 2 3 or 4 with respect to the aldehyde group. It has the same relation t80 isodul- citol or rliamnope C6HI2O6 m furfuraldehyde has to arabinose C5H,,05.Crystallised isodulcitol distilled with four times its weight of sul- phuric acid of 15 to 20" B yields a small quantity of acetone togetber with pure methylfurfuraldehyde identicltl with that from Fucus cesi- cutosus or wood tar but no furfuraldehyde is obtained. Fischer and Tafel have shown that isodulcitol is an aldehyde derived from normal bexane and according to Herzig it yields acetic acid on oxida- tion and hence contains a terminal methyl-group. Its conversion into methylfurfuraldehyde would involve the union of the chains 2 and 5 by means of an atom of oxygen the methyl-group occupying the Position 4.thus :- A VOL. LVIII. Li34 ABSTRACTS OF OHEMICAL PAPERS. Since furfuraldehyde is obtained from arabinose by dehydration it follows that isodulcitol is w-methylarabinose a relation which has often been suggested but has never previously been established The yield of methylfurfuraldehyde from isodulcitol is small but it suffices to detect the isodulcitol in substances in which its presence is not recognised by the usual methods and i t has been detected in several plants in which it was not known to exist. Since Fucus vesicu- losus yields methylf urfurddehyde (Zoc. cit.) it would seem that isodul- citol exists in marine plants.Selenium and Oxygen-derivatives in the Benzene Series. By C. CHABRII~ (Compt. rend. 109 568-570).-The action of nitric acid on phenyl eelenide (Abstr. 1889 1167) yields nitro-derivatives ; potassium permanganate or chromic acid yields indefinite oxidation- products ; hydrogen peroxide and hydrochloric acid yield compounds in which oxygen has been introduced into the phenyl-group. The action of selenious chloride SeOCI on benzene in presence of aluminium chloride yields two compounds according to the proportions of the reacting bodies. Diphenylselenone SeOPh is an amber-yellow liquid which boils at 230" under a pressure of 65 mm. ; sp. gr. a t 19.6 = 1.48. The other product PhSeO*C6HICl crystallises in white hexagonal prismatic lamellse with a fatty lustre ; it melts at 94" boils at 230" under a pressure of a few millimetres is insoluble in water but dissolves in alcohol and is attacked by cold nitric acid.Diphenylselenine when treated with bromine water yields the corn- pound SeO( C6H4Br).? which crystallises from alcohol in modified rhombic prisms melting a t 1'20". When mixed with hydrogen peroxide and hydrochloric acid and treated with a current of air diphenylselenine yields the compound SeO (c6HIc1)2 or Ph SeO*C6H,C12 which crystallises from boiling alcohol in small white prisms melts at 159" and is not attacked by cold nitric acid. The action of the compound Se(OH)&I2 on benzene in presence of aluminium chloride yields diphenylselenine and selenophenol. Action of Phosphorus Trichloride on Phenol.By R. ANSCH~TZ and W. 0. EMERY (Amer. C'hem. J. 11. 379-38i).-By the action of phosphorus trichloride on phenol the following three com- pounds were formed (compare Noack Abstr. 1883 735) and were separated by distillation under greatly diminished pressure :- Phenylphosphoryl dichloride PCl,-OPh ; sp. gr. 1.35412 at 20" (water at 4" = I) ; boiling a t 90' under 11 mm. pressure ; diphenyZphosphoryZ chloride PCl(OPh) ; sp. gr. 1,24378 a t 20" (water at 4" = 1) ; boil- ing at 172" under 11 mm. pressure ; tripheriyl p h o p h i t e P(OPh) ; sp. gr. 1.18428 at 20" (water at 4" = 1) ; boiling at 220" under 11 mm. pressure. The action of phosphorus pentachloride on the preceding com- pounds was investigated. In the cold no action takes place; at 100" crystalline compounds are formed soluble in chloroform and carbon tetrachloride.Chlorine additive-products were almost cer- tainty formed but they could not be isolated ; they were however C. H. B. C. H. B.ORGANIC CHEMISTRY. 35 obtained by passing dry chlorine over solutions of the phosphorous compounds in dry ether. Phenylphosphoryl tetrachloride PCl,*OPh prepared from chlorine and phenylphosphoryl dicbloride forms small plates soluble in chloroform and carbon tetrachloride insoluble in ether ; it is deliquescent and is decomposed by water normal phenyl pbosphate being formed. With sulphurous anhydride i t behaves like the corresponding phosphenyl compound giving thionyl chloride and the oxychloride POCl,-OPh boiling a t 121-122" under 11 mm. pressure. Diphenylphosphoryl trichloride PCl,(OPIi) formed from chlorine and diphenylphosphoryl chloride is a yellow oil solidifying to minute crystals soluble in chloroform insoluble in ether; it easily tlecomposes when heated and also when treated with water in which case phenyl phosphate is formed.Tt.~p~ie~zyll?li~~pla~j~yZ dichluride PC1,( OPh) prepared from chlorine and phenyl phosphite solidifirs a t a very low temperature ; when treated with water it decomposes into phenyl phosphate and hydrochloric acid. By the addition of dry bromine to etliereal solutions of the monn- and di-chlorides the compounds PC12Br2*OPh and PClBr,(OPh) were obtained ; these are very unstable substances. Phenylphosphrvl thiochloride PSC12*OPh was obtained by heating phenylphosphoryl dichloride with sulphur at 190" ; it has a sp.gr. of 1.40393 at 20" (water at 4" = I) boils at l19-i20° under 11 mm. pressure and is a highly refractive liquid soluble in ether and chloro- form. DipTien!il~jhosplioryl thiochzoride PSC1( OPh) prepared from diphenylphosphoryl chloride and sulphur heated aat 190" ; melts a t 63-64" and boils at 194" under 11 mm. pressure. Attempts to obtain the preceding two compounds by heating togeiher phenol and phosphorus thiochloride were unsuccessful hydrogen chloride and normal phenyl phosphate being formed. Tr+hen yl thiophosphate PS( OPh) was obtained by heating phenyl phosphite with sulphur at 190" ; it forms crystalline needles melting at 49-50" and boiling at 245" under 11 mmpressure; sp. gr. = 1.24411 at 20" (water at 4" = I). It is found that these thio-compounds have very nearly the same melting points and boiling points as the correspondiiig oxy-com- pounds.The existence of the compound PC14*OPh leads to the following view of the action of phosphorus pentachloride on hydroxj-com- pounds :- R-OH + PC1 = HC1 + RO*PC14 and RO-YCI = POCl + RC1. C. B. B. Apiole. By G. CIAMICIAN and P. SILBER (Bey. 22 2482-2490; compare Abstr. 1888 Ilc;O).-The authors give the name apionole to the tetrahydroxybenzene which forms the basis of apiole ; the dimethyl ether of tetrahydroxybenzene is therefore dimethylapionole and '' apiorie " is dimethylmetbyleneapionole Dimethylapionole C6Hz(0H),(OMe)2 is obtained when apiolic acid (2.5 grams) is heated at 180" for 4 to 6 hours with potash (8 gramP) and alcohol (10 c.c.).l u aqueous solutions ferrous sulphate produces after some time a blue coloration lead acetate a gelatinous precipitate ai:d silver nitid e a It melts a t 105-106" and boils at 298". d 236 ABSTRACTS OF CHEMICAL PAPERS. crystalline precipitate which immediately turns black. It dissolves in concen hated sulphuric acid yielding a yellow solution which quickly turns red and on warming becomes violet. The diacetyl- derivative C6H2(OMe),( crystallises from alcohol melts a t 144' and is soluble in ether warm alcohol and glacial acetic acid but only sparingly in hot and insoluble in cold water. It dissolves in warm concentrated sulphuric acid yielding a colourless solution which turns yellow and then brown on heating more strongly. Tetramethy lapioriole C6H2 ( OMe)4 prepared by treating the di- methyl-derivative with methyl iodide in methyl alcoholic potash solution crystallises from hot water in colourless needles melts at 81" and is readily soluble in alcohol ether benzene acetone and acetic acid but only sparingly in water. It dissolves in concentrated sul- phuric acid yielding a colourless solution which turns brownish-red on warming and in concentrated nitric acid with a yellow coloration.It is not acted on by hydrochloric acid a t loo" but at higher tem- peratures it is decomposed with evolution of methyl chloride. Apioneacry Eic acid CH2:O2:C6H( OMe) ,*CH C H *C 0 0 H prepared by boiling apiolaldehyde with acetic anhydride and sodium acetate crystal- lisea from hot alcohol in small jellow needles melts at 196" and is readily soluble in hot glacial acetic acid benzene and alcohol but only sparingly in ether and hot water and almost insoluble in cold water.It dissolves i n concentrated sulphuric acid with a yellow coloration the solution turning brown on warming. The sodium salt crystallises in microscopic needles and is readily soluble in water; in an aqueous solution of the sodium salt lead acetate barium chloride calcium chloride or zinc sulphate produces a colourless nickel nitrate or copper sulphate a green cobalt nitrate a red silver nitrate a light yellow and ferric chloride a reddish-brown precipitate. Apionecrotonic acid C Hz 0, CGH (OMe),*C H C Me-C 0 OH prepared from apiolaldehy de in like manner crystallises from alcohol in light yellow needles melts at 209" and is almost insoluble in water but soluble in ether hot alcohol and hot acetic acid.It dissolves in cnn- centrated sulphuric acid with a yellow coloration the solution turning bluish-green on warming. The sodium salt is readily soluble in water. The calcizim salt (C13H,306)2Ca + 5H20 crystallises from hot water in broad colourless needles and loses iCs water a t 100". The silver salt C13H13@6Ag is colourless and very sparingly soluble in water. In aqueous solutions of the sodium saIt barium chloFide magnesium sulphate or zinc sulphate produces a white. crystalline precipitate arid solutions of copper nickel cobalt and ferric salt8 also give a precipitation. When the calcium salt is distilled with lime a small quantity of a crystalline compound melting a t 83" is obtained.When calcium apiolate is distilled with lime it yields a mixture of substances some of which are volatile with steam ; the non-volatile residue crystallises from alcohol in needles melts a t 71-72' and seems to hare the composition C,H,O,. The nitro-compound (m. p. 117-118*) previously described (loc. cit.) and obtained by treating apiolic acid with nitric acid of sp. gr. 1.4 in glacial acetic acid solution has the composition C,H,N,O not C9H8N20 as previously given arid is probably dinitrapione.ORGANIC CHEIIJSTRY. 37 The nitro-compound (m. p. 116O) prepared from isapiole by Ginsberg (Abstr. 18F8 722) is probably identical with dinit'rapione and the compound (m. p. 137-138") obtained by the authors from apiolaldehyde is probably st nitro-derivative of apiolaldehyde.Chlorination and Bromination of Aniline Orthotoluidine and Paratoluidine in presence of Excess of a Mineral Acid. By R. HAFNER (Ber. 22 2524+-2541).-When chlorine is passed into an ice-cold solution of aniline in excess of 97 per cent. sul- phuric acid for about 18 hours almost the whole of the aniline remains unchanged only small quantities of parachloraniline being formed. Under the same conditions but employing 65 per cent. sul- phuric acid symmetrical trichloraniline (rn. p. 77") traces of a com- pound melting a t 63-64" probably trichlorophenol (m. p. 67-68') and considerable quantities of resinous products are formed but a large quantity of aniline remains unchanged. Chlorine acts energetic- ally on aniline in 40 per cent. ice-cold sulphuric acid solution ; the principal product is trichloraniline but trichlorophenol resinous products and traces of other compounds probably chloraniline and dichloraniline are also formed.When chlorine is passed into an ice-cold solution of aniline in excess of very concentrated (40 per cent.) hydrochloric acid for about 18 hours most of the base is converted into parachloraniline and tri- chloraniline but considerable quantities remain unchanged. Tri- chloraniline is also formed when chlorine (6 mol.) is passed into a solution of aniline (1 mol.) in ice-cold concentrated hydrochloric acid. In 30 per cent. ice-cold hydrochloric acid solution chlorine acts on aniline much more readily ; parachloraniline dichloraniline symmetrical trichloraniline and other compounds probably chloro- derivatives of phenol are formed and none of the base remains Unchanged.I n 20 per cent. hydrochloric acid solution under the same conditions trichloraniline chlorophenols and large quantities of resinous products 'itre formed. Bromine even when added in large excess has no appreciarble action on aniline in 97 per cent. sulphuric acid solution ; after four months' time only small quantities of symmetrical tribromaniline are formed. If a small quantity of iodine is mixed with the bromine the formation of tribromaniline takes place rather more readily. Tn 65 per cent. and i n 40 per cent. ice-cold snlphuric acid solution aniline is acted on by excess of bromine considerable quantities of tri- bromaniline being formed ; in the latter case small quantities of a compound probably tribromophenol are also formed.When aniline is treated with excess of bromine in 40 per cent. hydrochloric acid solution a reaction immediately takes place and the whole of the base is converted into tribromaniline ; in 20 per cent. hydrochloric acid solution small quantities of tri bromophenol are also formed. Aniline hydrobromide is completely converted into tribromaniline when treated with excess of bromine in a concentrated ice-cold soh- tion of potassium bromide ; the yield of the pure product is 90 per cent. of the theoretical quantity. Wheu chlorine is passed into an ice-cold 97 per cent. sulphuric acid F. S . I(.38 ABSTRACTS OF CHEMICAL PAPERS. solution of paratoluidine for about 24 hours metacliloroparatoluirline [Xe C1 NH = 1 3 41 and larger quantities of orthochloropara- toluidine [Me C1 NH = 1 2 41 are obtained but a consider- able quantity of the base remains unchanged. In 40 per cent.hydro- chloric acid solution the whole of the paratoluidine enters into reaction yielding metachloroparatoluidine metadichloroparatolnidine [Me Cl NH = 1 3 5 41 a crystalline compound probably orthochloroparatoluidine and oily products probably chlorinated de- rivatives of cyesol. When pal-atoluicfine is treated with excess of bromine in 39 per cent. ice-cold hydrochloric acid solution it is almost. completely con- verted in to met adibromoparaholui din e me 1 t ing a t 73 - 74" very small qiinntities of a bromocresol being also produced. I n 65 per cent. sulphuric acid solution under the same conditions large quantit,ies of metadibromoparatoluidine are formed.When orthotoluidine is treated with excess of chlorine in 913 per cent. ice-cold sulphuric acid solution it is partially converted into a chlorotoluidine ; bromine under the same conditions has no appre- ciable action even after eight days' time. Action of Nascent Nitrous Acid on varims Amines and Phenols. By A. DENINGER (J.pr. Chem. [el 407296-308).-When sodium nitrite ( 3 mols.) acts on an aqueous acid solution of aniline ortho- and para-nitrophenol and some resinous su bstarices are pro- duced in quantities dependent on the concentration acidity and temperature. The qaantity of orthonitrophenol produced is greater the more rapid the reaction and the higher the temperature above 65" ; i t varies from 0 to 50 grams whilst that of paranitrophenol varies from 0 to 33 grams per 100 grams of aniline.Air blown through the liquid diminishes the quantity of phenols produced as also does the presence of oxidising or reducing substances. The nature of the acid has no apparent effect. To obtain the best yield 10 grams of aniline 20 C.C. of sulphuric acid and 80 C.C. of water are mixed and cooled to 15" ; 300 grams of sodium nitrite in 100 C.C. of water are then added the solution heated in w water-bath and a large quantity of hot dilute sulphuric acid (1 1) immediately added. Alter the reaction the ortho-compound is distilled over with steam and thc para-compound crystallised from the residue. Nitric oxide alone appears to be evolved during the reaction.If orthotoluidine (10 grams) be substitued for aniline in the above process orthonitrocresol [Me OH NO = 1 2 31 (5to6 grams) melting a t 68-69' is obtained. By using a more dilute solution and allowing it t o stand for 14 days at 15-2b" paranitrocresol [Me OH NO = 1 '2 51 melting a t 96' is obtained. With paratoluidine (100 grams) only one nitrocrcsol (138 grams) melting a t 33-34" is obtainable. By acting on diamidoparadiphenyl and diamidoparadit)olyl respec- tively with sodium nitrite (6 mols.) in the way described above dinitrodiphenol (m. p. 260") and dinitrodicresol (m. p. 270') are pro- duced respectively. The subhate of diamidodicresol (dbstr. 1588 838) obtained by F. S. K.ORQANIC CHEMISTRY. 39 reducing the dinitrocresol is sparingly soluble in water ; by diazo- tising it and decomposing with hot sulphuric acid tetrahydroxyditolyl is obtained as a pleasant-smelling oil which is volatile with steam ; its aqueous solution gives a y ellowish-white precipitate with ferric chloride.With naph thylamine the above treatment yields dinitronaphthol and a little nitronaphthol ; when a-naphthylamine is treated with 2 mols. more sodium nitrite than is necessary for diazotising and distilled at once with steam P-nitro-+naphthol (m.p. 128") is ob- tained ; but i€ allowed to stand for 14 days at 10-15" a-nitro-a- naphthol is formed. /3-naphthylamine yields a-nitro-@-naphthol (m. p. 103"). Sulphanilic and orthotoluidinesulphonic acids yield by this treat- ment garnet-red crystals which lose the sulphonic acid group when treated with super-heated steam and yield nitrophenol and nitro- cresol respectively.Naphthionic acid yields nitronaphtholsulphonic acid. Salicylic acid and its ethereal salts yield nitrosalicylic acid and its ethereal salts. A new substance is obtained when paraphenolsulphonic acid is treated with sodium nitrite and sulphuric acid ; it is still under in- vestigation. A. Q. R. Some Nitrated Diazoamido-compounds. Ry S. NIEMEN- TOWSKI (Ber. 22 2562-2567).-When metanitraniline is diazotised in the manner described by Sandmeyer for paranitraniline (Abstr. 1885 981) a resinous precipitate is formed the moment the sodium nitrite solution is added This can be afterwards separated from the metanitrobenzonitrile by steam distillation. It crystallises from amyl alcohol in lustrous golden needles which melt a t 191-1'32" with decomposition.It has the formula C,,H,N504 and is identical with Griess' metadiazoamidonitrobenzene (m. p. 195.5 AnnaZen 121 2i2) and with Hallmann's dinitroamidoazobenzene (m. p. 175-176" Ber. 9 389). I n order to determine the constitution of the compound a qustntit'y of it was prepared by Hallmann's method ; the substance prepared by this method when crystallised from amyl alcohol also gave the m. p. 195". When the compound is heated with hydrochloric acid (sp. gr. = 1.17) for 10 hours at 185' meta- chloronitrohenzene is formed. Amy1 alcohol decomposes it at 185" with formation of metanitraniline and nitrobenzene. These reactions and the behaviour of the substance towards aromatic amines and phenols with which it yields dyes show that the compound is diazo- amidonitrobenzene.Hallmnnn's method (Zoc. cit.) is a very con- venient one for the preparation of nitrated diazoamido-corn- ponnds. DiuzoamidonitrotoZuene CI4H,,N,O4 (from metanitroparatoluidine) is prepared by treating metanitroparatoluidine (m. p. 114" 30.4 grams) suspended in alcohol (250 grams) with nitric acid (sp. gr. 1.52 7.5 grams) and with a saturated solution of potassium nitrite (8.5 grams). It crystallises from am371 alcohol in dark reddish-brown branched needles melts ah 169 dissolves very sparingly in alcohol,40 ABSTRACTS OF CHEJIICAL PAPERS. more readily in ether and carbon bisulphide and very easily in cold benzene acetone aiid chlorofwm. When heated with alcohol a t 1 70° it is decomposed into metanitroparatoluidine and metanitro- toluene.Diazoanzido?zitroto?zcene (from paranitro-orthotoluidine m. p. 107") crystallises from alcohol in long bright pellow needles melts at 212" with decomposition and is readily soluble in acetone benzene and chloroform. N. H. 31. Trinitrohydrazobenzene. By E. FISCHER (Annulen 253.1-5). -The author's process for preparing trinitrohydrazobenzene from picryl chloride and phenylhydrazine has been criticised by Willgerodt and Ferko (Abstr. 1888 830). In reply the author maintains that the process yields good results if the necessary conditions are observed. Symmetrical Nitrophenylhydrazines of the Aromatic Series. By C. W ILLGEEOUT ( J . pr. Cliem. [2] 40 264-270).-SSymmetrical picrylhydrazines are obtained by cohabating picryl chloride and the hydrochloride of the aromatic hydrazine (in molecular proportion) in alcohol a t the ordinary temperature. Picrylphenylhydrazine picr!j 1 ort hotoly 1 hydruzin e y icry lparatoly hydrazine and picryl -a-naph- thyEhydrazine have been thus obtained.All these decompose before they melt a t temperatures dependent on their state of division ; tbus picrylphenylhjdrazine in powder decomposes a t 177" whereas its crystals decompose at 181" (compare Abstr. 1888 829). T1.e author has studied the action of heat on the nitrophenyl- hydrazines in presence of various liquids and finds that the decom- positions which occur may be classified as follows :-(l.)- The liquid does not decompose the nitrohydrazineperse; in this case the hydrazine hydrogen reduces the nitro-group to 8 nitroso-group ; such liquids are water dilute hydrocliloric acid benzene and glacial acetic acid.(8.) The liquid is an oxidising agent ; the nitrobydrazine is oxidised to a nitroazo-compound. (3.) The liquid decomposes the nitro- hydrazine altogether. (4.) The liquid acts as a reducing agent such liquids being ethyl and methyl alcohols formic acid and acetone ; the first two and acetone convert picrylhydrazine into dinitrosonitroazo- benzene melting a t 219-220" ; formic acid converts it into a mixture of two substances melting a t 225" and 233". (5.) The liquid is an organic base ; in this case the nitrohydrazine is first converted into nit ro-nitroso-azo-compounds and these into polyazo-con1 pounds. The paper conclnde,s with a reply to Freund (Abstr.1889,977) whc criticises the author's and Ferko's former work (Abstr. 1888 829). A. G. B. w. c. w. Phenylhydrazone. By E. FISCHER and F. ACH (Annnlen 253 5 7-65) .-Acetor?Rdi?Litroplienylhydrazone CBHIONIOI is prepared by slowly adding acetonephenjlhydraeone (12 grams) to strong colour- less nitric acid (25 grams) Rurrounded by a freezing mixture ; this solution is allowed to drop into 100 grams of well-cooled f u z i n g nitric acid and the mixture is poured into ice water ; the product isORQANIC CHEMISTRY. 41 extracted with small quantities of ether and the residue purified by recrystallisation from alcohol. It melts a t 127" (uncorr.) is soluble in benzene chloroform ether and in hot alcohol and is quickly decomposed by hot alkaline solutions b u t less readily by acids.Phenylhydrazonelevulinic anhydride is converted into the paranitro- derivative N02*C6H4*N<,~,CH2>CH2. by fuming nitric acid. This snbstance crystallises in flat needles of a yellow colour is soluble in hot alcohol benzene and glacial acetic acid and melts a t 118-119". The alcoholic solution is converted into paraphenylenediamine by reduction with zinc-dust and acetic acid. Warm alcoholic potas- sium hydroxide or warm concentrated hydrochloric acid converts the anhydride into paranitrophenylhydrazonelevulinic acid NO2.C6H4.NH.N :C Me*C2H4*C 0 0 H. This acid forms orange-coloured needles soluble in acetone and hof alcohol; i t also dissolves in alkalis forming intense deep-red solutions. It darkens a t 190' and melts with decomposition a t 200".The ethyl salt melts at 156-157" with slight decomposition. It crystitllises in needles and dissolves freely in hot alcohol benzene and glacial acetic acid. The hydrazones of acetone and of acetaldehyde propaldehyde and oenanthaldehjde are decomposed by gently warming with pyruvic acid ; acetone or aldehyde is liberated and phenylhy drazonepyruvic acid is produced. The ketones and y-ketonic acids behave in the same way. Paranitropli,enyl?zydrmon ep yruvic acid N0,*C6H4*NH*N:CMe-C 0 OH is precipitated when pyruvic acid is added to a hot dilute solution of nitrophenylhydrazonelevulinic acid in hydrochloric acid. The acid is soluble in acetone and in warm alcohol and is decomposed by heat. N ' CMe w. c. w. Amidoximes and Azoximes.By F. TIEMANN (Ber. 22 2391- 2395 ; compare Abst. 1886 875).-The conversion of nitriles into amidoximes by the action of hydroxylamine may be considered to be a general reaction a s hitherto it has been found to apply to all cases except that of nitriles such as pentamethylbenzonitrile which cannot be or are only with difficulty converted into the' corresponding acid by the usual reagents. As a rule the formation of the amid- oxime takes place much more slowly with nitriles of high molecular weight and rich in carbon and the acid character of the product is less marked. The amidoximes combine readily with hydrogen cyanate phenyl- carbimide and phenylthiocarbimide yielding uramidoximes phenyl- uramidoximes and phenylthinramidoximes. The ethyl-derivatives of the amidoximes also combine with phenylthiocarbimide aud with phenylcarbimide.F. S. K. Phenylallenylamidoxime-derivatives. By H. WOLFF (Rer. 22 2395-240 1 ; compare Abstr. 1886 798) .-Phenylallenylethoxirne nitrite CHPh:CH*C(N*OEt)-O*NO separates in colourless needles when a solution of phenylallenylamidethoxime (1 mol.) in dilute sulphuric acid is treated with sodium nitrite (2 mols.) in the cold.48 ABSTRACTS OF CHEMICAL PAPERS. It turns yellow after a short time and is very unstable exploding alightly when treated with concentrated sulphuric acid or wben heated quickly. It melts at 61" is readily soluble in alcohol chloro- form benzene and ether but only sparingly in light petroleum and almost inPoluble in water. I t can be crystallised from alcohol a t temperatures below 55" but slight decomposition occurs.It is decomposed b y acids or alkalis yielding cinnamic acid. The chloride CHPh:CH.CCl:N*OEt separates as a yellowish oil when the amid- ethoxime is dissolved in excess of hydrochloric acid and the solution treated with sodium nitrite. It is soluble in ether alcohol benzene and chloroform but only sparingly soluble in light petroleum and carbon bisulphide and almost insoluble in water; it is not decom- posed when warmed for a short time with acids or bases. Phen y 1 dibromoprop eny lethoxime chloride C HBrP h- CHBr C CKN* OE t prepared hy warming the chloride with a slight excess of bromine is a solid compound readily soluble in ether benzene and chloroform but only sparingly in light petroleum and insoluble in water.Pheny la1 len y Ipheny luramidet Iioxime CHPh:CH*C (NOE t)*NH*CO*NBPh obtained by treating phenylallenylamidethoxime with phenylcarb- imide crystallises from dilute alcohol in colourless needles melts a t 155-156" and is readily soluble in alcohol ether benzene and chloroform but only sparingly in light petroleum hot water and hydrochloric acid and insoluble in potash and cold water. Phenylalleruy lp h enyluramidoxime CHPh:CH*C (NO H)*NH*CO*NHPh prepared in like manner from phenylallenylamidoxime crystallises from dilute alcohol in colourless needles melts a t 158-159" and is readily soluble in ether but only moderately so in benzene and chloroform sparingly in light petroleum and insoluble in cold water ; i t is only very sparingly soluble in acids and alkalis.Pheny 1 all eny luramidoxim e C H Ph CH*C (PU'OH) *NHX 0 -NH sepa- rates in colourless needles when an aqueous solution of phenylallenyl- amidoxime hydrochloride is treated with potassium cyanate ; it melts a t 158-159" and is readily soluble in alcohol and ether but only moderately in benzene and chloroform and sparingly in light petro- leum and cold water. It forms salts with acids and dissolves unchanged in alkalis but when treated with concentrated acids or alkalis a t the ordinary temperature it is reconverted into the amid- oxime. The platinoch7oride ( C,,HllN,O,),,H,PtC1 is crjstalline. E t h y l pJ~ei~ylallenylainidoximecarboxylu te CH Ph C €3- C (N H,) :N.O-CO OE t is obtained together with the hydrochloride of the amidoxime when phenylallenylamidoxime (2 mols.) is treated with ethyl chlorocarb- onate ( I mol.) in benzene solution.It is a crystalline unstable compound melts at 101" and is readily soluble in erher alcohol chloroform and benzene but only sparingly in light petroleum and insoluble in water.ORGANIC CHEJlISTRY. 43 Phen~lallen~lcarbonyli.nzidoxime CHPh:CH*C<gzg> is formed when the preceding compound is warmed with alkalis or heated above its melting point. It crystallises from dilute alcohol in slender needles melts a t 199-2200" and is readily soluble in alcohol ether benzene and chloroform but only sparingly in light petroleum and is insoluble in cold water. It has an acid reaction and in neutral solu- tions of the ammonium-derivative silver nitrate produces a white and copper sulphate a green precipitate.F. S. K. Substituted Amidoximes. By H. M ~ L L E R (Ber. 22 2401- 2412 ; compare Abstr. 1€W 875) .-Benzenylphenylcarbonylimid- oxime melting a t 166-1 67" is formed together with benzjlanil- idoxime hydrochloride when benzenylanilidoxime is treated with carbonyl chloride in benzene solution. Benzenylanilidoxime combines with chloral in the cold forming a colourless flocculent compound NHPh.CPh:NOH,C,C130H which melts a t 128-130" is readily soluble in alcohol ether chloroform and benzene and is decomposed by concentrated acids and boiling water . Ethylbenzamide COPh-NHEt prepared by gradually adding benzoic chloride to an ethereal solution of etbylamine in the cold separates fieom ether in large crystals melts a t 69-70" and is soluble in water tenzene chloroform and alcohol but only sparingly in light petroleum ; i t is moderately easily soluble in hydrochloric acid but insoluble in soda.Uenzoparutoluidide COPh*NH*C,'R,Me prepared from benzoic chloride and toluidine in like manner crystallises in plates and melts at 157-1563". Thiobenzoparatoluidide CSPh*NH*C,H,Me is hest prepared by warming the preceding compound with phosphorus pentasulphide ; it crystallises from dilute alcohol in long yellow needles melts a t 128-129' and is readily soluble in alcohol ether chloroform benzene light petroleum and soda but insoliible in water. Benzenylpuratoluidoxirne NOH:CPh*NH*C6H,Me prepared by heating t hiobenzotoluidine with hJdroxy1amine hydrochloride and sodium carbonate in dilute alcoholic solution ~rpt~nllises from dilute alcohol in long colourless needles melts at 176' and is readily soluble in ether chloroform benzene acids and alkalis but only moderately so in hot water.The hydrochloride C,4HliNz0,HCI crystallises in colourless needles and is sparingly soluble in water. Be~tzenylparafoluy lcarbontlli?nidozime C6&Me< >NO pre- pared by treating benzenyltol~iidoxime with ethyl chlorocarbonate in chloroform solution crystallises from dilute alcohol in yellowish needles melts at 163" and is readily soluble in ether chloroform benzene and light petroleum but insoluble in water acids and a1 kal i 9. Ethenylanilidoxime NOH:CMe*NHPh (m.p. 120-121"). is obtained when thiacetanilide is boiled with an alcoholic solution of hydroxyl- ainine hydrochloride and sodium carbonate.The hydyochloride CPh44 ABSTRACTS OF CHEMICAL PAPERS. CsHloNzO HCJ crystallises in colourless needles. The pZatinochZoride ( C8H,oN20),,H,PtC16 crystallises in slender yellow needles. The henzoyl-dei-ivative NOBz:CMe*NHPh crystallises from dilute alcohol in colourless needles melts a t 110" and is soluble in benzene chloro- form and ether but insoluble in water and light petroleum. Methenylanilidoxirne NOHlCH-NHPh prepared in like manner crystallises from a mixture of benzene and light petroleum in colour- less needles melts a t l l G o and is moderately easily soluble in water alcohol ether chloroform and benzene but almost in soluble in light petroleum. The hydrochloriide C7H8N20,HCl crystallises in needles. The pZatinocl~Zoride (C,H,N,O),,H,PtCI crystallises in yellowish needles.The benzoyl-derivative NOBz:CH*KHPh crystallises in colourless needles melts a t 14&-145" and is moderately easily soluble in alcohol ether chloroform and benzene but almost in- soluble in water and light petroleum. F. s. K. Action of Acetaldehyde and of Ethyl Acetoacetate on Benzenylamidoxime. By F. TIEMANN (Ber. 22 2412-2417).- prisms when an aqueous solution of acetaldehyde (1 mol.) and benz- enylamidoxime (1 mol.) is kept for some time in a warm place. It melts a t 82" and is readily soluble in alcohol ether acetone and benzene but only sparingly in hot and insoluble in cold water ; it is decomposed when heated with acids. The hydrochloride CgHloN,O,HCl prepared by passing hydrogen chloride into an ethereal solution of the base is crystalline.The platinochlorida ( C9H,,N,0),,HzPtCI is an orange-yellow compound fioluble in alcohol and decomposed by water. The base is converted into benzenyletheny lazoxime by potas- sium permanganate in cold dilute sulphuric acid solution. BenzenyZacetoetiienyZazoxirne CPh<Ng>C*CH,Ac - prepared by heating benzenylamidoxime with ethyl acetoacetate crystallises from boiling water in short yellowisli prisms melts a t 86" and i s readily soluble in alcohol ether benzene and acetone b u t only sparingly in light petroleum and boiling water ; it dissolves freely in alkalis but is insoluble in acids. When boiled with alkalis it is decomposed into benzenylethenylazoxime and acetic acid. The oxime CllHllN302 crystallises from alcohol in colourless needles melts at 80" and is soluble in ether benzene and hot water but almost insoluble in light petroleum and cold water.It is a feeble acid and reduces Fehliog's solution on warming. The hydrazone C1,H16N40 prepared by heating the ketone with phenylhydrazine crystallises from dilute alcohol in yellowish needles melts a t 126" and is insoluble in water and light petroleum but readily soluble in alcohol ether benzene and acetone. Paranitrobenzenylamidoxirne and Paramethylorthonitro- benzenylamidoxime. By J. WETSE ( B e y . 22 2418-2432).- Paranitrobeizzeriylamidoxime NO,*C,HI*C(NHz) :NOH is obtained together with paranitrobeneamide (m.p. 197") when paranitrobenzo- ni trile prepared from paranitraniline by Sandmeyer's method is Ethylidenebenxeny Zamidoxime CPheNH>CHMe NO separates in rhom- F.S. K.ORGANIC CHEMISTRY. 45 digested with hydroxylamine hydrochloride and sodium carbonate in aqueous solution. It crystallises in yellow needles melts at 169" distils without decomposition and gives all the reactions of amid- oximes ; it is moderately easily soluble in alcohol and hot water but rather sparingly in benzene ether and chloroform and insoIuble in light petroleum. The hydrochloride C7H7N303,HC1 crystallises from water in colonrless hygroscopic needles melts at 185" with decompo- sition and is soluble in alcohol but is reprecipitated ou adding ether. The ethyl-derivative NO2.C6H4*C(NH2):N*OEt is obtained by treating the amidoxime with sodium etboxide and digesting the resulting deep-red solution with ethyl iodide ; it is best obtained in a pure state by decomposing the hydrochloride with dilute soda.It forms large yellow prismatic crystals melts at 59-60' and is readily soluble in alcohol and ether but only moderately so in benzene and sparingly in light petroleum and hot water. The hydrochloride separates from akoholic ether in colourless crystals. Paranitrobenzenylethenylazoxime NO,*C,H,*C<- N>CMe prepared by dissolving the amidoxime in acetic anhydride crystallises in colourless plates melts a t 1U0 and is readily soluble in alcohol ether and benzene but only very sparingly in hot water. The corre- NO -.T sponding benzen,yl-compound N02*C6H4*O<~~>CPh prepared by warming the amidoxime wi t8h benzoic chlo~ide crystallises from alcohol in small colourless needles melts at 198" and sublimes wit'h- out decomposition when heated slowly but explodes when heated quickly. It is insoluble in light pet,roleum and only moderat.ely soluble in alcohol but readily i n ether benzene and glacial acetic acid.Eth y 1 parnnitro b enzen ytnmidoximecarbox y lnte NO,*CsH,*C (NH,)XO*COOEt is €ormed when the amidoxime is treated with ethyl chlorocarbonate in cold chloroform solution. It crystallises from cold dilute alcohol in small needles melts at 169" and is moderately easily soluble in alcohol ether benzene and chloroform but only very sparingly in water and insoluble in light petroleum. ParunitrobPnzenylcarbonylimidc~xime N02C,H4*C<NH>C0 is ob- tained when the preceding compound is boiled with alkalis or heated alone; it separates from alcohol in small yellow needles melts a t 286" and is insoluble in light petroleum and only very sparingly soluble in hot water but more readily in alcohol ether and benzene.It is a very stable compound and dissolves freely in alkalis; in a neutral solution copper sulphate produces 8 green precipitate. NO Carbon y ldi-purani t r o b enzen y 1 amidoaim e prepared by *treating the amidoxime with carbonyl chloride in benzene solution at the ordinary temperature crystallises in small jellowish needles melts at 236" and is very readily soluble in alcoholj46 ABSTRACTS OF CHEMICAL PAPERS. and moderately so in hot water but more sparingly in benzene and ether and insoluble in light petroleum ; it is converted into pnranitro- benzenvlcarbonvlamidoxime when warmed with alkalis.d Y E t h y 1 idm9para nit ro benz e mjla in idozi me N 02*C6 H,<g; > C HMe separates in dark yellow crystals when an aqueous solution of the amidoxims is treated with a slight excess of acetaldehyde and kept for some days ; it crystallises in needles melts at 153" and is readily soluble in alcohol ether benzene and chloroform but only sparingly in hot water and insoluble in light petroleum. It is not acted on by dilute acids or alkalis in the cold but oxidising agents convert it quantitatively into the a.zoxime. It is decomposed into its con- stituents when warmed with dilute hydrochloric acid. A yellow flocculent compound separahes from the solutiou when etbylidene- paranitrobenzenylamidoxime is treated with warm dilute soda.This substance melts a t 252" is very stable and is insoluble or onlyvery sparingly soluble in most ordinary solvents. It dissolves uncliaiiged in concentrated sulphuric acid and is not acted on by reducing or oxidising agents or when heated at 150" with concentrated hydro- chloric acid; it is decomposed by fuming nitric acid yielding a neutral compound which melts at about 180" and seems to be R dinitroethenylazoxime. Chloreth~lidelwparanit robelzzen~ilamidoairne NO NO,*C 6H4*C<NH > C H*C H2C1 is formed when the amidoxime is boiled with dichlorethyl ether in aqueous solutions. It crystsllises from dilute alcohol in yellow plates melts at 176" and is very readily soluble in alcohol but only mode- rately easily in benzene ether and water and insoluble in light petroleum.It re3embles the preceding compound in its chemical behaviour and yields a complex condensation-product when warmed with alkalis. EtA yiparaizitrobenzen ylozinie nitrite N02*C6H,*C( NOE tr).O*NO pre- pared by treating the amidoxime with sodium nitrite in cold dilute sulphuric acid solut'ion is a yell0 w very unstable flocculeiit com- pound melting a t 55" with explosive violence ; it is soluble in alcohol and ether but insoluble in water. It decomposes slowly a t the ordinary temperature with evolution of oxides of nitrogen and explodes when heated with water or when treated with concentrated sulphuric acid. > C*CH2Ac is formed when the amidoxime is digested with ethyl acetoacetate. I t crystallises from d-ilute alcohol in golden plates melts a t 140" and is readily soluble in alcohol and ether but only moderately so in benzene very sparingly in water and insoluble in light petroleum.When heated with alkalis it is quickly decomposed into acetic acid and nitrobenzenylethenylazoxime. Paramidobenien ylamidoxime NH?*C6H,*C(NH2):XOH prepared by reducing the nitr+compound with stanuoos cbloride and hydrochloric NO Paranitro benzeny lacetoet heny lazoxirne N D2*C H,*C<ORGANIC CHEMISTRY. 47 acid and decomposing the resulting salt with sodium carbonate crys- tallises in yellow plates turnx brown at lGO" and melts at 174" with decomposition. It is very readily soluble in alcohol but only mode- rately easily in benzene and ether sparingly i n hot water and in- soluble in light petroleum ; it gives the reactions of amidoximes and dissolves freely in alkalis.Paramethylorthonitrobenzonitrile [ CN NO2 Me = 1 2 41 pre- pared from metanitroparatoluidine by Sandmeyer's method crgstal- lises from water in long yellowish needles melts at 99" distils without decomposition and is readily soluble in alcohol ether benzene and chloroform but only sparingly in hot water and almost insoluble in light petroleum. Paramet hy lort honitrobenzeny lamidoxiime N02*C6H3&1e*C (NH?) :NOH is obtained by digesting rnethylnitrobenzonitrile with hydroxylamine in alcoholic solution and is best prepared in a pure state by decom- posing the copper-derivative with hydrogen sulphide. It crystallises in long yellow needles melts at 161" and shows the properties of an amidoxime ; it is moderately easily soluble in alcohol and hot water but only sparingly in benzene ether and chloroform and is insoluble in light petroleum.The hydrochloride CBHSNYOS,HC1 is a colonrless crystalline compound soluble in alcohol but reprecipitated on adding ether. Paramethylorthonitrobenzamide [CONH NO2 Me = 1 2 41 is formed in the preparation of the preceding compound. It crystallises from water in long yellow needles melts at 152" and is readily soluble in alcohol ether and benzene but almost insoluble in light petroleum ; it is converted into the corresponding acid when boiled with alkalis. Para rneth y 1 orthamidoben,zeny lamidoxime is produced in small quantities when methylnitrobenzenylamidoxime is reduced with stannous chloride and hydrochloric acid.It is a brown flocculent compound melts at about 166O and gives the reac- tions of aniidoximes. The hydrochloride is a colourless crystalline hygroscopic compound soluble in alcohol but reprecipitated on adding ether. F. S. K. Para- and Ortho-homobenzenylamidoxime and their De- By L. H. SCHUBART (Bey. 22 2433-2440; comparz rivatives. Abs tr. 1886 79 7) .-Parahomo benz eny letheny lazoxime prepared by boiling the amidoxime with acetic anhydride crystallises in colourless prisms melts at 80° and is readily soluble in alcohol ether chloroform and benzene but insoluble in acids and alkalis. Parahomobenzenylethoxime chloride C6H4Me*CCl:NOEt obtained by treating the amidethoxime with hydrochloric acid and sodium nitrite is a ,yellow oil boils at about goo" a.nd is soluble i n aloollol and ether. The corresponding bromide prepared in like manner is a48 ABSTRACTS OF CHEMICAL PAPERS.heavy brown oil; it decomposes at 155" and is readily soluble in ether chloroform and benzene. Parahomobenzenylp-openylazoxime-w-carboxylic acid C6H4Me*C<- "0 y>C*C2H4-COOH. A is formed when the benzenylamidoxime is melted with succinic an- hydride. It crystallises from boiling water in colourless needles melts at 138*5" and is soluble in alcohol ether chloroform and benzene. Parahomobenzenyluramidoxime C,H,Me*C(NOH)*NH*CO.NH pre- pared by treating the hydrochloride of the atnidoxime with potassium cyanate in aqueous solution crystallises in colourless needles melts a t 170" and is readily soluble in alcohol ether and benzene but only sparingly in water.The thiowuinidozime C,H,Me*C (NOH) *NH*CS.NHPh prepared by treating the amidsxime with phenylthiocarbirnide crys- tallises from hot water in colourless needles melts ot lYO" and is readily soluble in alcohol and ether but more spariiigIy in chloroform and benzene. Para<horno b enzen y lpheny luvani idoxime C6H4Me*C( NOH)*NH*CO*NHPh prepared from phenylcarbimide in like manner separates from dilute alcohol in colourless crystals melts a t 155" and is readily soluble in rtlcohol ether and hot water. Ethyl pamhornobenzenylnnzidoximecarboJ.ylate C6H4&fe-C (NH,):NO*COOEt is obtained by treating the amidoxime with ethyl chlorocarbonate i n chloroform solution ; it crystallises from dilute alcohol i n colourless needles melts a t ISO" and is readily soluble in alcohol ether chloro- form and benzene but only sparingly in light petroleum and water.PnrahomobenzenyEcarBonyZirnidoxime C6H4Me*CWNH>C0 NO crystal- lises from hot water in colourless needles melts at 220" and is soluble in ether alcohol and alkalis. Diparahomobenzenylnzoxime C6H4Me*C< >C*C6H4Me is formed when the amidoxime is heated with glacial acetic acid. It crystallises from dilute alcohol in long colourless needles melts a t 135" and is insoluble in water but readily soluble in ether benzene chloroform and light petroleum. C6H4Me*CeK NO I-_i > CHM e melts a t 127.5". and is readily soluble in alcohol ether and benzene but only sparingly in hot water. NO Etlr ylidenepara.12omobenz eny lainidonime Parahomobenzenylacetoetheny lctzoxinze C6H4Me*C<L YO N>C.CH2Ac - pared by treating the amidoxime with etbpl acetoacetate crystallisesORGANIC CHEMISTRY. 49 from boiling water in colourless needles melts at 97" and is readily soluble in alcohol ether and benzene.Orthohomobenzeny Zaniicloxime CsH,&Ie*C (NH,) :NOH obtained from homobenzonitrile (b. p. 195") crystallises from hot water in yellowish needles melts at 149.5" is readily soluble in alcohol ether and benzene and shows the characteristic reactions of amidoximes. The ethyl-derivative C,,H,,N,O forms colourless prismatic crystals melts at 140° and is readily soluble in ether alcohol and benzene. The benzoyl-derivative C,5Hl,Nz0 crystallises from dilute alcohol in needles melting at 145". Orthohornobenzenylbenzeny luzoxime C 6 H ~ e * C < ~ ~ > c P h prepared by dissolving the benzoyl-derivative (see above) in cold concentrated sulphuric acid crystallises in long colourless needles melts at 80° and is insoluble in acids alkalis and cold water but readily soluble in alcohol ether benzene and chloroform.F. S. I(. Action of Carbon Bisulphide on the Potassium Compound of Parahomobenzenylamidoxime. By L. H. SCHUBART (Ber. 22 2441-2442) .-A compound CSH,N,S2 is formed when parahomo- henzenylamidoxime (1 mol.) is dissolved in alcoholic potash and the solution boiled for about three hours with carbon bisulphide (1 mol.). It crystallises from alcohol in yellow needles melts at 165" and is soluble in ether chloroform benzene and alkalis. The compound C,H6N2S2 can be obtained from benzenylamidoxime in like manner.It crystallises from alcohol in yellow prisms and melts at 160". F. S. K. Xylenylzmidoxime and its Derivatives. By E. OYPENH EIMER (Ber. 22 'L442-2449).-Xylylonitrile [CN Mez = I 2 41 pre- pared from xnet3axylidine by Sandineyer's method separates from cold dilute alcohol in long colourless crystals melts a t 23-24' is volatile with steam and is readily soluble in alcohol and ether (compare Oasiorowski and Mere Abstr. 1885 772). Xylenylumidoxime CsH,Mcz.C( NH,):NOH is obtained when the preceding compound is heated with hydroxylamine for 5 to 6 hours at 80-85". It crystallises in colourless needles melts at 178" and is readily soluble in alcohol ether chloroform and hot water but only sparingly in cold water; it gives all the characteristic reactions of aruidoxirnes.The ethyl-derivative CI,H,,J,O crystallises in colourless iieedles melts at 172" and is readily soluble in alcohol ether chloroform benzene and hot water but only sparingly in cold water. The benzoyl-derivative CI6H,,N,O separates from dilute alcohol in colourless crystals melts at 158" and is only sparingly soluble in waher and light petroleum but readily in alcohol ether and chloro- f x m . Xy 1 en y Zb enzen y Zuzoxime CsH,Me2*C< N>C Ph prepared by heat- ing the beuzoyl-derivative described above crystallises in yellowish scales melts at 98" sublimes readily and is volatile with steam ; it is readily soluble in alcohol ether chloroform and benzene. NO VOL. LVIIT. e50 ABSTRACTS OF CHEMICAL PAPERS. Acety Zxy Zeny lamitloxime C6H3Me2-C(NHz) :NOAc obtained by treating the amidoxime with acetic chloride in ethereal solution crystallises from cold alcohol in colourless needles melts at 189" and is readily soluble in alcohol and chloroform but only sparingly in ether.The corresponding ethenyluzoxinte C,,H,,N,O is prepared by heating the amidoxime with acetic anhydride and distilling the product with steam; it separates from alcohol or ether in crystals and melts at 89". Xylenylazoximepropeql-w-carboxylic acid C 6 H 3 M e 2 0 C ~ ~ ~ ~ C ~ C 2 H 1 * C O O H prepared by fusing the amidoxime with succinic anhydride crys- tallises in long colourless needles melts at 112" and is readily soluble in alcohol ether benzene and chloroform ; it forms crystal- line salts with bases. SEth?/Z xyZenyZamidoxirr,ecarboxyZate C6H3Me*C(NHz):NO*COOEt is obtained by treating the amidoxime with ethyl chlorocarbonate in chloroform solution.I t crystallises from dilute alcohol in colourlesa needles melts at 142" and is readily soluble in alcohol ether and chloroform but only sparingly in light petroleum; it has feeble basic properties. Xy Zeny 1 carbon y lamidoxime C6H3Mez* CfNH > C 0 prepared by heating the preceding compound crystallises from hot water in needles melts at 182" and is readily soluble in alcohol and ether; it has acid properties. The compound CeH,2Nz0,CCI,*COH is formed by the direct combin- ation of its constituents ; it separates from a mixture of benzene and light petroleum i n crystals melts at 112" and dissolves unchanged in alcohol and ether but is decomposed by water and by dilute acids.Xylenyluramidoxime CsH,Me2*C(NOH).NH.CO*NHz separates in coiuiwless crysta,ls when the hydrochloride of the amidoxime is treated with potassium cyanate in ethereal solution. It melts at 155" is readily soluble in ether alcohol benzene and light petroleum but onlg sparingly in water; it combines with acids and also but less readily with bases. C6H3Mez.C(NOH)*NH*C0.NHPh crystallises from alcohol in light yellow scales melts at 138" and is soluble in alcohol ether benzene chloroform hot water and acids. XyZenyZphenyZthiuramidoxime C6H3Mez*C(NOH)*NH-CS*NHPh separates from dilute alcohol in light yellow crystals meIts at 150" and is soluble in alcohol ether benzene acids and boiling water but almost insoluble in alkalis.F. S. K. NO The phenyl-derivative Action of Sulphuric Acid and Selenic Acid on Aromatic Compounds. By ISTRATI (Bull. Xoc. Chim. [3] 1 480-481).- Finding that the prolonged action of sulphuric acid on benzene pro- duced a sulphonic acid sulphobeneide and a francein the author heated selenic acid sp. gr. 1.4 (200 grams) with pure benzene (50 c.c.)ORGANIC CHEMISTRY. 51 for 32 hours at 80" ; neither selenobenziile nor a francei'n was produced but after neutralisation of the acid by barium carbonate a small quantity of a crystalline organic compound which the author believes to be phenyl selenide (comp. Abstr. 1889,41) was extracted from the barium salt by hot water. Pentachlorobenzene similarly treated gave a corresponding result. New Data relating to France'ins.By ISTRATI (BUZZ. Xoc. Chiin. [3] 1 481487 ; compare Abstr. 1888 591).-When snlphuric acid is heated with halogen-derivatives of benzene it causes the migration of halogen-atoms and this determines the formation from the initial corn- pound of france'ins whose chlorine values differ. Thus from 1 2 4- trichlorobenzene three franceins resulting from the oxidation of di- tri- and tetra-chlorobenzenesulphonic acids are produced and these are accompanied by a small quantity of 1 2 4 5-tetrachloro- henzene. From 1 2 4 5-tetrachlorobenzene a francein is ob- tained which is separable into five france'ins of varying solubilities and compositions. Numerous analSses are given. T. G. N. Francei'n from 1 2 4 Trichlorobenzene. By ISTRATI ( B d . ~ O C .Cltinz. [3] 1 4.88-492) .-From comparative experiments which he has made as to the formation of france'ins from 1 2 4-tri- chlorobenzene the author finds that the yield of francein is de- pendent on the temperature and varies inversely as the amount of sulphonic acid remaining in the mixture a t the close of the operatmion. Action of Heat on a Mixture of Sulphuric Acid and Sul- phonic Derivatives. By ISTR~ATI (BUZZ. SOC. Ckim. [3] 1 49%- 496).-From experimental observations the author concludes that when a mixture of excess of snlphuric acid and a sulphonic acid or a sulphonate is heated regeneration of hydrocarbons with formation of water and of pyrosulphuric acid respectively occur while sulpho- benxide is formed as a condensation-product and a decomposition of the sulphonic acid into sulphurous anhydride hydrocarbon and oxygen determines the formation of a franceiin by the oxidation of unaltered sulphonic acid.T. G. N. T. G. N. T. G. N. a-Ketoaldehydes. By H. MGLLER and H. v. PECHMANN (BPT. 22 2556-2 56 1 ).-Benzoy lf ormaldehy de C OPh . CO H (Abstr. 18e8 146) is prepared by dissolving nitrosoacetophenone (30 grams) in a 35 per cent. solution of sodium hydrogen sulphite (120 grams) contained in a litre flask. When cold the whole solidifies to a yellowish crystalline mass and is then stirred with alcohol and glacial acetic acid (1 c.c.) and after some time filtered by suction. The product (30 or 40 grams at a time) is boiled with 11 parts of 17 per cent. sulphnric acid in a flask fitted with an upright condenser until one quarter of the liquid is boiled off.On cooling crystals of phenylglyoxal hydrate separate and are purified by crystallisation from boiling water. It dissolves in about 35 parts of water at 20". When heated with nitric acid (sp. gr. lath) benzoglformic acid is formed. When an aqueous solution is treated with phenylhydrazine dissolved in dil ntu ( phen ylglyosal) e S52 ABSTRACTS OF CHEMICAL PAPERS. acid thea-hydrazone NHPh*N:CPh*COH separates as a brown cryetal- line precipitate which may be obtained from alcohol in yellow plates melts a t 142-143",and is readily soluble in most solvents. The osazone C,,H18N is obtained by heating phenylglyoxal with phenylhydrazine acetate (2 mols.) or more conveniently from nitrosoacetophenone and an excess of phenylhydrazine ; it is identical with Laubmann's compound from benzoyl carbinol and phenylhydrazine (Abstr.1888 366). When the aldehyde is dissolved in aqueous soda and b:ded for a few minutes sodium lnandelate is formed. It is probable that i n the formation of mandelic acid from benzoylcarbinol (Rreuer and Zincke Abstr. 1880 645) and from acetophenone dibromide (Engler and Wohrle Abstr. 188'7 948) benzoylformaldehyde is formed as intermediate product (compare Zinoke Annalen 216 31 5). When phenylglyoxal is treated with ammonia a compound of the formula C,,Hl,N30 or C,H,,N,O is obtained. This crystallises from dilute alcohol in yellowish-white lustrous plates melting a t 192-193" and can be distilled; i t is soluble in alkalis and is not changed by sulphuric acid.Phenylglyoxal reacts with hydroxylamine yielding the cnnipound C16H,3N403. The latter melts a t 219' dissolves in alkalis and is pre- cipitated by acids as a white powder which becomes yellow when exposed to light. A7itrosomethyZ paratol!/Z fietone C6H4Me.C0.CH:NOH prepared by Gaiseti's method crystallises from benzene in colourless needles melting a t 100'. ParatohjZgZyoxaZ hydrate C6R,Me*CO.CH(OH) is prepared from the a,bove compound in a manner similar to phenylglyoxal. It crys- tallises from water in white matted needles softens at 95" melts a t 1OO-l0'Lo and is readily soIuble in alcohol ether and benzene but less soluble in water and light petroleum. When shaken with benzene containing thiophen and salphuric acid the latter becomes green. The aldehyde behaves towards alkalis like the phenyl-compound is oxidised by nitric acid (sp.gr. 1.4) to toluylformic acid and by per- mariganate to paratoluylic acid (m. p. 180'). The osazone C21H20N1 obtained by heating a solution of the aldehyde with an excess of phenylhydrazine acetate for 30 minutes on a water-bath crystallises in yellow needles melting a t 145". Naphthyl methyl ketone C,,H,,O melts a t 51-52' boils at .300-301" and when oxidised yields /3-naphthoic acid. It is not identical with the compound obtained by Claus and Feiss (Abstr. 1887 271) but possibly is with Pampel and Schmidt's (Abstr. 1887 252) compound. N. H. M. Isomeric Dinitroparatoluic Acids. By B. ROZA~SKI (Bey. 92 2675-268'2) .-By nitrating orthonitroparatoluic acid (Abstr. 1888 l088) two dinitro-derivdires were ohtnined and their consti- tution establisbed from the corresponding dinitrotoluenes.2 5-DinitroparufrnZiiic acid (COOH NO Me NO = 1 2 4 5 ) is very sparingly soluble in cold water easily in alcohol and acetone crystallises in needles and melts a t 158". The sodiu,nz salt (with 3H,O) forms glistening je:low scales ; the bui*ium saltORGANIC UHEJIIS'I'RT. 53 (with 2&H20) sIrlaI1 yellowish-white needles ; the calciimt salt (with 2H20) reddish-brown scales ; the ammonium salt lemon-yellow scales ; the siher salt a white amorphous powder; the copper salt a light- green powder ; the mercuric lead and i r o n salts white precipitates. 2 3-Dinitroparatoluic acid [COOH NO NO Me = 1 2 3 41 forms yellowish prisms soluble in alcohol and melts at 249".It a i d its salts are less soluble in most solvents than the 1 2 4 5 acid. The bariwn saZt (with 4H,O) forms pale-yellow needles; the calcium salt (with H,O) pale-yellow scales. The other salts are similar to those of the isomeric acid. L. T. T. Acetometanitrobenzoic Anhydride. By W. H. GREENE (Airier. Chenz. J. 11 414-415).-When dry silver metaniirobenzoate is treated with excess of cold acetic chloride and the product poured into water metanitrobenzoic acid is regenerated ; Liebermann's statement (this Journal 1877 ii 617) that metanitrobenzoylacetic acid (acetometanitrobenzoic anhydride) is formed is incorrect. Acetometanitrobenzoic anhydride is however obtained by treating sodium or silver metanitrobenzoate with acetic chloride and extract- ing the product with ether.It forms colourless needles which melt a t 45". It is insoluble in water but the presence of either water o r alcohol in the ether used for extraction CiLuSes complete decomposi- tion of the anhydride Action of Phosphorus Trichloride on Salicylic Acid. By R. ANSCHUTZ and W. 0. EMERY (Airier. CRein. J. 11 387-392).-When salicylic acid is heated with excess of phosphorus trichloride a t iO-8rj0 and the product distilled first at the ordinary pressure to get rid of tlie excess of phosphorus trichloride and then under reduced prfssure snlicyloplzosphorus chloride C7H403PCl. solidifies in the re- ceiver. This melts st 36-37" boils a t 127" under 11 mm. pressure decomposes under ordinary pressure a t about 245" and is soluble i n ether chloroform and benzene. With phosphorus pentachloride or with chlorine i t gives an additive-compound C7H403PC13 of sp.gr. = 1.5587 a t 20" (water at 4" = l) boiling at 168" under 11 nim. pressure ; this compound can also be obtained by the action of phos- phoieus pentachloride on salicylic acid. With bromine a similar com- pound CiH1O3PCIBr2 is obtained of sp. gr. 1.8852 a t 20" (water a t 4' = l) and boiling at 18.5-188" under 11 mm. pressure. Tlie following are given as the most probable formulae for salicylophos- p horus monochloride and its chlorine additive-prodxct respectively :- C. F. 13. C. I?. B. Constitution of Isoeuxanthone. By C. ARBENZ (Chem. Centr. 18H9 ii 73; from A r c h . Sci. p h y s . mat. Gen6z.e [3] 21 3'75).- Phenylsalicylic acid is converted by nitric acid into the dinitro- derivative NO,.CsH1(O.CsH,.NO,).COOH which may be split up into paranitrophenol and pararlitrosalicylic acid proving that bot 11 nitro-groups are in the para-position.Sulphuric acid converts the51 ABSTRACTS OF CHEMICA\L PAPERS. dinitro-derivative into dinitrodiphenyleneketona oxide which may be reduced to the diamido-derivative isoenxanthone. J. W. L. Oxidation of Orthocarboxycinnarnic Acid. By E. EHRLICH (Illonatsh. 10 574-577 ; compare Abstr. 1888 842).-The author has previously shown (Abstr. 1888 1306) that in alkaline solution &naphthol when oxidised with a limited quantity of permanganate gives rise to orthocarboxycinnamic acid COOH*CH:CH.CsH,*COOH ; whilst the employment of an excess of the oxidising agent leads to the formation of orthocarboxyphenylglyoxylic acid CO OH*C0.CsH4.C 0 OH.Thq former acid however is not to be regarded as an intermediate ~wnduct for when a 2 per cent. solution of permangaiiate is slowly run i 1 1 tj) a solution of orthocarboxycinnamic acid (10 grams) and potash ( I 0 grams) in water (1 litre) decolorisation ceases when about 80 per cent. of the permanganate theoretically required to convert it into orthocarboxyphenylglyoxylic acid has been added and the solution contains only orthobenzaldehydecarboxylic acid COH*C6Ho*COOH (yield 50 per cent.) which melts a t 98-99' reduces an ammoniacal solution of silver. and furnishes a compound with phenylhydrazine melting a t 107-108". The author has not succeeded in his endeavour to obtain orthobenzaldehydecarboxylic acid by the direct oxidation of /3-naphthol.G. 3'. M. Isomeric Derivatives of Ethylbeneene. By L. SEMPOTOWSKI (Ber. 22 2862-2G74).-When ethylbenzene is heated to boiling an equal volume of sulphuric acid added and then after cooling the mass is treated with a small quantity of ice-cold water only para-ethyl- 7,eueenesulphonic acid is formed ; this crystallises in long colourless deliquescent needles is sliyhtly soluble in water and has a rough bitter taste. The barium saZt (with H,O) forms colourless silky needles; the calcium salt silvery scales ; the coyper salt (with 4+H,O) light-bliie glistening scales decomposing a t 170'; the cadmium salt (with 7H,O) large transparent quadratic plates ; the potassium salt (with +H,O) micaceous scales decomposing at 150".All these salts are soluble in water. The sic@haniide C6H4Et.S02NH,[Et SO,NH = 1 41 crystallises from alcohol in flat micaceous prisms easily soluble in ether sparingly so in water and melting at 109". The constitution vas proved by the fusion of the potassium salt with potash when parahydroxybenzoic acid was formed. With a shorter fusion para- etltyZpheno2 C6H4Et.0H was obtained ; this forms long needles which melt at 45-46' boil a t 21:-3-214" and are sparingly soluble in water.* It is very soluble in alcohol and ether and its aqueous solution gives a violet-grey coloration with ferric chloride and a jellowisli-white precipitate with bromine-water. The metnsuZphoizic acid CsH,Et(S03H)*OH[Et S03H OH = 1 3 41 is formed both at high and low temperatures.It. is a * Probably identical with the a-ethylphenol of Beilstein and Kuhlberg rind of Fittig and Kiesow.-Abstmrtor.ORQASIC CHEMtS'l'RY. 55 reddish oil of phenol-like odour and miscible with water. The b a r i m salt forms colourless hexagonal plates decomposing a t 120" ; the potassium salt silky needles ; the calcium saEt colourless needles. On fusion with potash the acid yields protocatechuic acid proving the correctness of the constitution given. Netaparadihydroxyethylbenxene C6H,Et(OH) [Et OH OH = 1 3 41 is a liquid boiling at 295" and soluble in water. Its aqueous solution is coloured green by ferric chloride and this colour passes on the addition of soda through blue to claret colour. Orthobyomethy lbenzenemetasulphonic acid [Et Br SOsH = 1 2 3 or 51 was obtained by the sulphonation of bromethylbenzene. Its barium salt (with 3HzO) iorms colourless plates sparingly soluble in cold water; its potassium salt (with $H,O) colourless scales ; and the sulphamide glistening prisms melting at 104-105".Parabromethylbenzeneorthosulphonic acid similarly formed yields a crystalline barium salt (with 4H20) easily soluble i n water. The potas- sium salt forms easily soluble scales the sukhonamide large micaceous scales melting at 123-124". Barium orthoethylbenzenesulphonute (with H20) formed by debrom- inating the bromine-derivat'ive forms soluble scales ; the cadmium salt long soluble needles ; the potassium salt very soluble glistening scales. Barium o~thoethylphenolrnetasulplLonate forms microscopic scales.Barium nteta-ethyll~en~zenesulplzor~nte (with 2H20) obtained by debromin- d i n g the bromine-derivative forms crystals easily soluble in water ; the potassium salt easily soluble scales ; the sulphonarnicle glistening scales melting at 85-86" When fused with potash this acid yields meto-ethylphenol which forms a colourless oil liquid at -20" and boiling at 202-204". Barium meta-ethylphenolsulphonate forms easily soluble crystals. L. T. T. Disulphones and Trisulphones. By E. FROMM (Annnlen 235 135-167) .-Baurnann and Escalcs (Abstr. 1887 123) obtained ethylidenediethylsulphone by oxidising a-dithioethylpropionic acid. It is more conveniently prepared by acting on a mixhure of acetalde- hyde and ethyl mercaptan with zinc chloride. The resulting ethyl mcrcaptal of acetaldehyde (b.p. 186") is oxidised by agitation with a solution of potassium permanganate containing sulphuric acid. E thylidenediethylsulphoiie melts at 75" and boils at 3.20" with decomposition. The bromide melts at 115". Attempts to obtain substitution-products by the action of alkalis sodium ethoxide mer- captan or aniline on the bromide were unsuccessful (Abstr. 1888 357). Ethylidenediethylsulphone chloride CMeCl( S02Et) and sodium phenylsulphini te are formed by the action of benzenesulphonio chloride on ethylidenediethylsulphone and sodium ethoxide. The chloride can be prepared by exposing to direct sunlight for several days an aqueous solution of ethylidenediethylsulphone saturated with chlorine. It is deposited from an aqueous solution in needles which melt at 102-103".The iodide is prepared by boiling the disul- phone with an excess of iodine the crude product being treated56 ABSTRACTS OF CHESlICAT PAPERS. with a cold ~olution of sodium hydroxide then washed with coId water and finally recrystallised from boiling water. The iodide crystallises in needles and melts at 128-129" ; a t a higher tempera- ture it gives off iodine. Diethylsulphonedimet hylmethane has been described by Baumann (Abstr. 1887 123). It can be prepared by the action of methyl iodide on an alkaline aqueous solution of ethylidenediethylsulphone. Diethylsulphoneth ylrnethylmefhane is formed by boiling a mixture of sodium ethoxide ethyl iodide and ethylidenediethylsulphone in a flask with a reflux condenser. It forms quadratic crystals and melts at 76".The ethjl mercaptal of propaldehyde is lighter than water and boils between 196" and 200'. On oxidation with permanganate it yields propylidenediethylsulphone CH,*CH,.CH( SO,Ett) ; t'his crys- tallises in silky needles and melts a t 77-78". The ethyl mercaptal of isobiitaldehyde boils between 200 and 210"; i t is lighter than water. lsobut~lidenedie~hylsulphone melts a t 94" and crystal- lises in needles; it is almost insoluble in cold water. The ethyl mercapkal of benzaldehyde PhCH( SEt) is lighter than water and boils with decomposition a t 250-253". Benz~lidenedieth~7sul- phone melts at 133-134"; it is insoluble in cold water but is soluble in cold solutions of the alkalis. €37 the action of sodium ethoxide and methyl iodide i t is converted into diethjlsulphone- methylmethane.Diethylsulrphonemethnne prepared by the oxidation of the ethyl mercaptal of formaldehyde (from methylene chloride and sodinm ethyl mercaptide) is identicai with the disulphone Raumann ob- tained from ethyl orthothioformate (dbstr. 1887 124). It is converted into diethylsulphonedimethylmethane (sulphonal) by the action of methyl iodide in the presence of an alkali; this melts a t 12.5-126". D~ethillsul?,honedi~thyli,?ethniie is more difficult to prepare. It melts at 86-88'. An aqueous solution of diethylsulphonemethane readily absorbs chlorine formiug the dichloride CCl,(SO,Et),. It crystallises in needles and melts a t 98-99'. The corresponding diethylsulphonedibromomethane has already been described by Bau- mann (loc.cit.) . Diethyhdphonedi-iochmethane melts a t 176-177" b u t begins to turn brown at 170". It crystallises in needles and is sparingly solnble in hot water. DiphenylsuZpphonemethane CH,(SO,Ph) prepared by oxidising the phenyl rnercaptal of formaldehyde crystallises in needles and me1 ts a t 118-119". It is soluble in benzene and hot alcohol Diphenylsul- phonedimethylmethane melts at 128" and is soluble in hot alcohol. The corresponding diethyl-derivative melts at 130-131" and is sparingly soluble in hot alcohol. When diethylsulphonedibromomethane (1 mol.) is boiled with phenyl mercaptan (I mol.) and an aqueous solution of sodium hydroxide (rather more than 3 mols.) phenyl bisulphide and diethylsulphone- thiophenylmethano are formed. The former is deposited from the solu- tion on cooling whilst the latter separates out on acidifying the filtrate ; i t is washed with cold water and recrystallised from absolute alcohol.ORGANIC CHEIJTSTR Y.57 Diethylsulphonethiophenylmethane PhSCH( S02Et) crystallises in plates and melts at 86". It is sparingly soluble in hot water and .more readily soluble in a solution of sodium hydroxide. On oxidation by perman ganat e diet h y Isu 1 phonep h eny lsu Zpiokonern ethane PhSO,*CH( SO,E t) 2 is produced. This trisulphone melts a t 1ti5". It is less soluble in alcohol than in water and is precipitated from its aqueous solution by strong acids. The aqueous solution turns litmus red and decomposes carbonates. w. c. w. Phenylated Indoles. By W. H. TNCE (Annrzkn 253 35-44).- 3'- Pheriylindole yields a crystalline picrate soluble in benzene ether acetone and alcohol and melts at 105".The nitrosamine C14H,,N,0 forms minute yellow needles and melts a t 60-61"; it is freely soluble in benzene acetone ether and chloroform but is insoluble in Rolutioris of caustic alkalis. Phenylacetaldehydemethylphenylhydr- azone is formed by the interaction of phenylacetaldehyde and methyl- phenylhydrazine. The alcoliol ic solution of t h i s compound is decomposed by an alcoholic solution of hydrogen chloride with deposition of ammonium chloride. The liquid is neutralised with ammonia and evaporated leaving a residue of impure 1'-3'-methyZ- phenylindole; t h i s is purified by solution in etherand distillation in a vacuum. The pure indole dissolves i n benzene alcohol and ether ; its alcoholic solution gives a blue colour to a pine chip moistened w i t h hjdrochloric acid.The picrate forms dark brown needles and melts a t YO". Fischer and Schmidt (Abstr. 1888 958) pointed out that zinc chloride a t 170" converts 3'-phenylindole into 2'-phenylindole. In the same way zinc chloride a t 220" transforms 1'-3'-methylphenylindole into the 1'-2'-methylphenylindole described by Degen (Abstr. 1887 149). 3'-PhenyZ-13-nap72thindoZe is obtained by the action of alcoholic hydrogen chloride on the hydrazone produced by the inter- action of phenylacetaldehyde a n d /3-naphthylhydrazine ; it crystal- lizes in glistening needles and melts with decomposition a t 211" is soluble in benzene alcohol ether acetone and hot light petroleum and stains a pine chip green.The picrate forms reddish-brown needles melts a t 219-120" and is holuble in benzene acetone chloroform alcohol and ether. The 3'-phenyl-/3-naph t hindole is con- verted into 2'-phenyl-@-naphthindole by treatment with zinc chloride at 130". 2'-Phenyl-P-naphthindole can be more conreniently prc- pared by the action of zinc chloride on acetophenone-p-naphthgl- hydrazone obtained by the condensation of acetopbenone and j?-naphthylhydrazine. The hydrazone melts a t 150" but it begins to turn brown a t 117". /3-?zLtphthindoZe melts a t 129-1S0° and is freely soluble in alcohol ether and benzene. It forms a crystalline picrate (m. p. 165-166") which is soluble in benzene and ether. Benzidine- and Benzidinesulphone-sulphonic Acids. By P. GRIESS and C.DUISBLRG (Rer. 22 2459-2474).-l?enzidiwe- sulphonic acid NH,.C6H4*C6H3( NH,) .SO,H is formed in small quanti- w. c. w.58 ABSTRACTS OF CHEMICAL PAPERS. ties in the preparation of the disulphonic acid (compare Griess Abstr. 1881 428) and it can also be obtained in larger quantity by heating benzidine sulphate for 1& to 2 hours a t 1 70" with sulphuric acid mono- hydrate (about 6 parts). It is best prepared by heating benzidine sulphate at 170" for about 24 hours (D.R.