32 ABSTRACTS O F CHEMICAL PAPERS.Organic Chemistry.Etherification of Hydrobromic Acid. By A.'VILLIERS (Colt@rend., 90, 1488-1491) .-The extent to which hydrobromic acid,when treated with absolute alcohol and ft mixture of alcohol and water,undergoes etherification varies greatly with the temperature. Absolutealcohol, with different proportions of h ydrobromic acid, and heated atdifferent temperatures, gives the following results :-Percentage of acid etherified.+HBr + C2H60. AHBr + C2H60.At ordinary temperature, limit 658 days 68.0 52-57: 44" 9 7 79.6 59-97 7 100" 9 7 88.7 80.0The percentage of acid converted into ether is not so great as thatof the carbon acids, moreover, it is not fixed, but increases with thetemperature.These results show that combinations of alcohol with hydrobromicacid are formed analogous to hydrates,The presence of water decreases the extent of etherification, and inlarge quantity prevents any action from kaking place ; the quantity ofwater required to prevent the action increases with the temperature.This is probably due to the formation of hydrat.es of hydrobromic acid,and the dissociation of these hydrates as the temperature is raised.Hydrate of Methyl Iodide. By FORCRAND (Compt.rend., 90,1491--1493).-When a few drops of methyl iodide are placed in atube and a strip of filter-paper is introduced, crystals a.re deposited onthe edge of the paper after a short time. When all the iodide hasdisappeared from the glass a drop of water is seen at the end of eachcrystal, which increases as the crystal diminishes, and is finally absorbedby the filter-paper.During the formation of these crystals the tem-perature falls from about 16" to 15". By passing a current of moistair through the iodide large quantities of the crystals are formed, butwhen dry air is used, no crystals are formed, notwithstanding the tem-perature sinks to a greater extent. The crystals melt at -4", andtherefore cannot be ice. The analyses show them to have the com-L. T. 0'sORGANIC CHEMISTRY. 33position (CH,I),H,O.been obtained by Berthelot (Ann. Chim. Phys. [3], 66, 490).Similar compounds of carbon bisulphide haveL. T. 0's.Compound of Ether with Phosphorus Pentachloride. ByC. LIEBERMANN and L. LANDSHOFF (Ber., 13, 690-691).-A whitecrystalline compound is slowly deposited when absolute ether andfinely-powdered phosphorus pentachloride are well shaken together.The composition of the crystals could not be ascertained with accuracyon account of their rapid decomposition by moisture ; the analysesapproximately agree with the formula 2C4H,,0 + 3PC1, orP,C1,,CsH,*02.This substance is not a simple addition-product, since on addingwater to it ether is not set free, but phosphoric and ethylphosphoricacids are produced.On distillation, it splits up into phosphorus tri-chloride and a mixture of chlorinated organic derivatives. w. c. w.Action of Methyl Bromide and Methyl Iodide on Mono-methylamine. By E. DUVILLIER and A. BUISINE (Cowpi. rend., 90,1426-1427) .-When equal molecular proportions of methyl bromideand monomethylamine, dissolved in methyl alcohol, are heated at loo",the products of the reaction consist of unaltered monomethylamine,small quant<ities of di- and tri-methylamine, and large quantities oftetramethylammonium bromide.A similar result is obtained bytreating methylamine with inethyl iodide, the reaction being veryviolent. These reactions are similar to that of methyl nitrate onmonomethylamine, and they are all comparable with the action ofmethyl iodide on ammonia. L. 2'. 0,s.Amylamines from Inactive Amy1 Alcohol. By R. P. PLIXPTON(Compt. rend., 91, 433435).-A quantity of inactive amyl chloridewas prepared by Le Bel's process (Compt. rend., 77, 1021) from themixture of active and inactive alcohols resulting from fermentation.The chloride prepared in this way (b.p. 100.5") was without action onpolarised light when examined in a tube 1 meter long. Heated at 150"in a digester for one or two hours with a little more than its own weightof a saturated solution of ammonia in alcohol, it was converted intoa crystalline mass. From this the amylamine wits separated in theusual manner, and purified by repeated rectification over potash. Itboils at 96.5" under a pressure of 766 mm. (Wurtz, 95" ; Brazier andGosleth, 93"; Custer, 92-93') : a trace of moisture lowers the boilingpoint 2-3".Awylumine hydrochloride (inactive) is very soluble in hot alcohol,insoluble in ether. The platinochloride separates from hot water inplates.The aurochloride is obtained by slow evaporation in clino-rhombic crystals, resembling those of augite. It is soluble in alcoholand ether. The residue from the distillation of the amylamine con-tains inactive diamylamine and triamylamine. These were separatedas far as possible by fractional distillation, converted into hydrochlo-rides, and treated with ether, which dissolves triamylamine hydro-chloride only.Sp. gr. a t 22.5" = 0.7517.VOL. XL. 34 ABSTRACTS OF CHEMICAL PAPERS.Dz'antylnrnine, prepared from the hydrochloride purified by crystal-lisation from water, boils at 185" (Hofmann, 176" ; Custer. 187", forthe product obtained from nitrosodiamylamine). The liydrochloricleforms splendid plates, sparingly soluble in hot water. The plntinochlo-r i d e crpstallises well, is soluble in alcohol, but not in water.Theanrochloride forms needles soluble in alcohol, insoluble in water.It is anoleaginous liquid, insoluble in water. The h ydroch loride separatesfrom ether in slender prisms. It is very soluble in etlher and alcohol,less soluble in water; melts below 100". The platinoch,loride is in-soluble in water. The aurochloride crystallises from alcohol in needles,insoluble in water.1 kilo. of inactive amylarnine chloride gave 15-20 grams of amyl-amine, 150 grams of diamylamine, and about 130 grams of t'riamyl-amine. J. M. H. M.TriumyZumirLe boils a t 237" (uncorr.) (Hofmann, 256").Thiovaleraldehyde. By G. A. BARBAGLTA (Ber., 13, 1574j.-Schroeder (Ber., 4, 402) describes a solid thiovaleraldehyde obtainedby acting on valeraldehyde with aulphuretted hydrogen.Ry heatingsulphur and valeraldehyde at 250" in sealed tubes, a liquid valeralde-hyde, CsH,,S, has been obtained. It is a clear liquid of exceedinglydisagreeable odour, resembling that of garlic. It boils at 114-115" ;is insoluble in water, and easily miscible with alcohol or ether. Vale-rianic acid is formed during the reaction, which may be expressed asfollows :-4CsHloO + S, = 2CSH1,S + 2C5Hl002. P. P. B.Action of Chlorine on Di-isopropylketone. By G. A. BAR-BAGLIA and P. GUCCI (Ber., 13, 1570--1571).-iM0tz0chZor0-~li-i~0p~~p~/l-katone, C,HLIC1O, is obtained by acting on dry di-isopropylketone withdry chlorine ; it is a liquid having an odour resembling that of cam-phor and turpentine, and boils a t 141-142'.Dichloro-di-isopropylketone, C7HI2C1,0, is obtained by passing chlo-rine into the ketone and water; it is a liquid having an odour ofturpentine, and boils a t 175-1 76".T~ichZoro-di-isopropyllcetoiie, C7HIIC130, is obtained by the action ofchlorine on the vapours of di-isopropylketone ; it is a colourless liquid,which blackens on standing, and has a penetrating odour ; it boils a tThe further action of chlorine on di-isopropylketone is attendedwith the production of resinous bodies.Constitution of Lactones.By J. BREDT (Ber., 13, 748-749).-The author finds that isocaproic acid is converted, by oxidation withpotassium permanganate, into the lactone, C6Hlo02, identical with thelactone obtained by heating terebic acid, and infers that the lactonesought to be regarded as the phthalides of the fatty series.228-229".P. P.B.w. c. w.Propylacetal and Isobutylacetal. By J. GCRARD (Coinpt. rend.,91, 629-631).-Propylacetal is obtained by passing a current of non-inflammable phosphoretted hydrogen for several hours info a mixturORQANIC CHEMISTRY. 35of aldehyde and propylic alcohol. After the products have beenmashed with water and dried by contact with calcium chloride, thepropylacetal is isolated by fractional distillation, Itr is a colourlessliquid, b. p. 146-148" ; iiisoluble in water, but soluble in alcohol andi n ether; sp. gr. a t 22.5" = 0.825. It does not reduce ammoniacalsilver nitrate, and is not acted on by potassium, or by a boiling solu-tion of potash.Concentrated hydrochloric acid dissolves it withoutcoloration ; strong sulphuric acid carbonises it in the cold.Isobutylacetal is obtained in a similar manner, and its propertiesare similar to those of propylacetal ; b. p. 168-170" ; density a t 22"= 0.816. R. R.Dry Distillation of Calcium Isobutyrate. By G. A. BAR-BAOLIA and P. GUCCI ( B e y . , 13, 1571--1572).-Amongst the productsobtained by the distillation of calcium isobutyrate, beside di-isopro-pylketone, the authors have fonnd water, isobutgric acid, isobutyl-aldehyde (Popoff, Ber., 6, 125?5), methylpseudobutylketone (describedby Butlerow, Ber., 7 , 729), and a compound having the empiricalformula C,H,,O. This compound is a liquid having an odour re- u sembling that-of peppermint,'and boils at 150-152".P.P. B.Itaconic Anhydride. By R. ANSCH~~TZ and W. PETRI (Ber., 13,1539--1540).--lt has been shown in former communications (Ber.,10, 325 and 1881) that dibasic acids are easily converted into theiranhydrides by the action of acetic chloride, and that whilst fumaricacid is not attacked by this reagent, maleic acid is converted into itsanhydride (Ber., 12, 2281). Itaconic acid heated in the water-bathwith acetic cbloride is also converted into the anhydride.Itaconic anhydride, C5H4O3, crystallises from glacial acetic acid incolourless, transparent, compact columnar crystals ; it melts at 68" anddistils a t 139-140" under a pressure of SO mm. If distilled underthe ordinary pressure, it is converted into citraconic anhydride.Itaconic anhydride, mixed with glacial acetic acid or citraconic anhy-dride, remains liquid for a considerable length of time when cooledbelow its melting point.When dissolved in warm water, it is con-verted into itaconic acid. It crystallises from chloroform in clearprismatic crystals, belonging to the rhornbic system, which becomedull on exposure to the air. It resembles maleic anhydride in ap-pearance, and in its behaviour with acetic acid and chloroform.P. P. B.Decomposition of Citric Acid by Distillation. By R. ANSCH~TZ(Rer., 13, 1541-1543) .