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82 ABSTRACTS O F CHEMICAL PAPERS.O r g a n i c Chemistry.Derivatives of the Heptane from, Pinus Sabiniana. By F.P. VENABLE ( B e y . , 13, 1649--1G52).-HeptyZ bromide obtained fromthis heptane is a colourless liquid of sp. gr. 1.422 a t 17.5" ; it boils atHeptyZ iodide does not distil without decomposition under ordinarypressure.He$$ acetoacetate boils a t 250-260°, and is converted into methylethyl ketone, C5H11.CHMe.CH,.COMe, on saponification.Heptyl nzalomte (b. p. 263-265') is formed by the action of ethylmalonate, alcohol, heptyl bromide, and sodium. When saponifiedwith potash and the solution treated with hydrochloric acid, it yieldsheptylmalonic acid, a crystalline mass (m. p. 97-98'), little soluble inwater, readily so in alcohol, chloroform, or ether.The silver andbariuin salts are white precipitates insoluble in water and in alcohol.HeptyZacetic acid is obtained on heating the last-mentioned acid t o160". It is a colourless liquid (b. p. 232O), insoluble in water, soluble inalcohol and ether. The silver conipound is sparingly, the barium saltreadily, soluble in water.165-1 6 7'.It boils at 98" under 50 mm. pressure.0. H.Fermentation of Glycerol. By F. HOPPE-SEPLER (Bied. Centr.,1880, 621--622).--From a study of the products of the fermentationof glycerol, it appears probable that this fernientation depends on theformation and decomposition of lactic acid, as glycerol is decomposedinto the same products as the latter. J. I(. C.Di- and Tri-carbinols. By H. KOLBE ( J .pr. Chem. [ 2 ] , 22,147--165).-The author is of opinion that as primary, secondary, andtertiary carbinols correspond to primary, secondary, and tertiaryamines, EO di- and tri-carbinols will be found corresponding to di- andtri-amines. For instance, ethylenediamine, C,Ha( NHJ1, will have acorresponding ethylenedicarbinol, C2H4(CH2.0H)2 ; these di- and tri-carbinols can of course be primary, secondary, and tertiary in exactlythe same manner a s the di- and tri-amines are.The primary di- and tri-csrbinols, like the primary mono-carbinols,will be oxidisable to aldehydes and to acids. Only one of the aldehydesof the primary dicarbinols is known, that from ethy lenedicarbinolcorresponding with succinic acid. On the other hand, a large numberof the corresponding bibasic acids are known.Succinic acid, forexample, is the acid corresponding with ethylenedicarbiriol ; thealcohols belonging to malic, tartaric, and pyrotartaric acids are not yetknown.The secondary di- and tri-carbinols, like the secondary mono-carbinols, will only yield ketones on oxidation. Of the ketones ofthe secondary dicarbinols, our knowledge is very scanty. The com-pound called anthraquinone (which has nothing in common with thereal qninmes but a similarity in the empirical formula) belongs to thisclass, and may be regarded as the ketone of phthalic acidORGANIC CHEPtlISTRP. 83When reducing agents are discovered capable directly of removingoxygen from the alcohols, as many hydrocarbons can be prepared aswe now know alcohols.Then will be produced :-From methyl alcohol, MeOH, the hydrocarbon ........ MeH.,, dimethylcarbinol, Me,CH.OH, the hydrocarbon . . CH2(Me),.,, methylenedicarbinol, CH,( CH,.OH),, the hydro-,, methintricarbinol, CH( CH,.OH),, the hydrocarbon CH(CH3), ,, trimethintricarbinol, (CH),( COH),, the hydro-carbon ..................................carbon .................................. CH,(CH3),(CH) 3 (CH) 3This last hydrocarbon, trimethintrimethane, has the constitution ofbenzene. The same representation of the constitution of benzene isthus arrived at by comparison of the carbinols with their correspond-ing paraffins as arrived at by the author twelve years ago, on othergrounds.Pyrogallol (trimethintricarbinol) may be regarded as a tertiaryalcohol, standing in the same relation to benzene as trimethylcarbinolto trimethFlmethane. It cannot be denied that it differs in its pro-perties from trimethylcarbinol, but nevertheless scarcely more thantribasic tricarballylic acid differs from monobasic butyric acid.From the relations between benzene, phenol, and pyrogallol, it maybe inferred that not only dimethintricarbinol, (CH),( CH.OH),, butalso the compounds (CH)2(CH.0H)2CH2, (CH),(CH.OH)(CH,),,analogous to phenol, may be formed by the oxidation of dimethintri-methane, (CH),(CH,)3.The author remarks, that when in 1858 he foretold the existence ofsecondary and tertiary alcohols, the majority of chemists were stillfirmly attached to the type theory, and disbelieved in the possibilifyof the existence of such compounds.In the same way a t the presenttime, the belief in " structure " and " bonds '' prevents chemists fromcomprehending how secondary and tertiary di- and tri-carbinols canexist. F. L. T.Methylamine in Commercial Trimethylamine Hydrochlor-ide. By L. J. FISENBERG (AnnaZen, 205, 139--144).-The firstportion of this paper is a brief summary of the literature of trimethyl-amine and its various sources. The author purified the commercialtrimethylamine hydrochloride from ammonium chloride by evaporatingto dryness, and taking up the residua with alcohol and ether; onevaporating the latter, the syrupy residue was decomposed by potash,and the vapour (b. p. 53") passed into hydrochloric acid. The solu-tion of the hydrochloride was mixed with excess of platinic chloride,the platinochloride washed with absolute alcohol and evaporated oversulphuric acid.The platinochloride gave on analysis 36.5 per cent.platinum (theory requires 37.4 per cent.). On frequent boiling of theplatinum salt with alcohol the percentage of platinum increased aftereach operation, The identity of the platinochloride with that obtainedby Hofmann from trimethylamine (obtained from herring brine) is con-firmed by crystal measurements. From the ana.lyses of the platino84 ABSTRACTS OF CNEXICAL PAPERS.chloride and the percentage of chlorine in the hydrochloride, theauthor concludes that commercial trimethylamine hydrochloride con-tains methylamine ; the latter may be separated from the former bywashing with absolute alcohol. It appears that the solubilities of theplatinochloride of mono-, di-, and tri-methylamine in water are inverseto their solubilities in alcohol. The author believes that he hasobtained an alum of methylamine.V. H. V.Some Derivatives of Isobutaldehyde. By A. LIPP ( A n n n h ,205, 1-32) .-As aldehydes undergo reactions with ammonia, varyingaccording t o the nature of the qoups directly associated with thealdehydic group CHO, the author was induced to study this reaction,and that of hydrogen cyanide on the compound produced in the caseof an aldehyde containing st (CH)"' group. For this purpose isobut-aldehyde was chosen as typical.When ammonia gas is passed into an ethereal solution of isobutalde-hyde, water is gradually formed, and on evaporation of the etherglistening crystals belonging to the hexagonal system separate out(see also this Journal, 1880, Abstr., 611).The substance has theempirical $ormula CzeHs2ONc, and is formed according to the equation7C4H80 + 6NH3 = (C4Ha)70N,& + 6HzO. The same compoundmay be obtained by using it strong ammoniacal solution instead of thegas. The crystals melt at 31", and begin to decompose a t 90°, withevolution of ammonia ; they are with difficulty soluble in water, easilysoluble in alcohol and ether. On heating the substance to 145", athick oily liquid, C6H150, isomeric but not identical with conine,distils over (C28H62N60 = 3C8H15N + C4HaO + 3NH3).Action of Hydrogen Cyaaide o n the Issobutaldehyde Amrnonic Corn-pounc71.-By the action of a 30 per cent.solution of hydrogen cyanide,besides amidoisovaleronitril (Pfieff er, Ber., 5, 699), hydroxyisovalero-nitril is produced (CaH,),ON6H6 + 7HCN = 6C4HJVHzCN +C,Ha.O.HCN. At the same time, part of the amidoisovaleronitril isdecomposed into ammonia and imidoisovderonitril. By heating theproducts of the reaction with a 5 per cent. hydrochloric acid solution,the hydrochloride of the amidonitril is formed, which may be separatedby its insolubility in ether from the unaltered imido-a-hydroxynitrils.On saturating the residue with ammonia, the free amidonitril becomessoluble in ether. The solution is dried over calcium chloride andsaturated a t 0" with dry hydrochloric acid, when the hydrochloride ofamidoisovaleronitril is deposited.The author attributes to the com-pound of ammonia with isobutaldehyde the following formula :-Hydrochloride of amidois.ovaleronitri1, C3H7.CH( CN) .NH,HCl is awhite crystalline powder insoluble in ether, easily soluble in water andin absoiute alcohol. It volatilises without melting ; and with platinicchloride it forms golden scales of the platinochloride. By saturatingan aqueous solution of the hydrochloride with ammonia, and extract-ing with ether, the free base, C,H,.CH(CN)NHZ, is obtained as ayellow oil of strongly alkaline reaction. By standing over sulphuriORGANIC CHEMISTRT. 8 3acid it is gradually decomposed with formation of the correspondingimidonitril.Hydrochloride of amidoiswaleramide, C3H7.CH(NH2.HCl) .CONH2, isobtained by the action of fuming hydrochloric acid a t ordinary tem-peratures on the hydrochloride of the amidonitril. It crystallises inplates of the monosymmetrical system, easily soluble in water, spar-ingly soluble: in alcohol, insoluble in ether.The aqueous solution hasa strongly acid reaction. It forms a piatinochloride, which crystal-lises in the tetragonal system. By the action of silver oxide on thehydrochloride in water, amidoisovaleramide is obtained in solution ;it cannot, however, be isolated in the pure statre, as it decomposes evenin a vacuum with formation of amidoisovaleric acid,C,H7.CH(NH),.CONH, + H,O = C,H7.CH(NH,).COOH + NH3.a- Amidoiso valeric acid (a- Amidoisobuty Vorm ic acid),CHMe. CH( NH),.COOH,is obtained by heating the hydrochloride of the amidonitril with hydro-chloric acid of 1.1 sp.gr. ; after separating the ammonium chlorideby absolute alcohol, the hydrochloride of the amido-acid is decomposedwith silver oxide. Thus obtained, amidoisovaleric acid forms aglistening crystalline mass ; it dissolves easily in water, yielding aneutral solut'ion, but is only sparingly soluble in alcohol, and insolublein ether. The acid is identical withthat obtained by Clarke and Fittig from bromovderic acid (Awnaleiz,139, 200) ; and by Schmidt and Sachtleben from bromisobutylformicacid (ibid., 193, 106 ; and this Journal, Abstr., 1879, 140). It formssalts with acids and bases. The hydrochloride can be obtained as anintermediate product of the reaction described above, or by the directcombination of the acid with hydrochloric acid.This substance isezsily sohible in water and alcohol, the aqueous solutioii has a stronglyacid reaction. The copper salt of amidoisovaleric acid forms bluescaly crystals.It sublimes without melting.Hydrochloride of i?itidoisovalel.onitril,C3H7.CH( CN) .NH(HCl).CH( CN) .C3H7,is obtained as one of the products of the action of hydrogen cyanide onthe ammonia compound of isobutaldehyde (vide supr$) ; it can beseparated from hydroxyisovaleronitril by the insolubility of the hydro-chloride in ether. It crystallises in prisms, and is easily soluble in alco-hol, but is at the same time partially decomposed into hydrochloric acidand the imidonitril ; this decomposition is effected immediately bywater.It forms a, platinochloride, which crystallises in golden needles.ImidoisovaleronitriZ, C,H,.CH(CN).NH.CH( CN,.C3H,.-By the actionof ammonia on an ethereal solution of the hydrochloride, two isomericimidoisovaleronitriles are obtained, one crystalline, the other an oilyliquid. The solid isomeride melts a t 58". The hydrochlorides formedby the direct combination of hydrogen chloride with the two isomerides,are not distinguishable.E~droxyisoualeronitril, CHMe2.CH(OH) .CN, prepared by the directcombination of hydrogen cyanide with isobutalde hyde, CHMe,. CHO +HCN = CHiMe,.CH(OH).CN is a colourless oily liquid of sp. gr.VOL. XL. ?86 ABSTRACTS OF CHEMICAL PAPERS.95612, vhich does not solidify even a t - 17" ; it is easily soluble in alco-hol and ether.At 136", it decomposes into hydrogen cyanide and thealdehyde. It dissolves in strong hydrochloric acid, taking up a moleculeof water, and is converted into the corresponding amide,C3H,.CH(OH).CN + HZO = C,H,.CH(OH).CONH,.a-HydroxybzLty~ormanzide forms large scaly crystals (m. p. 104"),soluble in watler and alcohol, sparingly soluble in ether ; it distils un-changed. By heating with potash, ammonia is evolved, the amide isconverted into a-hydrozybutylformic acid, CHMe.CH( OH).COOH,identical with the acid obtained from bromvaleric acid by Clarkand Fittig (vide suprci), and by Ley and Popoff (Annalen, 174, Sl),and by Schmidt and Snchtleben (vide supr;) from bromisobutylformicacid.The acid may also be obtained by heating the corresponding nitrilwith conceiitrated hydrochloric acid ; the ammonium chloride formedin the reaction may be separated by cooling after partial evaporation.On taking up with ether and evaporating, a dark coloured acid oilremains, from which, after standing a short time over sulphuric acid,needle-shaped crystals of the acid separate out.When pure, it crystallisesin plates (m. p. 83"), belonging to the rhombic system ; it is easily solu-ble in water, alcohol, and ether. By heating for some time withdilute sulphuric or hydrochloric acid (1 : 3), it is decomposed intoformic acid and isobutnldehyde.The calcium salt (C5H903)2Ca + 4H20, is prepared by neutralisingthe acid with chalk; it crystallises in needles.When air-dried, itgives up 24 mols. H20, the remainder at 100-150".The magnesium salt (C5Hg03)2Mg + 2H20, crystallises in prisms;it loses its water a t 100-150". A hydrated zinc salt (C5Hg03)2Zn +2H,O, is obtained hy evaporating the nqueous solution over sulphuricacid ; on drying it in the air, an anhydrous zinc salh, (C5Hg03),Zn, isformed.The saltsin their solubility and other properties resemble those of hydroxy-valerianic acid obtained by Clark and Fittig.A copper salt, (C,H903)hCu f H2Q, WRS also obtained.V. H. V.Lead Formate Acetate. By J. PLOCHL (Ber., 13, 1645-1647).-To the three double salts of the lower members of the acetic acidseries, recently described by A. Fitz (Ber., 13, 1315; this Journal,Abstr.1880, p. 799), the author adds a fourth, obtaitied in the formof needles, readily soluble in water, sparingly in alcohol, of the formulaIt is impossible to separate acetic from formic acid by means of thesolubility in alcohol of their lead salts, as stated in many works on thesubject, because the formate passes into alcoholic solution togetherwith the acetate.The author contradicts the usud statement that 1 part of leadacetate is soluble in about 8 parts of strong alcohol. He found that15-16 parts of 80 per cent. alcohol was required to dissolve 1 part ofthe salt. 0. H.Pb(CZH30?)z + Pb(C2H3O,,CHOz) + 2H2OORGANIC CHEMIST R P . 81Amido-acids of a-Hydroxybutyric Acid. By E. DUVILLIEE(Ann. Chini. Pliys. [ S ] , 20, 185--206).-Many years ago Volhardtshowed that the synthesis of sarcosine or mekhyl-amido-acetic acidcould be effected by the action of methylamine on ethyl chloracetate ;by a similar reaction the author has prepared methy Zamidobntyric acid.Normal a-bromobutyric acid is carefully added to a very concen-trated solution of methylamine (prepared from dimethyl-oxamide),and the mixture heated in a closed vessel a t 100 for several hours.When the action is complete, the product is boiled with baryta aslong as methylamine is disengaged, and the excess of baryta is after-wards precipitated by dilute sulphuric acid.The filtrate, on beingevaporated on a water-bath and allowed to cool, solidifies to a massof slender needles, consisting of the hydrobromide of methylamido-Iju tyric acid.I n order t o purify the salt, it is dissolved in water ; silver carbo-nate added to remove the hydrobromic acid, and the filtrate eva-poi-ated to dryness.The residue, dissolved in alcohol and crystallised,furnishes perfectly pure methylamido-butyric acid.The results obtained by the analysis of this substance correspondedaccurately with the formula C5H11NOz, the constitutional formula ofwhich may be written CH,.CH,.CH(NHMe).COOH.The acid is very soluble in water and in boiling alcohol, but is in-soluble in ether. It has a slightly sweet taste and a weak acid reac-tion. It may be heated to 120" without alteration, but a t a highertemperature it is decomposed.The aurochloride and platinochloride, hydrochloride, sulphate,nitrate, and the copper salt of methylamidobutyric acid were pre-pared and analysed.They present no characteristics of specialinterest.Ethylam itlobutyric k d , CH,.CH,.CH( NHEt) . COOH, is preparedfrom ethylamine and bromobulyric acid by a process exactly similart'o that; descnibed above in the case of the methy4 compound. It is acrystalline substance, neutral to litmus, which can scarcely be dis-tinguiehed from its lower Eomologue by any reaction. Its salts arestrictly analogous to those already mentioned.Bx treating bromobutyric acid with an ethereal solution of aniline,p hen y Zumido butyrio acid, CH,. C HZ. C H. (NEIPh) . C 0 0 EI, is obtained .By crystallisation from water, in which it is very slightly solnble, itpresenh itself as a granular, white, very light powder.It is verysoluble in wood spirit, alcohol, and ether, and these solutions, like theaqueous, have a feeble acid reaction. It differs from methyl- andethyl-amidobutyric acids, in that when warmed with solution of silveror mercurous nitrate, it; produces a precipitate of metallic silver ormercury.The hydrochloride is easily prepared by dissolving the acid in dilutehydrochloric acid, and allowing the solution to evaporate slowly in awcuum; thus obtained, the salt forms groups of needles, which arevery soluble in water, but much less so in alcohol and ether. Thecrystals of the hydrochloride rapidly become brown when exposed tolight, and even in darkness, after the lapse of a certain time, theybecome perfectly black. J.W.h 58 ABSTRACTS O F CHEMICAL PAPERS.Two Remarkable Cases of Metamerism in Carbon Com-pounds. By L. SCHREINER ((J. pr. Chem. [2], 22, 353--360).-Theauthor has already described an easy method of making diethyl carbo-nate, CO(OEt), (Annalefi, 197), by slowly adding ethylchlorocarbo-nate (C1.CO.OEt) to dilute sodium ethylate solution contained in aflask provided with a condenser.This simple method has now been adopted by the author to preparecarbonates of the mixed alcohol radicals. Ethyl chlorocarbonate wasfirst allowed to act on sodium methylate. After washing the productwith water and drying it with calcium chloride, it was found to distilin greater part at 100" (730 mm. bar.), a small portion only comingover at 91", and consisting of dimethyl carbonate.The larger portion,boiling at 104", was proved by analysis and vapour-density determina-tion to be methylethyl carbonate, EtO.CO.OMe.By acting with methylchlorocarbonate on sodium ethylate, ethyl-methyl carbonate was obtained. Dimethyl carbonate was preparedin a similar manner.It was found that the methylethyl carbonate and ethylmethylcarbonate thus prepared are metameric bodies, a difference analogousto that already noticed between the corresponding glycollic compoundsbeing observable. The differences are tabulated as follows :-Carbondtea. Glycollate. - -- B. p. Sp. gr. B. p. Sp. gr.Dimethyl . . . . 91.0" 1.0600 134.5" 1.084.5Methylethyl . . 104.0 1.0372 138% 1.0746Ethylmethyl . . 115.5 1-0016 142.0 1.0105Diethyl .. . . . . 125.0 0.9735 158.4 0.9960The author also obtained two metameric derivatives of urea, namelyethylmethylurea and methylethvlnrex. Ethylmet hylurea was pre-pared by heating at 200" in a sealed tube a mixture of ethylic ethyl-amidoformate (EtHN.CO.OEt) with a solution of methylamine inabsolute alcohol. The substance was preoipitated from the alcoholicsolution by addition of ether, or after distillation of the alcohol, it wascrystallised from its aqueous solution by evaporation over phosphoricanhydride. The crystals are deliquescent, and melt at 105".The metameric methylethylurea was prepared in a similar wayfrom ethylic methylamido formate, MeHN.CO.OEt, and ethylamine.Its crystals were very similar t o those of the metameric body, butmelted at 75".After repeated fusion, each of these substances begins to fuse at91", and the fusion finishes at 112".This is considered to be due tothe change into MeHN.CO.ORle and EtHN.CO.OEt; the latter beingknown to fuse at 112.5", and the former probably fusing at 92'.Themetamerism of the pairs of compounds can only be explained by theassumption that the bonds of the carbon atom are not similar.The theoretical importance of the above facts will be evident.F. C.Borocitrates. By E. SCHETBE (Pharnz. J. Trans. [3], 11, 389-390) .--The borocitrates me specially valuable as remedies for diseaseORGANIC CHEMlSTRT. 89of the kidneys and for urinary calculi. Their solvent power forurates and phosphates is about twice that of lithium benzoate.Soonafter administration, boric acid may be detected in the urine, where itoccurs partly in the free and partly in the combined state. Schwartz(Sitzungsbericht d. Dorpater Nuturforscher Ges., 1879, 204) has shownthat the acid magnesium borocitrates, especially those containing theleast proportion of acid, are strong antiseptics against bacteria. Thediborocitrates are the best adapted for therapeutic purposes.Magnesium formi three borocitrates, all of which do not crystal-lise-Magnesium triborocitrate . . . . ( CsEI,O7)zMg,.(Ba’B3Os),.,, diborocitrate . . . . ( ~ 6 H ~ 0 7 ) ~ M g , . ( B 2 ~ z o ~ ) ~ .,, monoborocitrate . . (C6H707)zMg.BH0~.The preparations generally used gave the following results onC6H807* Mg. B (HO),.(1) .. 61.64 6.23 32.13(2) . . 73.50 8-83 16.67analysis :-Lithium borocitrntes are aIF easily soluble in water. They are-Lithium triborocitrate . . . . . . C&,L&O7.B,H&.,, diborocitrate . . . . . . ClsH6Li,07.B,Hz04.,, monoborocitrate . . . . C6H7LiO7.BHo2.Sodium 3orocitrates.-The three sodium salts are known, being pre-pared from the carbonate-Sodium triborocitrate . . . . . . C6H5Na307.B3H306.,, C6H,Naz07.B2H204.,, monoborocitrate . . . . C6H7NaO7.BHO2.Ammonium borocitrates in the moist state gradually decompose, butwhen dry are stable. Three exist, similar in composition t o the sodiuniand lithium compounds.Potassium Borccitrates.-The diborocitrate is crystalline, being theonly one which crysta!lises well.Iron Borocitrattx-Preparations have been made by dissolving ferrichydrate in solutions of the acid borocitrates.Two compounds pre-pared with sodium di- and mono-borocitrate contained 8 and 16 percent. of ii on respectively.By J. THOMSEN (Annulen, 205, 133-138).