-P. No. 44,779). It forms anhydrous crystals and is very sparingly soluble in boiling water and practically insoluble in alcohol and ether; it is decomposed when heated yielding a small quant'ity of benzidine. The hydrochloride C12H,,N2S0,,HCl separates from hot dilute hydrochloric acid in greyish nodular anhydrous crystals and is decomposed by boiling water.The barium salt (C,2HlIN2S03)2Ba + 5H20 is moderately easilg soluble in hot water and separates on cooling in small needles or plates. The tetrazo-compound is obtained when an excess of hydrochloric acid and a slight excess of sodium nitrite are added to an ice-cold alkaline solution of the sulphonic acid. It is readily soluble in water and combines with phenols hydroxysulphonic acids and aromatic hydroxycarboxy lic acids in alkaline solution and with arnines and amidosulphonic acids in sodium acetate solution forming yellow red and purple dyes. The compounds obtained with the hydroxycarbosylic acids phenols and amines respectirely are sparingly soluble ; the other dyes are readily soluble in water.They all dye unmordanted cotton wool in am alkaline bath and generally the shade produced is more distinctly purple than that obtained with tetrazodiphenyl dyes but not so much so as that produced with tetrazodipheny ldisulphonic acid colouring matters. Benzidinemetadisulphonic acid (compare Griess Zoc. cit.) is best prepared by heating benzidine sulphate (1 part) with sulphuric acid (2 parts) at 210" for 36 to 48 hours ; the yield of the pure compound is 90 per cent. The azo-compounds derived from the tetrazo-derivative do not dye vegetable fibres as readily as those obtained from the tetrazomonosulphonic acid but they have a more decided blue shade. Benzidine is not acted on by fuming sulphuric acid a t temperatures below 100-120" but the azo-compounds obtained from tetrazo- diphenyl and naphthylamines react with fuming sulphuric acid in the cold the hydrogen in the benzidine being substituted.Benzidinetrisulp7zoiLic acid C6H,(NH,)(S03H)2~C6H3(NH2)*S03H + 2H20 is obtained together with the tetrasulphonic acid when benzidine sulphnte is heated for a long time at 180-190" with sul- phuric acid monohydrate or when a solution of benzidine in a little hulphuric acid monohgdrate is heated at 160-1T0° poured into fuming sulphuric acid and heated again until a small portion gives only a slight precipitate when treated with water. The product is poured into water the solution filtered to separate small quantities of the disulphonic acid and neutralised with barium carbonate. The barium salt of the trisulphonic acid is readily soluble in cold water and can be easily separated from the salt of the tetrasulphonic acid which is only sparingly soluble.Benzidinetrisulphonic acid is pre- cipitated in soft colourless plates on adding concentrated hydro- chloric acid to a moderately concentrated solution of the barium salt. It is readily soluble in cold water but only sparingly i i i alcohol andORGANIC CHEMISTRY. 59 is reprecipihated from the alcoholic solution on adding ether; it is completely decomposed when heated. ci-ystallises in small colourless prisms and is precipitated from its coilcentrated aqueous solution on adding alcohol. The ba.rium salt (C,,H9N2S30,)2Ba3 + 12H~0 /2enzidiizetetrasulp~o~,ic acid CsH?(NH,) (SO,H)z.CsHz(NH,) (SOB) is precipitated in small colourless needles on adding hydrochloric acid t o a concentrated aqueous solution of the barium salt; it is very readily soluble in cold water and is also soluble in alcohol.The barium salt Cl?H8S10,,Ba + €?H,O cryst,allises in colourless needles or prisms aiid is very sparingly soluble in hot water and insoluble in alcohol. Benzidin esulp hone ?6H3(NH2)>SO? is best prepared by gradually adding benzidine sulphate (1 part) to a 20 per cent. sulphnric acid solution of sulphnric anhydride. and heating the mixture on the water- bath until i t is free from unchanged benzidine ; the product is poured on to ice and the benzidinesulphone sulphate is separated by filtrntiou and decomposed with soda. It crystallises in very small yellow anhydrous needles melts above 350° and is almost insoluble in boil- ing water and insoluble in alcohol ether and benzene.The salts are decomposed by water. The hydrochloride C12HloN2S02,2HC1 crystal- lises from hot dilute hydrochloric acid in which it is moderately easily soluble in almost colourless plates. crptallises in grey or colourless needles or plates and is only sparingly soluble in hot dilute sulphuric acid. The platinochZoride crystallises in small dark yellow plates and is insoluble in water. ,4 h ydroxybenzidine C12HllN2.0H is formed when the sulphone is heated a t 180" with caustic soda; it is a grey compound very sparingly soluble i n water but readily i n soda. The sulphate and l~ydrochloride are sparingly soluble in water. When benzidinesulphoiie hydrochloride is treated with sodium nit'rite in aqueous Eolution and the resulting brown amorphous tetrazo-compound reduced with stannous chloride and hydrochloric acid the hydrazine is obtained in small yellow needles sparingly soluble in water.The latter is decomposed when boiled with copper sulphate solution yielding a diphenylenesulphonic acid melting a t 2:'8" and identical with the compound obtained by Stenhouse (Annalen 156 332) from diphenylene sulphide. The azo-dyes obtained from benzidinesulphone differ from those of benzidine and benzidinesulp honic acids in possessing a marked blue shade. C,H3(NH,) The s u b h a t e CVZHIJ?~SO~,H2SOd + 1iH20 Beizzidi~~s.1Llphone~z~Z~~onic acid S03H-C6H2(NH2) <c6H3(NH2)> so - is formed together with the di- tri- and tetra-sulphonic -acid when the sulphone is heated with fuming sulphuric acid a t temperatures above 100'.The crude product is boured 01 to ice and after keep-60 Al3Sl'RACTS OF CIIENICAL PAPERS. i n g for some time the solution is filtered; the tri- and tetra-hulphonic acids being readily soluble in cold water pass into the filtrate whilst the mono- and di-sulphonic acid which are only sparingly soluble remain ou the filter. The residue is dissolved in soda and the mono- sulphonic acid is precipitated from the filtered solution by adding acetic acid ; the disulphonic acid in the filtrate is then precipitated by adding a large excess of hydrochloric or sulphuric acid. Benzi- dinesulphonesulphonic acid crystallises from hot water in which it is only sparingly soluble in small light-yellow needles and is almost insoluble in alcohol.The tetrazo-derivative is a reddish.brown amorphous compound ; i t combines with amines phenols and with their carboxglic and sulphonic acids forming dyes which are of a redder shade and are much more sparingly soluble than those derived from benzidinesulphonedisulphonic acid (see below). The ccr Zcium salt (Cl,H,NTS20,)2Ca + S&H20 crystallises in small yellow needles and is readily soluble in hot water but only moderately so in boiling alcohol and sparingly in cold water. The barium salt (with 3+H,O) crystallises in small golden needles and is more sparingly soluble in water than the calzium salt. Ben zidinesu @ honedisdphon ic acid 1$H,O separates in small light-yellow needles when a boiling aqueous solution is evaporated.It is inodermtely easily soluble in hot water but only sparingly in alcohol and almost insoluble in cold hydrochloric or sulphuric acid. The tetruzo-compound is a light- yellow voluminous substance ; i t combines with naphthols and naphttolsulphonic acids yielding purple to violet dyes and with naphthylamines and naphthylaminesulphonic acid Porming red or bluish-violet colouring matters. It yields beautiful reddish-violet or indigo-blue azo-dyes (sulphoneazurines) wi tli alkyl- and phenyl- naphthylamines. The calcium salt CI2H,N2S3O8Ca + i H 2 0 crystal- lises in yellow needles or plates and is readily soluble in hot but orily sparingly in cold water and insoluble in alcohol. The barium salt (with 4iH,O) crystallises in needles or very small prisms and is insoluble in alcohol and only very sparingly soluble in boiling water.The sodium salt crjstallises from hot concentrated aqueous solu- tions in long yellow needles and is only sparingly soluble in cold water. Orthotolidine yields analogous compounds to those obtained from benzidine under the same conditions. Ol.thotoliJirnesziZphon~c acid is vwy sparingly soluble in water and does not crystallise readily. The tetmzo-derivative is readily soluble in water. The barium salt loses 4 mols. H,O when dried a t 150". The disuZpyhonic acid crystallises from hot concentrated aqueous solutions in small colourless needles and is readily soluble in hot water. The tetrazo-derivative is insoluble in water. The salts are moderately emily soluble in water; the sodium salt crystallises in cuhes (with 4H,O) the ctcbium salt in plates (with 5H20) and the barium salt in needles (with 3H20).Tolidinesdphone is a greenish-yellow amorphous compound the salts OF which are very similar to those of benzidinesulphone (D.R.-P. No. 44,784). F. S. K. >so + yJL(NH,) (S0,H) C,H,(NH,)(SO,H)ORC INIC CHEMISTRP. 61 p-Naphthylhydrazine. By F. HAIJFF (Awnalen 253,24-35).- The derivatives of p-naphthylhgdrazine bear a close resemblance to the corresponding phenylhydrazine-derivatives. The acetyl-deriva- tire Cl,,H7*N2H,Ac. prepared by boiling p-naphthylhydrazine with glacial acetic acid for several hours in a reflux apparatus forms colourless needles soluble in alcohol chloroform and benzene and melts a t 164-165". Renzoylnnphthylhydruzine C,,H,*N~H,BZ is ob- tained on adding benzoic chloride to an ethereal solution of naphthyl- Iiydrazine (3 mols.) ; naphthylhydrazine hydrochloride is precipitated and the filtrate on being evaporated and the residus treated with a hot dilute solution of sodiiim hydroxide to remove unaltered benzoic chloride leaves the hg drazine.When pure it crystallises in needles melts at 154-155" and is soluble in hot alcohol ether benzene and chloroform. I n order to introduce a second benzoyl-group into the preceding compound it is necessary t o act on it with beuzoic chloride at a high temperature. The dibenzoyl-derivative C'10H7.N2HB~2 melts a t 162-163". B-NaphthyZsemicarbazide C1nH7*N?H2*CO*NHz prepared by the action of potassium cyanate on naphthylhydrazine hydrochloride is soluble in hot alcohol and acetic acid ; i t melts at 220" (uncorr.) and resembles the corresponding phenyl-derivative in its chemical pro- perties.It is decomposed by the action of hydrochloric acid in sealed tubes at 140° yielding naphthazine which has previously been described by Witt (Abstr. 1887 153). P-Naphthy Zthiosemicarbazide C,oH7*N2H2*CS*NHz is obtained by boil- i n g an alcoholic solution containing equal parts by weight of naphthyl- hydrazine hydrochloride and ammonium thiocyanate. This substance melts at 201 -202" (uiicorr.) and is soluble in hot aniline and alcohol. It is decomposed by hydrochloric acid in sealed tubes at 130-140" NH yielding napht~~y Zthiocarbizine CIOH7N< & . The carbizine melts at 2.53-2.54" and crystallises in plates. It is solublc in warm alcohol and forms a crystalline hydrochloride and platinochloride.A violet precipitate is formed when bleaching powder is added to the alcoholic solution of the base. Naphthylhydrazine naphthylthiocarbazin~te C,,H7*N2H2*C i3.S H,N,H,*Cl,H cry$tallises in plates and melts with decomposition at 145". It is soluble in warm alcohol. Ethyl-P-naphthylhydrazine is prepared by the action of ethyl iodide (2 mols.) on naphthylhydrazine in alcoholic solution. I t is a pale-yellow oil freely soluble in alcohol ether benzene and chloro- form. I t reduces warm Fehling's solution. The solution in ch1or.o- form is slowly decomposed by mercuric oxide yielding naphthylethyl- am i lie. w. c. w. Derivatives. of p-Naphthylhydrazine. By A. H [LLRINGHAUS (per. 22,2656-26.57).-ln reference to Hanff's work on th:s subject (preceding Abstract) the author states that he has also recently6% ABSTRACTS OF CHEMICAL PAPERS.obtained the acetyl-derivative the semicarbazide and the thiosemi- carbazide. L. T. T. Derivatives of the Two Isomeric Naphthenylamidoximes By E. RICHTER (Ber. 22 2449-2459; compare Abstr. 1887 374 also Ekstrand ibid. 373).-P-Napthenylamidoxime (m. p. 150) is readily soluble in alcohol and ether but only moderately easily in benzene and chloroform and insoluble in light petroleum. The COT- responding a-compound (m. p. 148-149") resembles the /?-deriva- tive in its behaviour with solvents. Benzoy 1-P-naphthenylamidoxime C,oH,*C(NH,):NOBz prepared by heating the amidoxirne with benzoic chloride crystallises from hot alcohol in colourless needles melts at 179' and is only sparingly soluble in cold alcohol ether benzene chloroform and light petroleurn insoluble in water.NO Naphtlteiaylbenzenylazoaime ClOH,*C< - N>CPh is formed when the preceding coinpound is boiled with water dilute acids or diluh alkalis or when i t is treated with concentrated sulphuric acid. I t crystallises from dilute alcohol in colourless plates melts a t 116" aild is readily soluble in alcohol ether benzene chloroform and light petroleum but almost insoluble in water. Acetyl-P-naphtheny lamidoxime CI:,H,2N20 crystallises from alcohol or benzene in yellowish needles melts a t 154" and is only sparingly soluble in ether chloroform a1.d light petroleum and insoluble in water ; when boiled with water or when treated with concentrated sulphuric acid it is converted into the azoxime melting at 85" (compare Ekstrand Zoc.cit.). Ethyl-P-napht hen y larnidoxirnecarboxy late C10H,*C ( NH2) :NOC OOE t separates from alcohol in colourless needles melts a t 121" and is readily soluble in alcohol ether benzene chloroform and acids but very sparingly in light petroleum and insoluble in water and alkalis. NO P-Nap hthen y lcarbon y limidoxime C > C 0 cry s tallises from hot benzene in cclourless needles melts a t 216" and is mode- rately soluble in alcohol ether and chloroform but sparingly in benzene and hot water. The sodium-derivative is crystalline. In an aqueous solution of the ammonium-derivative lead acetate produce? a white and copper sulphate an apple-green precipitate.P-Naphthe?j ylamidethoxime CIOH7.C ( NH2):NOEt crystallises from dilute alcohol in colourless needles melts a t 74-75" and is readily soluble in alcohol ether benzene chloroform light petroleum and hydrochloric acid but very sparingly in water and insoluble in alkalis. Ethylidene-@-naphthenylamidoxime C,oH,*C<NH>CHXe NO pre- pared by dissolving the amidoxime in acetaldehyde crystallises from hot water in colourless needles melting at 121-122". It is readily soluble in alcohol ether benzene and light petroleum very sparingly soluble in cold water and insoluble in acids aud alkalis.ORGANIC CHEBIISTRY. 63 NO Acet oe t heny I- &nap ht heny lazoxime C ,,H7 C<- N>C* C HzAc is f ovmed by boiling the amidoxime with ethyl acetoacetate ; it crystallises from hot water in nacreous plates melts a t 108-109" and is soluble iu alcohol ether benzene and chloroform but insoluble in light petroleum.Acetyl-a-na~hthenylamidoxirrLe crystallises from dilute alcohol in colourless needles melts at 129" and is insoluble in water but readily soluble in alcohol ether benzene and chloroform ; when treated with concentrated sulphuric acid or when boiled wit.h water it is converted into the azoxime (compare Ekstrand Zoc. cit.). Ethyl-a-napht?~enylanaidoxi~mecarbozylatu crystallises in colourless needles melts at 11l0 and is readily soluble in alcohol ether benzene and chloroform but only sparingly in light petroleum and insolnble in water. a- Naphthen.yZcarbonylimidoxirne prepared by boiling the preceding compound wit.h water or alkalis crystallises from dilute alcohol in colourless needles melts at 189" and is readily soluble in alcohol bnt only sparingly in ether benzene and chloroform and insoluble in light petroleum and water.I n aqueous solutions of the ammonium- derivative lead acetate produces a white and copper sulphate a green precipitate. F. S. K. Acetyl- and Ethyl-derivatives of Camphonitrophenol. By P. CAZENEUVE (Bull. SOC. Chiin. C3] 1 467-469 ; compare Abstr. 1889 CsN02 618) .-The acetyl-derivative of camphonitrophenol C8H14<l 1 C*OAc) after saponification and subsequent saturation with slight excess of hydrogen chloride gives with ferric chloride a violet-red coloration CH*N02 which indicates the forniation of the compound C,H,,< I The ethyl-derivative CsHld<E.oEt is made by heating sodium camphonitrophenoxide with excess oE ethyl iodide in sealed tubes at 120" for three hours; after separation of sodium iodide the liquid is evaporated to dryness and the residue crystallised from benzene.The compound forms large colourless flat crystals which melt at 54" and decompose on distillation. C(OH)2 T. G. N. Camphonitrophenol Phosphate. By P. CAZENEUVE (BUZZ. SOC. Chirn. [ 3],1,46!b--47 1) .-The normal phosphate ( C,,t€,,NO,),PO is prepared by boiling camphonitrophenol with phosphoras trichloride for several hours. It exists as an amorphous yellowish insoluble sub- stance which when heated decomposes without melting. Nitrophenol forms an analogous compound ( C6K4NO,),PO with phosphorus pent+ chloride only traces of metachloronitrobenzene being simultaneoiisly produced. This reaction confirms the constitution previously giveu to camphonitrophenol. T.G. N.64 ABSTRXCTS O F CHEJIICAL PAPERS Camphonitrophenol Benzoate and Phthalate. B J P. CAZE- C-NO N EUVE (BUZZ. Soc. Chim. [3] 1,471-4B).-The benzoate C,H,,< I I C-OBz i R prepared by the reaction of equal parts of camphonitrophenol and benzoic chloride at 100' ; it forms small crystals which are insoluble in water but soluble in hot alcohol ether and benzene; these melt a t 131" ; and partially volatilise a t 150" without decomposing. On saponification with alcoholic potash it yields potassium benzoate and the compound C,N,,< I C-NO C(OH)?' Phthalic chloride by a similar reaction forms a compound (N0o.C 10Hl,o)J&H,02 which melts at 275" with slight decomposition.T. G. N. Quercetin-derivatives. By J. HERZIG (LVonatsh. 10 561-567 ; compare Abst)r. 11388 1309) .-In a preyious communication the author has called attention to the fact that pure xanthorhamnin ie not the sole product obtained from Persian-berries by the method of Liebermann and Hijrmann (Abstr. 1879 'L71). It is now shown that besides xanthorhamnin the berries cont.ain a glucoside of rhamnetin or some nnstable molecular compound of the glucosides of rhamnetin and quercetin. This result is in accordance with the fact that Schutzenberger obtained two glucosides ( a - and P-rhamnin) from Persian-berries. His a-rhamnetin (from z-rhamnin) is evidently identical with rhamnetin his P-rhamnetin (from p-rhamnin) with quercetia.G. T. M. Scutellarin one of the Constituents of Scutellaria 19nceo- lwia. By I). TAKAHASHI (Chem. Centr. 1889 ii 100.)-The root of ScuteZZariu Zunceularia one of the labiatse is used medicinally in China and Japan. By extracting the root with ether agitating the ether extract with sodium hydroxide and acidifying the alkaline solu- tion a yellow. flocculent substance scutellnrin is obtained. It forms odourless and tasteless shining flat yellow needles melts at 199-199*5" is insoluble in cold little soluble in hot water very readily soluble in alcohol ether chloroform light petroleum and carbqn bisulphide ; soluble in sodium hydroxide and carbonate solut,ions ,but carbonic anhydride is not expelled from the latter. It dissolves in concentrated sulphuric acid with a yellow colora- tinn and water reprenipitates the substance unchanged. It dis- solves in nitric acid with red coloration and in like manlier in a solu- tion of sulphuric acid and potassium nitrite.Fehling's solution is llot reduced by it even after boiling with hydrochloric acid. J t does not combine with phenylhydrazine ; neither silver nitrate nor lead acetate precipitates it from its alcoholic solution but solu- tions of lead and copper acetates produce a yellow-red precipitate with the dcoholic solution. When treated with bromine in carbon bisulphide solution a substance crystdlising in yellowish needles is formed ; the determiriation of bromine in it however! gare unsatis- factory results. The el2mentary analysis of scutellarin give figuresORGANIC CHEMISTRY.65 which corresponded with the formula CloH,03 ; it contains neither nitrogen nor water of combination. 5 grams of scutellarin produced no effect when administered to a dog in an emulsion of milk and gum arabia The author believes it to be a phenol and possibly an isomeride of juglone. J. W. L. Crystallised Digitalin. Ry ARNAUP (Compt. rend. 109 6i9- 682) .-Digitalin prepared by Nativelle's method from the digitalis of the Vosges formed very thin brilliant white rectangular lamelh which melt at 243" dissolve in absolute alcohol to the extent of 0.650 part in 100 at 14" and also contrary to the statement of Schmiede- berg dissolve in boiling benzene. When subjected to fractioual solution the melting points of the different fractions varied only between 242" and 245".A second quantity prepared by Adrian melted at 245-246" and when dissolved fractionally in alcohol and benzene the melting points varied only between 243 and 245" as with the first sample. Digitalin is a distinct chemical individual and it is not necessary to denote it by any name such as digitoxin. It seems to be the typt. of a large group of compounds. C. H. B. Dihydropyrroline. By F. ANPERLINI (Ber. 22 2512-2515).- Dihydropyrroline hydrochloride is decomposed when heated givingr off vapours which colour pine-wood red ; it is partially decomposed by concentrated hydrochloric acid at 130-140". The uuroch loride. C4NH7,HAuC14 crystallises from cold water in small prisms melts at 152' and is slowly decomposed when boiled with water. The picrate CdNH7,C6H3N307 separates from water in yellow crystals melts at 156" arid is readily soluble in alcohol and water.Benzoy Zdihydropyrroline C4NH6Bz prepared by heating dihydro- pyrroline hydrochloride with benzoic chloride at 110" is an oily liquid boils at 160-161" (2 mm.) and is miscible with alcohol and ether but is insoluble in water. It dissolves freely in con- centrated hydrochloric acid yielding a salt which does not crptallise readily. Benz y Zdihy drop yrroline C4NH6*C H,Ph prepared by treating di - hydropyrroline with benzyl chloride boils at 150". The aurochloride CIIH,,N,HAnCl~ crystallises from water in yellow needles melting. at 111". E. S . K. Derivatives of Alkylpyrrolines. By C. U. ZANETTI (Bey. 22 2515-2519 ; cornrare Ciamician and Zanetti Abstr.1889 727).- 1-Ethylpyrroline boils at 129-130" (762 mm. corr.). The tetra- bromide melts at 83" and is converted into ethyl dibromomaleimide (m..p. 93-94") by cold nitric acid of sp. gr. 1.49. The diacGtyZ- derivative C4NHzEtAc is a crystalline compound melts at 58-59' boils a t about 183" (29 mm.) and is readily soluble in alcohol ether benzene light petroleum and warm water. When the mixture of c-ethylpyrrolinep boiling at 150" (compare Ciamician and Zanetti Zoc. cit.) is treated with acetic anhydride and sodium acet'ate an oil is obtained which can be separated by frac- VOL. LVIII. f66 ABSTRACTS OF CHEXICAL PAPERS. tional distillation into a portion boiling at 210-235" and a portion builing at 240-255". The former is volatile with steam and has the composition and properties of an 1-acetyl-c-ethylpyrrolins C4NH3EtAc.The latter after having been boiled with potash and repeatedly distilled in order to free it from 1-acetyl derivatives solidifies parti- ally when exposed to long continued cold and can thus be separated into its constituents ; the crystalline substance is an acetyl-deriva- tive melting a t 42-44" probably identical with the compound (m. p. 47") obtained by Dennstedt a a d Zimmermann from c-ethyl- pyrroline (compare Abstr. 1886 1043). Both the liquid and the solid compound give a silver-derivative which has the composition l-Propylpyrroliije C4NH4Pr is obtained in small quantities when potassium pyrroline is treated with propyl iodide but isomerides and other compounds are also formed; it) is a colourless oil hoiling a t 145-5-146*5" (755.8 mm.).Nitropyrroline-a-carboxylic Acids. By F. ANDERLINI (Ber. 22 %503-2506).-Methyl nitropyrroline-a-carbox~lafe NO,-C,NH,*COOMe (m. p. 197") is formed together with an isomeride (m.p. 179") and other nitro-compounds when finely divided methyl pyrroline-d- carboxylate is gradually added to ice-cold nitric acid of sp. gr. 1.5 aud the solution poured into cold water; after neutralising with soda and adding a lit'tle sodium carbonate the solution is extracted with ether It crystallises from boiling water in coloudess needles melting a t 197". The corresponding acid N0,.C4NH,COOH ob- tained by hydrolysing the ethereal salt with potash crystallises from water with 1 mol. H,O in light-yellow needles and is readily soluble in alcohol ether and hot water but only sparingly in benzene and cold water.I t loses its water when kept Over snlphuric acid under reduced pressure and the anhydrous crystals melt a t 217". Nethyl nitropyrroline-a-carboxylate (m. p. 179") is obtained together with other nitro-compounds when the alkaline solution from which the isomeride (m. p. 197") has been extracted is acidified and then extracted with ether. It can be isolated by hactionally cry stallising the crude product from water. It separates from dilute alcohol in yellow needles melting at 179". The corresponding acid crystallises from hot water with 1 mol. H,O in light-yellow needles and is readily soluble in alcohol ether and hot water and moderately so in benzene but .only sparingly in cold water.It loses its water when kept over sulphuric acid under reduced pressure the anhydrous compound melting a t 161". The mother-liquors from the preceding compound (m. p. 179") probably contain the third isomeride which has previously been pre- pared by Ciamician and Danesi (Abstr. 1882 875) from dinitro- pyrocolf but this compound could not be obtained in a pure condition. They also contain the methyl salt of a dinitropyrroline- carboxylic acid C4NH2(N02)2*COOMe ; this compound crystallises froin watler dilute alcohol and benzene in light-yellow plates melting a t about 113". F. S. K. C,HioNOAg. F. S. K.ORGXSIC CHEJIISTRY. 67 Molecular Weights of the Imidoanhydri 3es of Pyrroline- carboxylic and Indolecarboxylic Acids. By G. MAGNANLNI (Bw. 22 2j01-25Oq.Molecular weight determiuations by Raoult's method in naphthalene solution show that the molecular formula of pyrocoll is C10H6N202 that of tetramethylpyrocoll ClIH,,N,02 that of diacetylpyrocoll C14HloN20~ and that of the imidoanhydtide of a-indolecarboxylic acid C18H10N202. The depression constant of naphthalene was taken as 82 according to Raoulb. Action of Methyl Iodide on Tetramethyldihydropyridine. By F. ANDERLINI (Ber. 22 250d-f251l).-Pentamethyldihydro- py r i din e h y d riod i il e is obtained w h en t e trame t hy Id i hy d rop y rid in e (b. p. 158") is treated with methyl iodide (compare Cilimician and Anderlini Abstr. 1889 728) The free base boils at 188-190" (45-46" ; 7 mm.). A bnse C12H?,N is formed when pentamethyldihydropyridine is treated with niethyl iodide in the cold and the resulting oily hy- driodide distilled with potash; the base was not isolated.The uu?-ochZoride CI2Hz1N,HAuCl4 crystallises in thin golden needles melting a t 99-99.5". F. S. K. F. S. K. Synthesis of Oxypyridine and Piperidine Bases. By A. Lau~xsunc; (Ber. 22 2583-2590) .-a-Picolylalkins is obtained as a thick brown syrup by the action of formaldehyde on a-picoline and is purified by distillation under 20-30 mm. pressure. It is a colourless syrup boils at 179" nnder 25 mm. pressure dissolves readily in water and alcohol sparingly in ether i t is rather hygroscopic and can only be dried over fused potassium carbonate ; sp. gc". 1.111 a t 0". Theplcitinochloride (C7H9NO),,H,PtCl crystallises well in pristiis very readily soluble in hot water and melts a t 170" with effervesceuce.The aurochioride crpstallises in well- formed crystals rather sparingly soluble iii water. Vi,t ylpyridirw C5NHI.C2HB prepared by distilling the above com- pound under higher pressure o r in preseiice of potash is a colourless mobile liquid very readily soluble in alcohol ether and chloroform &c. but only sparingly in water. It boils with decomposition a t 158-13:! at t.he ordinary pressure but distils without decomposition a t 79-82' under 29 mm. pressure ; sp. gr. = 0.9985 a t 0". The ylutinocldoride (C,H7N)?,H2PtCI6 crystallises in needles or large plates melts a t 174" with decomposition and is rather readily solutle in water. The chuimhloyide cadnzioiodide bismuth iodide and rnemwocll loride cryst,aI- lise well. a-YipecoZyZalTcine C,NHlo.CH2*CH2*OH obtained by the action of sodium and alcohol t)n picolylalkine is a colourless crystalline base Tvhich melts at 31-32' aiid boils at 225-228'.It is very hygro- scopic and is readily soiuble water alcohol and ether. It is a strong base and turns red litmus blue. The yZutinocltZorit?e (C,H,,NO),,H,PtCI crystallises in splendid large transparent crys- tals like gypsum and melts at 158". f 268 ABSTRACTS OF CHEMICAL PAPERS. a-Meth?/ZpipecolineaZX;ine C,NH,Me*CH,2*CH2*OH is formed when a-pipecolylalkine dissolved i n metlipl iodide is Lrmted with methyl iodide and sodium at the ordinary temperature. When the methyl iodide has disappeared the alcohol is evaporated the residue re- peatedly extracted with ether the base converted into the hydro- chloride and warmed slightly with sodium nitrite.The nitrosamine which separates is removed by ether. The hydrochloride is then treated with potash and the tertiary base is extracted with ether and dried with potash. The aurochloride is crystalline ; the plafino- chloride cadmioiodide and periodide were also prepared. Vin ylpipwidine C,NH,,;C,H (?) is obtained from pipecolylalkin by the method previously employed for the preparation of tropidine from tropine (Annalen 217 118). It is a colourless liquid boils a t 146-148" is readily soluble in water and has an odour of tropidine aiid coniine. The aurochloride and p i c m t e crjstallise well and are rather soluble in water. a-Picolyl~2ethylaIkine7 C5NH4*CE3*CHMe*OH is formed in a manner himilar to a-picolylalkine from a-picoline and acetaldehyde and is purified by means of the platinochloride. It is yellowish boils a t 176-181" under 18 mm.pressure and is readily soluble in water alcohol and chloroform sparingly in ether. The plrctinochlorz'de ( CRHl,NO)2,H2PtC16 crystallises from hot water in small plates which melt R t 189" with decomposition ; the auroohEoride crystallises well. a-Pipecolylmetl~ylalkit~e C,NH,,*CH,*CHMe*OH melts at 47" boils at 224-226" and is readily solnble in water alcohol and ether The platinochloride melts at 149". I n its properties the base resemhles conydrine with which it is isomeric. N. H. M. Hydroxymetadiazines (Hydrsxypyrimidines). By E. v. ME YE^^ (J. pr. Chem. [2 ],40 303-304) .-Amidomethyldiphenylmetadiazine (Abstr.1889 578) melts at 1G8" not 172" ; it can also be obtained by acting on a mixture of ethyl cyanide and phenyl cyanide with sodium o r sodium ethoxide. Hydroxymethyldiphenylmeta#diazine (loc. cit.) melts at 250" not 256" ; it can also be obtained by the condensation of benzamidine and ethyl methylbenzoylacetate. By heating it with alkaline potassium permanganate adding dilute hydrochloric acid to the colourlew solu- tion dissolving the precipitate in weak ammonia filtering and again precipitating with hydrochloric acid a hy droe ydiphenylmetadiazinecar- boxylic acid C P h < ~ ~ ~ ~ ~ C C O O H is obtained ; this crystallises from alcohol in beautiful pale-yellow prisms melting at 236" with evolution of carbonic anhydride. When heated in a diphenylamine bath at 250" until evolution of carbonic anhydride ceases it leaves a yellow crystalline residue mostly soluble in potash ; if the preci- pitate obtained by adding hydrochloric acid to this potash solution is digested with weak ammonia and crystallised from alcohol yellowish slender needles CI6Hl2NZO which melt a t 280.5" (uncorr.) are ob- tained. These appear to be identicad with Pinner's diphenylhydroxy- pyrimidine (Abstr. 1889 lOOS) which melts at 284".ORGANIC CHEYISTRT.69 N ='CEt Hydrozymethylefhylmet?~ ylmetadiazine CMeGN ,c (bH)>CMe is obtained from acetamidine and ethyl propionylpropionate ; it melts at 167*5" and is isomeric with the hydroxy-base of cyanmetthethine melting at 150" (Abstr. 1885,646). A. G. B. Pyrimidimes. By A. PIXNER (Rer. 22 2609-2626 ;.compare Abstr. 1889 1006) .-The formation of the pyrimidines appears to take place in three stages. Employing benzamidine and ethyl acetoacetate as examples these stages are as follows :- I. NHXPh-XH + COOEt*CH,-COMe = NH CPh*NH*C 0 *CH2*COMe + EtO H. The ethyloxalylacetylbenzamidine already described (Abstr. 1889 1009) is the first-stage product in the formation of phenylhydroxy- pyrimidinecarboxyiic acid and may be easily converted into the latter by the action of soda. The compound obtained at the same time and melting at 263" is phenyIhydroxypyvimidinecarboxytbenzamidine N<g[k@-$>C*CO*N H C Ph N H the benzamidine haviii g reacted with the second carboxyl-group of the acetoxalate. It is converted int,o the above carboxylic acid by the action of soda.As already noted (Zoc. cit.) the free acid melts with decGmposition at 247" ; carbonic anhydride being evolved and phenylhydroxypyrimidine is formed. When benzamidine and ethyl acetomalonate react on one another one carboxyl-group is separated and the same pyrimidine formed as is obtained from ethyl acetoacetate. When ethyl acetosuccinate benzamidine hydrochloride and sodium hydroxide or potassium carbonate are mixed together two compounds are obtained melting respectively at 1 7 8 O and 212". The former (m. p. 1 7 Sv> is ethyl pheny lmet IL y lh y drox yp yrimidirkeacetnt e - I t is easily soluble in alcohol ether and acetone sparingly in water and crystallises in needles. When saponified with soda it yields phen.y lmethglhydrox ypyrimidineacetic m i d which crystallises in needles melts a t 259" and is soluble in alcohol.The needles crystallising at 212" have the formula C11H,oN202 and are probably succinylbenzimide ?H2'Co >N.CPh:NH. This compound forms the principal product CH,.CO if caustic soda is used for liberating the benzamidine from its hydro- chloride in the reaction whilst if potassium carbonate is employed the pyrimidine is the chief product.70 ABSTRACTS OF CHEMICAL PAPERS. With ethyl acetylglutarate benzamidine yields etlbylphen yluz ethyl- h y droxyp yrimidine~r~p~ona t e C P h q N N:C(OH)/ - '' eW2 C H,*C H,. C 0 0 E t which crystallises in needles is soluble in alcohol ether and acetone and melts a t 145". The.free acid forms a white powder almost in- soluble in water and alcohol and melting a t 215".When ethyl diacetosuccinate is mixed with benznmidine ethyl phe~iylmethylhydroxypyrimidineacetate (m . p. 178") and phenyl- met h y 1 ace tony l h y droa yp yrimidine C P he" 6 gy>C. CH,G OM e are formed. The latter is insoluble in acet,one soluble in alcohol ; it crvstallises in needles and melts at 225". The author was uuable to obtain the dipyrimidine C P h ~ N ~ c ~ o H ~ ~ - C ~ c I C H ~ ~ ~ CMe - N - CMe which he had anticipated the second' aceiyl-group appearing alwajs to be separated before the pyrimidine formation set in. A mixture of ethyl succinylsuccinnte and benznmidine yields a sub- stance easily soliible in alcohol and melting at 272" and another almost insoluble in the usual solvents. The fornier. tetra7~i/dl.owhe?.uZ- .I 1 .I ?~ycirox~ketopui?kasdine ~:C(oH)'f?CHz*~Hz crystallises in needles. CPh Pr'*C'CH,-CO The latter owing t o its insolubilit'y could not be thoroughly purified but appears to have the formula C,H,,N4O2 and to be dihydrocli- ~:C(OH)*~.CH,*$*N = CPh It dis- plieny ldih y clrox yantetrazine CPh=N*C*CH,.C*C(OH):N solves in boiling caustic soda yielding a crystalline sodiz~nz-deri.cat.iz;e C,,H,,Na,N,O + 4Hz0. The amidine of acetonecyanhydrin OH.CMe2*C (gH,):NH yields with e thy1 a cetoa cetate hydroxyisoprop y lmrfh ylhy d ~ o x y p yrimiditie OH.C?ile,.C~,:,(,,~~CH N-CMe crystallising in easily soluble needles and meltingat 98". If ethyl benzoylacetate is employed instead of the ace t oacet a t e h y droxy isoprop y @ heny lhy &ox yp y rimidine is formed. This crystallises in small glistening prisms sparingly soluble in water easily so in the usual organic solvents and melts at 198".L. T. T. Phenylhydrazonelevulinic Anhydride. By F. ACH (Annale?? 253 44-57). Two compounds are formed by the action of phos- phorus pentachloride on phenylhydrazonelevulinic anhydride a t 150. One contains 2 atoms of hydrogen less than the anhydride and the second compound is a monochloro-substitution-product of the first. The crude product of the reaction is poured into water containing ice. In the course of 24 hours phenylmethylchloropyridazone is deposited in crystals. The mother-liquor is rendered alkaline and treated with ether to extract the phenylrnethylpyridazone. The residue is redis- solved in 100 parts of boiling water to which a small quantity ofORGANIC CHEMISTRY.71 hydrochloric acid is added. On cooling the chloro-substitution-pro- duct crystallises out and the base is extracted from the mother-liquor as before. It is finally purified by precipitation as the hydrochloride by passing dry hydrogen chloride through its solution in benzene. NPh-N Phen?lEmeth?/~~yridazone CO< CH:CH>CMe is freely soluble iu alcohol ether chloroform benzene and acetone melts at 81-82' and has feeble basic properties ; its salts are decomposed by water. By the action of sodium on the hot alcoholic solution a crystalline base is produced which appears to have the composition C2,H,,N ; this melts at 200" and yields a sparingly soluble platinochloride. The solution in dilute sulphuric acid acquires a violet-blue colour on the addition of chromic or nitrous acid.Phenylmethylchloro/iyridazone C 0 < ~ ~ ~ ~ ~ > C M e crystallises ill flat prisms and melts at 136-137". I t is freely soluble in hot alcohol chloroform benzene and acetone and also dissolves in mineral acids but is reprecipitated unaltered from the acid solutions by water. The nitro-derivative melts at 210-213". The chlorine is displaced by ethoxyl by the action of alcoholic potassium hydroxide. PhenylmethyZathoxypyridazone melts at 14ti0 crystallises in flat prisms or plates and dissolves freely in hot alcohol benzene chloroform acetone and in hot water and is also soluble in strong acids. It is decomposed by heating at 125" in sealed tubes with hydrochloric acid yielding phenyZnzethyLhydroxypyyidazone.The hydroxy-derivative crystallises in needles and melts at 196". It is soluble in hot acetone benzene and chloroform in strong mineral acids and in alkalis. The addition of ferric chloride to the hydrochloric acid solution produces a red-brown coloration which turns to carmine on dilution. At 170" hydrochloric acid converts the hydroxy-componnd into phenyrnethyl- pyrazolecarboaylic acid I I >C*COOH. The acid is soluble in hot. alcohol chloroform benzene ether and in strong mineral acids C MeCH N-NPh melts at 165-166" and decomposes at 200" yielding phenylmethyl- pyrazole >CH probably identical with the phenylmethyl- Me*CH N-NPh pyrazole described by Knorr (Abstr. 1887 601). Phenylmethylpyrazole me1t.s at 34-36" and boils at 254-255" under 753 mm.pressure. It dissolves freely in ether alcohol chloro- form acetone benzene and light petroleum. The platinochloride forms orange-coloured needle-s haped crystals sparingly soluble in water. The pyrazole is convertled into the pyrazoline by the action of sodium on its alcoholic solntion. The pyrazoline melts at 73-75" and distils without decomposition. It is soluble in ether alcohol and benzene and gives the characteristic pyrazoline-colour reaction with ferric chloride or chromic acid. w. c. w. Synthesis of Quinazoline-derivatives. By C. PAAL and 31. BUSCH (Ber. 22 2683-2702) .-The authors have studied the action of orthonitrobenzyl chloride on the sodium-derivatives of form-52 ABSTRACTS OF CEEhlICAL PAPERS. anilide and of scetanilide and of some of their homologues.The met- nnilides did not give satisfactory results but with the fornianilides the following reactions (where R is an aromatic radicle) take place :- N0,-C6H4*CH2C1 + R-NNaaCOH = N0,.CsH4~CHz*NR~COH. On reduction the product yields quinazoline-derivatives Action of Orthonitrobenzyl Chloride on Sodium Formanilide.-Sodiuin formanilide is prepared by adding sodium to a benzene solution of form- anilide and then a proportional quantity of orthonitrobenzyl chloride is added. Orthonitrobenzy Iformanilide NOz.C6H4*CH,*NPh*COH is soluble in the usual organic solvents insoluble in water. It melts at i 7 " and forms yellow monosymmetric plates gixing the measure- ments a b c = 0.5477 1 1.085 and l3 = 69" 7'. This formanilide was also obtained by boiling ort~honitrohenzylaniline (Lellmann and Stickel Abstr.1886 793) with formic acid. When reduced with zinc and acetic or. hydrochlonic acid phenyldihydropuinuzoline C6H4<CH2.hph is formed ; this crystallises in hexagonal plates is N=CH almost insoluble in water and alkalis easily soluble in mineral acids alcohol ether &c. It melts at 95" and distils at a very high tem- perature with partial decomposition. When distilled with zinc-dust i t yields equal quantities of aniline and benzonitrile. Its sulphate ( Cl4H,,N,),,H,SO4 + 2Hz0 crystallises from water in needles loses water at 70" and melts at 79"; when free from water i t melts a t 140-143" ; the hydrochloride + 'LH,O forms glistening needles melting a t 80" ; the anhydrous salt melts at 221" and is easily soluble i n alcohol and ether.The pZatin.ochZoride forms yellow crystals me1 ting a t 208" ; the aurochloride orange scales ; the sfunnochlol-ide ( ',4HlzN,,HSnC13 flat white needles or scales melting a t 130-134". When heated with methyl iodide in closed tubes at loo" the quinazoline yields three derivatives the methiodide periodide Cl4Hl2NZMeI,I forming glistening golden-yellow scales melting at 157" ; the meth- iodide C14H12N2,Mel crystallising in white needles melting a t 170" ; and a third substance crystallising in prisms melting a t l80" which appears to be a second isomeric rnethiodide. When oxidised with potassium permangmate the quinazoline yields phenyllietodihydro- YH which crystdlises in almost colourless quinazoline C&< glistening scales or well-formed rhombic crystals giving the measure- ments a b c = 2.4228 1 3.2742.It melts at 139" and sublimes without decomposition. No hydroxylamine-derivative or phenyl- hydraaide could be obtained but with hydrazine (amidogen) it yields >C<&,; this forms y heny lketoh?y drazodihy dro quinazoline white glistening needles which melt at 204" and in small quantities siiblime without decomposition. The hydrochloride Cl4H,,NZO,HCl crystallises in glistening scales and melts at 213-214" ; it loses its CO*NPh' NH H*NPh N- CeH,OHGAXIC CHEJJISTRY. 73 hydrogen chloride ah a moderate heat. The platinochloride crystal- lises in yellow needles melting above 300". When the keto-base is t,reated in alcoholic solution with sodium phen yltetrahydroq.uinazolir~e c,H,< CH,.&Ph is formed which is soluble in organic solvents cyystallises in white needles melts at 117" and distils at a high tem- perature without decomposition.It is only feebly basic its salts decomposirig on the addition of water. It yields a hydrochloride a crystalline aceto-derit,atice and 8 nitrosamine. An unstable inter- mediate product containing the (CH-OH) group appears to be formed along with the tetrahydro-componnd but it could not be isolated When oxidised with permanganate the tetrahydro-derivative is recon- verted into the keto-compound but both here and in the original formation of the keto-derivative small quantities of a sparingly soluble nitrogenous crystalline compound melting at 219" are formed. Actiosn of Orthonits.obenzy1 Chloride on Sodium Formqmrato1uide.- The reactions here are similar to those with formanilide.Ortho- ?&itl'oI)enzy~ornzopas.a,tolziide N02*C6&*CH2*N (CaH,Me)*COH crys- tallises in pale yellow needles melting a t 79" and is easily soluble in the usual organic solventls. It may also be easily prepared from orthonitrobenzylparatoluidine (Lellniann and Stickel Zoc. &t.). Yura- NH. CH AT- c1U I.( - w II t oZy ldih ydropuinazoline C6H4 < cH?.& C6H,Me 7 is easily soluble iii alcohol ether benzene and chloroform sparingly so in light pet8roleurn. It crystallises in glistening white scales melts at 120" and distils with partial decomposition. Distilled witn zinc-dust. it yields the amine and nitrile like the phenyl-derivative. The hydrochloride with 2 mols.H20 forms flat white needles and melts at 85" the anhydrous salt at 251" ; the platinoch loride forms glistening yellow needles melting a t 216" ; the stannochloride sparingly soluble needles melting a t 165". Methyl iodide forms two derivatives namely the methiodide crystallis- ing in white needles melting a t 186" and green metallic needles which appear to be the methiodide periodide. On oxidation the base yields which crystal- iuaratolylketodihydropuiizazoliiLe C,H,< CO.k*CsH,Me' lises in micaceous needles sparingly soluble in boiling water easily in organic solvents and melting at 146". The hydrochloride forms white needles melting at 213-214" and is dissociated by slight rise in teni- perature ; the pltztinochloride forms golden yellow scales melting above 300".By oxidation pralietediii ydrop,LLinazolylbenzoic acid P is produced as well as the above quinazo- line; the acid forms white crystals sparingly soluble in organic solvents and melting at 320". The silver salt torms a white flocculent precipitate. Yarntoyltetrahydropuinazoline crystallises in white needles melts at 127" and is easily soluble in chloroform and benzene sparingly in ether and alcohol. It forms a red nitrosamine a white unstable hydro- chloride and a yellow unstable platinochloride. Action oj* Orthonitrobenzyl Chloride o n Sodiumformo-orthoto1uide.- The reactions are similar to those with the isomeric para-compouud. N I C H K F H C6H~<co~N.CaN,~COOH74 ABSTRACTS OF CHEMICAL PAPERS. Orthonitrobenzylformo-orthotoluids forms a Sellow oil which melt,s at 'i69 and decomposes on distillation.Orthotolyldi?iydroyuinazoline forms a yellow amorphous mass its platinochloride orange-yellow needles me1 ting at 210" and its stannochloride and hydrochloride could not be obtained in a crystalline form. When reduced in alco- holic solution with sodium the base appears t,o yield the tetrahydro- derivative but this was not obtained in a pure state. L. T. T. Hydrastine. By W. KERSTEIN (Chem. Centr. 1889 ii 91 from Zeit. Naturwiss. Halle 61 425-429).-According to the author's experiments hydrastine obtained from the root of Hydrastis cuncc- densis has the formula C21H2,N06 and forms colourless needles melt- ing at 132". The hydrochloride C21H,lN06,HCl and hydrobromide C H,,NO HBr are white micro-crystallire salts ; the hydriodide is two wnish- y el lo w.In addition to those reactions already described showing the rela- tion which exists between hydrastine and narcotiue the author finds that by oxidation with potassium permanganate in acid solution opianic acid and probably also cotarnine are formed. When dis- tilled in a current of steam niecotiine and trimethylamine are formed in the case of both these alkaloi'ds. On the other hand they do not show any similarity in their behaviour towards acetic anhydride acetic chloride water under pressure or dilute sulphuric acid. From hydrastine ethiodide by the action of potassium hydroxide solution ethylhydrlnstine is obtained ; it forms lemon-yellow crgstals which melt at 127". By the action of iodine hydrastine is split up into opianic acid and hydrastonine ; the latter is distivguished from tarconine methiodide in tha,t no formaldehyde is formed on boiling its icdide 31 hydroxide with barium hydi-oxide. In addition from the root of H?/drastis canndensis the author has separated phytosterin C,,H,O + H,O ; this forms plates melting a t 13:3" the solution of which in acetic anhydride gives a red coloration passing into intense blue with concentrated sulphuric acid.J. W. L. Formation of Optically Active Tropic Acids and Optically Active Atropines. By A. LADENBURG and C. HUNDT (Ber. 22 2 5 ~ ~ 2 5 9 2 ) .-A dilute aqueous alcoholic solution of quinine (1 mol.) was added to a hot aqueous solution of tropic acid (ni. p. 116-1 18- 1 mol.) and the whole evaporated down on a water-bath until crystal- lisation commenced. On cooling a quantity of dull white crystals separated (quinine dextrotropate) and on further evaporation of the mother-liquor an oil separated which gradually solidified to hard cyystals of a glassy lustre (quinine kevotropate). Quinine dextrotropate melts a t 186-187".The free acid cryst allises from ether in hard clear prisms and from water in clear plates melts a t 127-128" and showed a rotatory power of 71.4". Quinine Zcevotyopate was not obtained quite pure ; i t melts a t 178" The free acid which was also not obtained pure melted at 123" and showsd a rotatory power of 65-15'.ORGANIC CEEMTSTRY. 75 When treated with tropine and tropic acid (Aiznalen 206 274) both acids yield the corresponding atropines. Deztro-atropine cqstallises from alcohol in white lustrous needles melts a t 110-lll" and has a rotatory power of + 10".The auro- c h l w i d e forms dull deep-yellow crystals melting a t 146-147". Lcmo-atropiua is a crystalline powder melting a t 111". The auro- chloride crystallises in lustrous needles and melts a t 246". The base resembles hyoscyamine but the two are not identical which is due to the fact that the latter base has two active asymmetrical carbon- atoms whilst the former has only one. N. H 31. Bases contained in the young Shoots of Solanum Tubero- sum. By R. FIRBAS (ilfonafsh. 10 541-56O).-The two products the one crystalline and the other amorphous obtained in the prepara- tion of solanine from the young shoots of the potato are now shown contrary to earlier views not to be chemically identical.The author names the crystalline compound solanine. It has the formula C52H,sN0,s,4&H,0 and when dried a t 100" appears to be anhydrous or t o contain only half a molecule of water of crystullisation. From a solution in 85 per cent. alcohol it crystallises in coloiirless needles which melt a t 244" are almost insoluble in ether and alcohol and are readily dissolved by dilute hydrochloric acid. Xolanidine hydro- chloride 3(C4,H6,N02,Hc1)Hcl + H,O or l&H?O is obtained by boiling solanine with a 2 per cent. solution of hydrochloric acid. It is a slightly yellow powder which is only very sparingly soluble in water and carbonises without melting when heated to 287". Simul- taneously with solanidine hydrochloride. a sugar is formed in accord- ance with the equation C52Ev3N0,8 = C40H6,N02 + BC6H1,0s + 4H20.The amorphous substance obtained simultaneously with solanine and which the author names solaiLeine has when dried a t loo" the formula C53Hs7N013 or C5,H,NOl3. The loss of weight on heating the air-dried compound a t 100" corresponds with the formula C,,H,,KO + 3 i or 4H,O. It is a yellow horny perfectly amorphons substance melting a t 208" is more soluble in an 85 per cent. solution of alcohol than is solanine and on treatment with hydroctloric acid yields solanidine and a sugar in accordance with the equation C52H83N013 + H,O = C4,H6,N0 + 2C6HI2O6. The sugar obtained by the hydrolysis of solanine and solanaine forms a yellow amorphous mass with a caramel-like odour dissolves readily in water and wood-spirit and has a specific rotatory power of [z]D = + 28.6%.With phenylhydrazine hydrochloride and sodium acetate in aqueous solution i t forms a glucosazone melting at 199" and resembling the compounds obtained similarly from dextrose levulose and several other sugars. With nitric acid it gives no recog- nisable trace of mucic or saccharic acids. The general behaviour of the sugar points to the conclusion that it is some other sugar than dextrose or a mixture of sugars. Solunidine has the formula C4,,H61N0 or C4,H&N02 and is obtained from alcoholic solution in amorphous masses interspersed with needles melting a t 191". It dissolves readily in hot alcohol with difficulty in76 ABSTRACTS OF CHEMICAL PAPERS. ether and on treatment with excess of dilute sulphuric acid forms a sulphate 3(C40H6,N02,H~SO~),H,s0 + 8H20 ; this crystallises in scaly plates melting at 247” and is readily soluble in water.Its diacetyl-derivative CmH5,02NAc2 crystallises in needles melting at 203”. G. T. M. Cinnarnylcocaine from Coca Leaves. By C. LTEBERNANN (Ber. 22 2661-2662) .-Measurements of crystals and quantitative decomposition determications are given to show that the cinnamyl- coea’ine which t>he author prepared synthetically from ecgonine is identical with t h a t obtained by Giesel horn the coca leaf. L. T. T. Haematoporphyrin and Bilirubin. By If. v. NENCKI and A. ROTSCHY (Monatsh. 10 568-573 ; compare Abstr. 1858 304 and 971) .-The authors suggest that Raoult’s method may be employed with advantage to determine the molecular weights of unstable substances of organic origin and have investigated the practicability of the method in two cases.Making use of acetic acid and phenol as solvents hzematoporphyrin gave numbers varying bet ween 226 and 331 which correspond with the simple formula C,6H,eN20 (mol. wt. = 286). I n the case of bilirubin ethylene dibromide and phenol were used RS solvents. This compound has the same molecnlar formula and is consequently isomeric with hzematoporphyrin. The range in the numbers obtained in both cases is due to the compounds being only slightly dissolved by the solvents employed. The iso- merism of haematoporphyrin and bilirubrin is confirmed by the fact that on reduction with tin and hydrochloric acid two different urobilins are obtained.G. T. 31.20 ARSTHACTS OF CEEMICAL PAPERS.Organic Chemistry.Tetrabromides of Diallyl. By G. CIAMICIAR and F. ANDERLINI(Bey. 22 2497-!2500).-A small quantity of an oily bromide,C6H1,,Br1 is formed in preparing diallyl tetrabromide (m. p. 63") bytreating the hydrocarbon with bromine ; when the crude product iscrystallised from alcohol the liquid bromide remains in solution. Itboils at 135-140" (about 8 mm.) with slight decomposition and itsmolecular weight determined by Raoult's method in benzene solu-tion was found to be 325 as the average of two experiments.?-Pen tyleneglycol and its An'hydride (Tetrahydromethyl-furfuran). By A. LIPP (Bey. 22 2567-2573).-y-PentylenegIycol(Freer and Perkin Trans. 1887 836) mixes in all proportions withwater alcohol and chloroibrm is rather sparingly soluble in ether inpresence of moisture and is insoluble in light petroleum.At -18" itis quite viscid. It boils at 219-220" (under 713mm. pressure) anddoes not decompose at 236". Sp. gr. = 1.0003 a t 0" (water at 0" = 1).When heated with 35-40 per cent. hydrobromic acid for one hour at loo" the anhydride is formed ; this boils at 77-7.9" ; sp. gr. = 0.8748a t 0" (water a t 0" = 1). It !is not changed when heated with watera t 200-210".y-Penty Zene dihrornide CHBrMe.CH2*CH2*CHzBr is obtained byheating the glycol or the anhydride with 3 to 4 parts of fuming hydro-bromic acid for three hours at 100". I t boils at 200-202'with partialdecomposition is insoluble in water readily soluble in alcohol ether,chloroform and carbon bisulphide.Action of Lead Peroxide on Organic Substances in AlkalineSolution.By M. GLASER and T. MORAWSKI (Jfonatsh. 10 57%-584).-When a mixture of glycerol (2 grams) sodium or potassiumhydroxide (5-10 grams) and lead peroxide ('25 grams) contained inwater (100 c.c.) is gently heated a vigorous evolution of hydrogenoccurs sodium or potassium formato being simultaneously formed,according to the equation C3Hs03 + 3 0 = H2 + SH*COOH.About 97 per cent. of the theoret cal quantity of formic acid isproduced.Under somewhat similar circumstances ethylene glycol also yieIdshydrogen and formic acid (yield about 60 per cent.) G2H6Oz + 2 0 =F. S. K.Ammonia is also withaut action on it at 200".N. 3. &IORQANIC CHEMISTRY. 22H + 2CH,O2.peroxide with polyhydric alcohols in alkaline solution.The,authors intend to study the behaviour of lendG.T. 31.Action of Ammoniacal Cupric Oxide on Carbon Compounds.By C. VINCEPT and DELACHAXAL (Conzpt. rend. 109 615 -616).-Pure sorbite is completely precipitated by ammoniacal cupric oxide,and hence cannot be separated from mmnilol by means of this reagent(compare Guignet Abstr. 1889 1133).Action of Cuprammonium Sulphate on Sorbite. ByC. E. GUIGNET (Coiiipt. rend. 109,645).-Cupr,zmmonium sulphate un-doubtedly precipitates sorbite (preceding abstract) but it precipi-tates mannitol more rapidly and by fractional precipit,ation the authorhas been able repeatedly to separate pure mannitol from liquids whichalso contained sorbite. C.H. l3.C. H. B.Sorbite. By C. VINCEXT and DELACHANAL (Conipt. rend. 109,676-679).-Sorbtte exists in the fruit of all the wsaceSe and espe-cially in pears cherries arid plnms which contain 0.7 to 0 8 per cent.When heated with concentrated hydriodic acid it yields /3-hexyliodide which boils at 16'7" undera pressure of 753 min. ; when heatedwith alcoholic potash i t yields /3-hexylene boiling a t 68.5 under apressure of 735 mm. and acetic and butyric acids when oxidised.90 C.C. of water and 35 grams of red phosphorus were graduallymixcd with 150 grams of iodine in a capacious retort 60 grams ofcrystallised sorbite was added and the mixture gently heated. Anenergetic reaction took place and /3- hexyl iodide was obtained inalmost theoretical quantity no resinous products being formed.Mannitol yields the same /3- hexyl iodide when treated wit,h hydriodicacid.When heated with acetic anhydride and a small quantity of zincchloride sorbite yields a hexacetate C6H,(OAc) which is obtainedas a very thick colourless syrup on washing the crude product withwater dissolving in ether and evaporating the filtered ethereal solu-tions.It follows from these results that the constitution of anhydroussorbite is c6&( OH),.C. H. BTransformation of Cane Sugar .*into Dextrose. By J. BOCK(Che:;i. Cedr. 1889 ii 30 from Oster-ungar. xeit. Zucker. h i d .L w d w . 18 194) .-Cherries which had been preserved by heatingwith a hot concentrated solution of cane-sugar and which hadkept perfectly sound during the winter were allowed to remain forfour or five days in a loosely covered dish when it was found thatthey were coatedwith a white crystalline mass which after separationand recrystallisation proved to be dextrose.Levulose was notfound. The exact circums tames under which this change took placecould not be determined. J. W. L.Raffinose. By BERTHELOT (Conzpt. r e d . 109 548-550).-Theordinary crystals of raflinose are generally regarde.1 as having th28 ABSTRACTS OF UHEMXCAL PAPERS.composition C,,H,,016 + 5H20 but rafliriose from cotton seed sepa-rates from dilute alcohol in the form of a syrup which graduallysolidifies to lamellar crystals which contain 6 mols. H,O and aredifferent from the ordinary crystals.The rotatory power of theirsolution is however the same as that of a solution of the ordinar;)-crystals.The aut,hor confirms Tollens' observat'ion that good beer yeast fer-nients raffinose completely but that weak yeast ferments only aboutone-third even after 48 hours zlthough during the same time it willcompletely ferment eaccharose and glucose. I t seems most probabletlint uiider these conditions raffinose splits up into glucose whichferments and either a saccharose which has a sinall reducing powerlike lactose or a mixture of two glucoses only one of which hasreducing power. C. H. B.By D. LOISEAU(C'ompt. 1-e7atZ. 109 614-615).-111 a sealed paper dated March 5th'1888 the author described the following results Raffinose is com-pletely fermented by low bcer yeast but with high beer yeast onlyabout one-third of the total possible alcohol is formed whilst thesolution has a reducing power equivalent to that of a quantity ofglucose equivalent t o the amount of raEnose which has been fey-mented.It is probable that 2 mols. of raffinose are converted into1 mol. of laevogyrnte glucose which always ferments and twice thequaiitity of a dextrogyrate compoiind which is not fermented by highyeast. Prolonged contact with acids converts this compound intoglucose which is completely fermented by both forms of yeast.This difference in behaviour wit,h raflinose may be used as a meansof distinguishing between high and low yeast (compare Berthelot,preceding abstract). C. H.B.Lactose. By E. W. T. JOKES (Analyst 14 81-83).-Havingobtained some very pure crystallised lactose the author has redeter-mined the specific rotatory power and cupric reduction. For a solu-tion of 5 grams of the crystals C,,H2,0 + H,O in 100 c.c. pi.('-pared hot and of sp. gr. 1018.6 at 15*5" the values obtained are :-Fermentation of Rafhose by Beer Yeast.For C,2H,,01,.60.5"54.6CUO x 0.5723 = C1ZHZZO1I.CuO x 0.6024 = ClzH2z0,1 + H20.The determinations were made by O'Sullivan's method the cuprousoxide being converted iuto cupric oxide by careful ignition andweighed.Lactose is not affected optically or in reducing power by heatingwith citric acid whilst cane sugar is completely inverted. Thecryst,als do not lose their water by 24 11oui*s' heating in a water-oven,bnt if dissolved in water and re-dried the anhydrous sugar is obtainedin a few hours.31. J. SORGANIC CHEMISTRY. 23Methylhydrazine. By G. v. BR~~NING (Annalen 253 5-14).-I n order to prepare methylhydrazine nitrosomethylcarbamide,NO-NMe-CONH is first obtained by adding the theoretical quantity ofsolid sodium nitrite to a solution of methylcarbamide nitrate mixed wif hpowdered ice. Not more tban 50 grams of methylcarbamide nitrateshould be used in each operation. The nitroso-compound forms small,yellow crystalline plates and melts at 123-124" with decomposition.It is soluble in hot water alcohol and ether. The aqueous solutionis decomposed by prolonged boiling. Methylhydrazine is prepared byadding zinc-dust (4 parts) in small quantities to the nitroso-compoundsuspended in water (6 parts) and acetic acid ( 2 i parts) ; the tempe-rature of the mixture must be kept between 5" and 15" and theoperation lasts two to three hours.The product is filtered; thefiltrate acidified with hydrochloric acid concentrated and the thickliquid boiled with 3 pwts of strong hydrochloric acid for 12 hoursin a flask provided with a reflux condenser in order to decompose thecarbamide; the well-cooled liquid is then mixed with an excess ofsodium hydroxide and distilled in a current of steam the distilla-tion being stopped as soon as the distillate ceases to reduce l-'ehling'ssolution. The distillate consists of an aqueous solution of methyl-hydraziiie ammonia and methylamine. The latter compounds areremoved by boiling the solution briskly for eight hours in a flask witha reflux condenser.The methylhydrazine is converted into the acidsulphate which is deposited on the addition of absolute alcohol to theconcentrated solution. The free base is obtained by decomposing aconcentrated solution of the sulphate with sodium hydroxide. Thelast traces of water are removed by treating the base with bariumoxide in sealed tubes at 100". Methylhydrazine NHMe*NH2 is acolourless mobile liquid fuming in damp air. It boils a t 87" (745 mm.),and is miscible in all. proportions with water alcohol and ether. It,strongly red iices Fehling's solution at the ordinary temperature andattacks cork caoutchouc and the skin. The acid s d p h u t e ,N,HJfe,H2SO4 forms long white needles.It melts a t 139.5" anddecomposes a t 182". Unlike the normal sulphate it is insoluble inalcohol. The hydrochloride is precipitated from its alcoholic solutionby ether. The picrate isdeposited from alcohol in yellow needle-shaped crystals and melts a t162" with decomposition. Methylseinicarbazide NH,*CO*N2H,Me,prepared by the action of potassium cyannte on methylhydrazinesulphate. crystallises in prismatic plates and melts at 113". It isfreely soluble in water and alcohol. 1Clethylphenylthiosemicarbazide,NHPh.CS*N,H2Me is formed by the action of phenylthiocarbimide onan aqueous solution of methylhydrazine. This compound is solublein water and alcohol and melts at 143"; the aqueous solution isdecomposed by mineral acids.Dibenzoy Zmethylhydrazine N,HMeBz,,is freely soluble in alcohol and in dilute alkalis ; it melts at 143" andcrystallises in colourless needles. Metlylpicraxide N,H,Me*C,H,(NO,),,is formed when an alcoholic solution of picryl chloride is added to asolution of the base. It crystallises in yellow plates melts a t 171"with decomposit]ion and is freelv soluble in alcohol and ether.OxnZyZd inaethyZhydraci?ze N,H,Me*C,O,*N,H,Me melts at 221" butThe oxalate is soluble in warm alcohol2 4 Al3STHACTS OF CHEMICAL PAPERY.it begins to sublime about 160". It is soluble in alcohol and reducesFehling's solution when gently warmed. The nitroso-derivativecrystallises in plates and melts at 147" with decomposition.Action of Methylhydrazine on Dialdehydes and Diketones.By K.KOHLRAUSCH (A.nii.aZen 253 15-24).-Methylphenylhydr-azine yeacts with berizile a t loo" yielding b e n z i Z e m e t h y l ~ h e ~ ~ ~ ~ Z h ~ d ~ r a x o ~ ~ e COPh.CPIi:K*NMel,h a crystalline substance freely soluble in alcohol,ether and light petroleum. It melts a t 5.5-56" and is completelydecomposed a t 200" ; it is also decomposed by strong hydrochloricacid a t the ordinary temperature. Benzilemethylphenyiosuzone,C,Ph,(N*NMePh) is formed when a mixture of benzile (1 mol.) andmethylphenylhydrazine ('2; niols.) is heated a t 120" ; the crudeproduct is treated with hot dilute sulphuric acid to remove the excessof base and the red crystalline mass which is deposited when themixture cools is purified by recrystallisation from alcohol.The puresubstance forlns yellow needles soluble in ether arid acetone melts a t1 7 ~ - 1 8 ~ " and is decomposed a t 220' ; it is not readily attacked bystrong hydiw hloric acid.Olyoxulrtteti~ylp;pherLyl.,scizolze C,H2(N*NMePh) is deposited as ayellow pi-ecipttat,e when an aqueous solution of glyoxal is added tonil acetic acid solution of niethylpheiiylhydrazine. It melts a t217-218" and is completely decomposed a t 250". This osazone doesuot give a characteristic coloration with ferric chloride.i sfreely soluble in ether.. It melts a t 103-104" and begins to decom-pose a t 2 10'. 1'.2'.3'-MethylplienylacetylilLclole is formed whenmethylpheiiylhydrazone is fused with zinc chloride. The indolemelts a t 136" arid dissolves freelyin glacial acetic acid.It is decom-posed by strong hydrochloric acid a t loo" yielding Degen's1'.2-methylplie1rylindole (Abstr. 1887 149).Acet!jlu,:etonem~t~~~ZplisiLylh~drazirL~ CHi?Ac.CMe:N*NePh is ayeliow oil which can be distilled in a vacuum without decomposition.The compound formed by the action of niethylphenylhydrazine onan excess of acetonylacetone could not be isolated as it undergoesspon tsrieous decomposition losing a molecule of water and changinginto the methylphenylamidodimethylpyrroline described by Knorr(Abstr. 1887 276).a c e t o n y l i c e t o . r L e m ~ t ~ ~ y l ~ ~ ~ e n ~ I l ~ ~ ~ i y d r a % o n e C2H4( CMe:NMePh) isdeposited in the form of an oil which slowly crystallises when anaqueous solution of acet,onylacetone is added to excess of metliyl-phenyl hydrazine dissolved in acetic acid.The crystals melt at143-144!" and dissolve in alcohol ether benzene and light petroleum.The diliydrazone dissolves also in hydrochloric acid ; when this solu-tioii is heated the preceding pyrroline-compound appears to beformed. w. c. w.w. c. w.Be 7 b zoy 1 ace t o ? A e rn e 1 IL y lp h my 1 hg d r az 011 e C H A c * C P h N * N Me P h ,Derivatives of Dichloromaleimide. By G. CIAMICIAN and p.SICBEE (Ber. 22 fL490-2497).-Chlorar1ilidomaleimide (m. p.195-196") is decomposed when heated a.bore its melting- point; it issoluble in ether and hot alcohol but only sparingly in boiling waterORGANIC CEEMISTRP. 25It dissolves in hot dilute sulphuric acid,.yielding a colourless solution,and in alcoholic solutions dimethylanilme produces a reddish-browncoloration.Chloramidomaleinzide C,C102(NH,) :NH is obtained in sinallquantity when dichloromaleirnide is he8 ted under pressure withexcess of alcoholic ammonia. It ci~ystallises from water in goldenneedles melts a t 280" and is soluble in alcohol and ether but insolublein benzene.It dissolves in alkalis with a yellow coloration but thesolution becomes colourless on heating.Dich ZoromuZewnic acid COOH-C,Cl,-CO-NH + H20 prepared byheating dichloromaleiniide (8 grams) with ammonia (80 c.c.) in sealedtubes separates from water in crystalline aggregates melts a t 175"with decomposition and is soluble in ether alcohol and warm water,but insoluble in benzene.The silver salt CaHC1,N0,Ag2 crystallisesin colourless needles and explodes when heated.An orange-red compound CuH,,N,O or C,,H,,N,O2 separates incrystals when dichloromaleimide is heated with phenylhydrazine inalcoholic solution. This substance crystallises from boiling acetoneor glacial acetic acid in orange-red needles melts at 269-271" withdecomposition and is only sparingly soluble i n most ordinary solvents.It dissolves in concentrated sulphuric acid with an intense redcoloration and on adding water an orange-red flocculent substance isprecipitated. P. S. K.BJ- E. BAUMANN and E. F n o m ( B e y . 22,2600-26~9).-P-Trithioaldel~yde (Klinper Abstr. 1879 780) is formedwhen hydrogen sulphide is passed through a mixture of aldehyde(1 part) with alcohol previously saturated with hydrogen chloride(3 parts) ; crystals soon separate and the whole becomes solid.Theproduct is washed with water and crystallised from alcohol fromwhich it separates in Iong needles melting a t 125-126". A smallamount of a-trithioaldehyde melting a t 101-102" is also formed aswell as a few crystals of a substance melting a t 76" possibly Marck-wald's y-derivative (Abstr. 1886 865).a-Trithioaldehyde is obtained as the chief product when eqiral partsof aldehyde water and strong hydrochloric acid are used. It crlstal-lises from acetone ill splendid prisms an inch long. The /%compoundis also formed.p-'l'hiobenzaldehyde and ythiobenzaldehyde are formed when hydro-gen sulphide is passed through a mixture of benzaldeb yde and alcoholichydrogen chloride.The product is boiled with benzene until almostall is dissolved; on cooling the @compound separates in crystalshaving the ComposiLion sc7H6s + c6H6 (not C7H,S 4- CsHc Klinger) ;this gives up all the benzene a t ItjO" and a portion when kept a t theordinary temperature for a long time.y-T~~iobenzuZdehy~e C7H6S crystallises from Senzene in small,pointed needles melting a t 166-167". The crystals contain nobenzene of crystallisation. When the solution in benzene is treatedwith iodine the whole solidifies after some time being converted intothe p-derivative.When a - or P-trithioaldehyds is oxidised with potassium perman-Thioaldehydes26 ABSTRACTS OF CHEXICAL PAPERS.ganate they both give as end-product a trisdphone C6Rl2S3O6,together with products containing less oxygen (compare Guareschi,Abstr.1884 294). This forms slender needles softens at 340",becoming yellow and sublimes a t a higher temperature without melt-ing. It is almost insoluble in water very sparingly soluble in alcohol,ether chloroform and benzene more soluble in hot acetic acid; italso dissolves readily in strong nitric or sulphuric acid but is pre-cipitated by water. Alkalis dissolve it readily and it can be crystal-lised from ammonia and alkaline carbonates. The constitution oftrithioaldehyde sulphone is S02<CHMe.SO:>CHMe. CHMe* S 0 When analcoholic alkaline solution of the substance is treated with methyliodide the compound CgH18S3O6 melting at 302" is formed.I n asimilar manner ethyl- allyl- and benzyl-groups may be added.N. H. M.Thio-derivatives of Ketones. By E. BAUMANN and E. FROMX( B e r . 22 2.592-2599 ; compare Abstr. 1889 852).-ThioacetoneCSMe is formed as a readily volatile oil in the preparation of tri-thioacetone and tetrathioacetone (Zoc. cit.) but was not isolated owingto it's instability and the difficulty of separating it from trithioacetone.It is also produced together with ethyl sulpliide and other sulphur-derivatives when acetone-ethylmercaptole CMe,(SEt) is heatedabove 160". Owing to the very unpleasant odour of the compound,which is stronger tIhan that of any other known substance thesmallest traces of it being sufficient to infect whole districts the studyof the compound was not continued.Trithioacetone is decomposed by strong nitric acid with explosiveviolence.A further examination of the sulphone obtained by oxidising tri-thioacetone with potassium permanganate (loo.cit.) showed that thiscould be separated by crystallisation from alcohol inho two substances.The more sparingly soluble compound triacetnnetrisulphone C9H,,S306,crystallises from glacial acetic acid in slender needles which melt at.302" (uncorr.) and sublime readily. The more readily soluble com-pound CsHl8SsO4 is probably tritlzioacetonedisu~lio~e ; it melts at208".Acetonetrisulphone is not changed by acids and alkalis; it dis-solves in strong acids and is precipitated by water unchanged.Boiling fuming nitric acid has no action on it.Its constitution isprobably CMe2<S02,.CMe:>S02.The compound CgHl,S304 dissolves in bromine pielding an unstablebromine-derivative which readily decomposes with evolution of hy-drogen bromide. When gently heated with fuming nitric acid,the compound is oxidised with formation of much sulphuric acid.Probably the substance has the constitution S<C&e:,so:>CMe2.SO *CMeCMe -SON. H. M.The Introduction of Acid Radicles into Ketone Molecules.By L. CLAISEN (BUZZ. Xoc. Chin&. [S] 1 496-510 ; compare Abstr.ORGANIC CHEMISTRY. 