-When citric acid is distilled, the portioncoming over between 200-215" separates into two layers. If thesebe separated, and the heavier portion fractionated under reducedpressure (30 mm.), the following three fractions are obtained :-(l), 180"; (2), 120-130"; (3), 130-140".The author finds thatfractions (2) and (3) consist chiefly oE itaconic anhydride, whilst thefirst fraction consists of citraconic and itaconic anhydrides. Theformation of these anhydrides is explained as follows :-d 36 ABSTRACTS OF CHEMICAL PAPERS.COOH.CH,.C(OH). (COOH).CH,.COOH - H,O =COOH.CH2 C(CO0H) : CH.COOH.Aconitic acid.COOH.CH2.C(COOH) : CH.COOH - H2O =COOH. CH,.C-CO-C0OH.CH: C-CO CH-COHypothetical aconitic anhydride. Hypothetical aconitic anhydride.The first aconitic anhydride loses CO, and gives citraconic anhy-CH,.CO.dride, having the formula I >O ; whilst the second wouldCH,: C-COyield CO, and itaconie anhydride, to which the constitutional formulaCH3.C-C 0-CH-GOII >O is attributed.The author bas shown (preceding abstract) that itaconic anhy-dride is converted by heat into citraconic anhydride.Its formation inthe above case is accounted for by its being carried over by the currentof carbonic anhydride produced in the above decomposition.P. P. B.Mucobromic Acid. By H. B. HILL (Ber., 13, 734-739).-Bythe action of dry bromine (1 mol.) on mucobromic acid (2 mols.) at130-140°, a mixture of bromomucobromic and dibromosuccinic acidswith dibromomaleic anhydride is produced. The acid which is formedby dissolving the anhydride in water is identical with Kekul6’sdibromomaleic acid. The dibromo-fumaric acid which Limpricht andDelbriick (Annalen, 165, 293) obtained by heating mucobromic acidwith bromine and water is also identical with dibromomaleic acid.Mucobromic acid also yields dibromomaleic acid on oxidation withdilute nitric acid.w. c. w.Influence of Isomerism of Alcohols on the Formation ofEthereal Salts. By MENSCHUTKIN (An?. Chim. Phys. [5], 20, 289-361).-The author has endeavoured to throw light on the relationsof isomeric alcohols by a quantitative study of the formation ofethereal salts by heating the various alcohols witrh the same acid. Ona future occasion he proposes to extend the research by heating thesame alcohol with various acids. The present paper has reference tothe reaction of acetic acid with primary, secondary, and tertiaryalcohols and with phenols, a short account of which has alreadyappeared (this Journal, 1879; Abstr., 36, 214, and 215). Similarexperiments were carried out by Berthelot and PQan de St.Gillesin 1862 and 1863, but at that time the isomeric alcohols were littleknown.M&od of Bxperiment. -A certain quantity of the alcohol wasweighed out, and the theoretical equivalent of acetic acid added froma dropping pipette. About 0.3 gram of the mixture was then weigheORGANIC CHEMISTRY, 37carefully into a tube of 5 mm. diameter, of such a, length that themixture occupied half t o two-thirds of the volume. The tube wasscaled and suspended in a glycerol-bath, kept constant a t 1543. A tthe end of a certain number of hours the tubes were withdrawn fromthe bath and broken into stoppered flasks, containing about 50 C.C.ofalcohol. A few drops of an alcoholic solution of rosolic acid wereadded, and the free acetic acid titrated with standard baryta-water.The observations were made with a view to obtaining two sets ofnumbers-(1) the initial rate of ethertjication, expressed by the per-centage of acid found combined with the alcohol a t the end of thefirst hour; and (2) the limit of etheriJcation, expressed by the per-centage of acid converted into an acetate when etherification ceased.The error of experiment for the former determination areraged0.4 per cent. from themean.Acetic Ethers of the Primary Alcohols.-The alcohols, first purified asfar as possible, were in all cases dried over caustic baryta.The fol-lowing mode of procedure was adopted, as it was the only one thatafforded a guarantee of the completeness of the desiccation :-Thewhole quantity of purified alcohol was dried over baryta, distilled, andan etherification assay made ; the remainder was treated a second timewith baryta and distilled, and another etherification essay made. Ifthe second really agreed with the first, the experiments were assumedto be correct; if not, the drying and testing were repeated until twosuccessive series of results showed no appreciable difference. Theresults obtained in this way have already been given (Zoc. cit.,p. 36).With regard to the limit of etherificntion, Berthelot and St. Gillesconcluded that “ the equivalent proportions of acid and alcohol thatenter into combination are almost independent of the special nature ofthe acid or alcohol.” The results obtained by the author are opposedto this conclusion, and show on the other hand that (1) methyl alcoholis distinguished from all other alcohols by its high limit; (2) for theother members of the CnH2,+,.H0 series, the limit increases with in-crease of molecular weight, but is not influenced by isomerism;(3) alcohols of the unsaturated series have a considerably lower limitthan those OF the C,H2n+l.H0 series; the limit of ally1 alcohol, forexample, being 7.5 per cent.less than that of propyl alcohol.Acetic Eth ens of the SecorLdnry McohoZs.-The author’s mean resultsmay be exhibited briefly in the following table, similar to that for tlheprimary alcohols :-1 per cent.from the mean ; for the latter,Alcohol. Initial rate.Dimethylcarbinol (isopropyl alcohol) . 26.53E thylmethylcarbinol (secondary butylalcohol) ........................ 22.56Isopropylmethylcarbinol.. .......... 18.95Ethyl vinyl carbinol .............. 14-85Diethylcarbinol .................... 16-93Hexylmethylcarbinol (cnpryl alcohol). 21.19Diallycarbinol .................... 10.31Limit.60.5250.2859.3158.66630352-2550.138 ABSTRACTS OF CHEMTCAL PAPERS.Both the initial rate and the limit of etherification are thus muchlower for secondary than for primary alcohols. Comparing the formeramongst themselves, the highest initial rate is that of dimethylcar-binol ; whilst the two other alcohols of similar structure, ethylmethyl-carbinol and hexylmethylcnrbinol, have a lower rate almost identicalin the two cases.The influence of isomerism in lowering the rate isshown by comparing isopropylmethylcarbinol (18.95) with diethyl-carbinol (16.93). The relative initial rate is lowered by increase ofmolecular weight and by isomerism, as the following numbers show :-Dimethylcarbinol, 43.85 ; ethylmethylcarbinol, 38.10 ; hexylmethyl-carbinol, 34.16 ; isopropylmethylcarbinol, 31.95 ; diethylcarbinol, 28-86,The absolute and relative rates are also lower for alcohols containingunsaturated radicles than for those containing only CnB2n+l radicles,but this difference is not so great as it is with the primary alcohols.The limit of etherification of secondary alcohols does not show anincrease with increase of molecular weight, but is considerably lower€or the non-saturated than for the saturated series.Acetic Ethers of Tertiary AZcohoZs.-The reaction of tertiary alcoholswith acetic acid differs from that of primary and secondary alcohols,being generally complicated by dissociation of the compound etherinto olefine and acid, and the re-formation of the tertiary alcohol bycombination of the olefine with water in presence of acid ; and perhapscombination of the olefine with acid to form the ethereal salt.AHthese reactions are limited. After heating the mixture for a certaintime, equilibrium is established, which, as the formation of the olefineis a; case of dissociation, depends on the temperature.1.Formation of the Cornpound Ether with Elimination of Wafer.-On account of the partial dissociation of the ethereal salt into hydro-carbon and acid, the limit of etherification cannot be ascertained withaccuracy; but it is very much lower than in the case of pyimary orsecondary alcohols, and is attained in a comparatively short time.The quantity of acid etherified a t the end of 24 hours, compared withthe mean limit and the initial rate (absolute) of etherification, havealready been given (Zoc. cit., p. 216).2. Decomposition of the Ethereal Salt by the Water formed in theReaction.-In consequence of the relatively larger quantity of waterformed during the etherification of tertiary alcohols, this reactionproceeds to a much greater extent than in the case of primary andsecondary alcohols.3.Dissociation of the Compound Ether into Olefine und Acid.-Thisreaction occurs in all the cases studied, and reaches a limit dependenton the temperature employed. Equations representing the equilibriumof the system formed by a molecular mixture of trimethylcarbinol andacetic acid a t 155" have been given (Zoc. cit., p. 216).The author gives in detail the analytical data from which theseequations are deduced. The polymerisation of the olefines under theinfluence of sulphuric acid is explained by the author as the dissocia-tion of sulphovinic ethers of the tertiary alcohols, which it is knownare produced from these hydrocarbons by fixation of water.Acetic Ethers of PhenoEs.-The results of experiments with phenol,paracresol, thymol, and a-naphthol have been given (Zoc.cit., p. 217)ORGANIC CHEMISTRY. 39They show a striking resemblance in this respect t o tertiary alCohol6,with which the author suggests they should be classed ; their similarityin structure is shown by the position of the hydroxyl group, this beingin both cases attached to a carbon atom, whose remaining affinitiesare satisfied by carbon atoms. The continuity between the aromaticand other series is again shown by these experiments. No dissociationof the acetic ethers of this class was observed a t the temperature(155") employed. The general conclusions to be deduced from thewhole of the anthor's experiments have been pointed out in theremarks on each class.J. M. H. M.Influence of Isomerism of Monobasic Saturated Acids onEtherification. Ey N. MENSCHUTKIN (Bull. SOC. Chim. [3], 34, 87-388).