-The author in another paper (Ber., 13, l;388) has shown thatthe possible constitutional formulae of benzene can be arranged in ninegroups. Of these only two agree with the chemical characters of ben-zene (i.e., the three isomeric tri-derivatives). These two are KekulB’shexagon formula, with the alternate double and single bonds, andLadenberg’s formula with nine single bonds. The aut,hor proposes todecide between these formulse by his theory of the heats of combustionand formahion of the hydrocarbons, for by his researches he has shownthat for single and double bonds an equal amount of energy is deve-diborocitrate .. . . . . . .L. T. 0’s.Constitution of Benzene90 ABSTRACTS OF CHEMICAL PAPERS.loped, whilst for a triple bond the energy developed is nil. Thisapparently extraordinary result can be explained thus. If the energydeveloped by the single bond be expressed by r, by the second affinityby nil, by the third by -r, then the double bond will give an energyof Y, and a triple bond will give nil. This result is in perfect accord-ance with the chemical characters of the carbon compounds. In thecase of the paraffins, in which all the carbon atoms are combinedtogether by single affinities, and all the affinities .of the carhon atomsare satisfied, the author has shown that the splitting off of each affinityis associated with a heat absorption of 14,570 heat-units. In the un-saturated compounds, in which two or more carbon atoms are combinedtogether by $I double or a triple bond, these nmltiple bonds form the attack-it19 point for chemical reagents.For instance, when a molecule of chlorineacts on a molecule of ethylene, whereby the double bond of both car-bon atoms is converted into two single bonds, the chlorine can combinewith both carbon atoms with all the energy which corresponds to theaffinity between chlorine and carbon. The conversion of the doublebond into the two single bonds is not accompanied by an altera-tion of energy. In the case of acetylene, the conversion of the triplebond into a double and a single bond is associated with a developmentof energy in addition to that developed by the affinity of chlorine forcarbon.But when chlorine acts on a paraffin, there must be a split-ting off of a bond and anabsorption of 14,570 heat-units, whether thereaction consists in the expulsion of a hydrogen atom or a dissocia-tion into two hydrocarbon radicles. If the received hypothesis ofbenzene be correct, then the double bonds can be converted into singlebonds by very violent reactions, whilst in all feeble reactions therewill only be a substitution of the hydrogen atoms. The stability ofbenzene points to the absence of double bonds. According to theauthor’s researches ( v i d e suprd), the heat developed in the formation ofa hydrocarbon a t constant volume can be expressed by a formula(C,H,,) = -nd + ( 2 m + z + y ) ~ , in which d is the dissociation-heat of carbon = 39,200 heat-units, x and y the number of single anddouble bonds, and T the heat-absorption in the combination of twocarbon atoms, or one carbon atom and one hydrogen atom = 14,570heat-units.For benzene, adopting KekulB’s hypothesis, we havez = 3, y = 3, 2nz = 6 ; for Ladenburg’s hypothesis ~t: = 9, y = 0,2m = 6, and the heat of formation of gaseous benzene at constantvolume will be in the first case - 6 x 39,200 heat-units + 12 x14,570 heat-units = - 60,360 heat-units; in the second - 6 x 39,200heat-units + 1.5 x 14,570 heat-units = - 16,650 heat-units. Theheat of formation of benzene a t constant pressure is 1,160 heat-unitsgreater, and the value above will become - 59,200 or - 15,490.Ifthese values be subtracted from the heats of combustion of the con-stituents of benzene = 786,840, we have for the heat of combustion ofbenzene vapour, for the first hypothesis 786,840 + 59,200 = 846,040heat-units, and for the second 786,840 + 15,490 = 802,330 heat-units.The experimental value found was 805,800 heat-units. The agreementbetwe& the experimental value and that theoretically deduced byadopting Jhdenburg’s hypothesis points to the conclusion that “ tilesix cai*bon a:oiii.s of benzene are combined together by n i n e single bondsORGANIC CHEMISTRY. 91mzd the hypothesis adopted hitherto of a constitution of benzene with threesingle and three double bonds is iLot conjirnaed by experiwieiit.”Action of Phosphorus Trichloride on Benzene.By H.KOHLER (Rer., 13, 1623--1625).-The author has examined the bye-products obtained when phosphenyl chloride is prepared, in the hopeof finding diphenylphosphorus chloride or triphenylphosphine ; butfound that, besides the reaction PcZ3 + C6H6 = PClz.CGH, + HCl,only the following reactions took place, witlh production of diphenyl andphosphorus-V. H. V.2CGH6 = CsH,.C,H, + H2,2PCI3 + 3H2 = Pz + 6HC1.Action of Sulphuric Acid on the Substituted Nitro- andAmido-benzenes. By. J. POST (AnnuZen,, 205, 33--112).-Theauthor briefly refers to the researches of Hubuer, Ladenburg, Korner,and Nolting on the influence of a substituted element,jor of a groupingon a second grouping iutroduced into the benzene nucleus. Whennitrobenzene is converted into the nitrosulphonic acid, and this isreduced, there is formed a different body, or a% least a mixture ofisomerides differing from that obtained by the direct action of sul-phuric acid on aniline (Meyer and Stuber, AnnaZen,, 165, 165;Limpricht, ibid., 177, ’794; Post and Urlting, Ber., 12, 1460 ; thisJournal, Abst., 1880, 238).On the other hand, the author has established that when a hydroxylgroup is present, i.e., when ortho- or para-, nitro- or amido-phenol isconverted into the sulphonic acid, only one compound is produced.Ifthe nitrophenolsulphonic acids are reduced, the same compound is ob-tained as when the corresponding amidophenols are converted intosulphonic acids (Brackebusch, Ber., 7,163 ; Holst, Ber., 13, 611 ; Abst.,1880, 642).According to the researches of Kolbe and Gaube(Annalen, 147, 71) and Kekul6 (Zeits. f. Chem., 1867, 641), the samecompound is obtained by nitrating paraphenolsulphonic acid and byconverting orthonitrophenol into the sulphonic acid. The author bysnlphating paranitrophenol and nitrating orthophenolsulphonic acidobtained the same compound (Post, Ber., 6, 395, and Stuckenberg,Ber., 7, 1322 and 1055). According to Nolting (Monitscief~t$ 680)these reactions can be attributed entirely to the presence of thehydroxyl grouping ; accordingly the author has substituted brominefor the hydroxyl grouping, and has established that by sulphatingorthamidobrombenzene, and by sulphating and subsequently reducingorthobromnitrobenzene the same sulphobromamidobenzene is produced(Bar., 8, 1557), although it has not yet been settled whether the samehydrogen atom is replaced by the snlphonic group.Hiibncr explainsthese reactions by supposing that when an amido-group is sulphated,the NH, group, by its combination with sulphuric acid, acquiresnegative properties, and acts like the negative nitro-group. To testthis, the author has repeated Meyer, Strnbner. and Limpricht’s ex-periments ( v i d e szp-4). In order t o establish which hydrogen atom isreplaced by the sulphonic group, the author has investigated theinfluence of the presence of a second amido-group by nitrating their0.H92 ABSTRACTS OF CHEMICAL PAPERS.benzoyl derivatives, and subsequently removing the benzoyl groups.But these researches are incomplete, owing to the easy decompositionof the complex beuzoyl derivatives (Stuckenberg, Ber., 7, 1392, andIn order to decide between the isomerism or identity of the amido-phenolsulphonic acid from the nitrophenol, the author has studied thereaction of bromine and iodine on the paranitrophenolsulphonic acid,and investigated the iodo- and bromo-nitrophenolsulphonic acid, anddiiodo- and dibromo-nitrophenols formed in the reactions (Brackebusch,Ber., 7, 167). These compounds were isomeric with those obtained byArmstrong and Brown (this Journal, 25, 859) by the action of bro-mine and iodine, on nitrophenolsulphonic acid from orthonitrophenol.Sulphating Paranitrophenol (m.p. 115'). By J . POST (see alsoBer., 6, 395).-In this paper the only new chemical matter is the cor-rection of molecules of water of crystallisation of the barium salt ofthe paranitrophenolsulphonic acid : i n the former communication inthe Berichte the author attributed to the barium salt the formula~6H,(N02).S0,.0.BaH20, in this paper the author alters the formulaComparison of t h e salts of the nitrophenolsulphonic acidEorner.10, 380-385).to CCH,(NOZ) .SO,O.B*H20.[OH: SOSH: N O z = l : 2 : 41:-f--- Post..... H2O Potassium salt -Sodium .......... 2H,O 2H20 2H20Calcium .......... 3H20 H20 2$Hz0Barium .......... H20 HZO 2H2Oc -- anhyd. Copper ..........Lead ............- - 1&H20.Rer., 7, 1332, and 10, 55 ; this Journal, Abst., 1877, ii, 888).Acid. * Neutral. Neutral.-Nitrating Orthophmolsulphonic acid. By C. STUCKENBERG (alsoAmidophenobdphonic acids.Proof of the Identity and Isomerism of thze various Amidophenol-suZp,honic acids. By F. BRACKEB~JSCH (also Rer., 7, 163, and L. HOLST,Ber., 13, 617 ; this Journal, Abst., 1880, 642).Conversion of Orthophenolsulphonic acid into the Para-compound.By J. POST (also Ber., 8, 1547; this Journal, 1876, i, 579).Orthonitrarnido- and Orthodianzido-p henols and their Nitro-substi-tution Prodwcts. By C. STUCKLNBERG (also Ber., 7, 1322, and 10,380-385; Abst., 1877, ii, 193).-In this paper the only newchemical fact is the proof of the identity of the amidodinitrophenol[OH : NH2 : NO, : NO, or OH : NO, : NH2 : NO, = 1 : 2 : 4: 23,obtained by nitrating the monobenzoyl derivative of paramidonitro-phenol [OH : NH, : NO, or OH : NO, : NH, = 1 : 2 : 41, and subse-quently removing the benxoyl group with picramic acid,C6H20H(N02)2NH2 [OH : NO2 : NO, : NH, = 1 : 2 : 4 : 61.This shows that the ,author's paramidonitrophenol had the constitutionOH : NO, : NH, = 1 : 4 : 6.By J.POST (also Ber., 6, 395)ORGAKIC CHEMISTRY. 93Idroduction of BYorniNe and Iodine i n t o Nitrophen olsulpho17ic AcidBy 3’. BRACKEBUSCH (also Ber., 7 , 167).Sulphonic Acids f ronz hiitrainido- and Diamido- benzenes in Ortho-By J. Pow and E. HARDTUNG (also, Ber., 13, 38;Formation qf Amidosulphobenzeres f r o m Nitrobenzene and A n i l i n e .Oxidation of Nitrogenous Methglated Benzene Derivatives.[OH : S0,H: NOz=l: 2 : 41.u i ~ d Meta-Series.Abst., 1880, 394).By L.WITTING and J. POST (also Ber.., 12, 146cI; Abst., 1880, 238).V. H. V.By A. BRUCKNER ( A n n i l e n , 205, 113-133) .-PART I. Anhydro-,NH.benzamido~a7.atoZuic Acid, CaH,( )/C.C6&cooH[NH : Ilu’ = 1 : 21,N[ C : CCOH=l: 4].-Anhydrotolyldiamidobenzene was prepared eitherby the action of pnratoluic chloride on orthonitraniline, and re-ducing the tolylnitrmdide formed (Stover’s process, Ber., 7, 463,1314), or by the direct action of orthodiamidobenzene on para-toluic chloride. This latter reaction is so violent that it must bemoderated by the addition of benzene. Aft’er evaporation, a mixtureof a neutral and a basic substance is left.The neutral compoundmay be separated by solution in acetic acid, and precipitating withwater ; it forms colourless needles (m. p. 228’), and is most probablythe diparatoluide of orthodiamidobenzene, csH4( NHC 0. C6HiMe) 2.The basic substance is precipitated from the acetic acid solution bysodium carbonate, and is converted into the hydrochloride by hydro-chloric acid. It has the formula C6H4/ \C.C6H4Me[C:Me = 1 : 41,and belongs to the class of anhydro-bases. The author shows that itsproduction in the reaction above is due to the decomposition of thehydrochloride of the toludide into the anhydro-base and paratoluicacid-NH\ N /NH.C O. C6H4Me -N-CJL’ = CsH4/’ %.C6H4Me. +‘NH,C1.C0.CsH4 Me \NH,CI/c6H4~~e.COOH.The base separates out in golden flocks (m.p. 268”) ; its nitrate andsulphate crystallise in long needles.In order to obtain anhydrobenxamidoparatoluic acid, the anhydro-base is oxidised with chromic acid mixture, precipitated with excess ofwater, and the acid purified from the unoxidised base by converting itinto its ammonium salt. Its melting point lies above 300° ; it crps-tallises from water with 1i0H2, and from alcohol with 2H02. Avery soluble potassium salt, crystallising in glistening needles, andsparingly soluble barium and calcium salts are described. The silversalt is an insoluble precipitate, from which may be prepared thecorresponding ethyl salt (m. p. 242”), crystallising in slender needles.NH>C.CsHr)2C0.-The silver salt o€NA d ydrotolylketamine, (CsH494 ABSTRACTS OF CHEMICAL PAPERS.anhydrobenzamidotoluic acid when heated in a sealed tube is decom-posed ; on exhausting the crude prodnct of the reaction with alcohol,and evaporating the solution, crystalline needles (m.p. 277") ofanhydrotolylketamine separate out. A hydrochloride of this base,crystallising 'in long needles, and a platinochloride, are described.PART 11. Oaiclcltioi~ of A,i7,yt~rodiamic7o~aratolylxyl~?~~,NHC6H,Me2/ \C.CeH,Me.[C : Me = 1 : 41. 'dXylidine and paratnluic chloride react to form a hard compact mass,which is best. purified by dissolving the crude product in alcohol, preci-pitating with water, and separating the filtrate by distillation in acurrent of steam. The residue is purified by crystallising out fromalcohol.Pnratolylxylidine forms long colonrless needles (m. p. 137"),insoluble in water, soluble in alcohol and acetic acid. By directlynitrating paratolylxylidine with fuming nitric acid, some higher nitro-compound is formed. The mononitro-derivative can be prepared bythe action of fuming nitric acid on an acetic acid solution of para-tolylxylidine. I t forms golden needles (m. p. 187'). By reducingmononi troparatolylxylidine, it is converted in t o anhydroparatolyldia-midoxylene. The base forms colourless cryqtals (m. p. 217") ; its sul-phate, chloride, and nitrate are described. By its oxidation, an acid,soluble in alcohol, was obtained, but in quantity t'oo small for a miuuteexamination.PART 111.Oxidation of 2lenzotoZuidine.-Benzoparat oluidide is pre-pared by the direct action of benzoic chloride on paratoluidine ; theproduct is dissolved in concentrated acetic acid, and oxidised withexcess of chromic acid. The acetic acid solution is precipitated withwater, and the precipitated acid purified from the unoxidised tolnidideby solution in soda.Benzoparamidohenzoic acid, C,HI(COOH).NHBz[COOH : NHBz =1 : 41, thus prepared, forms stellate groups of needles (m. p. 278'),sparingly soluble in hot water, soluble in alcohol, ether, arid aceticacid. The copper salt is insoluble, the silver salt forms pearlyglistening needles ; the barium and calcium salts are also described.By heating with dilute sulphuric acid at 150-170", it is decomposedinto benzoic and pnramidobenzoic acids.Benzorthoamido1)enzoic acid, C,H4( COOH).NHBz[ COOH : NHBz =1 : 2].-Benzorthotoluidide prepared by a process analogous to thepara-compound crystallises in glassy needles (rn.p. 142')) insoluble incold, soluble in hot water. The orthotoluidide when oxidised withchromic acid gave negative results ; by heating with alkaline perman-p n a t e , it is converted into benzorthamidobenzoic acid. It crystalliseain needles (m. p. 18Zo), insoluble in water, soluble in alcohol andether. The barium and calcium salts crystallise with 8H20, and themagnesium and sodium salts with 4H20. An acid identical with thiswas obtained from orthoamidobenzoic acid by the direct replacementof the hydrogen atom in the amido grouping by benzoylORGANIC CHEMISTRY. 95PART IV.Oziidution of pal-ntolylanilide,C6H4Me.CONHPh(CONHPh : CH, = 1 : 4).Paratoluic chloride and aniline act Fiolently on one another; thepurified anilide crystallises in white needles (m. p. 140-141"),sparingly soluble in water, soluble in acetic acid. The preparation ofthe corresponding acid by oxidation with alkaline permanganate was afailure, nothing but terephthalic acid being produced.Some Constituents of the Essential Oil of OriganumVulgare and Thymus Serpyllum. By E. JAHNS (Arch. Pharm. [3],16, 277--280).-The essential oil of 01-iganum vzclgnre is shown tocontain the same phenols (carvtcrol principally) that are present in0. hirtum and 0. sniyrnmum, although in very small quantities. Theoil of T'hynaus serp.yZZum contains three phenols, one having a smell ofcreosote, the other two, which are removed by ether from the potas!isolution of crude phenols, are thj-mol and carvacrol. Great difficultywas experienced in obtaining the carvacrol in a solid form, as the pre-scnce of a small quantity of thymol lowers its melting point to - 17 O .Artificial and natural carvacrol are identical, the only differencebetween the two up to the present time having been that the naturalsubstance gave a reaction with ferric chloride, whereas the artificiallyprepared carvacrol gave no reaction.This is shown to be due to thesolvent, for when both are dissolved in alcohol, the reaction is similarin both cases. E. w. P.V. R. V.Action of Resorcinol on Urea.By K. RIRNRAUM and G. LURIE(Ber., 13, 1618--1621).-When a mixture of 1 part of resorcinol with2 of urea is heated a t ;150°, until evolution of gas has ceased, a crystal-line reddish-brown residue remains, insoluble in water, alcohol, ether,and in the usual solvents, soluble wit,h difficulty i n glacial acetic acid,readily soluble in ammonia and in alkali, and precipitated from its solu-tion by acids. Its formula corresponds with that of dih7JcZroayphen2/lei~ecymurate, 1 + 6H20.C~HS( O.CsH,.OH)zC,H,( O.C6H*. OH),Cyanuric acid heated with resorcinol at 250" yields the same corn-Phloroglucolphthalein and Diresorcinolphthalein. By G.LINK (Bey., 13,16~52--1656).-The former of these phthale'ins, obtainedby a process analogous to that by which A.Baeyer prepared fluorescein,forms reddish-brown microscopic needles, soluble in alkalis withoutfluorescence, and in water, alcohol, ether, and acetic acid ; it is inso-luble in benzene, chloroform, and carbon bisulphide. When heated, i tbegins to decompose, without fusion, a t 240". I t s composition come-sponds with the formula C,,K,,O7 = 0' \C/ \GO.pound. 0. H.CsH,(OH)z C6H4'C6H2 (0 H) 2 ' \-&/Dissolved in soda solution and treated with zinc-dust, it yields thecorresponding phthalin, in the form of a thick brown oil, becomin96 ABSTRACTS O F CHEMICAL PAPERS.solid on prolonged drying; it could not be obtained in a crystallisedcondition, however.Diresorcinolp7LthaZ~~~ is formed on fusing diresorcinolphthalic anhy-dride and stannic chloride.It forms silvery lamince or needles, con-taining 5!j mols. H,O, which are soluble in alkalis with a blue, and inconcentrated sulphuric acid with a brown coloration. It decomposesa t 245", without fusing.The corresponding phthalin crystallises in colonrless lamince, contain-ing SQ H20 ; it melts at 238", with partial decomposition. 0. H.Some Derivatives of Isophthalic Acid. By B. BEYER (J.py.Chew.. [el, 22, 351-352) .-A quantity of isophthalic acid, preparedby Fittig's process, was converted in part into chloride by heatingwith phosphorus pentachloride, and the chloride was converted intoamide by careful addition to aqueous ammonia solution. The amideis a light white powder (m. p. 265"), slightly soluble in boiling alcohol,and almost undissolved by the other usual solvents.When heatedwith phosphoric anhydride, it yields metadicyanbenzene (m. p. 156").The nitro-isophthalic acids were made by treating the acid withfuming nitric acid ; one of them crystallising in scales was that describedby Fittig (m. p. 249') ; but an isomeric acid crystallising in smallneedles was also obtained (m. p. 260").These derivalives of isophthalic acid were identified by a nitrogendetermination in each. Tile author intends to examine them fully.F. C.Preparation of Orcinolcarboxylic Acid (Pseudorcellic Acid).By H. SCHWARZ (Rer., 13, 1643--1645).-By a method identical withthat for the preparation of salicylic acid by Rolbe and v. Heyden, theauthor obtained from orcinol, orcinolcarboxylic acid identical with thatproduced by Senhofer and Brunner (Wiei~. Akud.Ber., 1880) by adifferent method. It is very readily soluble in alcohol and ether ; withdifficulty i n water, from which it crystallises in long white needles.Heated to fusion, carbonic anhydride is evolved, and orcinol is reformed,readily recognisable by the green fluorescence when heated with alkaliand chloroform. This pseudorcellic acid, unlike ordinary orcellic acid,does not yield an ethereal salt when boiled with alcohol.Compounds of Orthobenzoylbenzoic Acid with Phenols.By H. v. PECHMANN (Ber., 13, 1608-1618) .--MonoxydiphenylphthaleEn,formed on heating benzoy lbenzoic acid with phenol and stannic chloride,crystallises from ether in colourless crystals (m. p. 155"), soluble in allordinary solvents, excepting water and light petroleum. It dissolvesin alkalis with a violet colour, similar to that produced by phenol-phthalein.Acetykizonorcydiphen,ylphthale'i.r?, is obtained as a crystalline mass(in.p. 135--136"), on heating the former compound with acetic anhy-dride and sodium acetate. It yields a dibromo-compound (m. p. 196")on bromination.0. H.1Monoaydiphenylmethan.ecarboxylic acid,CsH,. CH (CGH4. OH). CGH,. COOHORGANIC CHEMISTRY. 97is obtained in colourless, shining crystals (m. p. 210') by reducing theoxydiphenylphthaleyn with zinc-dust.Monoxy7ph enylanthranol is formed on treating the phthalejin withconcentrated sulphuric acid, b u t could not be obtained in a crystallisedstate. By oxidation with sodium manganate, an oxanthranol wasobtained, which was converted into the corresponding acetyl-derivative,crystallising in needles (m.p. 207-WO"). 0. H.Vulpic Acid. By A. SPIEGEL (Bsr. 13, 1629--1635).-Theauthorhas investigated this acid, which has recently been studied by Mollerand Strecker (Annalen, 113, 56). He obtained from Cetraria vu@ina,collected fit Pontresina, in Switzerland, 1.5-2 per cent. of the acid,from the Scandinavian plant about 4 per cent. It melts at 148", andwhen heated to 200" splits up into methyl alcohol and pu7vic anhydride,CI8H1,,O4, which crystallises from benzene in the form of light yellowneedles (m. p. 120-121"), is but slightly soluble in alcohol, more readilyin hot chloroform, benzene, glacial acetic acid and acetone, insoluble inwater or in alkaline carbonates.It sublimes unchanged when care-fully heated. When heated with soda solution and acetone, it dissolves,and the addition of hydrochloric acid to the solution throws downpulvic acid, C18H1205 (m.. p. 214r-215;). The same acid is obtainedfrom vulpic acid by heating it with milk of lime and acidulating thesolution. It is readily soluble in alcohol, less SO in chloroform, ether,or acetic acid, and in water.Neutrulsilver pulvate crystallises in long needles. BariuwLpulvata forms brightyellow laminze, sparingly soluble in water. Calcium pulvate crystallisesin long yellow needles, and copper pulvate in dark blue needles. Thealkaline pulvates are very soluble, and crystallise with difficulty.The potassium salt, of efhi/Zpdvic acid is obtained on adding Dnlvioanhydride t o alcoholic potash.The free acid crptallises from alcoholin transparent yellow tablets (m. p. 127-128"). When heated, itdecomposes, with formation of ethyl alcohol.Methylpulvic acid is identical with vulpic acid.The formation of an acid ether in alkaline solution by the mereaddition of an alcohol to an anhydride is without parallel, but resemblesthe direct formation of the ethers of orsellic acid.Pulvamic acid, ClRHlaN03, formed by adding ammonia to pulvic anhy-dride, crystallises from benzene in monoclinic yellow prisms (m. p.220"). It is soluble in ordinary solvents, insoluble in water andmineral acids ; unaltered by nitrous acid.Dimethyl pulvate melts a t 138T139".MethyZ acetylpzdz:ate, CleHlo05AcMe, obtained by treating vulpic acidwith acetic anhydride, crystallises from alcohol in long silky needles(m.p. 156")) insoluble in soda solution.Well crystallised derivatives of vulpic acid are formed on treatingits amrnoniacal solution with zinc-dust. 0. H.Acid silver pdvate crystallises in tufts of yellow prisms.Action of Phosphenyl Dichloride on some Chlorides. By H.KOHLER (Ber., 13, 1626--1629).