271888 666 671 676 and 1889 5S4 619 850).-B re'sume' of theauthor's already published work on this subject concluding with adiscussion as to the theory of the reactions.Substituted Acrylic and Propiolic Acids.By C. F. MARERYand A. W. S w r H (Ber. 22 2659-2660) .-When a,!%dichloracrylicacid is dissolved in carbon bisulphidc and chlorine passed throughthe solution whilst it is exposed to sunlight tetrachloroproyiolzic acid,C,HCl,-COOH gradually crystallisea out. It forms large rhombicprisms is soluble in carbon bisulphide chloroform and water andmelts a t 76". Its barium salt crystallises in prisms ; its ca1ciu.m saltin needles; its potassium salt in plates. Its silver salt is very un-stable,When ap-dichloracrylic acid is heated with hydrobromic acid inclosed tubes a t 110-120" bromodichloI.opro~ionic acid is formed. It issoluble in water and boiling carbon bisulpliide ci-ystallises in prisms,and melts at 75-76'.When an aqueous solution of bromopropiolic acid is mixed withhypochlorous acid and left.in the dark chlorobro.ulzhydroxyacrzJlic acid,C,(OH)ClBr.COOH is formed. It is easily soluble in boiling wa.ter,is crystalline and melts a t 104-105". I t s silaer salt is soluble innitric acid and is very unstable in aqueous solution.T. G. N.L. T. T.Action of Phosphorus Pentachloride on Chloralide. Tetra-chlorethylidene Trichlorolactate. By R. ANSCH~TZ and A. R.HASLAM (Annalen 253 121-131).-The compound of the composi-tion C,HC1,O3 which the authors obtained by the action of phos-phorus pentachloride on chloralide (Abstr. 1887 9151 proves to bethe tetrachlorethylidene trichlorolactate. It boils a t 276" withoutdecomposition. Nethyl and ethyl alcohol act on this compound atthe ordinary temperature yielding hydrogen chloride and the ethylor methyl salts of trichloracetic and trichlorolactic acids.Normalpropyl and isobutyl alcohols act less energetically than ethyl alcohol.Normalpropyl trichlorolactcrte boils at 115-11 7" under 12 mm. pressure,and at 248-250" under the ordinary atmospheric pressure. Itssp. gr. a t 20° compared with water a t 4" is 1.51628. Isobutyl tri-chZorolactate boils at 111-i12" under 12 mm. pressnre and at236-238" under the normal atmospheric pressure. I t s sp. gr. at 20"is 1.53216. The chloride is slowly decomposed by water yieldingtrichloracetic and trichlorolactic acids. These results indicate thatthe constitution of the chloride is represented by the formulaCC;l,*y (OH)coo- >CC1.CCl,."w. c.w.Derivatives of Ethyl Acetoacetate. By R. SCH~~NBRODT(AwnaZea 253 168-205).-Ethyl monochlor~~cetoacetate is formedby passing chlorine into ethyl cupracetoacetate suspended in chloro-form until the green colour of the compound changes to grey. Byt h e prolonged action of chlorine a dichloro-substit'ution-product isobtained. Analogous resalts are produced when bromine is usedinstead of chlorine ; the sthylic salts of mono- and di-bromacetoaceti28 ABSTRACTS OF CHEMICAL PAPERS.acid have been described by Duisberg (Annalen 213 152 and 143).E t h y l iodacetoacetate prepared by the action of iodine on ethyl cupr-acetoacetate is a yellow oil miscible with ether and alcohol. Thealcoholic solution gives a blood-red coloration with ferric chloride.The compound is unstable.I t decomposes at 25" in a vacuum and itssp. gr. at 1P" is 1.7053 compared with water at the same temperature.It is converted into ethyl monochloracetoacetate by the action ofsilver chloride but with silver cyanide it yields hydrogen cyanide andethyl succinosuccinate. The product of the action of silver nitrite onethyl iodacetoacetnte is a yellvw oil probably ethyl nitroacetoacetate.This substance gives an intense blood-red coloration with ferricchloride and strong snlphuric acid. It does noC yield an amido-com-pound on reduction with tin and hydrochloric acid nor does it form asolid compou'nd with hydroxylamine. It combines with phenylhydr-azine yieldingphenylmethylisonitrosopyrnzolone [ 1 3 4 51 describedby Knorr (AWr. 1887,602).The same compound is formed by theaction of phenylhydrazine on the ethylic salt of monochlor- brom-,or iod-acetate. The reaction may be represented as follows CsFi,C103Bender (Abstr. 1888 53) has shown that in the ethereal solution,phenylhydrazine and ethyl monochloracetoacetate yield the ethylicsalt of p-phenyl azocrotonate. The author confirms the accuracy of thisobservation.Ethyl sodacetoacetate reacts with ethyl iodacetoacetate yieldingethyl diwetosuccinate. Metallic silver eliminates the iodine fromethyl iodacetoacetate and forms the ethyl diacetofumarate describedby Just (Abstr. 1886 141). Ethyl thiacetoacetate first prepared byBuchka (Abshr. 188.5 1200) is formed by boiling sulphur in a solu-tion of ethyl cupracetoacetate in benzene. I n the presence of alcohol,phosphorus acts on ethyl cupracetoacetate forming ethyl acetoacetateand triethyl phosphite.Arsenic trichloride is reduced by the coppercompound arsenic being liberated and ethyl mnochlorncetoacetateformed. Ethyl cupracetoacetate is not attacked by cyanogen. but nitro-gen peroxide acts on it with formation of the nitro-compound whichis produced by the action of silvei. nitrite on ethyl iodoacetoacetate.Attempts to displace a hydrogematom by copper in ethyl mrth-ace toacetate were unsuccessful. w. c. w.+ SNHPh*NHZ = CloHgN302 + 2NHzPh + NHdC1 + C,H,*OH.Ethyl Thiacetoacetate. By I(. BUCHKA and C. SPRAGUE (Bey.,22 2.541-2556 ; compare Ruchka Abstr.1885 1200 ; Delisle,Abstr. 1887 915 ; and Schonbrodt preceding abstract) .-Ethyl thi-acetoacetate is best prepared by Delisle's method; 100 grams ofethyl acetoacetate yield 60-70 grams of pure ethyl thiacetoacetate.Molecular weight determiiiations by Raoult's method in glacial aceticacid solution showd that the molecular formnla was C,,H,,O,S.It melts at about 76" b u t the melting point observed depends to aconsiderable extent on tlie rapidity of heating and on other conditions.The sodium-derivative C,,H,,O,SN& is formed when ethyl thiaceto-acet,ate is treated with sodium in ethereal solution.When ethyl thiacetoacetate is treated with phenylhydrazine,hydrogen sulphide is evolved and phenylmethylpyrazolonsketvORGANIC CHEMISTRY. 29phenyl hydrazon e ( pheny lme thyl p yrazolonenzobenzei~e) melting at156O identical with the compound obtained by K n o x (Abstr.1887,601) is formed together with a yellow substance which is insoluble inall ordinary neutral solvents. The compound obtained by Schon-brodt (Zoc. cit.) by treating ethyl chloro- bronio- or iodo-acetoacetatewith phenylhydrazine is not phenylrnethylisonitrosopyrazolone asstated by him but is identical with the phenylmethylpyrazolone-ketophenylhydrazone referred to above.The yellow compound which is obtained together with phenyl-methg1pyrazoloncketophenylhydrazone (see above) when ethyl thi-acetoacetate is treated with phenylhydrazine is decomposed whenheated but without melting ; it dissolves in alkalis and is reprecipi-tated on adding acids.It seems to have the composition C,,H,N,Sc) ;when heated with phenplhydraeine it is converted into phenyl-methyl pyrazoloneketophenyl hydrazone with evolution of hydrogensulphide small quantities of di-phenylmethylpyrazolone being alsoformed.Para f olylmethy Ipyrazoloneketoparatolylhydrazone,is formed w'hen et'hyl thiacetoacetate is Created wiGth qaratalylhydr-azine ; it crystallises from chlorofrom in orange needles melting a t216-217". When excess of the hydrazine is employed in the abovereaction a compound free from sul i)hur and probably correspondingwith di-phenylmethylpyrazolone is also obtained. If only a small quan-tity of the hydrazine is used a sulphur compound which is onlysoluble in alkalis is formed ; .this substance is converted into tolyl-methylpyrazoloneketotolylhydraaone (im.p. 216-21 7") when heatedwith paratolylhydrazine and when heated with phenylhydmzine ityields a compound. probably tol.ylmethy1pyrazoloneketophenylhydr-azone which crystnllises i n rcd needles melting a t 1.86".E thyl %hiacetoacetate combines with a-naphthylhydrazine yieldingsimilar compounds. I?. S. K.Dithioxamide (Cyanogen DimLphydrate). By J. FORM~NEK(Ber. 22 2655-26569. When a saturated solution of cupric sul-phate is treatod with ammonia untiltthe precipitate first formed is justredissolved potassium cyanide added in quantity just sufficient todischarge the blue colonr and then a rapid stream of hydrogen chloridepassed through the solu+ion the latter becomes first yellow and thenred; and if it is kept well cooled small red crystals of the formulaNH,-CS*CS*NH gradually separate out.L. T. T.Hydroxycitraconic Acid and its Derivatives. By P. MELIKOFFand M. FELDMANN (Annalen 253,87-95 j.-In dilute solutions hypo-uhlorous acid unites with cibraconic acid to form chlorocitramalicacid which has been described by Morawski (this Journ. 1875 142),and by Gottlieb (Annalen 160,101 j. The acid prepared by Gottlieb'sprocess melts a t 139". It is converted into Morawski's hydroxycitra-conic acid by the addition of potessium hydroxide in alcoholic solution30 ABSTRACTS OF CHEMTCAL PAPERS.The precipitate of pot,assium chloride and hydroxycitrctconate i swashed with alcohol and ether. It is khen dissolved i n water thehydroxy-acid liberated by sulphuric acid and extracted with ether.The acid melts a t 162" as stated by Scherks (Abstr.1885,513). Theethyl salt C,EI,O(COOEt) has the sp. gr. of 1.1376 at 0" and 1.1167at 22" compared with water at the same temperatures.Hydroxycitraconic acid dissolves in strong hydrochloric acid a t 0" ;and ether extracts from this solution a monochlorinated hydroxy-acid,CUOH*CH( OH)*CClMe*COOH crystallising in rhombic plates whichis an isomeride of the acid formed by the union of hypochlorons acidand citraconic acid COOH.CMe(OH)*CHCl*COOH. This acidmelts a t 162" and forms unstable salts. The compound which isformed by the addition of hydrobromic acid to hydroxycitraconic acidhas already been described by Scherks (Zoc.cit.). Hydroxycit,raconicacid is a glycidic acid as it is converted into amidocitramalic acidby the action of alcoholic ammonia at 100". The amido-acid formsshort prisms which seem to belong to the monoclinic system; itreddens litmus and decomposes carbonates. 100 C.C. of water at 18"dissolve 31 grams of the acid. It is almost insoluble in hot alcohol.The calcium and barium salts are amorphous. The hjdrochloride,OH.CsH,( NH,) (COOH),,HCI forms transparent prisms soluble inwater and alcohol. It melts a t 100" with decomposition. w. c . w.Acetonediacetic or Hydrochelidonic Acid. By J. VOLHARD(AnnuZen 253,206-236) .-The dilsctone of discetic acid is preparedby maintaining succinic acid in a state of slow ebullition for six hours.When a small quantity of the contents of the retort no longersolidifies on cooling but remains as a greasy mass the operation iscomplete.The crude product is repeatedly extracted with boilingchloroform ; on cooling succinic anhydride is deposited in crystals andthe lactone remains in solution. The chloroform is removed bydistillation the residue dissolved in water and the lactone is ngaiiiextracted from this aqueous solution by chloroforni. The lactoneforms transp3rent rhombic prisms u b c = 0.3649 1 0.9816 freelysoluble in chloroform acetone ether alcohol benzene and ethylacetate. It melts a t 75" and boils between 200 and 205"under 15 mm.pressure. The lactone dissolves in alkalis and in strong hydrochloric orhydrobromic acid yielding acetonediacetic acid CO( CH,*CH,*COOH),,which is identical with the hgdrochelidoiiic acid of Liebenand Haitinger( Monatsh. 5 353) and with Marckmald's propiondicarboxylic acid(Abstr.1888 678)The acid forms rhombic plates soluble in hot water and in alcohol.It melts a t 143O and decomposes at a higher temperature. Thenormal salts of the alkali metals are very soluble in water and do notcr-j-st:~llise well. The acid potassium sodium and ammonium saltsare anhydrous. The barium salt crjstallises with 2 and with 2; mols.H,O. The manganese salt C,H,MnO + fLH,O forms pale pink needles.The zinc and cadmium salts crjstallise in six-sided plates containing2 mols. H20. The silver salt C7H8Ag?03 is crjstalline and insoluble iORUANIC CHEMXSTRY. 31water.The dimethyl salt melts at 56' and boils with decompositionat 276-277" (uncorr.). The sp. gr. of the diethyl salt is 1.0862 at 13".Acetic chloride acetic anhydride and phosphoric anhydride convertthe acid into the lactone. The phenylhgdrazide of acetonediacetic acidmelts at 107 -108". The phenylhydrazide of the dimethyl salt meltsa t 88-90' and dissolves in ether benzene and hot alcohol. Thecorresponding diethyl compound melts at 67". The oximeof the acidcrystallises in prisms and melts with decomposition at 129". Theoximes of the dimethyl and diethyl salts form needles and melt at 52"and 38' respectively. w. c. w.Alkyl-derivatives of Methyluracil and Nitrourscil. BJ- R.BEHREKD (Annalen 253,65-68).-Ethyl bromide does not react w i t hfree methyluracil but it acts on potassium methylurscil forming mono-methyluracil and dimethyluracil.I t is probable that monethylmethyl-uracil is first formed. A portion of the monethylmethyluracil reactswith potassium methyluracil formingpotassium monethylmethyluracil.This is attacked by ethyl bromide yielding diethylmethyluracil.In a previous communication the author stated that methyl iodideacts on potassium methyluracil yielding trimethyluracil and thedihydride of methyluracil ; he now finds that the supposed dihydrideis identical with the dimethyluracil described by Hoffmann (nextAbstract). w. c. w.Alkyl-derivatives of Methyluracil. By J. HOFFMANN (Annalen,253 68-77).-Ethyl methyluracil and diethylmethyluracil areformed by the action of ethyl bromide or iodide (3 mols.) on potassiummethyluracil (1 mol.) in sealed tubes at 150; the excess of ethylbromide or iodide is removed from the crude product by distillation,the residue is dissolved in water and the aqueous solution treatedwith chloroform.The chloroform extract is then dried and distilled andthe residue dissolved in boiling alcohol ; on cooling crystals of ethyl-methyluracil are deposited. The mother-liquor contains monethyl- ariddiethyl-methyluracil. The former is deposited as a crystalline crust,but the diethyl-derivative can only be isolated by dropping a crystalof diethylmethyluracil into the mother-liquor when crystallisationtakes place. fithylmethyZuraci1 is deposited from ethyl bromide inprisms and from alcohol in needles.It is freely soluble in chloroformand in ethyl bromide and is much more soluble in hot than in coldalcohol. A crystalline silver salt C,H,E tAgN20z is obtained whensilver nitrate is added in sufficient quantity to produce a permanentturbidity t o a solution of ethylmethyluracil in a 10 per cent. solutionof potassium hydr0xid.e. Diethylnaetl/y Zz~racil crystallises in rhombicplates and melts at 52-53" dissolves freely in chloroform alcohol,ether and water and is decomposed by potassium hydroxide at theordinary temperature with liberation of ethylamine. Methjl bromideacts on potassium methyluracil at 140" forming dimethyluracil and tri-methyluracil. !Z'~*imethylz~raciZ melts at lo>" crystallises in rbombicplates and is freely soluble in chloroform alcohol and water aridsparingly soluble i n ether.Di~niethyluracii is insoluble in ether but ca32 ABSTRACTS OF CHEMICAL PAPERS.be reerystallised from hot alcohol. Methyluracil di-iodide C,H,N,O,I isformed by the action of iodine dissolved in strong hydriodic acid onmethyluracil. It is an unstable compound dissolvinq with decompo-sition in water alcohol and chloroform. The di-iodide furms deepNitrouracil-derivatives. By M. LEHMANN (Annalen 253,77-87).-Meth~lZnifrozcracil C,H,N30 + H20 is formed by theaction of methyl iodide on potassium nitrolnracil in sealed tubes a t140". It crystallises in long needles and is soluble in hot water.100 C.C. of water a t 20" dissolve 0.714 gram and 100 C.C. of alcohola t 17" dissolve 0.115 gram of the substance.It is less soluble inether chlorofsm benzene and methyl iodide than in water. Thepotassium silver and barium salts are crystalline; the silver andbarium salts me almost insoluble in cold water. Methylisobarbitiiricacid C5H6N203 is deposited in crystals when methplnitrouracil isrediiced by tin and hydrochloric acid ; the mother-liquor containsmethylamidoucacil in small quantiky. A neu,tral solution of methyl-amidouracil hydrochloride turns red on the addition of potassiumcyanate ; the d o u r is destroyed by hydrochioric acid and methylhy-droxyxanthine C6H8N403 is deposited a s a yellow crystalline powder.100 C.C. of water a t 16" dissolve .0*16 gram of rnethylhydroxyxan-thine. Methylnitrouracil i s decomposed by baryta-water a t 160-1 70",with liberation of methylamine ; dimethylnitrouracil under similartreatment yields dimethylamine.Dimethylnitrouracil melts at 154.5"and is deposited from hot water in needles eontairling 9 mol. H20.It does not unite with bases to form salts. The constitntion ofmethyl- and dimethyl-nitrouracil can be represented by the formulae,C o < ~ ~ e - ~ ~ NH'cH >C*NO and C O < ~ ~ ~ ~ ~ > C . S O . Methyhitro-methyluracil prepared by the action of methyl iodide on potassiumnitromethyluracil crystallises in needles and melts a t 149". Itunites with bases forming c r p t a lline salts. E t h y7nit rouracil,C,H,N304 + H,O forms silky needles and melts at 194.5 ; it is de-posited from alcohol in anhydrous crystals and is soluble in hotwater ether chloroform benzene and ethyl bromide.The potassiumand silver salts crystalhe in needles.Ethylisobarbituric acid C,H,N,O melts at 250" but begins todecompose at 230". It is soluble m hot but almost insoluble in coldviolet crystals. w. c. w.water. Ethylhdroz yxanthine crystallises in prisms which turn pinkon exposure to the air. Etl~lllrnethy Znitrouracil CO<N~e.CO>C.N02 NFtCHcrystallises from hot water in needles containing 1 mol. H,O. Thecrystals effloresce ; it melts at 109". itl;.thyleth~lnit,.ouracil,CO<NEt.Co >C*SO melts at 73" and crystallises in rhonibohedra,containing 1 mol. H20. The substance becomes anhydrous a t go',and remains liquid a t the ordinary temperature but solidifies on theaddition of water.NMe-CHI t is freely soluble in alcohol and ether.w. c. wORGANIC CHEMISTRY. 33FUCUSO~. By MAQUENNE (Compt. rend. 109 571-573).-DriedFucus vesiculosus was heated in an oil-bath at 160" with 4.5 parts ofsulphuric acid of 20" B and the product after neutralisntion wasdistilled and fractionated. Small quantities of water and acetonewere obtained together with two fractions boiling a t 162-163" and185-187" respectively. The fraction 162-163" consists of pure fur-furaldehyde the fraction 185 - 187" is methyIfurf.~raldehyde aliquid of sp. gr. 1.105 at 15". With ammonia it yields a crystallineproduct closely resembling furfuramide ; its hydrazone is an oilyliquid ; with silver oxide i t yields methylpyromucic acid melting at108-109".When treated with hydriodic acid it resinifies but doesnot carbonise and does not become green ; the product yields iodo-form when mixed with potassium hydroxide. With acetic anhydridein presence of fused sodium acetate it yields methylfurfuracrylicacid melting a t 157" and crystallising from boiling water or alcoholin small white needles which retain aboilt Q mol. H20. If methylfur-furaldehyde is heated with strong hydrochloric acid it becomes green,a reaction which Stenhouse observed with fucusol. The followingreaction serves to detect methylfurfuraldehyde in presence of a largeproportion of furfuraldehyde. One drop of the liquid is dissolved i n5-6 C.C. of alcohol of 90" and 1 C.C. of sulphuric acid of 60" is addedslowly without agitation; a green coloration appears at the junctionof the two liquids.The coloration persists even after agitation ifthe methylfurfuraldehyde is abundant but changes to grey if furfur-aldehyde is in excess. The reaction is similai- to that given by heptine(or its oxidation-products) from perseitol.This methylfurfuraldehyde is identical with that obtained by Hillfrom wood tar.Fucnsol is not a distinct compound as Stenhouse supposed but isa mixture of furfuraldehyde with about. 10 per cent. of methylfurfur-aldehyde. C. H. B.Relation between Sugars and Furfuran-derivatives. ByMAQUENNE (Compt. rend. 109 603-606) .-Methylfnrfnraldehydefrom Fucus (preceding Abstr.) yields acetic acid on oxidation andhence contains a terminal methyl-group and is one of the threeisomerides which contain the methyl-group in the position 2 3 or 4with respect to the aldehyde group.It has the same relation t80 isodul-citol or rliamnope C6HI2O6 m furfuraldehyde has to arabinose C5H,,05.Crystallised isodulcitol distilled with four times its weight of sul-phuric acid of 15 to 20" B yields a small quantity of acetone togetberwith pure methylfurfuraldehyde identicltl with that from Fucus cesi-cutosus or wood tar but no furfuraldehyde is obtained. Fischerand Tafel have shown that isodulcitol is an aldehyde derived fromnormal bexane and according to Herzig it yields acetic acid on oxida-tion and hence contains a terminal methyl-group. Its conversioninto methylfurfuraldehyde would involve the union of the chains2 and 5 by means of an atom of oxygen the methyl-group occupyingthe Position 4.thus :- AVOL. LVIII. L34 ABSTRACTS OF OHEMICAL PAPERS.Since furfuraldehyde is obtained from arabinose by dehydration,it follows that isodulcitol is w-methylarabinose a relation which hasoften been suggested but has never previously been established,The yield of methylfurfuraldehyde from isodulcitol is small but itsuffices to detect the isodulcitol in substances in which its presence isnot recognised by the usual methods and i t has been detected inseveral plants in which it was not known to exist. Since Fucus vesicu-losus yields methylf urfurddehyde (Zoc. cit.) it would seem that isodul-citol exists in marine plants.Selenium and Oxygen-derivatives in the Benzene Series.By C.CHABRII~ (Compt. rend. 109 568-570).-The action of nitricacid on phenyl eelenide (Abstr. 1889 1167) yields nitro-derivatives ;potassium permanganate or chromic acid yields indefinite oxidation-products ; hydrogen peroxide and hydrochloric acid yield compoundsin which oxygen has been introduced into the phenyl-group.The action of selenious chloride SeOCI on benzene in presence ofaluminium chloride yields two compounds according to the proportionsof the reacting bodies. Diphenylselenone SeOPh is an amber-yellowliquid which boils at 230" under a pressure of 65 mm. ; sp. gr. a t19.6 = 1.48. The other product PhSeO*C6HICl crystallises in white,hexagonal prismatic lamellse with a fatty lustre ; it melts at 94" boilsat 230" under a pressure of a few millimetres is insoluble in water,but dissolves in alcohol and is attacked by cold nitric acid.Diphenylselenine when treated with bromine water yields the corn-pound SeO( C6H4Br).? which crystallises from alcohol in modifiedrhombic prisms melting a t 1'20".When mixed with hydrogenperoxide and hydrochloric acid and treated with a current ofair diphenylselenine yields the compound SeO (c6HIc1)2 orPh SeO*C6H,C12 which crystallises from boiling alcohol in small,white prisms melts at 159" and is not attacked by cold nitricacid.The action of the compound Se(OH)&I2 on benzene in presence ofaluminium chloride yields diphenylselenine and selenophenol.Action of Phosphorus Trichloride on Phenol. By R.ANSCH~TZ and W. 0.EMERY (Amer. C'hem. J. 11. 379-38i).-By theaction of phosphorus trichloride on phenol the following three com-pounds were formed (compare Noack Abstr. 1883 735) and wereseparated by distillation under greatly diminished pressure :-Phenylphosphoryl dichloride PCl,-OPh ; sp. gr. 1.35412 at 20" (waterat 4" = I) ; boiling a t 90' under 11 mm. pressure ; diphenyZphosphoryZchloride PCl(OPh) ; sp. gr. 1,24378 a t 20" (water at 4" = 1) ; boil-ing at 172" under 11 mm. pressure ; tripheriyl p h o p h i t e P(OPh) ;sp. gr. 1.18428 at 20" (water at 4" = 1) ; boiling at 220" under 11 mm.pressure.The action of phosphorus pentachloride on the preceding com-pounds was investigated. In the cold no action takes place; at100" crystalline compounds are formed soluble in chloroform andcarbon tetrachloride.Chlorine additive-products were almost cer-tainty formed but they could not be isolated ; they were however,C. H. B.C. H. BORGANIC CHEMISTRY. 35obtained by passing dry chlorine over solutions of the phosphorouscompounds in dry ether. Phenylphosphoryl tetrachloride PCl,*OPh,prepared from chlorine and phenylphosphoryl dicbloride forms smallplates soluble in chloroform and carbon tetrachloride insoluble inether ; it is deliquescent and is decomposed by water normal phenylpbosphate being formed. With sulphurous anhydride i t behaves likethe corresponding phosphenyl compound giving thionyl chloride andthe oxychloride POCl,-OPh boiling a t 121-122" under 11 mm.pressure. Diphenylphosphoryl trichloride PCl,(OPIi) formed fromchlorine and diphenylphosphoryl chloride is a yellow oil solidifyingto minute crystals soluble in chloroform insoluble in ether; it easilytlecomposes when heated and also when treated with water in whichcase phenyl phosphate is formed.Tt.~p~ie~zyll?li~~pla~j~yZ dichluride,PC1,( OPh) prepared from chlorine and phenyl phosphite solidifirsa t a very low temperature ; when treated with water it decomposesinto phenyl phosphate and hydrochloric acid.By the addition of dry bromine to etliereal solutions of the monn-and di-chlorides the compounds PC12Br2*OPh and PClBr,(OPh),were obtained ; these are very unstable substances.Phenylphosphrvl thiochloride PSC12*OPh was obtained by heatingphenylphosphoryl dichloride with sulphur at 190" ; it has a sp.gr. of1.40393 at 20" (water at 4" = I) boils at l19-i20° under 11 mm.pressure and is a highly refractive liquid soluble in ether and chloro-form. DipTien!il~jhosplioryl thiochzoride PSC1( OPh) prepared fromdiphenylphosphoryl chloride and sulphur heated aat 190" ; melts a t63-64" and boils at 194" under 11 mm. pressure. Attempts toobtain the preceding two compounds by heating togeiher phenol andphosphorus thiochloride were unsuccessful hydrogen chloride andnormal phenyl phosphate being formed. Tr+hen yl thiophosphate,PS( OPh) was obtained by heating phenyl phosphite with sulphur at190" ; it forms crystalline needles melting at 49-50" and boiling at245" under 11 mmpressure; sp. gr. = 1.24411 at 20" (water at 4" = I).It is found that these thio-compounds have very nearly the samemelting points and boiling points as the correspondiiig oxy-com-pounds.The existence of the compound PC14*OPh leads to the followingview of the action of phosphorus pentachloride on hydroxj-com-pounds :-R-OH + PC1 = HC1 + RO*PC14 and RO-YCI = POCl + RC1.C. B.B.Apiole. By G. CIAMICIAN and P. SILBER (Bey. 22 2482-2490;compare Abstr. 1888 Ilc;O).-The authors give the name apionole tothe tetrahydroxybenzene which forms the basis of apiole ; the dimethylether of tetrahydroxybenzene is therefore dimethylapionole and'' apiorie " is dimethylmetbyleneapionole,Dimethylapionole C6Hz(0H),(OMe)2 is obtained when apiolic acid(2.5 grams) is heated at 180" for 4 to 6 hours with potash (8 gramP)and alcohol (10 c.c.).l uaqueous solutions ferrous sulphate produces after some time a bluecoloration lead acetate a gelatinous precipitate ai:d silver nitid e aIt melts a t 105-106" and boils at 298".d 36 ABSTRACTS OF CHEMICAL PAPERS.crystalline precipitate which immediately turns black. It dissolvesin concen hated sulphuric acid yielding a yellow solution whichquickly turns red and on warming becomes violet. The diacetyl-derivative C6H2(OMe),( crystallises from alcohol melts a t144' and is soluble in ether warm alcohol and glacial acetic acid,but only sparingly in hot and insoluble in cold water. It dissolvesin warm concentrated sulphuric acid yielding a colourless solution,which turns yellow and then brown on heating more strongly.Tetramethy lapioriole C6H2 ( OMe)4 prepared by treating the di-methyl-derivative with methyl iodide in methyl alcoholic potashsolution crystallises from hot water in colourless needles melts at 81",and is readily soluble in alcohol ether benzene acetone and aceticacid but only sparingly in water.It dissolves in concentrated sul-phuric acid yielding a colourless solution which turns brownish-redon warming and in concentrated nitric acid with a yellow coloration.It is not acted on by hydrochloric acid a t loo" but at higher tem-peratures it is decomposed with evolution of methyl chloride.Apioneacry Eic acid CH2:O2:C6H( OMe) ,*CH C H *C 0 0 H prepared byboiling apiolaldehyde with acetic anhydride and sodium acetate crystal-lisea from hot alcohol in small jellow needles melts at 196" and isreadily soluble in hot glacial acetic acid benzene and alcohol but onlysparingly in ether and hot water and almost insoluble in cold water. Itdissolves i n concentrated sulphuric acid with a yellow coloration thesolution turning brown on warming.The sodium salt crystallises inmicroscopic needles and is readily soluble in water; in an aqueoussolution of the sodium salt lead acetate barium chloride calciumchloride or zinc sulphate produces a colourless nickel nitrate or coppersulphate a green cobalt nitrate a red silver nitrate a light yellow,and ferric chloride a reddish-brown precipitate.Apionecrotonic acid C Hz 0, CGH (OMe),*C H C Me-C 0 OH preparedfrom apiolaldehy de in like manner crystallises from alcohol in lightyellow needles melts at 209" and is almost insoluble in water butsoluble in ether hot alcohol and hot acetic acid.It dissolves in cnn-centrated sulphuric acid with a yellow coloration the solution turningbluish-green on warming. The sodium salt is readily soluble inwater. The calcizim salt (C13H,306)2Ca + 5H20 crystallises from hotwater in broad colourless needles and loses iCs water a t 100". Thesilver salt C13H13@6Ag is colourless and very sparingly soluble inwater. In aqueous solutions of the sodium saIt barium chloFide,magnesium sulphate or zinc sulphate produces a white. crystallineprecipitate arid solutions of copper nickel cobalt and ferric salt8 alsogive a precipitation. When the calcium salt is distilled with lime asmall quantity of a crystalline compound melting a t 83" is obtained.When calcium apiolate is distilled with lime it yields a mixture ofsubstances some of which are volatile with steam ; the non-volatileresidue crystallises from alcohol in needles melts a t 71-72' andseems to hare the composition C,H,O,.The nitro-compound (m.p. 117-118*) previously described (loc.cit.) and obtained by treating apiolic acid with nitric acid of sp. gr.1.4 in glacial acetic acid solution has the composition C,H,N,O notC9H8N20 as previously given arid is probably dinitrapioneORGANIC CHEIIJSTRY. 37The nitro-compound (m. p. 116O) prepared from isapiole byGinsberg (Abstr. 18F8 722) is probably identical with dinit'rapione,and the compound (m.p. 137-138") obtained by the authors fromapiolaldehyde is probably st nitro-derivative of apiolaldehyde.Chlorination and Bromination of Aniline Orthotoluidine ,and Paratoluidine in presence of Excess of a Mineral Acid.By R. HAFNER (Ber. 22 2524+-2541).-When chlorine is passedinto an ice-cold solution of aniline in excess of 97 per cent. sul-phuric acid for about 18 hours almost the whole of the anilineremains unchanged only small quantities of parachloraniline beingformed. Under the same conditions but employing 65 per cent. sul-phuric acid symmetrical trichloraniline (rn. p. 77") traces of a com-pound melting a t 63-64" probably trichlorophenol (m. p. 67-68'),and considerable quantities of resinous products are formed but alarge quantity of aniline remains unchanged.Chlorine acts energetic-ally on aniline in 40 per cent. ice-cold sulphuric acid solution ; theprincipal product is trichloraniline but trichlorophenol resinousproducts and traces of other compounds probably chloraniline anddichloraniline are also formed.When chlorine is passed into an ice-cold solution of aniline inexcess of very concentrated (40 per cent.) hydrochloric acid for about18 hours most of the base is converted into parachloraniline and tri-chloraniline but considerable quantities remain unchanged. Tri-chloraniline is also formed when chlorine (6 mol.) is passed into asolution of aniline (1 mol.) in ice-cold concentrated hydrochloricacid. In 30 per cent. ice-cold hydrochloric acid solution chlorineacts on aniline much more readily ; parachloraniline dichloraniline,symmetrical trichloraniline and other compounds probably chloro-derivatives of phenol are formed and none of the base remainsUnchanged.I n 20 per cent. hydrochloric acid solution under thesame conditions trichloraniline chlorophenols and large quantities ofresinous products 'itre formed.Bromine even when added in large excess has no appreciarbleaction on aniline in 97 per cent. sulphuric acid solution ; after fourmonths' time only small quantities of symmetrical tribromaniline areformed. If a small quantity of iodine is mixed with the bromine,the formation of tribromaniline takes place rather more readily. Tn65 per cent. and i n 40 per cent. ice-cold snlphuric acid solution,aniline is acted on by excess of bromine considerable quantities of tri-bromaniline being formed ; in the latter case small quantities of acompound probably tribromophenol are also formed.When anilineis treated with excess of bromine in 40 per cent. hydrochloric acidsolution a reaction immediately takes place and the whole of thebase is converted into tribromaniline ; in 20 per cent. hydrochloricacid solution small quantities of tri bromophenol are also formed.Aniline hydrobromide is completely converted into tribromanilinewhen treated with excess of bromine in a concentrated ice-cold soh-tion of potassium bromide ; the yield of the pure product is 90 percent. of the theoretical quantity.Wheu chlorine is passed into an ice-cold 97 per cent.sulphuric acidF. S . I(38 ABSTRACTS OF CHEMICAL PAPERS.solution of paratoluidine for about 24 hours metacliloroparatoluirline[Xe C1 NH = 1 3 41 and larger quantities of orthochloropara-toluidine [Me C1 NH = 1 2 41 are obtained but a consider-able quantity of the base remains unchanged. In 40 per cent. hydro-chloric acid solution the whole of the paratoluidine enters intoreaction yielding metachloroparatoluidine metadichloroparatolnidine[Me Cl NH = 1 3 5 41 a crystalline compound probablyorthochloroparatoluidine and oily products probably chlorinated de-rivatives of cyesol.When pal-atoluicfine is treated with excess of bromine in 39 percent. ice-cold hydrochloric acid solution it is almost. completely con-verted in to met adibromoparaholui din e me 1 t ing a t 73 - 74" very smallqiinntities of a bromocresol being also produced.I n 65 per cent.sulphuric acid solution under the same conditions large quantit,ies ofmetadibromoparatoluidine are formed.When orthotoluidine is treated with excess of chlorine in 913 percent. ice-cold sulphuric acid solution it is partially converted into achlorotoluidine ; bromine under the same conditions has no appre-ciable action even after eight days' time.Action of Nascent Nitrous Acid on varims Amines andPhenols. By A. DENINGER (J.pr. Chem. [el 407296-308).-Whensodium nitrite ( 3 mols.) acts on an aqueous acid solution of aniline,ortho- and para-nitrophenol and some resinous su bstarices are pro-duced in quantities dependent on the concentration acidity andtemperature.The qaantity of orthonitrophenol produced is greater,the more rapid the reaction and the higher the temperature above65" ; i t varies from 0 to 50 grams whilst that of paranitrophenol variesfrom 0 to 33 grams per 100 grams of aniline. Air blown through theliquid diminishes the quantity of phenols produced as also does thepresence of oxidising or reducing substances. The nature of the acidhas no apparent effect. To obtain the best yield 10 grams of aniline,20 C.C. of sulphuric acid and 80 C.C. of water are mixed and cooled to15" ; 300 grams of sodium nitrite in 100 C.C. of water are then added,the solution heated in w water-bath and a large quantity of hot dilutesulphuric acid (1 1) immediately added.Alter the reaction theortho-compound is distilled over with steam and thc para-compoundcrystallised from the residue. Nitric oxide alone appears to be evolvedduring the reaction.If orthotoluidine (10 grams) be substitued for aniline in the aboveprocess orthonitrocresol [Me OH NO = 1 2 31 (5to6 grams),melting a t 68-69' is obtained. By using a more dilute solutionand allowing it t o stand for 14 days at 15-2b" paranitrocresol[Me OH NO = 1 '2 51 melting a t 96' is obtained. Withparatoluidine (100 grams) only one nitrocrcsol (138 grams) meltinga t 33-34" is obtainable.By acting on diamidoparadiphenyl and diamidoparadit)olyl respec-tively with sodium nitrite (6 mols.) in the way described above,dinitrodiphenol (m. p.260") and dinitrodicresol (m. p. 270') are pro-duced respectively.The subhate of diamidodicresol (dbstr. 1588 838) obtained byF. S. KORQANIC CHEMISTRY. 39reducing the dinitrocresol is sparingly soluble in water ; by diazo-tising it and decomposing with hot sulphuric acid tetrahydroxyditolylis obtained as a pleasant-smelling oil which is volatile with steam ;its aqueous solution gives a y ellowish-white precipitate with ferricchloride.With naph thylamine the above treatment yields dinitronaphtholand a little nitronaphthol ; when a-naphthylamine is treated with2 mols. more sodium nitrite than is necessary for diazotising anddistilled at once with steam P-nitro-+naphthol (m.p. 128") is ob-tained ; but i€ allowed to stand for 14 days at 10-15" a-nitro-a-naphthol is formed./3-naphthylamine yields a-nitro-@-naphthol(m. p. 103").Sulphanilic and orthotoluidinesulphonic acids yield by this treat-ment garnet-red crystals which lose the sulphonic acid group whentreated with super-heated steam and yield nitrophenol and nitro-cresol respectively. Naphthionic acid yields nitronaphtholsulphonicacid.Salicylic acid and its ethereal salts yield nitrosalicylic acid and itsethereal salts.A new substance is obtained when paraphenolsulphonic acid istreated with sodium nitrite and sulphuric acid ; it is still under in-vestigation. A. Q. R.Some Nitrated Diazoamido-compounds. Ry S. NIEMEN-TOWSKI (Ber. 22 2562-2567).-When metanitraniline is diazotisedin the manner described by Sandmeyer for paranitraniline (Abstr.,1885 981) a resinous precipitate is formed the moment the sodiumnitrite solution is added This can be afterwards separated from themetanitrobenzonitrile by steam distillation.It crystallises from amylalcohol in lustrous golden needles which melt a t 191-1'32"with decomposition. It has the formula C,,H,N504 and is identicalwith Griess' metadiazoamidonitrobenzene (m. p. 195.5 AnnaZen,121 2i2) and with Hallmann's dinitroamidoazobenzene (m. p.175-176" Ber. 9 389). I n order to determine the constitution ofthe compound a qustntit'y of it was prepared by Hallmann's method ;the substance prepared by this method when crystallised from amylalcohol also gave the m. p. 195". When the compound is heatedwith hydrochloric acid (sp.gr. = 1.17) for 10 hours at 185' meta-chloronitrohenzene is formed. Amy1 alcohol decomposes it at 185"with formation of metanitraniline and nitrobenzene. These reactionsand the behaviour of the substance towards aromatic amines andphenols with which it yields dyes show that the compound is diazo-amidonitrobenzene. Hallmnnn's method (Zoc. cit.) is a very con-venient one for the preparation of nitrated diazoamido-corn-ponnds.DiuzoamidonitrotoZuene CI4H,,N,O4 (from metanitroparatoluidine) isprepared by treating metanitroparatoluidine (m. p. 114" 30.4 grams),suspended in alcohol (250 grams) with nitric acid (sp. gr. 1.52,7.5 grams) and with a saturated solution of potassium nitrite(8.5 grams). It crystallises from am371 alcohol in dark reddish-brownbranched needles melts ah 169 dissolves very sparingly in alcohol40 ABSTRACTS OF CHEJIICAL PAPERS.more readily in ether and carbon bisulphide and very easily incold benzene acetone aiid chlorofwm.When heated with alcohola t 1 70° it is decomposed into metanitroparatoluidine and metanitro-toluene.Diazoanzido?zitroto?zcene (from paranitro-orthotoluidine m. p. 107")crystallises from alcohol in long bright pellow needles melts at 212"with decomposition and is readily soluble in acetone benzene andchloroform. N. H. 31.Trinitrohydrazobenzene. By E. FISCHER (Annulen 253.1-5).-The author's process for preparing trinitrohydrazobenzene frompicryl chloride and phenylhydrazine has been criticised by Willgerodtand Ferko (Abstr. 1888 830). In reply the author maintains thatthe process yields good results if the necessary conditions are observed.Symmetrical Nitrophenylhydrazines of the Aromatic Series.By C.W ILLGEEOUT ( J . pr. Cliem. [2] 40 264-270).-SSymmetricalpicrylhydrazines are obtained by cohabating picryl chloride and thehydrochloride of the aromatic hydrazine (in molecular proportion)in alcohol a t the ordinary temperature. Picrylphenylhydrazine,picr!j 1 ort hotoly 1 hydruzin e y icry lparatoly hydrazine and picryl -a-naph-thyEhydrazine have been thus obtained.All these decompose before they melt a t temperatures dependenton their state of division ; tbus picrylphenylhjdrazine in powderdecomposes a t 177" whereas its crystals decompose at 181" (compareAbstr. 1888 829).T1.e author has studied the action of heat on the nitrophenyl-hydrazines in presence of various liquids and finds that the decom-positions which occur may be classified as follows :-(l.)- The liquiddoes not decompose the nitrohydrazineperse; in this case the hydrazinehydrogen reduces the nitro-group to 8 nitroso-group ; such liquidsare water dilute hydrocliloric acid benzene and glacial acetic acid.(8.) The liquid is an oxidising agent ; the nitrobydrazine is oxidisedto a nitroazo-compound.(3.) The liquid decomposes the nitro-hydrazine altogether. (4.) The liquid acts as a reducing agent suchliquids being ethyl and methyl alcohols formic acid and acetone ; thefirst two and acetone convert picrylhydrazine into dinitrosonitroazo-benzene melting a t 219-220" ; formic acid converts it into a mixtureof two substances melting a t 225" and 233".(5.) The liquid is anorganic base ; in this case the nitrohydrazine is first converted intonit ro-nitroso-azo-compounds and these into polyazo-con1 pounds.The paper conclnde,s with a reply to Freund (Abstr. 1889,977) whccriticises the author's and Ferko's former work (Abstr. 1888 829).A. G. B.w. c. w.Phenylhydrazone. By E. FISCHER and F. ACH (Annnlen 253,5 7-65) .-Acetor?Rdi?Litroplienylhydrazone CBHIONIOI is prepared byslowly adding acetonephenjlhydraeone (12 grams) to strong colour-less nitric acid (25 grams) Rurrounded by a freezing mixture ; thissolution is allowed to drop into 100 grams of well-cooled f u z i n gnitric acid and the mixture is poured into ice water ; the product iORQANIC CHEMISTRY.41extracted with small quantities of ether and the residue purified byrecrystallisation from alcohol. It melts a t 127" (uncorr.) is solublein benzene chloroform ether and in hot alcohol and is quicklydecomposed by hot alkaline solutions b u t less readily by acids.Phenylhydrazonelevulinic anhydride is converted into the paranitro-derivative N02*C6H4*N<,~,CH2>CH2. by fuming nitric acid. Thissnbstance crystallises in flat needles of a yellow colour is soluble inhot alcohol benzene and glacial acetic acid and melts a t 118-119".The alcoholic solution is converted into paraphenylenediamineby reduction with zinc-dust and acetic acid. Warm alcoholic potas-sium hydroxide or warm concentrated hydrochloric acid convertsthe anhydride into paranitrophenylhydrazonelevulinic acid,NO2.C6H4.NH.N :C Me*C2H4*C 0 0 H.This acid forms orange-colouredneedles soluble in acetone and hof alcohol; i t also dissolves inalkalis forming intense deep-red solutions. It darkens a t 190' andmelts with decomposition a t 200". The ethyl salt melts at 156-157"with slight decomposition. It crystitllises in needles and dissolvesfreely in hot alcohol benzene and glacial acetic acid.The hydrazones of acetone and of acetaldehyde propaldehyde andoenanthaldehjde are decomposed by gently warming with pyruvicacid ; acetone or aldehyde is liberated and phenylhy drazonepyruvicacid is produced. The ketones and y-ketonic acids behave in thesame way.Paranitropli,enyl?zydrmon ep yruvic acid N0,*C6H4*NH*N:CMe-C 0 OH,is precipitated when pyruvic acid is added to a hot dilute solution ofnitrophenylhydrazonelevulinic acid in hydrochloric acid.The acidis soluble in acetone and in warm alcohol and is decomposed by heat.N ' CMew. c. w.Amidoximes and Azoximes. By F. TIEMANN (Ber. 22 2391-2395 ; compare Abst. 1886 875).-The conversion of nitriles intoamidoximes by the action of hydroxylamine may be considered to bea general reaction a s hitherto it has been found to apply to all cases,except that of nitriles such as pentamethylbenzonitrile which cannotbe or are only with difficulty converted into the' correspondingacid by the usual reagents. As a rule the formation of the amid-oxime takes place much more slowly with nitriles of high molecularweight and rich in carbon and the acid character of the product isless marked.The amidoximes combine readily with hydrogen cyanate phenyl-carbimide and phenylthiocarbimide yielding uramidoximes phenyl-uramidoximes and phenylthinramidoximes.The ethyl-derivativesof the amidoximes also combine with phenylthiocarbimide aud withphenylcarbimide. F. S. K.Phenylallenylamidoxime-derivatives. By H. WOLFF (Rer.,22 2395-240 1 ; compare Abstr. 1886 798) .-Phenylallenylethoxirnenitrite CHPh:CH*C(N*OEt)-O*NO separates in colourless needleswhen a solution of phenylallenylamidethoxime (1 mol.) in dilutesulphuric acid is treated with sodium nitrite (2 mols.) in the cold48 ABSTRACTS OF CHEMICAL PAPERS.It turns yellow after a short time and is very unstable explodingalightly when treated with concentrated sulphuric acid or wbenheated quickly.It melts at 61" is readily soluble in alcohol chloro-form benzene and ether but only sparingly in light petroleum andalmost inPoluble in water. I t can be crystallised from alcohol a ttemperatures below 55" but slight decomposition occurs. It isdecomposed b y acids or alkalis yielding cinnamic acid. The chloride,CHPh:CH.CCl:N*OEt separates as a yellowish oil when the amid-ethoxime is dissolved in excess of hydrochloric acid and the solutiontreated with sodium nitrite. It is soluble in ether alcohol benzene,and chloroform but only sparingly soluble in light petroleum andcarbon bisulphide and almost insoluble in water; it is not decom-posed when warmed for a short time with acids or bases.Phen y 1 dibromoprop eny lethoxime chloride C HBrP h- CHBr C CKN* OE t ,prepared hy warming the chloride with a slight excess of bromine isa solid compound readily soluble in ether benzene and chloroform,but only sparingly in light petroleum and insoluble in water.Pheny la1 len y Ipheny luramidet Iioxime,CHPh:CH*C (NOE t)*NH*CO*NBPh,obtained by treating phenylallenylamidethoxime with phenylcarb-imide crystallises from dilute alcohol in colourless needles melts a t155-156" and is readily soluble in alcohol ether benzene andchloroform but only sparingly in light petroleum hot water andhydrochloric acid and insoluble in potash and cold water.Phenylalleruy lp h enyluramidoxime,CHPh:CH*C (NO H)*NH*CO*NHPh,prepared in like manner from phenylallenylamidoxime crystallisesfrom dilute alcohol in colourless needles melts a t 158-159" and isreadily soluble in ether but only moderately so in benzene andchloroform sparingly in light petroleum and insoluble in coldwater ; i t is only very sparingly soluble in acids and alkalis.Pheny 1 all eny luramidoxim e C H Ph CH*C (PU'OH) *NHX 0 -NH sepa-rates in colourless needles when an aqueous solution of phenylallenyl-amidoxime hydrochloride is treated with potassium cyanate ; it meltsa t 158-159" and is readily soluble in alcohol and ether but onlymoderately in benzene and chloroform and sparingly in light petro-leum and cold water.It forms salts with acids and dissolvesunchanged in alkalis but when treated with concentrated acids oralkalis a t the ordinary temperature it is reconverted into the amid-oxime.The platinoch7oride ( C,,HllN,O,),,H,PtC1 is crjstalline.E t h y l pJ~ei~ylallenylainidoximecarboxylu te,CH Ph C €3- C (N H,) :N.O-CO OE t,is obtained together with the hydrochloride of the amidoxime whenphenylallenylamidoxime (2 mols.) is treated with ethyl chlorocarb-onate ( I mol.) in benzene solution. It is a crystalline unstablecompound melts at 101" and is readily soluble in erher alcohol,chloroform and benzene but only sparingly in light petroleum andinsoluble in waterORGANIC CHEJlISTRY. 43Phen~lallen~lcarbonyli.nzidoxime CHPh:CH*C<gzg> is formedwhen the preceding compound is warmed with alkalis or heatedabove its melting point.It crystallises from dilute alcohol in slenderneedles melts a t 199-2200" and is readily soluble in alcohol ether,benzene and chloroform but only sparingly in light petroleum and isinsoluble in cold water. It has an acid reaction and in neutral solu-tions of the ammonium-derivative silver nitrate produces a white,and copper sulphate a green precipitate. F. S. K.Substituted Amidoximes. By H. M ~ L L E R (Ber. 22 2401-2412 ; compare Abstr. 1€W 875) .-Benzenylphenylcarbonylimid-oxime melting a t 166-1 67" is formed together with benzjlanil-idoxime hydrochloride when benzenylanilidoxime is treated withcarbonyl chloride in benzene solution.Benzenylanilidoxime combines with chloral in the cold forming acolourless flocculent compound NHPh.CPh:NOH,C,C130H whichmelts a t 128-130" is readily soluble in alcohol ether chloroform,and benzene and is decomposed by concentrated acids and boilingwater .Ethylbenzamide COPh-NHEt prepared by gradually addingbenzoic chloride to an ethereal solution of etbylamine in the cold,separates fieom ether in large crystals melts a t 69-70" and is solublein water tenzene chloroform and alcohol but only sparingly inlight petroleum ; i t is moderately easily soluble in hydrochloric acid,but insoluble in soda.Uenzoparutoluidide COPh*NH*C,'R,Me prepared from benzoicchloride and toluidine in like manner crystallises in plates andmelts at 157-1563".Thiobenzoparatoluidide CSPh*NH*C,H,Me is hest prepared bywarming the preceding compound with phosphorus pentasulphide ;it crystallises from dilute alcohol in long yellow needles melts a t128-129' and is readily soluble in alcohol ether chloroform,benzene light petroleum and soda but insoliible in water.Benzenylpuratoluidoxirne NOH:CPh*NH*C6H,Me prepared byheating t hiobenzotoluidine with hJdroxy1amine hydrochloride andsodium carbonate in dilute alcoholic solution ~rpt~nllises from dilutealcohol in long colourless needles melts at 176' and is readilysoluble in ether chloroform benzene acids and alkalis but onlymoderately so in hot water.The hydrochloride C,4HliNz0,HCI,crystallises in colourless needles and is sparingly soluble in water.Be~tzenylparafoluy lcarbontlli?nidozime C6&Me< >NO pre-pared by treating benzenyltol~iidoxime with ethyl chlorocarbonate inchloroform solution crystallises from dilute alcohol in yellowishneedles melts at 163" and is readily soluble in ether chloroform,benzene and light petroleum but insoluble in water acids anda1 kal i 9.Ethenylanilidoxime NOH:CMe*NHPh (m.p.120-121"). is obtainedwhen thiacetanilide is boiled with an alcoholic solution of hydroxyl-ainine hydrochloride and sodium carbonate. The hydyochloride,CP44 ABSTRACTS OF CHEMICAL PAPERS.CsHloNzO HCJ crystallises in colourless needles. The pZatinochZoride,( C8H,oN20),,H,PtC16 crystallises in slender yellow needles. Thehenzoyl-dei-ivative NOBz:CMe*NHPh crystallises from dilute alcoholin colourless needles melts a t 110" and is soluble in benzene chloro-form and ether but insoluble in water and light petroleum.Methenylanilidoxirne NOHlCH-NHPh prepared in like manner,crystallises from a mixture of benzene and light petroleum in colour-less needles melts a t l l G o and is moderately easily soluble in water,alcohol ether chloroform and benzene but almost in soluble in lightpetroleum.The hydrochloriide C7H8N20,HCl crystallises in needles.The pZatinocl~Zoride (C,H,N,O),,H,PtCI crystallises in yellowishneedles. The benzoyl-derivative NOBz:CH*KHPh crystallises incolourless needles melts a t 14&-145" and is moderately easilysoluble in alcohol ether chloroform and benzene but almost in-soluble in water and light petroleum. F. s. K.Action of Acetaldehyde and of Ethyl Acetoacetate onBenzenylamidoxime. By F.TIEMANN (Ber. 22 2412-2417).-prisms when an aqueous solution of acetaldehyde (1 mol.) and benz-enylamidoxime (1 mol.) is kept for some time in a warm place. Itmelts a t 82" and is readily soluble in alcohol ether acetone andbenzene but only sparingly in hot and insoluble in cold water ; it isdecomposed when heated with acids. The hydrochloride CgHloN,O,HCl,prepared by passing hydrogen chloride into an ethereal solution ofthe base is crystalline. The platinochlorida ( C9H,,N,0),,HzPtCI isan orange-yellow compound fioluble in alcohol and decomposed bywater. The base is converted into benzenyletheny lazoxime by potas-sium permanganate in cold dilute sulphuric acid solution.BenzenyZacetoetiienyZazoxirne CPh<Ng>C*CH,Ac - prepared byheating benzenylamidoxime with ethyl acetoacetate crystallises fromboiling water in short yellowisli prisms melts a t 86" and i s readilysoluble in alcohol ether benzene and acetone b u t only sparingly inlight petroleum and boiling water ; it dissolves freely in alkalis butis insoluble in acids. When boiled with alkalis it is decomposed intobenzenylethenylazoxime and acetic acid.The oxime CllHllN302,crystallises from alcohol in colourless needles melts at 80" and issoluble in ether benzene and hot water but almost insoluble in lightpetroleum and cold water. It is a feeble acid and reduces Fehliog'ssolution on warming. The hydrazone C1,H16N40 prepared by heatingthe ketone with phenylhydrazine crystallises from dilute alcohol inyellowish needles melts a t 126" and is insoluble in water and lightpetroleum but readily soluble in alcohol ether benzene and acetone.Paranitrobenzenylamidoxirne and Paramethylorthonitro-benzenylamidoxime.By J. WETSE ( B e y . 22 2418-2432).-Paranitrobeizzeriylamidoxime NO,*C,HI*C(NHz) :NOH is obtained,together with paranitrobeneamide (m.p. 197") when paranitrobenzo-ni trile prepared from paranitraniline by Sandmeyer's method isEthylidenebenxeny Zamidoxime CPheNH>CHMe NO separates in rhom-F. S. KORGANIC CHEMISTRY. 45digested with hydroxylamine hydrochloride and sodium carbonate inaqueous solution. It crystallises in yellow needles melts at 169",distils without decomposition and gives all the reactions of amid-oximes ; it is moderately easily soluble in alcohol and hot water butrather sparingly in benzene ether and chloroform and insoIuble inlight petroleum.The hydrochloride C7H7N303,HC1 crystallises fromwater in colonrless hygroscopic needles melts at 185" with decompo-sition and is soluble in alcohol but is reprecipitated ou adding ether.The ethyl-derivative NO2.C6H4*C(NH2):N*OEt is obtained bytreating the amidoxime with sodium etboxide and digesting theresulting deep-red solution with ethyl iodide ; it is best obtained in apure state by decomposing the hydrochloride with dilute soda. Itforms large yellow prismatic crystals melts at 59-60' and isreadily soluble in alcohol and ether but only moderately so in benzene,and sparingly in light petroleum and hot water.The hydrochlorideseparates from akoholic ether in colourless crystals.Paranitrobenzenylethenylazoxime NO,*C,H,*C<- N>CMe preparedby dissolving the amidoxime in acetic anhydride crystallises incolourless plates melts a t 1U0 and is readily soluble in alcohol,ether and benzene but only very sparingly in hot water. The corre-NO-.T ,,sponding benzen,yl-compound N02*C6H4*O<~~>CPh prepared bywarming the amidoxime wi t8h benzoic chlo~ide crystallises fromalcohol in small colourless needles melts at 198" and sublimes wit'h-out decomposition when heated slowly but explodes when heatedquickly. It is insoluble in light pet,roleum and only moderat.elysoluble in alcohol but readily i n ether benzene and glacial aceticacid.Eth y 1 parnnitro b enzen ytnmidoximecarbox y lnte,NO,*CsH,*C (NH,)XO*COOEt,is €ormed when the amidoxime is treated with ethyl chlorocarbonatein cold chloroform solution.It crystallises from cold dilute alcoholin small needles melts at 169" and is moderately easily soluble inalcohol ether benzene and chloroform but only very sparingly inwater and insoluble in light petroleum.ParunitrobPnzenylcarbonylimidc~xime N02C,H4*C<NH>C0 is ob-tained when the preceding compound is boiled with alkalis or heatedalone; it separates from alcohol in small yellow needles melts a t286" and is insoluble in light petroleum and only very sparinglysoluble in hot water but more readily in alcohol ether and benzene.It is a very stable compound and dissolves freely in alkalis; in aneutral solution copper sulphate produces 8 green precipitate.NOCarbon y ldi-purani t r o b enzen y 1 amidoaim e,prepared by *treating the amidoxime with carbonyl chloride inbenzene solution at the ordinary temperature crystallises in small,jellowish needles melts at 236" and is very readily soluble in alcohol46 ABSTRACTS OF CHEMICAL PAPERS.and moderately so in hot water but more sparingly in benzene andether and insoluble in light petroleum ; it is converted into pnranitro-benzenvlcarbonvlamidoxime when warmed with alkalis.d YE t h y 1 idm9para nit ro benz e mjla in idozi me N 02*C6 H,<g; > C HMe,separates in dark yellow crystals when an aqueous solution of theamidoxims is treated with a slight excess of acetaldehyde and keptfor some days ; it crystallises in needles melts at 153" and is readilysoluble in alcohol ether benzene and chloroform but only sparinglyin hot water and insoluble in light petroleum.It is not acted on bydilute acids or alkalis in the cold but oxidising agents convert itquantitatively into the a.zoxime. It is decomposed into its con-stituents when warmed with dilute hydrochloric acid. A yellow,flocculent compound separahes from the solutiou when etbylidene-paranitrobenzenylamidoxime is treated with warm dilute soda. Thissubstance melts a t 252" is very stable and is insoluble or onlyverysparingly soluble in most ordinary solvents. It dissolves uncliaiigedin concentrated sulphuric acid and is not acted on by reducing oroxidising agents or when heated at 150" with concentrated hydro-chloric acid; it is decomposed by fuming nitric acid yielding aneutral compound which melts at about 180" and seems to be Rdinitroethenylazoxime.Chloreth~lidelwparanit robelzzen~ilamidoairne,NO NO,*C 6H4*C<NH > C H*C H2C1,is formed when the amidoxime is boiled with dichlorethyl ether inaqueous solutions. It crystsllises from dilute alcohol in yellow plates,melts at 176" and is very readily soluble in alcohol but only mode-rately easily in benzene ether and water and insoluble in lightpetroleum.It re3embles the preceding compound in its chemicalbehaviour and yields a complex condensation-product when warmedwith alkalis.EtA yiparaizitrobenzen ylozinie nitrite N02*C6H,*C( NOE tr).O*NO pre-pared by treating the amidoxime with sodium nitrite in cold dilutesulphuric acid solut'ion is a yell0 w very unstable flocculeiit com-pound melting a t 55" with explosive violence ; it is soluble in alcoholand ether but insoluble in water.It decomposes slowly a t theordinary temperature with evolution of oxides of nitrogen andexplodes when heated with water or when treated with concentratedsulphuric acid. > C*CH2Ac,is formed when the amidoxime is digested with ethyl acetoacetate.I t crystallises from d-ilute alcohol in golden plates melts a t 140" andis readily soluble in alcohol and ether but only moderately so inbenzene very sparingly in water and insoluble in light petroleum.When heated with alkalis it is quickly decomposed into acetic acidand nitrobenzenylethenylazoxime.Paramidobenien ylamidoxime NH?*C6H,*C(NH2):XOH prepared byreducing the nitr+compound with stanuoos cbloride and hydrochloricNO Paranitro benzeny lacetoet heny lazoxirne N D2*C H,*CORGANIC CHEMISTRY.47acid and decomposing the resulting salt with sodium carbonate crys-tallises in yellow plates turnx brown at lGO" and melts at 174" withdecomposition. It is very readily soluble in alcohol but only mode-rately easily in benzene and ether sparingly i n hot water and in-soluble in light petroleum ; it gives the reactions of amidoximes anddissolves freely in alkalis.Paramethylorthonitrobenzonitrile [ CN NO2 Me = 1 2 41 pre-pared from metanitroparatoluidine by Sandmeyer's method crgstal-lises from water in long yellowish needles melts at 99" distils withoutdecomposition and is readily soluble in alcohol ether benzene andchloroform but only sparingly in hot water and almost insoluble inlight petroleum.Paramet hy lort honitrobenzeny lamidoxiime N02*C6H3&1e*C (NH?) :NOH,is obtained by digesting rnethylnitrobenzonitrile with hydroxylaminein alcoholic solution and is best prepared in a pure state by decom-posing the copper-derivative with hydrogen sulphide.It crystallisesin long yellow needles melts at 161" and shows the properties of anamidoxime ; it is moderately easily soluble in alcohol and hot water,but only sparingly in benzene ether and chloroform and is insolublein light petroleum. The hydrochloride CBHSNYOS,HC1 is a colonrless,crystalline compound soluble in alcohol but reprecipitated on addingether.Paramethylorthonitrobenzamide [CONH NO2 Me = 1 2 41 isformed in the preparation of the preceding compound.It crystallisesfrom water in long yellow needles melts at 152" and is readilysoluble in alcohol ether and benzene but almost insoluble in lightpetroleum ; it is converted into the corresponding acid when boiledwith alkalis.Para rneth y 1 orthamidoben,zeny lamidoxime,is produced in small quantities when methylnitrobenzenylamidoximeis reduced with stannous chloride and hydrochloric acid. It is abrown flocculent compound melts at about 166O and gives the reac-tions of aniidoximes. The hydrochloride is a colourless crystalline,hygroscopic compound soluble in alcohol but reprecipitated on addingether.F. S. K.Para- and Ortho-homobenzenylamidoxime and their De-By L. H. SCHUBART (Bey. 22 2433-2440; comparz rivatives.Abs tr. 1886 79 7) .-Parahomo benz eny letheny lazoxime,prepared by boiling the amidoxime with acetic anhydride crystallisesin colourless prisms melts at 80° and is readily soluble in alcohol,ether chloroform and benzene but insoluble in acids and alkalis.Parahomobenzenylethoxime chloride C6H4Me*CCl:NOEt obtained bytreating the amidethoxime with hydrochloric acid and sodium nitrite,is a ,yellow oil boils at about goo" a.nd is soluble i n aloollol andether. The corresponding bromide prepared in like manner is 48 ABSTRACTS OF CHEMICAL PAPERS.heavy brown oil; it decomposes at 155" and is readily soluble inether chloroform and benzene.Parahomobenzenylp-openylazoxime-w-carboxylic acid,C6H4Me*C<- "0 y>C*C2H4-COOH.Ais formed when the benzenylamidoxime is melted with succinic an-hydride.It crystallises from boiling water in colourless needles,melts at 138*5" and is soluble in alcohol ether chloroform andbenzene.Parahomobenzenyluramidoxime C,H,Me*C(NOH)*NH*CO.NH pre-pared by treating the hydrochloride of the atnidoxime with potassiumcyanate in aqueous solution crystallises in colourless needles meltsa t 170" and is readily soluble in alcohol ether and benzene but onlysparingly in water. The thiowuinidozime,C,H,Me*C (NOH) *NH*CS.NHPh,prepared by treating the amidsxime with phenylthiocarbirnide crys-tallises from hot water in colourless needles melts ot lYO" and isreadily soluble in alcohol and ether but more spariiigIy in chloroformand benzene.Para<horno b enzen y lpheny luvani idoxime,C6H4Me*C( NOH)*NH*CO*NHPh,prepared from phenylcarbimide in like manner separates from dilutealcohol in colourless crystals melts a t 155" and is readily soluble inrtlcohol ether and hot water.Ethyl pamhornobenzenylnnzidoximecarboJ.ylate,C6H4&fe-C (NH,):NO*COOEt,is obtained by treating the amidoxime with ethyl chlorocarbonate i nchloroform solution ; it crystallises from dilute alcohol i n colourlessneedles melts a t ISO" and is readily soluble in alcohol ether chloro-form and benzene but only sparingly in light petroleum and water.PnrahomobenzenyEcarBonyZirnidoxime C6H4Me*CWNH>C0 NO crystal-lises from hot water in colourless needles melts at 220" and is solublein ether alcohol and alkalis.Diparahomobenzenylnzoxime C6H4Me*C< >C*C6H4Me is formedwhen the amidoxime is heated with glacial acetic acid. It crystallisesfrom dilute alcohol in long colourless needles melts a t 135" and isinsoluble in water but readily soluble in ether benzene chloroform,and light petroleum.C6H4Me*CeK NO I-_i > CHM e,melts a t 127.5".and is readily soluble in alcohol ether and benzene,but only sparingly in hot water.NOEtlr ylidenepara.12omobenz eny lainidonime,Parahomobenzenylacetoetheny lctzoxinze C6H4Me*C<L YO N>C.CH2Ac,-pared by treating the amidoxime with etbpl acetoacetate crystalliseORGANIC CHEMISTRY.49from boiling water in colourless needles melts at 97" and is readilysoluble in alcohol ether and benzene.Orthohomobenzeny Zaniicloxime CsH,&Ie*C (NH,) :NOH obtainedfrom homobenzonitrile (b. p. 195") crystallises from hot water inyellowish needles melts at 149.5" is readily soluble in alcohol ether,and benzene and shows the characteristic reactions of amidoximes.The ethyl-derivative C,,H,,N,O forms colourless prismatic crystals,melts at 140° and is readily soluble in ether alcohol and benzene.The benzoyl-derivative C,5Hl,Nz0 crystallises from dilute alcohol inneedles melting at 145".Orthohornobenzenylbenzeny luzoxime C 6 H ~ e * C < ~ ~ > c P h preparedby dissolving the benzoyl-derivative (see above) in cold concentratedsulphuric acid crystallises in long colourless needles melts at 80°,and is insoluble in acids alkalis and cold water but readily solublein alcohol ether benzene and chloroform.F. S. I(.Action of Carbon Bisulphide on the Potassium Compoundof Parahomobenzenylamidoxime. By L. H. SCHUBART (Ber. 22,2441-2442) .-A compound CSH,N,S2 is formed when parahomo-henzenylamidoxime (1 mol.) is dissolved in alcoholic potash and thesolution boiled for about three hours with carbon bisulphide (1 mol.).It crystallises from alcohol in yellow needles melts at 165" and issoluble in ether chloroform benzene and alkalis.The compound C,H6N2S2 can be obtained from benzenylamidoximein like manner. It crystallises from alcohol in yellow prisms andmelts at 160".F. S. K.Xylenylzmidoxime and its Derivatives. By E. OYPENH EIMER(Ber. 22 'L442-2449).-Xylylonitrile [CN Mez = I 2 41 pre-pared from xnet3axylidine by Sandineyer's method separates fromcold dilute alcohol in long colourless crystals melts a t 23-24' isvolatile with steam and is readily soluble in alcohol and ether(compare Oasiorowski and Mere Abstr. 1885 772).Xylenylumidoxime CsH,Mcz.C( NH,):NOH is obtained when thepreceding compound is heated with hydroxylamine for 5 to 6 hoursat 80-85". It crystallises in colourless needles melts at 178" and isreadily soluble in alcohol ether chloroform and hot water but onlysparingly in cold water; it gives all the characteristic reactions ofaruidoxirnes.The ethyl-derivative CI,H,,J,O crystallises in colourlessiieedles melts at 172" and is readily soluble in alcohol ether,chloroform benzene and hot water but only sparingly in cold water.The benzoyl-derivative CI6H,,N,O separates from dilute alcohol incolourless crystals melts at 158" and is only sparingly soluble inwaher and light petroleum but readily in alcohol ether and chloro-f x m .Xy 1 en y Zb enzen y Zuzoxime CsH,Me2*C< N>C Ph prepared by heat-ing the beuzoyl-derivative described above crystallises in yellowishscales melts at 98" sublimes readily and is volatile with steam ; it isreadily soluble in alcohol ether chloroform and benzene.NOVOL. LVIIT. 50 ABSTRACTS OF CHEMICAL PAPERS.Acety Zxy Zeny lamitloxime C6H3Me2-C(NHz) :NOAc obtained bytreating the amidoxime with acetic chloride in ethereal solution,crystallises from cold alcohol in colourless needles melts at 189",and is readily soluble in alcohol and chloroform but only sparinglyin ether.The corresponding ethenyluzoxinte C,,H,,N,O is preparedby heating the amidoxime with acetic anhydride and distilling theproduct with steam; it separates from alcohol or ether in crystalsand melts at 89".Xylenylazoximepropeql-w-carboxylic acid,C 6 H 3 M e 2 0 C ~ ~ ~ ~ C ~ C 2 H 1 * C O O H ,prepared by fusing the amidoxime with succinic anhydride crys-tallises in long colourless needles melts at 112" and is readilysoluble in alcohol ether benzene and chloroform ; it forms crystal-line salts with bases.SEth?/Z xyZenyZamidoxirr,ecarboxyZate C6H3Me*C(NHz):NO*COOEt isobtained by treating the amidoxime with ethyl chlorocarbonate inchloroform solution.I t crystallises from dilute alcohol in colourlesaneedles melts at 142" and is readily soluble in alcohol ether andchloroform but only sparingly in light petroleum; it has feeblebasic properties.Xy Zeny 1 carbon y lamidoxime C6H3Mez* CfNH > C 0 prepared byheating the preceding compound crystallises from hot water inneedles melts at 182" and is readily soluble in alcohol and ether; ithas acid properties.The compound CeH,2Nz0,CCI,*COH is formed by the direct combin-ation of its constituents ; it separates from a mixture of benzene andlight petroleum i n crystals melts at 112" and dissolves unchanged inalcohol and ether but is decomposed by water and by dilute acids.Xylenyluramidoxime CsH,Me2*C(NOH).NH.CO*NHz separates incoiuiwless crysta,ls when the hydrochloride of the amidoxime istreated with potassium cyanate in ethereal solution.It melts at155" is readily soluble in ether alcohol benzene and light petroleum,but onlg sparingly in water; it combines with acids and also butless readily with bases.C6H3Mez.C(NOH)*NH*C0.NHPh,crystallises from alcohol in light yellow scales melts at 138" and issoluble in alcohol ether benzene chloroform hot water and acids.XyZenyZphenyZthiuramidoxime C6H3Mez*C(NOH)*NH-CS*NHPh,separates from dilute alcohol in light yellow crystals meIts at 150",and is soluble in alcohol ether benzene acids and boiling water,but almost insoluble in alkalis.F. S. K.NOThe phenyl-derivative,Action of Sulphuric Acid and Selenic Acid on AromaticCompounds. By ISTRATI (Bull. Xoc. Chim. [3] 1 480-481).-Finding that the prolonged action of sulphuric acid on benzene pro-duced a sulphonic acid sulphobeneide and a francein the authorheated selenic acid sp. gr. 1.4 (200 grams) with pure benzene (50 c.c.ORGANIC CHEMISTRY. 51for 32 hours at 80" ; neither selenobenziile nor a francei'n was produced,but after neutralisation of the acid by barium carbonate a smallquantity of a crystalline organic compound which the author believesto be phenyl selenide (comp. Abstr. 1889,41) was extracted from thebarium salt by hot water. Pentachlorobenzene similarly treated gavea corresponding result.New Data relating to France'ins.By ISTRATI (BUZZ. Xoc. Chiin.[3] 1 481487 ; compare Abstr. 1888 591).-When snlphuric acidis heated with halogen-derivatives of benzene it causes the migration ofhalogen-atoms and this determines the formation from the initial corn-pound of france'ins whose chlorine values differ. Thus from 1 2 4-trichlorobenzene three franceins resulting from the oxidation of di-,tri- and tetra-chlorobenzenesulphonic acids are produced and theseare accompanied by a small quantity of 1 2 4 5-tetrachloro-henzene. From 1 2 4 5-tetrachlorobenzene a francein is ob-tained which is separable into five france'ins of varying solubilitiesand compositions. Numerous analSses are given. T. G. N.Francei'n from 1 2 4 Trichlorobenzene.By ISTRATI ( B d .~ O C . Cltinz. [3] 1 4.88-492) .-From comparative experiments whichhe has made as to the formation of france'ins from 1 2 4-tri-chlorobenzene the author finds that the yield of francein is de-pendent on the temperature and varies inversely as the amount ofsulphonic acid remaining in the mixture a t the close of the operatmion.Action of Heat on a Mixture of Sulphuric Acid and Sul-phonic Derivatives. By ISTR~ATI (BUZZ. SOC. Ckim. [3] 1 49%-496).