-The relative initial velocity (at the end of one hour a t 155" C.)and limit of etherification of primary, secondary, and tertiary mono-basic fatty acids are compared :-Primary acids. Initial velocity. Limit.Formic acid.. .......... 61-69 64.23 (at 100" C.)Normal butyric acid.. ... 33.25 69.52 ,,Normal caproic acid.. ... 33.08 69.81 ,.Acetic acid ............ 44.36 67.38 (at 155 C.)Propionic acid ......... 41.18 68.70 ,,Normal caprylic acid .... 30.86 70.87 ,,Isobutyric acid ......... 29.03 69.51 ,,Trimethyl-acetic acid.. .. 8.25 72.65 ,,Secondary acids.Methylethyl acetic acid. . 21.50 73.71 ,,Tertiary acids.Dimethylethyl-acetic acid 3.45 74.15 ,,V.H. V.Oxidation-products of Dimethyluric Acid. By C. F. MABERYand H. B. HILL (Ber., 13, 73'3-740) .-Methylalloxan and methylcar-bamide are formed by the oxidation of dimethyluric acid with nitricacid or with hydrochloric acid and potassium chlorate. In the lattercase a small quantity of a compound having the composition C6H,NzOsis produced. This substance crystallises i n prisms (m. p. 160') whichare sparingly soluble in cold water.Methylparabanic acid (m. p. 149") is formed from dimethyluricConversion of Terebenthene into Cymene. By BRU$RE(Conzpt. rend., 90,1428-14-29).-When terebenthene is dropped slowlyinto boiling sulphuric acid mixed with 2 mols. of water, a mixture ofcymene with unaltered terebenthene and water distils over.This an-altered terebenthene is polymerised by agitation with concentratedsulphuric acid and the cymene purified bey a final distillation. Thewater is separated out from the product, the sulphurous acid neutralisedwith sodium carbonate, and the remaining liquid dried and fraction-It appears to act as an acid.acid by long-continued boiling with nitric acid. w. c. w40 ABSTRACTS OF CHEMICAL PAPERS.ally distilled. Unsuccessful attempts were made to substitute otherbodies for sulphuric acid, which is very violent in its action, but onheating 1 mol. of terebenthene with 1 mol. of ethyl sulphate a t 120"for 10-15 hours, the mixture assumes a violet colour, and containscymene, et,her, and sulphurous acid.By allowing terebenthene andethyl sulphate to remain in contact for some time at loo', the mixturegradually becomes homogeneous. The liquid produced is heavier thanwater, is stable at the ordinary temperature, of a lemon-yellow colour,and peculiar odour. When cooled to -20" the mixture separates intotwo layers, one of terebenthene, the other of ethyl sulphate. The homo-geneous solution appears to be a very unstable combination of tereben-thene and ethyl sulphate, ~loH16.S04(C2H5)2, which readily splits upinto cymene and ether-Remarks on Kelbe's Discovery of a New Cymene in LightResin Oil (Resin Spirit). By H. E. ARMSTRONG and W. A. TILDEN( B e y . , 13, 1548--1549).-The authors draw attention to the fact thatthey have been engaged for some time in the investigation of "resinspirit'," and have already published some account of their results (thisJournal, Trans., 1879, 275, and Ber., 12, 176).Whilst acknowledgingthe right of Kelbe to continue the investigation of the new hydrocarbon,the authors wish to reserve the further study of resin spirit.P. P. B.Synthesis of Hexmethylbenzene and of Mellitic Acid. ByC. FRIEDNL and J. M. CRAFTS ( C o q ~ t . rend., 91, 257-260).-1n aprevious paper (Compt. reid., 84, 1394), the authors announced theformation of tetramethylbenzene by passing a current of methyl chlo-ride through a warm mixture of benzene with aluminium chloride ; at,the same time they suspected the presence of pentamethylbenzene andhexmethylbenzene amongst the products.By operating with tolueneinstead of benzene they have succeeded in preparing these two com-pounds in considerable quantity.On purification by fractional distillation and pressure of the solidproduct, three distinct compounds are obtained, boiling constantly at190", 225", and 264", and melting a t 110", 50", and 164' respectively.The first of these bodies is tetramethylbenzene, the second penta-methylbenzene, and the third hexmethylbenzene. The vapour-den-sities of the two latter are 5.27, 5.73 (experiment), correspondingwith 5.12 and 5.61 (theory). Attempts were also made to purifythese substances by fractional crystallisation from alcohol and by theaction of strong sulphuric acid, which attacks the less methylatedbenzene hydrocarbon first.Neit'her of these methods was successful.By oxidising hexmethylbenzene with dilute nitric acid or with nitricacid and potassium permanganate, a mixture of acids was obtained,amongst which there appenred to be a small quantity of mellitic acid.When potassium permanganate alone was used for the oxidation, andthe action allowed to spread over several months, a much larger quan-tity of meilitic acid (as potassium mellitate) was obtained, whicORGANIC CHEMISTRY. 41was identified by its reactions with salts of barium, calcium, zinc,copper, silver, and magnesium, and by analysis of the silver salt.J. M. H. M.Paraditolylnitrosarnine. By A. LEHNE (Ber., 13,1544--1545) .-Gerber (Dissertation, Zurich, 1874) and J. Cosack (Bey., 13,1092) havealready obtained this body.The author prepares it by heating dito-lylamine in alcohol with hydrochloric acid and then adding a solutionof sodium nitrite. It is insoluble in water, but soluble in ether, ben-zene, and light petroleum, and sparingly so in alcohol. I t crystal-lises from light petroleum in golden-yellow rhombic crystals. Bro-mine acts on this nitrosamine, forming tetrabromditolylamine,(C7H5Brz),NH, which me1t.s at 162". It has been described by Gerber(Zoc. cit.).Heznit~-oditoZyZainine, Cl4H8(NOZ),NH, is prepared by the carefulnitration of paraditolylnitrosamine, it may also be obtained from para-ditolylamine. It crystallises from glacial acetic acid in yellow crys-tals, which melt a t 258O, and is sparingly soluble in the ordinarysolvents.Its acetic acid solution on reduction with zinc-dust gives adeep-red coloration. Hexnitroditolylamine corresponds with thenitro-derivative of diphenylamine, used as n dye under the name of" tiurantia." P. P. B.It may also be obtained directly from ditolylamine.Paraditolylhydrazine. By A. LEHNE (Ber., 13, 1546-1 547).-This compound is prepared by the reduction of ditolylnitrosaminewith zinc and acetic acid in a mariner analogous to Fischer's prepara-tion of diphenylhydrazine (Hydrazinverbiiidungen ; Miinchen).Fai.aditoZyZhydrazine, (C,H,),N,H,, crystallises from benzene incolourless leaflets, melting at 171-172". It is easily soluble in alco-hol and benzene, sparingly in ether, and almost -insoluble in lightpetroleum.When dry it does not change on exposure to the air, itschloroform solution, however, becomes blue under these circumstances.T h e hydrocldoride, ( C7H7),N2H2.HC1, is an unstable salt ; it crystal-lises in slender colourless needles. It is easily soluble in water, and itssolution on cooling decomposes into basic salt and free acid, on warm-ing the salt is again formed.dfonob enzoy ZdituZ y Zhydrazine, ( C7H,) ,N,H. C,H,CO, is obtained byacting on a solution of the base in benzene with benzoic chloride. Itcrjstallises in slender colourless needles, melting at 186.5". Its solutionin benzene becomes dark green on exposure to the air. Nitrous acidconverts ditolylhydrazine into ditolylnitrosamine. Ditolylhydrazineis converted by bromine into tetrabromoditolylamine, and by nitricacid into hexnitroditolylamine.Oxidising agents, such as ferricchloride or mercuric oxide, convert it into ditolylamine.P. P. B.Azo-derivatives. By J. H. STKBRINS (Ber., 13, 715-718).-Azobenzenehydroxybenzo~c acid, PhN,.CsH3(OH) .COOH, is deposited inorange-coloured needles from an alkaline mixture of diazobenzenenitrate and salicylic acid. The crystals are soluble in alcohol andinsoluble in water. A sulphonic acid is obtained by the action ofsulphuric acid42 ABSTRACTS OF CHEMICAL PAPERS.Phloroglucin~arazobeizzen esuZp3hoiiic mid, CRH4( HSO,) .N2. C6H2( OH),,crystallises in yellow plates, having a metallic lustre. The sodiumsalt is prepared by mixing sodium paradiazobenzenesulphonnte withan alkaline solution of phloroglncin. The precipitated salt is purifiedby solution in hot water and rep~ecipitntion by sodium chloride.Axobeizze,iediu?n.idotoluene, C6H5.B2.C6H2Me(NH2)2, is obtained inyellow needles soluble in alcohol, by treating with ammonia the pro-duct of the action of a-toluylenediamine on diazobenzene.This baseforms a hydrochloride, crystallising in orange-coloured needles, whichdissolve freely in water. With an excess of hydrochloric acid, anunstable scarlet coloured crystalline compound is produced. Thehydrochloride also forms crystalline double salts with metallic chlo-rides.Uinm.):doazonc7phthaZene, CloH7.N2.CloH5(NH2)2, prepared from diazo-naphthalene nitrate and diamidonaphthalene, unites with acids to formbrown coloured salts.A mbenmnecresoZsuZp honk acid, CsH5.N2.CeH2Me (H SO,). OH, obtainedby the action of diazobenzene nitrate on an alkaline solution of cresol-sulphonic acid, forms brown, needle-shaped crystals, having a strongmetallic lustre. It dissolves in alcohol, forming a solution whichdyes silk or wool yellow. w. c. w.Action of Hydrochloric Acid on Organic Amides (Preli-minary). By L. SCHULERUD (J. pr. Chem. [el, 22, 288-290).-When amidobenzoic acid is heated in a stream of dry hydrochloric acidgas, ammonium chloride sublimes, and a solid amorphous residueremains in the retort. This body is nnactled on by the ordinarysolvents, but is soluble in concentrated sulphuric acid, and is preci-It does not melt when[eated, but chars and decomposes. Analysis gave no satisfactoryresult.When heaked with hydrochloric acid gas, salicylamide splits upinto disalicylamide and ammonia.A part of the amide sublimesunaltered, water and phenol are also evolved. Disalicylamide is ayellowish-white, asbestos-like body, consisting of small, woolly needles,insoluble in water, but tolerably soluble in hot alcohol and acetic acid.The alcoholic solution gives a yellowish-red to blood-red precipitatewith ferric chloride. The diamide (m. p. 197-199") dissolves inalkalis with a yellow colour, and forms compounds with metals. Thesilver compound, (C,H,( OH). CO),NAg, is crystalline, and of a yellowcolour.Salicylamide absorbs hydrochloric acid slowly at ordinary tempera-tures, with formation of a compound, from which a stream of dry airgradually expels the gas in the cold.The gas is also expelled bywarming the compound either alone or with water or alcohol. Whenhydrochloric acid is passed into a solution of salicylamide in dry ether,brilliant acicular crjstals are formed, consisting of 2C6H4( OH).CONB, + HCl. Hjdroxybenzamide is obtained by leaving the ether ofhydroxybenzoic acid in contact with strong ammonia. It forms colour-less thin plates (m. p. 167" uncorr.), which dissolve readily in hotwater and in alcohol. G. T. Aitated from the solution unchanged by waterORGANIC CHEMISTRY. 