-1odine monochloride acts violentl98 ABSTRACTS OF CI3EMICAL PAPERS.on phosphenyl chloride, free iodine sepamtes, and phosphenyl tetra-chloride is produced-PClZCcH, + 2IC1 = PCldCGH, + 1,.Neither tin chloride noy silicinm chloride acts on the phosphenylchloride.Titanic chloride yields the compound PClaC6H5.Antimoiiy tri-cliloride mixes with the phosphenyl chloride in all proportions, withoutformation of a definite chemical compound. The pentachloride, how-ever, is readily acted on, with the formation of antimovy phosp2ietLylsirperchloride, PCl4CGH5.SbCl5, a solid, hygroscopic substance, fumingwhen exposed to the air, and decomposing on heating with the produc-t ion of pamdich lor0 benzene-PCI,C,H,,SbCl, = PCI, + SbCI, + HCl + C,H,Cl,.0. H.Baeyer's Process for the Synthesis of Indigotin. By ROSEN-sq IEHL ( A m . Ckirn. Phys. [53, 21, 286-288) .-&eyer has describedtwo processes for the preparation of indigotin from cinnamic or phenyl-acrylic acid : this is first converted into ortho-nitro-cinnamic acid by t'heusual method, the ortho-derivative being appareirtly the only one fromwhich indigotin can be obtained.In one process, the ortho-nitro-cinnainic acid is converted (in the same way that cinnamic acid istransformed into phenyl-oxyacrglic acid) into ortho-nitro-phenpl-oxyacrylic acid, which when heated a t 110", swells up and graduallydarkens in colour. When the product thus formed is treated withalcohol, an insoluble residue of indigotin remains, but the yield isonly very small, and the decomposition is probably highly compli-cated.The second Drocess gives much better resiiltq. The ortho-nitro-cinnamic acid is converted by the action of bromine, and subsequenttreatment with a boiling alcoholic solution of potash into ortho-nitro-phenyl-propiolic acid, and when this acid is heated a t 110" with itmixture of' an alkali and a reducing agent, preferably a mixture ofsodium carbonate and glucose, indigotin separates out in the crystal-line form, C9H,NO* + H20 = CsH5N0 + C02 + E20.If a fabric be impregnated with a mixture of the acid, glucose, andsodium carbonate, and heated to the required temperature, by meansof superheated steam, for example, indigotin is formed.and is firmlyfixed in the fibres of the cloth. The importance of this reaction incolour-printing is obvious.It would appear that the plienyl group in the indigotin is capableof undergoing various substitutions, with production of colouringmatters giving different shades of blue. C. H. B.New Hydrocarbon from Sequoia Gigantea.By G. LUNGEand T. STEINKAULER (Bey., 13, 1656--1658).-From the leaves of theCalifornian giant pine, Sequoia gigantea, the authors obt,ained whitelaminar crystals with bluish fluorescence (m. p. 105"; b. p. 290-300"). This substance is very readily soluble in all ordinary solventOXGAMC CHEMISTRT. 99except water, and has the formula C1,Hl,. It is isomeric withfluorene, and the authors propose for it the term seyuoieKe.Besides this substance, the leaves of the Sequoia yield threedifferent oils, boiling respectively a t 155", 190--2OO", and a t 240" C.0. H.Combinat ions of Anthracene with the Oxides of Nitrogen.C. LIEBERMANN and L. LINDEMANN (Her., 13, 1584--1590).-Nitro-compounds of anthracene have not hitherto been obtained, because ontreatment with nitric acid, anthraceiie a t once yields anthraquinone andnitro-anthraquinones.By acting on anthracene dissolved in glacialacetic acid with nitrous acid vapours, the authors have obtainedvarious additive products.Anthracene Nitrate, C~4Hlo.N0,H.-A current of nitrous acid ispassed into glacial acetic acid at 30", in which anthracene is sus-pended ; it dissolves, and crystals soon separate from the brown solu-tion. These washed with alcohol and recrystallised from benzene,form white needles or prisms, melting, with decomposition, a t 12,5".The compound, C14H10.2N02, is obtained if the temperature is notallowed to rise above 15". The anthracene alters but little in appear-ance, but gradually becomes converted into the new compound.Thismay readily be separated from the anthracene by boiling with benzene,in which it is sparingly soluble ; it may be purified by crystallisationfrom toluene. It is very sparingly soluble in alcohol, forms whitelaminae, fusing at 194", and decomposing a few degrees above that point,leaving nitrosoanthrone, Cl4H9NO2, or C6H4 : CO.CH(Nc)) : C6H4, theterm anthrone being proposed for such anthracene derivatives as con-t'ain one of the carbon atoms of the central Cz group in the form ofcarboxyl. Nitrosoanthrone is more readily obtained in the form of ayellow powder bv heating the compound C,IHl,.N0.3H with dilutealkali. It crystallises from alcohol in beautiful long yellow iieedles(m. 1). 146").Nits.osohydranthroIae, C,rHllNOz, is obtained in the form of a flesh-coloured precipitate on neutralising the alkaline filtrate from thenitrosoanthrone with acids, the liquid being kept cool.cCodium nitrosohydranthrone, C14H10NOLNa,, separates on the additionof concentrated soda, solution to an alkaline solution of the previouscompound, as long yellow needles.Nitrosoanthrone heated with alcoholic potash, or with tin andglacial acetic acid, is readily converted into the corresponding hjdr-anthrone.On oxidising the various nitro-compounds with chromic acid, pureanthraquinone is formed, proving that the nitrogen group is joined tothe central Cz group.On heating a, mixture of nitrosoanthrone and phosphorus penta-chloride at 180', a grey mass is produced, which after treatment withboiling alcohol and crystallisation from a mixture of light petroleumand benzene yields dichlorunthracene tetrachloride, Cl4H8Cl6, in theform of white needles (m. p.205-207'). Treated with boilingalcoholic potash, it turns yellow, and yields tefr~clzZoraizthracer,e,Cl4HGClI, very little sohble in alcohol, more so in boiling glacia100 ABSTRACTS OF CHEMICAL PAPERS.acetic acid, and crystallising in yellow needles (m. p. 152’). Byoxidation with chromic acid, a well crystallised dichloranthraquinoneis formed, giving an alizarin coloration on fusion with potash. Thehydroxyanthraquinone produced has not yet been examined.0. H.Derivatives of Anthraquinone. By C. LIXRERMANN (Ber., 13,1.596-1 603) .-Experiments were undertaken to decide which of thetwo possible formulse for anthraquinol, proposed by Grabe and Lieber-CH(0H) ,C(OH),mann, was correct, C6H4’ ‘(&Ha or C6H4’ I ~ C ~ H I .‘co-’ ‘C(0H)By acetylisation, the monacetyl derivative was the only one thatcould be recognised with certainty, the existence of a diacetyl com-pound being doubtful.Anthraquinol treated with excess of ethyl iodide, or amyl iodide,vields only mono-substitution derivatives. Y EthyZoxyanthrone, c6H4<CI-I-OEt.) GO- >c6&, erystallises in stronglyrefractive rhombic prisms (m. ‘p. 10~-107”) : the alcoholic solutionhas a beautiful blue fluorescence. On heating the compound, it distilswith loss of water.On treatmentwith fuming nitric acid, the ethyl derivative yields a di?~itro-cornpound,CIaH,(NO,),( OH).OEt, and by reduction with hydriodic acid andred phosphorus, a hydrocarbon, C16Hlfi, ethylanthracene dihyclride, isproduced, the amyloxyanthrone giving the corresponding hydride,Cl9Hz2.Both are colourless oily liquids of high boiling point. Bothoxyanthrones dissolve in concentrated sulphuric acid, forming cherry-red solutions, from which water precipitates needles, dissolving inalcohol with magnificent preen fluorescence.The author concludes that the constitution of anthraquinol is repre-Amyloxymthrone forms shining colonrless crystals.CO- sented by the formula, C6&< C H ( ~ H ) > C ~ H ~ . 0. H.Reduction-products of Camphor. By H. SCHROTTER ( B e y . , 13,1621-1623) .-Camphor distilled over heated zinc-dust yields benzene,toluene, paraxylene, and cymene. Hence the products are identicalwith those obtained by the action of fused zinc chloride on camphor(Fittig, Koebrich, and Jilke, Annalen, 145, 129). Instead of laurene,described by Fittig, the author obtained further a hydrocarbon boilingbetween i64-167”, and probably a pseudocumene.By C.0. CECH ( J . pr. C‘J6em. [2], 22, 39,5-398).-The author communicates some preliminary work on the subject of thisoil. During the roasting of coffee berries, the odour of the oil is veryapparent, and it may be seen on the surface of the concentrated extractof coffee in the form of small drops. The quantity of oil presentvaries according to the source and condition of the berries, being from8-13 per cent., and of this a t least one-half is volatilised during theprocess of roasting.No considerable escape of gas or oil vapour occurs0. H.Coffee OilORGANIC CHEMISTRY. 101during the roasting until the berries turn brown. At that stage, theberries are turned out and tossed in the air so as to cool themvery rapidly and prevent their burning ; the oil vapour is thus lost,but might be saved by connecting the roasting drum with an exhaustorwhich would prevent the risk of the berries catching fire, and wouldrender it possible to remove and condense the vapour of the oil. Theoil thus obtained would doubtless be of value for liqueurs.The preparation of the oil was carried out by extracting it from50 11)s. of powdered coffee berries of various kinds by means of ether-alcohol.I n this way about 1,200 grams of a green, transparent,thick oil were obtained. It deposited crystals of caffe'ine after stand-ing for a time ; and after three years separated into crystalline fattyacids, and a clear green layer of liquid oil, the crystals forming abouttwo-thirds of the whole. .F. C.Palembang Benzoin. By E. SAALFELD ( A d . Pharm. [3], 16,280).-Palembang benzo'in from Sumatra is free from cinnamic acid,and gives a yield of 10 per cent. of benzoic acid. It is better adaptedfor preparing the tincture than the Siamese gun, as the colour of thetincture is lighter, has a fainter odour, and does not become milkyLight Resin Oil. By W. A. TILDEN (Ber., 13,160&1607).-The distillate boiling under 80" consists chiefly of isobutazdehyde ;between 103-104" a mixture of hydrocarbons distils ; these partiallypolymerise on treatment with sulphuric acid diluted with 25 per cent.of water and an oil, boiling between 245-247' is obtained.Heatedwith sulphuric acid until sulphurous anhydride is evolved, a blackliquid is obtained which yields an intensely green solution whendiluted with alcohol, and soon deposits a green precipitate. Thehydrocarbons left undissolved by dilute sulphuric acid, heated with amixture of concentrated and fuming sulphuric acid, separate into aportion not acted on, consisting apparently of a heptane (b. p.95-97', sp. gr. a t 15" 0-763), whilst the green sulphuric solu-tion, on dilution with water, yields a black precipitate, probably ofthe empirical formula C2,H2,03.On oxidation with nitric acid thisfurnishes two acids, of which one readily crystallises ; these have notyet been examined.When the fraction distilling between 103-104" is shaken withwater in contact with air, it yields the crystalline substance C10H2404,described by Tichborne (Pharm. J. Trans. [3], 1, 302).The fractions of higher boiling point were free from toluene, butcontained an optically inactive terpene.The Bitter Principle and Resin of Hops. By M. ISSLEIB(Arch. Pharrn. [ 3 ] , 16, 345-363) .-The literature of the subject isfirst discussed, the discrepancies existing between the statements of thevarious authors are pointed out, the cause of these discrepancies beingthe imperfect methods employed for the separation of the various sub-stances present in the hops.By the term " bitter principle " is to beunderstood substances which under the influence of boiling acids oralkalis, and sometimes ferments, break up into sugar and some other.when added to water, but is precipitated in flocks. E. w. P.0. H.VOL. XL. 102 ABSTRACTS OF CHEMICAL PAPERS.substance, belonging then, as a rule, to the glucosides. They have for themost part a bitter taste, an acid or neutral reaction: and a few of themcontain nitrogen. They differ from the alkalo‘ids in not containingnitrogen and in their feeble action on the animal economy, picrotoxin,colchicin, and a few others being exceptions. At the same time asthe author examined the extract of hops, he also examined the com-position of “ lupulin,” which, according to Ives, is a yellow powderfound at the base of the scales of the hop cones.After a preliminary and comparative trial of the effects of hot andcold water, ether and alcohol, on both lupulin and hops, he proceedsto describe the method he has employed for the isolation of the bitkei.principle.An extract of hops with cold water was treated with animalcharcoal, and the charcoal after careful drying was exhausted with90 per. cent. alcohol ; the result was a yellow solution, which onpartial evaporation yielded a precipitate of a brown resin ( a ) , and inthe solution a bitter substance remained which could not, be crystal-lised. Ether removes from the aqueous solution of the above only thebitter principle ( b ) , leaving another substance which is not bitter( c ) , dissolved in the water.The true “ bitter ” amounts to only 0.004per cent. of the hops, whereas when lupulin is submitt,ed to a likeprocess the yield is 0.11 per cent. of the lupixlin employed. The“bitter” ( b ) , which is pale yellow, darkens at 60”, and if the tem-peratnre remains constant for some time it can be powdered; it issoluble in cold water, alcohol, benzene, &c., and is amorphous, non-nitrogenous, and slightly acid. Alkalis dissolve it with an intenseyellow coloration, but no colour is produced by the addition of ferrousor ferric salts. From analysis, it would seem to be of the compositionCz9H4sOlo, and under the influence of sulphuric acid it is decomposedinto “ lupulic ” acid and “ lupuliretin,” thus :-2czgH46oio + 31-I20 = CioH16O4 + C,oH82019.Bitter principle.Lupuliretin. Lupulic acid.Of the properties of lupulic acid, no description is given, except thatit is crystalline, as the quantity at hand was insufficient for its exami-nation, but the barium salt was prepared, and has the formula-The resin (a), referred to above, which is separated during theevaporation of the alcoholic extract from the charcoal, has the com-position C1,H,,O3, and .forms compounds with lead, barium, and cal-cium. The substance (c) is probably an oxidation product of theessential oil of bops, and is produced as follows :-CioHuO + 50 = CiuHmO6.Oil of hops. Insoluble aub-stance ( c ) .Such substances are often produced during the exhaustion of anyplant with alcohol, being at first soluble, but after evaporation of thealcohol become insoluble.The results are then, that in the hop arecontained a pseudoglucoside, C29H4601t3, which splits up into “ lupulic ORGANIC CHEMISTRY. 103acid and lupuliretin, which last is formed from the hop resin bytaking up the elements of water-CIOH14O3 + H'40 = CIOH1604,Hop resin.and this resin is produced by an oxidation of hop oil-CioHi& + Oa = CioHuO, + 2&O.Oilof hops.whilst the substance (c) insoluble in ether, is produced by simple oxida-tion of the oil of hops, CioHi8O + 5 0 = C10H1806. E. W. P.Resin of Leptandra. By J. U. LLOYD (Pharm. J. Trans. [ 3 ] , 11,370--371).-The author is of opinion that the resin of leptandra ofcommerce does not consist merely of the resin precipitated by pouringan alcoholic: extract of Leptptnndra uirginica into water.To prepare the resin, the root is extracted with alcohol, the extractis evaporated to the consistency of a syrup, and poured into ten timesits volume of water, when the resin separates out.The supernatantliquid from this is decanted and boiled with 5 per cent. sulphuric aciduntil it loses its bitter taste, and a further quantity of resin is thus sepa-rated. The precipitated resin is heated in a steam-bath with constantstirring until it reaches such a consistency t,hat when cold it willbreak ; it is then broken into fine pieces and exposed t'o the air t o dry.The resin prekipitated by the sulphuric acid is dried by simply expos-ing it to the atmosphere.The solid alcoholic extract is prepared bymixing the extract evaporated to the consistency of a thick syrup withsome of the dried resin prepared as above, and finally drying themixture in a current of warm air.The author considers that the bitter principle which remains insolution after the alcoholic extract is poured into water is a glucoside,but gives no proof of the fact other than the taste disappears when thesolution is boiled with sulphuric acid. L. T. 0's.Gloriosa Superba. By C. J. H. WARDEN (Pham. J. Trans. [3],11, 495-496).-With a view t o throw light on the poisonous principleof the Gloriosa superbu (an Indian plant, nat. ord. Liliaceae) the authorhas undertaken a chemico-physiological research.The botanical cha-racters of the plant are fully described. Its juice has a strongly acidreaction and slightly bitter taste ; the old roots have a sweet taste.The root of the plant collected before flowering, when cut and driedin the air, in some parts assumes a yellow colour, which is also pro-duced by. moistening the root with an alkaline solution ; the colour isdestroyed by acids. The fresh roots contain 81.06 per cent. moisture.The amoiint of extractive matter in fresh and old roots differs, thatof the latter being much less than that of the former-New root. Old root.Alcoholic extract .......... 13.01 6.05Aqueous ,, .......... 23.98 19.41Ash.. ..................... 4.58 4.47i 104 ABSTRACTS OF CHEMICAL PAPERS.The aqueous extract of the fresh roots is of a reddish colour, hasa bitter taste and strongly acid reaction ; it reduces Fehling’ssolution ; contains a trace of tannic acid ; caustic alkalis darken itscolour.The alcoholic extract contains a dark and light resin (a and @), alsoa bitter principle, superbin.These are separated by pouring the con-centrated extract into water acidulated with acetic acid. The tworesins are precipitated ; the solution is neutralised with sodium car-bonate and filtered from a trace of resin which is thrown down ; thefiltrate is acidulated with sulphuric acid and precipitated with tannicacid. The precipitate is collected, mixed with an equal bulk of limeand a little water, the mass dried, and extracted with boiling alcohol.On evaporating the alcoholic solution superbin is left : i t is a violentpoison, 0.047 gram being sufficient to kill a full-grown cat.The resins are separated by treating the mixture with benzene, inwhich the @-resin is soluble and the a nearly insoluble.The traceof a-resin dissolved is separated by evaporating the solution until allthe benzene is expelled, and agitating the residue with ether and sodiumcarbonate ; the p-resin is dissolved and the a-resin remains in cornbi-nation with the sodium carbonate; on evaporation, the p-resin isobtained.The dark resin is purified by repeated solution in potash and preci-pitation by dilute acid. Another method to separate the resin is totreat the root with lime and digest with alcohol, when the 6-resin isdissolved, or by dissolving the mixed resin, in alcohol, adding milk oflime, and after evaporating to dryness boiling out the &resin withalcohol.The a-resin which remains apparently in combination withthe lime may be separated from it by heating with dilute hydrvchloricacid.Tartaric acid is also contained in the root.Gloriosn superba and Scilla maritinin belong to the same family;it is probable that their active principles are closely allied, if notidentical.I n a future paper, the chemical properties and physiological actlionsof the various constituents will be described, L. T. 0’s.Viburnum Prunifolium. By H. ALLEN (Pharm. J. Trans. [3],11, 413-414) .-The alcoholic extract of the root of Viburnum pruni-foZium contains a colouring matter which is precipitated on additionof lead acetate, and a brownish resin of very bitter taste, which it isimpossible to obtain free from sugar ; it is, however, probably a gluco-side.The colouring matter, from wliich the lead is separated bymeans of sulphuretted hydrogen, gives with gelatin a brown preci-pitate of tannate, with ferric chloride a greenish-black. It has anastringent slightly bitter taste. The lead sulphide precipitate, whenboiled with alcohol, gives a solution yielding precipibates withmercuric chloride, ferric chloride, soda and potash, and with leadacetate..The ethereal extract yields viburnin, obtained by Kramer fromT-ibzwnum, opdus, a yellowish-green mass with bitter taste, soluble inalcohol, sparingly soluble in water.The residue from the ethereaORGANlC CHEMISTRY. 105extract, when treated with water, yields oxalic, malic, and citricacids.By extracting the bark with water and distilling the extract withsulphuric acid, valeric acid is obtained.The ash, which amounts to about 9 per cent., consists of thesulphates and chlorides of calcium, magnesium, potassium, andiron. L. T. 0’s.Eriodictyon Californicum. By W. C. HOLZHAUER (Pharnz. J.Trnsss. [3], 11, 170).-The leaves were exhausted with alcohol andwith water. The alcoholic extract contained a pale yellow volatileoil, lighter than water, of aromatic taste and smell ; and a yellowish-white crystalline substance, tasteless and odourless, insoluble in coldwater and benzene, sparingly soluble in hot water, imparting to it anacid reaction, very soiuble in chloroform, ether, and alcohol.Tanninwas also found in the extract.In the aqueous extract gum was detected, associated with somebrown colouring matter and with tannin.On adding water to the ethereal extract, a resinous precipitate basobtained, and the siipernatnnt liquid contained a crystalline substancesimilar to that contained in the alcoholic extract.The resinous precipitate consisted of a vegetable wax, caoutchouc,and a brittle resin of amber colour, having an aromatic slightly bittertaste and a faint odour. L. T. 0’s.A r a b SpinOSa. By L. H. HOLDEN (Pharm. J. Trans. [3], 11,210).-The barks of the Aralia spinosa, or false prickly ash, and theXccrLthoxyZum, or true prickly ash, differ very much in their physicalproper ties.The former presents a comparatively large number of spines, abouta quarter of an inch long, thin, slender, tapering to a fine point,having round or oval bases ; the bark breaks with tough, but nearlysmooth fracture.The latter has only a few spines of the same lengthas those of the former but with two edged with linear bases of aboutthree-quarters of an inch in length. The bark is brittle, and has anon-fibrous fract’tire.The Arulin spinosn bark is extracted with alcohol, and the extractevaporated to dryness ; the residue mixed with alcohol to form a pasteis treated with benzene, which removes the fat. The residue is thenexhausted with ether to remove tannin and resin. The tannin givesa precipitate with lead acetate, a green colour with ferric salts,and a ruby-red with potash.It coagulates albumin, is astringent,and soluble in ether, alcohol, and water. The residue is a brownopaque fusible solid, volatile a t high temperatures ; it is slightlymid; soluble in alcohol and ether, but insoluble in water, benzene,and chloroform.When the residue from the alcoholic extract is dissolved in waterand the solution treated with lead acetate, a precipitate is formed,which carries down mechanically the bitter principle; this may beseparated by washing the precipitate with alcohol. On evaporatin106 ABSTRACTS OF CHEMICAL PAPERS.the alcoholic solution, a light yellow glucoside is obtained, towhich the name aralz'in is given. It is neutral, soluble in alcohol,dilute acetic acid, and water, with which it froths excessively onagitation ; it is insoluble in benzene, chloroform, and ether.Hydro-chloric and sulphuric acids bleach araliin, the characteristic odour ofthe plant being evolved. It gives no precipitate with lead acetate,platinum chloride, or mercuric chloride ; it does not give any of thereactions for the alkalo'ids.When nraliin is dissolved in dilute hydrochloric acid and the soh-tion is boiled, a white, tasteless, and odourless precipitate is formed, forwhich the name araliretin, has been adopted. The solution con-tained sugar. When araliin is boiled with potash, an amber colouris prodnced. Tannic acid, on boiling, produces a flocculent preci-pitate. L. T.0's.Analysis of Damiana. By A. B. PARSONS (Pharrn. J. Trans. [3],11, 271--272).