-From experimental observations the author concludes thatwhen a mixture of excess of snlphuric acid and a sulphonic acid ora sulphonate is heated regeneration of hydrocarbons with formationof water and of pyrosulphuric acid respectively occur while sulpho-benxide is formed as a condensation-product and a decompositionof the sulphonic acid into sulphurous anhydride hydrocarbon andoxygen determines the formation of a franceiin by the oxidation ofunaltered sulphonic acid.T. G.N.T. G. N.T. G. N.a-Ketoaldehydes. By H. MGLLER and H. v. PECHMANN (BPT. 22,2556-2 56 1 ).-Benzoy lf ormaldehy de C OPh . CO H(Abstr. 18e8 146) is prepared by dissolving nitrosoacetophenone(30 grams) in a 35 per cent. solution of sodium hydrogen sulphite(120 grams) contained in a litre flask. When cold the whole solidifiesto a yellowish crystalline mass and is then stirred with alcohol andglacial acetic acid (1 c.c.) and after some time filtered by suction. Theproduct (30 or 40 grams at a time) is boiled with 11 parts of 17 percent.sulphnric acid in a flask fitted with an upright condenser until onequarter of the liquid is boiled off. On cooling crystals of phenylglyoxalhydrate separate and are purified by crystallisation from boiling water.It dissolves in about 35 parts of water at 20". When heated withnitric acid (sp. gr. lath) benzoglformic acid is formed. When anaqueous solution is treated with phenylhydrazine dissolved in dil ntu( phen ylglyosal),e 52 ABSTRACTS OF CHEMICAL PAPERS.acid thea-hydrazone NHPh*N:CPh*COH separates as a brown cryetal-line precipitate which may be obtained from alcohol in yellow plates,melts a t 142-143",and is readily soluble in most solvents. The osazone,C,,H18N is obtained by heating phenylglyoxal with phenylhydrazineacetate (2 mols.) or more conveniently from nitrosoacetophenoneand an excess of phenylhydrazine ; it is identical with Laubmann'scompound from benzoyl carbinol and phenylhydrazine (Abstr.1888,366). When the aldehyde is dissolved in aqueous soda and b:ded fora few minutes sodium lnandelate is formed. It is probable that i nthe formation of mandelic acid from benzoylcarbinol (Rreuer andZincke Abstr. 1880 645) and from acetophenone dibromide (Englerand Wohrle Abstr. 188'7 948) benzoylformaldehyde is formed asintermediate product (compare Zinoke Annalen 216 31 5).When phenylglyoxal is treated with ammonia a compound of theformula C,,Hl,N30 or C,H,,N,O is obtained. This crystallises fromdilute alcohol in yellowish-white lustrous plates melting a t192-193" and can be distilled; i t is soluble in alkalis and is notchanged by sulphuric acid.Phenylglyoxal reacts with hydroxylamine yielding the cnnipoundC16H,3N403. The latter melts a t 219' dissolves in alkalis and is pre-cipitated by acids as a white powder which becomes yellow whenexposed to light.A7itrosomethyZ paratol!/Z fietone C6H4Me.C0.CH:NOH prepared byGaiseti's method crystallises from benzene in colourless needlesmelting a t 100'.ParatohjZgZyoxaZ hydrate C6R,Me*CO.CH(OH) is prepared fromthe a,bove compound in a manner similar to phenylglyoxal.It crys-tallises from water in white matted needles softens at 95" melts a t1OO-l0'Lo and is readily soIuble in alcohol ether and benzene butless soluble in water and light petroleum.When shaken with benzenecontaining thiophen and salphuric acid the latter becomes green.The aldehyde behaves towards alkalis like the phenyl-compound isoxidised by nitric acid (sp. gr. 1.4) to toluylformic acid and by per-mariganate to paratoluylic acid (m. p. 180'). The osazone C21H20N1,obtained by heating a solution of the aldehyde with an excess ofphenylhydrazine acetate for 30 minutes on a water-bath crystallisesin yellow needles melting a t 145".Naphthyl methyl ketone C,,H,,O melts a t 51-52' boils at.300-301" and when oxidised yields /3-naphthoic acid. It is notidentical with the compound obtained by Claus and Feiss (Abstr.,1887 271) but possibly is with Pampel and Schmidt's (Abstr. 1887,252) compound. N. H. M.Isomeric Dinitroparatoluic Acids.By B. ROZA~SKI (Bey.,92 2675-268'2) .-By nitrating orthonitroparatoluic acid (Abstr.,1888 l088) two dinitro-derivdires were ohtnined and their consti-tution establisbed from the corresponding dinitrotoluenes.2 5-DinitroparufrnZiiic acid (COOH NO Me NO = 1 2 4 5 )is very sparingly soluble in cold water easily in alcohol andacetone crystallises in needles and melts a t 158". The sodiu,nz salt(with 3H,O) forms glistening je:low scales ; the bui*ium salORGANIC UHEJIIS'I'RT. 53(with 2&H20) sIrlaI1 yellowish-white needles ; the calciimt salt (with2H20) reddish-brown scales ; the ammonium salt lemon-yellow scales ;the siher salt a white amorphous powder; the copper salt a light-green powder ; the mercuric lead and i r o n salts white precipitates.2 3-Dinitroparatoluic acid [COOH NO NO Me = 1 2 3 41forms yellowish prisms soluble in alcohol and melts at 249".It a i dits salts are less soluble in most solvents than the 1 2 4 5 acid.The bariwn saZt (with 4H,O) forms pale-yellow needles; the calciumsalt (with H,O) pale-yellow scales. The other salts are similar tothose of the isomeric acid. L. T. T.Acetometanitrobenzoic Anhydride. By W. H. GREENE (Airier.,Chenz. J. 11 414-415).-When dry silver metaniirobenzoate istreated with excess of cold acetic chloride and the product pouredinto water metanitrobenzoic acid is regenerated ; Liebermann'sstatement (this Journal 1877 ii 617) that metanitrobenzoylaceticacid (acetometanitrobenzoic anhydride) is formed is incorrect.Acetometanitrobenzoic anhydride is however obtained by treatingsodium or silver metanitrobenzoate with acetic chloride and extract-ing the product with ether.It forms colourless needles which melt a t45". It is insoluble in water but the presence of either water o ralcohol in the ether used for extraction CiLuSes complete decomposi-tion of the anhydride,Action of Phosphorus Trichloride on Salicylic Acid. By R.ANSCHUTZ and W. 0. EMERY (Airier. CRein. J. 11 387-392).-Whensalicylic acid is heated with excess of phosphorus trichloride a tiO-8rj0 and the product distilled first at the ordinary pressure to getrid of tlie excess of phosphorus trichloride and then under reducedprfssure snlicyloplzosphorus chloride C7H403PCl. solidifies in the re-ceiver.This melts st 36-37" boils a t 127" under 11 mm. pressure,decomposes under ordinary pressure a t about 245" and is soluble i nether chloroform and benzene. With phosphorus pentachloride orwith chlorine i t gives an additive-compound C7H403PC13 of sp. gr.= 1.5587 a t 20" (water at 4" = l) boiling at 168" under 11 nim.pressure ; this compound can also be obtained by the action of phos-phoieus pentachloride on salicylic acid. With bromine a similar com-pound CiH1O3PCIBr2 is obtained of sp. gr. 1.8852 a t 20" (water a t4' = l) and boiling at 18.5-188" under 11 mm. pressure. Tliefollowing are given as the most probable formulae for salicylophos-p horus monochloride and its chlorine additive-prodxct respectively :-C. F.13.C. I?. B.Constitution of Isoeuxanthone. By C. ARBENZ (Chem. Centr.,18H9 ii 73; from A r c h . Sci. p h y s . mat. Gen6z.e [3] 21 3'75).-Phenylsalicylic acid is converted by nitric acid into the dinitro-derivative NO,.CsH1(O.CsH,.NO,).COOH which may be split upinto paranitrophenol and pararlitrosalicylic acid proving that bot 11nitro-groups are in the para-position. Sulphuric acid converts th51 ABSTRACTS OF CHEMICA\L PAPERS.dinitro-derivative into dinitrodiphenyleneketona oxide which maybe reduced to the diamido-derivative isoenxanthone. J. W. L.Oxidation of Orthocarboxycinnarnic Acid. By E. EHRLICH(Illonatsh. 10 574-577 ; compare Abstr. 1888 842).-The authorhas previously shown (Abstr. 1888 1306) that in alkaline solution,&naphthol when oxidised with a limited quantity of permanganate,gives rise to orthocarboxycinnamic acid COOH*CH:CH.CsH,*COOH ;whilst the employment of an excess of the oxidising agent leads tothe formation of orthocarboxyphenylglyoxylic acid,CO OH*C0.CsH4.C 0 OH.Thq former acid however is not to be regarded as an intermediate~wnduct for when a 2 per cent.solution of permangaiiate is slowly runi 1 1 tj) a solution of orthocarboxycinnamic acid (10 grams) and potash( I 0 grams) in water (1 litre) decolorisation ceases when about 80 percent. of the permanganate theoretically required to convert it intoorthocarboxyphenylglyoxylic acid has been added and the solutioncontains only orthobenzaldehydecarboxylic acid COH*C6Ho*COOH(yield 50 per cent.) which melts a t 98-99' reduces an ammoniacalsolution of silver.and furnishes a compound with phenylhydrazine,melting a t 107-108". The author has not succeeded in his endeavourto obtain orthobenzaldehydecarboxylic acid by the direct oxidation of/3-naphthol. G. 3'. M.Isomeric Derivatives of Ethylbeneene. By L. SEMPOTOWSKI(Ber. 22 2862-2G74).-When ethylbenzene is heated to boiling anequal volume of sulphuric acid added and then after cooling the massis treated with a small quantity of ice-cold water only para-ethyl-7,eueenesulphonic acid is formed ; this crystallises in long colourless,deliquescent needles is sliyhtly soluble in water and has a rough,bitter taste. The barium saZt (with H,O) forms colourless silky needles;the calcium salt silvery scales ; the coyper salt (with 4+H,O) light-bliie,glistening scales decomposing a t 170'; the cadmium salt (with 7H,O),large transparent quadratic plates ; the potassium salt (with +H,O),micaceous scales decomposing at 150".All these salts are soluble inwater. The sic@haniide C6H4Et.S02NH,[Et SO,NH = 1 41,crystallises from alcohol in flat micaceous prisms easily soluble inether sparingly so in water and melting at 109". The constitutionvas proved by the fusion of the potassium salt with potash whenparahydroxybenzoic acid was formed. With a shorter fusion para-etltyZpheno2 C6H4Et.0H was obtained ; this forms long needles whichmelt at 45-46' boil a t 21:-3-214" and are sparingly soluble in water.*It is very soluble in alcohol and ether and its aqueous solution givesa violet-grey coloration with ferric chloride and a jellowisli-whiteprecipitate with bromine-water.The metnsuZphoizic acid CsH,Et(S03H)*OH[Et S03H OH =1 3 41 is formed both at high and low temperatures. It.is a* Probably identical with the a-ethylphenol of Beilstein and Kuhlberg rind ofFittig and Kiesow.-AbstmrtorORQASIC CHEMtS'l'RY. 55reddish oil of phenol-like odour and miscible with water. The b a r i msalt forms colourless hexagonal plates decomposing a t 120" ; thepotassium salt silky needles ; the calcium saEt colourless needles. Onfusion with potash the acid yields protocatechuic acid proving thecorrectness of the constitution given.Netaparadihydroxyethylbenxene C6H,Et(OH) [Et OH OH =1 3 41 is a liquid boiling at 295" and soluble in water.Itsaqueous solution is coloured green by ferric chloride and this colourpasses on the addition of soda through blue to claret colour.Orthobyomethy lbenzenemetasulphonic acid [Et Br SOsH =1 2 3 or 51 was obtained by the sulphonation of bromethylbenzene.Its barium salt (with 3HzO) iorms colourless plates sparingly solublein cold water; its potassium salt (with $H,O) colourless scales ; andthe sulphamide glistening prisms melting at 104-105".Parabromethylbenzeneorthosulphonic acid similarly formed yields acrystalline barium salt (with 4H20) easily soluble i n water. The potas-sium salt forms easily soluble scales the sukhonamide large micaceousscales melting at 123-124".Barium orthoethylbenzenesulphonute (with H20) formed by debrom-inating the bromine-derivat'ive forms soluble scales ; the cadmiumsalt long soluble needles ; the potassium salt very soluble glisteningscales.Barium o~thoethylphenolrnetasulplLonate forms microscopic scales.Barium nteta-ethyll~en~zenesulplzor~nte (with 2H20) obtained by debromin-d i n g the bromine-derivative forms crystals easily soluble in water ;the potassium salt easily soluble scales ; the sulphonarnicle glisteningscales melting at 85-86" When fused with potash this acid yieldsmeto-ethylphenol which forms a colourless oil liquid at -20" andboiling at 202-204".Barium meta-ethylphenolsulphonate forms easily soluble crystals.L.T. T.Disulphones and Trisulphones. By E. FROMM (Annnlen 235,135-167) .-Baurnann and Escalcs (Abstr.1887 123) obtainedethylidenediethylsulphone by oxidising a-dithioethylpropionic acid.It is more conveniently prepared by acting on a mixhure of acetalde-hyde and ethyl mercaptan with zinc chloride. The resulting ethylmcrcaptal of acetaldehyde (b. p. 186") is oxidised by agitation with asolution of potassium permanganate containing sulphuric acid.E thylidenediethylsulphoiie melts at 75" and boils at 3.20" withdecomposition. The bromide melts at 115". Attempts to obtainsubstitution-products by the action of alkalis sodium ethoxide mer-captan or aniline on the bromide were unsuccessful (Abstr. 1888,357). Ethylidenediethylsulphone chloride CMeCl( S02Et) and sodiumphenylsulphini te are formed by the action of benzenesulphoniochloride on ethylidenediethylsulphone and sodium ethoxide.Thechloride can be prepared by exposing to direct sunlight for severaldays an aqueous solution of ethylidenediethylsulphone saturated withchlorine. It is deposited from an aqueous solution in needles whichmelt at 102-103". The iodide is prepared by boiling the disul-phone with an excess of iodine the crude product being treate56 ABSTRACTS OF CHESlICAT PAPERS.with a cold ~olution of sodium hydroxide then washed with coIdwater and finally recrystallised from boiling water. The iodidecrystallises in needles and melts at 128-129" ; a t a higher tempera-ture it gives off iodine.Diethylsulphonedimet hylmethane has been described by Baumann(Abstr. 1887 123). It can be prepared by the action of methyliodide on an alkaline aqueous solution of ethylidenediethylsulphone.Diethylsulphoneth ylrnethylmefhane is formed by boiling a mixture ofsodium ethoxide ethyl iodide and ethylidenediethylsulphone in aflask with a reflux condenser. It forms quadratic crystals and meltsat 76".The ethjl mercaptal of propaldehyde is lighter than water andboils between 196" and 200'.On oxidation with permanganate ityields propylidenediethylsulphone CH,*CH,.CH( SO,Ett) ; t'his crys-tallises in silky needles and melts a t 77-78". The ethyl mercaptalof isobiitaldehyde boils between 200 and 210"; i t is lighterthan water. lsobut~lidenedie~hylsulphone melts a t 94" and crystal-lises in needles; it is almost insoluble in cold water. The ethylmercapkal of benzaldehyde PhCH( SEt) is lighter than water,and boils with decomposition a t 250-253".Benz~lidenedieth~7sul-phone melts at 133-134"; it is insoluble in cold water but issoluble in cold solutions of the alkalis. €37 the action of sodiumethoxide and methyl iodide i t is converted into diethjlsulphone-methylmethane.Diethylsulrphonemethnne prepared by the oxidation of the ethylmercaptal of formaldehyde (from methylene chloride and sodinmethyl mercaptide) is identicai with the disulphone Raumann ob-tained from ethyl orthothioformate (dbstr. 1887 124). It isconverted into diethylsulphonedimethylmethane (sulphonal) by theaction of methyl iodide in the presence of an alkali; this melts a t12.5-126". D~ethillsul?,honedi~thyli,?ethniie is more difficult to prepare.It melts at 86-88'.An aqueous solution of diethylsulphonemethanereadily absorbs chlorine formiug the dichloride CCl,(SO,Et),. Itcrystallises in needles and melts a t 98-99'. The correspondingdiethylsulphonedibromomethane has already been described by Bau-mann (loc. cit.) .Diethyhdphonedi-iochmethane melts a t 176-177" b u t begins to turnbrown at 170". It crystallises in needles and is sparingly solnble inhot water.DiphenylsuZpphonemethane CH,(SO,Ph) prepared by oxidising thephenyl rnercaptal of formaldehyde crystallises in needles and me1 ts a t118-119". It is soluble in benzene and hot alcohol Diphenylsul-phonedimethylmethane melts at 128" and is soluble in hot alcohol.The corresponding diethyl-derivative melts at 130-131" and issparingly soluble in hot alcohol.When diethylsulphonedibromomethane (1 mol.) is boiled withphenyl mercaptan (I mol.) and an aqueous solution of sodium hydroxide(rather more than 3 mols.) phenyl bisulphide and diethylsulphone-thiophenylmethano are formed.The former is deposited from the solu-tion on cooling whilst the latter separates out on acidifying the filtrate ;i t is washed with cold water and recrystallised from absolute alcoholORGANIC CHEIJTSTR Y. 57Diethylsulphonethiophenylmethane PhSCH( S02Et) crystallises inplates and melts at 86". It is sparingly soluble in hot water and .morereadily soluble in a solution of sodium hydroxide. On oxidation byperman ganat e diet h y Isu 1 phonep h eny lsu Zpiokonern ethane,PhSO,*CH( SO,E t) 2,is produced.This trisulphone melts a t 1ti5". It is less soluble inalcohol than in water and is precipitated from its aqueous solution bystrong acids. The aqueous solution turns litmus red and decomposescarbonates. w. c. w.Phenylated Indoles. By W. H. TNCE (Annrzkn 253 35-44).-3'- Pheriylindole yields a crystalline picrate soluble in benzene ether,acetone and alcohol and melts at 105". The nitrosamine C14H,,N,0,forms minute yellow needles and melts a t 60-61"; it is freelysoluble in benzene acetone ether and chloroform but is insoluble inRolutioris of caustic alkalis. Phenylacetaldehydemethylphenylhydr-azone is formed by the interaction of phenylacetaldehyde and methyl-phenylhydrazine. The alcoliol ic solution of t h i s compound isdecomposed by an alcoholic solution of hydrogen chloride withdeposition of ammonium chloride.The liquid is neutralised withammonia and evaporated leaving a residue of impure 1'-3'-methyZ-phenylindole; t h i s is purified by solution in etherand distillation in avacuum. The pure indole dissolves i n benzene alcohol and ether ; itsalcoholic solution gives a blue colour to a pine chip moistened w i t hhjdrochloric acid. The picrate forms dark brown needles and meltsa t YO". Fischer and Schmidt (Abstr. 1888 958) pointed out that zincchloride a t 170" converts 3'-phenylindole into 2'-phenylindole. In thesame way zinc chloride a t 220" transforms 1'-3'-methylphenylindoleinto the 1'-2'-methylphenylindole described by Degen (Abstr.1887,149).3'-PhenyZ-13-nap72thindoZe is obtained by the action of alcoholichydrogen chloride on the hydrazone produced by the inter-action of phenylacetaldehyde a n d /3-naphthylhydrazine ; it crystal-lizes in glistening needles and melts with decomposition a t 211" issoluble in benzene alcohol ether acetone and hot light petroleum,and stains a pine chip green. The picrate forms reddish-brownneedles melts a t 219-120" and is holuble in benzene acetone,chloroform alcohol and ether. The 3'-phenyl-/3-naph t hindole is con-verted into 2'-phenyl-@-naphthindole by treatment with zinc chlorideat 130". 2'-Phenyl-P-naphthindole can be more conreniently prc-pared by the action of zinc chloride on acetophenone-p-naphthgl-hydrazone obtained by the condensation of acetopbenone andj?-naphthylhydrazine.The hydrazone melts a t 150" but it begins toturn brown a t 117". /3-?zLtphthindoZe melts a t 129-1S0° and is freelysoluble in alcohol ether and benzene. It forms a crystalline picrate(m. p. 165-166") which is soluble in benzene and ether.Benzidine- and Benzidinesulphone-sulphonic Acids. ByP. GRIESS and C. DUISBLRG (Rer. 22 2459-2474).-l?enzidiwe-sulphonic acid NH,.C6H4*C6H3( NH,) .SO,H is formed in small quanti-w. c. w58 ABSTRACTS OF CHEMICAL PAPERS.ties in the preparation of the disulphonic acid (compare Griess Abstr.,1881 428) and it can also be obtained in larger quantity by heatingbenzidine sulphate for 1& to 2 hours a t 1 70" with sulphuric acid mono-hydrate (about 6 parts).It is best prepared by heating benzidinesulphate at 170" for about 24 hours (D.R.-P. No. 44,779). It formsanhydrous crystals and is very sparingly soluble in boiling water andpractically insoluble in alcohol and ether; it is decomposed whenheated yielding a small quant'ity of benzidine. The hydrochloride,C12H,,N2S0,,HCl separates from hot dilute hydrochloric acid ingreyish nodular anhydrous crystals and is decomposed by boilingwater. The barium salt (C,2HlIN2S03)2Ba + 5H20 is moderatelyeasilg soluble in hot water and separates on cooling in small needlesor plates. The tetrazo-compound is obtained when an excess ofhydrochloric acid and a slight excess of sodium nitrite are added toan ice-cold alkaline solution of the sulphonic acid. It is readilysoluble in water and combines with phenols hydroxysulphonic acids,and aromatic hydroxycarboxy lic acids in alkaline solution and witharnines and amidosulphonic acids in sodium acetate solution formingyellow red and purple dyes.The compounds obtained with thehydroxycarbosylic acids phenols and amines respectirely aresparingly soluble ; the other dyes are readily soluble in water. Theyall dye unmordanted cotton wool in am alkaline bath and generallythe shade produced is more distinctly purple than that obtained withtetrazodiphenyl dyes but not so much so as that produced withtetrazodipheny ldisulphonic acid colouring matters.Benzidinemetadisulphonic acid (compare Griess Zoc. cit.) is bestprepared by heating benzidine sulphate (1 part) with sulphuric acid(2 parts) at 210" for 36 to 48 hours ; the yield of the pure compoundis 90 per cent.The azo-compounds derived from the tetrazo-derivativedo not dye vegetable fibres as readily as those obtained from thetetrazomonosulphonic acid but they have a more decided blueshade.Benzidine is not acted on by fuming sulphuric acid a t temperaturesbelow 100-120" but the azo-compounds obtained from tetrazo-diphenyl and naphthylamines react with fuming sulphuric acid inthe cold the hydrogen in the benzidine being substituted.Benzidinetrisulp7zoiLic acid C6H,(NH,)(S03H)2~C6H3(NH2)*S03H +2H20 is obtained together with the tetrasulphonic acid whenbenzidine sulphnte is heated for a long time at 180-190" with sul-phuric acid monohydrate or when a solution of benzidine in a littlehulphuric acid monohgdrate is heated at 160-1T0° poured intofuming sulphuric acid and heated again until a small portion givesonly a slight precipitate when treated with water.The product ispoured into water the solution filtered to separate small quantities ofthe disulphonic acid and neutralised with barium carbonate. Thebarium salt of the trisulphonic acid is readily soluble in cold water,and can be easily separated from the salt of the tetrasulphonic acid,which is only sparingly soluble. Benzidinetrisulphonic acid is pre-cipitated in soft colourless plates on adding concentrated hydro-chloric acid to a moderately concentrated solution of the barium salt.It is readily soluble in cold water but only sparingly i i i alcohol anORGANIC CHEMISTRY.59is reprecipihated from the alcoholic solution on adding ether; it iscompletely decomposed when heated.ci-ystallises in small colourless prisms and is precipitated from itscoilcentrated aqueous solution on adding alcohol.The ba.rium salt,(C,,H9N2S30,)2Ba3 + 12H~0,/2enzidiizetetrasulp~o~,ic acid,CsH?(NH,) (SO,H)z.CsHz(NH,) (SOB),,is precipitated in small colourless needles on adding hydrochloric acidt o a concentrated aqueous solution of the barium salt; it is very readilysoluble in cold water and is also soluble in alcohol. The barium salt,Cl?H8S10,,Ba + €?H,O cryst,allises in colourless needles or prisms,aiid is very sparingly soluble in hot water and insoluble in alcohol.Benzidin esulp hone ?6H3(NH2)>SO? is best prepared by graduallyadding benzidine sulphate (1 part) to a 20 per cent.sulphnric acidsolution of sulphnric anhydride. and heating the mixture on the water-bath until i t is free from unchanged benzidine ; the product is pouredon to ice and the benzidinesulphone sulphate is separated by filtrntiouand decomposed with soda. It crystallises in very small yellow,anhydrous needles melts above 350° and is almost insoluble in boil-ing water and insoluble in alcohol ether and benzene. The salts aredecomposed by water. The hydrochloride C12HloN2S02,2HC1 crystal-lises from hot dilute hydrochloric acid in which it is moderatelyeasily soluble in almost colourless plates.crptallises in grey or colourless needles or plates and is onlysparingly soluble in hot dilute sulphuric acid.The platinochZoridecrystallises in small dark yellow plates and is insoluble in water.,4 h ydroxybenzidine C12HllN2.0H is formed when the sulphone isheated a t 180" with caustic soda; it is a grey compound verysparingly soluble i n water but readily i n soda. The sulphate andl~ydrochloride are sparingly soluble in water.When benzidinesulphoiie hydrochloride is treated with sodiumnit'rite in aqueous Eolution and the resulting brown amorphous,tetrazo-compound reduced with stannous chloride and hydrochloricacid the hydrazine is obtained in small yellow needles sparinglysoluble in water. The latter is decomposed when boiled with coppersulphate solution yielding a diphenylenesulphonic acid melting a t2:'8" and identical with the compound obtained by Stenhouse(Annalen 156 332) from diphenylene sulphide.The azo-dyes obtained from benzidinesulphone differ from those ofbenzidine and benzidinesulp honic acids in possessing a marked blueshade.C,H3(NH,)The s u b h a t e ,CVZHIJ?~SO~,H2SOd + 1iH20,Beizzidi~~s.1Llphone~z~Z~~onic acid S03H-C6H2(NH2) <c6H3(NH2)> so -is formed together with the di- tri- and tetra-sulphonic -acid whenthe sulphone is heated with fuming sulphuric acid a t temperaturesabove 100'.The crude product is boured 01 to ice and after keep60 Al3Sl'RACTS OF CIIENICAL PAPERS.i n g for some time the solution is filtered; the tri- and tetra-hulphonicacids being readily soluble in cold water pass into the filtrate whilstthe mono- and di-sulphonic acid which are only sparingly soluble,remain ou the filter.The residue is dissolved in soda and the mono-sulphonic acid is precipitated from the filtered solution by addingacetic acid ; the disulphonic acid in the filtrate is then precipitatedby adding a large excess of hydrochloric or sulphuric acid. Benzi-dinesulphonesulphonic acid crystallises from hot water in which it isonly sparingly soluble in small light-yellow needles and is almostinsoluble in alcohol. The tetrazo-derivative is a reddish.brown,amorphous compound ; i t combines with amines phenols and withtheir carboxglic and sulphonic acids forming dyes which are of aredder shade and are much more sparingly soluble than those derivedfrom benzidinesulphonedisulphonic acid (see below).The ccr Zciumsalt (Cl,H,NTS20,)2Ca + S&H20 crystallises in small yellow needles,and is readily soluble in hot water but only moderately so inboiling alcohol and sparingly in cold water. The barium salt (with3+H,O) crystallises in small golden needles and is more sparinglysoluble in water than the calzium salt.Ben zidinesu @ honedisdphon ic acid,1$H,O separates in small light-yellow needles when a boilingaqueous solution is evaporated. It is inodermtely easily soluble inhot water but only sparingly in alcohol and almost insoluble in coldhydrochloric or sulphuric acid. The tetruzo-compound is a light-yellow voluminous substance ; i t combines with naphthols andnaphttolsulphonic acids yielding purple to violet dyes and withnaphthylamines and naphthylaminesulphonic acid Porming red orbluish-violet colouring matters.It yields beautiful reddish-violet orindigo-blue azo-dyes (sulphoneazurines) wi tli alkyl- and phenyl-naphthylamines. The calcium salt CI2H,N2S3O8Ca + i H 2 0 crystal-lises in yellow needles or plates and is readily soluble in hot butorily sparingly in cold water and insoluble in alcohol. The bariumsalt (with 4iH,O) crystallises in needles or very small prisms and isinsoluble in alcohol and only very sparingly soluble in boiling water.The sodium salt crjstallises from hot concentrated aqueous solu-tions in long yellow needles and is only sparingly soluble in coldwater.Orthotolidine yields analogous compounds to those obtained frombenzidine under the same conditions.Ol.thotoliJirnesziZphon~c acid isvwy sparingly soluble in water and does not crystallise readily. Thetetmzo-derivative is readily soluble in water. The barium salt loses4 mols. H,O when dried a t 150". The disuZpyhonic acid crystallisesfrom hot concentrated aqueous solutions in small colourless needles,and is readily soluble in hot water. The tetrazo-derivative is insolublein water. The salts are moderately emily soluble in water; thesodium salt crystallises in cuhes (with 4H,O) the ctcbium salt in plates(with 5H20) and the barium salt in needles (with 3H20).Tolidinesdphone is a greenish-yellow amorphous compound thesalts OF which are very similar to those of benzidinesulphone (D.R.-P.,No.44,784). F. S. K.>so + yJL(NH,) (S0,H)C,H,(NH,)(SO,HORC INIC CHEMISTRP. 61p-Naphthylhydrazine. By F. HAIJFF (Awnalen 253,24-35).-The derivatives of p-naphthylhgdrazine bear a close resemblance tothe corresponding phenylhydrazine-derivatives. The acetyl-deriva-tire Cl,,H7*N2H,Ac. prepared by boiling p-naphthylhydrazine withglacial acetic acid for several hours in a reflux apparatus formscolourless needles soluble in alcohol chloroform and benzene andmelts a t 164-165". Renzoylnnphthylhydruzine C,,H,*N~H,BZ is ob-tained on adding benzoic chloride to an ethereal solution of naphthyl-Iiydrazine (3 mols.) ; naphthylhydrazine hydrochloride is precipitated,and the filtrate on being evaporated and the residus treated with ahot dilute solution of sodiiim hydroxide to remove unaltered benzoicchloride leaves the hg drazine.When pure it crystallises in needles,melts at 154-155" and is soluble in hot alcohol ether benzene andchloroform. I n order to introduce a second benzoyl-group into thepreceding compound it is necessary t o act on it with beuzoic chlorideat a high temperature. The dibenzoyl-derivative C'10H7.N2HB~2 meltsa t 162-163".B-NaphthyZsemicarbazide C1nH7*N?H2*CO*NHz prepared by theaction of potassium cyanate on naphthylhydrazine hydrochloride issoluble in hot alcohol and acetic acid ; i t melts at 220" (uncorr.) andresembles the corresponding phenyl-derivative in its chemical pro-perties. It is decomposed by the action of hydrochloric acid insealed tubes at 140° yielding naphthazine which has previously beendescribed by Witt (Abstr.1887 153).P-Naphthy Zthiosemicarbazide C,oH7*N2H2*CS*NHz is obtained by boil-i n g an alcoholic solution containing equal parts by weight of naphthyl-hydrazine hydrochloride and ammonium thiocyanate. This substancemelts at 201 -202" (uiicorr.) and is soluble in hot aniline and alcohol.It is decomposed by hydrochloric acid in sealed tubes at 130-140",NHyielding napht~~y Zthiocarbizine CIOH7N< & . The carbizine meltsat 2.53-2.54" and crystallises in plates. It is solublc in warmalcohol and forms a crystalline hydrochloride and platinochloride.A violet precipitate is formed when bleaching powder is added to thealcoholic solution of the base.Naphthylhydrazine naphthylthiocarbazin~te,C,,H7*N2H2*C i3.S H,N,H,*Cl,H,,cry$tallises in plates and melts with decomposition at 145".It issoluble in warm alcohol.Ethyl-P-naphthylhydrazine is prepared by the action of ethyliodide (2 mols.) on naphthylhydrazine in alcoholic solution. I t is apale-yellow oil freely soluble in alcohol ether benzene and chloro-form. I t reduces warm Fehling's solution. The solution in ch1or.o-form is slowly decomposed by mercuric oxide yielding naphthylethyl-am i lie. w. c. w.Derivatives. of p-Naphthylhydrazine. By A. H [LLRINGHAUS(per. 22,2656-26.57).-ln reference to Hanff's work on th:s subject(preceding Abstract) the author states that he has also recentl6% ABSTRACTS OF CHEMICAL PAPERS.obtained the acetyl-derivative the semicarbazide and the thiosemi-carbazide. L.T. T.Derivatives of the Two Isomeric NaphthenylamidoximesBy E. RICHTER (Ber. 22 2449-2459; compare Abstr. 1887,374 also Ekstrand ibid. 373).-P-Napthenylamidoxime (m. p. 150)is readily soluble in alcohol and ether but only moderately easily inbenzene and chloroform and insoluble in light petroleum. The COT-responding a-compound (m. p. 148-149") resembles the /?-deriva-tive in its behaviour with solvents.Benzoy 1-P-naphthenylamidoxime C,oH,*C(NH,):NOBz prepared byheating the amidoxirne with benzoic chloride crystallises from hotalcohol in colourless needles melts at 179' and is only sparinglysoluble in cold alcohol ether benzene chloroform and light petroleurn,insoluble in water.NO Naphtlteiaylbenzenylazoaime ClOH,*C< - N>CPh is formed whenthe preceding coinpound is boiled with water dilute acids or diluh:alkalis or when i t is treated with concentrated sulphuric acid.I tcrystallises from dilute alcohol in colourless plates melts a t 116" aildis readily soluble in alcohol ether benzene chloroform and lightpetroleum but almost insoluble in water.Acetyl-P-naphtheny lamidoxime CI:,H,2N20 crystallises from alcoholor benzene in yellowish needles melts a t 154" and is only sparinglysoluble in ether chloroform a1.d light petroleum and insoluble inwater ; when boiled with water or when treated with concentratedsulphuric acid it is converted into the azoxime melting at 85"(compare Ekstrand Zoc. cit.).Ethyl-P-napht hen y larnidoxirnecarboxy late C10H,*C ( NH2) :NOC OOE t,separates from alcohol in colourless needles melts a t 121" and is readilysoluble in alcohol ether benzene chloroform and acids but verysparingly in light petroleum and insoluble in water and alkalis.NO P-Nap hthen y lcarbon y limidoxime C > C 0 cry s tallisesfrom hot benzene in cclourless needles melts a t 216" and is mode-rately soluble in alcohol ether and chloroform but sparingly inbenzene and hot water.The sodium-derivative is crystalline. In anaqueous solution of the ammonium-derivative lead acetate produce? awhite and copper sulphate an apple-green precipitate.P-Naphthe?j ylamidethoxime CIOH7.C ( NH2):NOEt crystallises fromdilute alcohol in colourless needles melts a t 74-75" and is readilysoluble in alcohol ether benzene chloroform light petroleum andhydrochloric acid but very sparingly in water and insoluble inalkalis.Ethylidene-@-naphthenylamidoxime C,oH,*C<NH>CHXe NO pre-pared by dissolving the amidoxime in acetaldehyde crystallises fromhot water in colourless needles melting at 121-122".It is readilysoluble in alcohol ether benzene and light petroleum very sparinglysoluble in cold water and insoluble in acids aud alkalisORGANIC CHEBIISTRY. 63NO Acet oe t heny I- &nap ht heny lazoxime C ,,H7 C<- N>C* C HzAc is f ovmedby boiling the amidoxime with ethyl acetoacetate ; it crystallises fromhot water in nacreous plates melts a t 108-109" and is soluble iualcohol ether benzene and chloroform but insoluble in lightpetroleum.Acetyl-a-na~hthenylamidoxirrLe crystallises from dilute alcohol incolourless needles melts at 129" and is insoluble in water but readilysoluble in alcohol ether benzene and chloroform ; when treated withconcentrated sulphuric acid or when boiled wit.h water it is convertedinto the azoxime (compare Ekstrand Zoc.cit.).Ethyl-a-napht?~enylanaidoxi~mecarbozylatu crystallises in colourlessneedles melts at 11l0 and is readily soluble in alcohol ether benzene,and chloroform but only sparingly in light petroleum and insolnblein water.a- Naphthen.yZcarbonylimidoxirne prepared by boiling the precedingcompound wit.h water or alkalis crystallises from dilute alcohol incolourless needles melts at 189" and is readily soluble in alcohol bntonly sparingly in ether benzene and chloroform and insoluble inlight petroleum and water.I n aqueous solutions of the ammonium-derivative lead acetate produces a white and copper sulphate a greenprecipitate. F. S. K.Acetyl- and Ethyl-derivatives of Camphonitrophenol. By P.CAZENEUVE (Bull. SOC. Chiin. C3] 1 467-469 ; compare Abstr. 1889,CsN02 618) .-The acetyl-derivative of camphonitrophenol C8H14<l 1 C*OAc)after saponification and subsequent saturation with slight excess ofhydrogen chloride gives with ferric chloride a violet-red coloration,CH*N02 which indicates the forniation of the compound C,H,,< IThe ethyl-derivative CsHld<E.oEt is made by heating sodiumcamphonitrophenoxide with excess oE ethyl iodide in sealed tubesat 120" for three hours; after separation of sodium iodide the liquidis evaporated to dryness and the residue crystallised from benzene.The compound forms large colourless flat crystals which melt at54" and decompose on distillation.C(OH)2T. G.N.Camphonitrophenol Phosphate. By P. CAZENEUVE (BUZZ. SOC.Chirn. [ 3],1,46!b--47 1) .-The normal phosphate ( C,,t€,,NO,),PO isprepared by boiling camphonitrophenol with phosphoras trichloride forseveral hours. It exists as an amorphous yellowish insoluble sub-stance which when heated decomposes without melting. Nitrophenolforms an analogous compound ( C6K4NO,),PO with phosphorus pent+chloride only traces of metachloronitrobenzene being simultaneoiislyproduced. This reaction confirms the constitution previously giveuto camphonitrophenol.T. G. N64 ABSTRXCTS O F CHEJIICAL PAPERSCamphonitrophenol Benzoate and Phthalate. B J P. CAZE-C-NO,N EUVE (BUZZ. Soc. Chim. [3] 1,471-4B).-The benzoate C,H,,< I I C-OBzi R prepared by the reaction of equal parts of camphonitrophenol andbenzoic chloride at 100' ; it forms small crystals which are insolublein water but soluble in hot alcohol ether and benzene; these melta t 131" ; and partially volatilise a t 150" without decomposing. Onsaponification with alcoholic potash it yields potassium benzoate andthe compound C,N,,< IC-NO,C(OH)?'Phthalic chloride by a similar reaction forms a compound,(N0o.C 10Hl,o)J&H,02,which melts at 275" with slight decomposition. T. G. N.Quercetin-derivatives.By J. HERZIG (LVonatsh. 10 561-567 ;compare Abst)r. 11388 1309) .-In a preyious communication theauthor has called attention to the fact that pure xanthorhamnin ienot the sole product obtained from Persian-berries by the method ofLiebermann and Hijrmann (Abstr. 1879 'L71). It is now shownthat besides xanthorhamnin the berries cont.ain a glucoside ofrhamnetin or some nnstable molecular compound of the glucosides ofrhamnetin and quercetin. This result is in accordance with the factthat Schutzenberger obtained two glucosides ( a - and P-rhamnin)from Persian-berries. His a-rhamnetin (from z-rhamnin) is evidentlyidentical with rhamnetin his P-rhamnetin (from p-rhamnin) withquercetia. G. T. M.Scutellarin one of the Constituents of Scutellaria 19nceo-lwia.By I). TAKAHASHI (Chem. Centr. 1889 ii 100.)-The rootof ScuteZZariu Zunceularia one of the labiatse is used medicinally inChina and Japan. By extracting the root with ether agitating theether extract with sodium hydroxide and acidifying the alkaline solu-tion a yellow. flocculent substance scutellnrin is obtained. It formsodourless and tasteless shining flat yellow needles melts at199-199*5" is insoluble in cold little soluble in hot water veryreadily soluble in alcohol ether chloroform light petroleum andcarbqn bisulphide ; soluble in sodium hydroxide and carbonatesolut,ions ,but carbonic anhydride is not expelled from the latter.It dissolves in concentrated sulphuric acid with a yellow colora-tinn and water reprenipitates the substance unchanged.It dis-solves in nitric acid with red coloration and in like manlier in a solu-tion of sulphuric acid and potassium nitrite. Fehling's solutionis llot reduced by it even after boiling with hydrochloric acid.J t does not combine with phenylhydrazine ; neither silver nitratenor lead acetate precipitates it from its alcoholic solution but solu-tions of lead and copper acetates produce a yellow-red precipitatewith the dcoholic solution. When treated with bromine in carbonbisulphide solution a substance crystdlising in yellowish needles isformed ; the determiriation of bromine in it however! gare unsatis-factory results. The el2mentary analysis of scutellarin give figureORGANIC CHEMISTRY. 65which corresponded with the formula CloH,03 ; it contains neithernitrogen nor water of combination.5 grams of scutellarin producedno effect when administered to a dog in an emulsion of milk andgum arabia The author believes it to be a phenol and possiblyan isomeride of juglone. J. W. L.Crystallised Digitalin. Ry ARNAUP (Compt. rend. 109 6i9-682) .-Digitalin prepared by Nativelle's method from the digitalis ofthe Vosges formed very thin brilliant white rectangular lamelh,which melt at 243" dissolve in absolute alcohol to the extent of 0.650part in 100 at 14" and also contrary to the statement of Schmiede-berg dissolve in boiling benzene. When subjected to fractioual solution,the melting points of the different fractions varied only between242" and 245".A second quantity prepared by Adrian melted at 245-246" andwhen dissolved fractionally in alcohol and benzene the meltingpoints varied only between 243 and 245" as with the first sample.Digitalin is a distinct chemical individual and it is not necessaryto denote it by any name such as digitoxin.It seems to be the typt.of a large group of compounds. C. H. B.Dihydropyrroline. By F. ANPERLINI (Ber. 22 2512-2515).-Dihydropyrroline hydrochloride is decomposed when heated givingroff vapours which colour pine-wood red ; it is partially decomposedby concentrated hydrochloric acid at 130-140". The uuroch loride.C4NH7,HAuC14 crystallises from cold water in small prisms melts at152' and is slowly decomposed when boiled with water. The picrate,CdNH7,C6H3N307 separates from water in yellow crystals melts at156" arid is readily soluble in alcohol and water.Benzoy Zdihydropyrroline C4NH6Bz prepared by heating dihydro-pyrroline hydrochloride with benzoic chloride at 110" is an oilyliquid boils at 160-161" (2 mm.) and is miscible with alcoholand ether but is insoluble in water.It dissolves freely in con-centrated hydrochloric acid yielding a salt which does not crptallisereadily.Benz y Zdihy drop yrroline C4NH6*C H,Ph prepared by treating di -hydropyrroline with benzyl chloride boils at 150". The aurochloride,CIIH,,N,HAnCl~ crystallises from water in yellow needles melting. at111". E. S . K.Derivatives of Alkylpyrrolines. By C. U. ZANETTI (Bey. 22,2515-2519 ; cornrare Ciamician and Zanetti Abstr.1889 727).-1-Ethylpyrroline boils at 129-130" (762 mm. corr.). The tetra-bromide melts at 83" and is converted into ethyl dibromomaleimide(m..p. 93-94") by cold nitric acid of sp. gr. 1.49. The diacGtyZ-derivative C4NHzEtAc is a crystalline compound melts at 58-59',boils a t about 183" (29 mm.) and is readily soluble in alcohol ether,benzene light petroleum and warm water.When the mixture of c-ethylpyrrolinep boiling at 150" (compareCiamician and Zanetti Zoc. cit.) is treated with acetic anhydrideand sodium acet'ate an oil is obtained which can be separated by frac-VOL. LVIII. 66 ABSTRACTS OF CHEXICAL PAPERS.tional distillation into a portion boiling at 210-235" and a portionbuiling at 240-255". The former is volatile with steam and has thecomposition and properties of an 1-acetyl-c-ethylpyrrolins C4NH3EtAc.The latter after having been boiled with potash and repeatedlydistilled in order to free it from 1-acetyl derivatives solidifies parti-ally when exposed to long continued cold and can thus be separatedinto its constituents ; the crystalline substance is an acetyl-deriva-tive melting a t 42-44" probably identical with the compound(m.p. 47") obtained by Dennstedt a a d Zimmermann from c-ethyl-pyrroline (compare Abstr. 1886 1043). Both the liquid and thesolid compound give a silver-derivative which has the compositionl-Propylpyrroliije C4NH4Pr is obtained in small quantities whenpotassium pyrroline is treated with propyl iodide but isomerides andother compounds are also formed; it) is a colourless oil hoiling a t145-5-146*5" (755.8 mm.).Nitropyrroline-a-carboxylic Acids.By F. ANDERLINI (Ber.,22 %503-2506).-Methyl nitropyrroline-a-carbox~lafe,NO,-C,NH,*COOMe,(m. p. 197") is formed together with an isomeride (m.p. 179") andother nitro-compounds when finely divided methyl pyrroline-d-carboxylate is gradually added to ice-cold nitric acid of sp. gr. 1.5aud the solution poured into cold water; after neutralising withsoda and adding a lit'tle sodium carbonate the solution is extractedwith ether It crystallises from boiling water in coloudess needlesmelting a t 197". The corresponding acid N0,.C4NH,COOH ob-tained by hydrolysing the ethereal salt with potash crystallises fromwater with 1 mol. H,O in light-yellow needles and is readily solublein alcohol ether and hot water but only sparingly in benzene andcold water.I t loses its water when kept Over snlphuric acid underreduced pressure and the anhydrous crystals melt a t 217".Nethyl nitropyrroline-a-carboxylate (m. p. 179") is obtained togetherwith other nitro-compounds when the alkaline solution from whichthe isomeride (m. p. 197") has been extracted is acidified and thenextracted with ether. It can be isolated by hactionally cry stallisingthe crude product from water. It separates from dilute alcohol inyellow needles melting at 179". The corresponding acid crystallisesfrom hot water with 1 mol. H,O in light-yellow needles and is readilysoluble in alcohol ether and hot water and moderately so in benzene,but .only sparingly in cold water.It loses its water when keptover sulphuric acid under reduced pressure the anhydrous compoundmelting a t 161".The mother-liquors from the preceding compound (m. p. 179")probably contain the third isomeride which has previously been pre-pared by Ciamician and Danesi (Abstr. 1882 875) from dinitro-pyrocolf but this compound could not be obtained in a purecondition. They also contain the methyl salt of a dinitropyrroline-carboxylic acid C4NH2(N02)2*COOMe ; this compound crystallisesfroin watler dilute alcohol and benzene in light-yellow plates meltinga t about 113". F. S. K.C,HioNOAg.F. S. KORGXSIC CHEJIISTRY. 67Molecular Weights of the Imidoanhydri 3es of Pyrroline-carboxylic and Indolecarboxylic Acids. By G.MAGNANLNI (Bw.,22 2j01-25Oq. Molecular weight determiuations by Raoult'smethod in naphthalene solution show that the molecular formula ofpyrocoll is C10H6N202 that of tetramethylpyrocoll ClIH,,N,02 thatof diacetylpyrocoll C14HloN20~ and that of the imidoanhydtide ofa-indolecarboxylic acid C18H10N202. The depression constant ofnaphthalene was taken as 82 according to Raoulb.Action of Methyl Iodide on Tetramethyldihydropyridine.By F. ANDERLINI (Ber. 22 250d-f251l).-Pentamethyldihydro-py r i din e h y d riod i il e is obtained w h en t e trame t hy Id i hy d rop y rid in e(b. p. 158") is treated with methyl iodide (compare Cilimician andAnderlini Abstr. 1889 728) The free base boils at 188-190"(45-46" ; 7 mm.).A bnse C12H?,N is formed when pentamethyldihydropyridine istreated with niethyl iodide in the cold and the resulting oily hy-driodide distilled with potash; the base was not isolated. Theuu?-ochZoride CI2Hz1N,HAuCl4 crystallises in thin golden needlesmelting a t 99-99.5".F.S. K.F. S. K.Synthesis of Oxypyridine and Piperidine Bases. By A.Lau~xsunc; (Ber. 22 2583-2590) .-a-Picolylalkins,is obtained as a thick brown syrup by the action of formaldehydeon a-picoline and is purified by distillation under 20-30 mm.pressure. It is a colourless syrup boils at 179" nnder 25 mm.pressure dissolves readily in water and alcohol sparingly in ether :i t is rather hygroscopic and can only be dried over fused potassiumcarbonate ; sp. gc". 1.111 a t 0". Theplcitinochloride (C7H9NO),,H,PtCl,,crystallises well in pristiis very readily soluble in hot water and meltsa t 170" with effervesceuce.The aurochioride crpstallises in well-formed crystals rather sparingly soluble iii water.Vi,t ylpyridirw C5NHI.C2HB prepared by distilling the above com-pound under higher pressure o r in preseiice of potash is a colourless,mobile liquid very readily soluble in alcohol ether and chloroform &c.,but only sparingly in water. It boils with decomposition a t 158-13:!at t.he ordinary pressure but distils without decomposition a t 79-82'under 29 mm. pressure ; sp. gr. = 0.9985 a t 0". The ylutinocldoride,(C,H7N)?,H2PtCI6 crystallises in needles or large plates melts a t 174"with decomposition and is rather readily solutle in water.Thechuimhloyide cadnzioiodide bismuth iodide and rnemwocll loride cryst,aI-lise well.a-YipecoZyZalTcine C,NHlo.CH2*CH2*OH obtained by the action ofsodium and alcohol t)n picolylalkine is a colourless crystalline baseTvhich melts at 31-32' aiid boils at 225-228'. It is very hygro-scopic and is readily soiuble water alcohol and ether. It is astrong base and turns red litmus blue. The yZutinocltZorit?e,(C,H,,NO),,H,PtCI crystallises in splendid large transparent crys-tals like gypsum and melts at 158".f 68 ABSTRACTS OF CHEMICAL PAPERS.a-Meth?/ZpipecolineaZX;ine C,NH,Me*CH,2*CH2*OH is formed whena-pipecolylalkine dissolved i n metlipl iodide is Lrmted with methyliodide and sodium at the ordinary temperature. When the methyliodide has disappeared the alcohol is evaporated the residue re-peatedly extracted with ether the base converted into the hydro-chloride and warmed slightly with sodium nitrite.The nitrosaminewhich separates is removed by ether. The hydrochloride is thentreated with potash and the tertiary base is extracted with ether anddried with potash. The aurochloride is crystalline ; the plafino-chloride cadmioiodide and periodide were also prepared.Vin ylpipwidine C,NH,,;C,H (?) is obtained from pipecolylalkinby the method previously employed for the preparation of tropidinefrom tropine (Annalen 217 118). It is a colourless liquid boils a t146-148" is readily soluble in water and has an odour of tropidineaiid coniine. The aurochloride and p i c m t e crjstallise well and arerather soluble in water.a-Picolyl~2ethylaIkine7 C5NH4*CE3*CHMe*OH is formed in a mannerhimilar to a-picolylalkine from a-picoline and acetaldehyde and ispurified by means of the platinochloride.It is yellowish boils a t176-181" under 18 mm. pressure and is readily soluble in water,alcohol and chloroform sparingly in ether. The plrctinochlorz'de,( CRHl,NO)2,H2PtC16 crystallises from hot water in small plates whichmelt R t 189" with decomposition ; the auroohEoride crystallises well.a-Pipecolylmetl~ylalkit~e C,NH,,*CH,*CHMe*OH melts at 47" boilsat 224-226" and is readily solnble in water alcohol and ether,The platinochloride melts at 149". I n its properties the base resemhlesconydrine with which it is isomeric.N. H. M.Hydroxymetadiazines (Hydrsxypyrimidines). By E. v. ME YE^^(J. pr. Chem. [2 ],40 303-304) .-Amidomethyldiphenylmetadiazine(Abstr. 1889 578) melts at 1G8" not 172" ; it can also be obtainedby acting on a mixture of ethyl cyanide and phenyl cyanide withsodium o r sodium ethoxide.Hydroxymethyldiphenylmeta#diazine (loc. cit.) melts at 250" not256" ; it can also be obtained by the condensation of benzamidine andethyl methylbenzoylacetate. By heating it with alkaline potassiumpermanganate adding dilute hydrochloric acid to the colourlew solu-tion dissolving the precipitate in weak ammonia filtering and againprecipitating with hydrochloric acid a hy droe ydiphenylmetadiazinecar-boxylic acid C P h < ~ ~ ~ ~ ~ C C O O H is obtained ; this crystallisesfrom alcohol in beautiful pale-yellow prisms melting at 236" withevolution of carbonic anhydride.When heated in a diphenylaminebath at 250" until evolution of carbonic anhydride ceases it leavesa yellow crystalline residue mostly soluble in potash ; if the preci-pitate obtained by adding hydrochloric acid to this potash solutionis digested with weak ammonia and crystallised from alcohol yellowishslender needles CI6Hl2NZO which melt a t 280.5" (uncorr.) are ob-tained. These appear to be identicad with Pinner's diphenylhydroxy-pyrimidine (Abstr. 1889 lOOS) which melts at 284"ORGANIC CHEYISTRT. 69N ='CEt Hydrozymethylefhylmet?~ ylmetadiazine CMeGN ,c (bH)>CMe isobtained from acetamidine and ethyl propionylpropionate ; it meltsat 167*5" and is isomeric with the hydroxy-base of cyanmetthethinemelting at 150" (Abstr.1885,646). A. G. B.Pyrimidimes. By A. PIXNER (Rer. 22 2609-2626 ;. compareAbstr. 1889 1006) .-The formation of the pyrimidines appears totake place in three stages. Employing benzamidine and ethylacetoacetate as examples these stages are as follows :-I. NHXPh-XH + COOEt*CH,-COMe =NH CPh*NH*C 0 *CH2*COMe + EtO H.The ethyloxalylacetylbenzamidine already described (Abstr. 1889,1009) is the first-stage product in the formation of phenylhydroxy-pyrimidinecarboxyiic acid and may be easily converted into the latterby the action of soda. The compound obtained at the same timeand melting at 263" is phenyIhydroxypyvimidinecarboxytbenzamidine,N<g[k@-$>C*CO*N H C Ph N H the benzamidine haviii g reactedwith the second carboxyl-group of the acetoxalate.It is converted int,othe above carboxylic acid by the action of soda. As already noted(Zoc. cit.) the free acid melts with decGmposition at 247" ; carbonicanhydride being evolved and phenylhydroxypyrimidine is formed.When benzamidine and ethyl acetomalonate react on one another,one carboxyl-group is separated and the same pyrimidine formed asis obtained from ethyl acetoacetate.When ethyl acetosuccinate benzamidine hydrochloride and sodiumhydroxide or potassium carbonate are mixed together two compoundsare obtained melting respectively at 1 7 8 O and 212". The former (m. p.1 7 Sv> is ethyl pheny lmet IL y lh y drox yp yrimidirkeacetnt e,-I t is easily soluble in alcohol ether and acetone sparingly in water,and crystallises in needles.When saponified with soda it yieldsphen.y lmethglhydrox ypyrimidineacetic m i d which crystallises in needles,melts a t 259" and is soluble in alcohol. The needles crystallising at212" have the formula C11H,oN202 and are probably succinylbenzimide,?H2'Co >N.CPh:NH. This compound forms the principal productCH,.COif caustic soda is used for liberating the benzamidine from its hydro-chloride in the reaction whilst if potassium carbonate is employed,the pyrimidine is the chief product70 ABSTRACTS OF CHEMICAL PAPERS.With ethyl acetylglutarate benzamidine yields etlbylphen yluz ethyl-h y droxyp yrimidine~r~p~ona t e C P h q N N:C(OH)/ - '' eW2 C H,*C H,. C 0 0 E t ,which crystallises in needles is soluble in alcohol ether and acetone,and melts a t 145".The.free acid forms a white powder almost in-soluble in water and alcohol and melting a t 215".When ethyl diacetosuccinate is mixed with benznmidine ethylphe~iylmethylhydroxypyrimidineacetate (m . p. 178") and phenyl-met h y 1 ace tony l h y droa yp yrimidine C P he" 6 gy>C. CH,G OM e,are formed. The latter is insoluble in acet,one soluble in alcohol ;it crvstallises in needles and melts at 225". The author was uuable toobtain the dipyrimidine C P h ~ N ~ c ~ o H ~ ~ - C ~ c I C H ~ ~ ~ CMe - N - CMewhich he had anticipated the second' aceiyl-group appearing alwajsto be separated before the pyrimidine formation set in.A mixture of ethyl succinylsuccinnte and benznmidine yields a sub-stance easily soliible in alcohol and melting at 272" and anotheralmost insoluble in the usual solvents.The fornier. tetra7~i/dl.owhe?.uZ- . I 1 .I?~ycirox~ketopui?kasdine ~:C(oH)'f?CHz*~Hz crystallises in needles.CPh Pr'*C'CH,-COThe latter owing t o its insolubilit'y could not be thoroughly purified,but appears to have the formula C,H,,N4O2 and to be dihydrocli-~:C(OH)*~.CH,*$*N = CPh It dis-plieny ldih y clrox yantetrazine,CPh=N*C*CH,.C*C(OH):Nsolves in boiling caustic soda yielding a crystalline sodiz~nz-deri.cat.iz;e,C,,H,,Na,N,O + 4Hz0.The amidine of acetonecyanhydrin OH.CMe2*C (gH,):NH yieldswith e thy1 a cetoa cetate hydroxyisoprop y lmrfh ylhy d ~ o x y p yrimiditie,OH.C?ile,.C~,:,(,,~~CH N-CMe crystallising in easily soluble needlesand meltingat 98".If ethyl benzoylacetate is employed instead ofthe ace t oacet a t e h y droxy isoprop y @ heny lhy &ox yp y rimidine,is formed. This crystallises in small glistening prisms sparinglysoluble in water easily so in the usual organic solvents and meltsat 198". L. T. T.Phenylhydrazonelevulinic Anhydride. By F. ACH (Annale??,253 44-57). Two compounds are formed by the action of phos-phorus pentachloride on phenylhydrazonelevulinic anhydride a t 150.One contains 2 atoms of hydrogen less than the anhydride and thesecond compound is a monochloro-substitution-product of the first.The crude product of the reaction is poured into water containing ice.In the course of 24 hours phenylmethylchloropyridazone is depositedin crystals.The mother-liquor is rendered alkaline and treated withether to extract the phenylrnethylpyridazone. The residue is redis-solved in 100 parts of boiling water to which a small quantity oORGANIC CHEMISTRY. 71hydrochloric acid is added. On cooling the chloro-substitution-pro-duct crystallises out and the base is extracted from the mother-liquoras before. It is finally purified by precipitation as the hydrochlorideby passing dry hydrogen chloride through its solution in benzene.NPh-N Phen?lEmeth?/~~yridazone CO< CH:CH>CMe is freely soluble iualcohol ether chloroform benzene and acetone melts at 81-82',and has feeble basic properties ; its salts are decomposed by water.By the action of sodium on the hot alcoholic solution a crystallinebase is produced which appears to have the composition C2,H,,N ; thismelts at 200" and yields a sparingly soluble platinochloride. Thesolution in dilute sulphuric acid acquires a violet-blue colour on theaddition of chromic or nitrous acid.Phenylmethylchloro/iyridazone C 0 < ~ ~ ~ ~ ~ > C M e crystallises illflat prisms and melts at 136-137".I t is freely soluble in hotalcohol chloroform benzene and acetone and also dissolves inmineral acids but is reprecipitated unaltered from the acid solutionsby water. The nitro-derivative melts at 210-213". The chlorine isdisplaced by ethoxyl by the action of alcoholic potassium hydroxide.PhenylmethyZathoxypyridazone melts at 14ti0 crystallises in flatprisms or plates and dissolves freely in hot alcohol benzene chloroform,acetone and in hot water and is also soluble in strong acids.It isdecomposed by heating at 125" in sealed tubes with hydrochloric acid,yielding phenyZnzethyLhydroxypyyidazone. The hydroxy-derivativecrystallises in needles and melts at 196". It is soluble in hot acetone,benzene and chloroform in strong mineral acids and in alkalis. Theaddition of ferric chloride to the hydrochloric acid solution producesa red-brown coloration which turns to carmine on dilution. At 170",hydrochloric acid converts the hydroxy-componnd into phenyrnethyl-pyrazolecarboaylic acid I I >C*COOH. The acid is soluble inhot. alcohol chloroform benzene ether and in strong mineral acids,C MeCHN-NPhmelts at 165-166" and decomposes at 200" yielding phenylmethyl-pyrazole >CH probably identical with the phenylmethyl-Me*CHN-NPhpyrazole described by Knorr (Abstr.1887 601).Phenylmethylpyrazole me1t.s at 34-36" and boils at 254-255"under 753 mm. pressure. It dissolves freely in ether alcohol chloro-form acetone benzene and light petroleum. The platinochlorideforms orange-coloured needle-s haped crystals sparingly soluble inwater. The pyrazole is convertled into the pyrazoline by the actionof sodium on its alcoholic solntion. The pyrazoline melts at 73-75"and distils without decomposition. It is soluble in ether alcohol andbenzene and gives the characteristic pyrazoline-colour reaction withferric chloride or chromic acid.w. c. w.Synthesis of Quinazoline-derivatives. By C. PAAL and 31.BUSCH (Ber. 22 2683-2702) .-The authors have studied the actionof orthonitrobenzyl chloride on the sodium-derivatives of form52 ABSTRACTS OF CEEhlICAL PAPERS.anilide and of scetanilide and of some of their homologues. The met-nnilides did not give satisfactory results but with the fornianilides thefollowing reactions (where R is an aromatic radicle) take place :-N0,-C6H4*CH2C1 + R-NNaaCOH = N0,.CsH4~CHz*NR~COH.On reduction the product yields quinazoline-derivatives,Action of Orthonitrobenzyl Chloride on Sodium Formanilide.-Sodiuinformanilide is prepared by adding sodium to a benzene solution of form-anilide and then a proportional quantity of orthonitrobenzyl chlorideis added.Orthonitrobenzy Iformanilide NOz.C6H4*CH,*NPh*COH issoluble in the usual organic solvents insoluble in water. It melts ati 7 " and forms yellow monosymmetric plates gixing the measure-ments a b c = 0.5477 1 1.085 and l3 = 69" 7'. This formanilidewas also obtained by boiling ort~honitrohenzylaniline (Lellmann andStickel Abstr. 1886 793) with formic acid. When reduced withzinc and acetic or. hydrochlonic acid phenyldihydropuinuzoline,C6H4<CH2.hph is formed ; this crystallises in hexagonal plates isN=CHalmost insoluble in water and alkalis easily soluble in mineral acids,alcohol ether &c. It melts at 95" and distils at a very high tem-perature with partial decomposition. When distilled with zinc-dust,i t yields equal quantities of aniline and benzonitrile.Its sulphate,( Cl4H,,N,),,H,SO4 + 2Hz0 crystallises from water in needles loseswater at 70" and melts at 79"; when free from water i t melts a t140-143" ; the hydrochloride + 'LH,O forms glistening needlesmelting a t 80" ; the anhydrous salt melts at 221" and is easily solublei n alcohol and ether. The pZatin.ochZoride forms yellow crystalsme1 ting a t 208" ; the aurochloride orange scales ; the sfunnochlol-ide,( ',4HlzN,,HSnC13 flat white needles or scales melting a t 130-134".When heated with methyl iodide in closed tubes at loo" the quinazolineyields three derivatives the methiodide periodide Cl4Hl2NZMeI,I,forming glistening golden-yellow scales melting at 157" ; the meth-iodide C14H12N2,Mel crystallising in white needles melting a t 170" ;and a third substance crystallising in prisms melting a t l80" whichappears to be a second isomeric rnethiodide. When oxidised withpotassium permangmate the quinazoline yields phenyllietodihydro-YH which crystdlises in almost colourless quinazoline C&<glistening scales or well-formed rhombic crystals giving the measure-ments a b c = 2.4228 1 3.2742.It melts at 139" and sublimeswithout decomposition. No hydroxylamine-derivative or phenyl-hydraaide could be obtained but with hydrazine (amidogen) it yields>C<&,; this forms y heny lketoh?y drazodihy dro quinazoline,white glistening needles which melt at 204" and in small quantities,siiblime without decomposition. The hydrochloride Cl4H,,NZO,HCl,crystallises in glistening scales and melts at 213-214" ; it loses itsCO*NPh'NH H*NPhN- CeHOHGAXIC CHEJJISTRY.73hydrogen chloride ah a moderate heat. The platinochloride crystal-lises in yellow needles melting above 300". When the keto-base ist,reated in alcoholic solution with sodium phen yltetrahydroq.uinazolir~e,c,H,< CH,.&Ph is formed which is soluble in organic solvents,cyystallises in white needles melts at 117" and distils at a high tem-perature without decomposition. It is only feebly basic its saltsdecomposirig on the addition of water. It yields a hydrochloride acrystalline aceto-derit,atice and 8 nitrosamine. An unstable inter-mediate product containing the (CH-OH) group appears to be formedalong with the tetrahydro-componnd but it could not be isolated,When oxidised with permanganate the tetrahydro-derivative is recon-verted into the keto-compound but both here and in the originalformation of the keto-derivative small quantities of a sparingly solublenitrogenous crystalline compound melting at 219" are formed.Actiosn of Orthonits.obenzy1 Chloride on Sodium Formqmrato1uide.-The reactions here are similar to those with formanilide.Ortho-?&itl'oI)enzy~ornzopas.a,tolziide N02*C6&*CH2*N (CaH,Me)*COH crys-tallises in pale yellow needles melting a t 79" and is easily soluble inthe usual organic solventls. It may also be easily prepared fromorthonitrobenzylparatoluidine (Lellniann and Stickel Zoc. &t.). Yura-NH. CH,AT- c1U I.( - w II t oZy ldih ydropuinazoline C6H4 < cH?.& C6H,Me 7 is easily soluble iiialcohol ether benzene and chloroform sparingly so in light pet8roleurn.It crystallises in glistening white scales melts at 120" and distils withpartial decomposition.Distilled witn zinc-dust. it yields the amine andnitrile like the phenyl-derivative. The hydrochloride with 2 mols.H20 forms flat white needles and melts at 85" the anhydrous salt at251" ; the platinoch loride forms glistening yellow needles melting a t216" ; the stannochloride sparingly soluble needles melting a t 165".Methyl iodide forms two derivatives namely the methiodide crystallis-ing in white needles melting a t 186" and green metallic needles whichappear to be the methiodide periodide. On oxidation the base yieldswhich crystal- iuaratolylketodihydropuiizazoliiLe C,H,< CO.k*CsH,Me'lises in micaceous needles sparingly soluble in boiling water easily inorganic solvents and melting at 146".The hydrochloride forms whiteneedles melting at 213-214" and is dissociated by slight rise in teni-perature ; the pltztinochloride forms golden yellow scales meltingabove 300". By oxidation pralietediii ydrop,LLinazolylbenzoic acid,P is produced as well as the above quinazo-line; the acid forms white crystals sparingly soluble in organic solvents,and melting at 320". The silver salt torms a white flocculent precipitate.Yarntoyltetrahydropuinazoline crystallises in white needles melts at127" and is easily soluble in chloroform and benzene sparingly inether and alcohol.It forms a red nitrosamine a white unstable hydro-chloride and a yellow unstable platinochloride.Action oj* Orthonitrobenzyl Chloride o n Sodiumformo-orthoto1uide.-The reactions are similar to those with the isomeric para-compouud.N I C HK F HC6H~<co~N.CaN,~COO74 ABSTRACTS OF CHEMICAL PAPERS.Orthonitrobenzylformo-orthotoluids forms a Sellow oil which melt,s at'i69 and decomposes on distillation. Orthotolyldi?iydroyuinazolineforms a yellow amorphous mass its platinochloride orange-yellowneedles me1 ting at 210" and its stannochloride and hydrochloridecould not be obtained in a crystalline form. When reduced in alco-holic solution with sodium the base appears t,o yield the tetrahydro-derivative but this was not obtained in a pure state.L. T. T.Hydrastine. By W. KERSTEIN (Chem. Centr. 1889 ii 91 fromZeit. Naturwiss. Halle 61 425-429).-According to the author'sexperiments hydrastine obtained from the root of Hydrastis cuncc-densis has the formula C21H2,N06 and forms colourless needles melt-ing at 132". The hydrochloride C21H,lN06,HCl and hydrobromide,C H,,NO HBr are white micro-crystallire salts ; the hydriodide istwo wnish- y el lo w.In addition to those reactions already described showing the rela-tion which exists between hydrastine and narcotiue the author findsthat by oxidation with potassium permanganate in acid solution,opianic acid and probably also cotarnine are formed. When dis-tilled in a current of steam niecotiine and trimethylamine areformed in the case of both these alkaloi'ds. On the other hand,they do not show any similarity in their behaviour towards aceticanhydride acetic chloride water under pressure or dilute sulphuricacid.From hydrastine ethiodide by the action of potassium hydroxidesolution ethylhydrlnstine is obtained ; it forms lemon-yellow crgstalswhich melt at 127". By the action of iodine hydrastine is split upinto opianic acid and hydrastonine ; the latter is distivguishedfrom tarconine methiodide in tha,t no formaldehyde is formed onboiling its icdide 31 hydroxide with barium hydi-oxide.In addition from the root of H?/drastis canndensis the author hasseparated phytosterin C,,H,O + H,O ; this forms plates melting a t13:3" the solution of which in acetic anhydride gives a red coloration,passing into intense blue with concentrated sulphuric acid.J. W. L.Formation of Optically Active Tropic Acids and OpticallyActive Atropines. By A. LADENBURG and C. HUNDT (Ber. 22,2 5 ~ ~ 2 5 9 2 ) .-A dilute aqueous alcoholic solution of quinine (1 mol.)was added to a hot aqueous solution of tropic acid (ni. p. 116-1 18-,1 mol.) and the whole evaporated down on a water-bath until crystal-lisation commenced. On cooling a quantity of dull white crystalsseparated (quinine dextrotropate) and on further evaporation of themother-liquor an oil separated which gradually solidified to hardcyystals of a glassy lustre (quinine kevotropate).Quinine dextrotropate melts a t 186-187". The free acid cryst allisesfrom ether in hard clear prisms and from water in clear plates,melts a t 127-128" and showed a rotatory power of 71.4".Quinine Zcevotyopate was not obtained quite pure ; i t melts a t 178"The free acid which was also not obtained pure melted at 123" andshowsd a rotatory power of 65-15'ORGANIC CEEMTSTRY. 75When treated with tropine and tropic acid (Aiznalen 206 274),both acids yield the corresponding atropines.Deztro-atropine cqstallises from alcohol in white lustrous needles,melts a t 110-lll" and has a rotatory power of + 10". The auro-c h l w i d e forms dull deep-yellow crystals melting a t 146-147".Lcmo-atropiua is a crystalline powder melting a t 111". The auro-chloride crystallises in lustrous needles and melts a t 246". The baseresembles hyoscyamine but the two are not identical which is due tothe fact that the latter base has two active asymmetrical carbon-atoms whilst the former has only one. N. H 31.Bases contained in the young Shoots of Solanum Tubero-sum. By R. FIRBAS (ilfonafsh. 10 541-56O).-The two products,the one crystalline and the other amorphous obtained in the prepara-tion of solanine from the young shoots of the potato are now shown,contrary to earlier views not to be chemically identical. The authornames the crystalline compound solanine. It has the formulaC52H,sN0,s,4&H,0 and when dried a t 100" appears to be anhydrous,or t o contain only half a molecule of water of crystullisation. Froma solution in 85 per cent. alcohol it crystallises in coloiirless needles,which melt a t 244" are almost insoluble in ether and alcohol and arereadily dissolved by dilute hydrochloric acid. Xolanidine hydro-chloride 3(C4,H6,N02,Hc1)Hcl + H,O or l&H?O is obtained byboiling solanine with a 2 per cent. solution of hydrochloric acid. Itis a slightly yellow powder which is only very sparingly soluble inwater and carbonises without melting when heated to 287". Simul-taneously with solanidine hydrochloride. a sugar is formed in accord-ance with the equation C52Ev3N0,8 = C40H6,N02 + BC6H1,0s +4H20.The amorphous substance obtained simultaneously with solanine,and which the author names solaiLeine has when dried a t loo" theformula C53Hs7N013 or C5,H,NOl3. The loss of weight on heating theair-dried compound a t 100" corresponds with the formula C,,H,,KO + 3 i or 4H,O. It is a yellow horny perfectly amorphons substance,melting a t 208" is more soluble in an 85 per cent. solution of alcoholthan is solanine and on treatment with hydroctloric acid yieldssolanidine and a sugar in accordance with the equation C52H83N013 +H,O = C4,H6,N0 + 2C6HI2O6.The sugar obtained by the hydrolysis of solanine and solanaineforms a yellow amorphous mass with a caramel-like odour dissolvesreadily in water and wood-spirit and has a specific rotatory power of[z]D = + 28.6%. With phenylhydrazine hydrochloride and sodiumacetate in aqueous solution i t forms a glucosazone melting at 199",and resembling the compounds obtained similarly from dextrose,levulose and several other sugars. With nitric acid it gives no recog-nisable trace of mucic or saccharic acids. The general behaviour ofthe sugar points to the conclusion that it is some other sugar thandextrose or a mixture of sugars.Solunidine has the formula C4,,H61N0 or C4,H&N02 and is obtainedfrom alcoholic solution in amorphous masses interspersed with needlesmelting a t 191". It dissolves readily in hot alcohol with difficulty i76 ABSTRACTS OF CHEMICAL PAPERS.ether and on treatment with excess of dilute sulphuric acid forms asulphate 3(C40H6,N02,H~SO~),H,s0 + 8H20 ; this crystallises inscaly plates melting at 247” and is readily soluble in water. Itsdiacetyl-derivative CmH5,02NAc2 crystallises in needles melting at203”. G. T. M.Cinnarnylcocaine from Coca Leaves. By C. LTEBERNANN(Ber. 22 2661-2662) .-Measurements of crystals and quantitativedecomposition determications are given to show that the cinnamyl-coea’ine which t>he author prepared synthetically from ecgonine isidentical with t h a t obtained by Giesel horn the coca leaf.L. T. T.Haematoporphyrin and Bilirubin. By If. v. NENCKI andA. ROTSCHY (Monatsh. 10 568-573 ; compare Abstr. 1858 304 and971) .-The authors suggest that Raoult’s method may be employedwith advantage to determine the molecular weights of unstablesubstances of organic origin and have investigated the practicabilityof the method in two cases. Making use of acetic acid and phenol assolvents hzematoporphyrin gave numbers varying bet ween 226 and331 which correspond with the simple formula C,6H,eN20 (mol.wt. = 286). I n the case of bilirubin ethylene dibromide and phenolwere used RS solvents. This compound has the same molecnlarformula and is consequently isomeric with hzematoporphyrin. Therange in the numbers obtained in both cases is due to the compoundsbeing only slightly dissolved by the solvents employed. The iso-merism of haematoporphyrin and bilirubrin is confirmed by the factthat on reduction with tin and hydrochloric acid two differenturobilins are obtained. G. T. 31