43Alphatoluylamide. By C. L. REIXER (Bey., 13, 741).-In thepreparation of benzyl cyanide by the action of potassium cyanide onbenzyl chloride, a-toluylamide is obtained as a bye-product.Thetoluylamide is found in the retort,, after the benzyl cyanide has beendistilled over i n a current of steam. w. c. w.Phenyl- and Tolyl-thiocarbimide Glycollide. By M. VOLTZKOW(Rer., 13, 1579--1580).-The author describes some homologues ofphenylt8hiocarbimide-glycollide (this Journal, 38, 659), which havebeen obtained in a similar manner.>CO, obtainedfrom paratolplthiocarbimide and monochloracetic acid ; it crystallisesfrom hot wat>er in small leaflets or needles (m. p. 162"), easily solublein the ordinary solvents. It is decomposed by boiling with baryta-water in a manner analogous to the phenyl-derivative, yielding para-toluidine, barium carbonate, and barium thioglycollate.Orthotolylthiocarbimide-glyco~licle is prepared in a manner similar tothe para-compound ; it crystallises in white, shining needles (m.p. 120°),and is easily soluble in the ordinary solvent's. b y boiling with baryta-water, it is resolved into orthotohidine, carbonic anhydride and thio-glycollic acid.When phenyl- or tolyl-thiocarbimide is heated with monochloraceticacid alone, then compounds are formed having the formule CsHsNOC1and C9HIoNOCl. The former is obtained from phenylthiocarbimide, thelatter from to 1 y 1 thiocarbimid e.PnratoZylthiocarbimide-glycollide, C,H,.N C<--,- S.CH,P. P. B.Guanylthiocarbamide and some Guanylguanidines. By E.RAMBERGER (Bey., 13,1580-1384) .-The author regards Rathke's thio-dicyandiamine (Ber., 11, %7), guanylthiocarbamide, and the compounddescribed by the same author (this Journal, 34, 804)) having theformula NHPti.CS.NPh.C(NH,) : NHPh, as a triphenylated panyl-thiocarbamide. The following derivatives of this guanylthiocarbamidehave been obtained :-GuaiLyl~he,L2llthiocarbamida, CsSN,H,,, prepared by acting upon guani-dine carbonate with phenylthi ocarbimide, crystallises in white, shining,strongly refractive, monoclinic crystals (m.p. 175-1 76"). It dissolvesin alcohol, yielding an alkaline solution. It is a base, and is easilysoluble in acids. Its hydrochloride, C,SN,H,,.HCl, cryst>allises in long3silky needles, and is more easily soluble in alcohol than water; onwarming, its aqueous solution evolves sulphuretted hydrogen. Thissolution gives a yellow precipitate with platinum chloride, and a dirtyviolet precipitate with copper sulpiiate, becoming black on boiling,owing to its conversion into sulphide.The picrute, C,SN,H,,.C,H,(NO,),OH, crystallises in yellow needles.The oauZl_rte crystallises in white, shining scales.The mdphate cryvs-tallises in shining leaflets ; its aqueous solution decomposes whenwarmed, forming a yellow powder, which is soluble in alcohol. Byheating with hydrochloric acid a t 185", the base is resolved intocarbonic anhydride, sulphuretted hydrogen, aniline, and perhap44 ABSTRACTS OF CHEMICAL PAPERS.guanidine, and may therefore be represented by either of the twofollowing formulae :-NHPh NHPh"<NH.C(NH,) : NH Or "<N: C(NH,)iPhenyZguanyZguanidine, NH C(NHPh).NH.C(NH,) : NH.Thenitrat.e of this base is obtained by treating guanylphenylthiocarbamidewith ammoniacal silver nitrate ; it has the composition C9H6H1203, andmelts at 208-209". It is easilysoluble in alcohol and water, and thebase is precipitated from its aqueous solutions in a flocculent state bysoda, but becomes crystalline on standing.When guanylphenylthiocarbamide is treated with an alcoholic solutionof mercuric chloride, the hydrochloride C,N5Hi.HC1 is obtained ; andthe sulphate is obtained by treatment with silver sulphate. Whentreated with moist silver oxide, the hydrochloride yields the free baseCsH,H,,, which crystallises in white leaflets ; it is easily soluble in alco-hol and in water, and is precipitated from its aqueous solutions by soda.DipiLenylguamylgunnid~ne, N Ph C(NHPh).NH.C(NH,) : NH.Thenitmte of this base is obtained by treating guanylphenylthiocarbamidewith silver nitrate in presence of aniline. It crystallises from water inshining white needles united in groups (m. p. 231'). The free baseis precipitable on adding soda to the aqueous solution of the nitrate.The base is unchanged by exposure to the air, and is more easily solublein alcohol than water, forming an alkaline solution. P. P. €3.Constitution of the Thiourethanes. By C. LIEBERMANN (Bsr., 13, '682-689) .-The acid nature of phenyllhiouretlzane, PhN : C (SH) .OEt,is shown by the fact that this substance dissolves in dilute solutions ofpotash, soda, or baryta, and is reprecipitated from these solutions onthe addition of an acid.Phenylthiourethane forms metallic compounds,which are obtained as crystalline precipitates when certain metallicsalts are added to its alcoholic solution, e.g., PhNC (Spb).OEt +H20; PhN : C(SAg).OEt, and PhN : C(SHgCl.HCI).OEt. By theaction of methyl and ethyl iodides on the silver salt at loo', methyl andethylderivatives have been prepared. PhN : C(SMe).OEt is an oilyliquid (b. p. 260-265'), soluble in strong hydrochloric axid, but repre-cipitated on dilution with water. The hydrochloric acid solution giveswith platinum chloride an orange-coloured crystalline precipitate,which is sparingly soluble in cold alcohol.EtZiy~7~enylthiourethal.Le, PhN : C( SEt).OEt, when freshly prepared,is an oily liquid (b. p. 275"), which slowly solidifies to a crystallinemass (m.p. 30"). The platinochloride resembles that of the precedingcompound.The ethyl compound is decomposed by the action of dilute sulphuricacid at 200" into aniline and ethyl thiocarbonate, according to the fol-lowing equation :-PhN:C(SEt).OEt + H,O = Ph.NH2 + EtO.CO.SEt.When phenylthiourethane is heated with dilute sulphuric acid, itsplits up into aniline, alcohol, carbonic oxide, and sulphuretted hydro-gen.PhN:C(SH).OEt f 2H20 = Ph.NH, + CO, + HZS + EtHOORGANIC CHEBIlSTRY. 45On boiling a mixture of methylphenyl thiourethane, aniline, andalcohol in a flask connected with an upright condenser, methylmer-captan and diphenylcarbamide are produced.PhN: C(SMe).OEt + PhNH, + H20 = EtHO $- MeHS +I f alcoholic ammonia is substitmuted for aniline in the precedingexperiment, miline and monophenylguanidine will be produced.From the preceding reactions the author concludes that thioure-thanes have the constitution R.N : C<oE.The formation of phenyl-thiocarbamidoglycollide by the action of monochloracetic acid onphenylthiourethane, must be represented as follows :-NHPh.CO.NHPh.SMPhN: C(SH).OEt + ClCH,.COOH = HCl + EtHO +PhN: C < s * ~ ~ > C O . -w. c. w.Para- and Ortho-tolylthiourethanes. By C. LIEBERNANNand S. NATANSON (Ber., 13, 1575--1579).-1n favour of the viewsalready advanced by one of the authors (Bey., 13, 682), as to the con-stitution of phenylthiourethane, the formation of phenylurethanesulphide, NPh : C(OEt).S2.C(OEt) : NPh, is cited.This compoundis obtained by decomposing silver phenylthiourethane,with iodine. It crystallises from alcohol in colourless rhombic prisms,and melts at 102".ParatoZylthioz.crethane, C,H,N C (OEt) .SH, is prepared in a, mannersimilar to the plienyl derivative, viz., by heating paratolylthiocarba-mide with alcohol a t 130". It forms colourless transparent crystals,melting at 87".Ortlzotoly Ithiourethane is prepared from the orthotolylthiocarbamide.It is an oil.Both the tolylthiourethanes are soluble in dilute alkalis, and are re-precipit'ated by acids. Ammoniacal silver nitrate precipitates the silversalts from alcoholic solutions of the tolylthiaurethanes. The methyl andethyl derivatives of these tolylthiourethanes have been obtained by de-composing the silver salts with methyl and ethyl iodides respectively,These derivatives may also be obtained by boiling solutions of thetolylthiourethanes in caustic alkalis with methyl or ethyl iodide.The methyl and ethyl salts are oils, which distil above 250" withoutdecomposition.The ethyl derivative of paratolylthiourethane yields mercaptanwhen heated with ammonia ak 150"; with dilute sulphuric acid a tPhN : C(OEt).SAg,200", paratoluidine sulphate and ethyl.thiocarbonate are formed.P. P. B.Introduction of the Hydroxyl Group by Direct Oxidation,By R. MEYER and A. BAUR (Ber., 13, 1495--1500).--In continuingtheir investigatsions (Ber., 11, 1283, 1787, 1790, 2172; and 12, 1071,2238), the authors have submitted the potassium cymenesulphonat46 ABSTRACTS OF CHEhITCAL PAPERS.