-The results of the analysis of Damiana (Turneraaphrodisiaca) are :-Moisture, at 113-125" C:. .............. 9.06Ash.. ................................ 8.37Chlorophyll, soft resin and volatile oil .... 8.06Hard brown resin.. .................... 6.39Sugar, colour, and extmctive matter ...... 6.42Tannin .............................. 3.46Bitter substance. ....................... 7.08Gum ................................ 13.50Starch isomerides ...................... 6.25Acid and alkali extracts.. ............... 10.02Albuminoids ....Cellulose. .......The medicinal properties(1.) Volatile oil, whichsence of-oils....................... 14-88 ......................5.0398.42of Dsmiana may be attributed to the pre-seems to be allied to the terebinthinate(2.) Soft resin, an oleo-resin in consistence, having a brown colourand very acrid taste, soluble in alcohol (80-90 per cent.), chloroform,ether, carbon-bisulphide, benzene, and light petroleum ; it is onlysparingly soluble in ammonia and potash. It produces unpleasantirritant effects.(3.) Hard brown resin (m. p. 85") is tasteless, soluble in alcohol ;forms soluble soaps with ammonia and potash. It probably consistsof two different resins and some colouring matter.(4.) Bitter principle of light brown colour. It is amorphous,soluble in water and alcohol, but insoluble in ether, chloroform, ben-zene, light petroleum, and carbon bisulphide.It is not a glncoside,nor does it yield a precipitate with lead acetate ; it is a very valuabletonicORQANIC CHEMISTRY. 107(5.) The gum, which is contained in large quantities in the plantis white, but becomes black on exposure to the air.(6.) The tannin has no astringent properties, but gives a greenish-brown colour with ferric salts. Damiana appears also to containminute quantities of volatile and non-volatile organic acids, which givea purple precipitate with ferric chloride; these are not included inthe above analysis.By H. REINSCH (J. pr. Chem. [2], 22, 188--191).-Theauthor’s son, P. Reinsch (Bot. Centr., 4 and 5, ISSO), from a micro-scopical examination of coal, finds that it consists for the most part oftranslucent globules, 0.13 to 0.24 mm.in diameter, giving a blackcross with polarised light ; besides which, there is a dark opaquefibrous structure of diverse form, and rarely occurring in cell-likeformations. The properties of the globules reminded the author ofthose of chcnopodin found by him in 1863 in Clhenopod;um albuin(Neu. Jahrb. f. Pharm., 20, 268).In order to ascertain whether the globules consisted of chenopodin,some powdered coal was boiled with water, but the soluble productwas found to be chiefly sodium chloride, with traces of iron and nochenopodin. By extracting the portion insoluble in water with alco-hol (94 per cent.), a clear yellowish solution was obtained, blueby reflected light, and having an odour of coal-tar. This solution wasconcentrated by distillation on the water-bath.On cooling, a verysmall quantity of delicate snow-white flakes were found in the upperportion of the retort ; these resembled chenopodin, and appeared underthe polariscope as a net of delicate polnrising needles. The residue inthe rettort had a slight smell of tar. On evaporating a drop, distinctcrystals were obtained, showing no cross, however, under the polari-scope. The distilled spirit was perfectly clear, but sliglitly fluorescent,and when mixed with a large quantity of water, became bright blue byreflected light. The author considers the crystalline body, whichpartly evaporates with the alcohol, to be altered chenopodin.No crystalline sublimate was obtained by the dry distillation of coalat the temperature of melting lead.From the quantity of water ob-tained, the author considers that coal contains more than 5 to 8 percent. of oxygen (uumbers usually given for oxygen + nitrogen). I nconclusion, the aathor directs attention to his observation of the largeamount of phosphoric anhydride in coal (Jahresb., 26, 317), which i ncoals he examined amounted to 1 per cent., and this, on burning thecoal, necessarily escapes into the air, since coal ash contains meretraces of phosphoric anhydride. The atmosphere is accordingly notonly a source of carbonic anhydride for plants, but also, from thelarge arnount of coal consumed, a source of phosphoric anhydride.L. T. 0’s.Coal.4’. L. T.Composition of Aesculin and Aesculetin. By C. LIEBERXANNand R.KNIETSCH (Ber., 13, 159W--l596).-According to the authors,acetylueicuktin contains only two acet’yl groups, and has the formulaC9Ha04Acz, instead of three such groups, as stated by Nachbauerand Sciiiif. Hence SchiE’s formula for aesculetin,CJ3,(OH) (COH),.CHOI08 ABSTRACTS OF CHEMICAL PAPERS.is doubtful. It only admits of the introduction of two bromine atomsinto the benzene group or into the molecule of aesculetin, whilst Lie-bermann and Knietsch obtained on heating a solution of the substancein glacial acetic acid with three molecules of bromine, a yellow crystal-line powder, which after crystallisatioii from alcohol forms long yellowneedles, C,H3Br304 (m. p. 240'). Tribromaesculetin treated withsodium acetate and acetic anhydride, yields ti.lbrumd.iacetaesculetin,C9HBr,(AcO),02, crystallising from alcohol in long, white, verythin needles (m.p. 180-182"). The same compound is formed bythe action of bromine 011 a hot solution of acetaesculetin in glacialacetic acid.The authors confirm Rochleder's empirical formulze for aesculetin,C9H604, and for aesculin, Cl5HI6O9.Aesculin, recry s t a k e d from its aqueous solution, loses 24 per cent.= l&H,O on drying a t 120-130" C. If bromine is gradually added toa cooled solution of aesculin in glacial acetic acid, R white precipitate ofdibromaesculin (m. p. 1!33-195"), C1,H,,B_riOg is obtained. It yieldsneedles of a dib.roni~ent~cetaescuZ~~, C15H9A~5Br209 (in. p. 2O3--'LO(io).Treated with concentrated sulphuric acid, it yields dihrom aesculetin,C,H4Br,O4, slightly soluble in water, and crystallising from alcohol i nyellowish needles (171.p. 233"), which may be converted into dihro/izdi-acetaesculetin, C,H2&2Br204 (m. p. 177"). 0. El.Aspidospermine and Paytine. By N. WULFSBERG (Plzann. J.Trans. [3], 11, 269-271).-The author makes a botanical comparisonbetween the " white payta bark," which yields paytiiie, and the " whitequebracho bark," which yields aspidospermine, and then procceds tomake a comparison between the chemical results obtained by Hessewith payttirie (Annnlen, 154, 287), and by Fraude with aspidospermine(Rer., 11, 2189, and 12, 1560).Pay t in e.Colourless prisms.Bitter taste.Readily soluble in alcohol andether.Sparingly soluble in water.M. p.156" C.Heated above m. p. chars, andyields oily distillate.Crystalline hydrochloride, hy-driodide and nitrate. Sulphate,oxalate, chromate, and nitro-picrate are amorphous.Hydrochloride soluble in 16.6Darts water a t 15".A spidospal-mine.White prismatic crystals, withBitter taste.Soluble in 48 parts alcohol (99' per cent.) a t 14" C., and in 136Sparingly soluble in water.He,ated above m. p. decom-poses, evolving irritating va-pour, having some resemblanceto odour of acrole'in.simple shining facets.parts ether a t 14" C.M. p. 205-208°C.Does not form crystalline salts.Hydrochloride readily soluble inwaterORGANIC CHEMISTRY. 109SoIutions of hydrochloride pre-cipitated by mercuric chloride(yellowish).Picric acid gives yellow flocks.Chromate, a yellow amorphousprecipitate.Hydrochloride gives with PtCj, ayellow precipitate, which whenboiled with hydrochloric acid,gives a brown-red solution,changing in colour to blue,with separation of blue preci-pitate.Mercuric chloride gives white pre-cipitate with hydrochloride.Picric acid yellow precipitate.Potassium chromat,e and dichro-mate give yellow precipitates inconcen t rated solutions.PtCI, gives yellow flocculent pre-cipitate, which when dissolvedand boiled with PtCI, is colonreddeep violet.From this comparison the author considers it probable that thesetwo alkaloids are identical.The different formulE proposed for the two compounds by the twoauthors may be explained by the fact that Hesse dried his paytine at130---140” C., whereby 1 molecule of water of crystallisation is drivenoff.And, moreover, he finds that, in different samples crystallisedfrom different solvents, the water of crystallisation behaves very dif-ferently ; Frmude, however, states that in the preparation of aspido-spermine, a high temperature is to be avoided. If, then, to Hesse’sformula for paytine, C,,H,,N,O,, a molecule of water be added, a for-mula is obtained agreeing more closely with the result o€ Fraude’sanalyses than either of the forrnuke proposed by him (viz., CzlH24N,0z*and C2zH30N202). The results of the analyses of the platinochloridedo not, correspond very well on account of the reducing action of theakalojid.The geissopermine of Hesse is distinguished from aspidospermineand paytine by its sparing solubility in ether, and the purple-red colnurit gives wihh nitric acid ; it does not reduce platinum chloride, and hasthe formula C,,H,,N20z.H,0.Should the identity of these two alkalo’ids be established, the authorproposes to retain the name paytine. The payta-bark on account ofits richness in starch and the absence of volatile compounds, is suitablefor the manufacture of brandy,DitaYne.By E. HARNACK (Ber., 13, 1G48). Controversial reply toHesse (Amden, 203, 144).L. T. 0’s.Lepidine. By S. HOOGEWERFF and W. A. VAN Dow (Rer., 13,1639-1640) .-When cinchonine is decomposed by potash, lepidine isfound in considerable quantity in that portion of the product whichboils a t 250-270”.It was obtained in a pure state by precipitatingthe solution of the 8cid sulphate with alcohol, recrystallising the sul-phate, and decomposing it with potash. Lepidine prepared in this way* The analytical results do not agree with this fqrmula3 10 A33STRACTS OF CHEMICAL PAPERS.boils a t 256-258'. I t s acid sulphrcte ( C,oHgN),H2S0,, ciptallises inneedles; the clichromate, from hot water, in golden-yellow needles, whichbecome brown when exposed to light, and decompose a t 100-110".Lepidine pZatinochZoride (C,,HgN.HC1),PtCl4 + 2H20, forms orange-red needles. With silver nitrate, lepidine yields white needles(CIOHgN)2AgN03, fusing below 100".On oxidation with alkaline permanganate, lepidine first yields methylpyl.idinedic,arbozyZir, acid, which is subsequently converted into pyri-dinetricurboz ylic L L C ~ I ~ .Lepidine therefore should be considered as a methylquinoline.Apophyllic Acid.By E. v. GERICHTEN (Ber., 13, 1635-1638).On treating apophyllic acid with hydrochloric acid (sp. gr. 1.185) a t240°, methyl chloride is produced, together with a nitrogenous acid.The latter crystallises in short prisms (m. p. 2G6-268"), and sublimeswith partial decomposition ; the solution is precipitated by lead, silver,and barium salts. Copper acetate produces no change in the cold, but onheating a flocculent precipitate separates, which redissolves on cooling ;on prolonged heating, it becomes crystalline, and then remains in-soluble in cold water. Ferrous sulphate does not produce a, precipi-tate, When the acid is heated with soda-lime, it decomposes withformation of p y r i d i n e . Its composition is represented by the formula,C,H,N04, and corresponds with that of a pyridineclicadoxylic acid,C,H,N(COOH),.It appears to be identical with that obtained byHoogewerff and van Dorp (Ber., 13, Sl), and with the cinchomeyonicacid of Weidel (Ber., 12, 1145).The author is of opinion that the cinchona alknloiids and those ofopium must also be considered to be derivative# of pyridine andquinoline.Cotarnine appears to contain the COOMe group of apophyllicacid. 0. H.0. H.Investigation of the Processes of Decomposition occurringduring the Rotting of Eggs. By C. 0. CECH ( J . pr. Chenz. [2],22, 338-344).-l'he main causes of rotting are high temperatureand moisture. The various stages of decomposition are classed inseven groups : -( 1.) When exposed to warmth and moist>ure and notfertilised, the albumin first becomes watery, and the membrane inclos-ing the yolk bursts, allowing a partial mingling to occur a t the surfaceof the contact of the yolk and albumin. (2.) As the decompositionproceeds the contents become a homogeneous cheesy mass, first white,then yellow, and finally greenish in colour.(3.) They then graduallychange into a 3-ellsw or greenish liquid. (4.) If the fresh uiifertilisedegg is kept a t rest and a t a constant temperature of' about 14" withexclusion of moisture, the yolk remains entire, and after the gaseousproducts of decomposition and the water of the albumin have escapedby diffusion through the shell, the residue forms a crust round t,heflattened yolk, the shell appearing half empty.(5.) When the outerpart of the yolk is very firm, the decomposition is often limited tothe albumin, the yolk remaining unaltered in form as a black mass.(6.) Iu fertilised eggs, containing the " tread," the decompositioORGANIC CHENISTRP. 111commences at the middle of the egg, and the albumin is often unalteredwhilst the yolk has become watery. (7.) All ihe above-mentionedchanges proceed with a rapidity dependent on the temperature andmoisture of the air, and on whether the eggs are a t rest or not. Some-times the pores of the shell become closed, and the gaseous productsbecome confined under pressure, causing the egg to burst sponta-neously or when opened.The author reserves the account of qualitative and quantitativechanges occurring during these seven kinds and stages of putrefactionfor another paper, and considers only the possibility of applying rotteneggs to some technical purpose.A number of rotten eggs were freed from their shells, and the con-tents evaporated to dryness, partly in mass and partly in groups asabove.A fatty mass, free from the smell of rotten eggs, was obtained ;and from this an amount of oil was extracted which equalled in amountthat obtainable from an equal quantity of fresh eggs. The residuewas a dirty white earthy mass containing coagulated albumin, nitro-genous substances and salts. Studied in groups, it was found thateggs from class (3) contained from 2 to 3 per cent.less oil than fresheggs ; but eggs from class (2) gave an excess of from 1 to 2 per cent.,and from class (4) all the oil of the fresh egg was obtainable. Rotteneggs on an average yielded 10.5 per cent. of oil, whilst fromfresh eggs11.27 per cent. was obtained.The entire dried residues, as well as the extracted oil, could beeasily saponified with soda; the soap thus obtained is perfectly freefrom smell, and forms a good lather; the dry particles in theresidue which remain unsaponified, impart to the soap a mottled ap-pearance, and in no way spoil its smell or appearance. If the fat isextracted before being saponified, the residue would be valuable forthe preparation of manure, since the ash of the yolk contains 60.1per cent.of phosphoric acid. F. C.Researches on the Physical Chemistry of Blood. By G.HEFNER (-7. pr. Chew,. [Z], 22, 362--388).-The author minutelydescribes investigations undertaken with freshly devised apparatus,the object of which was to redetermine the number of C.C. of oxygenat 0" and under 1 metre pressure, which 1 gram of the colouringmatter of the blood can retain in feeble chemical combination. Theresult thus obtained leads also to a, revision of the molecular weightsof haemoglobin and oxyhaemoglobin.The absorption coeflicient, as above defined, had been already foundto be 1.16, after the experimental result had been corrected for theoxygen absorbed by the serum, assuming that liquid to have the samecoefficient of absorption as water.This assumption being unproved,and the correct determination of the coefficient being necessary for thespectrophototnetric determination of oxygen in blood, the furtherexamination was undertaken.The fundamental expression, 7c = a h + bp, where k = the totalvolume of gas absorbed reduced to 0" and 1 metre pressure, h = thequantity of haemoglobin present., p = the pressure under which absorp-tion occurs, a is a constant representing the quantity of gas chemicall112 ABSTRACTS OF CHEMICAL PAPERS.held by unit of colouring matter, b the quantity absorbed by theliquid, and varying with the pressure p . The constants were deter-mined from a large series of experiments, in which 12, and k werenoted when the temperature was uniform, but pressure varied.I nthe first set of absorptiometric experiments, carbonic oxide was 77sedinstead of oxygen, because it is free from the source of error arisingfrom the combination of oxygen with the metallic impurities of themercury and the organic matters present in the blood.Preparation of Reduced Blood Solution.-Defibrinated dog's bloodwas diluted from eight to ten times, and reduced by passing throughit hydrogen gas prepared from zinc and dilute snlphuric acid, andpurified by passing through potassium permanganate solution, sodasolution, and water successively. A special apparatus was usedt o prevent loss of the blood by frothing. After about two hours,200 C.C. changed to a beautiful purple-violet colour, and showed onlythe reduction-band in the spectrum.The liquid was then transferredto a bulb provided with two stopcocks, and exposed to a Sprengelvacuum a t a temperature of 30" to remove all hydrogen and carbonicanhydride from solution. I t was then preserved in the bulb, the stop-cock of which had been closed after the vacuous portion had beenallowed to fill with mercury.Determination of the H03nzogZcjbin.-T he quantity of haemoglobin wasestimated as oxyhtlemoglobin by the spectroscope in the way alreadydescribed (this Journal, 16, YlO), and after dilution to an exte.ntestimated by careful w.eighing, the determination was always madein liquids of two different degrees of dilution, and a,lso for each liquidon two different regions of the spectrum. The accuracy of the deter-mination, as well as the purity and suitability of the liquid, was thusmade certain.The absoiptiometer employed by the author was a modified form ofWiedemann's ; it is figured and fully described. Its principle consistsin agitating the known volume of reduced blood solution with anexcess of the pure gas in a vessel closed by stopcocks, and then ascer-taining the weight of mercury which enters after agitation owing tothe absorption of it portion of the gas, precautions being taken toprevent the contact of the blood and gas whilst the latter is being in-troduced, and to maintain the temperature and prehsure of the gasuniform both before and after agitation.The mercury to be weighedwas obtained after the agitation in a pulverised condition, and requiredtreatment with strong sulphuric acid to cause the minute globules tounite ; it was then washed and dried. The gas was always employedin a moist condition. In all cases experiments were made with twosuch apparatus, capable of holding different quantities of blood. Thetrustworthiness of this apparatus was first proved by determiningby its means the coefficient of absorption of carbonic anhydride ; t,henumber obtained closely agreed with that found by Bunsen. Sincethe blood solution could not be long preserved unaltered, it was ne-cessary to make a number of sets of determinations, each set requiringa freshly made solution.From a number of experiments with carbonic oxide, the value ofa = 1.20, and of b = 0.6305 ; the latter divided by the volume of blooOROANlC CHEMISTRY. 113solution gives 0.01979, a coefficient for serum less than that for purewater.Experiments were then made with oxygen : the results obtainedwith this gas showed much more variation than those with carbonicoxide. The constants found were as follows : n = 1.25 ; Z, = 2.117.From the latter, it appears that the coefficient for serum is greaterthan that for pure water, a result doubtless due to the nnion of oxygenwith the impurities of the mercury and the organic matter of theserum. Further experiments were made with pure aqueous solutionof the colouring matt,er, to eliminate the latter source of error. I nsome experiments the coefficient for oxygen was found t o be smallerthan that for carbonic oxide. This was doubtless due to the evolutionof carbonic anhydride formed by the oxidation of organic matter inthe blood, Taking into consideration the probable error in each ex-periment, and calculating the coefficient ( a ) from the results obtainedwith both carbonic oxide and oxygen, the value 1.202 was obtained.Two determinations were then made by allowing carbonic oxide toact on blood saturated with oxygen. The oxygen was thus replacedby carbonic oxide, arid was determined by an analysis of the residualmixture of ca,i-bonic oxide and oxygen, which was removed by theSprengel pump (Zeits. f. Phys. Chenz., 1, 313). The author does notconsider that this method gives the whole amount of oxygen, sincesome is fixed by union with metallic impurities of the mercury, byorganic matter in the blood, and by the grease on the stopcocks. Thenumbers obtained in two experiments were 1.17 and 1.18.Finally, ur),diZuted defibrinated blood, which had been violentlyshaken with air at 20" and 727 mm. pressure, was freed from oxygenby the Sprengel pump, and the volume of oxygen was determined.After allowing for that dissolved by the serum, and determining thehemoglobin by the spectroscope in a portion diluted 151 times, thecoefficient of absorption was found to be 1.1988.From all the above det>erminations, the most probable value of thecoefficient appears to be 1.202.Assuming that 1 molecule of hEmoglobin unites with 1 moleculeof oxygen, the molecular weight of haemoglobin would be 14,133, andof oxyhcemoglobin, 14,165 : the numbers calculated from the mosttrustworthy results of analyses of oxghaemoglobin are 14,129 and14,161. These agree well with the formula CsJsH,,?jN,,,FeS,O,,, forhcemoglobin, and this would give for the coefficient of absorption foroxygen by calculation the number 1.202, which is identical with thatfound by the above experiments. Should this molecular weight becorrect, it proves the molecule of haemoglobin to be a t least five timesas heavy as that of albumin.The author in conclusion expresses a hope that the determinationof these constants may render possible the application of the simpleand exact spectrophotometric method to the determination of the pro-portion of oxygen in the blood as i t enters and leaves different organsa t rest and repose, and thus lead to a knowledge of the '' physiologyof o~;ye;en.'~ * F. C