ISSN:0368-1769    

DOI:10.1039/CA8905800020

出版商:RSC    

年代:1890

数据来源: RSC

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J O U R N A L 5. B. ASHER ARON. C. F. BAKER, B.Sc. D. BENDIX. A. G.BLOXAM. C. H. BOTHALMLEY. B. BRAUNER, Ph.D. B. H. BROUGH. H. G. COLMAN, Ph.D. H. CROMPTON. W. D. HALLIBURTON, M.D., B.Sc. F. 5. KIPPINB, Ph.D., D.Sc. J. W. LEATHER, Ph.D. D. A. LOUIS. T. MAXWELL, M.D., B.Sc. N. H. J. MILLER, Ph.D. OF G. T. MOODY, U.Sc. J. M. H. MUNRO, D.Sc. T. G. NICHOLSON. E. W. PREVOST, Ph.D. R. ROUTLEDGE, B.Sc. M. J. SALTER. JAMES TAYLOR, B.Sc. L. T. THORNR, Ph.D. J. B. TINGLE, Ph.D. H. K. TOMPKINS, B.Sc. G. W. DE TUNZELXANN, B.Sc. J. WALKER, D.Sc., P.D. W. C. WILLIAMS, B.Sc. W. P. WYNNE, B.Sc. THE CHEMICAL SOCIETY. H. E. ARMSTRONG, Ph.D., F.R.S. WYNDHAM R. DUNSTAN. F. R. JAPP, M.A., Ph.D., F.R.S. H. F. MORLEY, M.A., D.Sc. HUGO MULLER, Ph.D., F.R.S. W. H. PERKIN, Ph.D., F.R.S. 1 W. RAMSAY, Ph.D., F.R.S.W. J. RUSSELL, Ph.D., F.R.S. J. MILLAR THOMSON, F.R.S.E. T. E. THORPE, Ph.D., F.R.S. W. P. WYNNE, B.Sc. @bitm : C. E. GROVES, F.R.S. 8&- Qbitztax : A. J. GREENAWAY. Vol. LVIII. Part 11. 1890. ABSTRACTS. LONDON: GURNEY & JACKSON, 1, PATE~RNOSTER RCW, 1890.LONDON : HARRISON AND SONS, PRINTERS I N ORDINARY TO EER NAJESTY, 4 ~ . MARTIP’S LANE.J O U R N A L5. B. ASHER ARON.C. F. BAKER, B.Sc.D. BENDIX.A. G.BLOXAM.C. H. BOTHALMLEY.B. BRAUNER, Ph.D.B. H. BROUGH.H. G. COLMAN, Ph.D.H. CROMPTON.W. D. HALLIBURTON, M.D., B.Sc.F. 5. KIPPINB, Ph.D., D.Sc.J. W. LEATHER, Ph.D.D. A. LOUIS.T. MAXWELL, M.D., B.Sc.N. H. J. MILLER, Ph.D.OFG. T. MOODY, U.Sc.J. M. H. MUNRO, D.Sc.T. G. NICHOLSON.E. W. PREVOST, Ph.D.R. ROUTLEDGE, B.Sc.M. J. SALTER.JAMES TAYLOR, B.Sc.L. T. THORNR, Ph.D.J. B. TINGLE, Ph.D.H. K. TOMPKINS, B.Sc.G. W. DE TUNZELXANN, B.Sc.J. WALKER, D.Sc., P.D.W. C. WILLIAMS, B.Sc.W. P. WYNNE, B.Sc.THE CHEMICAL SOCIETY.H. E. ARMSTRONG, Ph.D., F.R.S.WYNDHAM R. DUNSTAN.F. R. JAPP, M.A., Ph.D., F.R.S.H. F. MORLEY, M.A., D.Sc.HUGO MULLER, Ph.D., F.R.S.W. H. PERKIN, Ph.D., F.R.S.1 W. RAMSAY, Ph.D., F.R.S.W. J. RUSSELL, Ph.D., F.R.S.J. MILLAR THOMSON, F.R.S.E.T. E. THORPE, Ph.D., F.R.S.W. P. WYNNE, B.Sc.@bitm :C. E. GROVES, F.R.S.8&- Qbitztax :A. J. GREENAWAY.Vol. LVIII. Part 11.1890. ABSTRACTS.LONDON:GURNEY & JACKSON, 1, PATE~RNOSTER RCW,1890LONDON :HARRISON AND SONS, PRINTERS I N ORDINARY TO EER NAJESTY,4 ~ . MARTIP’S LANE

ISSN:0368-1769    

DOI:10.1039/CA89058FP055

出版商:RSC    

年代:1890

数据来源: RSC

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76 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture, Reduction of Nitrates by the Cholera Bacteria. By R. J. PETRI (Chein. Centr., 1889, ii, 45, from Centr. Bacliteriologie u. Parisitenkunde, 5, No. 1’7).-The cholera bacteria are found to reduce nitrates to nitrites, and the aathor remarks that an oxidation of ammonia by these bacteria would therefore appear highly improbable. J. W. L. By E. KRAMER (Monatssh., 10, 467- 505) .-Mucous fermentation is the process by which certain solutions of sugars or carbohydrates, such as saccharose, glucose, lactose, mannitol, starch, and mucilage, containing the necessary quantity of albuminoids and mineral salts, are converted into a ropy condition. In the process a mucous substance of the formula CsHl0O5 is generally formed simultaneously with variable quantities of mannitol and carbmic anhydride, although in the fermentation of milk the prodnc- Mucous Fermentation.VEGETABLE PHY SIOLOGT AND AGRICULTURE.77 tion of all these compounds has not been determined with certainty. The formation of free hydrogen and of lactic and butyric acids in ropy fermention is due to the use of impure cultures, and is not the result of the mucous ferment, which is a micro-organism belonging to the bacteria. Previously the mucous fermentation was considered to be due to Pasteur’s so named Micrococcus visco.rus (which. however, does not exist as described by him), b u t is now shown. in the case of thq different solutions investigated, to be the result of the action of a t least three totally different micro-organisms.It also appears that no true mucous fermentation is hrought about by Prazmowsky’s Leuconostoc niesenterivides and Bucillus polynayxu or by Cohn’s Asco- coccus Billrothii. The solutions of carbohydrates which have been investigated can be classed into three divisions according to the nature of the ferment capable of producing change in them. The first division consists of neutral or slightly alkaline solutions containing saccharose, albu- minoi’ds, and mineral salts, such as decoctions of barley, of rice, and of maize, to which saccharose has been added ; and the juice of the carrot, beet-root, and onion. The fermentation is produced by Kramer’s Bacillus viscosw sncchnri, and affects the saccharose. To tbe second division belong acid solutions (for example, wine) containing the albuminoiids and mineral salts and glucose.In these the fermen- tation is caused by Kramm’s Bacillus ‘~‘isosus vini. The third divi- sion consists of nearly neutral-acid or alkaline-solutions containing lactose, albuminoids, and mineral salts, such as milk. This class is said by Schmidt-Mulheim to be fermented by a coccus 1 p in diameter, and capable also of fermenting mannitol. Kramer’s Bucillus viscosu.~ sacchari occurs in the form of short rods slightly rounded at the ends, and having a thickness of 1 p a n d a length of from 2 5 to 4 p. They are often joined together, forming strings of as many as 50, and show no individual movement, but only Brown’s so-called “ molecular motion.” When placed on slices of carrot,, ii blackish mucus 5s formed, but on isinglass or gelatin made up with saccharose, it produces spreading white colonies ; it liquifies the gelatin, and is very active a t 22”.The coccus thrives only in neutral or slightly alkaline fluids? producing no change what- ever when free acids are present. Kramer’s Bacillus riscosus vini forms rods 0.6 to 0.8 p in thickness, and from 2 to6 p in length,often occurring in chains 14 p in length; and belongs to the anaikobic bacteria, whilst the previously described ferment is aikobic. It can only exist in wines or in acid solutions of glucose. The mucous substance of the formula C,H,,O, may be regarded as “ metamorphosed ” cellulose. It is precipitated from the fermented liquid by alcohol, by basic lead acetate, and by barjta-water, in the form of a white, insoluble, amorphous, stringy mass, which has a specific rotatory power of [ u ] D = + 195 ; is not coloured by iodine, and is dis- solved by solutions of the caustic alkalies, forming a, yellow liquid, from which alcohol precipitates a compound as a white, scaly mass.The mucous substance is not to be regarded as being directly produced from the nourishing fluid, but as a secondary product of assimilation of the ferment. Similarly the formation of mannitol is to be attributed to78 ABSTRACTS O F CHERlICAL PAPERS. the action of tbe nascent hydrogen and carbonic anhpdride, the primary products of the action of the living organism on the dissolved glucose. G. T. M. Decomposition of Albumin by Anaerobic Ferments.By M. v. NENCKI (M(o.,zafsh., 10, 506-5'25).-The author has investigated the decomposition of serum albumin by three anaerobic bacilli, namely, Eucillus liquefaciens magnus, Bacillus spinosus, and the Rauseh- brand bacillus. The fermentations were conducted in a specially arranged flask, and in an atmosphere of nitrogen, hydrogen, or car- bonic anhydride. On distillation, after saturation with oxalic acid, the fermented liquid gave gaseous products and liquid fatty acids. On exhaustion with ether, t'he evaporated residue furnished, besides a small quantity of fatty acids, only phenylpropionic acid, parahydroxy- phenylpropionic acid, and scatolacetic acid. The relative quantity in which these three acids are formed depends on the bacillus used and on the length of the fermentation.Scatolacetic acid, C&< Nt;?>C-CH2*COOH, crystallises from hot water in prisms o r six-sided plates, dissolves readily in alcohol and ether, melts at 134' (uncor.): and on treatment, with potassium nitrite and acetic acid forms a yellow, crystalline magma of the charac- teristic nitroso-compound, C,H7N(NO)*CzH,O2, which melts with decomposition a t 135". Taking these results into consideration, the author shares Salkowski's opinion that there a1-e a t least three aromatic group? in albumin, and that these are repyesented by (1) tyrosine, OH*C,H,.C H,*CH(NH,).COOH, (2) phenylamidopro- pionic acid, and (3) scatolamidoacetic acid. When the anaerobic fermentation takes place in the absence of hydrogen, tyrosine is reduced to ammonia, and parahydroxyphenylpropionic acid ; phenyl- amidopropionic acid to phenylpropionic acid, and scatolamidoacetic acid to scatolacetic acid.I n the presence of air, these three acids furnish oxidation-products, which may be regarded as being produced as follows :- Phenylacetic acid, benzoic acid, and phenylethylamine from phenylpropionic acid; parahydroxyphenylacetic acid, paracresol, parahydroxybenzoic acid, and phenol from parahFdroxyphenylacetic acid, and scatolecarboxylic acid, scatole and indole from scatolacetic acid. G. T. M. Gases Evolved during the Putrefaction of Serum Albumin. By &I. v. NKNCKI and N. SIEBER (Mo?iatsh., 10, 526-531).-The bad smelling gas evolved during the putrefaction of albumin by Bacillus liquefaciens ma,ynus (compare preceding abstr.) contains 97.1 per cent.of carbonic anhydride, hydrogen sulphide, and other gases absorbable by potash, and 2.63 per cent. of free hydrogen. The putrid smell is due in all probability to the presence of inethyl mercaptan, for the anthor has proved that that compound is evolved during the putrefaction of flesh by the Einphysem bacteria. CM G. T. M. Formation of Paralactic Acid during the Fermentation of Sugar. By M. v. NENCKI and N. SIEBER (iWonatsh., 10, 532-540.)- In the preparation of a pure culture of the 1Zauscldwand bacillus, theVEGE'r ABLE PK YSIOLOGY AND AGRICULTURE. 79 authors observed that the fluid taken from the swelling on an inoculat.ed guinea-pig coiitained not merely the organism which until now was the sole recognised bacillus producing the symptoms, but also an anasrobic micrococcus.The coccns has on the average a diameter of 0.6 p, but possesses no very characteristic form ; appear- ing usually in a shape resembling that of diplocoucus, more seldom in strings of 3, 4, or 5, and at tirnes in groups resembling staphylococcus. The authors name the new ferment micrococcus a c i d i ynralnctici, because. during its growth, it converts grape sugar into sarco- or pitra-lactic acid. The Ruuschbrand bacillu.~, on the other hand, con- verts sugar into the ordinary lactic acid of fermentation, out of wliicli butyric acid is then formed, with evolution of carbonic anhydride and hydrogen. If in fermenting sugar a culture containing both the bacillus and the micrococcus is employed, lactic and parillsctic acids are simnlt,aneously formed.G. T. N. Function of Ammonium Salts in the Nutrition of Higher Plants. By A. MuNw (Compt. rend., 109, 646--648).-Soil free from nitrates was mixed with ammonium sulphate, and the mixture carefully sterilised. It was then sown with various plants, every precaution being taken to prevent the introduction of the nitric ferment either at this stage or subsequently. A corresponding set of experiments was made in which the nitric ferment was present. I n the latter case a considerable quantity of the ammonium sulphnte was nitrified. I n the first case no nitrates were present at the close of the experiments, and yet the plants flotirished vigorously. The quantities of nitrogen in the seeds and the plants were as follows :- I n the I n the Derived from the seed.plant. ammonium sulphate. Broad-bean.. 37 mgr. 956 mgr. 915 mgr. Home-bean.. 16 ,, 105 ), 89 9 , Maize ...... 3 ., 211 ), 208 $, Bar1 ey ...... U* 7 ,, 50 7 , 49.:3 ) ) Hemp.. .... 0.5 ,, 115 ,, 114.5 ,, It is evident that the higher plants have the power of directly ntilising the nitrogen of ammonium salts, and that preliminary nitri- fication is not essential. c. H. R. Fixation of Nitrogen by Leguminosae. By E. B R ~ A L ( C o n ~ t . rend., 109, 6iO-573 ; compare Abstr., 1888, 13N) .-Spanish beans were grown in a mixture of river gravel, fine sand, and flints, which contained very little nitrogen. They were freely exposed to air, and from time to time were watered with very dilute solutions of potas- sium chloride and calcium phosphate.I n March, the roots were inoculated with bacteria from tubercles on the roots of Cystisa. A t first the growth was vigorous, then the plants languished, but in June they recovered, flourished, and reached matnrity. The total gain of nitrogen was 1.4872 gram for a total weight of dried plants of 64.3 grams. At the same time the 10 kilos of gravel, &c., gained80 ABSTRACTS OF CHEMICAL PAPERS. 0.481 gram, corresponding with a gain of 98.31 kilos. per hectare of surface exposed. Lucerne qrowing in a pot in sandy soil was inoculated with a frag- ment of tuberculous root of lucerne, freely exposed to air, and watered with effluent water. The total nitrogen in the water used did not exceed 0.1 gram, and the net gain of nitrogen was 3.258 gram for a total weight of dried crop, including roots, of 97.8 gram.At the same time the soil gained 3.460 grams. This behaviour of the legurninom when growing on soils very poor in nitrogen explains their well-known utility as " improving crops." C. H. B. Investigations on Lactarins Piperatus. By R. CHODAT and P. CHUIT (Chenz. Cenfy., 1889, ii, 144,145, from Arch. sci. phys. nat., GerGve, 5, 385403).-After expressing the juices of L~ctariiis piperahs, and extracting the residue with alcohol, it was found that mannitol, a white, crystalline acid, lactaric acid, and a pitchy substance had dissolved. The latter has been named piperon. It is solid at ordinary tempera- tures, but melts on the hand, and has the pepper-like smell of the fungas. Heated with water in t'he presence of either a little alkali or acid, it remains unchanged.It con'tains no nitrogen, and is pre- sent in the milk of 5. piperatus. Lactaric acid, C15HB002, the next lower homologuc to palmitic acid (which has been found by Thoerner in other fungi), melts a t 69-5-70', is little soluble in cold alcohol, readily soluble in hot. It exists in the free state in this fungus to the extent of 7.3 per cent. of the dry substance. The authors could not find any poisonous sub- stance in this fungus either by chemical or physiological means. Pectic Compounds in Plants. By L. MANGIN (Compt. rend., 109, 579-552) .-Pectic compounds, both neutral and acid, are essen- tial constituents of plant structures. Their presence is recogoised by means of certain dyes, such as phenosafranin, methylene blue, Ris- mark brown, Paris violet, &c., whidh stain the pectic compounds but, do not stain the cellulose, provided that they are used in neutral soln- tions or in solutions feebly acidified with acetic acid.Nit,rogenous compounds, lignin, and cutin are stained by the same dyes, hut 01; treatment with acid the pectic compounds are decolorised, whilst the others remain stained. Other dyes, such as acid green, acid brown, nigrosin, indulin, crocein, ponceaax, in neutral solution stain the nitrogenous substances, lignin, cutin, &c, but not the pectic com- pounds, and mixtures of these dyes with those of the first group make excellent double stains, which readily distinguish pectic corn- pounds from lignin, cutin, and the nitrogenous compounds. The author has extracted pectic acid from plant structures which take the stain, and has found that after its removal they remain colourless if treated with the same dyes.If a section of any plant, except a mushroom, is treated for 24 hours with Schmeizer's reagent, the cells are filled wit\h a gelatinous mass enclosed in the cell walls left intact by the section-cutter. It would seem that the cellulose does not diffuse across the membranes, and J. W. L.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 81 after the sections are washed with water and acetic acid, they have their original strnctnre, although somewhat deformed, and the mem- branes retain their thickness except in those rare cases where the cell walls consist exclusively of cellulose. After this treatment, the cell walls, which consist of insoluble pectic acid, give no colora- tion with the ordinary iodine reagents, whilst the contents of the cells become deep blue.On the other hand, the cell walls are deeply stained by methylene blue, whilst the contents remain colourless. The cell walls dissolve readily in ammonium oxalate solution. Pectic compounds are constant constituents of the cell membranes, and are found, though less frequently, in the cell contents, and even in some cases (Allizim porrum, Glyceria aquatzlis) in the nucleus. By T. SCHLOESING, Junr. (Compt. rend., 109, 618-620, 673--676).-The large volume of air with- drawn from the soil in Boussingault's method introduces several errors. The author withdraws about 15 C.C. through a steel tube of very narrow diameter, and analyses it volumetrically.The air was drawn from the soil, as a rule, a t two depths, 25 to 30 em., repre- senting the true soil, and 50 to 60 cm., representing the subsoil. It consisted of nitrogen, oxygen, and carbonic anh.ydride, without any measurable quantity of any combustible gas. The proportion of carbonic anhydride in the soil varied from 0.45 to 11.:39 per cent., and in the subsoil from 0.0 to 8.80 per cent.; the proportion of oxygen varied from 13.52 to 20.03 per cent. in the soil, and from 13-21 t o 20.98 in the subsoil. As a rule, a low proportion of carbonic anhy- dride is accompanied by a high proportion of oxygen and rice vend. The greater the depth, the greater, as a rule, the proportion of car- bonic anhydride, but in one set of samples taken in June, when the air was calm and the temperature high, this law did not hold good.The atmosphere of the same soil shows great variations, owing doubtless, to the varying frequeacy with which it is renewed in con- sequence of changes in the atmospheric pressure. Other conditions being constant, the composition of the atmosphere in the soil will show considerable variations in different parts of the same field. It is essential to remember that the gases in the soil are quite as capable of trnnslatory motion as the water. Influence of the Composition of the Soil on the Physical Properties of Plants. By G. VILLE (Compt. ?-end., 109, 628-631). -The height of plants is in direct relation to the fertility of the soil. I n the case of plants in which nitrogen-derivatives are the domillant constituents, a deficiency of nitrogen in the soil has a greater effect than a deficiency of any other constituent. I n one and the same year, the same plant will attain to different heights in different soils, but variations due to a deticiency of fertilising agents are always in the same direction.The height a t a given period of growth is practically the same in different years. 'J'he weight, of similar crops varies from year to year, hut the variations are always in the same direction for any given variations in the composition of the soil. C. H. B. The Atmosphere in Soils. C. H. B. VOL. LVIII. 9112 ABSTRACTS OF CHEMICAL PAPERS. The proportion of carrotene in plants depends on the fertility of the soil, and increases with it.Variations in the proportion of chloro- phyll follow the same order as variations in the proportion of carro- tene. C. H. B. Production of so-called Sweet Fodder. By E. MACH (Bied. CejLtr., 18, 622-624, from Firoler landwirtsch. Blatter, 8,137-139).- The object of the experiments was to determine whether the loss of food-substance in the preservation of green fodder by Pry’s process is essentially smaller than in the preparation of sour fodder by bhe older methods. Two samples from a five months’ old preen maize silo were examined: the one was taken from the middle and was well preserved, the other from the edge, and badly preserved. They con- tained respectively 80.84 and 82.26 per cent. of water arid volatile matter. The following table shows the percentage composition of the two samples (calculated on the dry substance), as well as the consti- tuents of a sample of sweet maize, and the average cornposition of fresh, green maize (also on the dry substance) :- ----- Nitrogenous substance .........Non-nitrogenous extract ....... Crude fat .................... Crude fibre .................. Crude ash.. .................. Pure ash . . . . . . . . . . . . . . . . . Total free acid (as lactic acid) . . Dry substance.. .............. Volatile acids (as acetic acid) ... Ensilage. Good. -- 8.56 3 *26 60 *13 33 *31 15.00 10 -00 - - - Bad. -- 9.81 3 *19 56 *13 30.65 12 *423 8 -71 - - - Sweet maize. -- 5 *60 3 *19 52 ‘27 28.34 7 -76 4.91 2 *oo 0 -65 - Average composition of fresh green maize. 9.37 3.12 52-50 30 -00 6 - 2 5 - - - 16 -00 The fresh ensilage of good quality contained 0.320 per cent.(in fresh substance) of alcohol, 0.531 per cent. of free acid (calciilated as lactic acid), 0.657 per cent. of volatile acids (as acetic acid), and 0.986 per cent. of total volatile acids (as acetic acid). The corre- sponding numbers for the bad sa.mple are 0.280, 0.316, 0.356, and 0.535. The sweet maize prepared by Fry’,s method does not differ essentially from the average composition of fresh maize. The sugar of the fresh maize has disappeared completely, whilst alcohol and free acids have been formed, The fact that a larger amount of volatile acid was found than total free acid is due t o the liberation of volatile acids (originally present as salts) in the distillation of the substance in presence of tannic acid.Analyses of the ensilage a t a later period are also given. The whole of the free acid was found to consist of acetic and butyric acids ; lactic acid was not preseiit. N. H. M.76 ABSTRACTS OF CHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture,Reduction of Nitrates by the Cholera Bacteria. By R. J.PETRI (Chein. Centr., 1889, ii, 45, from Centr. Bacliteriologie u.Parisitenkunde, 5, No. 1’7).-The cholera bacteria are found toreduce nitrates to nitrites, and the aathor remarks that an oxidationof ammonia by these bacteria would therefore appear highlyimprobable. J. W. L.By E. KRAMER (Monatssh., 10, 467-505) .-Mucous fermentation is the process by which certain solutionsof sugars or carbohydrates, such as saccharose, glucose, lactose,mannitol, starch, and mucilage, containing the necessary quantity ofalbuminoids and mineral salts, are converted into a ropy condition.In the process a mucous substance of the formula CsHl0O5 is generallyformed simultaneously with variable quantities of mannitol andcarbmic anhydride, although in the fermentation of milk the prodnc-Mucous FermentationVEGETABLE PHY SIOLOGT AND AGRICULTURE.77tion of all these compounds has not been determined with certainty.The formation of free hydrogen and of lactic and butyric acids inropy fermention is due to the use of impure cultures, and is not theresult of the mucous ferment, which is a micro-organism belongingto the bacteria. Previously the mucous fermentation was consideredto be due to Pasteur’s so named Micrococcus visco.rus (which.however,does not exist as described by him), b u t is now shown. in the case ofthq different solutions investigated, to be the result of the action ofa t least three totally different micro-organisms. It also appears thatno true mucous fermentation is hrought about by Prazmowsky’sLeuconostoc niesenterivides and Bucillus polynayxu or by Cohn’s Asco-coccus Billrothii.The solutions of carbohydrates which have been investigated canbe classed into three divisions according to the nature of the fermentcapable of producing change in them. The first division consists ofneutral or slightly alkaline solutions containing saccharose, albu-minoi’ds, and mineral salts, such as decoctions of barley, of rice, andof maize, to which saccharose has been added ; and the juice of thecarrot, beet-root, and onion.The fermentation is produced byKramer’s Bacillus viscosw sncchnri, and affects the saccharose. To tbesecond division belong acid solutions (for example, wine) containingthe albuminoiids and mineral salts and glucose. In these the fermen-tation is caused by Kramm’s Bacillus ‘~‘isosus vini. The third divi-sion consists of nearly neutral-acid or alkaline-solutions containinglactose, albuminoids, and mineral salts, such as milk. This class issaid by Schmidt-Mulheim to be fermented by a coccus 1 p in diameter,and capable also of fermenting mannitol.Kramer’s Bucillus viscosu.~ sacchari occurs in the form of short rodsslightly rounded at the ends, and having a thickness of 1 p a n d alength of from 2 5 to 4 p.They are often joined together, formingstrings of as many as 50, and show no individual movement, butonly Brown’s so-called “ molecular motion.” When placed on slicesof carrot,, ii blackish mucus 5s formed, but on isinglass or gelatinmade up with saccharose, it produces spreading white colonies ; itliquifies the gelatin, and is very active a t 22”. The coccus thrivesonly in neutral or slightly alkaline fluids? producing no change what-ever when free acids are present. Kramer’s Bacillus riscosus vini formsrods 0.6 to 0.8 p in thickness, and from 2 to6 p in length,often occurringin chains 14 p in length; and belongs to the anaikobic bacteria,whilst the previously described ferment is aikobic.It can onlyexist in wines or in acid solutions of glucose.The mucous substance of the formula C,H,,O, may be regarded as“ metamorphosed ” cellulose. It is precipitated from the fermentedliquid by alcohol, by basic lead acetate, and by barjta-water, in the formof a white, insoluble, amorphous, stringy mass, which has a specificrotatory power of [ u ] D = + 195 ; is not coloured by iodine, and is dis-solved by solutions of the caustic alkalies, forming a, yellow liquid, fromwhich alcohol precipitates a compound as a white, scaly mass. Themucous substance is not to be regarded as being directly produced fromthe nourishing fluid, but as a secondary product of assimilation of theferment. Similarly the formation of mannitol is to be attributed t78 ABSTRACTS O F CHERlICAL PAPERS.the action of tbe nascent hydrogen and carbonic anhpdride, theprimary products of the action of the living organism on the dissolvedglucose. G.T. M.Decomposition of Albumin by Anaerobic Ferments. ByM. v. NENCKI (M(o.,zafsh., 10, 506-5'25).-The author has investigatedthe decomposition of serum albumin by three anaerobic bacilli,namely, Eucillus liquefaciens magnus, Bacillus spinosus, and the Rauseh-brand bacillus. The fermentations were conducted in a speciallyarranged flask, and in an atmosphere of nitrogen, hydrogen, or car-bonic anhydride. On distillation, after saturation with oxalic acid,the fermented liquid gave gaseous products and liquid fatty acids.On exhaustion with ether, t'he evaporated residue furnished, besides asmall quantity of fatty acids, only phenylpropionic acid, parahydroxy-phenylpropionic acid, and scatolacetic acid.The relative quantityin which these three acids are formed depends on the bacillus usedand on the length of the fermentation.Scatolacetic acid, C&< Nt;?>C-CH2*COOH, crystallises from hotwater in prisms o r six-sided plates, dissolves readily in alcohol andether, melts at 134' (uncor.): and on treatment, with potassium nitriteand acetic acid forms a yellow, crystalline magma of the charac-teristic nitroso-compound, C,H7N(NO)*CzH,O2, which melts withdecomposition a t 135". Taking these results into consideration, theauthor shares Salkowski's opinion that there a1-e a t least threearomatic group? in albumin, and that these are repyesented by(1) tyrosine, OH*C,H,.C H,*CH(NH,).COOH, (2) phenylamidopro-pionic acid, and (3) scatolamidoacetic acid.When the anaerobicfermentation takes place in the absence of hydrogen, tyrosine isreduced to ammonia, and parahydroxyphenylpropionic acid ; phenyl-amidopropionic acid to phenylpropionic acid, and scatolamidoaceticacid to scatolacetic acid. I n the presence of air, these three acidsfurnish oxidation-products, which may be regarded as being producedas follows :- Phenylacetic acid, benzoic acid, and phenylethylaminefrom phenylpropionic acid; parahydroxyphenylacetic acid, paracresol,parahydroxybenzoic acid, and phenol from parahFdroxyphenylaceticacid, and scatolecarboxylic acid, scatole and indole from scatolaceticacid.G. T. M.Gases Evolved during the Putrefaction of Serum Albumin.By &I. v. NKNCKI and N. SIEBER (Mo?iatsh., 10, 526-531).-The badsmelling gas evolved during the putrefaction of albumin by Bacillusliquefaciens ma,ynus (compare preceding abstr.) contains 97.1 percent. of carbonic anhydride, hydrogen sulphide, and other gasesabsorbable by potash, and 2.63 per cent. of free hydrogen. Theputrid smell is due in all probability to the presence of inethylmercaptan, for the anthor has proved that that compound isevolved during the putrefaction of flesh by the Einphysem bacteria.CMG. T. M.Formation of Paralactic Acid during the Fermentation ofSugar. By M. v. NENCKI and N. SIEBER (iWonatsh., 10, 532-540.)-In the preparation of a pure culture of the 1Zauscldwand bacillus, thVEGE'r ABLE PK YSIOLOGY AND AGRICULTURE.79authors observed that the fluid taken from the swelling on aninoculat.ed guinea-pig coiitained not merely the organism which untilnow was the sole recognised bacillus producing the symptoms, butalso an anasrobic micrococcus. The coccns has on the average adiameter of 0.6 p, but possesses no very characteristic form ; appear-ing usually in a shape resembling that of diplocoucus, more seldom instrings of 3, 4, or 5, and at tirnes in groups resembling staphylococcus.The authors name the new ferment micrococcus a c i d i ynralnctici,because. during its growth, it converts grape sugar into sarco- orpitra-lactic acid. The Ruuschbrand bacillu.~, on the other hand, con-verts sugar into the ordinary lactic acid of fermentation, out of wliiclibutyric acid is then formed, with evolution of carbonic anhydride andhydrogen.If in fermenting sugar a culture containing both thebacillus and the micrococcus is employed, lactic and parillsctic acidsare simnlt,aneously formed. G. T. N.Function of Ammonium Salts in the Nutrition of HigherPlants. By A. MuNw (Compt. rend., 109, 646--648).-Soil freefrom nitrates was mixed with ammonium sulphate, and the mixturecarefully sterilised. It was then sown with various plants, everyprecaution being taken to prevent the introduction of the nitricferment either at this stage or subsequently. A corresponding setof experiments was made in which the nitric ferment was present.I n the latter case a considerable quantity of the ammonium sulphntewas nitrified.I n the first case no nitrates were present at the closeof the experiments, and yet the plants flotirished vigorously. Thequantities of nitrogen in the seeds and the plants were asfollows :-I n the I n the Derived from theseed. plant. ammonium sulphate.Broad-bean.. 37 mgr. 956 mgr. 915 mgr.Home-bean.. 16 ,, 105 ), 89 9 ,Maize ...... 3 ., 211 ), 208 $,Bar1 ey ...... U* 7 ,, 50 7 , 49.:3 ) )Hemp.. .... 0.5 ,, 115 ,, 114.5 ,,It is evident that the higher plants have the power of directlyntilising the nitrogen of ammonium salts, and that preliminary nitri-fication is not essential. c. H. R.Fixation of Nitrogen by Leguminosae.By E. B R ~ A L ( C o n ~ t .rend., 109, 6iO-573 ; compare Abstr., 1888, 13N) .-Spanish beanswere grown in a mixture of river gravel, fine sand, and flints, whichcontained very little nitrogen. They were freely exposed to air, andfrom time to time were watered with very dilute solutions of potas-sium chloride and calcium phosphate. I n March, the roots wereinoculated with bacteria from tubercles on the roots of Cystisa. A tfirst the growth was vigorous, then the plants languished, but inJune they recovered, flourished, and reached matnrity. The totalgain of nitrogen was 1.4872 gram for a total weight of dried plantsof 64.3 grams. At the same time the 10 kilos of gravel, &c., gaine80 ABSTRACTS OF CHEMICAL PAPERS.0.481 gram, corresponding with a gain of 98.31 kilos.per hectare ofsurface exposed.Lucerne qrowing in a pot in sandy soil was inoculated with a frag-ment of tuberculous root of lucerne, freely exposed to air, and wateredwith effluent water. The total nitrogen in the water used did notexceed 0.1 gram, and the net gain of nitrogen was 3.258 gram for atotal weight of dried crop, including roots, of 97.8 gram. At thesame time the soil gained 3.460 grams.This behaviour of the legurninom when growing on soils very poorin nitrogen explains their well-known utility as " improving crops."C. H. B.Investigations on Lactarins Piperatus. By R. CHODAT and P.CHUIT (Chenz. Cenfy., 1889, ii, 144,145, from Arch. sci. phys. nat., GerGve,5, 385403).-After expressing the juices of L~ctariiis piperahs, andextracting the residue with alcohol, it was found that mannitol, a white,crystalline acid, lactaric acid, and a pitchy substance had dissolved.The latter has been named piperon.It is solid at ordinary tempera-tures, but melts on the hand, and has the pepper-like smell of thefungas. Heated with water in t'he presence of either a little alkalior acid, it remains unchanged. It con'tains no nitrogen, and is pre-sent in the milk of 5. piperatus.Lactaric acid, C15HB002, the next lower homologuc to palmitic acid(which has been found by Thoerner in other fungi), melts a t69-5-70', is little soluble in cold alcohol, readily soluble in hot. Itexists in the free state in this fungus to the extent of 7.3 per cent.ofthe dry substance. The authors could not find any poisonous sub-stance in this fungus either by chemical or physiological means.Pectic Compounds in Plants. By L. MANGIN (Compt. rend.,109, 579-552) .-Pectic compounds, both neutral and acid, are essen-tial constituents of plant structures. Their presence is recogoised bymeans of certain dyes, such as phenosafranin, methylene blue, Ris-mark brown, Paris violet, &c., whidh stain the pectic compounds but,do not stain the cellulose, provided that they are used in neutral soln-tions or in solutions feebly acidified with acetic acid. Nit,rogenouscompounds, lignin, and cutin are stained by the same dyes, hut 01;treatment with acid the pectic compounds are decolorised, whilst theothers remain stained.Other dyes, such as acid green, acid brown,nigrosin, indulin, crocein, ponceaax, in neutral solution stain thenitrogenous substances, lignin, cutin, &c, but not the pectic com-pounds, and mixtures of these dyes with those of the first groupmake excellent double stains, which readily distinguish pectic corn-pounds from lignin, cutin, and the nitrogenous compounds. Theauthor has extracted pectic acid from plant structures which take thestain, and has found that after its removal they remain colourless iftreated with the same dyes.If a section of any plant, except a mushroom, is treated for 24 hourswith Schmeizer's reagent, the cells are filled wit\h a gelatinous massenclosed in the cell walls left intact by the section-cutter. It wouldseem that the cellulose does not diffuse across the membranes, andJ.W. LVEGETABLE PHYSIOLOGY AND AGRICULTURE. 81after the sections are washed with water and acetic acid, they havetheir original strnctnre, although somewhat deformed, and the mem-branes retain their thickness except in those rare cases where thecell walls consist exclusively of cellulose. After this treatment,the cell walls, which consist of insoluble pectic acid, give no colora-tion with the ordinary iodine reagents, whilst the contents of the cellsbecome deep blue. On the other hand, the cell walls are deeplystained by methylene blue, whilst the contents remain colourless.The cell walls dissolve readily in ammonium oxalate solution.Pectic compounds are constant constituents of the cell membranes,and are found, though less frequently, in the cell contents, and even insome cases (Allizim porrum, Glyceria aquatzlis) in the nucleus.By T.SCHLOESING, Junr. (Compt.rend., 109, 618-620, 673--676).-The large volume of air with-drawn from the soil in Boussingault's method introduces severalerrors. The author withdraws about 15 C.C. through a steel tubeof very narrow diameter, and analyses it volumetrically. The airwas drawn from the soil, as a rule, a t two depths, 25 to 30 em., repre-senting the true soil, and 50 to 60 cm., representing the subsoil. Itconsisted of nitrogen, oxygen, and carbonic anh.ydride, without anymeasurable quantity of any combustible gas. The proportion ofcarbonic anhydride in the soil varied from 0.45 to 11.:39 per cent.,and in the subsoil from 0.0 to 8.80 per cent.; the proportion ofoxygen varied from 13.52 to 20.03 per cent.in the soil, and from 13-21t o 20.98 in the subsoil. As a rule, a low proportion of carbonic anhy-dride is accompanied by a high proportion of oxygen and rice vend.The greater the depth, the greater, as a rule, the proportion of car-bonic anhydride, but in one set of samples taken in June, when theair was calm and the temperature high, this law did not hold good.The atmosphere of the same soil shows great variations, owingdoubtless, to the varying frequeacy with which it is renewed in con-sequence of changes in the atmospheric pressure. Other conditionsbeing constant, the composition of the atmosphere in the soil willshow considerable variations in different parts of the same field.Itis essential to remember that the gases in the soil are quite as capableof trnnslatory motion as the water.Influence of the Composition of the Soil on the PhysicalProperties of Plants. By G. VILLE (Compt. ?-end., 109, 628-631).-The height of plants is in direct relation to the fertility of thesoil. I n the case of plants in which nitrogen-derivatives are thedomillant constituents, a deficiency of nitrogen in the soil has agreater effect than a deficiency of any other constituent. I n one andthe same year, the same plant will attain to different heights indifferent soils, but variations due to a deticiency of fertilising agentsare always in the same direction. The height a t a given period ofgrowth is practically the same in different years.'J'he weight, ofsimilar crops varies from year to year, hut the variations are alwaysin the same direction for any given variations in the composition ofthe soil.C. H. B.The Atmosphere in Soils.C. H. B.VOL. LVIII. 112 ABSTRACTS OF CHEMICAL PAPERS.The proportion of carrotene in plants depends on the fertility ofthe soil, and increases with it. Variations in the proportion of chloro-phyll follow the same order as variations in the proportion of carro-tene. C. H. B.Production of so-called Sweet Fodder. By E. MACH (Bied.CejLtr., 18, 622-624, from Firoler landwirtsch. Blatter, 8,137-139).-The object of the experiments was to determine whether the loss offood-substance in the preservation of green fodder by Pry’s processis essentially smaller than in the preparation of sour fodder by bheolder methods.Two samples from a five months’ old preen maizesilo were examined: the one was taken from the middle and was wellpreserved, the other from the edge, and badly preserved. They con-tained respectively 80.84 and 82.26 per cent. of water arid volatilematter. The following table shows the percentage composition of thetwo samples (calculated on the dry substance), as well as the consti-tuents of a sample of sweet maize, and the average cornposition offresh, green maize (also on the dry substance) :------Nitrogenous substance .........Non-nitrogenous extract ....... Crude fat ....................Crude fibre ..................Crude ash.. ..................Pure ash . . . . . . . . . . . . . . . . .Total free acid (as lactic acid) . .Dry substance.. .............. Volatile acids (as acetic acid) ...Ensilage.Good.--8.563 *2660 *1333 *3115.0010 -00- --Bad.--9.813 *1956 *1330.6512 *4238 -71 ---Sweetmaize.--5 *603 *1952 ‘2728.347 -764.912 *oo0 -65-Averagecompositionof freshgreen maize.9.373.1252-5030 -006 - 2 5---16 -00The fresh ensilage of good quality contained 0.320 per cent. (infresh substance) of alcohol, 0.531 per cent. of free acid (calciilated aslactic acid), 0.657 per cent. of volatile acids (as acetic acid), and0.986 per cent. of total volatile acids (as acetic acid). The corre-sponding numbers for the bad sa.mple are 0.280, 0.316, 0.356, and0.535.The sweet maize prepared by Fry’,s method does not differ essentiallyfrom the average composition of fresh maize. The sugar of the freshmaize has disappeared completely, whilst alcohol and free acids havebeen formed, The fact that a larger amount of volatile acid wasfound than total free acid is due t o the liberation of volatile acids(originally present as salts) in the distillation of the substance inpresence of tannic acid.Analyses of the ensilage a t a later period are also given. The wholeof the free acid was found to consist of acetic and butyric acids ; lacticacid was not preseiit. N. H. M