(cymene from camphor) to the action of potassium permanganafe. Inthis way potassium hydroxypropylsulphobeiizoate is formed, thus :-C6H,MePr.So3H + 0 4 = CooH.C,H,(Hso,).C,H,(OH).The potassium sult, CloHl,,S06Kz + 2H,O, crystallises from absolutealcohol in beautiful shining needles, but is deposited in rhombic tableson slow evaporation of the alcoholic solution; and from its aqueous so-lution in large rhombic crystals: By evaporation with hydrochloricacid, the potassium salt is converted into an acid which combinesdirectly with bromine, and probably has the formulaCOO H.C6H3 ( S O,H) . C3H5.That the hydroxypropylsnlphobenzoic acid does not contain thehydroxyl in the ‘‘nucleus’’ is shown by its solution yielding nocoloration with ferric chloride.The introduction of a hydroxyl groupin this cymene is contrary to the experience that such action takesplace only in presence of the tertiary group (CH). The authorthinks this is explained by the inter-molecular changes which haveoften been observed in cymene derivatives, a change resultirig in theconversion of normal propyl into isopropyl. This oxidation of themethyl group is similar to what takes place in the animal organism(Gerichten, Rer., 11, 369), and also to the oxidat’ion of chlorocymene(Claus and Wimmel, Ber., 13, 9@2), and dibromocymene.Cymenesulphonic acid when oxidised by nitric acid yields para-tolylsulphonic acid, C6H&fe(SO,H).COOH + 2H&, crystallising inneedles, which are not hygroscopic.The results from the study ofthe salts of this acid agree with those of Fischli (Ber., 12, 615), savethat the authors find the following formulze for the barium and leadsalts, viz., C8H6S05Ba + 4Hz0 and CsH&305Pb + 3+H20. The melt-ing point of the amide was found to be 218’.Oxidation of cinnamic acid by potassium permanganate yieldschiefly henzaldehy de and benzoic acid, whilst mandelic acid yieldsbenzoylformic acid, C6H5.C0.COOH. Hunaeus and Zincke (Bey., 10,1489) obtained the same result by oxidising mandelic acid with nitricacid. P. P. B.A Fourth Mononitrophenol. By F. FITTICA (Bey., 13, 711-715) .-Liquid mononitrophenol is best prepared by slowly droppingstrong sulphuric acid into a mixture of phenol, 10 grams ; alcohol, 10 ;ether, 10 ; and 8 grams of nitric acid (sp.gr. 1.4). As soon as theliquid begins to boil, it is poured into water. A current of air isblown through the layer of liquid floating on the water, in order toexpel the ether, and t,he heavy oil which separates out is well washedwith water and distilled in a current of steam. Ether first passesover, and then an oily liquid, the greater portion of which solidifiesafter being in contact with calcium chloride for some days. Thefraction which still remains liquid consists of a mixture of orthonitro-phenol and the new nitro-phenol. The orthonitrophenol is partly re-moved by distillation in steam; the portion which does not solidifyi y dissolved in dilute soda, and the sparingly soluble orthonitrophenolsalt separated from the new nitrophenate by crystallisation.ThORGANIC CHEMISTRY. 47fourth mononitrophenol is liquid at the ordinary temperature, but it,solidifies at 0" to a pale yellow crystalline mass (m. p. 34"). It yieldsan amidophenol crystallising in needles (m. p. 150°), which dissolvereadily in water. w. c. w.New Nitrophenols. By F. FITTICA (Ber., 13, 153.5-1538).-The boiling point of the fourth nitrophenol, already described by theauthor (preceding abstract), cannot be determined, as it is changed atthis temperature into orthonitrophenol. By reducing the compound ofnitrophenol and phmol (Zoc. &.) with tin and hydrochloric acid, orby reducing the fourih nit'rophenol under special conditions with tinand hydrochloric acid, a fourth amidophenol is obtained.I t crystal-lises from alcohol in needles (m. p. 151"). The hydrochloride ofthis amidophenol crystallises in greyish-white needles, which sublimeat 230" with partial decomposition. The sulphate is a white powder,consisting of small crystalline needles, soluble in water.A fifth nitrophenol is obtained by treating the tarry residue obtainedafter separation of orthonitrophenol from the para-compound withsoda, By this means a solid sodium salt is-obtained, which is pressedand treated with acid, and the oil obtained submitted to the action ofalkali and acid again. The oil obtained solidifies partially, and bycrystallisation from ether the new nitrophenol is obtained in yellowneedles (m.p. 105-106"). It yields an amidophenol, melting at150".In concluding, the author replies to the criticism of Claus (Ser.,13, 891) on the author's former communication (Zoc. cit.).P. P. B.Action of Bromine on Benzyl Cyanide and on PhenylaceticAcid at High Temperatures. By C. L. REIMER (Ber., 13, 742-748) .--DicyanostiZberbe, CN.PhC CPh.CN, is formed, together with asmall quantity of benzoic acid, when bromine is allowed to dropslowly into a flask containing benzyl cyanide at a temperatnre of 170".The product, after purification by washing with water, and solationin a mixture of alcohol and chloroform, is moistened with ether, andpressed between bibulous p p e r to remove resinous impurities. Thesolution of the residue in warm benzene deposits on cooling glisteningcrystalline plates (m.p. 1 5 8 O ) , which are soluble in chloroform, ben-zene, carbon bisulphide, glacial acetic acid, and in hot, alcohol.Dicyanostilbene is decomposed by alcoholic potash, with evolution ofammonia. If hvdrochloric acid is added to the solution after thealcohol has bein expelled by boiling, diphenylfurnaric anhydride,PhC : CPh/ \ is precipitated. This substance is deposited from alcohol oc . o . co'in pale yellow needles, and from carbon bisulphide in prisms. Itmelts at 155", and sublimes without decomposition. The free acidcorresponding to the anhydride cannot be isolated, but several of itssalts hare been prepared. The potassium salt forms colourless needles,which dissolve freely in water; the barium salt is crystalline, andsparingly soluble.Neutral silver diphenylf umarate, C16H,,Ag20a, i48 ABSTRACTS OF CHEMICAL PAPERS.amorphous ; the acid salt, C16H11Ag04, is crystalline. Both are verysparingly soluble.Bthyl diphenylfumarate crystallises in prisms (m. p. 54")) whichdissolve freely in chloroform and carbon bisulphide.By the action of ammonia on diphenylfumaric anhydride at 180",diphenylfunzarimide, C16H1002.NH2, is obtained in yellow needle-shapedcrystals, insoluble in water, but soluble in alcohol. This substancemelts a t 213", and sublimes without decomposition a t a higher tem-perature. On reduction with zinc and hydrochloric acid, dicyano-stil-bene yields a crystalline compound (m. p. 208"), having the composi-tion CI6H14N2.Diphenylfumaric anhydride and benzoic acid are also producedwhen the product of the action of bromine on phenylncetic acid a t230' is treat)ed with alcoholic potash. w.c. w.Action of Ethyl Chlorocarbonate on Phenols. By G. BENDER(Ber.? 13, 696--703).-The author has examined the products of theaction of ethyl chlorocarbonate on potassium salts of the differentphenols.Under these conditions quinol yields diethylic phenyldiox ycarbonate,C,H,(O.COOEt),. This compound is deposited from an alcoholicsolution in colourless needles (m. p. lolo), soluble in ether, but in-soluble in water.ResorcinoL-When ethyl chlorocarbonate acts on resorcinol, carbonicoxide escapes, and mono- and diethyl-resorcinol are formed.Catechol (pyrocatechin) gives a crystalline compound (m.p. 1 IS"),haying the composition C7Hi03, which yields diorthotolylcarbamidewhen boiled with orthotoluidine.From pyrogallol an ethyl salt having the composition c6H3 (O),iC.OEtis obtained. This substance melts a t 105", and distils between 250"and 280" with partial decomposition. It is deposited from an alcoholicsolution in pearly scales. Ortho-, meta-, and para-cresol yield threeliquid isomeric ethylic tolylcarbonates, CJ&.MeO.COOEt, which boilrespectively a t 236", 246") and 245".From orcinol, the compound C16H120a is obtained in yellow needles,which are sparingly soluble in alcohol, and melt with decompositionat 195".P-Napht7mZ yields a white amorphous mass, having the composition(CloH70)2C(OEt),.It boils at 298-301".a-NaphthoZ forms ethyl-naphthol carbonate, CloH70.COOEt, whichcrystallises in colourless rhombic plates (m. p. 31'). This body is de-composed by boiling ; alcohol distils over, carbonic anhydride escapes,and yellow needle-shaped crystals are deposited (m. p. 240°), of the w. c. IT.Methylenecaffeic and Methylenehomocaffeic Acids and theirBy C. LORENZ (Rer., 13, 756- 761).-Met7~ylenecaffeiccomposition ( CloH6)2C02.Derivatives.acid or ~ e t ~ y l e l z e d i o x ~ p h s n y l a c r y l i c acid,is prepared by boiling a mixture of piperonal, sodium acetate, andacetic anhydride for six hours in a flask fitted with an upright con-CH2 : 0 2 : C,HS.CH : CH.COOHORGANIC CHEMISTRY. 49denser. The aqueous solution of the product is extracted with ether,and the ethereal extract treated with soda.On the addition of hydro-chloric acid to the sodium salt, the methylenecaffeic acid (m. p. 232")is precipitated. It is insoluble in water, but dissolves freely inalcohol and ether. The copper, Iead, and zinc salts of this acid aresparingly soluble in water. On reduction with sodium amalgam, theacid takes up 2 atoms of hydrogen, forming methylenehydrocaffeic ormethylenedioxyphenylpropionic acid, CH, : 0, C6H3. (CH,),.COOH,which crystallises in colourless needles (m. p. 84"). The lead andzinc salts which form needle-shaped crystals, and the silver salt whichcrystallises in glistening scales, are sparingly soluble in water.Meth y leize-a- Izom,ocafeic or methyl e.l;r ed ioa~~henylmethacrlllic a cid,CH, : 0, : C,H3.CH CMe.COOH, obtained by the action of sodiumacetate and propionic anhydride on piperonal, is deposited from dilutealcohol in colourless prisms (m.p. 193"), soluble in alcohol and ether.The copper and lead salts of this acid are insoluble in water, the zincsalt is sparingly solnble.By the action of water and sodium amalgam, this acid is convertediilto m e t l ~ ? / l e n , e - a - h o n z o ~ ~ ~ a r ~ c ~ ~ ~ e ~ c or methylenedioxyphenylisobutyricacid, CHI? : 0, C6H3.CH2.CHMe.COOH, which crystallises in prisms(m. p. 77") of a yellow colour. It is soluble in alcohol and ether.Methylenecaff eic and methylene-a-homocaff eic acids occupy an inter-mediate position between piperonylic acid, C8H604, and hydropipericacid, Cl2HI2O4.w. c. w.Nitrometaxylenesulphonic Acid. By W. HARMSEN (Ber., 13,1558-1568) .-ParanitrometaxyZene, C6H$fe.Me.NO2 [ 1 . 3 . 41, is0btaine.d by nitrating metaxylene ; it is a liquid which boils at 243-244" (corr.), and remains liquid at - 2 O O . Its constitution was shownt o be the above by converting it into a xylidine, which yields Jacob-sen's metaxylenol, C6H3.Me.Me.0H [l . 3 . 