ISSN:0368-1769    

DOI:10.1039/CA8814000082

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年代:1881

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114 ABSTRACTS OF CHEMICAL PAPERS.P h y s i o l o g i c a l C h e m i s t r y .Nutritive Value of Glycerol. By E. MUNK and others (Bied.Centr., 1680,654-65$).-Experiment~s with dogs showed that glyceroldoes not economise the decomposition of albumin in the organism,nor does it take the place of carbohydrates or fats when given as food.Relations between Work and the Decomposition of Foodin the Body. By 0. KELLNER (Bied. Centr., 1880, 584-594).-Inthese experiments a horse was caused to go through the same amountof work every day, until the separahn of nitrogen in the urinebecame constant. The work was then trebled, the diet remaining thesame, and it was found that the quantity of nitrogen in the urine in-creased. This also occurred when larger quantities of nitrogenousfood were given; and the amount of secreted nitrogen returned tothe original limit only when a sufficient diet of farinaceous food wasallowed, thus showing that the carbohydrates may be considered as asource of muscular activity.When an animal is in good workingcondition, about half the quantity of additional farinaceous diet maybe expended in work.J. I(. C.J. K. C.Hydrolytic Action of the Pancreas and Small Intestine. ByH. T. BROWN and 3. HERON (Annulen, 204,228-251).-An aqueousextract of the pancreas, as well as the finely-divided gland itself, con-verts starch into maltose and achroo-dextrin ( f ) . On prolongedstanding, dextrose is also formed. Neither the aqueous extract northe gland itself has any action on cane-sugar. The inversion of cane-sugar, noticed by some observers, is due to the development of bac-teria.The small intestine has the power of inverting cane-sugar, ofconverting maltose into dextrose, and of acting on starch as a weakferment. The tissue of the intestine is much more active than theaqueous extract. The action of the intestineseems to have no relationto the number of Lieberkuhn and Brunner's glands, but to depend moreon the distribution of Peyer's glands. In the conversion of starch intoreadily diffusible dextrose capable of assimilation, the action of thepancreas and Peyer's glands seems to be mutual and interdependent.The pancreas converts the starch into maltose, and the Peyer's glandsthen complete the process of conversion into dextrose.By R.ENGEL (Anm. Chim.Phys. [ S ] , 20, 2SO--'L40).-Wohler was the first to show that benzoicacid during its passage through the animal system was converted intohippuric acid ; and more recently Baumann has observed that phenolunder similar circumstances is capable of combining with sulphuricacid, forming an ethereal snlphate, which is afterwards eliminatedby the urine as a potassium or sodium salt ; at the present day theexistence of phenol in the urine, especially of herbivora,'is well estab-lished. Again, Nencki has shown that indole and indican can bedetected in the animal economy ; the former is the result of the putre-G. Ti. A.Phenol in the Animal EconomyVEGETABLE PHYSIOLOGY AND AGRICULTURE. 115faction of albumino'ids, whether by decomposition in air, or by theagency of the pancreatic digestion, whilst a subcutaneous injectionof indole is found to pass out of the system as indican ; researches ofthe same nature have also established that phenol and other analogouscompounds are produced by the putrefaction of albuminojids togetherwith indole, and that the quantity of indole diminishes exactly in pro-portion as the phenol increases ; a portion of this phenol is eliminatedin the excreta, but by far the greater part passes away in the form ofpotassium-phenyl sulphate as before stated.One of themost constant products of the decomposition of albuminoyds is tyro-sine, a body which is found both in the spleen and pancreas, andwhich in certain cases of degeneration of the liver appears in notablequantity in the urine.The injestion of tyrosine determines an aug-mentation of potassium-phenyl sulphate in the urine ; there can belittle doubt, therefore, but that the phenol is produced by the decom-position of the tyrosine.To detect the presence of phenol, the liquid is acidulated with sul-phurio acid and distilled, the distillate is tested either with ironperchloride which gives a blue colour, or with bromine-water ; thislatter reagent is exceedingly sensitive, giving even with very dilutesolutions of phenol a white crystalline insoluble precipitate of tribromo-phenol. This reaction may also be made a quantitative one ifrequired, the weight of the phenol present being equal to ___ of theweight of the tribromo-compound found. Baumann estimates thephenyl sulphate present in urine by precipitating and removing thesulphates with barium chloride and acetic acid, and then boiling thesolution with hydrochloric acid ; the ethereal sulphate is thus decom-posed, and a fresh precipitate of barium sulphate is obtained. Fromthe weight of the latter, the weight of phenyl sulphate present is easilycalculated. J. W.Phenol appears also to be formed from another source.28.410