ISSN:0368-1769    

DOI:10.1039/CA8905800076

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

ANALYTICAL CHEAIISTRT. 83 An a 1 y t i c a1 C h e m i s t r y. Estimation of Phosphorus in Phosphor-tin. By W. HEMPEL (Her., 22, 2478).-Phosphor-tin is best analpsed by Wohler’s chlo- rine method as employed in the analysis of Fahl-ore. The stannic chloride and phosphoric chloride which are formed are collected in concentrated nitric acid (about 10 c.c.) ; the vessel is washed out with dilute nitric acid (1 : 2),. and the phosphoric acid is precipi- tated with ammonium molybdate and estimated directly. F. S. K. Recognition of Phosphoric Acid of Mineral Origin. By J. STOKLASA (Chern. Centr., 1889, ii, 57, from Listy. Chem., 13, 153-154) .-The author contends that the percentage of fluorine in bones as given by different authors is decidedly too high. Raw bones do not Rhow any fluorine by the Loren2 reaction, whilst incinerated bones give only a slight indication of the presence of this element Lvhen tested in the same way. On the other hand, the author found the fossil bones of Elephas primigenius to contain 3.54 and 4.36 per cent.of ferric oxide and 2.08 and 52-98 per cent. of fluorine respectively in tlwo different specimens. Bones found in the older alluvids on the island of Festigos contained 2.42 per cent. of‘ ferric oxide, 1.58 of fluorine, 80.04 of tricalcium phosphate. Superphosphates prepared from this phosphate and also from bones were testetl by the Lorenz reaction, with the result that fluorine was only found in the former, whilst of the several samples of the latter class of super- phosphates only that from hone-ash gave any indication of fluorine, and then but slightly.On the other hand, remarks the author, Lorenz seems to have overlooked the fact that a series of mineral phosphates exist which contain but very little fluorine. J. W. L. Rapid Method of Estimating Arsenic. By E. POLENSKE (Chem. Centr., 1889, ii, 58-59, from Pharm. Zeit., 34, 299-300). -The method consists in evolving the arsenic as hydrogen arsenide in a Marsh apparatus, deposition of the arsenic in a tube having three bulbs blown on it, and weighing first that part of the tube containing the ‘‘ mirror,” and secondly the tube after dissolving OE the arsenic. The evolution flask is recommended to be of a capacity of 250 c.c., and to contain 80-100 grams of zinc. The apparatus includes an acid funnel 30 cm.long, having a U-formed bend, and the evolution flask is also connected with a washing flask containing lead nit.rate solution, to which is attached a tube containing calcium chloride, and a t the farther end, potash. The decomposing tube is attached to this. All air is expelled from the apparatus, first, by adding 5 C.C. of concentrated sulphuric acid and 20 C . C . of wat(’r, and the re- agents are at the same time tested for arsenic by heating the tube. The solution should not contain more than 4-5 milligrams of arsenic, and is allowed to drop into the acid funnel from a burette a t the rate of 0.5-1.0 C.C. per minute. The gas escaping from the end of the 9 284 ABSTRACTS OF CHEMICAL PAPERS. tube is passed through a solution of silver nitrate, and the evolut.ion should not be too rapid for the bubbles to be counted.During the evolution of the hydrogen arsenide, two hunsen lamps are placed under the second and third bulbs : in order to test whether all the arsenic is evolved from the flask, the first is heated, and i f a " mirror " forms it must be driven onwards into the second bulb, and after a time the same test may be applied again. When it is thus proved that arsenic no longer escapes from the flask, the tube is disconnected and reversed,and any arsenic which may have been deposited iu the third bulb is driven into the narrow tube between the second and third bulbs. All the arsenic having been thus collected in this part of the tube, it is cut off and weighed, and after dissolving off the arsenic with nitric acid, it i s weighed again. the difference giving the weight- of arsenic.Metallic salts aria organic substances interfere with the acciiracy of the method. Behaviour of Silicates when Fused with Phosphates. By K. HAUSHOFER (Chem. Centr., '1889, ii, 53, from Sitzungsber. der mat h.-naturzu. Abt. ba?yr. Akrrd. Wiss., 1889, 8-1 l).-Many silicates, when fused to a bead with an alkaline phosphate in the blowpipe, swell up, evolve gases, and finally insoluble silica, either in the form of a skeleton or as flakes, is deposited. The evolution of gases is referred by the author to the presence of chlorine, sulphates, or water, and h e draws attention to this part of the reaction as an aid in the recognition of the silicate under examination. For instance, hauyn and sodalite, owing to the evolution of the chlorine and $ulphuric anhydride, may be distinguished from nepheline, which is but slowly attacked.In like manlier, humite is distinguished from olivine by the evolution of hydrofluoric acid, and tourmaline and axinite from beryl. The micas of the scapolite group, epidote and vesiivian, lose their water of eonstitu t'ion, whereas the felspars, amphibole, and granites are but slowly attacked. Similar distinctions may be drawn between crystallised kaumerite and the dense rhodo- chrome, and between pyrophyllite and agalmstolite. Technical Analysis of Commercial Sodium Sulphide. By B. SHETLIK (Chem. Centr., 1889, ii, 211, from Listy. Chem., 12, 205- 206).-10 grams of the sulphide is dissolved in water, the solution diluted to i$ litre, and 50 C.C.titrated with normal sulphuric acid, phenolphthalein being used as an indicator. If the titration is made in the cold, the quantity of acid required must be doubled, whereas if it is carried out a t a boiling heat and the acid added until the red colour does not reappear on further boiling the solution, the acid used is equivalent to the sulphide. Insoluble sulphides which are de- composed by dilute acid may be titrated in this way. Qualitative Analysis of the Ammonium Sulphide Re- cipitate. By P. MATER (Ber., 22, 2627--26:10).-The presence of chromium in t,his precipitate renders impracticable the separation by solntion in hydrochloric acid and precipitation of the iron and aluminium by boiling with sodium acetate, since the chromium is sometimes wholly and sometimes partially prccipitated, whilst if no J.W. L. J. W. L. J. w. L.ASALYTICAL CHEMISTRY. 85 iron is present, it all remains in the filtrate. The author has found that the presence of excess of iron (at least 5 atoms to every atom of chromium) ensures the total precipitation of the chromium. He, therefore, recommends t h a t where chromium is suspected and iron is not present in large quantities, ferric chloride should be- added in excess before boiling with sodium acetate. L. T.. T. Analysis of Aluminium Sulphate. By F. BETLSTSIN arid T. GROSSET (Chem. Centr., 1889, ii, 60; from Melanges, Yhys. Chim. Bull., St. Pe'tersbourg, 13, 42--47).--The authors recommend the fol- lowing method. 1-2 grams of substance is dissolved in 5 C.C. of water, 5 C.C.of a cold saturated solution of ammonium sulphate added, and the mixture well stirred during a quarter of an hour. 50 C.C. of 95 per cent. alcohol is added, and the precipitated ammonia alum filtered off and washed with 50 C.C. of alcohol. The filtrate contains all the free acid, which is deteimined by concentratiiig and titrating with decinormal alkali. The whole of the aluminium sulphate is precipitated as ammonia alum. Estimation of Chromium and Copper in Iron and Steel. By C. REIXHARDT (Clrenz. Centr., lt89, ii, bU-61, frcim Stahl w. Eistn 9, 404--405).-For the determination of chromium, 10 grams of borings or filings are dissolved with 100 C.C. hjdrochloric acid in a covered beaker of 500 C.C. capacity, first without heat, then at a boil- ing heat, oxidised with potassium clilorate, concentrated to one half the volume, filtered into a &litre Erlenmeycr flask, and the insoluble residue washed several times with dilute hydrochloric acid on the filter, and finally with water.The solution is now reduced a t a boiling heat hy the a,ddition of 10-20 C.C. of sodium hypophosphite solutiou (200 grams in 400 C.C. of water), and afternards the chromium is pre- cipitated by the addition of zinc oxide in excess. The precipitate is dissolved in hydrochloric acid, a little more hypophosphite added, and the precipitation repeated. The chromium is separated from the zinc by precipitation with ammonia, which precipitation must be re- peated. The chromic oxide, after ignition, is iused, together with the insoluble portion of the material, with 8 grams of a mixture of 4 parts of sodium chloride, 1 part of sodium carbonate, and 1 part of potassium chlorate.From the dissdvad flux, the manpnese is pre- cipitated with alcohol, the silicic acid with lijdrochloric acid and a little sulphurous acid, and the chromium finally precipated as oxide with ammonia. The copper is determined iii 10 grams of the material : the hydrochloric acid solution is reduced with sodium hypophosphite, and the copper precipitated with hydrogen sulphide. Volumetric Estimation of Chromium in Iron and Steel. By E. WAHLHERG (Chem. Centr., 1889, ii, 194, from Bcrg. a. Huttenni. Zeit., 48, 18G-181).-0~5 gram of the metal is dissolved in boiliud. nitric acid, sp. gr. 120, evaporated to dryness, ground up, transfern*d to a platinum crucible, mixed with a mixture of 2 grams of magnesm, 1 gram of potassium chlorate, and 1 gram of fiodium carbonate, aud the whole heated, at first gently, then in the blast flame for one hour.J. W. L. J. W. L.86 A BSTKACTS OF CHEMICAL PAPERS. The mass is dissolved out with 50-100 C.C. of water, any s m a l l quantity of manganic acid reduced by a drop or two of alcohol, acidified with sulphuric acid, arid the chromic acid estimated by adding a known quantity of ferrous sulpbate and determining the amount unosidised by titrating with potassium perrnanganate. J. W. L. Microscopical Test for Tantalum and Niobium. By K. HAUSHOFER (Chem. Centr., 1889, ii, 62-63, from Sitzungsber. der math.-nnturzu. Abt. bayr. Akad. Wiss., 1889, 3-8).-The substance to be tested is fused with a very small bead of sodium carbonate in the hottest part of the bunsen flame €or 30-40 seconds.It is then treated on the object glass with one drop of water, and the form of the crystals left as the water evaporates is noted; i f tantalic acid is present in excess, these are hexagonal plates, wliereas an excess of niobic acid causes the formation of hexagonal prisms. If the residue is treated with hydrochloric acid, the colombite acids ci-gstallise out. Addition of sodium hydroxide, slightly warm, causes the formation of hexagonal plates, consisting partly of stars and prisms. A simple test for the columbite acids consists in boiling 20 millgrams of the mineral with 0.8 C.C. of concentrated sulphuric acid, the solution being poured off from the insoluble part, diluted to 2-3 c.c., and a little zinc-dust added ; the solut,ion becomes sapphire- blue in a few minutes.J. W. L. By E. WALLER (A?zaZ!lst, 14, 108-112).- Attention is directed to the fact that in cases where, either from exces- sive hardness or from the presence of magnesium salts, it is neces- sary to dilute a water before applying the soap test, the results may vary widely according to the degree of dilution employed, especinllj- i f no deduction is made for the soap required to give a lather with pure water. The hardness of a mixture of calcium and magnesium solutions appears to be less than that of either of the individual solu- tions apart. M. J. S. Estimation of Chlorine in Water. By A. HAZEN (Amer. Ghem. J., 11, 409-414).-An investigation of the ordinary method of esti- mating chlorine in water by titration with a silver solution, using potassium chromate as an indicator.It is found that an excess of silver is always required to make the colour reaction apparent ; this excess is smaller the greater the amount of chromate used, provided that this does not colour the liquid so much as to obscure the end- point; i t is also smaller when the rolume of the liquid titrated is small. The amount of silver chloride precipitated also influences the result, and, other things being equal, the excess of silver solution used is nearly proportional to the amount of silver precipitated. To correct for this, the use of a silver solution 1 per cent. stronger than its normal value is recommended. It is still better to staudardise the silver solution against a solution of sodium chloride; with such a solution, and making a correction for the volume of liquid titrated, accurate results were obtained.If the amount of chlorine is small, the water must be concentrated, a very little sodium carbonate being added to prevent loss of liydrochloric acid on boiling. Hardness of Water. C. F. B.ANALYTICAL CHEMISTRY. 87 Dynamical Theory of Albuminoi’d Ammonia. By R. B. WARDER (Amer. Cheni. J., 11, 365-:378).-The integral calculus is applied t’o obtain formulae representing the distillation of an aqueous solution of ammonia, and the conversion of albuminoid matter into ammonia by alkaline permanganate. It is assumed that the “ coefficient of vola- tility”-that is, the ratio of the conceritration in any small portion of the distillate to that of the liquid in the retort-is constant.I n the case of the formation of albuininold ammonia, the law of mass action is applied, and the particular formula is investigated which represents the reaction between one molecule each of three different substances (permanganate, ,potash, and a nitrogenous substance). Curves are given representing the formulaz obtained. It is found that the rate of formation of albuminoid ammonia varies with the amounts of per- manganate and of potash present, and also with the rate of distilla- tion, and with the concentration of the original solution. The calcu- lated ratios of the am0unt.s of ammonia in successive portions of the distillate do not agree with those obtained by experiment ; this dis- crepancyis attributed to the fact that there is not one simple reaction taking place, but several ; ,and hence the curve actually obtained is the resultant of a number of curves.It is also found that the amount of ammonia left in the retort when the distillation is stopped, as calculated from the formula, is much less than that actually left. This is attributed to the formation of intermediate compounds which only yield ammonia with great diffi- culty. The author finally concludes that Wanklyn’s ammonia process gives valuable but purely cornparatire results, and is useless for the absolute estimation of organic nitrogen. Estimation of Ferrocyanide in Gas-lime. By 0. KXORLAUCH (Chem. Centr., 1889, ii, 211-212, from J.Gasbpleucht. u. Wasser- z-ersorg, 32, 450-459).-10 grams of the well mixed and finely ground-up gas-lime is digested, with frequent agitation, for 15-16 hours with 50 C.C. of 10 per cent. potassium hydroxide in a, flask graduated on the neck at 250 C.C. and a t 255 C.C. The volume is thsn made up to 255 c.c., the whole well mixed, and filtered; 100 C.C. of the filtrate is added to a hot solution of ferric chloride (containing 60 grams of ferric chloride and 200 C.C. of hydrochloric acid in the litre), the precipitate collected and washed with hot water, the funnel being covered meanwhile. The, filter-paper with the precipitate is agaiii transferred to the beaker in which the precipitation took place, the precipitate treated with 20 C.C. of 10 per cent. potassium hydroxide, and the whole then transferred to a 250 C.C. flask and made up to that volume.50 to 100 C.C. of the solution is filtered from the insoluble ferric hydrate and paper, 3-5 C.C. dilute sulphuric acid added, and the solution titrated with standard solution of cupric sulphate, which has been standardised with a solution of potassium ferrocyanide (4 grams in 1 litre). If hydrogen sulphide is present, it must be removed before the titration by adding 1-2 grams of lead carbonate. In applying t h i s volumetric method for determining hydroferrocyanic acid with cupric sulphate, the indicator used is a drop of ferric chloride on a piece of filter-paper to which is applied a drop of the solution C. F. B.88 AHSTRACTS OF OHEAIICAL PAPERS. under experiment ; so long as an excess of potassium ferrocyanide is present, the formation of prussian-blue will at once take place.Towards the end of the titration it is necessary to filter very small quantities of the solution into a dilute solution of ferric chloride, when the last traces of soluble ferrocyanide can be observed. Absorption of Bromine by Fatty Acids. By G. HALPHEN (-7. Pharm. [ 5 ] , 20, 247--249).-The process may be applied either to fats or to the fatty acids obtained from them; the results differ in the t w o cases, but are comparable amongst themselves. A saturated aqueous solution of bromine atid one of sodium hvdroxide coloured with eosin are required. 20 C.C. of soda-lye at 36" B. is added to 980 C.C. of water and 2 grams of eosin. 20 C.C. of carbon bisulphide and 10 C.C.ot bromine solution of known strength are placed in a flask provided with a cork. The soda fiolution is run in gradually from a burette. After each addition, the flask is closed and shaken four or five times, and the addition repeated until the brown colour passes to a salmon tint. The bromine solution is titrated by means of the sodium sollx- tion before each estimation, as its strength varies constantly. 'LO C.C. of carbon bisulphide is placed in a 250 C.C. flask, 1 gram of fatty acid is added, and an excess of bromine to the amount of about 0.5 gram. The flask is shaken up and allowed to remain for five hours ; at the end of this time the absorption is complete. The excess of bromine is titrated by means of the soda solution; the brown mass formed gradually passes to a white, soapy solution which becomes rosy on the addition of a few drops of the soda solution in excess.The vegetable oils absorb much more bromine than does lard, so that their presence in lard can thus be easily detected.-J. T. Note.-The standard solutions could not be originated by the method given. J. 'l'. Estimation of Citric Acid in Lemon Juice. By R. WILLIAMS (Annalyst, 14, 25-29).-The object of this paper is to recommend the use of sodium hydroxide with phenolphthalein as indicator for de- termining the acidity of lemon juice, instead of sodium carbonate with litmus-paper. Normal sodium citrate blues litmus-paper, but has no effect on yhenolphthaleih ; accordingly titrations of' pure citric acid made with sodium hydroxide and the latter indicator give numbers agreeing closely with theory, whilst those with the carbonate and litmus are low.Kevertheless, for some unexplained reason, the carbonate gives higher results than the hydroxide when applied to lemon juice, and estimations by precipitation as calcium salt agree better with the latter than with the former, being in fact generally lower than either. M. J. S. J. W. L. Impurities in Commercial Salicylic Acid. By B. FISCHER (J. Pharnz. [5], 20, 258-261 ; from Pharm. Zeit., 1889, 329, after Pharm. Zeit. RUSR., 2889, 28, 378) .-Salicylic acid contains cresotic acid when manufactured from impure phenol containing cresol. The presence of potash in the sodium hydrate employed occasions the formation of parahydroxjbenzoic acid ; this acid is also produced ifASALYTICAL CHENIS'I'RY.89 the temperature is too low at the time when the current of carbonic anhydride is passed, whilst too high a temperature at this stage results in the production of hydroxyisophthalic acid, due to the action of the gas on tlie sodium sslicylate already formed. Lastly, particularly in presence of iron salts, brown or yellow compounds are formed by oxidation, which are insoluble in water, and give a yellow colour to the salicylic acid. In a well-conducted process, parahydroxybenzoic and hydroxyisophthalic acids are usually not formed in quantities exceed- ing 0.4 per cent., and the first is easily removed by washing, as it is readily soluble in water. The second acid is less soluble in water, and may amount to 1 per cent.in certain cases. Cresotic acid is tho most important impurity, as apart from its obscure physiological action, its presence is very objectionable. The amount of cresotic acid present may be estimated by titrating with decinornial baryta solution, using phenolphthalein as indicator. Owing to the difference in their molecular weights, less solution is required to saturate cresotic acid than is required by salicjlic acid, but great care is needed to obtain satiafactory results, and certain accidental impuri- ties should be previously sought for, namely, water, colouring matters, and sodium chloride. With this view, dissolve in ether ; if the solu- tion is not clear, filter, evaporate, and dry first at 6U", then in a vacuum over sulphuric acid. In the absence of these impurities, it is necessary to dry the sample.The bsryta solution is standardised by the use of pure salicylic acid obtained by converting the commercial acid into the calcium salt, recrystallising, and then deconiposing the salt by means ofhydrochloric acid. For the detection of cresotic acid, 15 C.C. of waCer and 1 t o 2 grams of calcium carbonate are boiled in a 200 C.C. flask ; 3 grams of the salicylic acid is added, and the flask is agitated over a flame until the volume is reduced to about 5 C.C. By this time some crystals have formed. After cooling, the mother- liquor is transferred to a test tube and evaporated to 1 C.C. On rubbing this with a glass rod, crystallisation sets in. 1 C.C. of water is added, and the liquid filtered through a small plug of cotton.The filtrate is made up to 1 C.C. and hydrochloric acid is added ; if the original acid contained 3 t o 5 per cent. of ci*esotic acid, there separates out a mixture of acids which fuses in boiling water and collects at the bottom of the test tube in the form of thick, oily drops. The test does not succeed with less than 1 per cent. Hydroryisophthalic acid may be separated from salicylic acid by distillation in a current of steam. The first acid remains in the still as a light-grey powder or as small lumps. By dissolving i t in sufficient hydrochloric acid and filtering through charcoal, i t can be obtained in the form of slender, white needles, which fuse with decomposition about 300-305". The author has found in one sample of commercial salicylic acid 0.3 per cent.hydroxyisophthalic acid, and in another 5.3 per cent. of cresotic acid. By F. JEAN (2 Pharm. [ 5 ] , 20, 337--341).--The author's method comprises the determination of the density, melting point of the fatty acids, the elevation of temperature under the induence of sulphuric acid, and the refractive power. To determine the density, Wesphal's balauce is employud. To determine tlie J. T. Oil Testing.sn AHS'L'RAGTS OF CHEMICAL PAPERS. nielting point, a special apparatus is employed consisting of a thin U-shaped tube, in the two limbs of which are platinum wires nearly touching the bottom of the tube. A lager of solid acid comes between t'he ends of the wire, but this is displaced by mercury which has been charged in one side of the tube, when the temperature of a surrounding beaker of water has reached the melting point of ttle enclosed acid.The mercury causes electrical contact between the wires, and the transmitted current rings a bell when the temperature is read off, as given by a thermometer immersed in the bath. 'I'o determine the rise in temperature when mixed with sulphuric acid, a small beaker 4 cm. diameter and 6 cm. high is marked to contain 15 c.c., and in this is placed an acid tube provided with a stopper having a small tube through which air can be blown into the interior, and a small glass tube reaching from the bottom of the acid tube, and just passing through its side towards the upper end, so that on blowing into the acid tube its cont'ents are expelled and mixed with oil i n the beaker.15 C.C. of the oil to be tested is placed in the beaker and heated to 40", the acid tube is charged with 5 C.C. of sulphuric acid a t 65" B. and placed within the beaker; the whole is allowed to cool down to SO", and is then placed in a felt-lined box, when the acid is transferred to the oil by blowing and well mixed with it, the temperature is carefully observed, and the maximum reached is noted. I n general, when this temperature and the density of the oil are satisfactory, t,he sample may be regarded as pure. Oils which have been oxidised or otherwise changed require treatment with alcohol, or, better still, saponification, before determining the rise in temperature. Sometimes when the rise of temperatare is nearly the same for two oils, that of their two fatty acids may differ much more.One or two results may be given of oils and their acids:-Olive oil 41*5", acid 45"; linseed oil G l O , acid 109"; colza (Pas-de-Calais) 37", acid 44" ; ditto (India) 37", acid 46". To determine the refractive power of the oil, a, special oleorefractometer is employed which is not described. The index of refraction only vmies within narrow limits for the same species if care be taken to remove excess of acid by treatment with alcohol. The purity of a sample may be safely affirmed when the index of' refraction, the rise in temperature, and the density agree with a standard oil of known purity. J. T. By W. BISHOP (J. Pharm. [ 5 ] , 20, 244-247).- If this oil is shaken for a short time with pure hydrochloric acid cf 21-22" B. in the proportion of 8 of oil to 12 of acid, no special effect is produced, but if the oil is exposed to air and solar light for some days, and the same test is applied, the mixture becomes green and, after rt time, the colour is found to be con6ned to $he acid layer.I f the action of air and light be much prolonged, the green colour is intensified, and after a still longer period, a bluiali- violet, flocculent precipitate is produced. The green acid solution gives an absorption-spectrum almost exactly coinciding with that of chlorophyll. The application of this reaction will serve to indicate, when the results are positive, that a sample of sesame oil has been Oil of Sesame.ANALYTICAL CHIC31 ISTHY. 91 exposed to light and air for some time, and is not probably of recent production.Such an oil added to olive oil in the proportion of 5 to 10 per cent. can be easily detected by this method, whilst 10 to 20 per cent,. of oil of sesame may be detected in the same way after soiiie days’ exposure. 3 . T. By E. H. AMAGAT and F. JEAN (Compt. rend., 109, 616--617).--L)eterrnination of the refractive index in a refractometer of special construction is a delicate and trustwortthy means of detecting adulterations in oils and fats. The variations in the refractive indices of samples of the same oil from different sources are very slight, and distinctive differences are observed between vegetable oils, animal oils, and mineral oils. As little as 10 per cent. of oleomargarin can be detected in bnttei-. Optical Examination of Oils and Fats.U. H. B. Analysis of Fats and Oils. By J. MUTER and L. DE KOKINGH ( A d y s t , 14, 61--65).-The authors’ object has been to re-determine the iodine absorption (Hubl’s) of the liquid fatty acids from various oils and fats under conditions which should be as nniform as possible, and should exclude any alteration of the acids either by exposure to air or by drying a t a high temperature. A weighed portion of the fat is saponified with alcoholic potash, and the solution accurately neutralised with acetic acid. It is then poured into an excess of a boiling solution of lead acetate. The pre- cipitate is washed, then transferred to a stoppered bottle and treated with ether. The ether solution is filtered from lead stenrate, &c., into a Muter’s “olei’n tube,” in which it is decomposed by dilute hydrochloric acid.The volume of the ethereal solution of the fatty acids having been read, an aliquot part is run into a flask and most of the ether distilled off. The ether vapour protect’s the fatty acids from the air. Alcohol is then added, and the solution is titrated with soda ; this gives the total amount of the liquid fatty acids, calculatinv them as oleic acid. Another portion of the ethereal solution contain- ing 0.5 gram of the fatty acid is then evaporated in a bottle through which a stream of carbonic anhydride is being passed. When the last traces of ether are removed, 50 C.C. of Hubl’s reagent is instantly added, and the bottle, having been stoppered, is placed i n the dark for 12 honrs, side by side with a blank, after which the excess of iodine is titrated by thiosulphate.The authors anticipate that the “ iodine absorbing power ” thus ascertained will permit the amount, of any admixture of fats to be calculated with more precision than has hit herto been possible. M. J. S. Extraction of Fat from Milk Solids. By H. D. RICHMOKI) (AnaZyst? 14, 121--130).-0f the 15 or more msthods which havcb been proposed for the extraction of the fat from the dry residue of milk, those of Adams (paper coil), Soxhlet (plaster of Paris), and Storch (pdmice) give the highest and most concordant, but yet not identical results. The author has reinvestigated these three methods, using kieselguhr in place of pumice. I n Adams’ method, some analysts extract the paper coils with ether for a short time before92 ABSTRACTS OF CHEMICAL PAPERS.using them ; others apply a correction based on blank experiments wihh the,same batch of paper. The author finds that the complete extraction of the paper with ether requires a, very prolonged treat- ment; the total extract in 7& hours being more than three tirlles as much as that obtained in the first 1i hour. The matter extracted consists chiefly of the calcium salt of a resinous acid. The most complete and rapid extraction is obtained by the use of alcohol con- taining 10 per cent. of acetic acid. After 3 or 4 hours' treatment with this reagent in a Soxhlet's apparatus, nothing soluble in &her remains. With the plaster and kieselguhr methods, the chief requisite is to grind the dried residue to a very fine powder, and to extract it with ether for at least 3 hours.Working in this waj-, the three methods agree closely. From the results of numerous determi- nations by the three methods, the author has developed a new formula for deducing the percentage of f a t from that of total solids and the specific gravity : T = 1.17 P - 0.263 - (apparently a mis- print for -+ 0.263 -), where T is the percentage of total solids, F that of fat, D is the specific gravity of the milk, and G = 1000 (D - I). This formula gives results which do not differ materially from those of Hehner and Richmond's older formula (AnaZyst, 13, 32). The most satisfactory method of estimating the total solids appears to be the evaporation of not more than 2 grams of milk in a flat-bottomed basin and drying for 1 or 14 hour.Volumetric Method for the Estimation of Fat in Milk, &c. By C. L. PARSONS (Analyst, 14,181-187).-This method is proposed as one which can be carried out a t the dairy by unskilled persons. 100 C.C. of the milk is placed in a, bottle 11 inches high and 14 in diameter. 10 C.C. of soda solution (made by dissolving 1 part of commercial caustic soda in 2 parts of water) is added, then 5 C.C. of alcoholic soap solution (1 ounce of Castile soap to the gallon). 50 C.C. of gasoline (free from residue) is next added; the bottle is corked and shaken hard five or six times during half-an-hour. The petroleum solution of the fat is then allowed to rise to the surface. Should it fail t o do so, 5 C.C. or more of the alcoholic soap solution may be added and gently mixed in.When the upper layer is perfectly clear, 25 C.C. of it is withdrawn and evaporated in a small flask, which has its neck cut off obliqiiely. Two drops of strong acetic acid is added to the fat, which is then dried at 120" for 14 hours and drained from the flask into a measuring tube graduated in twentieths of a cubic centimeter. A table given in the paper converts the readings of the volume of the fat into percentages. G D G D M. J. S. The necessary precautions are fully described. M. J. S. Condensed Milk and the Estimation of Casein and Lact- albumen. By H. FABER (Analyst, 14, 141--147).-The author proposes to employ the estimation of the relative proportions of ca,sePn and lactalbumen as a means of distinguishing between fresh milk and that which hae been condensed arid afterwards diluted with water.ANALT TlCAL CHERll STKY.93 Fresh milk contains from 0.35 to 0.45, or perhaps more, of lactalbumen. By boiling the milk about two-thirds of this is coagulated, or SO modified that it is precipitated together with the case'in. The heating to ahout 75"' to which condensed milk must be subjected in order to sterilise it, has a similar effect. The two albuminoids can be sepa- rated by Sebelien's method. The casein is first precipitaked by magnesium sulphate, 2 vols. of the saturated solution of that salt being first added, and then as much of the powdered crystals as the mixture is able to dissolve ; the precipitate is washed with a saturated solution of magnesium sulphate ; and the lactalbnmen i s precipitated from the filtrate by either tannic acid or phosphotuiigstic acid.In these precipitates, the nitrogen is estimated by Kjeldahl's method. Test analyses show that the separation is very exact. Estimation of Soluble and Insoluble Fatty Acids in Butter. By W. JOHNSTONE (Analyst, 14, 113-114) and H. D. RICHMOND (ibid., 153--155).--Instead of estimating the volatile fatty acids by the Reichert process, the author prefers the following method. The butter is saponified with a known quantity of alcoholic potash and the excess found by titration. The alcohol having been removed by boiling, an excess of acid is added, and the insoluble fatty acids are filtered off and washed. After ail*-drying they are dissolved by ether and weighed after evaporation. They are now again saponified by standard potash, and the amount they neutrafise is ascertained.The difference between these two titrations gives the amount of fatty acid soluble in water, which thus estimated is considerably higher than is shown by Reichert's process. The author hints that the results of the latter may be vitiated by the production of propionic, acetic, and formic acids by the action of potash on the glycerol. Richmond, commenting on the above process, shows that the results given cannot possibly be correct, the total fatty acids, together wit11 the glycerol residue corresponding t o the potash neutralised, adding up to more than the weight of the butter taken, and that this is due to the titration of the insoluble acids being performed in aqueous solution.The results by Reichert's process, when corrected for the recognised average deficiency of &, add up almost exactly to 100 per cent. He points out that at the temperature of the water-bath potash has no action on glycerol. M. J. 8. M. J. S. Examination of Lard for Adulteration. By T. S . GLADDING (Analyst, 14, 32--.34).-The following tests should all be applied to a, suspected sample:-(1) specific gravity at 100'; (2) Hiibl's iodine test ; (3) BecLi-Millian test (Abstr., 1889,319) ; (4) Dalican's " Titre " test; (5) Belden's microscopic test for beef fat (Analyst, 13, SO). Dalican's " titre " is the temperature of crystallisation of the fatty acids. These are to be prepared from the sample by saponification, washed well with hot water, and filtered through dry paper into a test- tube.The crystallising point is then taken with a thermometer graduated t o tenths of a degree. The titre of lard may range from 36.4" to 41.4" ; iodine absorption from 57 to 68.4 per cent., a high titre being associated with a low kdine absorption, and vice vers6.9 4 ABSTRACTS OF CHEMICAL PAPERS. The titre of beef fat is about 41.6 to 44; iodine absorption, 43.8 to 40; that of cotton-seed oil, 33.3, iodine absorption, 108. The one adultmerant will therefore to some extent mask the other; they are, however, respectively revealed by Bechi’s and Belden’s tests, The high specific gravity of cotton-seed oil affords the onlv means of esti- mating the amount of i t present. (See also Abstr., 1889, 319, 659.) M. J. S. Action of Acids on Benzoic Sulphinide and Analysis of By I.REMSEN and W. &I. BURTON (Anzer. Chewi. J., u Saccharin.” l1,403408).-When benzoic sulphinide, C6H4<co >NH [ = 1 : 21, so2 is bniled with dilute acids, hydrogen ammonium orthosulphobenzoate, COOH.C,H4*S03NH, [= I : 21 is formed, toqether with a little ( wthosulphaminebenzoic acid, C OOH.C6H,.S02NH2. The best strength of acid is that obtained by diluting strong hydrochloric acid of sp. gr. 3 -17 with 8 to 10 times its volume of water. Commercial “ saccharin ” is found to be a mixture of parasulph- aminebenzoic acid, benzoic sulphinide, and hydrogen potasqinm ortho- sulphobenzoate, the amount of sulphinide present being somewhat less than 50 per cent. To analyse it, 2 grams are boiled for one hour with 100 C.C.of dilute hydrochloric acid (1-8) in a flask of 250 C.C. capacity, provided v-ith a reflux condenser. The clear solution is then evaporated to nbont 15 c.c., wheii the parasulphaminebenzoic a,cid separates out ; it is dried a t 80” and weighed. The filtrate, containing hydrogen am- monium orthosulphobenzoate (from the decomposition of the sul- phinide) and the hydrogen potassium salt of the same acid, is evaporated ; the residue is weighed, and the amount of potassium in it is estimated by heating a portion with sulphuric acid, and weighing the potassium sulphate formed. Two samples of saccharin were analysed, each five times ; the mean percentage composition of each is given below. Benzoic COOH*C,H, *S02NHZ. sulphinide. C00hT*C,H4.SO3K. I ...... 50.00 42.86 7.12 II ......44.49 48.3:3 7.99 C. F. B. Estimation of Morphine in Opium. By F. A. FL~CKIGER (Arch. Pharm. [ 3 ] , 27, 721-732, ’7t 9-i72).-The author discusses various points which arise in the estimation of morphine, and arrives a t the following fairly good, although not qnite perfect, method. 8 grams of opium powder is placed in a folded filter of 12 cm. diameter with a little tapping, and is dried a t 100”. After half an hour 10 C.C. of ether mixed with 10 C.C. of chloroform is poured over it, the covered funnel being frequently struck, and finally 10 C.C. more of chloroform is poured on. After all possible liquid has run through, tlhe filter with its contents is opened out and dried a t a gentle heat. Next the powder is vigorously and repeatedly shaken in a flask with 80 C.C.of water and filtered after two hours. 42.5 grams of the filtrate is well and often shaken in a weighed flask with 7-5 C.C.AShLY TICAL CHEMISTRY. 95 of alcohol (0.83 sp. gr.), 15 C.C. of ether, and 1 C.C. of ammonia (0.96). After six hours, the contents of the flask are poured on to a double- folded filter of 10 cm. diameter, and the morphine is washed on to the filter with about 10 C.C. of water. This is dried, returned to the dried flask, and dried at 100" until its weight becomes constant. This pro- cess with a particular sample gave 12.90, 13.12, 13.35 per cent. of morphine, which was not pure white, but which dissolved completely in lime-water with very little colour.. As an appendix the author criticises in some detail an article by E.R. Squibb in the "Ephemeris '' for July, on morphine estimation, and, although be sees many defects in the process given, he remarks that the comprehensive paper desei-veu the fullest consideration. J. T. Analysis of Pepper and the occurrence of Piperidine in the same. By W. JOHNSTONE (Analyst, 14, 41-49).-Moisture and ash. -A weighed portion is dried at 100' and then incinerated in a muffle. The ash is treated successively with water and hydrochloric acid, and the amount of insoluble matter noted. Oil.-20 grams is distilled with water ; the distillate is shaken with ether, the ethereal solution is evaporated at a very low temperature, and the residue is dried over sulphuric acid. Piperidine.-20 grams is dist'illed as for the oil determination, and the distillate is titrated with N/lO sulphuric acid (compare Abstr., 1889, 298).That the piperidine is not derived from the hydrolysis of piperine is shown by the fact that pure piperine yields no piperidine when distilled with water, also that in distilling pepper with water, piperidine soon ceases to come over, although the amount obtained is very small in comparison with the piperine present. Piperine.-10 grams is digested at 100" in a closed bottle with 3 grams of potash dissolved in 25 C.C. of water and 25 C.C. of alcohol. The bottle (4 oz.) should have tlhe neck ground flat and be closed by a plate of caoutchouc pressed tightly upon it by a screw-frame. After 4-6 hours' digestion, the bottle is cooled, the contents are washed into a large flask and distilled as long as the distillate is alkaline.The theoretical yield of pipedine is obtained. Crude Fibre.-A small quantity is boiled for half an hour in a flask with inverted condenser with 200 C.C. of dilute sulphuric acid (12.5 grams per litre). The residue is twice boiled with water, then with 200 C.C. of potash (12.5 grams per litre), and again twice with water. It is collected on a tared filter, dried and weighed, and any ash it contains deducted. Nitrogen.-Determined by soda-lime, as usual. Alcoholic Extract.-10 grams is extracted with 95 per cent, alcohol in a Soxhlet's apparatus for 24 hours. The alcohol is distilled off and the extractive matters dried at 100". St,arch.-The exhausted residue from the preceding is, without drying, washed into a flask with 200 C.C. of water and 20 C.C.of hydrochloric acid (1.121) and heated in boiling water for three hours. After cooling, the liquid is filtered, neutrdised with soda, made up to 500 c.c., and titrated with Fehling's solution. In 13 genuine samples from various localities, the moisture ranged9 ri ABSTRACTS OF CHEMICAL PAPERS. from 12 to 15 per cent., ash 1.07 to 4.46 (long pepper 7 57), oil 0.53 to 1.87, piperidine 0.21 to 0.77, piperine 5.21 to 13.03, fibre 4.2 to 15.05, starch 29.6 to 53.5, ash insoluble in acid 0.06 to 0.62 (long pepper 1-47), Any larger amount of insoluble ash would probably be the best indication of a fraudulent addition. M. J. S. Detection of Cocai'ne Hydrochloride. By M. GOELDNER (Arch. Phai-m. [31, 27, $99; from Pharm. Zeit., 34, 471).-The author believes that the following is a charactelistic test for cocaine. 6 or 7 drops of pure, strong sulphuric acid are added to some crystals of resorcinol in a porcelain basin, and the latter is moved to and fro a little, then a litt,le cocaine hydrochloride is added to t'he yellow liquid.A som+ what strong reaction follows, and a splendid, blue coloration is imme- diately obtained; a drop of sodium hydroxide changes this to a light- rose colour. The reaction goes more quickly with powdered resorcinol in place of crystals. Verysmall quantities of the reamgent give no colour reaction. Other alkaloids give nothing approaching to this reaction. J. T. Estimation of Indigotin for Commercial Purposes. By F. A. OWEN (Chem. Centr., 1889, ii, 217-213; from J. dmer. Chem. SOC., 10, 178).-J gram of the substance is weighed on a watch-glass, dried a t lOO", finely powdered, rubbed with water to a thin paste, and washed into a 250 C.C.flask. 3 grams of zinc-dust and 6 grams of sodium hydroxide are added, the solution dilut,ed to a little above the mark, shaken up now and then, and after the reaction is complete (during which the solution must remain green, red or brownish streaks indicate that the reduction has been carried too far ; a froth indicates the presence of too much zinc), 50 C.C. of the clear liquid is exposed to the air for half an hour, acidified with hydrochloric acid, and filtered through a well-wnshed filter, dried a t loo", and weighed. J. W. L.ANALYTICAL CHEAIISTRT. 83An a 1 y t i c a1 C h e m i s t r y.Estimation of Phosphorus in Phosphor-tin.By W. HEMPEL(Her., 22, 2478).-Phosphor-tin is best analpsed by Wohler’s chlo-rine method as employed in the analysis of Fahl-ore. The stannicchloride and phosphoric chloride which are formed are collectedin concentrated nitric acid (about 10 c.c.) ; the vessel is washed outwith dilute nitric acid (1 : 2),. and the phosphoric acid is precipi-tated with ammonium molybdate and estimated directly.F. S. K.Recognition of Phosphoric Acid of Mineral Origin. ByJ. STOKLASA (Chern. Centr., 1889, ii, 57, from Listy. Chem., 13,153-154) .-The author contends that the percentage of fluorine inbones as given by different authors is decidedly too high. Raw bonesdo not Rhow any fluorine by the Loren2 reaction, whilst incineratedbones give only a slight indication of the presence of this elementLvhen tested in the same way.On the other hand, the authorfound the fossil bones of Elephas primigenius to contain 3.54 and4.36 per cent. of ferric oxide and 2.08 and 52-98 per cent. of fluorinerespectively in tlwo different specimens. Bones found in the olderalluvids on the island of Festigos contained 2.42 per cent. of‘ ferricoxide, 1.58 of fluorine, 80.04 of tricalcium phosphate. Superphosphatesprepared from this phosphate and also from bones were testetl bythe Lorenz reaction, with the result that fluorine was only found inthe former, whilst of the several samples of the latter class of super-phosphates only that from hone-ash gave any indication of fluorine,and then but slightly.On the other hand, remarks the author,Lorenz seems to have overlooked the fact that a series of mineralphosphates exist which contain but very little fluorine.J. W. L.Rapid Method of Estimating Arsenic. By E. POLENSKE(Chem. Centr., 1889, ii, 58-59, from Pharm. Zeit., 34, 299-300).-The method consists in evolving the arsenic as hydrogen arsenidein a Marsh apparatus, deposition of the arsenic in a tube having threebulbs blown on it, and weighing first that part of the tube containingthe ‘‘ mirror,” and secondly the tube after dissolving OE the arsenic.The evolution flask is recommended to be of a capacity of 250 c.c.,and to contain 80-100 grams of zinc. The apparatus includes anacid funnel 30 cm. long, having a U-formed bend, and the evolutionflask is also connected with a washing flask containing lead nit.ratesolution, to which is attached a tube containing calcium chloride, anda t the farther end, potash.The decomposing tube is attachedto this. All air is expelled from the apparatus, first, by adding 5 C.C.of concentrated sulphuric acid and 20 C . C . of wat(’r, and the re-agents are at the same time tested for arsenic by heating the tube.The solution should not contain more than 4-5 milligrams of arsenic,and is allowed to drop into the acid funnel from a burette a t the rateof 0.5-1.0 C.C. per minute. The gas escaping from the end of the9 84 ABSTRACTS OF CHEMICAL PAPERS.tube is passed through a solution of silver nitrate, and the evolut.ionshould not be too rapid for the bubbles to be counted.During theevolution of the hydrogen arsenide, two hunsen lamps are placedunder the second and third bulbs : in order to test whether all thearsenic is evolved from the flask, the first is heated, and i f a " mirror "forms it must be driven onwards into the second bulb, and after a timethe same test may be applied again. When it is thus proved thatarsenic no longer escapes from the flask, the tube is disconnected andreversed,and any arsenic which may have been deposited iu the thirdbulb is driven into the narrow tube between the second and thirdbulbs. All the arsenic having been thus collected in this part of thetube, it is cut off and weighed, and after dissolving off the arsenicwith nitric acid, it i s weighed again.the difference giving the weight-of arsenic. Metallic salts aria organic substances interfere with theacciiracy of the method.Behaviour of Silicates when Fused with Phosphates. ByK. HAUSHOFER (Chem. Centr., '1889, ii, 53, from Sitzungsber. dermat h.-naturzu. Abt. ba?yr. Akrrd. Wiss., 1889, 8-1 l).-Many silicates,when fused to a bead with an alkaline phosphate in the blowpipe,swell up, evolve gases, and finally insoluble silica, either in theform of a skeleton or as flakes, is deposited. The evolution of gasesis referred by the author to the presence of chlorine, sulphates, orwater, and h e draws attention to this part of the reaction as an aid inthe recognition of the silicate under examination. For instance,hauyn and sodalite, owing to the evolution of the chlorine and$ulphuric anhydride, may be distinguished from nepheline, which isbut slowly attacked.In like manlier, humite is distinguished fromolivine by the evolution of hydrofluoric acid, and tourmaline andaxinite from beryl. The micas of the scapolite group, epidote andvesiivian, lose their water of eonstitu t'ion, whereas the felspars,amphibole, and granites are but slowly attacked. Similar distinctionsmay be drawn between crystallised kaumerite and the dense rhodo-chrome, and between pyrophyllite and agalmstolite.Technical Analysis of Commercial Sodium Sulphide. ByB. SHETLIK (Chem. Centr., 1889, ii, 211, from Listy. Chem., 12, 205-206).-10 grams of the sulphide is dissolved in water, the solutiondiluted to i$ litre, and 50 C.C.titrated with normal sulphuric acid,phenolphthalein being used as an indicator. If the titration is madein the cold, the quantity of acid required must be doubled, whereas ifit is carried out a t a boiling heat and the acid added until the redcolour does not reappear on further boiling the solution, the acid usedis equivalent to the sulphide. Insoluble sulphides which are de-composed by dilute acid may be titrated in this way.Qualitative Analysis of the Ammonium Sulphide Re-cipitate. By P. MATER (Ber., 22, 2627--26:10).-The presence ofchromium in t,his precipitate renders impracticable the separation bysolntion in hydrochloric acid and precipitation of the iron andaluminium by boiling with sodium acetate, since the chromium issometimes wholly and sometimes partially prccipitated, whilst if noJ.W. L.J. W. L.J. w. LASALYTICAL CHEMISTRY. 85iron is present, it all remains in the filtrate. The author has foundthat the presence of excess of iron (at least 5 atoms to every atom ofchromium) ensures the total precipitation of the chromium. He,therefore, recommends t h a t where chromium is suspected and iron isnot present in large quantities, ferric chloride should be- added inexcess before boiling with sodium acetate. L. T.. T.Analysis of Aluminium Sulphate. By F. BETLSTSIN arid T.GROSSET (Chem. Centr., 1889, ii, 60; from Melanges, Yhys. Chim.Bull., St. Pe'tersbourg, 13, 42--47).--The authors recommend the fol-lowing method. 1-2 grams of substance is dissolved in 5 C.C.of water,5 C.C. of a cold saturated solution of ammonium sulphate added, andthe mixture well stirred during a quarter of an hour. 50 C.C. of95 per cent. alcohol is added, and the precipitated ammonia alumfiltered off and washed with 50 C.C. of alcohol. The filtratecontains all the free acid, which is deteimined by concentratiiig andtitrating with decinormal alkali. The whole of the aluminiumsulphate is precipitated as ammonia alum.Estimation of Chromium and Copper in Iron and Steel.By C. REIXHARDT (Clrenz. Centr., lt89, ii, bU-61, frcim Stahl w. Eistn9, 404--405).-For the determination of chromium, 10 grams ofborings or filings are dissolved with 100 C.C. hjdrochloric acid in acovered beaker of 500 C.C. capacity, first without heat, then at a boil-ing heat, oxidised with potassium clilorate, concentrated to one halfthe volume, filtered into a &litre Erlenmeycr flask, and the insolubleresidue washed several times with dilute hydrochloric acid on thefilter, and finally with water.The solution is now reduced a t a boilingheat hy the a,ddition of 10-20 C.C. of sodium hypophosphite solutiou(200 grams in 400 C.C. of water), and afternards the chromium is pre-cipitated by the addition of zinc oxide in excess. The precipitate isdissolved in hydrochloric acid, a little more hypophosphite added, andthe precipitation repeated. The chromium is separated from thezinc by precipitation with ammonia, which precipitation must be re-peated. The chromic oxide, after ignition, is iused, together withthe insoluble portion of the material, with 8 grams of a mixture of 4parts of sodium chloride, 1 part of sodium carbonate, and 1 part ofpotassium chlorate.From the dissdvad flux, the manpnese is pre-cipitated with alcohol, the silicic acid with lijdrochloric acid and alittle sulphurous acid, and the chromium finally precipated as oxidewith ammonia. The copper is determined iii 10 grams of the material :the hydrochloric acid solution is reduced with sodium hypophosphite,and the copper precipitated with hydrogen sulphide.Volumetric Estimation of Chromium in Iron and Steel. ByE. WAHLHERG (Chem. Centr., 1889, ii, 194, from Bcrg. a. Huttenni.Zeit., 48, 18G-181).-0~5 gram of the metal is dissolved in boiliud.nitric acid, sp.gr. 120, evaporated to dryness, ground up, transfern*dto a platinum crucible, mixed with a mixture of 2 grams of magnesm,1 gram of potassium chlorate, and 1 gram of fiodium carbonate, audthe whole heated, at first gently, then in the blast flame for one hour.J. W. L.J. W. L86 A BSTKACTS OF CHEMICAL PAPERS.The mass is dissolved out with 50-100 C.C. of water, any s m a l lquantity of manganic acid reduced by a drop or two of alcohol,acidified with sulphuric acid, arid the chromic acid estimated byadding a known quantity of ferrous sulpbate and determining theamount unosidised by titrating with potassium perrnanganate.J. W. L.Microscopical Test for Tantalum and Niobium. By K.HAUSHOFER (Chem. Centr., 1889, ii, 62-63, from Sitzungsber. dermath.-nnturzu.Abt. bayr. Akad. Wiss., 1889, 3-8).-The substanceto be tested is fused with a very small bead of sodium carbonatein the hottest part of the bunsen flame €or 30-40 seconds. It isthen treated on the object glass with one drop of water, and theform of the crystals left as the water evaporates is noted; i ftantalic acid is present in excess, these are hexagonal plates, wliereasan excess of niobic acid causes the formation of hexagonal prisms. Ifthe residue is treated with hydrochloric acid, the colombite acidsci-gstallise out. Addition of sodium hydroxide, slightly warm, causesthe formation of hexagonal plates, consisting partly of stars andprisms. A simple test for the columbite acids consists in boiling20 millgrams of the mineral with 0.8 C.C.of concentrated sulphuricacid, the solution being poured off from the insoluble part, diluted to2-3 c.c., and a little zinc-dust added ; the solut,ion becomes sapphire-blue in a few minutes. J. W. L.By E. WALLER (A?zaZ!lst, 14, 108-112).-Attention is directed to the fact that in cases where, either from exces-sive hardness or from the presence of magnesium salts, it is neces-sary to dilute a water before applying the soap test, the results mayvary widely according to the degree of dilution employed, especinllj-i f no deduction is made for the soap required to give a lather withpure water. The hardness of a mixture of calcium and magnesiumsolutions appears to be less than that of either of the individual solu-tions apart. M.J. S.Estimation of Chlorine in Water. By A. HAZEN (Amer. Ghem.J., 11, 409-414).-An investigation of the ordinary method of esti-mating chlorine in water by titration with a silver solution, usingpotassium chromate as an indicator. It is found that an excess ofsilver is always required to make the colour reaction apparent ; thisexcess is smaller the greater the amount of chromate used, providedthat this does not colour the liquid so much as to obscure the end-point; i t is also smaller when the rolume of the liquid titrated issmall. The amount of silver chloride precipitated also influences theresult, and, other things being equal, the excess of silver solutionused is nearly proportional to the amount of silver precipitated.Tocorrect for this, the use of a silver solution 1 per cent. stronger thanits normal value is recommended. It is still better to staudardise thesilver solution against a solution of sodium chloride; with such asolution, and making a correction for the volume of liquid titrated,accurate results were obtained. If the amount of chlorine is small,the water must be concentrated, a very little sodium carbonate beingadded to prevent loss of liydrochloric acid on boiling.Hardness of Water.C. F. BANALYTICAL CHEMISTRY. 87Dynamical Theory of Albuminoi’d Ammonia. By R. B. WARDER(Amer. Cheni. J., 11, 365-:378).-The integral calculus is applied t’oobtain formulae representing the distillation of an aqueous solution ofammonia, and the conversion of albuminoid matter into ammonia byalkaline permanganate.It is assumed that the “ coefficient of vola-tility”-that is, the ratio of the conceritration in any small portion ofthe distillate to that of the liquid in the retort-is constant. I n thecase of the formation of albuininold ammonia, the law of mass actionis applied, and the particular formula is investigated which representsthe reaction between one molecule each of three different substances(permanganate, ,potash, and a nitrogenous substance). Curves aregiven representing the formulaz obtained. It is found that the rateof formation of albuminoid ammonia varies with the amounts of per-manganate and of potash present, and also with the rate of distilla-tion, and with the concentration of the original solution.The calcu-lated ratios of the am0unt.s of ammonia in successive portions of thedistillate do not agree with those obtained by experiment ; this dis-crepancyis attributed to the fact that there is not one simple reactiontaking place, but several ; ,and hence the curve actually obtained isthe resultant of a number of curves.It is also found that the amount of ammonia left in the retort whenthe distillation is stopped, as calculated from the formula, is muchless than that actually left. This is attributed to the formation ofintermediate compounds which only yield ammonia with great diffi-culty. The author finally concludes that Wanklyn’s ammonia processgives valuable but purely cornparatire results, and is useless for theabsolute estimation of organic nitrogen.Estimation of Ferrocyanide in Gas-lime.By 0. KXORLAUCH(Chem. Centr., 1889, ii, 211-212, from J. Gasbpleucht. u. Wasser-z-ersorg, 32, 450-459).-10 grams of the well mixed and finelyground-up gas-lime is digested, with frequent agitation, for 15-16hours with 50 C.C. of 10 per cent. potassium hydroxide in a, flaskgraduated on the neck at 250 C.C. and a t 255 C.C. The volume is thsnmade up to 255 c.c., the whole well mixed, and filtered; 100 C.C. ofthe filtrate is added to a hot solution of ferric chloride (containing60 grams of ferric chloride and 200 C.C. of hydrochloric acid in thelitre), the precipitate collected and washed with hot water, the funnelbeing covered meanwhile. The, filter-paper with the precipitate isagaiii transferred to the beaker in which the precipitation took place,the precipitate treated with 20 C.C. of 10 per cent.potassium hydroxide,and the whole then transferred to a 250 C.C. flask and made up to thatvolume. 50 to 100 C.C. of the solution is filtered from the insolubleferric hydrate and paper, 3-5 C.C. dilute sulphuric acid added, andthe solution titrated with standard solution of cupric sulphate, whichhas been standardised with a solution of potassium ferrocyanide(4 grams in 1 litre). If hydrogen sulphide is present, it must beremoved before the titration by adding 1-2 grams of lead carbonate.In applying t h i s volumetric method for determining hydroferrocyanicacid with cupric sulphate, the indicator used is a drop of ferric chlorideon a piece of filter-paper to which is applied a drop of the solutionC.F. B88 AHSTRACTS OF OHEAIICAL PAPERS.under experiment ; so long as an excess of potassium ferrocyanide ispresent, the formation of prussian-blue will at once take place.Towards the end of the titration it is necessary to filter very smallquantities of the solution into a dilute solution of ferric chloride,when the last traces of soluble ferrocyanide can be observed.Absorption of Bromine by Fatty Acids. By G. HALPHEN(-7. Pharm. [ 5 ] , 20, 247--249).-The process may be applied either tofats or to the fatty acids obtained from them; the results differ inthe t w o cases, but are comparable amongst themselves. A saturatedaqueous solution of bromine atid one of sodium hvdroxide coloured witheosin are required. 20 C.C.of soda-lye at 36" B. is added to 980 C.C.of water and 2 grams of eosin. 20 C.C. of carbon bisulphide and 10 C.C.ot bromine solution of known strength are placed in a flask providedwith a cork. The soda fiolution is run in gradually from a burette.After each addition, the flask is closed and shaken four or five times,and the addition repeated until the brown colour passes to a salmontint. The bromine solution is titrated by means of the sodium sollx-tion before each estimation, as its strength varies constantly. 'LO C.C.of carbon bisulphide is placed in a 250 C.C. flask, 1 gram of fatty acidis added, and an excess of bromine to the amount of about 0.5 gram.The flask is shaken up and allowed to remain for five hours ; at theend of this time the absorption is complete.The excess of bromineis titrated by means of the soda solution; the brown mass formedgradually passes to a white, soapy solution which becomes rosy onthe addition of a few drops of the soda solution in excess.The vegetable oils absorb much more bromine than does lard, sothat their presence in lard can thus be easily detected.-J. T.Note.-The standard solutions could not be originated by themethod given. J. 'l'.Estimation of Citric Acid in Lemon Juice. By R. WILLIAMS(Annalyst, 14, 25-29).-The object of this paper is to recommend theuse of sodium hydroxide with phenolphthalein as indicator for de-termining the acidity of lemon juice, instead of sodium carbonate withlitmus-paper.Normal sodium citrate blues litmus-paper, but has noeffect on yhenolphthaleih ; accordingly titrations of' pure citric acidmade with sodium hydroxide and the latter indicator give numbersagreeing closely with theory, whilst those with the carbonate and litmusare low. Kevertheless, for some unexplained reason, the carbonategives higher results than the hydroxide when applied to lemon juice,and estimations by precipitation as calcium salt agree better withthe latter than with the former, being in fact generally lower thaneither. M. J. S.J. W. L.Impurities in Commercial Salicylic Acid. By B. FISCHER(J. Pharnz. [5], 20, 258-261 ; from Pharm. Zeit., 1889, 329, afterPharm. Zeit. RUSR., 2889, 28, 378) .-Salicylic acid contains cresoticacid when manufactured from impure phenol containing cresol. Thepresence of potash in the sodium hydrate employed occasions theformation of parahydroxjbenzoic acid ; this acid is also produced iASALYTICAL CHENIS'I'RY.89the temperature is too low at the time when the current of carbonicanhydride is passed, whilst too high a temperature at this stage resultsin the production of hydroxyisophthalic acid, due to the action ofthe gas on tlie sodium sslicylate already formed. Lastly, particularlyin presence of iron salts, brown or yellow compounds are formed byoxidation, which are insoluble in water, and give a yellow colour to thesalicylic acid. In a well-conducted process, parahydroxybenzoic andhydroxyisophthalic acids are usually not formed in quantities exceed-ing 0.4 per cent., and the first is easily removed by washing, as it isreadily soluble in water.The second acid is less soluble in water,and may amount to 1 per cent. in certain cases. Cresotic acid is thomost important impurity, as apart from its obscure physiologicalaction, its presence is very objectionable. The amount of cresoticacid present may be estimated by titrating with decinornial barytasolution, using phenolphthalein as indicator. Owing to the differencein their molecular weights, less solution is required to saturatecresotic acid than is required by salicjlic acid, but great care isneeded to obtain satiafactory results, and certain accidental impuri-ties should be previously sought for, namely, water, colouring matters,and sodium chloride.With this view, dissolve in ether ; if the solu-tion is not clear, filter, evaporate, and dry first at 6U", then in avacuum over sulphuric acid. In the absence of these impurities, it isnecessary to dry the sample. The bsryta solution is standardised bythe use of pure salicylic acid obtained by converting the commercialacid into the calcium salt, recrystallising, and then deconiposing thesalt by means ofhydrochloric acid. For the detection of cresotic acid,15 C.C. of waCer and 1 t o 2 grams of calcium carbonate are boiled ina 200 C.C. flask ; 3 grams of the salicylic acid is added, and the flaskis agitated over a flame until the volume is reduced to about 5 C.C.By this time some crystals have formed.After cooling, the mother-liquor is transferred to a test tube and evaporated to 1 C.C. Onrubbing this with a glass rod, crystallisation sets in. 1 C.C. of wateris added, and the liquid filtered through a small plug of cotton.The filtrate is made up to 1 C.C. and hydrochloric acid is added ; if theoriginal acid contained 3 t o 5 per cent. of ci*esotic acid, there separatesout a mixture of acids which fuses in boiling water and collects atthe bottom of the test tube in the form of thick, oily drops. The testdoes not succeed with less than 1 per cent. Hydroryisophthalicacid may be separated from salicylic acid by distillation in a currentof steam. The first acid remains in the still as a light-grey powderor as small lumps. By dissolving i t in sufficient hydrochloric acidand filtering through charcoal, i t can be obtained in the form of slender,white needles, which fuse with decomposition about 300-305".Theauthor has found in one sample of commercial salicylic acid 0.3 per cent.hydroxyisophthalic acid, and in another 5.3 per cent. of cresotic acid.By F. JEAN (2 Pharm. [ 5 ] , 20, 337--341).--Theauthor's method comprises the determination of the density, meltingpoint of the fatty acids, the elevation of temperature under theinduence of sulphuric acid, and the refractive power. To determinethe density, Wesphal's balauce is employud. To determine tlieJ. T.Oil Testingsn AHS'L'RAGTS OF CHEMICAL PAPERS.nielting point, a special apparatus is employed consisting of a thinU-shaped tube, in the two limbs of which are platinum wires nearlytouching the bottom of the tube.A lager of solid acid comesbetween t'he ends of the wire, but this is displaced by mercury whichhas been charged in one side of the tube, when the temperature of asurrounding beaker of water has reached the melting point of ttleenclosed acid. The mercury causes electrical contact between thewires, and the transmitted current rings a bell when the temperatureis read off, as given by a thermometer immersed in the bath. 'I'odetermine the rise in temperature when mixed with sulphuric acid, asmall beaker 4 cm. diameter and 6 cm. high is marked to contain15 c.c., and in this is placed an acid tube provided with a stopperhaving a small tube through which air can be blown into the interior,and a small glass tube reaching from the bottom of the acid tube,and just passing through its side towards the upper end, so that onblowing into the acid tube its cont'ents are expelled and mixed withoil i n the beaker.15 C.C. of the oil to be tested is placed in thebeaker and heated to 40", the acid tube is charged with 5 C.C. ofsulphuric acid a t 65" B. and placed within the beaker; the whole isallowed to cool down to SO", and is then placed in a felt-lined box,when the acid is transferred to the oil by blowing and well mixedwith it, the temperature is carefully observed, and the maximumreached is noted. I n general, when this temperature and the densityof the oil are satisfactory, t,he sample may be regarded as pure.Oils which have been oxidised or otherwise changed require treatmentwith alcohol, or, better still, saponification, before determining therise in temperature.Sometimes when the rise of temperatare isnearly the same for two oils, that of their two fatty acids may differmuch more. One or two results may be given of oils and theiracids:-Olive oil 41*5", acid 45"; linseed oil G l O , acid 109"; colza(Pas-de-Calais) 37", acid 44" ; ditto (India) 37", acid 46". Todetermine the refractive power of the oil, a, special oleorefractometer isemployed which is not described. The index of refraction only vmieswithin narrow limits for the same species if care be taken to removeexcess of acid by treatment with alcohol. The purity of a samplemay be safely affirmed when the index of' refraction, the rise intemperature, and the density agree with a standard oil of knownpurity.J. T.By W. BISHOP (J. Pharm. [ 5 ] , 20, 244-247).-If this oil is shaken for a short time with pure hydrochloric acid cf21-22" B. in the proportion of 8 of oil to 12 of acid, no specialeffect is produced, but if the oil is exposed to air and solar light forsome days, and the same test is applied, the mixture becomesgreen and, after rt time, the colour is found to be con6ned to $heacid layer. I f the action of air and light be much prolonged, thegreen colour is intensified, and after a still longer period, a bluiali-violet, flocculent precipitate is produced. The green acid solutiongives an absorption-spectrum almost exactly coinciding with that ofchlorophyll. The application of this reaction will serve to indicate,when the results are positive, that a sample of sesame oil has beenOil of SesameANALYTICAL CHIC31 ISTHY.91exposed to light and air for some time, and is not probably of recentproduction. Such an oil added to olive oil in the proportion of 5 to10 per cent. can be easily detected by this method, whilst 10 to 20per cent,. of oil of sesame may be detected in the same way aftersoiiie days’ exposure. 3 . T.By E. H. AMAGATand F. JEAN (Compt. rend., 109, 616--617).--L)eterrnination of therefractive index in a refractometer of special construction is a delicateand trustwortthy means of detecting adulterations in oils and fats.The variations in the refractive indices of samples of the same oil fromdifferent sources are very slight, and distinctive differences areobserved between vegetable oils, animal oils, and mineral oils.Aslittle as 10 per cent. of oleomargarin can be detected in bnttei-.Optical Examination of Oils and Fats.U. H. B.Analysis of Fats and Oils. By J. MUTER and L. DE KOKINGH( A d y s t , 14, 61--65).-The authors’ object has been to re-determinethe iodine absorption (Hubl’s) of the liquid fatty acids from variousoils and fats under conditions which should be as nniform as possible,and should exclude any alteration of the acids either by exposure toair or by drying a t a high temperature.A weighed portion of the fat is saponified with alcoholic potash,and the solution accurately neutralised with acetic acid.It is thenpoured into an excess of a boiling solution of lead acetate. The pre-cipitate is washed, then transferred to a stoppered bottle and treatedwith ether. The ether solution is filtered from lead stenrate, &c.,into a Muter’s “olei’n tube,” in which it is decomposed by dilutehydrochloric acid. The volume of the ethereal solution of the fattyacids having been read, an aliquot part is run into a flask and most ofthe ether distilled off. The ether vapour protect’s the fatty acidsfrom the air. Alcohol is then added, and the solution is titrated withsoda ; this gives the total amount of the liquid fatty acids, calculatinvthem as oleic acid. Another portion of the ethereal solution contain-ing 0.5 gram of the fatty acid is then evaporated in a bottle throughwhich a stream of carbonic anhydride is being passed.When thelast traces of ether are removed, 50 C.C. of Hubl’s reagent is instantlyadded, and the bottle, having been stoppered, is placed i n the darkfor 12 honrs, side by side with a blank, after which the excess ofiodine is titrated by thiosulphate. The authors anticipate that the“ iodine absorbing power ” thus ascertained will permit the amount,of any admixture of fats to be calculated with more precision than hashit herto been possible. M. J. S.Extraction of Fat from Milk Solids. By H. D. RICHMOKI)(AnaZyst? 14, 121--130).-0f the 15 or more msthods which havcbbeen proposed for the extraction of the fat from the dry residue ofmilk, those of Adams (paper coil), Soxhlet (plaster of Paris), andStorch (pdmice) give the highest and most concordant, but yet notidentical results.The author has reinvestigated these three methods,using kieselguhr in place of pumice. I n Adams’ method, someanalysts extract the paper coils with ether for a short time befor92 ABSTRACTS OF CHEMICAL PAPERS.using them ; others apply a correction based on blank experimentswihh the,same batch of paper. The author finds that the completeextraction of the paper with ether requires a, very prolonged treat-ment; the total extract in 7& hours being more than three tirlles asmuch as that obtained in the first 1i hour. The matter extractedconsists chiefly of the calcium salt of a resinous acid. The mostcomplete and rapid extraction is obtained by the use of alcohol con-taining 10 per cent.of acetic acid. After 3 or 4 hours' treatmentwith this reagent in a Soxhlet's apparatus, nothing soluble in &herremains. With the plaster and kieselguhr methods, the chiefrequisite is to grind the dried residue to a very fine powder, and toextract it with ether for at least 3 hours. Working in this waj-, thethree methods agree closely. From the results of numerous determi-nations by the three methods, the author has developed a newformula for deducing the percentage of f a t from that of total solidsand the specific gravity : T = 1.17 P - 0.263 - (apparently a mis-print for -+ 0.263 -), where T is the percentage of total solids, F thatof fat, D is the specific gravity of the milk, and G = 1000 (D - I).This formula gives results which do not differ materially from thoseof Hehner and Richmond's older formula (AnaZyst, 13, 32).Themost satisfactory method of estimating the total solids appears to bethe evaporation of not more than 2 grams of milk in a flat-bottomedbasin and drying for 1 or 14 hour.Volumetric Method for the Estimation of Fat in Milk, &c.By C. L. PARSONS (Analyst, 14,181-187).-This method is proposed asone which can be carried out a t the dairy by unskilled persons. 100 C.C.of the milk is placed in a, bottle 11 inches high and 14 in diameter.10 C.C. of soda solution (made by dissolving 1 part of commercialcaustic soda in 2 parts of water) is added, then 5 C.C.of alcoholicsoap solution (1 ounce of Castile soap to the gallon). 50 C.C. ofgasoline (free from residue) is next added; the bottle is corked andshaken hard five or six times during half-an-hour. The petroleumsolution of the fat is then allowed to rise to the surface. Should itfail t o do so, 5 C.C. or more of the alcoholic soap solution may be addedand gently mixed in. When the upper layer is perfectly clear, 25 C.C.of it is withdrawn and evaporated in a small flask, which has its neckcut off obliqiiely. Two drops of strong acetic acid is added to the fat,which is then dried at 120" for 14 hours and drained from the flaskinto a measuring tube graduated in twentieths of a cubic centimeter.A table given in the paper converts the readings of the volume of thefat into percentages.GDGDM.J. S.The necessary precautions are fully described.M. J. S.Condensed Milk and the Estimation of Casein and Lact-albumen. By H. FABER (Analyst, 14, 141--147).-The authorproposes to employ the estimation of the relative proportions of ca,sePnand lactalbumen as a means of distinguishing between fresh milk andthat which hae been condensed arid afterwards diluted with waterANALT TlCAL CHERll STKY. 93Fresh milk contains from 0.35 to 0.45, or perhaps more, of lactalbumen.By boiling the milk about two-thirds of this is coagulated, or SOmodified that it is precipitated together with the case'in. The heatingto ahout 75"' to which condensed milk must be subjected in order tosterilise it, has a similar effect.The two albuminoids can be sepa-rated by Sebelien's method. The casein is first precipitaked bymagnesium sulphate, 2 vols. of the saturated solution of that saltbeing first added, and then as much of the powdered crystals as themixture is able to dissolve ; the precipitate is washed with asaturated solution of magnesium sulphate ; and the lactalbnmen i sprecipitated from the filtrate by either tannic acid or phosphotuiigsticacid. In these precipitates, the nitrogen is estimated by Kjeldahl'smethod. Test analyses show that the separation is very exact.Estimation of Soluble and Insoluble Fatty Acids in Butter.By W. JOHNSTONE (Analyst, 14, 113-114) and H. D. RICHMOND(ibid., 153--155).--Instead of estimating the volatile fatty acids bythe Reichert process, the author prefers the following method.Thebutter is saponified with a known quantity of alcoholic potash andthe excess found by titration. The alcohol having been removed byboiling, an excess of acid is added, and the insoluble fatty acids arefiltered off and washed. After ail*-drying they are dissolved by etherand weighed after evaporation. They are now again saponified bystandard potash, and the amount they neutrafise is ascertained. Thedifference between these two titrations gives the amount of fattyacid soluble in water, which thus estimated is considerably higherthan is shown by Reichert's process. The author hints that theresults of the latter may be vitiated by the production of propionic,acetic, and formic acids by the action of potash on the glycerol.Richmond, commenting on the above process, shows that the resultsgiven cannot possibly be correct, the total fatty acids, together wit11the glycerol residue corresponding t o the potash neutralised, addingup to more than the weight of the butter taken, and that this is dueto the titration of the insoluble acids being performed in aqueoussolution.The results by Reichert's process, when corrected for therecognised average deficiency of &, add up almost exactly to 100 percent. He points out that at the temperature of the water-bathpotash has no action on glycerol.M. J. 8.M. J. S.Examination of Lard for Adulteration. By T. S . GLADDING(Analyst, 14, 32--.34).-The following tests should all be applied toa, suspected sample:-(1) specific gravity at 100'; (2) Hiibl's iodinetest ; (3) BecLi-Millian test (Abstr., 1889,319) ; (4) Dalican's " Titre "test; (5) Belden's microscopic test for beef fat (Analyst, 13, SO).Dalican's " titre " is the temperature of crystallisation of the fattyacids.These are to be prepared from the sample by saponification,washed well with hot water, and filtered through dry paper into a test-tube. The crystallising point is then taken with a thermometergraduated t o tenths of a degree. The titre of lard may range from36.4" to 41.4" ; iodine absorption from 57 to 68.4 per cent., a hightitre being associated with a low kdine absorption, and vice vers69 4 ABSTRACTS OF CHEMICAL PAPERS.The titre of beef fat is about 41.6 to 44; iodine absorption, 43.8 to40; that of cotton-seed oil, 33.3, iodine absorption, 108.The oneadultmerant will therefore to some extent mask the other; they are,however, respectively revealed by Bechi’s and Belden’s tests, Thehigh specific gravity of cotton-seed oil affords the onlv means of esti-mating the amount of i t present. (See also Abstr., 1889, 319, 659.)M. J. S.Action of Acids on Benzoic Sulphinide and Analysis ofBy I. REMSEN and W. &I. BURTON (Anzer. Chewi. J., u Saccharin.”l1,403408).-When benzoic sulphinide, C6H4<co >NH [ = 1 : 21, so2is bniled with dilute acids, hydrogen ammonium orthosulphobenzoate,COOH.C,H4*S03NH, [= I : 21 is formed, toqether with a little( wthosulphaminebenzoic acid, C OOH.C6H,.S02NH2.The best strengthof acid is that obtained by diluting strong hydrochloric acid of sp. gr.3 -17 with 8 to 10 times its volume of water.Commercial “ saccharin ” is found to be a mixture of parasulph-aminebenzoic acid, benzoic sulphinide, and hydrogen potasqinm ortho-sulphobenzoate, the amount of sulphinide present being somewhat lessthan 50 per cent.To analyse it, 2 grams are boiled for one hour with 100 C.C. ofdilute hydrochloric acid (1-8) in a flask of 250 C.C. capacity, providedv-ith a reflux condenser. The clear solution is then evaporated tonbont 15 c.c., wheii the parasulphaminebenzoic a,cid separates out ; itis dried a t 80” and weighed. The filtrate, containing hydrogen am-monium orthosulphobenzoate (from the decomposition of the sul-phinide) and the hydrogen potassium salt of the same acid, isevaporated ; the residue is weighed, and the amount of potassium init is estimated by heating a portion with sulphuric acid, and weighingthe potassium sulphate formed.Two samples of saccharin wereanalysed, each five times ; the mean percentage composition of eachis given below.BenzoicCOOH*C,H, *S02NHZ. sulphinide. C00hT*C,H4.SO3K.I ...... 50.00 42.86 7.12II ...... 44.49 48.3:3 7.99C. F. B.Estimation of Morphine in Opium. By F. A. FL~CKIGER(Arch. Pharm. [ 3 ] , 27, 721-732, ’7t 9-i72).-The author discussesvarious points which arise in the estimation of morphine, and arrivesa t the following fairly good, although not qnite perfect, method.8 grams of opium powder is placed in a folded filter of 12 cm.diameter with a little tapping, and is dried a t 100”.After half anhour 10 C.C. of ether mixed with 10 C.C. of chloroform is poured overit, the covered funnel being frequently struck, and finally 10 C.C.more of chloroform is poured on. After all possible liquid has runthrough, tlhe filter with its contents is opened out and dried a t agentle heat. Next the powder is vigorously and repeatedly shakenin a flask with 80 C.C. of water and filtered after two hours. 42.5 gramsof the filtrate is well and often shaken in a weighed flask with 7-5 C.CAShLY TICAL CHEMISTRY. 95of alcohol (0.83 sp. gr.), 15 C.C. of ether, and 1 C.C. of ammonia (0.96).After six hours, the contents of the flask are poured on to a double-folded filter of 10 cm.diameter, and the morphine is washed on to thefilter with about 10 C.C. of water. This is dried, returned to the driedflask, and dried at 100" until its weight becomes constant. This pro-cess with a particular sample gave 12.90, 13.12, 13.35 per cent. ofmorphine, which was not pure white, but which dissolved completelyin lime-water with very little colour.. As an appendix the authorcriticises in some detail an article by E. R. Squibb in the "Ephemeris ''for July, on morphine estimation, and, although be sees many defectsin the process given, he remarks that the comprehensive paper desei-veuthe fullest consideration. J. T.Analysis of Pepper and the occurrence of Piperidine in thesame. By W.JOHNSTONE (Analyst, 14, 41-49).-Moisture and ash.-A weighed portion is dried at 100' and then incinerated in a muffle.The ash is treated successively with water and hydrochloric acid, andthe amount of insoluble matter noted.Oil.-20 grams is distilled with water ; the distillate is shaken withether, the ethereal solution is evaporated at a very low temperature,and the residue is dried over sulphuric acid.Piperidine.-20 grams is dist'illed as for the oil determination, andthe distillate is titrated with N/lO sulphuric acid (compare Abstr.,1889, 298). That the piperidine is not derived from the hydrolysisof piperine is shown by the fact that pure piperine yields nopiperidine when distilled with water, also that in distilling pepperwith water, piperidine soon ceases to come over, although the amountobtained is very small in comparison with the piperine present.Piperine.-10 grams is digested at 100" in a closed bottle with3 grams of potash dissolved in 25 C.C. of water and 25 C.C. of alcohol.The bottle (4 oz.) should have tlhe neck ground flat and be closed bya plate of caoutchouc pressed tightly upon it by a screw-frame. After4-6 hours' digestion, the bottle is cooled, the contents are washedinto a large flask and distilled as long as the distillate is alkaline.The theoretical yield of pipedine is obtained.Crude Fibre.-A small quantity is boiled for half an hour in a flaskwith inverted condenser with 200 C.C. of dilute sulphuric acid (12.5grams per litre). The residue is twice boiled with water, then with200 C.C. of potash (12.5 grams per litre), and again twice with water.It is collected on a tared filter, dried and weighed, and any ash itcontains deducted.Nitrogen.-Determined by soda-lime, as usual.Alcoholic Extract.-10 grams is extracted with 95 per cent, alcoholin a Soxhlet's apparatus for 24 hours. The alcohol is distilled off andthe extractive matters dried at 100".St,arch.-The exhausted residue from the preceding is, withoutdrying, washed into a flask with 200 C.C. of water and 20 C.C. ofhydrochloric acid (1.121) and heated in boiling water for three hours.After cooling, the liquid is filtered, neutrdised with soda, made up to500 c.c., and titrated with Fehling's solution.In 13 genuine samples from various localities, the moisture range9 ri ABSTRACTS OF CHEMICAL PAPERS.from 12 to 15 per cent., ash 1.07 to 4.46 (long pepper 7 57), oil 0.53to 1.87, piperidine 0.21 to 0.77, piperine 5.21 to 13.03, fibre 4.2 to15.05, starch 29.6 to 53.5, ash insoluble in acid 0.06 to 0.62 (longpepper 1-47), Any larger amount of insoluble ash would probably bethe best indication of a fraudulent addition. M. J. S.Detection of Cocai'ne Hydrochloride. By M. GOELDNER (Arch.Phai-m. [31, 27, $99; from Pharm. Zeit., 34, 471).-The authorbelieves that the following is a charactelistic test for cocaine. 6 or 7drops of pure, strong sulphuric acid are added to some crystals ofresorcinol in a porcelain basin, and the latter is moved to and fro a little,then a litt,le cocaine hydrochloride is added to t'he yellow liquid. A som+what strong reaction follows, and a splendid, blue coloration is imme-diately obtained; a drop of sodium hydroxide changes this to a light-rose colour. The reaction goes more quickly with powdered resorcinolin place of crystals. Verysmall quantities of the reamgent give nocolour reaction. Other alkaloids give nothing approaching to thisreaction. J. T.Estimation of Indigotin for Commercial Purposes. By F. A.OWEN (Chem. Centr., 1889, ii, 217-213; from J. dmer. Chem. SOC.,10, 178).-J gram of the substance is weighed on a watch-glass,dried a t lOO", finely powdered, rubbed with water to a thin paste, andwashed into a 250 C.C. flask. 3 grams of zinc-dust and 6 grams ofsodium hydroxide are added, the solution dilut,ed to a little above themark, shaken up now and then, and after the reaction is complete(during which the solution must remain green, red or brownishstreaks indicate that the reduction has been carried too far ; a frothindicates the presence of too much zinc), 50 C.C. of the clear liquid isexposed to the air for half an hour, acidified with hydrochloric acid,and filtered through a well-wnshed filter, dried a t loo", and weighed.J. W. L