41, by means of the diazo-reaction.Nitroxylenesulphonic acid, C6H,(Me),(NOz).S03H, was obtained byheating the above nitro-derivative with sulphuric acid and convertingthe product into calcium salt, which gave the free acid when decom-posed by sulphuric acid. It crystallises from water in small hygro-scopic needles, and from dilute nitric acid in long colourless needles(m.p. 1 2 2 O ) .The ctr1cizl.m salt, [C,H,Me,(NO,).SO,],Ca 4- 6H,O, c r y s t a l h a inslender pale-yellow prisms, having a vitreous lustre ; it effloresces onexposure to the air ; at 18.5" it dissolves in 16 parts of water.The magnesium salt, [ C6H2Me2(N02).S03],Mg + 9H20, formsoctaq-onal plates, which are sparingly soluble in water.The sodium salt, CGH2Mez(NO2) .S03Na + H,O, crystallises inshining needles.The same acid is obtahed by nitrating a-metaxylene sulphonic acid?the constitution of which is C6H3Me.Me.S03H [l . 3 . 41 ; thereforethe constitution of the nitrometaxylenesulphonic acid is-C6H3.Me.Me.So3H.NO2. [l . 3 . 4. 61. P. P. B.VOL. XL. 50 ABSTRACTS OF CHEMICAL PAPERS.cdsophthalosulphonic Acid.By 0. JACOBSEE and H. L~SNIES(Bey., 13, 1556-1 558) .-When sodium a-metasylenesulphonateis oxidised by potassium permanganate and the manganese dioxideremoved by treatment with hydrochloric acid it yields an acid potas-sium a-isophth,alosuZphonate, C6H3( COO),( S03)H2K + 2H20. It crys-tallises in colourless brittle needles, having a vitreous lustre, and issparingly soluble in cold water.a- I s o ~ ~ h ~ t h a Z o s u ~ h o n i c acid, C6H3(COOH)2.S0,H + H20, is obtainedby decomposing the insoluble lead salt with snlphuretted hydrogen ; itcrystallises in colourless flat needles. It resembles the 7- isophthalo-sulphonic acid (Ber., 13, 704), and is more easily crystallised from sul-phuric acid than from water. Fused with potash, it yields a-hydroxy-isophthalic acid.It melts between 235-240", and is more easilysoluble in water than the anhydrosulphonamine-isophthalic acid.Barium iso~htl~nZosu.~horLnte, C6H3( COO)z(SO,)HBa + 3H,O, is ob-tained as a white crystalline precipitate by adding barium chloride tothe solution of the free acid or its acid potassium salt. Bariumchloride produces a precipitate only after some time in a solution ofthe acid in ammonia ; under the same conditions sulpf~onamineiso-phthalic acid gives a precipitate also, the anhydro-acid does not, how-ever, give a precipitate with barium chloride.Isophthalosulphonic and anhydrosulphonamine-iscphthalic acids be-have differeiitIy with silver nitrat'e. In the case of the former, neitherthe free .acid nor its potassium salt gives a precipitate with silvernitrate, whilst the latter, either as free acid or potassium salt, gives avoluminous precipitate, which becomes crystalline on standing.el- Isophthalosulphonic Acid and 7-Hydroxyisophthalic Acid.By H.LONNIES (Ber., €3, 703-707).-y-lsophthalosulplionic acid,C6H3(SOJH)(COOH)2 [I : 3 : 51, is prepared by heating isophthnlicacid with fuming sulphuric acid a t 200" for six hours. The liquid isthen diluted with twice its volume of water which precipitates theunaltered isophthalic acid : the sulphonic acid is deposited as a crys-talline mass on cooling. The sulphonic acid is deposited from dilutesulphuric acid in colourless prisms containing 2 niols. H,O. Thecrystals are deliquescent a t the ordinary temperature, but begin toeffloresce a t 60".The anhydrous acid melts a t 257" with decomposi-tion.The barium salt, [C,H,(SO,) (C00)2]2Ba3 + 8H20, crystallking insilky needles, and the calcium salt crystallking in transparent prisms,are freely soluble in water. A solution of the sodium salt yieldsprecipitates with mercuric nitrate, ferric chloride, copper acetate, andlead acetate.The preparation and properties of yhydroxyisophthalic acid havebeen described by Heine (Ber., 13,491). The anhydrous acid nielts a t288", and requires 3,280 times its weight of water at 5" for completesolution. A solution of the potassium salt is precipitated by ferricchloride, barium chloride, copper sulphate, silver nitrate, and leadacetate. Zinc sulphate does not, yield an immediate precipitate, butafter some time small prismatic crystals are deposited which areP.P. B.sparingly soluble in water. w. c. wORGANIC CHEMISTRY. 51Anhydrosulphonamine-isophthalic Acid. By 0. JACOB SE N(Ber., 13, 1554--1555).-A further examination of the body formedby the oxidation of sulphonamine-metatoluic acid, has confirmed theviews of Remsen (this Journal, 38, 258), viz., tl& anhydrosulphon-amine-isophthalic acid is obtained.Amarine and Lophine. By E. FISCHER and H. TROSCHKE (Ber.,13, 706-711) .-Amarine dichromate, ( C21H18Nz)2H2Cr207, is throwndown as a yellow precipibate when chromic acid is added to a solutionof amarine in dilute acetic acid. The solution of this salt in glacialacetic acid is converted into Zophhze by boiling.A solution of lophinein glacial acetic acid is oxidised by chromic acid a t 100" with theformation of benzamide and dibenzamide.Lophine dissolves in strong sulphuric acid at 170", forming a disul-phonic acid, which is sparingly soluble in water and alcohol. It isnot attacked by strong hydrochloric acid, but is reduced to lophine bysodium-amalgam.The mono-sodium salt, Cz,H14N2( S03)2X'aH + 2Hz0, crystallises inwhite needles, sparingly soluble in alcohol and in water.An unstable crystalline compound, C21H16N2Br6.HBr, is produced bythe action of bromine on lophine hydrobromide.The authors believe that amarine and lophine contain the group>C.C6€€,. The formula for lophine, C2,HI6N2, was con-P. P. B.C6H5-C. NCcH5--6.NIfirmed by the vaponr-density determination. w. c. w.Indoline. By E. GIRAUD (Compt. reml., 90, 1429-1430 j .-Flavindin dissolved in dilute soda is treated with sodium-amalgam(3 per cent.), when a dirty yellow powder is precipitated; this iswashed, dissolved in alcohol, and the solution diluted with water,when the indoline is precipitated, and may be purified by sublimation.It is probably formed according to the equation, C32H,*N*05 + 14H =2(C16H14N,) + 5H20. It gives the same reaction with picric acid asthe indoline described by Schiitzenberger. When dissolved in chloro-form and treated with chlorine, it yields a chlorinated derivative,C,,H,,N,CI,. An orange-yellow dinitro-compound, C16H12N2(N02)2, isobtained by treating indoline with nitric acid ; it is soluble in alcohol,but insoluble in water.By treating indoline with fuming sulphuricacid a t 180°, and saturating the product with sodium carbonate,CiGHJJ,( S03Na)2 is obtained.Derivatives of Anthraquinonesulphonic Acid. By D. A.MCHUUL (Ber., 13, 692-694). - A~thrapuinonesul2r,honic chloride,ClaH,O2.SO2C1, is prepared by heating equivalent quantities of an-thraquinonesulphonic acid and phosphorus pentachloride at 180" forfour hours. The residue which remains after the phosphorus oxychlo-ride is distilled off is extracted with hot water and recrystallised fromboiling benzene. The chloride crystallises in pale-yellow plates(m. p. 193") which dissolve in benzene, toluene, and glacial aceticacid. By the action of water at 160°, it is converted into anthra-quinonesulphonic acid.L.T. 0's.e 52 ABSTRACTS OF CHEMICAL PAPERS.Anthrapuinonesulphaamide, ClaH7O2. S02NH2, formed by heating thesulphonic chloride with alcoholic ammonia at 140", is deposited froma solution in glacial acetic acid in long yellow crystals (m. p. 2 6 1 O )which are insoluble in alcohol, toluene, chloroform, and carbon bisul-phide.,4nthraquinonesuZphaniZide, C14H702.NHPh, obtained by heating thesulphonic chloride with a solution of aniline in toluene at 180", formslong brown prisms (m. p. 1 9 3 O ) soluble in alcohol and glacial aceticacid.AnthraqzLinonedimethyZarnidoplienylsulphone, CI4H,O,.SO.,C,H4.NMez(m. p. 17l0), is obtained by the process described by Michler andSalathe (Ber., 12, 1789 ; this Journal, 38, 108) for preparinga-~a~~htl~yldimethyZamidopkeiiyZ~.ulpphone.The reduction of the sulphonic chloride by sodium-amalgam yieldssodium anthracenesulphonate, sodium anthracenehydridesulphonate, w.c. w.Gum Resin from Arizona and California. By J. M. STILL-NANN (Ber., 13, 754--756).-The resinous substance found on thetwigs of the Larrea ilfexicana and Acacia gyeggii in Arizona andCalifornia, appears to be identical with Indian shellac. I t is composedof resin, &c., soluble in alcohol, 61.7; colouring matter soluble inwater, 1.4 ; soluble in soda, 26.3 ; insoluble residue, 6.0 ; colouring w. c. w.and a small quantity of anthraquinone.matter soluble in soda and loss, 4.6 per cent.A Substance Extracted from Thalictrum Macrocarpum.ByM. HANRIOT and E. DOASSANS (BuJZ. Xoc. Chiin. [2], 34, 83-84).-In a former communication the authors described a yellow crystallinesubstance from the Thalictrum macrocarpurn, which was named bythem "thalictrin." They propose t o change the name to macro-carpin. In order to obtain this substance, the roots of the thalictrumare exhausted with alcohol, the excess of which is distilled off in avacuum ; it is then purified from a resin by ether, and finally precipi-tated with distilled water. Macrocarpin is a yellow substance, crys-tallising in needles, soluble in water and alcohol, but insoluble inether ; its best solvent is amyl alcohol. It is neutral, precipitated byacids, but soluble in ammonia. The analyses gave : C = 58-25 ; H =5.67 ; 0 = 86.08.Owing to the small quantity at the authors' disposal,they were unable to study the products of decomposition and assigna formula. V. H. V.Thalictrine. By E. DOASSANS (BUZZ. Xoc. Chim. [el, 34, 84).-By exhausting crude macrocarpin with ether, an alkaloid, thalictrine,is obtained ; a colourless crysialline substance, insoluble in cold andwarm water, soluble in ether and in alcohol. With hydrogen nitrate,it gives crystals of thalictrine nitrate. In its properties and reac-tions it resembles most nearly aconitine.Catechin. By C. LIEBERMANN and TAUCHERT (Ber., 13, 694-696).The catechin used in these experiments was prepared from catechu byLoewe's process (Zeits. Anal. Chem., 1874, 113), but it was recrystal-V. H. VORGANlC CHEMISTRY.53lised twice from hot water before it was treated with ethyl acetate.It is deposited from an aqueous solution in minute needie-shapedcrystal!, having the composition C2,H,0g + 5H20. Dincetic cntechin,C21H1SAc209, obt'ained by the action of acetic anhydride and sodiumacetate on catechin, crystallises in yellow needles and prisms (m. p.130°), which are insoluble in water and ligroin, but dissolve freely inother solvents.Dichloracetic catechin, C21H16C12&09 (m. p. 16!1°), is prepared bypassing chlorine through a concentrated solution of diacetic catechinin glacial acet,ic acid: the substance is precipitated on the additionof water. Muizobromncetiecatechin, Cz1H,,BrAc2Og, is deposited from an alcoholic solution inwhite needles (m.p. 120").The existence of these compounds shows that catechin has the corn-It is sol-uble in alcohol and ethyl acetate.position C21H200,. W. c. w.Alkannin. By G. CARNELUTTI and R. NASINI (Bey., 13,1514-1516) .