ISSN:0368-1769    

DOI:10.1039/CA8814000114

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年代:1881

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VEGETABLE PHYSIOLOGY AND AGRICULTURE. 115 Chemistry of Vegetable Physiology and Agriculture. Alcoholic Fermentation in the Roots of an Apple Tree. By P. v. TIEGHEM (Bied. Cenfr., 1880, 688-689).-Owing, according to the author, to the great dampness of the soil, the cells in the roots of an apple tree underwent an alcoholic fermentation for some time, during which the tree presented a sickly appearance. Fermenting Power of Diastase. By M. J. KJELDAHL (Bied. Centr., 1880, 689-691) .-The relation of the strength in diastase of two solutions of malt-extract may be expressed by their relative power of affecting a given weight of gelatinised starch under the same con- ditions, when the quantities of extract used are not very large : the limits of temperature between which the greatest fermenting action t8akes place are from 54" to 63" ; the presence of small quantities of mineral acids assists the action.J. K. C. J. K. C.116 ABSTRACTS OF CHEXICAL PAPERS. Ammonia in Plants. By H. PELLXT ( B i e d . Centr., 1880, 673- 675).-As the ammonia, in beetroot seems to be present in the form of ammonium-magnesium phosphate, the finely-grated roots were digested with hydrochloric acid, and distilled with magnesia ; 0.19 per cent. of ammonia was found in the dry root; part oE this amount may, however, arise from the decomposition of amido-compounds present. in the plant. Similar experiments were made with the liquid ex- pressed from muscle, and with yeast. Ox muscle gave 0.15, and yeast 0.059 per cent. ammonia. J. K. C. Chemical Composition of Linseed. By A.LADUREAU ( B i d Centr., 1880, 670-671).-Russian linseed when grown in France becomes valueless after the second generation : according to the author, this is due to the ash of the seed losing more than half its phosphoric acid by being cultivated in French soil. J. K. C. Composition of Oats. By L. GRANDEAU and A. LECLERC ( B i d Centr., 1880, 669--670).--The authors have performed 120 analyses of oats; the mean result of these, together with the maximum and minimum quantity of each constituent, are given in the following table :- Mean. Maximum. Minimum. Water.. . . . . . . . . . . . . . . 12.01 15.50 8.50 Protei'n . . . . . . . . . . . . . . 9.80 12.43 7-1 2 Nitrogen-free extract . . 59.09 64-65 48.60 Fat .................. 4.58 7.1 3 2.77 Fibre ................ 11.20 14.89 6.73 Ash ..................3.32 6.14 2.06 J. R. C. Fattening of Oxen. By A. VOELCRER (Bied. Centr., 1880, 660- 661).-A comparison of the fattening effects of oil cake with that of a mixture of Indian corn meal and cotton seed cake, given as fodder to yonng oxen, was in favour of the latter mixture, both on the score of cheapness and efficiency. J. K. C. Cultivation of Furze. By SCHIRMER-NEUHANS ( B i d . C'errtr., 1880, 678--679) -On dry soils, the cultivation of dwarf furze as fodder may be substituted with advantage for clover : analysis of the dried substance gave the following results :-Ash, 5.78 ; fibre, 46.80 ; albumin, 9-76 ; fat, 1-92 ; nitrogen-free extract, 33-74 per cent. J. K. C. Use of Lupines as Fodder. By v. PUTTKAMMER and others (Bied. Ceiitr., 1880, 661--664).-The fsvonrable effect of steaming on lupine seeds has been confirmed in many cases by the authors.J. K. C. Cultivation of Soja Bean. By C. 0. HARZ (Bied. Centr., 1880, 671-673).--Various kinds of this bean were planted in the neigh- bourhood of Munich, but did not thrive in a satisfactory manner, as the climate was too cold for them. J. I(. C.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 117 Cultivation of various kinds Of Beet. By J. GODEFROV and A. DOUDOUY ( B e d . Centr., 1850, 652 -654).-Chemical manures such as sulphate of ammonia, superphosphate, &c., gave better results with the larger kinds of roots than stable dung : the “ mammoth ’’ pro- duced the largest crop. J. K. C. Drainage Water from Moorland. By R.SCHILLER (Biecl. Cedr., 1880, 636--638) .-The water contained generally about 100 grams of dissolved solids to the gallon, consisting chiefly of sulphates of lime and magnesia: the amount of nitrates was greater in the summer months than in winter. J. K. C. Behaviour of Phosphates in Water charged with Carbonic Acid. By H. ALBERT and R. WAGNER ( B i e d . Cent?-., 1889, 640- 647) .-The authors find that precipitated dicalcium phosphate is easily soluble in water charged with carbonic acid, and is not thrown down by calcium carbonate : solutions of alkaline nitrate or carbonate also readily dissolve this phosphate. Precipitated phosphate of iron or alumina is not SO easily attacked by any of these solvents, espe- cially if it has been well dried. All kinds of soil absorb phosphoric acid from these solutions, the amount of absorption being determined by the time of contact only in the case of soils rich in lime, and in this respect carbonic acid solutions of dicalcium phosphate play the same part as aqueous solutions of superphosphate, the absorption being the more complete the more lime there is present in the soil.J. K. C. Organic Matters in Soil ; Examination of Grandeads Theory. By 0. PITSCH (.Landw. Versuchs.-Stat., 26, 15O).-This long paper is a reportdof the author’s examination of the theory of Grandeau as to the value of humus in the soil. The words employed by Gmndeau himself when enunciating his theory in the “ Annales de la Station agronomique de 1’Est ” are as follows :- 1. The mineral constituents of the soil are the true nourishment of plants, and have the property of traversing vegetable tissues, the roots inclusive. 2.Organic matters are of the highest, importance in the development of vegetables. They are not themselves assimilated by the roots, but play the part of media between the soil and the plant; they combine with mineral matters, and form soluble com- pounds, which the roots of the plants decompose in their turn, seizin7 on the inorganic and leaving the combustible matter untouched. This matter is the indispensable vehicle required to transfer and render available the mineral matters powerless to nourish plants without their help. 3. Fertile soils offer their mineral ingredients to plants in a state similar to that in which they are contained in stable manures.This theory, if correct, woulcl give a new insight into the nourish- ment of plants, and as Grandeau estimates the valuable combiiiations of humus with inorganic substances by the amount of so-called “ matiere noire,” which can be extracted from the soil by ammonia, it would then offer it11 easy method of calculating the value of all soilsd VOL. XL. Ic118 ABSTRACTS OF CHEMTCAL PAPERS. and not only so, but would enable the farmer to bring his soil up to any desired standard of fertility. The opinions of practical men agree to a certain extent with this theory (Ville and his followers excepted), and it has found considerable confirmation from the experimental cultivation of sandy soils-in certain instances the mixture of peaty soil with sand and road-scrapings giving exceedingly good results.The author asserts that all or nearly all Grandeau's own experiments were made with sandy and forest soils, that few or none were made with true clays, and that the physical condition of the soils so experi- mented on, caused by the addition of the organic matter would in great part account for the successful results. Impressed by the import- ance of the subject, the author undertook its searching examination. l i e obtained samples of 13 soils from various farms in the Netherlands, the cultivators of which gave him full information as to their methods of farming, and the productiteness of their soils. The method em- ployed by Grandeau for the separation of his " matiere noire '' was to place 300 or 400 grams of the clay in a large funnel, in which was a smaller one containing pieces of broken glass or porcelain, remove the lime by treatment with dilute HC1 (10-25 C.C.to the litre of water), wash the residue to neutral reaction and dry. An aliquot part was then exhausted of its " matiAre noire " by dilute ammonia (half water), the filtrate evaporated to dryness, ignited, and the P,O, esti- mated in the ash ; the author suggests certain improvements, but they are unsuitable for abstraction. Even with modifications, however, the author does not think that this mode of soil examination will displace that already in use ; he allows that ih may prove a valuable addition to present methods, and thinks, as a result of the many analyses performed during the investigation, that the amount of P,O, contained in the ammoniacnl extract is even a better measure of the productive capacity of different soils than is the quantity of P,05 found in the acid extract as now prepared.An improvement, he believes, would be to estimate the P,05 in botb ways ; t!hen should the acid extract contain a large, and the ammonia- cal a small percentage, the soil would require a manure rich in organic matters ; if the reverse be the case then one containing abundance of phosphates should be applied, whilst if both extracts are proportion- ally pcor or rich the fertility of the soil will be less or greater accord- ingly. These conclusions, however, are considered as independent of the theory of plant nutrition under examination, which requires that although plants can by their roots extract nutritious matter, not only from solutions, hut from the solid particles with which they come in direct contact, still profitable results cannot be obtained unless solvents be present t o offer a ready supply t o their roots.And further that it is the presence of humus matter which causes the transfer of the inorganic matter to the plant by directly modifying the chemical character of these mineral combinations. The author does not agree with this view, and thinks it more reasonable to believe tlhat the roots of the plants or matters in the soil other than humus have a solvent power similar to that of acids.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 119 He reviews some of the experiments relied on by Grandeau as proof of the correctness of his views, one beiiig the growing of certain seeds in quartz sand, exhausted with acid, washed, and supplied with dilute " matiere noire ;" the experiment proves simply that i t is capbZe of nourishing piants, but proves not,hing more, and from elementary analyses of two saniples of that substance, the author found it to con- tain all inorganic substances required for the nurture of vegetables; that it does yield those matters is not denied, but for the support of the theory it must be h r t h e r proved that the presence of humus is indis- peizsable, and sufficient evidence of this had not been adduced.Another experiment of Grandeau referred to, is one in which a sample of Russian black earth was divided into two portions, one exhausted of its " mati&re noire," the other not ; kidney beans were planted in both, in the exhausted sample the show of leaves was extremely small, and they quickly shed, in the other portion the growth was healthy and development of leaves normal.The author's explanation of this is that the tye:itment with dilute ammonia necessary to remove the " matiere noire " removed at the same time the inorganic nutritive hatters formerly present. Another experiment relied on by Grandeau is one in which four boxes, each a square meter of surface, were planted with various seeds, two boxes containing clayey and two light calcareous soil : one box of each was mixed with a certain proportion of peaty earth coiitaining little phosphoric anhydride ; the product of the boxes containing the admixture was in all instances considerably higher than the unmixed samples.Grandeau himself admits that, the physical condition of the former was much superior to that of the latter ; and in this fact Gut- author finds sufficient explanation of increased production, it being allowed by all practical farmers that the diligent working of the soil considerably influences the crop. The aut'hor concludes that a critical examination of the proofs advanced shows that not one of them neces- sarily compels the adoption of the theory, whilst none of them are contradictory to it nor to other theories, previously either partially or wholly formulated by Simon, Mulder, and Dettmer. Previous experiments of the author on the solubility of phosphates in ammonium citrate led him to try the effect of ammonium hnmate in the expectation that its behaviour towards phosphates would be similar ; the process of obtaining the pure humic acid is described a t length, and its combination with ammonia, hut it is too long for abstraction.The ammonium humate was found in fact to exercise quite as solvent an effect on the phosphates as the ammonium citrate ; and when mixed intimately in the soil during cultivation, it would come into so many point's of contact with the particles of phosphate that it should exercise even a more potent effect. The author concludes by declining to accept the theory of Grandeau, but admits the very great importance chemically and physically of humus in soils ; he asserts, however, that its value varies with the iiature of the soil ; and, further, that whilst Ville and his followers who insist that inorganic substances are the only valuable manure materials err in one direction, Grandeau errs as greatly in the other by the exorbitant value Be places on organic matter.J. F. k 2120 ABSTRACTS OF CHEMICAL PAPERS. Solubility of Certain Manure Materials. By A. MORGEN (Landw. Vwszcchs.-Stcct., 26, 51-75) .-The number of nitrogenous substances employed in the manufacture of artificial manures is very large. An impression prevails that they all require about the same period of time for their decomposition in the soil, and chemical analysis attaches equal importance to the nitrogen contained in all. Practice, however, shows that the actual value of such substances to the farmer depends greatly on the time they require to decompose and render their valuable constituents available for plant nutrition.The subject has not hitherto been experimentally treated in Ger- many, and the author of the present paper gives a report of numeroiis experiments intended to throw light on it. They were ma,de with horn meal and leather meal, substances prepared from manufacturers' waste by steaming aiid drying. The experiments were divided into three series, in oneof which the samples were treated with water for a lengthened period in the water-bath at a high temperature, with the addition in certain cases of a little sewage water to hasten decomposi- tion. The second series was similar to the first, except that the samples were left exposed to the air a t the natjural temperature of the atmosphere in a garden. The third differed from the other two in treating, not equal quantities of the substances, but quantities con- taining equal amounts of nitrogen.I n the first series, 5 to 10 grams of each substance were placed in a litre of distilled water, with, in two cases, 5 C.C. of sewage water added, and kept a t 30" C. in a water-bath for 131 days. The amount of nitrogen which had passed into solution a t the end of that time was in the case of the leather meal one-third, and of the horn meal two- thirds of the total contained in the samples. The addition of sewage water does not appear to have affected the result, except in augment- ing the amount of nitrogen in the form of ammonium compounds ; the concentration of the solutions does not appear to have a t all affected the results. In the second series some of the specimens were boiled before sub- mitting them to prolonged action of the air and sun.These showed slightly lower numbers, owing probably to the boiling having rendered albuminous substances insoluble. The total results were very similar to those of the first series, and strongly in favour of the horn meal. The third series yielded slightly different yet generally similar results, and all the experiments confirm the verdict of practical men that the nitrogen in horn (and bone) meals is much more valuable as a manure ingredient than that contained in leather meal. It must be borne in mind that the whole object of the leather manu- facturer is to render his leather insoluble, and that some mode of re- moving the tannic acid must be found before waste leather will be as easy of decomposition as bone or horn meal. J.F. Experiments with Various Phosphates as Manure. By E. WEIN (Bied. Cemtr., 1880, 647--651).-The soil in which these experi- ments were carried out was a mixture of sand and cakium carbonate. Peas and oats were manured in different plots with various forms of phosphate, soluble and insoluble, and in every case dicalciuni phos-AIfALY TICAL CHEMISTRY. 1 2 1 phate yielded the best result. The author explains this by assuming t'hat in the presence of excess of calcium carbonate, soluble phosphate of lime is converted into tricalcium phosphate, which is not readily absorbed by the roots, whereas dicalcium phosphate does not undergo this change.J. K. C. Pigeons' Dung. By E. WEIN (Bied. Centr., 1880, 693).-A sample taken from a church tower gave the following results on analysis :-Water, 10.99 ; organic and volatile bodies, 56.65 ; ash, 33.36 ; nitrogen, 2.25 ; phosphoric acid, 2-04 ; and potash, 5.49 per cent. J. K. C. Manure for Fruit Trees. (Bied. Centr., 1880, 693.)-Experi- ments which were carried on in Potsdarn sho'wed the most suitable ilianure for fruit trees to be a mixture of potash sulphate and super- phosphate, which increased the number of blossoms considerably. J. K. C. Manuring of Vines. By P. WAGNER and H. PRINZ ( B i d Ce?ttr., 1880, 638-640).--TTines extract yearly from the soil only about three- fourths of the quantity of potash and phosphoric acid extracted by cereals ; the amount of manure applied is, however, generally greater.J. I(. C.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 115Chemistry of Vegetable Physiology and Agriculture.Alcoholic Fermentation in the Roots of an Apple Tree. ByP. v. TIEGHEM (Bied. Cenfr., 1880, 688-689).-Owing, according tothe author, to the great dampness of the soil, the cells in the roots ofan apple tree underwent an alcoholic fermentation for some time,during which the tree presented a sickly appearance.Fermenting Power of Diastase. By M. J. KJELDAHL (Bied.Centr., 1880, 689-691) .-The relation of the strength in diastase oftwo solutions of malt-extract may be expressed by their relative powerof affecting a given weight of gelatinised starch under the same con-ditions, when the quantities of extract used are not very large : thelimits of temperature between which the greatest fermenting actiont8akes place are from 54" to 63" ; the presence of small quantities ofmineral acids assists the action. J.K. C.J. K. C116 ABSTRACTS OF CHEXICAL PAPERS.Ammonia in Plants. By H. PELLXT ( B i e d . Centr., 1880, 673-675).-As the ammonia, in beetroot seems to be present in the formof ammonium-magnesium phosphate, the finely-grated roots weredigested with hydrochloric acid, and distilled with magnesia ; 0.19 percent. of ammonia was found in the dry root; part oE this amount may,however, arise from the decomposition of amido-compounds present.in the plant. Similar experiments were made with the liquid ex-pressed from muscle, and with yeast.Ox muscle gave 0.15, and yeast0.059 per cent. ammonia. J. K. C.Chemical Composition of Linseed. By A. LADUREAU ( B i dCentr., 1880, 670-671).-Russian linseed when grown in Francebecomes valueless after the second generation : according to the author,this is due to the ash of the seed losing more than half its phosphoricacid by being cultivated in French soil. J. K. C.Composition of Oats. By L. GRANDEAU and A. LECLERC ( B i dCentr., 1880, 669--670).--The authors have performed 120 analysesof oats; the mean result of these, together with the maximum andminimum quantity of each constituent, are given in the followingtable :-Mean. Maximum. Minimum.Water.. . . . . . . . . . . . . . . 12.01 15.50 8.50Protei'n . . .. . . . . . . . . . . 9.80 12.43 7-1 2Nitrogen-free extract . . 59.09 64-65 48.60Fat .................. 4.58 7.1 3 2.77Fibre ................ 11.20 14.89 6.73Ash .................. 3.32 6.14 2.06J. R. C.Fattening of Oxen. By A. VOELCRER (Bied. Centr., 1880, 660-661).-A comparison of the fattening effects of oil cake with that of amixture of Indian corn meal and cotton seed cake, given as fodder toyonng oxen, was in favour of the latter mixture, both on the score ofcheapness and efficiency. J. K. C.Cultivation of Furze. By SCHIRMER-NEUHANS ( B i d . C'errtr.,1880, 678--679) -On dry soils, the cultivation of dwarf furze asfodder may be substituted with advantage for clover : analysis of thedried substance gave the following results :-Ash, 5.78 ; fibre, 46.80 ;albumin, 9-76 ; fat, 1-92 ; nitrogen-free extract, 33-74 per cent.J.K. C.Use of Lupines as Fodder. By v. PUTTKAMMER and others (Bied.Ceiitr., 1880, 661--664).-The fsvonrable effect of steaming on lupineseeds has been confirmed in many cases by the authors.J. K. C.Cultivation of Soja Bean. By C. 0. HARZ (Bied. Centr., 1880,671-673).--Various kinds of this bean were planted in the neigh-bourhood of Munich, but did not thrive in a satisfactory manner, asthe climate was too cold for them. J. I(. CVEGETABLE PHYSIOLOGY AND AGRICULTURE. 117Cultivation of various kinds Of Beet. By J. GODEFROV andA. DOUDOUY ( B e d . Centr., 1850, 652 -654).-Chemical manures suchas sulphate of ammonia, superphosphate, &c., gave better results withthe larger kinds of roots than stable dung : the “ mammoth ’’ pro-duced the largest crop. J.K. C.Drainage Water from Moorland. By R. SCHILLER (Biecl. Cedr.,1880, 636--638) .-The water contained generally about 100 grams ofdissolved solids to the gallon, consisting chiefly of sulphates of limeand magnesia: the amount of nitrates was greater in the summermonths than in winter. J. K. C.Behaviour of Phosphates in Water charged with CarbonicAcid. By H. ALBERT and R. WAGNER ( B i e d . Cent?-., 1889, 640-647) .-The authors find that precipitated dicalcium phosphate iseasily soluble in water charged with carbonic acid, and is not throwndown by calcium carbonate : solutions of alkaline nitrate or carbonatealso readily dissolve this phosphate.Precipitated phosphate of ironor alumina is not SO easily attacked by any of these solvents, espe-cially if it has been well dried. All kinds of soil absorb phosphoricacid from these solutions, the amount of absorption being determinedby the time of contact only in the case of soils rich in lime, and inthis respect carbonic acid solutions of dicalcium phosphate play thesame part as aqueous solutions of superphosphate, the absorption beingthe more complete the more lime there is present in the soil.J. K. C.Organic Matters in Soil ; Examination of GrandeadsTheory. By 0. PITSCH (.Landw. Versuchs.-Stat., 26, 15O).-Thislong paper is a reportdof the author’s examination of the theory ofGrandeau as to the value of humus in the soil.The words employed by Gmndeau himself when enunciating histheory in the “ Annales de la Station agronomique de 1’Est ” are asfollows :-1.The mineral constituents of the soil are the true nourishment ofplants, and have the property of traversing vegetable tissues, theroots inclusive. 2. Organic matters are of the highest, importancein the development of vegetables. They are not themselves assimilatedby the roots, but play the part of media between the soil and theplant; they combine with mineral matters, and form soluble com-pounds, which the roots of the plants decompose in their turn, seizin7on the inorganic and leaving the combustible matter untouched. Thismatter is the indispensable vehicle required to transfer and renderavailable the mineral matters powerless to nourish plants without theirhelp.3. Fertile soils offer their mineral ingredients to plants in astate similar to that in which they are contained in stable manures.This theory, if correct, woulcl give a new insight into the nourish-ment of plants, and as Grandeau estimates the valuable combiiiationsof humus with inorganic substances by the amount of so-called“ matiere noire,” which can be extracted from the soil by ammonia, itwould then offer it11 easy method of calculating the value of all soilsdVOL. XL. I118 ABSTRACTS OF CHEMTCAL PAPERS.and not only so, but would enable the farmer to bring his soil up toany desired standard of fertility. The opinions of practical men agreeto a certain extent with this theory (Ville and his followers excepted),and it has found considerable confirmation from the experimentalcultivation of sandy soils-in certain instances the mixture of peatysoil with sand and road-scrapings giving exceedingly good results.The author asserts that all or nearly all Grandeau's own experimentswere made with sandy and forest soils, that few or none were madewith true clays, and that the physical condition of the soils so experi-mented on, caused by the addition of the organic matter would ingreat part account for the successful results.Impressed by the import-ance of the subject, the author undertook its searching examination.l i e obtained samples of 13 soils from various farms in the Netherlands,the cultivators of which gave him full information as to their methodsof farming, and the productiteness of their soils.The method em-ployed by Grandeau for the separation of his " matiere noire '' was toplace 300 or 400 grams of the clay in a large funnel, in which was asmaller one containing pieces of broken glass or porcelain, remove thelime by treatment with dilute HC1 (10-25 C.C. to the litre of water),wash the residue to neutral reaction and dry. An aliquot part wasthen exhausted of its " matiAre noire " by dilute ammonia (halfwater), the filtrate evaporated to dryness, ignited, and the P,O, esti-mated in the ash ; the author suggests certain improvements, but theyare unsuitable for abstraction.Even with modifications, however, the author does not thinkthat this mode of soil examination will displace that already in use ;he allows that ih may prove a valuable addition to present methods,and thinks, as a result of the many analyses performed during theinvestigation, that the amount of P,O, contained in the ammoniacnlextract is even a better measure of the productive capacity of differentsoils than is the quantity of P,05 found in the acid extract as nowprepared.An improvement, he believes, would be to estimate the P,05 in botbways ; t!hen should the acid extract contain a large, and the ammonia-cal a small percentage, the soil would require a manure rich in organicmatters ; if the reverse be the case then one containing abundance ofphosphates should be applied, whilst if both extracts are proportion-ally pcor or rich the fertility of the soil will be less or greater accord-ingly.These conclusions, however, are considered as independent of thetheory of plant nutrition under examination, which requires thatalthough plants can by their roots extract nutritious matter, not onlyfrom solutions, hut from the solid particles with which they come indirect contact, still profitable results cannot be obtained unless solventsbe present t o offer a ready supply t o their roots.And further that itis the presence of humus matter which causes the transfer of theinorganic matter to the plant by directly modifying the chemicalcharacter of these mineral combinations. The author does not agreewith this view, and thinks it more reasonable to believe tlhat theroots of the plants or matters in the soil other than humus have asolvent power similar to that of acidsVEGETABLE PHYSIOLOGY AND AGRICULTURE.119He reviews some of the experiments relied on by Grandeau as proofof the correctness of his views, one beiiig the growing of certain seedsin quartz sand, exhausted with acid, washed, and supplied with dilute" matiere noire ;" the experiment proves simply that i t is capbZe ofnourishing piants, but proves not,hing more, and from elementaryanalyses of two saniples of that substance, the author found it to con-tain all inorganic substances required for the nurture of vegetables; thatit does yield those matters is not denied, but for the support of thetheory it must be h r t h e r proved that the presence of humus is indis-peizsable, and sufficient evidence of this had not been adduced.Anotherexperiment of Grandeau referred to, is one in which a sample ofRussian black earth was divided into two portions, one exhausted ofits " mati&re noire," the other not ; kidney beans were planted in both,in the exhausted sample the show of leaves was extremely small, andthey quickly shed, in the other portion the growth was healthy anddevelopment of leaves normal. The author's explanation of this isthat the tye:itment with dilute ammonia necessary to remove the" matiere noire " removed at the same time the inorganic nutritivehatters formerly present.Another experiment relied on by Grandeau is one in which fourboxes, each a square meter of surface, were planted with various seeds,two boxes containing clayey and two light calcareous soil : one box ofeach was mixed with a certain proportion of peaty earth coiitaininglittle phosphoric anhydride ; the product of the boxes containing theadmixture was in all instances considerably higher than the unmixedsamples.Grandeau himself admits that, the physical condition of theformer was much superior to that of the latter ; and in this fact Gut-author finds sufficient explanation of increased production, it beingallowed by all practical farmers that the diligent working of the soilconsiderably influences the crop. The aut'hor concludes that a criticalexamination of the proofs advanced shows that not one of them neces-sarily compels the adoption of the theory, whilst none of them arecontradictory to it nor to other theories, previously either partially orwholly formulated by Simon, Mulder, and Dettmer.Previous experiments of the author on the solubility of phosphatesin ammonium citrate led him to try the effect of ammonium hnmatein the expectation that its behaviour towards phosphates would besimilar ; the process of obtaining the pure humic acid is described a tlength, and its combination with ammonia, hut it is too long forabstraction.The ammonium humate was found in fact to exercisequite as solvent an effect on the phosphates as the ammonium citrate ;and when mixed intimately in the soil during cultivation, it wouldcome into so many point's of contact with the particles of phosphatethat it should exercise even a more potent effect.The author concludes by declining to accept the theory of Grandeau,but admits the very great importance chemically and physically ofhumus in soils ; he asserts, however, that its value varies with theiiature of the soil ; and, further, that whilst Ville and his followerswho insist that inorganic substances are the only valuable manurematerials err in one direction, Grandeau errs as greatly in the otherby the exorbitant value Be places on organic matter.J. F.k 120 ABSTRACTS OF CHEMICAL PAPERS.Solubility of Certain Manure Materials. By A. MORGEN(Landw. Vwszcchs.-Stcct., 26, 51-75) .-The number of nitrogenoussubstances employed in the manufacture of artificial manures is verylarge. An impression prevails that they all require about the sameperiod of time for their decomposition in the soil, and chemical analysisattaches equal importance to the nitrogen contained in all.Practice,however, shows that the actual value of such substances to the farmerdepends greatly on the time they require to decompose and rendertheir valuable constituents available for plant nutrition.The subject has not hitherto been experimentally treated in Ger-many, and the author of the present paper gives a report of numeroiisexperiments intended to throw light on it. They were ma,de withhorn meal and leather meal, substances prepared from manufacturers'waste by steaming aiid drying. The experiments were divided intothree series, in oneof which the samples were treated with water for alengthened period in the water-bath at a high temperature, with theaddition in certain cases of a little sewage water to hasten decomposi-tion.The second series was similar to the first, except that thesamples were left exposed to the air a t the natjural temperature ofthe atmosphere in a garden. The third differed from the other twoin treating, not equal quantities of the substances, but quantities con-taining equal amounts of nitrogen.I n the first series, 5 to 10 grams of each substance were placed in alitre of distilled water, with, in two cases, 5 C.C. of sewage wateradded, and kept a t 30" C. in a water-bath for 131 days. The amountof nitrogen which had passed into solution a t the end of that time wasin the case of the leather meal one-third, and of the horn meal two-thirds of the total contained in the samples.The addition of sewagewater does not appear to have affected the result, except in augment-ing the amount of nitrogen in the form of ammonium compounds ; theconcentration of the solutions does not appear to have a t all affectedthe results.In the second series some of the specimens were boiled before sub-mitting them to prolonged action of the air and sun. These showedslightly lower numbers, owing probably to the boiling having renderedalbuminous substances insoluble. The total results were very similarto those of the first series, and strongly in favour of the horn meal.The third series yielded slightly different yet generally similarresults, and all the experiments confirm the verdict of practical menthat the nitrogen in horn (and bone) meals is much more valuableas a manure ingredient than that contained in leather meal. Itmust be borne in mind that the whole object of the leather manu-facturer is to render his leather insoluble, and that some mode of re-moving the tannic acid must be found before waste leather will be aseasy of decomposition as bone or horn meal. J. F.Experiments with Various Phosphates as Manure. By E.WEIN (Bied. Cemtr., 1880, 647--651).-The soil in which these experi-ments were carried out was a mixture of sand and cakium carbonate.Peas and oats were manured in different plots with various forms ofphosphate, soluble and insoluble, and in every case dicalciuni phosAIfALY TICAL CHEMISTRY. 1 2 1phate yielded the best result. The author explains this by assumingt'hat in the presence of excess of calcium carbonate, soluble phosphateof lime is converted into tricalcium phosphate, which is not readilyabsorbed by the roots, whereas dicalcium phosphate does not undergothis change. J. K. C.Pigeons' Dung. By E. WEIN (Bied. Centr., 1880, 693).-Asample taken from a church tower gave the following results onanalysis :-Water, 10.99 ; organic and volatile bodies, 56.65 ; ash,33.36 ; nitrogen, 2.25 ; phosphoric acid, 2-04 ; and potash, 5.49 percent. J. K. C.Manure for Fruit Trees. (Bied. Centr., 1880, 693.)-Experi-ments which were carried on in Potsdarn sho'wed the most suitableilianure for fruit trees to be a mixture of potash sulphate and super-phosphate, which increased the number of blossoms considerably.J. K. C.Manuring of Vines. By P. WAGNER and H. PRINZ ( B i d Ce?ttr.,1880, 638-640).--TTines extract yearly from the soil only about three-fourths of the quantity of potash and phosphoric acid extracted bycereals ; the amount of manure applied is, however, generally greater.J. I(. C