ISSN:0368-1769    

DOI:10.1039/CA8905800083

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

9 i General and Physical Chemistry. Emission Spectrum of Ammonia. By G. MAGNANINI ( Z e i t . physikal. Chern., 4, 435-440) .-The author has determined the positions of a large number of the lines of the ammonia spectrum. These are compared with the lines of Hasselberg’s second hydrogen spectrum, with which they show a remarkable coincidence. Absorption Spectrum of Nitrosyl Chloride. By G. MAGNANINI (Zeit. physikol. Chem., 4, 427-428).-The absorption spectrum of nitrosyl chloride vapour consists of six absorption bands in the orange and green parts of the spectrum. The wave-lengths corresponding with these bands and their relative intensities are given. By S. KALISCHER (Ann. Phys. Chem. [2], 37, 528).-The author observes that Righi (Abstr., 1889, 555) appears to have misunderstood a remark made by him in a former note (ibid., 3).He had pointed out that selenium cells often give an E.M.F. before exposure to light, and that, therefore, before experimenting on the influence of light on them, they should be tested in the dark to see if they already give any E.M.F. He had no inten- tion of asserting the necessity of actually manufacturing the cells in darkness, and preventing their even being exposed to light before experimenting with them. Electrical Conductivity of Hydrogen Chloride in Different Solvents. By I. KABLUKOFF (Zeit. physikal. CRem., 4, 429434).- The conductivity of solutions of hydrogen chloride in benzene, xylene, hexana, and ether is excessively small, that in ether being greatest and that in benzene the least. The molecular conductivity of the solution in ether is found to decrease with rising dilution. Solutions of hydrogen chloride in methyl, ethyl, isobntyl, and isoamyl alcohols have a somewhat greater conductivity.The methyl alcohol solutio~is have the highest conductivity, being about four times greater than the ethyl and 30 times greater than the isobutyl alcohol solutions. Amy1 alcohol, like ether, gives a decreasing molecular conductivity with rising dilution. Hydrogen chloride was also examined i n aqueous solutions of ethyl alcohol. The presence of ethyl alcohol is found to greatly decrease the conductivity of hydrogen chloride in water, An addition of 6 per cent. of alcohol causing a decrease of 20 per cent. in the conductivity. If a solution of benzene saturated with hydrogen chloride is allowed to remain for two or three days, crystals separate out which melt without decomposition, and can be sublimed a t high temperature.They are probably of the composition CsH6,3HCI. H. C. H, C. Electromotive Force of Selenium. G. W. T. H. C. VOL. LTlII. h98 ABSTRACTS OF OHEMIOAL PAPERS. Electrical Coqductivity of Solid Mercury. Bp L. GRUNMACH (Ann. Phys. Chem. [2], 37, 308--515).-As the result of a further experimental investigation of this subject,, tbe author finds that the apparent resistance of mercury when just melted is 2-5 times its value just before liquefaction begins. The value 1.5 formerly obtained by the author (Abstr., 1889, 201) is, therefore, too small. The value now obtained by him is smaller than that given by Cailletet and Bouty, namely 0.4, and the anthor attributes the difference between his present and former results, and between both of them and that obtained by Cailletet and Bouty, in great part to the change in volume which mercury undergoes in passing from the solid to the liquid state, and the effects of this change of volume on the resistance, depending as they do on the dimensions of the tubes and their regularity of bore.The degree to which the result is affected in this manner cannot be determined until these changes of volume have been measured, and the author states that an investigaticn of this point has been commenced. The results of the investigation described in this paper confirm the conclusion formerly arrived at by the author, that the temperature- coefficient of decrease of resistance for solid mercury decreases from the solidifying point down to -80°, the lowest temperature at which observations were made.The values obtained for this coefficient i n the former and present series of observations respectively are given below :- Range of Tempemture-coefficient. Temperature-coefficient. temperature. First series. Second series. -80" to -70" 0~0010 0-0008 -70 ,, -60 0*0010 0*0011 -60 ,, -50 0.0012 0.0015 -50 ,, -40 0.001 7 0.0023 The results of the present investigation therefore confirm the con- clusion formerly arrived at by the author, that assuming the truth of Clausius's law expressing the relation between the electrical resist- ances of simple metals and their absolute temperatures, then mercury must be considered a8 an exception. G.W. T. Thermoelectric Currents between Amalgamated Zinc and Zinc Sulphate. By K. A. BRANDER (Ann. Phys. Chem. [2], 37, 457-462).-The primary object of the investigation was to determine the relation between the E.M.F. developed and the difference of temperature between the electrodes. The electrodes, of amalgamated zinc, were placed in two vessels communicating by means of a siphon, and filled with a solution of zinc sulphate. One of these vessels was kept at the temperature of the place of observation, while the temperature of the other was gradually raised. The author found that, within the limits of errors of observation, the E.M.F. was proportional to the difference of temperature, until thisOEXERAL AND PHYSICAL CHENISTRT.99 difference exceeded 20.45", after which the E.M.F. appeared to increase rather more rapidly than the temperature difference. A few experi- ments were also made to determine the effect of varying the concen- tration of the zinc sulphate solution, and their results showed that the E.M.F. increased with the concentration. G. W. T. Electrochemistry and Thermochemistry of some Organic Acids. By H. JAHN (Anla. Phys. Cliem. [2], 37,40843). B'ormic Acid.-When a solution of sodium formate in water was acidified with formic acid and subjected to electrolysis, i t yielded hydrogen and carbonic anhydride. The sodium salt must first be resolved into sodium and the group HC02, the former forming sodium hydroxide with the water of solution, whilst the latter must either break up into carbonic anhydride and hydrogen or form formic acid again with the water of solution, according to the equation 2H + CO, + H20 = 2H2C02 + 0, the free oxygen then combining with a portion of the formic acid to form carbonic anhydride and water.Now Bunge has shown that in the electrolysis of formic acid no hydrogen is given off at the anode, which excludes the first explanation, and shows that a simple combus- tion of the acid takes place at the anode. The results were confirmed by determinations of the amount of gas liberated by the passage of a measured quantity of electricity. The author made a series of determinations of the heat of combus- tion of formic acid which agreed very well together, and their mean gave 62.87 cal. as the heat of combustion of a milligram mole- cule of formic acid.Thomsen obtained the value 60.2 cal., and the author observes that this may be considered as a very cloAe agreement, considering that, as Ostwald has shown, the heat of combustion varies considerably with the temperature. Acetic Acid.-A solution of sodium acetate in water was electro- lysed at the temperature 0". A considerable quantity of carbonic anhydride was formed, and after the gds given off had been freed from this, the residue was found to consist of hydrogen and ethane, about 65 per cent. of the former and 35 per cent. of the latter. Very slight traces of iodoform were obtained from the liquid residue in the electrolytic cell, From this i t follows that the action consisted in the setting free of acetic acid at the anode, and its combination with the oxygen simultaneously liberated; but if this took place entirely in the manner usually assumed, 2C2H402 = C2H, + 2C0, + H,O, the volumes of hydrogen and of ethane wodd have been equal.The excess of hydrogen present, combined with the absence of free oxygen, shows that, part of the acetic acid must have been burnt to form carbonic anhydride and water, according to the equation C2H402 + O4 = 2C02 + 2H20. In some quantitative experiments made with stronger currents, the proportion of hydrogen was found to be somewhat smaller. The proportion of hydrogen present in the evolved gases was also found to diminish as the strength of the solution wos increased. These results show that the complete com- bustion of the acetic acid to carbonic anhydride and water is favoured h X100 ABSTRACTS OF CHEMICAL PAPERS.by increasing the strength of the decomposing current, and by dimi- nishing the strength of the solution. Assuming Thornsen's values for the heats of solution required for the calculation, the author determined the heat of combust,ion of the milligram molecule of liquid acetic acid to water and gaseous carbonic anhydride to be 208.81 cal., which is in very fair agreement with the values 210.3 obtained by Fabre and Silbermann, and 210.79 obtained by Stobmann. It follows from the last result that the heat absorbed in the formation of one milligram molecule of liquid acetic acid from amorphous carbon and water vapour is 121.61 cal. Propionic Acid.-The results obtained with acetic acid suggested that propionic acid would probably be resolved into normal butane and carbonic anhydride, and t,he electrolysis of a solution of sodium propionate in water, acidified with propionic acid, showed that this reaction did actually occur, but it was veiled to a considerable extent by the decomposition of part of the acid into ethylene and carbonic anhydride, evidently according to the equation C2H602 + 0 = C,H, + CO, + H20.The author considers that the results of his experi- ments with acetic and propionic acids point to the conclusion that the ethane and butnnc formed during electrolysis are the results of the decomposition of double molecules, which exist in concentrated solu- tions, but are broken up into simple molecules when the solutions are diluted. Oxalic Acid.-The electrolysis of an aqueous solution of potassium oxalate a t the temperature 0" gave a gas consisting only of carbonic anhydride and hydrogen, so that the oxalic acid set free at the anode must have been completely burned to carbonic anhydride and water, according to the equation H2C20, + 0 = 2C0, + H20.The heat of combustion of oxalic acid per milligram molecule was found to be 74.49 oal. G. W. T. Thermochemistry of Methyl Alcohol and Solid Methyl Salts. By F. STOHMANN, C. KLEBER, and H. LANGBEIN ( J . p . Ohm. [ A ] , 40, 342-364) .-The authors give details of the determination of the following thermal values (see table, y . 101). The figures in the sixth column represent the exces,s or deficiency of the heat of combustion of the methyl salt when compared with the sum of the heats of combustion of the acid from which it is formed and methyl alcohol (compare Berthelot, Mhanique Chirnique, 1, 407).The authors then point out the difference bettween the heats of combustion of the various isomerides in this table, and also give a table showing the value of the affinity constant K (Ostwald, Abstr,, 1889, 818) for 24 acids, 20 of which agree with the rule.GENERAL AND PHYSICAL CHEMISTRY. Table of thermochemical results with methyl-compounds. Methyl gallate.. ......... Methyl P-naphthoate ..... Dinrethgl phthalate (liquid) Dimethyl phthalate (solid) Substance. C&H806 .. C12HloO.: . ClQHlo04. C10H1004 . Formula. Dimethyl terephthalate ... Dimethyl oxalate. ........ Dimethyl succinate (solid). ,) ,, (liquid) Dimethyl fumarate ......,, citrate. ........ Methyl alcohol. .......... Trimethyl trimesate ...... Hexamethyl mellitate.. ... Citric acid .............. C10Hl004 . C4H604 .. C&l,Od. . C6H100d.. CGH,04 .. CVHI,O;. . CH,O.. .. C12H&6 . C,e131sO12. C,H,O, .. Molesular weight. 152 166 162 184 186 194 194 194 194 118 146 146 144 252 234 426 192 32 Heat of cumbus- tiou. Cal. 896 -0 €069 '3 1213.6 801 *3 1402 -4 1120 -4 1113 -9 1117 *'7 1112 *2 402 -1 703 *6 708 -5 664 *7 1292 5 983 -5. 1825 -6 474 *6 170.6 Heat of forma- tion." Cal. 132 .O 121 -7 71.4 226 .7 70 -6 164 *6 171 -1 1'73 *3 172 ,8 180 *9 205 -4 200-5 175.3 249 *5 345 - 5 487-4 365 - 4 61 -4 101 - ' 0 . 5 -3.5 -0.7 1-3-4 -3.4 - 1 . ~ 1 -1.7 -0.1 -0.7 -5.6 -3-4 -13.1 + 2 * 9 -13 ' 8 - - - - * C = 94 Cals.; H2 = 69 Cals.A. G. B. Thermochemistry of' Nicotine. By A. COLSON (Covyt. r e d . , 109, 743-745) .--Nicoti?ze.-Heat of dissolution + 6-6 Cals. at about 15" ; heat of neutralisation by hydrochloric acid, 1st equivalent = 8.05 Cals. ; 2nd equivalent = 3.47 Cals. Total heat of neutyalisation by 4 mols. HC1 = 12-06 Cals. With sulphuric acid, 1st equivalent = 9.54 Cals.; total heat of neutralisation by excess of acid = 13.46 Cals. It is evident that the two basic functions of nicotine have very different energies, a fact which is also shown by colour reagents. With litrnius as indicator, nicotine has only one basic function, but with dimethyl-orange it Gas two. The author has also made the following determinations :- Pyridine. Piperidine. Csls. Cals.Heat of dissolution.. ................ 2.25 6-50 Heat of neutralisation, 1 mol. HC1 .... 5.20 13-01 - 7 , Y9 1.5 mol. HC1 . . 5.20. ,Y 9 ) 13.68 1 mol. H2S04 . . - C. H. B. Apparatus for making Vapour-density Determinations under Reduced Pressure. By J. F, EYKMAN (Ber., 22, 275&2758).-- The author describes with the aid of diagrams an apparatus in which vapour-density determinations may be made under reduced pressure, and in an atmosphere of hydrogen or some other indifferent g&s. The apparatus consists of it bulb-tube (A), somewhat similar in102 ABSTRACTS OF CHEMICAL PAPERS. shape to that employed in V. Meyer's method; this is heated by some suitable vapour in the ordinary way. A weighed quantity of the liquid, the vapour-density of which is to be determined, is placed in a small, sealed, pipette-shaped tube, and suspended in a chamber in the upper extremitly of the bulb-tube (A).The latter is connected a t the top with a graduated manometer tube, placed perpendicularly and open below, and also with a 3-way cock, so that it can be exhausted and filled with hydrogen or any other gas. The apparatus having been completely filled with hydrogen, it is exhausted as com- pletely as pos>ible, the open end of the manometer being immersed in mercury ; the bulb-tube is then heated a t a constant temperature, and hydrogen is allowed to enter until the required pressure is obtained. As soon as no more mercury flows out of the manometer tube, the pressure is noted on the scale, and the neck of the bulb containing the substance is broken without opening the apparatus, by an inge- nious device, so that i t drops to the bottom of the bulb-tube (A), and is there converted into vapour.The pressure is thereby increased, and the mercury which flows from the manometer tube is collected in a tared vessel ; the increase of pressure is ascertained either by weigh- ing the mercurg, the diameter of the msiiometer tube having been previously determined, or from the difference in tlhe readings on the manometer scale. The vapour-densi ty is calculated from the increase of pressure produced by the vaporisation of a known weight of the substance in a vessel of known volume under known conditions of temperafure and pressure. Experiments with safrole (b. p. 232"), ethyl cinnamate (b. p. 271"), naphthylamine (b.p. 300°), phenylpropionic acid (b. p. ZOO0), and other sitbstances gave very satisfactory results. The apparatus can be employed also for making determinations by V. Meyer's method in the usual way. I?. S. K. Specific Volumes of some Ethereal Salts of the Oxalic Acid Series. By A. WIENS (Annalen, 253, 289-318 ; compare W. Lossen, Abstr., 1888, 335).-A comparison of the molecular volumes of meta- meric ethereal salts of oxalic, malonic, succinic, and glutaric acids, containing normal alkyl radicles, shows that the larger the quantity of carbon in the acid radicle the smaller the molecular volume a t 0". This is generally the case at the boiling point also, but two exceptions were noticed, the molecular volume of ethyl propyl malonate being smaller than that of ethyl succimte, and that of bntyl malonate smaller than that of propyl butyl succinate ; these exceptions may be due to the uncertainty of the determinations at the boiling point.The difference in molecular volume corresponding with the difference in composition increases in homologous series with the quantity of carbon in the compound. The difference between the molecular volume of ethyl methyl succinate and ethyl butyl succinate, for example, is 71.3 ; that bet,ween ethyl butyl succinate and ethyl heptyl succinate, 76.4. The same has been found to hold good for ethereal salts of monobasic acids, ethers, phenol ethers, and nlkyl iodides. A comparison of the molecular volumes a t 0" shows that an increase by the group C'H, in the empirical formula corresponds with variousOESERAL AND PHYSICAL CHEMISTRY. 103 differences in molecular volume, according to the manner in which this increase takes place.The increase in molecular volume by the conversion of the group CnH2n+l into ( CH2)z*CnHzn+tl (excluding methyl salts) is, on the average, 16.8 for each CH? group, but the difference between the ethyl and methyl salts is, on the average, 18.1. The increase, due t o the conversion of the group CH2 into (CH,)., is, on the average, 16 for each additional CH2 group, but when the group CH, is converted into CHMe (ethyl into isopropyl, for example), the corresponding increase in molecular volume is, on the average, 17.7. The numerous experimental determinations are given in tables. F. S. I(. Absorption of Gases by Mixtures of Alcohol and Water.By 0. LCBARSCH (Ann. Phys. Chem. [2], 37, 524-525).-The author observes that the publicat,ion of Muller's determinations of the absorp- tion of carbonic snhydride by mixtures of alcohol and water (Abstr., 1889, 816) has induced him to publish the results obtained so far in an investigation of the absorption of various gases by mixtures of alcobol and water ; these are given in the accompanying table, showing the percentages by volume of the gases absorbed at 20" and 760 mm. pressure by solutions containing the various percentages of alcohol (by weight) given in the first horizontal line :- Percentage of alcohol.. .. 0-00 9-09 16.67 23.08 2857 33'33 5 0 W 66.67 80~00 Oxygen. .. .. 2-98 2-78 2.63 2.52 2-49 2-67 3-50 4.95 5-66 Hydrogen. ,.1-93 1.43 1.29 1-17 1.04 1.17 2.02 2.55 - Csrbonicoxide 2.41 1.87 1.75 1.68 1-50 1'94 3'20 - - The table shows that the minimum absorption for all three gases occurs at about the same proportion of alcohol to water, and this is the same as that found by Muller for carbonic anhydride, and there- fore it seems probable that other gases will be found to behave in the same way. G. W. T. Simultaneous Solubility of Sodium and Potassium Chlorides. By A. @,CARD (Compt. rend., 109, 740-743).-The sum of the salts dissolved between -20" and +180" is represented by a straight line, yf$" = 27.0 + 0-0962t. Calculating from this coefficient the tem- perature at the limit of solubility, that is, the point at which, by reason of the increase in the proportion of salt and the decrease in the proportion of water, the latter has disappeared, the temperature obtained is 738", which, according to Carnelly, is the melting point of potassium chloride.In presence of potassium chloride, the curve of solubility of sodium cliloride between -20" and + 75" is parallel with the axis of tempera- ture. Beyond 75" it decreases, and at 97" becomes identical with that of potassium chloride, after which it decreases to 120", and then becomes constant (16.7 per cent.). The solubility of potassium chloride alone is represented between104 ABSTRACTS OF CHEMICAL PAPERS. I -10" and + 75" by a right line with a coeficient 0.1470, and bztween 75" and 180" by a second right line, which has a coefficient of 0.0793, and a limiting point at 913", or considerably above the melting point of the salt.In presence of sodium chloride, the curve of solubility of potassium chloride between -20" and + 75" is a right line y = 10.3 + 0.0962i ; from 75" to 120" the solubility increases rapidly, and above 120" it is represented by a righ't line with the same coefficient as between -20" and +75". Its limit,ing point is 913", and hence the curves of solu- bility of potassium chloride alone and in presence of sodium chloride are not parallel, but converge to 913". At the limiting point for the mixed salts, 738", the proportion of the two salts would be 16.7 per cent. of sodium chloride and 83.3 per cent. of potassium chloride. The total quantity of chlorine is prac- tically equal to the sum of the metals. The curve representing the quantity of chlorine in solution is a right line ; that liepresenting the sum of the salts is also a right line ; and hence the sum of the metals is likewise represented by a right line.The curve of the chlorine and the curve of the sum of the metals intersect at 738". C. H. B. Determination of Molecular Weights of Substances from the Boiling Points of their Solutions. By H, W. WILEY (Chem. News, 60,189-190) .-"The appnratus employed consisted of an oval- round bottom flask of about 200 C.C. capacity," with a side tube from the neck connected with a condenser to keep volume of liquid constant. A thermometer graduated to tenths, but capable of being read to 0.02 of a degree was employed, the bulb being enveloped in fine copper foil to prevent interference of bubbles of steam.Sodium chloride was used to determine the fkctor, the number obtained, 8.968, was used for calculating the results in the following table ; the volume of wat)er being in all cases 150 C.C. ; the temperature of boiling water was 99.50" except during the experiments with sodium nitrate, when it was 99.44". K C1. ................. KBr., ................ EI ................... KNO, ................ E,Cr,Oj .............. NaN03 ............... Saccharose ............ Oxslic acid.. .......... 6 *O 6 '0 9 '0 6 '0 18 -0 6 . 0 20 *o 6 .O ~ _ _ _ _ _ _ _ _ _ _ Total rise of temperature. -- 0 '35O 0 *29 0 *33 0 *33 0 *38 0 *42 0.20 0 -20 ~ ~~ Molecular weiglit. Calculated. -- 76 -91 123 -7 163 '1 108 *7 283 -2 85.4 643-2 179 *4! Theoretical. 74.5 119 .o 166 -0 101 -0 295 -0 85.0 342 *O 90 -0 --- It will be noticed that the two organic compounds give double the theoretical molecular weight by this method.The resultsGENERAL AND PHYSICAL CHEMISTRY. 105 obtained with salts containing water of crystallisation do not agree with the molecular weights with or without this water. These results were obt,ained quig independently of those of Beckman. D. A. L. Behaviour of Colloi’d Substances wlith Respect to Raoult’s Law. By E. PATERNO (Zeit. physikal. Chem., 4, 457--461).-The reduction of the freezing point by colloid substances in water is very slight, and therefore leads to very high numbers for the molecular weights of such substances (Brown and Morris, Trans., 1889, 462). This, the author has observed, is the case with gallic and tannic acids ; which behave like collo’ids in aqueous solution and give molecular weights many times greater than those ordinarily accepted for these substances.If, however, solutions in acetic acid are taken, the behaviour is found to be perfectly nornial, and the reduction of the freezing point is that corresponding with the ordinary simple mole- cular weights. Hence substances only behave as colloids towards certain solvents, and the author holds that when a solid dissolves as a colloid, the laws of freezing are not applicable to its solutions. H. C. Can Raoult’s Method distinguish between Atomic and Molecular Union ? By R. ANSCH~~TZ (Annalen, 253, 343-347 ; compare Anschutz and Pulfrich, Abstr., 1888, 1273).-The depres- sion produced by naphthalene picrate in the freezing point of benzene corresponds with that which would be produced by its constituent parts present together in an uncombined state.The author concludes therefore that the combination of the coniponents of naphthalene picrate and analogous substances such as dimethyl diacetjlracemate is not dependent on atomic union in the sense of the valence theory, but on molecular union. If Raoult’s method is capable of deciding between atomic and molecular union, it could be employed for determining the valency of elements. F. S. I(. Kinetic Nature of Osmotic Pressure. By G. BREDIG (Zeit. physikal. Chem., 4, 444-456) .-In replying to certain objections raised by Pupin against the Van’t Hoff theory of osmotic pressure (Abstr., 1888, 7i8), the author develops an equation for the behaviour of a dissolved substance which is similar to that of Van der Wads for the behariour of gases.A special point of interest is, that account is taken of the presence and specific attraction of the solvent. and in this way an explanation of the mechanism of solution is obtained, which, it is claimed, is of wider application than that of Nernst (this vol., p. 3), in which this attraction is neglected. Sphere of Action of Molecular Forces. By B. GALITZINE (Zeit. physiknl. Chem., 4, 417426).-By a process of theoretical reasoning similar to that already employed by Van der Waals, and using data given by Nadeschdin for several of the ethereal salts of the fatty acids in the critical condition, the author arrives at the conclusicsn that the sphere of action of the molecular forces is proportional to H.C.106 ABSTRACTS OF CElEMIOAL PAPERS. the masses of the attracting molecules. attraction is inversely proportional to the square of the distance. He also concludes that the H. C. Fluid Crystals. By 0. LEHMANN (Zed. physilcal. Chem., 4, 462- 472).-Under the name of "fluid crystals," the author describes a cbolesteryl benzoate first prepared by Reinitzer, which, although apparently melting at 145", behaves between 145" and 178" towards polarised light as though still having crystalline structure. In other respects the substance is in a perfectly liquid condition between these temperatures. H. C. New Gas Burners. By M. GROGER (Zeit. any. Qhem., 1889,329- 331).-These are in general form similar to Bunsen burners, but instead of having any means of regulating the entry of air at the bottoni of the mixing tube, the top of the burner is made conical, and there is a screw arrangement by which a solid cone can be raised within, so as partially to close the opening.By this means a flame of any character can be obtained, from a luminous one to one approaching that of a blowpipe, whilst the size of the flame can be greatly reduced without altering its character, and without risk of its flashing down. A burner on the same principle giving a flat flame is also described. M. J. S.9 iGeneral and Physical Chemistry.Emission Spectrum of Ammonia. By G. MAGNANINI ( Z e i t .physikal. Chern., 4, 435-440) .-The author has determined thepositions of a large number of the lines of the ammonia spectrum.These are compared with the lines of Hasselberg’s second hydrogenspectrum, with which they show a remarkable coincidence.Absorption Spectrum of Nitrosyl Chloride.By G. MAGNANINI(Zeit. physikol. Chem., 4, 427-428).-The absorption spectrum ofnitrosyl chloride vapour consists of six absorption bands in the orangeand green parts of the spectrum. The wave-lengths correspondingwith these bands and their relative intensities are given.By S. KALISCHER (Ann.Phys. Chem. [2], 37, 528).-The author observes that Righi (Abstr.,1889, 555) appears to have misunderstood a remark made by him in aformer note (ibid., 3). He had pointed out that selenium cells oftengive an E.M.F. before exposure to light, and that, therefore, beforeexperimenting on the influence of light on them, they should be testedin the dark to see if they already give any E.M.F.He had no inten-tion of asserting the necessity of actually manufacturing the cells indarkness, and preventing their even being exposed to light beforeexperimenting with them.Electrical Conductivity of Hydrogen Chloride in DifferentSolvents. By I. KABLUKOFF (Zeit. physikal. CRem., 4, 429434).-The conductivity of solutions of hydrogen chloride in benzene, xylene,hexana, and ether is excessively small, that in ether being greatestand that in benzene the least. The molecular conductivity of thesolution in ether is found to decrease with rising dilution. Solutionsof hydrogen chloride in methyl, ethyl, isobntyl, and isoamyl alcoholshave a somewhat greater conductivity.The methyl alcohol solutio~ishave the highest conductivity, being about four times greater thanthe ethyl and 30 times greater than the isobutyl alcohol solutions.Amy1 alcohol, like ether, gives a decreasing molecular conductivitywith rising dilution. Hydrogen chloride was also examined i naqueous solutions of ethyl alcohol. The presence of ethyl alcohol isfound to greatly decrease the conductivity of hydrogen chloridein water, An addition of 6 per cent. of alcohol causing a decrease of20 per cent. in the conductivity.If a solution of benzene saturated with hydrogen chloride is allowedto remain for two or three days, crystals separate out which meltwithout decomposition, and can be sublimed a t high temperature.They are probably of the composition CsH6,3HCI.H. C.H, C.Electromotive Force of Selenium.G.W. T.H. C.VOL. LTlII. 98 ABSTRACTS OF OHEMIOAL PAPERS.Electrical Coqductivity of Solid Mercury. Bp L. GRUNMACH(Ann. Phys. Chem. [2], 37, 308--515).-As the result of a furtherexperimental investigation of this subject,, tbe author finds that theapparent resistance of mercury when just melted is 2-5 times itsvalue just before liquefaction begins.The value 1.5 formerly obtained by the author (Abstr., 1889, 201)is, therefore, too small. The value now obtained by him is smallerthan that given by Cailletet and Bouty, namely 0.4, and the anthorattributes the difference between his present and former results, andbetween both of them and that obtained by Cailletet and Bouty, ingreat part to the change in volume which mercury undergoes inpassing from the solid to the liquid state, and the effects of thischange of volume on the resistance, depending as they do on thedimensions of the tubes and their regularity of bore.The degree towhich the result is affected in this manner cannot be determined untilthese changes of volume have been measured, and the author statesthat an investigaticn of this point has been commenced.The results of the investigation described in this paper confirmthe conclusion formerly arrived at by the author, that the temperature-coefficient of decrease of resistance for solid mercury decreases fromthe solidifying point down to -80°, the lowest temperature at whichobservations were made.The values obtained for this coefficient i n the former and presentseries of observations respectively are given below :-Range of Tempemture-coefficient.Temperature-coefficient.temperature. First series. Second series.-80" to -70" 0~0010 0-0008-70 ,, -60 0*0010 0*0011-60 ,, -50 0.0012 0.0015-50 ,, -40 0.001 7 0.0023The results of the present investigation therefore confirm the con-clusion formerly arrived at by the author, that assuming the truth ofClausius's law expressing the relation between the electrical resist-ances of simple metals and their absolute temperatures, then mercurymust be considered a8 an exception. G. W. T.Thermoelectric Currents between Amalgamated Zinc andZinc Sulphate.By K. A. BRANDER (Ann. Phys. Chem. [2], 37,457-462).-The primary object of the investigation was to determinethe relation between the E.M.F. developed and the difference oftemperature between the electrodes.The electrodes, of amalgamated zinc, were placed in two vesselscommunicating by means of a siphon, and filled with a solution ofzinc sulphate. One of these vessels was kept at the temperature ofthe place of observation, while the temperature of the other wasgradually raised.The author found that, within the limits of errors of observation, theE.M.F. was proportional to the difference of temperature, until thiOEXERAL AND PHYSICAL CHENISTRT. 99difference exceeded 20.45", after which the E.M.F. appeared to increaserather more rapidly than the temperature difference.A few experi-ments were also made to determine the effect of varying the concen-tration of the zinc sulphate solution, and their results showed that theE.M.F. increased with the concentration. G. W. T.Electrochemistry and Thermochemistry of some OrganicAcids. By H. JAHN (Anla. Phys. Cliem. [2], 37,40843).B'ormic Acid.-When a solution of sodium formate in waterwas acidified with formic acid and subjected to electrolysis, i tyielded hydrogen and carbonic anhydride. The sodium saltmust first be resolved into sodium and the group HC02, theformer forming sodium hydroxide with the water of solution,whilst the latter must either break up into carbonic anhydride andhydrogen or form formic acid again with the water of solution,according to the equation 2H + CO, + H20 = 2H2C02 + 0, thefree oxygen then combining with a portion of the formic acid to formcarbonic anhydride and water.Now Bunge has shown that in theelectrolysis of formic acid no hydrogen is given off at the anode,which excludes the first explanation, and shows that a simple combus-tion of the acid takes place at the anode. The results were confirmedby determinations of the amount of gas liberated by the passage of ameasured quantity of electricity.The author made a series of determinations of the heat of combus-tion of formic acid which agreed very well together, and their meangave 62.87 cal. as the heat of combustion of a milligram mole-cule of formic acid. Thomsen obtained the value 60.2 cal., and theauthor observes that this may be considered as a very cloAe agreement,considering that, as Ostwald has shown, the heat of combustion variesconsiderably with the temperature.Acetic Acid.-A solution of sodium acetate in water was electro-lysed at the temperature 0".A considerable quantity of carbonicanhydride was formed, and after the gds given off had been freedfrom this, the residue was found to consist of hydrogen and ethane,about 65 per cent. of the former and 35 per cent. of the latter. Veryslight traces of iodoform were obtained from the liquid residue in theelectrolytic cell, From this i t follows that the action consisted inthe setting free of acetic acid at the anode, and its combinationwith the oxygen simultaneously liberated; but if this took placeentirely in the manner usually assumed, 2C2H402 = C2H, + 2C0, +H,O, the volumes of hydrogen and of ethane wodd have been equal.The excess of hydrogen present, combined with the absence of freeoxygen, shows that, part of the acetic acid must have been burntto form carbonic anhydride and water, according to the equationC2H402 + O4 = 2C02 + 2H20.In some quantitative experimentsmade with stronger currents, the proportion of hydrogen was foundto be somewhat smaller. The proportion of hydrogen present in theevolved gases was also found to diminish as the strength of thesolution wos increased. These results show that the complete com-bustion of the acetic acid to carbonic anhydride and water is favouredh 100 ABSTRACTS OF CHEMICAL PAPERS.by increasing the strength of the decomposing current, and by dimi-nishing the strength of the solution.Assuming Thornsen's values for the heats of solution required forthe calculation, the author determined the heat of combust,ion of themilligram molecule of liquid acetic acid to water and gaseous carbonicanhydride to be 208.81 cal., which is in very fair agreement with thevalues 210.3 obtained by Fabre and Silbermann, and 210.79 obtainedby Stobmann.It follows from the last result that the heat absorbedin the formation of one milligram molecule of liquid acetic acid fromamorphous carbon and water vapour is 121.61 cal.Propionic Acid.-The results obtained with acetic acid suggestedthat propionic acid would probably be resolved into normal butaneand carbonic anhydride, and t,he electrolysis of a solution of sodiumpropionate in water, acidified with propionic acid, showed that thisreaction did actually occur, but it was veiled to a considerable extentby the decomposition of part of the acid into ethylene and carbonicanhydride, evidently according to the equation C2H602 + 0 = C,H, + CO, + H20.The author considers that the results of his experi-ments with acetic and propionic acids point to the conclusion that theethane and butnnc formed during electrolysis are the results of thedecomposition of double molecules, which exist in concentrated solu-tions, but are broken up into simple molecules when the solutions arediluted.Oxalic Acid.-The electrolysis of an aqueous solution of potassiumoxalate a t the temperature 0" gave a gas consisting only of carbonicanhydride and hydrogen, so that the oxalic acid set free at the anodemust have been completely burned to carbonic anhydride and water,according to the equation H2C20, + 0 = 2C0, + H20. The heatof combustion of oxalic acid per milligram molecule was found to be74.49 oal.G. W. T.Thermochemistry of Methyl Alcohol and Solid MethylSalts. By F. STOHMANN, C. KLEBER, and H. LANGBEIN ( J . p . Ohm.[ A ] , 40, 342-364) .-The authors give details of the determinationof the following thermal values (see table, y . 101). The figures inthe sixth column represent the exces,s or deficiency of the heat ofcombustion of the methyl salt when compared with the sum of theheats of combustion of the acid from which it is formed and methylalcohol (compare Berthelot, Mhanique Chirnique, 1, 407).The authors then point out the difference bettween the heats ofcombustion of the various isomerides in this table, and also give atable showing the value of the affinity constant K (Ostwald, Abstr,,1889, 818) for 24 acids, 20 of which agree with the ruleGENERAL AND PHYSICAL CHEMISTRY.Table of thermochemical results with methyl-compounds.Methyl gallate...........Methyl P-naphthoate .....Dinrethgl phthalate (liquid)Dimethyl phthalate (solid)Substance.C&H806 ..C12HloO.: .ClQHlo04.C10H1004 .Formula.Dimethyl terephthalate ...Dimethyl oxalate. ........Dimethyl succinate (solid).,) ,, (liquid)Dimethyl fumarate ......,, citrate.........Methyl alcohol. ..........Trimethyl trimesate ......Hexamethyl mellitate.. ...Citric acid ..............C10Hl004 .C4H604 ..C&l,Od. .C6H100d..CGH,04 ..CVHI,O;. .CH,O.. ..C12H&6 .C,e131sO12.C,H,O, ..Molesularweight.15216616218418619419419419411814614614425223442619232Heat ofcumbus-tiou.Cal.896 -0€069 '31213.6801 *31402 -41120 -41113 -91117 *'71112 *2402 -1703 *6708 -5664 *71292 5983 -5.1825 -6474 *6170.6Heat offorma-tion."Cal.132 .O121 -771.4226 .770 -6164 *6171 -11'73 *3172 ,8180 *9205 -4200-5175.3249 *5345 - 5487-4365 - 461 -4101-' 0 .5-3.5-0.71-3-4-3.4- 1 . ~ 1-1.7-0.1-0.7-5.6-3-4-13.1+ 2 * 9-13 ' 8----* C = 94 Cals.; H2 = 69 Cals.A. G. B.Thermochemistry of' Nicotine. By A. COLSON (Covyt. r e d . ,109, 743-745) .--Nicoti?ze.-Heat of dissolution + 6-6 Cals. at about15" ; heat of neutralisation by hydrochloric acid, 1st equivalent =8.05 Cals. ; 2nd equivalent = 3.47 Cals. Total heat of neutyalisationby 4 mols. HC1 = 12-06 Cals. With sulphuric acid, 1st equivalent= 9.54 Cals.; total heat of neutralisation by excess of acid =13.46 Cals. It is evident that the two basic functions of nicotinehave very different energies, a fact which is also shown by colourreagents. With litrnius as indicator, nicotine has only one basicfunction, but with dimethyl-orange it Gas two.The author has also made the following determinations :-Pyridine.Piperidine.Csls. Cals.Heat of dissolution.. ................ 2.25 6-50Heat of neutralisation, 1 mol. HC1 .... 5.20 13-01- 7 , Y9 1.5 mol. HC1 . . 5.20.,Y 9 ) 13.68 1 mol. H2S04 . . -C. H. B.Apparatus for making Vapour-density Determinations underReduced Pressure. By J. F, EYKMAN (Ber., 22, 275&2758).--The author describes with the aid of diagrams an apparatus in whichvapour-density determinations may be made under reduced pressure,and in an atmosphere of hydrogen or some other indifferent g&s.The apparatus consists of it bulb-tube (A), somewhat similar i102 ABSTRACTS OF CHEMICAL PAPERS.shape to that employed in V. Meyer's method; this is heated bysome suitable vapour in the ordinary way.A weighed quantity ofthe liquid, the vapour-density of which is to be determined, is placedin a small, sealed, pipette-shaped tube, and suspended in a chamber inthe upper extremitly of the bulb-tube (A). The latter is connecteda t the top with a graduated manometer tube, placed perpendicularlyand open below, and also with a 3-way cock, so that it can beexhausted and filled with hydrogen or any other gas. The apparatushaving been completely filled with hydrogen, it is exhausted as com-pletely as pos>ible, the open end of the manometer being immersed inmercury ; the bulb-tube is then heated a t a constant temperature, andhydrogen is allowed to enter until the required pressure is obtained.As soon as no more mercury flows out of the manometer tube, thepressure is noted on the scale, and the neck of the bulb containingthe substance is broken without opening the apparatus, by an inge-nious device, so that i t drops to the bottom of the bulb-tube (A), andis there converted into vapour.The pressure is thereby increased,and the mercury which flows from the manometer tube is collected ina tared vessel ; the increase of pressure is ascertained either by weigh-ing the mercurg, the diameter of the msiiometer tube having beenpreviously determined, or from the difference in tlhe readings on themanometer scale. The vapour-densi ty is calculated from the increaseof pressure produced by the vaporisation of a known weight of thesubstance in a vessel of known volume under known conditions oftemperafure and pressure.Experiments with safrole (b.p. 232"), ethyl cinnamate (b. p. 271"),naphthylamine (b. p. 300°), phenylpropionic acid (b. p. ZOO0), andother sitbstances gave very satisfactory results.The apparatus can be employed also for making determinations byV. Meyer's method in the usual way. I?. S. K.Specific Volumes of some Ethereal Salts of the Oxalic AcidSeries. By A. WIENS (Annalen, 253, 289-318 ; compare W. Lossen,Abstr., 1888, 335).-A comparison of the molecular volumes of meta-meric ethereal salts of oxalic, malonic, succinic, and glutaric acids,containing normal alkyl radicles, shows that the larger the quantityof carbon in the acid radicle the smaller the molecular volume a t 0".This is generally the case at the boiling point also, but two exceptionswere noticed, the molecular volume of ethyl propyl malonate beingsmaller than that of ethyl succimte, and that of bntyl malonate smallerthan that of propyl butyl succinate ; these exceptions may be due tothe uncertainty of the determinations at the boiling point.The difference in molecular volume corresponding with the differencein composition increases in homologous series with the quantity ofcarbon in the compound.The difference between the molecularvolume of ethyl methyl succinate and ethyl butyl succinate, for example,is 71.3 ; that bet,ween ethyl butyl succinate and ethyl heptyl succinate,76.4. The same has been found to hold good for ethereal salts ofmonobasic acids, ethers, phenol ethers, and nlkyl iodides.A comparison of the molecular volumes a t 0" shows that an increaseby the group C'H, in the empirical formula corresponds with variouOESERAL AND PHYSICAL CHEMISTRY.103differences in molecular volume, according to the manner in whichthis increase takes place. The increase in molecular volume by theconversion of the group CnH2n+l into ( CH2)z*CnHzn+tl (excludingmethyl salts) is, on the average, 16.8 for each CH? group, but thedifference between the ethyl and methyl salts is, on the average, 18.1.The increase, due t o the conversion of the group CH2 into (CH,)., is,on the average, 16 for each additional CH2 group, but when the groupCH, is converted into CHMe (ethyl into isopropyl, for example), thecorresponding increase in molecular volume is, on the average, 17.7.The numerous experimental determinations are given in tables.F.S. I(.Absorption of Gases by Mixtures of Alcohol and Water. By0. LCBARSCH (Ann. Phys. Chem. [2], 37, 524-525).-The authorobserves that the publicat,ion of Muller's determinations of the absorp-tion of carbonic snhydride by mixtures of alcohol and water (Abstr.,1889, 816) has induced him to publish the results obtained so far inan investigation of the absorption of various gases by mixtures ofalcobol and water ; these are given in the accompanying table, showingthe percentages by volume of the gases absorbed at 20" and 760 mm.pressure by solutions containing the various percentages of alcohol(by weight) given in the first horizontal line :-Percentage ofalcohol.. ..0-00 9-09 16.67 23.08 2857 33'33 5 0 W 66.67 80~00Oxygen. .. .. 2-98 2-78 2.63 2.52 2-49 2-67 3-50 4.95 5-66Hydrogen. ,. 1-93 1.43 1.29 1-17 1.04 1.17 2.02 2.55 -Csrbonicoxide 2.41 1.87 1.75 1.68 1-50 1'94 3'20 - -The table shows that the minimum absorption for all three gasesoccurs at about the same proportion of alcohol to water, and this isthe same as that found by Muller for carbonic anhydride, and there-fore it seems probable that other gases will be found to behave in thesame way. G. W. T.Simultaneous Solubility of Sodium and Potassium Chlorides.By A. @,CARD (Compt. rend., 109, 740-743).-The sum of the saltsdissolved between -20" and +180" is represented by a straight line,yf$" = 27.0 + 0-0962t.Calculating from this coefficient the tem-perature at the limit of solubility, that is, the point at which, byreason of the increase in the proportion of salt and the decrease inthe proportion of water, the latter has disappeared, the temperatureobtained is 738", which, according to Carnelly, is the melting pointof potassium chloride.In presence of potassium chloride, the curve of solubility of sodiumcliloride between -20" and + 75" is parallel with the axis of tempera-ture. Beyond 75" it decreases, and at 97" becomes identical with thatof potassium chloride, after which it decreases to 120", and thenbecomes constant (16.7 per cent.).The solubility of potassium chloride alone is represented betwee104 ABSTRACTS OF CHEMICAL PAPERS.I-10" and + 75" by a right line with a coeficient 0.1470, and bztween75" and 180" by a second right line, which has a coefficient of 0.0793,and a limiting point at 913", or considerably above the melting pointof the salt.In presence of sodium chloride, the curve of solubility of potassiumchloride between -20" and + 75" is a right line y = 10.3 + 0.0962i ;from 75" to 120" the solubility increases rapidly, and above 120" it isrepresented by a righ't line with the same coefficient as between -20"and +75".Its limit,ing point is 913", and hence the curves of solu-bility of potassium chloride alone and in presence of sodium chlorideare not parallel, but converge to 913".At the limiting point for the mixed salts, 738", the proportion ofthe two salts would be 16.7 per cent.of sodium chloride and 83.3 percent. of potassium chloride. The total quantity of chlorine is prac-tically equal to the sum of the metals.The curve representing the quantity of chlorine in solution is a rightline ; that liepresenting the sum of the salts is also a right line ; andhence the sum of the metals is likewise represented by a right line.The curve of the chlorine and the curve of the sum of the metalsintersect at 738". C. H. B.Determination of Molecular Weights of Substances fromthe Boiling Points of their Solutions. By H, W. WILEY (Chem.News, 60,189-190) .-"The appnratus employed consisted of an oval-round bottom flask of about 200 C.C. capacity," with a side tube fromthe neck connected with a condenser to keep volume of liquidconstant.A thermometer graduated to tenths, but capable of beingread to 0.02 of a degree was employed, the bulb being enveloped infine copper foil to prevent interference of bubbles of steam. Sodiumchloride was used to determine the fkctor, the number obtained, 8.968,was used for calculating the results in the following table ; the volumeof wat)er being in all cases 150 C.C. ; the temperature of boiling waterwas 99.50" except during the experiments with sodium nitrate, whenit was 99.44".K C1. .................KBr., ................EI ...................KNO, ................E,Cr,Oj ..............NaN03 ...............Saccharose ............Oxslic acid.. ..........6 *O6 '09 '06 '018 -06 .020 *o6 .O~ _ _ _ _ _ _ _ _ _ _Total riseoftemperature.--0 '35O0 *290 *330 *330 *380 *420.200 -20~ ~~Molecular weiglit.Calculated.--76 -91123 -7163 '1108 *7283 -285.4643-2179 *4!Theoretical.74.5119 .o166 -0101 -0295 -085.0342 *O90 -0---It will be noticed that the two organic compounds give doublethe theoretical molecular weight by this method. The resultGENERAL AND PHYSICAL CHEMISTRY. 105obtained with salts containing water of crystallisation do not agreewith the molecular weights with or without this water. Theseresults were obt,ained quig independently of those of Beckman.D. A. L.Behaviour of Colloi’d Substances wlith Respect to Raoult’sLaw.By E. PATERNO (Zeit. physikal. Chem., 4, 457--461).-Thereduction of the freezing point by colloid substances in water is veryslight, and therefore leads to very high numbers for the molecularweights of such substances (Brown and Morris, Trans., 1889, 462).This, the author has observed, is the case with gallic and tannic acids ;which behave like collo’ids in aqueous solution and give molecularweights many times greater than those ordinarily accepted for thesesubstances. If, however, solutions in acetic acid are taken, thebehaviour is found to be perfectly nornial, and the reduction of thefreezing point is that corresponding with the ordinary simple mole-cular weights. Hence substances only behave as colloids towardscertain solvents, and the author holds that when a solid dissolves asa colloid, the laws of freezing are not applicable to its solutions.H. C.Can Raoult’s Method distinguish between Atomic andMolecular Union ? By R.ANSCH~~TZ (Annalen, 253, 343-347 ;compare Anschutz and Pulfrich, Abstr., 1888, 1273).-The depres-sion produced by naphthalene picrate in the freezing point of benzenecorresponds with that which would be produced by its constituentparts present together in an uncombined state. The author concludestherefore that the combination of the coniponents of naphthalenepicrate and analogous substances such as dimethyl diacetjlracemateis not dependent on atomic union in the sense of the valence theory,but on molecular union.If Raoult’s method is capable of deciding between atomic andmolecular union, it could be employed for determining the valency ofelements. F. S. I(.Kinetic Nature of Osmotic Pressure. By G. BREDIG (Zeit.physikal. Chem., 4, 444-456) .-In replying to certain objectionsraised by Pupin against the Van’t Hoff theory of osmotic pressure(Abstr., 1888, 7i8), the author develops an equation for the behaviourof a dissolved substance which is similar to that of Van der Wadsfor the behariour of gases. A special point of interest is, that accountis taken of the presence and specific attraction of the solvent. and inthis way an explanation of the mechanism of solution is obtained,which, it is claimed, is of wider application than that of Nernst (thisvol., p. 3), in which this attraction is neglected.Sphere of Action of Molecular Forces. By B. GALITZINE (Zeit.physiknl. Chem., 4, 417426).-By a process of theoretical reasoningsimilar to that already employed by Van der Waals, and using datagiven by Nadeschdin for several of the ethereal salts of the fattyacids in the critical condition, the author arrives at the conclusicsnthat the sphere of action of the molecular forces is proportional toH. C106 ABSTRACTS OF CElEMIOAL PAPERS.the masses of the attracting molecules.attraction is inversely proportional to the square of the distance.He also concludes that theH. C.Fluid Crystals. By 0. LEHMANN (Zed. physilcal. Chem., 4, 462-472).-Under the name of "fluid crystals," the author describes acbolesteryl benzoate first prepared by Reinitzer, which, althoughapparently melting at 145", behaves between 145" and 178" towardspolarised light as though still having crystalline structure. Inother respects the substance is in a perfectly liquid condition betweenthese temperatures. H. C.New Gas Burners. By M. GROGER (Zeit. any. Qhem., 1889,329-331).-These are in general form similar to Bunsen burners, butinstead of having any means of regulating the entry of air at thebottoni of the mixing tube, the top of the burner is made conical,and there is a screw arrangement by which a solid cone can be raisedwithin, so as partially to close the opening. By this means a flameof any character can be obtained, from a luminous one to oneapproaching that of a blowpipe, whilst the size of the flame can begreatly reduced without altering its character, and without risk ofits flashing down. A burner on the same principle giving a flatflame is also described. M. J. S