-This body was obtained by extracting commercial colouringmatter with dilute potash solution ; this extract mas shaken with etherto remove a reddish-brown acid, an impurity present in the alkanninobtained by Pelletier, Bolley, and Weydler. The solution in potashwhen saturated with carbonic anhydride gives a precipitate of alkan-nin, which was further purified by solution in ether. It is obtainedas a dark reddish-brown mass, with metallic lustre, and is sparinglysoluble in the ordinary solvents ; it is most easily soluble in chloro-form and glacial acetic acid.Its alcoholic solution is not changed byexposure to light or by continued boiling. The analytical results showits formula to be C15Hld04, whilst Pelletier obtained Cl,Hlo04, andBolley and Weydler C,,H,O8 from their analyses.Acetic and benzoic-chlorides have no action on alkannin ; a diacetylderivative, Cl,Hl,04Ac2, is obtained by heating it with acetic anhy-dride and sodium acetate: it is a brown powder which crystallisesfrom glacial acetic acid in dirty yellow crystalline grains.A barium salt containing 2 atoms of barium t,o 3 molecules ofalkannin is obtained by precipitating the alcoholic solution withammonincal barium chloride.Nitric acid or bromine in alkaline solution oxidises alkannin tooxalic and succinic acids. Bromine acts on solid alkannin, but noton its solutions.Alkannin appears to be related to santalin.P. P. B.Derivatives of Santonin. By S. CANNIZZARO and J. CARNELUTTI(Bey., 13,1516 -1517).-By the fusion of santonous and isosantonousacids with barium hydrate (Bey., 12, 15i4) the authors obtained abody having the formula C12Hc,20. Since this body when distilledwith zinc-dust yields a hydrocarbon, C12H12, whose physical properties,and the properties of its picric acid compound, and of its tribromo-derivative, show it to be dimethylnaphthalene, the authors conclude thatthe compound C12H120 is dimethylnaphthol. The dimethylnaphthalenecontains the methyl groups in the same relative position that the bro-mine atoms occupy in Glaser's dibrornonaphthelene (m.p. 80.5 -81")54 ABSTRACTS OF CHEMICAL PAPERS.Santonous acid distilled over zinc-dust yields some dimethyl-A small quan-P. P. B.naphthol, also dimethylnaphthalene and propylene.tits of xylene appears to be formed.Cyanethine, and New Bases derived from it. By E. V. MEYER(J. pr. Chem. [el, 22,261-288).-Cyanethine was discovered 33 yearsago by Kolbe and Frankland (Annden, 65, 'LG9), and its homologuecyanmethine has been since described by Bayer (this Journal, 1871,Cyanethine is prepared by acting on tolerably large pieces of cleansodium with ethyl cyanide in a retort provided with an upright con-denser, the upper end of which is air-tight, and has a bent glasstube fitted to it which dips into mercury.The apparatus is filledwith carbonic anhydride ; one-third of the ethyl cyanide is added atfirst, and the rest gradually as the reaction becomes less violent. Theexcess of cyanide is removed by distillation, and the yellow-colouredproduct powdered and washed with water. It is then dried on porousplates and crystallised from alcohol (of 90 per cent.). The chief pro-cesses of the reaction are shown by the following equations :-397).Na + C,H,CN = NaCN + CzH5Na + C,EI,CN = C,H,NnCN + HCZH, + H = C2HG.Cyanethine melts at 189". One part dissolves in 1,365 to 1,380 partsof water at 17", but it is tolerably soluble in alcohol.* A concentrated solution of cyanethine in hydrochloric acid crystal-lises in large transparent striated prisms, which, when dried overquicklime and sulphnric acid, contain about 1 mol.of water. Thesecrystals dried at 110", have the composition C9H,,N3.HC1.Cyanethine forms a double salt, (C9H15N3)2.AgN03, with silvernitrate. It is also shown by the action of ethyl iodide to belong tothe tertiary bases. Nitrous acid has no marked action on it, but it isoxidised by permanganate with formation of formic acid as the chiefproduct; carbonic anhydride is evolved at the same time, while anammonium salt is found in the solution together with a second acid,probably propionic.When c-j-anethine is heated with tolerably concentrated mineralacid, it yields a monncid base containing oxygen, CgH140N2. Thisbase crystallises from hot water in fine tufts of brilliant needles: fromalcohol in long striated prisms ; when precipitated by ammonia fromone of its salts, it forms intricate, sometimes dendritic, aaicular masses ;carefully heated, it sublimes in small needles far below its meltingpoint, which lies between 156" and 157".One part of this base re-quires 133 parts of water for solution, but it does not impart anyalkaline reaction to the water. It is most soluble in chloroform andbenzene. The salts are soluble in water, to which they give an acidreaction, and for the most part crystallise well.The hydrochloride, C9H,,0N2.HC1, is obtained by evaporation of thehydrochloric acid solution and drying at 110" as a white flocculentcrystalline powder, small quantities of which sublime in minute prismsORGAXIC CHEDIISTRY.55The pZatknoc7~Zoride, (C,HlrON2.HC1)z.PtClr, forms yellow rhombicplates which dissolve easily in water, but sparingly in alcohol.The nitrate, CgHIION2.HN03, cry stallises in fine (probably mono-clinic) prisms which undergo decomposition a t 1 0 0 O . The acid oxalate,CgHl4ONz,CZO4Hz, is anhydrous.The body which has act'ed as a base in the above salts can alsoexchange an atom of hydrogen for one of silver. The siher salt,C,H,,AgON,, is precipitated as a white, bulky, microscopic crystallinepowder which is readily soluble in ammonia and in dilute nitric acid.Similar compounds could not, however, be obtained with copper, lead,&c. The ready solubility of the base, C9€1140N2, in alkalis, seems t oindicate that it forms compounds with them, but it is separated fromthem again by carbonic anhydride. The reaction with ethyl iodideshows that it belongs to the tertiary bases.It unites with aceticchloride t o form the compound CgHl,ONz.CH,COC1. As this base is notaltered by heating with acetic anhydride at 180", the oxygen wouldseem to be united with hydrogen as hydroxyl. Heating with excessof hydriodic acid a t 200" decomposes a small part of the base withformation of ammonia and probably propionic acid.Potassium permanganate in acid solution oxidises it, the nitrogenbeing evolved in the form of ammonia ; in alkaline solutions propionicacid (and probably a little acetic acid) is also formed. When treatedwith phosphorus pentachloride, a new base is produced of the formulaC9H,,C1N2.This base is a bright yellow oil with an unpleasant odour,and cannot be distilled a t the ordinary pressure without decomposi-tion. I t is insoluble in water. On heati=g with ammonia and alcohol, *cyanethine is re-formed, which shows that cyanethine contains a mole-cule of amidogen. When alcoholic potash acts on the compoundCgH,,C1N2 a new base, CgH13(OEt)N2, is formed ; it is a faintly-colouredoil with a cabbage-like smell. It can be distilled without change at269" to 231". Strong hydrochloric acid converts it into the baseCgH140N2 or C9Hl,(OH)N,. When the base C9HI4C1N2 is acted on byzinc and hydrochloric acid a double zinc salt, ( CgHl~Nz.HC1),.ZnCl2, isformed, but it is not improbable that this salt contains also ananalogous base, C9H16Nz.On continued agitation, the base, C9H14Nz, dissolves in water in con-siderable quantities, and imparts to it an alkaline reaction ; when thesolution is heated, the base separates in oily drops.It is a clear liquidwith high refractive power and an unpleasant narcotic smell ; whenthe rapour is inhaled, it produces a heavy feeling in the head, so thatgreat care is necessary in working with it. It boils at 204--205", andis easily volatilised in steam. It does not reduce Pehling's solution ;an ammoniacal solution of a silver salt is only reduced on continuedheating. Powerful oxidising agents such as chromic acid, &c., actenergetically on it. Crystalline salts of the base have not been ob-tained. The above properties of the base strongly resemble those ofconine, and its physiological action is similar, but more violent thanthat of conine.It may perhaps be cyanoconine for C,H14(CN)N =CgHI4N,. If this is the case, the bases described in the paper may beexpressed as follows :56 ABSTRACTS OF CHEMICAL PAPER§.CgH,Nz = CsH14( CN)N, cyanoconine.CgHIaClNz = C,H&l (CN) N, chlorocyanoconine.C9HdOH)N2 = CsHI3( OH) (CN)N, oxycyanoconine.CgH13(0C2H5)N2 = C,Hl,(OCzH5) (CN)N, oxyethylcyanoconine.C9H13(NH,)N2 = C8Hu(NHz) (CN)N, amidocyanoconine =cyanethine. G. T. A.Bases of the Pyridine Series. By 0. DE CONINCK (Compt. rend.,91, 296--297).-The bases of this series formed in the distillation ofcinchonine with potash have been separated and purified by theauthor. They are isomeric with the bases of the same name found incoal-tar napht,ha, and in Dippel's oil. After separating them as faras possible by fractional distillation, the different fractions are treatedwith excess of hydrochloric acid, agitated two or three t,imes withether, the ether separated, and excess of potash solution added.Theseparated bases are taken up by ether; the ethereal solution dried overpotash and distilled.Lutidine, C7HgN, is a colourless, mobile, strongly refracting liquid,with peculiar odour and burning taste. It is very hygroscopic, andalmost insoluble in water. Boiling point, 155" ; vapour-density, 3.8(found) ; 3.71 (calculated) ; sp. gr. at O", 0.9593.Lutiiiine hydnxhloride, C7HgN.HC1, forms white, deliquescent,lamellar crystals.The hydrobromide is similar. The plntinochloridecrystallises in fine orange-red needles ; treated with boiling water, itloses 2 mols. HCI, and crystallises in yellow needles. The auro-chloride is a shining yellow powder.Collidiite, C8Hl1N, boils a t 195", and is similar in appearance andVapour-density, 4.25 (found) ; 4.19 (calcu-Lted) ; sp. gr., 0.9656 at 0". The platinochloride is an orange-redpowder, transformed by boiling water into minute yellow needles.Parvolzne has not yet been obtained quite pure; it boils at about220".roperties to lutidine.The platinochloride forms a, brownish-yellow powder.Lutidine from Dippel's oil is of sp. gr. 0.946 i;nd b. p. 155.5".Collidine 9 7 9 ) ,, 0.944 180.Parvoline 9 ) 9, 7 9 bo& at 188.J.M. H. M.Crystalline Quinoidine Borate. By J. JOBST (Ber., 750-751).