ISSN:0368-1769    

DOI:10.1039/CA8814000115

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

AIfALY TICAL CHEMISTRY. 1 2 1 An a 1 y t i c a 1 C h e m i s t r y . On Accurate Perception of Colour-change in Titration. By A. DUPRE (AnaZyst [lSSO], 5, 123).-The author views the coloured liquid to be titrated through a glass cell filled with a solu- tion of the same colouring substance as that contained in the liquid itself, and yielding a colour of about equal intensity. The change of tiiit becomes then strikingly manifest even in very dilute solutions. The method has been tried in the titration of chlorides in drinking- water by standard silver nitrate, using neutral potassium chromate as indicator, a glass cell with parallel faces at little less than half an iuch apart being filled with the neutral chromate solution, and interposed batween the eye and the water contained in a porcelain dish.‘the change of turmeric from yellow to brown is also readily per- ccived through a turmeric cell. In titrating lime in water with decinornial sulphuric acid, she dish was half covered with a porcelain plate, and neutral cochineal solution was filled into the cell. At first the tint of the water is widely different from that of the porcelain plate, but when neutrality is reached these tints appear identical if the strength of the cochineal solution i n the cell and in the water have been fairly matched. The method will be generally applicable to all similar cases when a colour-change has to be accurately noted. F. C.122 ABSTRACTS OF CHEMICAL PAPERS. Action of Uranyl Salts on Turmeric Paper. By C. ZIMMER- MANN (Annnlen, 204, 224-225) .-Uranyl salts colour turmeric paper brown.The nitrate has a much stronger action than the sulphate and acetate. The brown tint lies midway between that produced by alkalisand by boric acid. It may be distinguished from the first by its appearing in a faintly acid solution, from the latter by its dis- appearance on addition of free mineral acids. The brown colour passes into a violet-black when sprinkled with diluted sodium carbonate, and this last is conyerted by hydrochloric acid into the original yellow, whilst the brown produced by boric acid is converted into a blue to black by sodium carbonate, and is restored on addition of hydrochloric acid. Separation of the Heavy Metals of the Ammonium Sul- phide Group. By C. ZIMMERMANN (Annalen, 204, 226-227).- This is an appendix to a paper in the AiznaZeiz, 199, 1, describing t,he separation of zinc from the other metals of the same group by means of ammonium thiocyanate and sulphuretted hydrogen.The most excellent rcsultts have been obtained by substituting thiocyanic acid, prepared as follows :-Two parts of lead acetate are shaken up with one part of ammonium thiocyanate ; the precipitate is washed with cold water and decomposed by sulphuretted hydrogen. The snlphuretted hydrogen is then removed by a current of air. The method of analysis is either to mix the liquid containing the metals with excess of sodium carbonate, or to neutralise it as nearly as possible. I n the first case the precipitate is dissolved in the thio- cyanic acid ; in the second case some ammonium thiocyanate is added to the acid.The solution is then, if necessary, diluted, and sulphn- retted hydrogen is passed into it. It is next warmed gently on the water-bath, and proceeded with according to the niethod described in the previous paper. G. T. A. G. T. A. Occurrence and Estimation of some Nitrates in Vegetable Substances. By I. BING (J.ppr. Chenz. [2], 22, 348-351).--Nitrates have been discovered and estimated in tobacco-leaves, and in various roots, leaves, and blossoms by, Schlosing and others. The author has determined the nitrates in several kinds of Chinese tea, in mate, valonia, and coffee by Tiemann’s modification of Schulze’s process. The extract from about 20 grams of substance was concentrated, and mixed whilst nearly boiling with lead acetate in the smallest possible excess ; the yellowish flocculent precipitate is washed by decantation, and finally filtered by suction.The filtrate, mixed with a little strong sodium sulpbate solution, is evaporated down to about 20 C.C. and filtered from lead sulphate; it is then distilled with addition of a little paraffin to prevent frothing. The nitric acid is probably present in the form of potassium nitrate ; calculated as such, the percentages found in the air-dried substances were as follows :-Four varieties of Chinese tea gave an average of 0.051 ; mat8&, 0.052 ; vaionia, 0.075 ; and coffee, when raw, 0.054, when roasted, 0.041. It is evident, therefore, that a certain proportion of nitrates are destroyed during the roasting of coffee. An analysis of the mat6 showed that it closely resembledANALYTICAL CHEMISTRY.123 Chinese tea in composition. The nitric acid was absorbed in every estimation by ferrous chloride, and there never remained more than Arsenious Sulphide as a Poison, and its Importance in Judicial Cases. By J. OSSIKOVSZKY (J. pr. Chem. [2], 22, 323- 338) .-It is generally supposed that arsenious sulphide, whether chemically Precipitated or in the form of auripigment, has no poison- ous action on the living organism. A case of poisoning having occurred in which food containing arsenious sulphide was suspected, the author considers that arsenioiis oxide must have been present either as an original impurity or as a product by chemical change of the sulphide. A sample of auripigment was found by Tardieu to contain as an im- purity much arsenious oxide, and the author considers it d priori possible that during the process of putrefaction of organic bodies arsenious sulphide may be converted into oxide by the action of ozone.Experiments were made by exposing a mixture of arsenious sul- phide, water, and pieces of decomposing pancreas t,o a temperature of 35-40" for a period of seven days ; samples for analysis were removed a t intervals and filtered, the filtrate on being acidified yielded a preci- pitate of arsenious sulphide, and the acid filtrate was tested for arseni- ous and arsenic acids. It was found that precipitated arsenious sul- phide was much more rapidly oxidised under these circumstances than the more compact crFstalline auripigment, but the result obhined from both forms of sulpliide was similar.The albuminoiid bodies present, on decomposition, yielded ammonia, which dissolved a portion of the sulphjde as such ; this was precipitated on acidifying the liquid with hydrochloric acid ; the arsenioas sulphide was also oxidised to arseni- ous acid, and to a smaller extent to arsenic acid; the quantities of these oxidation products formed increasing in proportion to the time. A considerable quantity of phosphoric acid was simultaneously formed from the pancreas. Further experiments proved that in the absence of the pancreas, the presence of water a t a moderate heat was sufficient to convert the pre- cipitated arsenious sulphide into arsenious but not into arsenic: acia. The author further tried the effect of making the liquid, in which arsenious sulphide and decomposing organic matter were present, alkaline with sodium carbonate, so as to imitate the conditions exist- ing in the large intestine where alkaline secretions would mingle with the food.I t was found that the quantity of oxidiPed arsenic com- pounds formed was quite sufficient to produce poisoning. 0.3 C.C. of unabsorbed gas. B. c. The conclusions arrived a t are :- 1. That during the decomposition of organic bodies easily oxidisable bodies are oxidised, and that arsenious sulphide under such circum- stances is converted into arsenious acid, and to a small extent into arsenic acid. The precipitated sulphide undergoes oxidation more readily than auripigment. 2. I n cases of poisoning by arsenious sulphide, the oxidation pro- ducts appear more or less quickly, accordiiig to the nature of the decomposing body; the presence of water and heat also exerts much influence.124 ABSTRACTS OF CHEMICAL PAPERS.3. The quantity of oxidation products is directly proportional t o the duration of the decomposition ; hence it becomes impossible to deter- mine whether sufficient arsenious acid was present to prove fatal a t the time the food was taken when the suspected article has been sub- mitted to examination only after a considerable interval. From a I ong-delayed chemical examination therefore conclusions cannot with certainty be drawn. P. c. Ash of Light-colomred Cod Liver Oil. By E. A. VANDERBURG (Pharm,. 1. Trans. [3], 11, 189).-l’hc inorganic ingredients of light- coloured Lofodin cod liver oil were determined-first, the acids, phos- phoric and sulphuric, by saponification, and after separation of the fatty acids, as ferric phosphate and barium sulphate ; secondly, the bases, lime, magnesia, and soda, by carbonising the oil, treating the residue with hydrochloric acid, separating tbe phosphoric acid from the solution and estimating lime as oxalate, the magnesia as magne- sium ammonium phosphate, and the soda as sulphate.In this way 0.37805 per cent. inorganic matter was found. P206. so,. CaO. MgO. NZlJO. 0,09135 0.07100 0.15150 0.00880 0.0.5540 By direct incineration of 35 grams of oil no appreciable quantity of ash was left. By igniting English oil, 0.002 per cent. of ash was left, consisting chiefly of iron, whilst De Jongh’s leaves 0.009 per cent.of ash, consist- ing of iron and calcium. The results do not agree with those of De Jongh’s. Elementary Analysis of Organic Salts of Alkalis and Alka- line Earths. By H. SCHWARZ and P. PASTROVICH ( B e y . , 13,1641- 1643).-The salts are mixed with p u ~ e chromic oxide and burntl in a platinum boa,t in a current of oxygen, the combustion tube being charged with copper oxide. Carbon and hydrogen are obtained as usual, whilst the contents of the boat are exhausted with water, and the chromate formed titrated with standard lead solution. Test experiments gave ver-j satisfactory results. Nitro-compounds should be mixed with chromic oxide and copper oxide. 0. H. L. T. 0’s. Analysis of Iodine-Iron Cod Liver Oil. By E. A. VANDER- BURG (Phamn. J.Tg-a?ts. [ 3 ] , 11, 189--190).-The iron may be deter- mined by igniting 20 grams of oil in a platinum dish, which should not be more than one-sixth full. The oil should be gently heated until the colour changes to a brownish-red, when combustible gases are evolved, which may be ignited, and will continue to burn for some t,ime. When the burning ceases, the oil is again heated until more in- flammable gases are given off, which are treaked as before. As soon as the oil is completely carbonised, the residue is strongly ignit,ed until all the carbon is consumed, and the ash consisting of ferric oxide is then weighed. That the ssli consists of pure ferric oxide, may be subse-TECHNICAL CHEMISTRY. 125 yuently tested by reduction with zinc and sulphuric acid, and titration with potassium permariganate.The weight of ash multiplied by 0’7 gives the quantity of iron in the oil ; it should amount to 0.27 per cent. To determine the iodine, 5 grams of oil are saponified with alcoholic potash, the soap carbonised, and the residue washed with water. The iodine in the solution is estimated as palladium iodide. L. T. 0’s. Testing of Mustard Oil. By F. A. YL~~CKIGER (Pliamn. J. Z’rms. [ 31, 11, 472--473).--hIustard oil is frequently adulterated with mrbon bisulphide, and therefore it is of great consequence to be able to readily detect its presence. This map be done by distilling the oil a t a low temperature, when the carbon bisulphide passes over, and may be converted into ammonium thiocyanate by treatment with alcoholic ammonia.A better way of treating the distillate, if the quantity obtained will allow of its being adopted, is to take its boiling point and specific gravitx, since in presence of ammonia, mustard oil decomposes to a small extent, traces of ammonium thiocyauate being for rued. The principal compound formed by the action of ammonia on inustard oil, namely, thiosinamine, C4HBN,S, may be used to deter- mine the value of the mustard oil. A weighed quantity of the oil is treated with alcoholic ammonia until the smell of mustard oil has entirely disappeared. The solution is then evapomted to dryness and weighed. A moderate heat must be used in order to reduce the quantity of ammonium thiocyanate formed to a minimum. Mustard oil when exposed t o the direct rays of the sun darkens in colour, and a brown deposit forms.The oil then gives a red d o u r with ferric chloride, arid the compound thus formed is insoluble in ether, it is therefore not due to the presence of thiocyanic acid. When the formation of xanthic acid is used as a test for the presence of Carbon bisulphide in mustard oil, care must be taken that all traces of the oil are removed, as its presence may lead to deceptive con- clusions, unless very dilute alcoholic potash is used in the reaction. Pure mustard oil exposed to diffused sunlight undergoes no change. If, however, it contains carbon bisulphide, the colour changes to a very dark brown, and a dirty brown-red deposit is formed. L. T. 0’s.AIfALY TICAL CHEMISTRY. 1 2 1An a 1 y t i c a 1 C h e m i s t r y .On Accurate Perception of Colour-change in Titration.By A.DUPRE (AnaZyst [lSSO], 5, 123).-The author views thecoloured liquid to be titrated through a glass cell filled with a solu-tion of the same colouring substance as that contained in the liquiditself, and yielding a colour of about equal intensity. The change oftiiit becomes then strikingly manifest even in very dilute solutions.The method has been tried in the titration of chlorides in drinking-water by standard silver nitrate, using neutral potassium chromate asindicator, a glass cell with parallel faces at little less than half an iuchapart being filled with the neutral chromate solution, and interposedbatween the eye and the water contained in a porcelain dish.‘the change of turmeric from yellow to brown is also readily per-ccived through a turmeric cell.In titrating lime in water with decinornial sulphuric acid, she dishwas half covered with a porcelain plate, and neutral cochineal solutionwas filled into the cell.At first the tint of the water is widelydifferent from that of the porcelain plate, but when neutrality isreached these tints appear identical if the strength of the cochinealsolution i n the cell and in the water have been fairly matched.The method will be generally applicable to all similar cases whena colour-change has to be accurately noted. F. C122 ABSTRACTS OF CHEMICAL PAPERS.Action of Uranyl Salts on Turmeric Paper. By C. ZIMMER-MANN (Annnlen, 204, 224-225) .-Uranyl salts colour turmeric paperbrown.The nitrate has a much stronger action than the sulphateand acetate. The brown tint lies midway between that produced byalkalisand by boric acid. It may be distinguished from the first byits appearing in a faintly acid solution, from the latter by its dis-appearance on addition of free mineral acids.The brown colour passes into a violet-black when sprinkled withdiluted sodium carbonate, and this last is conyerted by hydrochloricacid into the original yellow, whilst the brown produced by boric acidis converted into a blue to black by sodium carbonate, and is restoredon addition of hydrochloric acid.Separation of the Heavy Metals of the Ammonium Sul-phide Group. By C. ZIMMERMANN (Annalen, 204, 226-227).-This is an appendix to a paper in the AiznaZeiz, 199, 1, describingt,he separation of zinc from the other metals of the same group bymeans of ammonium thiocyanate and sulphuretted hydrogen.Themost excellent rcsultts have been obtained by substituting thiocyanicacid, prepared as follows :-Two parts of lead acetate are shaken upwith one part of ammonium thiocyanate ; the precipitate is washedwith cold water and decomposed by sulphuretted hydrogen. Thesnlphuretted hydrogen is then removed by a current of air.The method of analysis is either to mix the liquid containing themetals with excess of sodium carbonate, or to neutralise it as nearlyas possible. I n the first case the precipitate is dissolved in the thio-cyanic acid ; in the second case some ammonium thiocyanate is addedto the acid.The solution is then, if necessary, diluted, and sulphn-retted hydrogen is passed into it. It is next warmed gently on thewater-bath, and proceeded with according to the niethod described inthe previous paper.G. T. A.G. T. A.Occurrence and Estimation of some Nitrates in VegetableSubstances. By I. BING (J.ppr. Chenz. [2], 22, 348-351).--Nitrateshave been discovered and estimated in tobacco-leaves, and in variousroots, leaves, and blossoms by, Schlosing and others. The author hasdetermined the nitrates in several kinds of Chinese tea, in mate, valonia,and coffee by Tiemann’s modification of Schulze’s process. The extractfrom about 20 grams of substance was concentrated, and mixed whilstnearly boiling with lead acetate in the smallest possible excess ; theyellowish flocculent precipitate is washed by decantation, and finallyfiltered by suction.The filtrate, mixed with a little strong sodiumsulpbate solution, is evaporated down to about 20 C.C. and filteredfrom lead sulphate; it is then distilled with addition of a littleparaffin to prevent frothing. The nitric acid is probably present in theform of potassium nitrate ; calculated as such, the percentages foundin the air-dried substances were as follows :-Four varieties of Chinesetea gave an average of 0.051 ; mat8&, 0.052 ; vaionia, 0.075 ; and coffee,when raw, 0.054, when roasted, 0.041. It is evident, therefore, that acertain proportion of nitrates are destroyed during the roasting ofcoffee. An analysis of the mat6 showed that it closely resembleANALYTICAL CHEMISTRY.123Chinese tea in composition. The nitric acid was absorbed in everyestimation by ferrous chloride, and there never remained more thanArsenious Sulphide as a Poison, and its Importance inJudicial Cases. By J. OSSIKOVSZKY (J. pr. Chem. [2], 22, 323-338) .-It is generally supposed that arsenious sulphide, whetherchemically Precipitated or in the form of auripigment, has no poison-ous action on the living organism. A case of poisoning having occurredin which food containing arsenious sulphide was suspected, the authorconsiders that arsenioiis oxide must have been present either as anoriginal impurity or as a product by chemical change of the sulphide.A sample of auripigment was found by Tardieu to contain as an im-purity much arsenious oxide, and the author considers it d prioripossible that during the process of putrefaction of organic bodiesarsenious sulphide may be converted into oxide by the action of ozone.Experiments were made by exposing a mixture of arsenious sul-phide, water, and pieces of decomposing pancreas t,o a temperature of35-40" for a period of seven days ; samples for analysis were removeda t intervals and filtered, the filtrate on being acidified yielded a preci-pitate of arsenious sulphide, and the acid filtrate was tested for arseni-ous and arsenic acids.It was found that precipitated arsenious sul-phide was much more rapidly oxidised under these circumstances thanthe more compact crFstalline auripigment, but the result obhined fromboth forms of sulpliide was similar.The albuminoiid bodies present,on decomposition, yielded ammonia, which dissolved a portion of thesulphjde as such ; this was precipitated on acidifying the liquid withhydrochloric acid ; the arsenioas sulphide was also oxidised to arseni-ous acid, and to a smaller extent to arsenic acid; the quantities ofthese oxidation products formed increasing in proportion to the time.A considerable quantity of phosphoric acid was simultaneously formedfrom the pancreas.Further experiments proved that in the absence of the pancreas, thepresence of water a t a moderate heat was sufficient to convert the pre-cipitated arsenious sulphide into arsenious but not into arsenic: acia.The author further tried the effect of making the liquid, in whicharsenious sulphide and decomposing organic matter were present,alkaline with sodium carbonate, so as to imitate the conditions exist-ing in the large intestine where alkaline secretions would mingle withthe food.I t was found that the quantity of oxidiPed arsenic com-pounds formed was quite sufficient to produce poisoning.0.3 C.C. of unabsorbed gas. B. c.The conclusions arrived a t are :-1. That during the decomposition of organic bodies easily oxidisablebodies are oxidised, and that arsenious sulphide under such circum-stances is converted into arsenious acid, and to a small extent intoarsenic acid. The precipitated sulphide undergoes oxidation morereadily than auripigment.2.I n cases of poisoning by arsenious sulphide, the oxidation pro-ducts appear more or less quickly, accordiiig to the nature of thedecomposing body; the presence of water and heat also exerts muchinfluence124 ABSTRACTS OF CHEMICAL PAPERS.3. The quantity of oxidation products is directly proportional t o theduration of the decomposition ; hence it becomes impossible to deter-mine whether sufficient arsenious acid was present to prove fatal a tthe time the food was taken when the suspected article has been sub-mitted to examination only after a considerable interval. From aI ong-delayed chemical examination therefore conclusions cannot withcertainty be drawn. P. c.Ash of Light-colomred Cod Liver Oil. By E. A. VANDERBURG(Pharm,. 1.Trans. [3], 11, 189).-l’hc inorganic ingredients of light-coloured Lofodin cod liver oil were determined-first, the acids, phos-phoric and sulphuric, by saponification, and after separation of thefatty acids, as ferric phosphate and barium sulphate ; secondly, thebases, lime, magnesia, and soda, by carbonising the oil, treating theresidue with hydrochloric acid, separating tbe phosphoric acid fromthe solution and estimating lime as oxalate, the magnesia as magne-sium ammonium phosphate, and the soda as sulphate. In this way0.37805 per cent. inorganic matter was found.P206. so,. CaO. MgO. NZlJO.0,09135 0.07100 0.15150 0.00880 0.0.5540By direct incineration of 35 grams of oil no appreciable quantity ofash was left.By igniting English oil, 0.002 per cent.of ash was left, consistingchiefly of iron, whilst De Jongh’s leaves 0.009 per cent. of ash, consist-ing of iron and calcium.The results do not agree with those of De Jongh’s.Elementary Analysis of Organic Salts of Alkalis and Alka-line Earths. By H. SCHWARZ and P. PASTROVICH ( B e y . , 13,1641-1643).-The salts are mixed with p u ~ e chromic oxide and burntl in aplatinum boa,t in a current of oxygen, the combustion tube beingcharged with copper oxide. Carbon and hydrogen are obtained asusual, whilst the contents of the boat are exhausted with water, andthe chromate formed titrated with standard lead solution. Testexperiments gave ver-j satisfactory results.Nitro-compounds should be mixed with chromic oxide and copperoxide.0. H.L. T. 0’s.Analysis of Iodine-Iron Cod Liver Oil. By E. A. VANDER-BURG (Phamn. J. Tg-a?ts. [ 3 ] , 11, 189--190).-The iron may be deter-mined by igniting 20 grams of oil in a platinum dish, which should notbe more than one-sixth full. The oil should be gently heated untilthe colour changes to a brownish-red, when combustible gases areevolved, which may be ignited, and will continue to burn for somet,ime. When the burning ceases, the oil is again heated until more in-flammable gases are given off, which are treaked as before. As soonas the oil is completely carbonised, the residue is strongly ignit,ed untilall the carbon is consumed, and the ash consisting of ferric oxide isthen weighed. That the ssli consists of pure ferric oxide, may be subseTECHNICAL CHEMISTRY.125yuently tested by reduction with zinc and sulphuric acid, and titrationwith potassium permariganate. The weight of ash multiplied by 0’7gives the quantity of iron in the oil ; it should amount to 0.27 per cent.To determine the iodine, 5 grams of oil are saponified with alcoholicpotash, the soap carbonised, and the residue washed with water. Theiodine in the solution is estimated as palladium iodide.L. T. 0’s.Testing of Mustard Oil. By F. A. YL~~CKIGER (Pliamn. J.Z’rms. [ 31, 11, 472--473).--hIustard oil is frequently adulterated withmrbon bisulphide, and therefore it is of great consequence to be ableto readily detect its presence. This map be done by distilling the oila t a low temperature, when the carbon bisulphide passes over, andmay be converted into ammonium thiocyanate by treatment withalcoholic ammonia. A better way of treating the distillate, if thequantity obtained will allow of its being adopted, is to take its boilingpoint and specific gravitx, since in presence of ammonia, mustard oildecomposes to a small extent, traces of ammonium thiocyauate beingfor rued.The principal compound formed by the action of ammonia oninustard oil, namely, thiosinamine, C4HBN,S, may be used to deter-mine the value of the mustard oil. A weighed quantity of the oil istreated with alcoholic ammonia until the smell of mustard oil hasentirely disappeared. The solution is then evapomted to dryness andweighed. A moderate heat must be used in order to reduce thequantity of ammonium thiocyanate formed to a minimum.Mustard oil when exposed t o the direct rays of the sun darkens incolour, and a brown deposit forms. The oil then gives a red d o u rwith ferric chloride, arid the compound thus formed is insoluble inether, it is therefore not due to the presence of thiocyanic acid.When the formation of xanthic acid is used as a test for the presenceof Carbon bisulphide in mustard oil, care must be taken that all tracesof the oil are removed, as its presence may lead to deceptive con-clusions, unless very dilute alcoholic potash is used in the reaction.Pure mustard oil exposed to diffused sunlight undergoes no change.If, however, it contains carbon bisulphide, the colour changes to avery dark brown, and a dirty brown-red deposit is formed.L. T. 0’s