ISSN:0368-1769    

DOI:10.1039/CA8905800097

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

106 ABSTRACTS OF CElEMIOAL PAPERS. In o r g a n i c C h e mi s t r y. Hydrogen Peroxide. By G. TANMANN (Zeit. physikal. Chem., 4, 441-443) .-The spontaneous decomposition of hydrogen peroxide in alkaline solution is found to be independent of the amount or nature of the base which is present. It appears probable from the author's experiments that it is really caused by the presence of traces of metallic oxides, such as the oxide of iron, dissolved in the alkali. It is shown that the addition of small quantities of such oxides in- creases enormously the rate of decomposition. The freezing points of aqueous solutions of hydrogen peroxide were determined, and from these a molecular reduction of 8-79 was found. Hydrogen peroxide being a, non-electrolyte, this number would correspond with the formula H404.[3 3, 1, 695--699).-A review of the known hydrochlorides of chlorides, and a discussion of their probable constitution. H. C. Hydrochlorides of Chlorides. By R. ENGEL (BUZZ. SOC. Chim. T. G. N. Iodic Acid. By H. LESCEUR (BiiZZ. SOC. Chim. [3], 1, 563).-The crystals of iodic acid deposited from its solution in dilute or moderately concentrated nitric acid are monohydrated, TV hereas those obtained from the solution of iodic acid in concentrated nitric acidINORQANIO CHEMISTRY. 107 are anhydrous. The author thinks that the crystals deposited from solution in nitric acid of intermediate strength are mixtures of the hydrated and anhydrous varieties. Iodic Acid; Double Salts of Iodic Acid with other Acids. B.y C. W. RLOMSTRAND ( J .p r . Chem. [g], 40, 305-340 ; compare Abstr., 1887, 337) .-In the oxygen-acids of phosphorus and iodine only one atom of oxygen is strongly united to the phosphorus and iodine, the radicles being PO-0 and 10.0 respectively, thus differing from the oxygen-acids of nitrogen, chlorine, and bromine, where two atoms of oxygen are equally strongly united to the nitrogen, chlorine, or bromine, the radicIes being NO,, C102, and BrO, respectively. I n support of the above statement, the author has prepared double salts of iodic acid with other acids which may be regarded as conden- sation-products, requiring for their formation an extra-radicle oxygen atom, analogous to that which is allowed to exist in aldehyde and to be the cause of the easy polymerisation of that substance; thus, C,H,:O + O:C,H, = C2H,:O2:CzB4.The formula for iodic acid thus becomes HO-IO:O. Potassium sulphatoiodate was obtained by mixing potassium pyro- sulphate (1 mol.) and iodate (If mol.) in concentrated solution, and its formula found to be identical with that of Marignac's salt KO-1 O(OH)*O*SO,*OK. Potussium molybdoiodate, KO*IO(OH)*O~MoO,~OH + H,O, is ob- tained as a white precipitate on adding a concentrated solution of potassium nitrate to a solution of sodium molybdate and iodic acid in nitric acid ; it crystallises with disculty in short needles, and is sparingly soluble in water. Ammonium moly bdoiodate is obtained in the same way, and has similar properties, but contains no water of crystallisation. The thallium and lead salts were obtained.Molybdo- iodic acid is obtained as a yellowish, transparent mass on evaporating the solution formed by the action of dilute sulphuric acid on a mixture of barium iodate and molybdate. Several of its reactions with in- organic and organic salts are given. Potassium tungstoiodate, KO. WO,.O-IO(OH)OK + H20, is obtained by adding, by degrees, a solution of iodic acid to one of potassium tungstate ; after some hours, a crystalline magma is obtained, more than 90 per cent. of which consists of slender needles of the tungsto- iodate, the rest being tabular crystals of acid tungstate. Potassium chromoiodate bas been described by Berg (Abstr., 1887, 776) ; the author's analyses of this salt leave some doubt both as to the amount of water it contains and as to its formula.T. G. N. The author has also obtained an ammoniwm triiodate, NH,O*IO( OH).O.IO( OH)*O*IO,, of which the crystallography is given, and a sodium triiodate, N a ~ * I O ( O H ) ~ O ~ I ~ ~ O ~ ) * O ~ I ~ ~ + +H,O. Specific Gravity of Ammonia Solutions. By G. LUNGE and T. WIERNIK (Zeit. m g . Chem., 1889, 181--183).-The authors have redetermined with extreme care the sp. gr., referred to water a t 15", percentage of ammonia, and coefficient of expansion of ammonia A. G. B.108 ABSTRACTS O F CHEMICAL PAPERS. solutions of 24 different strengths. their table :- The following is an abstract of I--- --- 0 -990 0.980 0 -970 0.960 0 *950 0 *940 2 -31 4 30 7 -31 9 -91 12 -72 15 *63 Correction of t,he sp. gr. for f lo. Specific gravity at 15". 0 -00020 0 -00023 0 -00025 0 *00029 0 *00034 0 -00039 0 '930 0 -920 0 910 0 *goo 0 *890 0 -880 Percentage of NH? -- 1.8 -64 21 *75 24 *99 28 *33 31 *75 35 -60 Correction of t.he ep.gr. for f lo. --- 0 *00042 0 -00047 0 *00052 0 -00057 0 -00061 - M. J. S. A Derivative of Boric and Phosphoric Acids. By G. MEYER (Ber., 22, 2919).-When a mixture of boric and phosphoric acids is heated to redness, a very inert, white substance, P04B, is formed. It reddens moist litmus paper, but seems not to be dissolved by boiling water, and only to be very slowly attacked by boiling aqueous alkalis. Fusion with alkalis or alkaline carbonates causes instant decomposition, and fusioE with sodium chloride also yields a soluble inel t . L. T. T. By E. P. HARRIS (Ckem. Cent., 1889, ii, 283-284) .-The author has successf idly prepared silicon by means of Gatterman's method, ignition of fine sand with magnesium powder, and in addition to the already known halogen-derivatives, he has prepared a &con nitride, NH2*SiN, by acting on silicon chloride or silicon iodide with dry ammonia, whereby a considerable development of heat takes place.If the flux, obtained in the pre- paration of the silicon, be treated with dilute hydrochloric acid to dissolve out the magnesium oxide. silicon chloroform is obtained Silicon. It is a snow-white powder. u as a light, colourless, inflammable liquid, boiling a t 42-44". J. W. L. Preparation of the Chlorides of Silicon, Aluminium, &c. By H. N. WARREN (Chem. News, 60, 158).-Iron alloys of silicon or aluminium are heated to redness in a clay crucible and a current of chlorine gas is passed into the mass, suitable means being adopted to collect the volatile products. With chlorine and silicon-iron, the ferric chloride is condensed first, then the silicon chloride ; if hydrogen chloride is used instead of chlorine, the ferrous chloride formed re- mains in the crucible and silicon chloroform distils off.The aluminium chloride obtained from aluminium-iron is purified by mixing with iron borings and distilling, or if the aluminium-iron alloy is mixed with common salt previous to submitting it to the action of chlorine, a sublimate of aluminium sodium chloride is obtained. D. A. L. Combining Energy of Rubidium. By N. BEKETOFF (Chew.. Centr., 1889, ii, 245, from Bull. Acad., St. Pe'tsrsbourg [2], 1, 117-118).-Preparation of the metal.-Rubidium hydroxide is precipitated fromINORQANIC GHEMl STRY. 109 the sulphate by barium hydroxide, calcined in a silver dish, and heated with fine aluminium clippings in an iron cylinder in a furnace ; the cylinder being connected with a glass tube by means of an iron tube. A mixture of 1 equivalent of rubidium hydroxide and 1: equiva- lents of aluminium gives the best results. From 113 grams of hydroxide and 31 grams of aluminium, 31 grams of very pure rubidium was obtained. J. W. L. Potassium Plumbate. Crystalline Hydrated Thallic Oxide. By D. CARNEGIE (Chern. News, 60, 113).-Potassium plumbate is formed when potassium plumbite, obtained by dissolving litharge in molten potash, is strongly heated, with free access of air, for some time.The colourless aqueous solution has strongly oxidising pro- perties ; it evolves chlorine with excess of dilute hydrochloric acid or with dilute sulphuric acid when the latter is added rapidly in excess, lead sulphate being also formed, the chlorine in this case being derived from the potassium chloride present as an impurity in the potash ; when boiled with litharge, it yields lead peroxide and potassium plumbite ; whilst with mnnganous sulphate it gives hydrated man- ganic oxide, and dilute sulphuric acid added slowly produces a brown precipitate of hydrated lead peroxide, Pb02,H20. Fused potash dissolves small quantities of thallic oxide, and the resulting yellow mass when treated with water yields a reddish- brown precipitate of the hydrated thallic oxide.If, however, the fusion is continued for some time, a mass of very light, glistening, microscopic, hexagonal plates is produced, of the composition T1,0,,3H20; they are brown in colour but transmit yellow light. They are unaffected by a temperatnre of 340", and are readily soluble in dilute hydrochloric and sulphuric acids, but generally a slight reduction to thalloas salt takes place. D. A. L. Influence of Hydrogen Chloride on the Solubility of Cuprous Chloride and of Lead Chloride. By R. ENGEL (Bull. SOC. C'hi?~., [3], 1, 693--695).-The amount of cuprous chloride dissolved bv hydrochloric acid increases with the hydrogen chlor ide present. A saturated solution of cuprous chloride in hydrochloric acid when cooled to -40" deposits cuprons chloride crystals, no hydrochloride of cuprous chloride being formed.The presence of hydrogen chloride a t first determines a diminished solubility of lead chloride, and it is not until a considerable amount of hydrogen chloride is present that an increasing solubility obtains ; this the author thinks is due to tbe formation of the soluble hydro- chloride of lead chloride. Solubility tables for each of the above salts in hydrochloric acid of various strengths are given. Oxysulphides of Mercury. By T. POLECK (Ber., 22,2859-2861 ; compare Poleck and Goercki, Abstr., 1888, 1166j.--The anthop's further experiments have shown that the oxysulphides of mercury are not known, and that their existence is highly improbable. T. G. N. I!'. S. K.110 ABSTRAOTS OF CHEMICAL PAPERS. Aluminium Amalgam and its use in Thermochemistry.By J. B. BAILLE and C. FERY (Ann. Chim. Phys. [S], 17, 246-256).- Aluminium amalgam was first described by one of the authors iu 1875. Experiments in sealed tubes in an atmosphere of indifferent gas show that solution of aluminium by mercury proceeds more rapidly the higher the temperature, and i~ especially active a t the boiling point of mercury. It is, however, the liqnid metal and not its vaponr which attacks the aluminium. The quantity of aluminium dissolved a t first increases with the time, but attains a maximum at the end of about two hours ; it is independent of the pressure inside the tube and of the extent of metallic surface ia contact, but is pro- portional to the quantity of mercury present. When the mercury cools, crystals of the amalgam separate as a thick paste on the surface ; it has the composition A1,Hg3.In moist air it rapidly oxidises with formation of the hydroxide, Al?O(OH),. It decomposes water at the ordinary temperature, the change being especially rapid with very thin sheets of aluminium amalgamated on the surface. T t is attacked by nit& acid, which has no action on aluminium alone, and rapidly decomposes a solution of potassium hydroxide with evolution of hydrogen. If aluminium amalgam is mixed with antimony amalgam, metallic antimony separates at the surface in small crystals, and after a time the aluminium oxidises, so that the mercury is obtained free from both metals. When, on the other hand, lead amalgam is added to the aluminium amalgam, the aluminium separates at the surface and is rapidly oxidised.This phenomenon is analogous to the expulsion of aluminium from its alloys with copper, tin, &c., by mixing the fused alloys with lead. The action of moist air on amalgamated aluminium foil in the calorimeter was utilised for the determination of the heat of forma- tion of aluminium oxide and the hydroxides. The results obtained were as follows :-Al2O3? 392.6 Cals. ; Al2O(0H),, 394.6 Cals. ; A12(0H),, 395.6 Gals. The formation of the aluminium amalgam and the displacement of the aluminium by lead are accompanied by no appreciable thermal disturbance. C. H. B. Preparation of Manganese from Manganese Chloride and Magnesium. By E. GLATZEL (Ber., 22, 2857-2859).-Manganese can be prepared by heating a mixture of finely divided, anhydrous manganese chloride (1 00 gmms) and dry, powdered potassium chloride (200 grams) in a covered Hessian crucible until it just melts, and then adding magnesium (15 grams) in portions of 3-4 grams, a t intervals of 2-3 minutes; if the fused mass is too hot a very violent reaction occurs, and the contents of the crucible are thrown out.The crucible is covered again, heated more strongly, and then allowed to cool slowly i n the furnace. The yield of manga- nese is 20-25 grams, the metal containing traces only of silica, and being quite free from magnesium. The specific gravity of manganese, as the average of four determi- nations, was found to be 7.3921 at 22". F. S . K.MINERALOGICAL CHEMISTRT. 11 t Reduction of Ferric Bromide by Boiling.By L. L. DE KONINCK (Zeit. ang. Chsm., 1889, 149) .-A solution of ferric bromide containing excess of bromine begins to show the presence of a ferrous salt as soon as the excess of bromine has been expelled by boiling. Ferric bromide, free from bromine and from ferrous salt, can only be obtained by passing air through the solution in the cold. The excess of bromine is very tenaciously retained. M. J. S.106 ABSTRACTS OF CElEMIOAL PAPERS.In o r g a n i c C h e mi s t r y.Hydrogen Peroxide. By G. TANMANN (Zeit. physikal. Chem., 4,441-443) .-The spontaneous decomposition of hydrogen peroxide inalkaline solution is found to be independent of the amount or natureof the base which is present. It appears probable from the author'sexperiments that it is really caused by the presence of traces ofmetallic oxides, such as the oxide of iron, dissolved in the alkali.Itis shown that the addition of small quantities of such oxides in-creases enormously the rate of decomposition.The freezing points of aqueous solutions of hydrogen peroxidewere determined, and from these a molecular reduction of 8-79 wasfound. Hydrogen peroxide being a, non-electrolyte, this numberwould correspond with the formula H404.[3 3, 1, 695--699).-A review of the known hydrochlorides of chlorides,and a discussion of their probable constitution.H. C.Hydrochlorides of Chlorides. By R. ENGEL (BUZZ. SOC. Chim.T. G. N.Iodic Acid. By H. LESCEUR (BiiZZ. SOC. Chim. [3], 1, 563).-Thecrystals of iodic acid deposited from its solution in dilute ormoderately concentrated nitric acid are monohydrated, TV hereas thoseobtained from the solution of iodic acid in concentrated nitric aciINORQANIO CHEMISTRY. 107are anhydrous.The author thinks that the crystals deposited fromsolution in nitric acid of intermediate strength are mixtures of thehydrated and anhydrous varieties.Iodic Acid; Double Salts of Iodic Acid with other Acids.B.y C. W. RLOMSTRAND ( J . p r . Chem. [g], 40, 305-340 ; compareAbstr., 1887, 337) .-In the oxygen-acids of phosphorus and iodineonly one atom of oxygen is strongly united to the phosphorus andiodine, the radicles being PO-0 and 10.0 respectively, thus differingfrom the oxygen-acids of nitrogen, chlorine, and bromine, where twoatoms of oxygen are equally strongly united to the nitrogen, chlorine,or bromine, the radicIes being NO,, C102, and BrO, respectively.I n support of the above statement, the author has prepared doublesalts of iodic acid with other acids which may be regarded as conden-sation-products, requiring for their formation an extra-radicle oxygenatom, analogous to that which is allowed to exist in aldehyde and tobe the cause of the easy polymerisation of that substance; thus,C,H,:O + O:C,H, = C2H,:O2:CzB4. The formula for iodic acid thusbecomes HO-IO:O.Potassium sulphatoiodate was obtained by mixing potassium pyro-sulphate (1 mol.) and iodate (If mol.) in concentrated solution, andits formula found to be identical with that of Marignac's saltKO-1 O(OH)*O*SO,*OK.Potussium molybdoiodate, KO*IO(OH)*O~MoO,~OH + H,O, is ob-tained as a white precipitate on adding a concentrated solution ofpotassium nitrate to a solution of sodium molybdate and iodic acidin nitric acid ; it crystallises with disculty in short needles, and issparingly soluble in water.Ammonium moly bdoiodate is obtained inthe same way, and has similar properties, but contains no water ofcrystallisation. The thallium and lead salts were obtained. Molybdo-iodic acid is obtained as a yellowish, transparent mass on evaporatingthe solution formed by the action of dilute sulphuric acid on a mixtureof barium iodate and molybdate. Several of its reactions with in-organic and organic salts are given.Potassium tungstoiodate, KO.WO,.O-IO(OH)OK + H20, is obtainedby adding, by degrees, a solution of iodic acid to one of potassiumtungstate ; after some hours, a crystalline magma is obtained, morethan 90 per cent. of which consists of slender needles of the tungsto-iodate, the rest being tabular crystals of acid tungstate.Potassium chromoiodate bas been described by Berg (Abstr., 1887,776) ; the author's analyses of this salt leave some doubt both as tothe amount of water it contains and as to its formula.T. G. N.The author has also obtained an ammoniwm triiodate,NH,O*IO( OH).O.IO( OH)*O*IO,,of which the crystallography is given, and a sodium triiodate,N a ~ * I O ( O H ) ~ O ~ I ~ ~ O ~ ) * O ~ I ~ ~ + +H,O.Specific Gravity of Ammonia Solutions. By G. LUNGE andT.WIERNIK (Zeit. m g . Chem., 1889, 181--183).-The authors haveredetermined with extreme care the sp. gr., referred to water a t 15",percentage of ammonia, and coefficient of expansion of ammoniaA. G. B108 ABSTRACTS O F CHEMICAL PAPERS.solutions of 24 different strengths.their table :-The following is an abstract ofI--- ---0 -9900.9800 -9700.9600 *9500 *9402 -314 307 -319 -9112 -7215 *63Correctionof t,he sp. gr.for f lo.Specificgravityat 15".0 -000200 -000230 -000250 *000290 *000340 -000390 '9300 -9200 9100 *goo0 *8900 -880Percentageof NH?--1.8 -6421 *7524 *9928 *3331 *7535 -60Correctionof t.he ep. gr.for f lo.---0 *000420 -000470 *000520 -000570 -00061-M. J.S.A Derivative of Boric and Phosphoric Acids. By G. MEYER(Ber., 22, 2919).-When a mixture of boric and phosphoric acids isheated to redness, a very inert, white substance, P04B, is formed. Itreddens moist litmus paper, but seems not to be dissolved by boilingwater, and only to be very slowly attacked by boiling aqueousalkalis. Fusion with alkalis or alkaline carbonates causes instantdecomposition, and fusioE with sodium chloride also yields a solubleinel t . L. T. T.By E. P. HARRIS (Ckem. Cent., 1889, ii, 283-284) .-Theauthor has successf idly prepared silicon by means of Gatterman'smethod, ignition of fine sand with magnesium powder, and in additionto the already known halogen-derivatives, he has prepared a &connitride, NH2*SiN, by acting on silicon chloride or silicon iodide withdry ammonia, whereby a considerable development of heat takesplace.If the flux, obtained in the pre-paration of the silicon, be treated with dilute hydrochloric acid todissolve out the magnesium oxide. silicon chloroform is obtainedSilicon.It is a snow-white powder.u as a light, colourless, inflammable liquid, boiling a t 42-44".J. W. L.Preparation of the Chlorides of Silicon, Aluminium, &c.By H. N. WARREN (Chem. News, 60, 158).-Iron alloys of silicon oraluminium are heated to redness in a clay crucible and a current ofchlorine gas is passed into the mass, suitable means being adopted tocollect the volatile products. With chlorine and silicon-iron, theferric chloride is condensed first, then the silicon chloride ; if hydrogenchloride is used instead of chlorine, the ferrous chloride formed re-mains in the crucible and silicon chloroform distils off.The aluminiumchloride obtained from aluminium-iron is purified by mixing withiron borings and distilling, or if the aluminium-iron alloy is mixedwith common salt previous to submitting it to the action of chlorine,a sublimate of aluminium sodium chloride is obtained.D. A. L.Combining Energy of Rubidium. By N. BEKETOFF (Chew..Centr., 1889, ii, 245, from Bull. Acad., St. Pe'tsrsbourg [2], 1, 117-118).-Preparation of the metal.-Rubidium hydroxide is precipitated froINORQANIC GHEMl STRY. 109the sulphate by barium hydroxide, calcined in a silver dish, andheated with fine aluminium clippings in an iron cylinder in a furnace ;the cylinder being connected with a glass tube by means of an irontube.A mixture of 1 equivalent of rubidium hydroxide and 1: equiva-lents of aluminium gives the best results. From 113 grams ofhydroxide and 31 grams of aluminium, 31 grams of very purerubidium was obtained. J. W. L.Potassium Plumbate. Crystalline Hydrated Thallic Oxide.By D. CARNEGIE (Chern. News, 60, 113).-Potassium plumbate isformed when potassium plumbite, obtained by dissolving litharge inmolten potash, is strongly heated, with free access of air, for sometime. The colourless aqueous solution has strongly oxidising pro-perties ; it evolves chlorine with excess of dilute hydrochloric acid orwith dilute sulphuric acid when the latter is added rapidly in excess,lead sulphate being also formed, the chlorine in this case being derivedfrom the potassium chloride present as an impurity in the potash ;when boiled with litharge, it yields lead peroxide and potassiumplumbite ; whilst with mnnganous sulphate it gives hydrated man-ganic oxide, and dilute sulphuric acid added slowly produces a brownprecipitate of hydrated lead peroxide, Pb02,H20.Fused potash dissolves small quantities of thallic oxide, and theresulting yellow mass when treated with water yields a reddish-brown precipitate of the hydrated thallic oxide.If, however,the fusion is continued for some time, a mass of very light, glistening,microscopic, hexagonal plates is produced, of the compositionT1,0,,3H20; they are brown in colour but transmit yellow light.They are unaffected by a temperatnre of 340", and are readily solublein dilute hydrochloric and sulphuric acids, but generally a slightreduction to thalloas salt takes place.D. A. L.Influence of Hydrogen Chloride on the Solubility of CuprousChloride and of Lead Chloride. By R. ENGEL (Bull. SOC. C'hi?~.,[3], 1, 693--695).-The amount of cuprous chloride dissolved bvhydrochloric acid increases with the hydrogen chlor ide present. Asaturated solution of cuprous chloride in hydrochloric acid whencooled to -40" deposits cuprons chloride crystals, no hydrochlorideof cuprous chloride being formed.The presence of hydrogen chloride a t first determines a diminishedsolubility of lead chloride, and it is not until a considerable amount ofhydrogen chloride is present that an increasing solubility obtains ;this the author thinks is due to tbe formation of the soluble hydro-chloride of lead chloride.Solubility tables for each of the above salts in hydrochloric acid ofvarious strengths are given.Oxysulphides of Mercury. By T.POLECK (Ber., 22,2859-2861 ;compare Poleck and Goercki, Abstr., 1888, 1166j.--The anthop'sfurther experiments have shown that the oxysulphides of mercuryare not known, and that their existence is highly improbable.T. G. N.I!'. S. K110 ABSTRAOTS OF CHEMICAL PAPERS.Aluminium Amalgam and its use in Thermochemistry. ByJ. B. BAILLE and C. FERY (Ann. Chim. Phys. [S], 17, 246-256).-Aluminium amalgam was first described by one of the authors iu1875. Experiments in sealed tubes in an atmosphere of indifferentgas show that solution of aluminium by mercury proceeds morerapidly the higher the temperature, and i~ especially active a t theboiling point of mercury.It is, however, the liqnid metal and notits vaponr which attacks the aluminium. The quantity of aluminiumdissolved a t first increases with the time, but attains a maximum atthe end of about two hours ; it is independent of the pressure insidethe tube and of the extent of metallic surface ia contact, but is pro-portional to the quantity of mercury present.When the mercury cools, crystals of the amalgam separate as athick paste on the surface ; it has the composition A1,Hg3. In moistair it rapidly oxidises with formation of the hydroxide, Al?O(OH),.It decomposes water at the ordinary temperature, the change beingespecially rapid with very thin sheets of aluminium amalgamated onthe surface.T t is attacked by nit& acid, which has no action onaluminium alone, and rapidly decomposes a solution of potassiumhydroxide with evolution of hydrogen.If aluminium amalgam is mixed with antimony amalgam, metallicantimony separates at the surface in small crystals, and after a timethe aluminium oxidises, so that the mercury is obtained free fromboth metals. When, on the other hand, lead amalgam is added tothe aluminium amalgam, the aluminium separates at the surface andis rapidly oxidised. This phenomenon is analogous to the expulsionof aluminium from its alloys with copper, tin, &c., by mixing thefused alloys with lead.The action of moist air on amalgamated aluminium foil in thecalorimeter was utilised for the determination of the heat of forma-tion of aluminium oxide and the hydroxides.The results obtainedwere as follows :-Al2O3? 392.6 Cals. ; Al2O(0H),, 394.6 Cals. ;A12(0H),, 395.6 Gals.The formation of the aluminium amalgam and the displacement ofthe aluminium by lead are accompanied by no appreciable thermaldisturbance. C. H. B.Preparation of Manganese from Manganese Chloride andMagnesium. By E. GLATZEL (Ber., 22, 2857-2859).-Manganesecan be prepared by heating a mixture of finely divided, anhydrousmanganese chloride (1 00 gmms) and dry, powdered potassiumchloride (200 grams) in a covered Hessian crucible until it justmelts, and then adding magnesium (15 grams) in portions of3-4 grams, a t intervals of 2-3 minutes; if the fused mass is toohot a very violent reaction occurs, and the contents of the crucibleare thrown out. The crucible is covered again, heated more strongly,and then allowed to cool slowly i n the furnace. The yield of manga-nese is 20-25 grams, the metal containing traces only of silica,and being quite free from magnesium.The specific gravity of manganese, as the average of four determi-nations, was found to be 7.3921 at 22". F. S . KMINERALOGICAL CHEMISTRT. 11 tReduction of Ferric Bromide by Boiling. By L. L. DEKONINCK (Zeit. ang. Chsm., 1889, 149) .-A solution of ferric bromidecontaining excess of bromine begins to show the presence of a ferroussalt as soon as the excess of bromine has been expelled by boiling.Ferric bromide, free from bromine and from ferrous salt, can onlybe obtained by passing air through the solution in the cold. Theexcess of bromine is very tenaciously retained. M. J. S

ISSN:0368-1769    

DOI:10.1039/CA8905800106

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. M i n e r a l o g i c a l Chemistry. 11 t Native Lead in Sweden. By L. J. IGELSTROM (Jahrb. f. Min., 1889, ii, Mem., 32--36).-The Pajsberg manganese and iron ore mine twenty years .. ago yielded small quantities of native lead. At the Sjo mine in Orebro, the author discovered on January 24, 1889, this rare native metal in the neotokite (black manganese silicate) in the form of small laminae with brilliant lustre. It closely resembles electrolytically deposited lead. The neotokite occurs in dolomite, and is accompanied by specular iron ore. B. H. B. Atacamite in Chili. By L. DARAPSKY (Juhrb. f. Min., 1889, ii, Mem., l--18).-The author gives a complete bibliographyof the subject,, as well as the results of his own investigations. On comparing the results of all the analyses published, it is found impossible to refer all the occurrences of atacamite to a typical formula, although the formula CuC1,,3Cu0,3~Hz0 is the closest approximation.The irregular development of the crystals and variations in the angles appear to indicate that atacamite is not a mineralogical unit, but, like the felspars, is composed of two or more members. The terminal members are believed to be CuClZ,3Cu0,3HzO and CuCI2,4Cu0,6H20. With reference to the formation of atacamite, the auhhor shows that processes producing a similar compound in the laboratory are impossible in nature. Tbe only processes worthy of consideration arc the formation by heating a mixture of basic copper nitrate and sodium chloride at 20O0, or a mixture of the former with copper sulphate and sodium chloride at 100".The presence of gypsum and calcite in the deposits and the intimate mixture of ferric oxide and cuprous oxide, however, clearly point to pyrites and similar minerals as the mother substances, which probably were highly decomposed before they came into contact with' the salt of the sea-water. In all probability, the principal cementing material of the aqueous oxy- chloride is water, and it is impossible for atacamite to have been formed by a replacement of the water of hydration of the chloride by oxide. B. H. B. Cerium and Yttrium Phosphates from South Norway, By C. W. BLOMSTRAND (Jahrb. f. Nin., 1889, ii, Ref. 44-46, from Geol.112 ABSTRACTS OF OHEMIOAL PAPERS. Fb'ren. i Stockholm fGrhandl., 9, 160.)-The author gives the results of analyses of monazite from Moss (light brown crystals), from Dillingsii (1.large fragments with crystal planes, and 2. small, prismat,ic crystals), from Moss (large, orange crystals), from Lonneby (large prismatic crystals, 1. brownish-yellow, and 2. ash-grey), from Arendal, from Naresto, and from Hvalo (1. large, yellowish-brown crystals, and 2. violet-brown lump). From the results of these nine analyses, the author concludes that the monazites are normal salts of tribasic phosphoric acid, with the excess of bases in combination wit,h siliuic acid. In conclusion, the author gives the results of two analyses of xenotime from Hvalo and from Naresto. B. H. B. Pleonectite, a New Mineral from Sweden. By L. J. IGELSTR~M (Jahrb. f. LWin., 1889, ii, Mem., 40--43).-At the Sjo mine, Orebro, this new mineral has been found in narrow veins in a mixture of haus- mnnnite, rhodonite, and calcite.It occurs in association with arsenio- pleite. It has a greyish-white colour, a hardness of 4, and a vitreous lustre. I t does not occur in crystals. A qualitative analysis indicated that the mineral is a chlorine-bearing lead antimonio-arsenate, with an inconsiderable proportion of water. I n composition and appearance, i t most closely resembles hedyphme, a mineral discovered by Breitbaupt in 1830, but is distinguished from that mineral by its infusibility before the blowpipe. The suggested name is derived from T ~ O V ~ C T ~ W (to have more) in allusion to the antimony minerals already discovered in the Sjo mine.A quantitative analysis of pleoneotite will subsequently be published, B. H. B. Synthesis of Quartz, Corundum, &c. By W. BRUHNS (Jahrb. f Mia., 1889, ii, Mem., 62-65).--By the investigations of DaubrBe, St. Claire-Deville, Hautefeuille, De Chronstchoff, and Doelter, the action of fluorine as mineralising agent has been widely recognised. Whereas these investigators invariably worked with high temperatures, the author bas succeeded in obtaining similar results with temperatures not exceeding 300°, and with high Rteam pressure. His apparatus consists of, a firmly closed platinum crucible hermetically sealed in a steel case. By placing freshly precipitated ferric hydrate in the apparatus with ammonium fluoride, and heating for 10 hours at 250°, the author obtained crystallised ferric oxide. Freshly precipitated and ignited alumina, heated with water and a trace of ammonium fluoride for 10 hours at 300°, yielded hexagonal pyramids of corundum Quartz crystals were obtained in a similar manner from amorphous silica.A remarkable result was obtained by acting with hydrofluoric acid on pulverised potash-felspar. The felspar employed was micro- cline, having the following percentage composition : - Si02. A120,. K20. Na,O. Total. 64-33 18.61 13.49 3.56 99.99 After heating for 53 hours with hydrofluoric acid at 30O0,small crystals of tridymite were obtained ; whilst the lid of the platinum vessel was covered with a crust of an isotropic regular compound ofMINERALOGICAL OHEMISTRY. 113 silica, aluminn, potash, and fluorine, Experiments made with the expectation of obtaining titanic anhydride, tin oxide, andalnsite, and topaz were unsuccessful. Another experiment, in which powdered iron was mixed with ferric oxide, amorphous titanic anhydride, and hydrofluoric acid, yielded crystals of titaniferous iron and magnetite.B. H. B. Formation of Silicates. By J. LEMBERG (Juhrh. f. Min., 1889, ii, Ref., 34-36 ; from Zeit. deutsch. geol. Ges., 39, 559).-By the action of solutions of various sodium silicates on kaolin at high temperatures, the author has obtained zeolites of the analcime series. In nature only one member of this series is known. By treatment with potassium salts, the analcimes obtained were converted into the corresponding members of the (anhydrous) leucite series. Of this series, too, only one member occurs in nature. Leucites containing a proportion of silica different from that of the mineral leucite, appear to be split u p at a high temperature into orthoclase and leucite. By the action of kaolin on solutions of potassium carbonate or sodium carbonate, re- spectively, at a high temperature, a potassium-nepheline or cancrinite was formed; in both cases carbonic anhydride was also formed.This suggests a new source for carbonic anhydride in nature, kaolin itself being able to drive out the carbonic acid from the alkali car- bonates. This change may also be effected if kaolin i 4 mixed with calcium carbonate aiid subjected to the action of a hot solution of sodium chloride or potassium chloride, when calcium chloride is formed, and subsequently alkali carbonate, which acts on the kaolin.These reactions lead the author to speculate as to the genesis of cancrinite and analcime, and of felspar and elaolite in the preseiice of cancrinite. B. H. B. Mineralogy of the French Creek Mines. By J. EGERMAN (JahrG. f. Min., 1859, ii, Ref. 17--18).-1n the shafts of ft magnetite mine at French Creek, Pennsylvania, the following minerals have been met with : iron pyrites, copper pyrites, apophyllite, desrnine, and garnet in large crystals, and small crystals of calcite, orthoclase, pyroxene, and aragonite ; masses of pyrallolite and erythrite, and needles of byssolite in calcite. Perfect crystals of apophyllite, 14 mm. side, gave on analysis the following results :- Si02. CaO. K20. H,O. Total. Sp. gr.51.63 25.42 6.27 16.58 99.90 2.35 An analysis of the desmine gave- SiOp AlzO,. CaO. MgO. E20. H,O. Total. 58.00 13.40 7.80 1-40 1.03 18.30 99-93 B. H. B. Calamine and Apophyllite from the United States. YOL. LVIII. i By J. EGERMAN (Jahrb..f. JIin., 1889, ii, Ref. 256; from Proc. Acnd. Nat. S c i . Philadelphia, 1889, 32--35).-The author gives analyses of (I)114 ABSTRACTS OF CHEMICAL PAPERS. calamine from Friedensville, New Jersey, and of (11) apophyllite from St. Peters, Chester Co., Pennsylvania. The results are a.s follows :- SiOP Fe203. ZnO. CaO. K20, H20. Total. I. 24.32 2.12 65.05 - - 7.86 99.35 11. 51.63 - - 25.42 6.25 16.58 99.88 The sp. gr. of the apophyllite is 2.35. B. H. B. Anthochroite, a New Mineral from Sweden.. By L. J. IGELSTROU (Juhrb. f.Min., 1889, ii, Mem., 36--39).-At Jacobsberg, in Wermland, there are two mines, one yielding braunite, the other hausmannite. Both mines are in the same Archaan limestone sur- rounded by granulite. The new mineral is met with only in the braunite mine. It is obtained by dissolving the braunite in hydro- chloric acid. I t also occurs in association with garnet, idocrrtse, manganese-epidote, mica, and all the minerals known at this mine, and it is met with in narrow veins in the limestone. The grains are optically biaxial. The hardness is 5+, and the chemical composition as follows :- The violet residue is anthochroite. Si02. MnO. CaO. MgO. M,03 and Fe20,. K20 and NhO. Total. 51.6 3.4 23.3 13-5 1 *4 [6*8] 100.00 The mineral is thus a bisilicate of lime, magnesia, and manganese.Violan and richterite resemble it in composition, but not in appear- ance and optical properties. The name, derived from (L*vOos, flower, and XpGpa, colour, is considered suitable on account of the brilliant colour of the new mineral and of the mixture in which it occurs. Tourmaline-bearing Copper Ores from Chili. By A. v. GRODDECK (J0hrb.f. Min., 1889, ii, Ref. 113-115 ; from Zeit. deutsch. geol, Ges., 1887, 239-266) .-The association of tourmaline with Chilian copper ores has been previously noticed. The author has examined a series of ores from Tamaya, in which this association is well exhibited, the tourmaline occurring both in the sulphnretted and oxidised copper ores and also in the calcite and quartz gangue and in the spathose, quartzose, micaceous, and chloritic containing- rocks.The crystals are mostly 0.1 to 0.5 mm. in length, and are strongly pleochrok. Si02. A1203. B203. FeO. CaO. MgO. N+O. K20. H2O. F. Total. 36.34 32.22 10.87 8.31 0.79 3.92 3.14 0.22 3.89 trace 99.70 Natrolite from Monte Baldo. By G. LUZZATTO (Jahrb. f. Min., 1889, ii, Ref. 28 ; from Riuista di iilineralogia e Cristallograjia italiana, 4, 54-55) .-Carefully selected, clear and transparent crystals gave on analysis the following results :- SiO,. A1203. Na20. CaO. H20. Total. B. H. B. On analysis they yielded- B. H. B. 4'7.16 26.76 16.18 0.28 9.57 99.95 These results correspond with the formula Na,A1,Si,Olo + 2H,O. B. H. B.MINERALOGICAL CHEMISTRY. 115 Eruptive Rocks of the Rhone. By H. LENK (Jahrb. f. Min., 1889, ii, Ref.74-79 ; from Xitzber. Wurtzburger phys.-nzed. Ges., 1886).-The author gives the results of a microscopic examination of the constitution of the eruptive rocks of the Rhone. Eigbt analyses are given of the various rocks. The author distinguishes seven groups of these rocks :-1. phonolites ; 2. glass basalts (limburgit,e) ; 3. nepheline basalts ; 4. felspar basalts ; 5 . nepheline-plagioclnse basalts (identical with basanite) ; 6. hornblende basalts ; 7. dolorites. The Transcaspian Naphtha District. By H. SJ~GREN ( J U I ! , ~ . f. Min., 1889, ii, Reef. 102-105, from Juhrb. k. k. geoZ. Reichsunst., 37, 47--62).-The author has subjected the mud from the Baku mud volcanoes to careful examination, and .found i t to yield on analysis :- Si02. A1,03. FenOJ. MnO. MgO. CaO.KnO. Na.20. B20. Total. B. H. B. 57.98 15.60 9.66 0.40 4.52 1-08 3.25 1.34 5.75 99-56: The microscopic investigation showed that the principal consti- tuents were isotropic, glassy grains, frequently very impure, pure whibe and reddish-hrown, isotropic grains, a pyroxenic niinenl, green amphibole, felspar with and without twinning striation, quartz, calcite in rhombohedrs, magnetite, and iron pyrites. Tile remainder of the paper deals with the geology of the district, the author con- cluding that the naphtha emanates from great depths. B. H. B. An nndescribed Meteoric Iron from East Tennessee. By F. A. GENTH (Jahrb. f. Min., 1889, ii, Ref. 42; from PTOC. Acad. Xat. Sciences of PhiZadeZph.ia).-This meteorite appears to have fallen in 1860 at a distzmce of 10 miles from Cleveland, East Tennessee.Its original weight was about 1154 kilos. The mean of three analyses gav- Fe. Ni. Co. Cu. P. S. Total. Sp. gr. 89-60 8.80 0.67 0.12 0.32 0.01 99-52 7-.521 B. H. B. Meteorites of Alfianello and Concepcion. By C. FRIEDHE131 (Jahrb. f. Min., 1889, ii, Ref., 278-279; from Sitz-Ber. d. k. preuss. Akad. Wiss. Berlin, 13, 345--36i).-The analysis of the meteorite of Alfianello gave 7.92 per cent. nickel-iron (I), 7.78 troilite, 0.60 chrome- iron, 37.38 olivine (11), 46.29 bronzite and augibe (111) :- r. Ir. m. Fe.. .... 88.84 SiO, ...... 34.92 53.86 Ni.. .... 10.09 A1203 ..... - 5.76 co ..... 1.07 FeO ...... 13.79 10.55 Mn .... 0.26 CaO ...... - 7-73 MgO .... 51.26 21.68 These results differ considerably from those previously published by Maissen, Plight, and v.Foullon. The meteorite that fell in 1880 between Nogay& and Concepcion i;!I lli ABSTRACTS OF CHEMICAL PAPERS. was briefly described by Websky and DaubrBe. The complete analysis gave the results shown under IV, and that of the portion soluble in hydrochloric acid the results shown under V :- Si03 A1,03. Fe203. Cr203. MnO. CaO. MgO. Alkalis. kV. 27-22 2-35 30.64 0.38 0.09 2.56 19.24 0.18 V. 26.67 2.24 30.42 - 2.25 18.79 0.12 Ni. Co. Cu.Sn. Ignition. Insoluble. 7-7 IV. 1-61 trace 14.47 - V. 1.46 0.18 - - 1.82 With ether, 0.21 per cent. of a yellow bituminous substance was extracted, which volatilised at 200". When ignited in a current of oxygen t.he meteorite yielded carbonic anhydride (= 1.56 of carbon) and 14-03 per cent. of water.Treated with boiling water, 40 grams of the meteorite yielded (in grams)- SOB. S,O2. EzO. Na20. MgO. CaO. c1. 0.5001 0,0551 0.0059 0,0479 0.0750 0.1450 0*0009 There was also contained in the meteorite 327 per cent. of sulphur, 0.064 per cent. of phosphorus, 2.08 per cent. of sulphuric anhydride, and 0.034 per cent. of nitrogen. B. H. B.MINERALOGICAL CHEMISTRY.M i n e r a l o g i c a l Chemistry.11 tNative Lead in Sweden. By L. J. IGELSTROM (Jahrb. f. Min.,1889, ii, Mem., 32--36).-The Pajsberg manganese and iron ore minetwenty years .. ago yielded small quantities of native lead. At theSjo mine in Orebro, the author discovered on January 24, 1889, thisrare native metal in the neotokite (black manganese silicate) in theform of small laminae with brilliant lustre.It closely resembleselectrolytically deposited lead. The neotokite occurs in dolomite,and is accompanied by specular iron ore. B. H. B.Atacamite in Chili. By L. DARAPSKY (Juhrb. f. Min., 1889, ii,Mem., l--18).-The author gives a complete bibliographyof the subject,,as well as the results of his own investigations. On comparing theresults of all the analyses published, it is found impossible to referall the occurrences of atacamite to a typical formula, although theformula CuC1,,3Cu0,3~Hz0 is the closest approximation. Theirregular development of the crystals and variations in the anglesappear to indicate that atacamite is not a mineralogical unit, but,like the felspars, is composed of two or more members. The terminalmembers are believed to be CuClZ,3Cu0,3HzO and CuCI2,4Cu0,6H20.With reference to the formation of atacamite, the auhhor showsthat processes producing a similar compound in the laboratory areimpossible in nature.Tbe only processes worthy of consideration arcthe formation by heating a mixture of basic copper nitrate andsodium chloride at 20O0, or a mixture of the former with coppersulphate and sodium chloride at 100". The presence of gypsum andcalcite in the deposits and the intimate mixture of ferric oxide andcuprous oxide, however, clearly point to pyrites and similar mineralsas the mother substances, which probably were highly decomposedbefore they came into contact with' the salt of the sea-water. In allprobability, the principal cementing material of the aqueous oxy-chloride is water, and it is impossible for atacamite to have beenformed by a replacement of the water of hydration of the chloride byoxide.B. H. B.Cerium and Yttrium Phosphates from South Norway, ByC. W. BLOMSTRAND (Jahrb. f. Nin., 1889, ii, Ref. 44-46, from Geol112 ABSTRACTS OF OHEMIOAL PAPERS.Fb'ren. i Stockholm fGrhandl., 9, 160.)-The author gives the resultsof analyses of monazite from Moss (light brown crystals), fromDillingsii (1. large fragments with crystal planes, and 2. small,prismat,ic crystals), from Moss (large, orange crystals), from Lonneby(large prismatic crystals, 1. brownish-yellow, and 2. ash-grey), fromArendal, from Naresto, and from Hvalo (1. large, yellowish-browncrystals, and 2.violet-brown lump). From the results of these nineanalyses, the author concludes that the monazites are normal salts oftribasic phosphoric acid, with the excess of bases in combination wit,hsiliuic acid. In conclusion, the author gives the results of twoanalyses of xenotime from Hvalo and from Naresto. B. H. B.Pleonectite, a New Mineral from Sweden. By L. J. IGELSTR~M(Jahrb. f. LWin., 1889, ii, Mem., 40--43).-At the Sjo mine, Orebro,this new mineral has been found in narrow veins in a mixture of haus-mnnnite, rhodonite, and calcite. It occurs in association with arsenio-pleite. It has a greyish-white colour, a hardness of 4, and a vitreouslustre. I t does not occur in crystals. A qualitative analysis indicatedthat the mineral is a chlorine-bearing lead antimonio-arsenate, with aninconsiderable proportion of water. I n composition and appearance,i t most closely resembles hedyphme, a mineral discovered byBreitbaupt in 1830, but is distinguished from that mineral by itsinfusibility before the blowpipe.The suggested name is derivedfrom T ~ O V ~ C T ~ W (to have more) in allusion to the antimony mineralsalready discovered in the Sjo mine. A quantitative analysis ofpleoneotite will subsequently be published, B. H. B.Synthesis of Quartz, Corundum, &c. By W. BRUHNS (Jahrb. fMia., 1889, ii, Mem., 62-65).--By the investigations of DaubrBe,St. Claire-Deville, Hautefeuille, De Chronstchoff, and Doelter, theaction of fluorine as mineralising agent has been widely recognised.Whereas these investigators invariably worked with high temperatures,the author bas succeeded in obtaining similar results with temperaturesnot exceeding 300°, and with high Rteam pressure.His apparatusconsists of, a firmly closed platinum crucible hermetically sealed ina steel case. By placing freshly precipitated ferric hydrate in theapparatus with ammonium fluoride, and heating for 10 hours at 250°,the author obtained crystallised ferric oxide. Freshly precipitatedand ignited alumina, heated with water and a trace of ammoniumfluoride for 10 hours at 300°, yielded hexagonal pyramids of corundumQuartz crystals were obtained in a similar manner from amorphoussilica. A remarkable result was obtained by acting with hydrofluoricacid on pulverised potash-felspar. The felspar employed was micro-cline, having the following percentage composition : -Si02.A120,. K20. Na,O. Total.64-33 18.61 13.49 3.56 99.99After heating for 53 hours with hydrofluoric acid at 30O0,smallcrystals of tridymite were obtained ; whilst the lid of the platinumvessel was covered with a crust of an isotropic regular compound oMINERALOGICAL OHEMISTRY. 113silica, aluminn, potash, and fluorine, Experiments made with theexpectation of obtaining titanic anhydride, tin oxide, andalnsite,and topaz were unsuccessful. Another experiment, in whichpowdered iron was mixed with ferric oxide, amorphous titanicanhydride, and hydrofluoric acid, yielded crystals of titaniferous ironand magnetite. B. H. B.Formation of Silicates.By J. LEMBERG (Juhrh. f. Min., 1889,ii, Ref., 34-36 ; from Zeit. deutsch. geol. Ges., 39, 559).-By the actionof solutions of various sodium silicates on kaolin at high temperatures,the author has obtained zeolites of the analcime series. In nature onlyone member of this series is known. By treatment with potassiumsalts, the analcimes obtained were converted into the correspondingmembers of the (anhydrous) leucite series. Of this series, too, onlyone member occurs in nature. Leucites containing a proportion ofsilica different from that of the mineral leucite, appear to be split u pat a high temperature into orthoclase and leucite. By the action ofkaolin on solutions of potassium carbonate or sodium carbonate, re-spectively, at a high temperature, a potassium-nepheline or cancrinitewas formed; in both cases carbonic anhydride was also formed.This suggests a new source for carbonic anhydride in nature, kaolinitself being able to drive out the carbonic acid from the alkali car-bonates. This change may also be effected if kaolin i 4 mixed withcalcium carbonate aiid subjected to the action of a hot solution ofsodium chloride or potassium chloride, when calcium chloride isformed, and subsequently alkali carbonate, which acts on the kaolin.These reactions lead the author to speculate as to the genesis ofcancrinite and analcime, and of felspar and elaolite in the preseiice ofcancrinite.B. H. B.Mineralogy of the French Creek Mines. By J. EGERMAN(JahrG. f. Min., 1859, ii, Ref. 17--18).-1n the shafts of ft magnetitemine at French Creek, Pennsylvania, the following minerals havebeen met with : iron pyrites, copper pyrites, apophyllite, desrnine, andgarnet in large crystals, and small crystals of calcite, orthoclase,pyroxene, and aragonite ; masses of pyrallolite and erythrite, andneedles of byssolite in calcite. Perfect crystals of apophyllite, 14 mm.side, gave on analysis the following results :-Si02.CaO. K20. H,O. Total. Sp. gr.51.63 25.42 6.27 16.58 99.90 2.35An analysis of the desmine gave-SiOp AlzO,. CaO. MgO. E20. H,O. Total.58.00 13.40 7.80 1-40 1.03 18.30 99-93B. H. B.Calamine and Apophyllite from the United States.YOL. LVIII. iBy J. EGERMAN (Jahrb..f. JIin., 1889, ii, Ref. 256; from Proc. Acnd. Nat.S c i .Philadelphia, 1889, 32--35).-The author gives analyses of (I114 ABSTRACTS OF CHEMICAL PAPERS.calamine from Friedensville, New Jersey, and of (11) apophyllite fromSt. Peters, Chester Co., Pennsylvania. The results are a.s follows :-SiOP Fe203. ZnO. CaO. K20, H20. Total.I. 24.32 2.12 65.05 - - 7.86 99.3511. 51.63 - - 25.42 6.25 16.58 99.88The sp. gr. of the apophyllite is 2.35. B. H. B.Anthochroite, a New Mineral from Sweden.. By L. J.IGELSTROU (Juhrb. f. Min., 1889, ii, Mem., 36--39).-At Jacobsberg, inWermland, there are two mines, one yielding braunite, the otherhausmannite. Both mines are in the same Archaan limestone sur-rounded by granulite. The new mineral is met with only in thebraunite mine. It is obtained by dissolving the braunite in hydro-chloric acid.I t also occurs inassociation with garnet, idocrrtse, manganese-epidote, mica, and allthe minerals known at this mine, and it is met with in narrow veinsin the limestone. The grains are optically biaxial. The hardness is5+, and the chemical composition as follows :-The violet residue is anthochroite.Si02. MnO. CaO. MgO. M,03 and Fe20,. K20 and NhO. Total.51.6 3.4 23.3 13-5 1 *4 [6*8] 100.00The mineral is thus a bisilicate of lime, magnesia, and manganese.Violan and richterite resemble it in composition, but not in appear-ance and optical properties. The name, derived from (L*vOos, flower,and XpGpa, colour, is considered suitable on account of the brilliantcolour of the new mineral and of the mixture in which it occurs.Tourmaline-bearing Copper Ores from Chili. By A.v.GRODDECK (J0hrb.f. Min., 1889, ii, Ref. 113-115 ; from Zeit. deutsch.geol, Ges., 1887, 239-266) .-The association of tourmaline withChilian copper ores has been previously noticed. The author hasexamined a series of ores from Tamaya, in which this association iswell exhibited, the tourmaline occurring both in the sulphnrettedand oxidised copper ores and also in the calcite and quartz gangueand in the spathose, quartzose, micaceous, and chloritic containing-rocks. The crystals are mostly 0.1 to 0.5 mm. in length, and arestrongly pleochrok.Si02. A1203. B203. FeO. CaO. MgO. N+O. K20. H2O. F. Total.36.34 32.22 10.87 8.31 0.79 3.92 3.14 0.22 3.89 trace 99.70Natrolite from Monte Baldo.By G. LUZZATTO (Jahrb. f. Min.,1889, ii, Ref. 28 ; from Riuista di iilineralogia e Cristallograjia italiana,4, 54-55) .-Carefully selected, clear and transparent crystals gaveon analysis the following results :-SiO,. A1203. Na20. CaO. H20. Total.B. H. B.On analysis they yielded-B. H. B.4'7.16 26.76 16.18 0.28 9.57 99.95These results correspond with the formula Na,A1,Si,Olo + 2H,O.B. H. BMINERALOGICAL CHEMISTRY. 115Eruptive Rocks of the Rhone. By H. LENK (Jahrb. f. Min.,1889, ii, Ref. 74-79 ; from Xitzber. Wurtzburger phys.-nzed. Ges.,1886).-The author gives the results of a microscopic examination ofthe constitution of the eruptive rocks of the Rhone. Eigbt analysesare given of the various rocks. The author distinguishes sevengroups of these rocks :-1.phonolites ; 2. glass basalts (limburgit,e) ;3. nepheline basalts ; 4. felspar basalts ; 5 . nepheline-plagioclnsebasalts (identical with basanite) ; 6. hornblende basalts ; 7. dolorites.The Transcaspian Naphtha District. By H. SJ~GREN ( J U I ! , ~ .f. Min., 1889, ii, Reef. 102-105, from Juhrb. k. k. geoZ. Reichsunst.,37, 47--62).-The author has subjected the mud from the Bakumud volcanoes to careful examination, and .found i t to yield onanalysis :-Si02. A1,03. FenOJ. MnO. MgO. CaO. KnO. Na.20. B20. Total.B. H. B.57.98 15.60 9.66 0.40 4.52 1-08 3.25 1.34 5.75 99-56:The microscopic investigation showed that the principal consti-tuents were isotropic, glassy grains, frequently very impure, purewhibe and reddish-hrown, isotropic grains, a pyroxenic niinenl,green amphibole, felspar with and without twinning striation, quartz,calcite in rhombohedrs, magnetite, and iron pyrites.Tile remainderof the paper deals with the geology of the district, the author con-cluding that the naphtha emanates from great depths.B. H. B.An nndescribed Meteoric Iron from East Tennessee. By F.A. GENTH (Jahrb. f. Min., 1889, ii, Ref. 42; from PTOC. Acad. Xat.Sciences of PhiZadeZph.ia).-This meteorite appears to have fallen in1860 at a distzmce of 10 miles from Cleveland, East Tennessee. Itsoriginal weight was about 1154 kilos. The mean of three analysesgav-Fe. Ni. Co. Cu. P. S. Total. Sp. gr.89-60 8.80 0.67 0.12 0.32 0.01 99-52 7-.521B. H. B.Meteorites of Alfianello and Concepcion. By C. FRIEDHE131(Jahrb. f. Min., 1889, ii, Ref., 278-279; from Sitz-Ber. d. k. preuss.Akad. Wiss. Berlin, 13, 345--36i).-The analysis of the meteorite ofAlfianello gave 7.92 per cent. nickel-iron (I), 7.78 troilite, 0.60 chrome-iron, 37.38 olivine (11), 46.29 bronzite and augibe (111) :-r. Ir. m.Fe.. .... 88.84 SiO, ...... 34.92 53.86Ni.. .... 10.09 A1203 ..... - 5.76 co ..... 1.07 FeO ...... 13.79 10.55Mn .... 0.26 CaO ...... - 7-73MgO .... 51.26 21.68These results differ considerably from those previously published byMaissen, Plight, and v. Foullon.The meteorite that fell in 1880 between Nogay& and Concepcioni;I lli ABSTRACTS OF CHEMICAL PAPERS.was briefly described by Websky and DaubrBe. The completeanalysis gave the results shown under IV, and that of the portionsoluble in hydrochloric acid the results shown under V :-Si03 A1,03. Fe203. Cr203. MnO. CaO. MgO. Alkalis.kV. 27-22 2-35 30.64 0.38 0.09 2.56 19.24 0.18V. 26.67 2.24 30.42 - 2.25 18.79 0.12Ni. Co. Cu.Sn. Ignition. Insoluble.7-7 IV. 1-61 trace 14.47 -V. 1.46 0.18 - - 1.82With ether, 0.21 per cent. of a yellow bituminous substance wasextracted, which volatilised at 200". When ignited in a current ofoxygen t.he meteorite yielded carbonic anhydride (= 1.56 of carbon)and 14-03 per cent. of water. Treated with boiling water, 40 gramsof the meteorite yielded (in grams)-SOB. S,O2. EzO. Na20. MgO. CaO. c1.0.5001 0,0551 0.0059 0,0479 0.0750 0.1450 0*0009There was also contained in the meteorite 327 per cent. of sulphur,0.064 per cent. of phosphorus, 2.08 per cent. of sulphuric anhydride,and 0.034 per cent. of nitrogen. B. H. B

ISSN:0368-1769    

DOI:10.1039/CA8905800111

出版商:RSC    

年代:1890

数据来源: RSC