-The substance described by Pavesi (Za Farmncia, 1879, 26) as aquinoidine borate is merely a mixture of boric acid and qninoidine,from which the base is completely removed by recrystallisation. w. c. w.Hyoscine. By A. LADENBTJRG (Ber., 13, 1549--1554).-1n aformer communication (Ber., 13,910), the author stated, that an alka-lo'id accompanies hyoscyamine, which is known as " amorphoushyoscyamine." To this the author gives the name hyoscine ; it is ob-tained in commerce as a syrup, from which, by conversion into theaurochloride and recrystallisation of the latter, it may be obtained ina tolerably pure state. When the hyoscine obtained from the auro-chloride is decomposed by barytn, it yields tropic acid and a baseisomeric with tropine, which is styled pseudotropineORGANIC CHEMISTRY, 57Pseudotropine forms a white crystalline mass ; it boils at 241-243"(tropine boils a t 229').Its platilzochZoride ( C,H,,NOHC1),.PtjCl4, hasbeen obtained in well-defined crystals, belonging to the rhombicsystem, a complete description of which is given. The auwrhlnride,CsH,NO.HCl.AuC1,, has a solubility similar to that of tropineaurochloride ; the appearance of the crystals is, however, different.The picrate and double salt with meycuric chloride have been obtained inwell- defined crystals.The aurochloride of hyoscyine may be obtained pure by first boilinghyoscyine hydrochloride with animal charcoal. The aurochlorideprepared from the hydrochloride so purified crystallises well, and meltsat 198".The reactions of hyoscyine are similar to those of hyoscyamine.Potassio-mercuric iodide gives a light yellow amorphous precipitate,with acid solution of hyoscyine, and mercuric chloride, an amorphousprecipitate ; in some cases an oil is obtained.Iodine solution gives ablack oily periodide, and potassium ferrocyanide a white amorphousprecipitate.The physiological action of hyoscyine resembles that of atropine.Atropine, hyoscyamine, and hyoscyine are isomerides, whi 1st homa-fropine is a homologne containing CH, less than these alkaloids.Ptomaines considered in Relation to Judicial Chemistryand Toxicology. By T. HUSENANN (Arch. Pharm. [3], 16, 169-181).-The name "ptomaines" has been given by Selmi to bodieswhich have been detected in exhumed corpses, and resemble the vege-table alkalo'ids in their chemical reactions and physiological effects.The author gives a summary of the observations already published onthis class of bodies, and considers the very important bearing they haveon the study of poisons and on forensic medicine.It becomes ex-tremely important to discover, if possible, reactions which will distin-guish between these poisonoiis bodies, which are the result of putre-factive processes, and those very similar vegetable principles which,when administered, may produce death. Bodies of the " ptomaine "class seem to have different physiological actions. Some appear toact as poisons, others are inactive : whilst others again counteract theeffects of poisonous substances.The study of these bodies embraces also the poisonous effects pro-duced by food in certain conditions of putrefaction or ferruentation.Panum showed that albuminous substances by putrefaction yielded apoisonous body, acting like a ferment, soluble in water, insoluble inalcohol, and capable of withstanding a temperature of 100".This hasbeen confirmed by Bergmann, who describes a compound calledsepsin, generated by putrefaction.It appears from the researcbes of Panum and of Schweninger, thatcompounds having different physiological actions are produced a t dif-ferent stages of decay.Sonnenschein and Zuelzer found in an anatomical maceration fluidan alkaloid which resembled atropine in its action, and poisonoussausages produced a similar effect; the existerice of a product ofdecay which caused tetanic symptoms was also noticed.Aebi andP. P. B58 ABSTRACTS OF CHEBIICAL PBPERS.Schwazenbach detected a compound allied to an ethereal salt inextract from dead bodies. Substances derived from putrefaction ofmaize certainly produce tetanic symptoms, as was first proved byLombroso and Erba ; and this action has been traced to the presenceof basic substances. It appears probable, however, that drowsiness,loss of sensation, and. weakening of the action of the heart may bedue to the presence of acid bodies in the extract of putrefied maize,since lactic acid and sodium lactate produce effects similar to those ofmorphine.Lombroso thinks that the tetanic and narcotic action ofextract of putrefied maize, and its beneficial effect on several skinaffections, indicate the possible origin of pellagra in diseased or putridmaize. This mould explain the prevalence of pellagra in the SouthEuropean maize-growing countries, and in other countries it mayoriginat'e from the putrefaction of albumino'id * substances of othercereals. This kind of putrefaction cannot be caused by artificial heat,aIthough it occurs only in hot summer weather, and probably thereforerequires the presence of special microscopic organisms. A similar ex-planation may be applied to tetanic symptoms caused by wounds andprevented by the Lister treatment. Frequently the tetanising principlein the maize extract has its action marked by it narcotic substance ;just as Ranke showed that the physiological action of strychnine inbodies long buried may be masked by ptomaines.Lombroso's siiggestion that skin complaints may be due to putre-factive products of maize has its known analogues in erysipelas causedby wound poisoning, and in skin eruptions caused by eating bad fishand other putrefying substances.Such poisonous effects ape: however,often produced by parts of living organisms, as for instance by thebeard of the mussel; and they are not produced on all individuals,since dogs accustomed to eat decomposing substances are not affectedby putrefactive principles.The relation of these products of putrefaction to certain diseases isevident from tbe fact, that Sonnenschein's alkalo'id is found in thebodies of patients dying from typhus fever, a.nd many individualspoisoned by decomposing food show marked typhus symptoms.I n many cases of poisoning by cheese, it was found that the badeffect was not due to vegetable growths or to microscopic organisms5and the clieese was frequently fresh.It appears from the study of the literature concerning ptoma'ines,that they are usually produced in bodies which, after brief exposure,have been excluded from air, as in buried bodies, sausages, and tinnedfoods; and further, in these cases, the production chiefly occurs in theinternal portions. Cases, however, are known where similar principleshave been present in comparatively fresh substances which have beenconstantly exposed to the air : hence under the name " ptomaines "must be included all alkalojidal products of decay, whether formed inPapain. By A. WURTZ (Covnpt. rend., 90,1379--1385).-The sapof the Carica papaya contains a soluble ferment, which the author andRouchut have described (this Journal, 1879, Abst., 1048). The fer-ment is obtained by making incisions in the bark of the tree and in thethe presence or absence of air. F. cVEGETABLE PHYSIOLOGY AND AGRICULTURE. 59unripe fruit, when a milky sap exudes, which coagulates on exposureto the air. By expressing the liquid from the coagnlum, and addingalcohol to it, a precipitate of papain is obtained. Papain is also ob-tained from the coagulum by triturating it with water several times,concentrating the solutions, and adding alcohol. Prepared in this wayit differs slightly in composition from that obtained from the liquidportion of the sap. Papain of another composition is also obtainedby mixing the sap obtained from the fruit with water to form apulp, filtering, concentrating the solution, and adding alcohol. Bywashing the residue and concentrating the filtrate, a further quantityof papain is obtained. It appears, therefore, that the solubleferment of Carica papaya is not of constant composition. All thepreparations contain from 4 to 10 per cent. of ash, whilst afterdeducting the ash the percentage of carbon varies from 46 to 53, andthat of nitrogen from 14 to 18 ; it also contains about 2.2 per cent. ofsulphur. Those preparations giving the greatest percentage of carbonwere obtained either by dialping the precipitate obtained withalcohol, or by precipitating adhering albumin, &c., with subacetate oflead, and separating the excess of lead with sulphuretted hydrogen,and precipitating the papain with alcohol. The ferment thus obtainedacts energetically on fibrin, and its composition resembles that of thealbuminoids. It is very soluble in water, dissolving in less than itsown weight like gum. The solution when boiled or allowed t o standfor some time becomes turbid, but the papain does not coagulate likealbumin. Hydrochloric and nitric acids precipitate papain, but theprecipitates are soluble in excess. Orthophosphoric and acetic acidsdo not give precipitates with papain, but with metaphosphoric acid aprecipitate is formed. Subacetate of lead produces st turbidity inpapain solutions; on adding potash and boiling, it becomes black.Millon’s reagent gives a yellowish-white precipitate, which on boilingbecomes brick-red. Papain does not act so energetically on fibrineas the t r y p i n e of Kiihne.The author has also obtained a saponifiable fat, and a nitrogenousbody from the juice of the Ca~icapapnya. L. T. 0’s