ISSN:0368-1769    

DOI:10.1039/CA8814000121

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

TECHNICAL CHEMISTRY. T e c h n i c a1 Chemistry. 125 A Photo-electric Regulator for Painted-glass Furnaces. By R. GERMAIN (Coinpi. rend., 91, 688--69O).-The muffle in which the glass is heated is provided with a window of very refractive alumina glass, so that the red glow within may reach a distant mirror. This mirror concentrates the rays on a sphere of selenium, and the modifica- tion in the electric conductivity of that substa,nce thus induced acts an a mechanical arrangement, whereby the fire bars are withdrawn, and the fuel allowed to fall out as soon as the right temperature to fuse the enamels is attained. R. R.126 ABSTRACTS OF CHEMICAL PAPERS. Disinfecting Power of the Chlorphenols. By C. 0. CECH (J. pr. Chew. [2], 22, 345--347).-1tt has often been noticed that the addition of bleaching powder to carbolic acid in dressing wounds causes healing to take place more rapidly than when the acid is used alone.It has been shown by Diamin that phenol and bleaching powder react on one another, forniing mono-, di-, and tri-chlorophenol, which may be isolated and separated by treatment with a strong acid, and distillation with aqueous vapour. The author, considering that these chlorophenols are probably formed when carbolic acid and bleaching powder are used together in dressing a, wound, and exert a, healing power greater than that of carbolic acid alone, attempted to prepare chlorophenols in quantity by the above process; it proved dangerous on the large scale, and direct treatment of phenol by chlo- rine gas was resorted to.A red crystalline mass was obtained, from which white crystals are obtainable by pressure between filter-paper ; after purifying these crystals by precipitation from their alcoholic solution by water, they were dissolved in alcohol, and the bandages were impregnated with this solution. These crystals consist of a mixture of three chlorophenols, in which trichlorophenol predomi- nates, and is probably the most useful. The chlorophenols present the advantage over phenol of being less corrosive and poisonous, and trichloyophenol probably has most advantage in these respects : its value as a disinfectant remains to be decided by the use of the chloro- Wickerheim's Preservative Fluid. By H. STRUVE and 0. JACOB- SEN (Biecl. Centr., 1880, 613--615).-This fluid is made by mixing together 100 C.C.water, 40 C.C. glycerol, 10 C.C. methyl alcohol, 3.33 grams alum, 0.40 gram saltpetre, 2 grams potash, and 0.66 gram arsenious oxide. I n the place of alum and potash, an equivalent quantity of potassium sulphate is recommended. phenol bandages. E'. c. J. K. C. Action of Soda on Cast-iron. By H. BRUKCK and C. GRXERE (Ber., 13, 725--726).-A cast-iron vessel which was used for fusing soda a t a red heat, was in the coume of time converted into a friable mass, composed of minute crjst'alline scales of sp. gr. 2 - 9 2 The crystals have the composition Be,O,.H:,O, but contain about 1.7 per cent. of Mn,O,. w. c. IT. New Method of Fermentation. By M. DELBR~CK and G. HEIKZELMANN (Bied. C'entr., 1880, 622-624) .-As the use of thick mashes for fermentation is attended with the development of too high a temperature, the authors recommend that the process should be com- menced at about 19" or 20' R., and that the temperature of the mash be kept from rising too high by means of cooling apparatus. The time saved in this way is considerable.J. K. C. Mashing of Grapes. By E. MACH and PORTELE (Bded. Centr., 1880, 619-620). In this investigation, a small incision was made in each grape, and the fleshy core was pressed out, the liquid which ran off at the same time was kept separate, as also the liquid which couldTECHNICAL CHEMISTRY. 12% be pressed out of the skins. It was found that the first contained the greatest quantity of acid and cream of tartar, and the least amount of sugar, the liquid running off being richest in sugar, and yielding the strongest must.J. K. C. Saccharine Matters in the Fruit of the Coffee Plant. By BOUSSINGAULT (Conzpt. ?*end., 91, 639--642).--The dried fruit of the coff'ee plant contains :-Mannite, 2.21 ; inverted sugar, 8.73 ; cane- sugar, 2.37. From this it will be seen that the amount of sugar present in the fruit is too small to enable it t o be profitably utilised as a source of alcohol, although the readiness with which it ferments had suggested that idea to Humboldt. Action of Animal Charcoal in the Sugar Manufacture, By H. PELLET (Ann. C'l~iin. Phys. [ 5 ] , 20, 89--95).-Alkaline nitrates and chlorides are but little absorbed by animal black, but caustic lime on the contrary is absorbed in largc quantity; the question which presented itself was whether lime salts were absorbed to the same ex- tent as lime in the free state.Various solutions were made contain- i n g in different proportions sugar, calcium glucosnte, potash, lime, and alkaline salts ; these having been carefully analysed beforehard, were submitted to the action of purified animal charcoal a t a temperature of 90-95" for a short time, and after filtration were reanalysed. The actual results are given in a series of tables, of which the following may be taken as a fair summary :- That lime salts can be absorbed in certain proportion by animal black. That free potash can also be absorbed by the black, and that its presence considerably augments the proportion of lime salts ab- sorbed; in the latter case a larger proportion of potash itself is taken up.That the presence of free lime does not sensibly modify the action of potash as far as regards the absorption of lime salts by the black. That free lime is almost wholly absorbed, the presence of sugar beicg without influence on the action. When there esists simultaneously free and combined lime in a solu- tion, animal black absorbs the same proportion of the free lime, whilst its absorptive power for the saline lime is considerably dimi- nished. The presence of sugar and foreign salts generally affects the absorp- tive power of animal black but little. An investigation into the alkalinity of new charcoal and of charcoal which had been used and calcined several times, showed that whilst a fresh black had an alkalinity of more than 0.15 per cent.(returned as lime), an old sample contained only 0.05 per cent., or not one-third that in a new one ; as a necessary consequence, therefore, and from a consideration of the foregoing experiments, a new black should absorb a larger proportion of lime salts than an old one ; in actual practice such is always found to be the case. Inversion of Sugar during Manufacture. By DURIN (Bied. Cedr., 1880, G18--619).-According to the author, this is due t o the R. R. J. W.128 ABSTRACTS OF CHEMICAL PAPERS. oxidation, and consequent acidification of the sugar during the pro- cess of manufacture, and can be avoided by the use of a small quant,ity of alkali. J. K. C. Separation of Sugar from Molasses. Ry J~~NEMANN and C. SCHEIBLER (Bied. Cp77t~., 1880, 687--688).--The method of Junemann consists i n the precipitation of sugar by means of lime in hot solution and mashing the precipitate under presslire at 172"; according to Scheibler, however, this method presents difficulties which make it unsuccessful in practice.J. K. C. Manufacture of Vinegar by Means of Bacteria. By E. WURM (I'har1n. ?J. Trans. [3], 11, 136-134) .-According to Pasteur, the formation of vinegar from alcohol is due to the vegetation of the bactcrium, Mycodema aceti. Liebig, however, maintained that it is due to chemical and not physiological action, since no Mycode?-nla aceti could be detected by microscopic examination on a shaving froin the bottom of a vinegar generator which had been in use for 25 years. Mayer and De Knierym, however, distinctly proved that the ferment exists in great quantity on the shavings of the vinegar generator.The author has carried out the manufacture according to the direc- tions of Pasteur, and most satisfactory results have been obtained. 200 liters of a mixture of alcohol, water, and vinegar, with mineral salts, namely, potassium phosphate, 0.01 per cent. ; calcium phosphate, 0.01 per cent. ; magnesium phosphate, 0.01 per cent. ; ammonium phosphate, 0.02 per cent., are placed in a large wooden vat well closed with a woodencover, access to air being obtained through small open- ings a t the side. The mycoderma are sown by means of a wooden spatula. The liquid in the vats is maintained a t 25-30" C., and t'he temperature of the surrounding atmosphere a t about 30" C. Pasteur limits the amount of vinegar to 1 per cent., but a liquid so slightly acid is easily invaded by Saccharomyces mycoderma, which hinders the generation of the acetic fungus.Experiments prove that with from 0.5-1.2 per cent. of acetic acid present, the Xacchcrronyces mycodernza multiply exclusively ; with 1.6 per cent. the Mycoderma aceti pre- dominate, and with 2 per cent. the latter alone multiply. The liquid in the vat originally contained 2 per cent. of alcohol, and as this is converted into vinegar fresh quantities are added, unt'il the vinegar has attained the required strength. When the surface of the vat becomes entirely covered with bacteria, the surroundicg tempera- ture being 30" C., that of the liquid rises to 34" C., and a strong odour of acetic acid is apparent.The augmentation of the acid varies from 0.2-2.4 per cent. daily. The loss of alcohol in this process is much less than in the generators with shavings, which in the preparation of crude vinegar amounts to 23 per cent., but in the case of stronger vinegar 12 to 15 per cent. I n this process, however, there is only loss from evaporation at the beginning, it being afterwards prevented by the layers of fungus. The total loss is from 10 to 15 per ceat., one portion of which is used by the bacteria in forming their substance, and the other converted into ethyl acetate a t the high temperature of the solution.TECHNICAL CHERIISTRT. 129 An addition of alcohol should not be made when there is more than 0.5 per cent. in the vat, and it should be added in such a way that the liquid coming in contact with the fungus does not contain more than 0.5 per cent.The greater proportion of acid in the liquid, the more nearly should the quantity of alcohol added equal the quantity used up. When the vinegar has reached the required strength, it is drawn off into vats, where it is clarified and freed from mycoderma. The precautions to be observed are-the sowing of pure bacteria, a uniform temperature of 80", and a well regulated addition of alcohol. The chief advantages of this process are its cheapness and the great, economy of space, and it much greater yield. The generation of " vinegar eels " is of great inconvenience, since by their motion they destroy the pellicle of the mycodernia, and pre- vent its reforming. If they multiply to any great extent, the tempera- ture of the liquid falls, but by preventing the cooling, the parts of the pellicle destroyed may be reproduced, in which case the eels take refuge in the upper parts of the vessel, and form a ring of viscosity above the layer of bacteria.In t'his process, however, they haw not time to multiply so as to become injurious, since the vats are emptied every 10-14 days. The mycoderma used for sowing must not come from a liquid infected with eels. The microscopic examination of the ferment shows that tbree different forms can be observed. Whether they are from the same organism in different stages of development, or three different organisms capable of producing acetic acid, remains to be proved. With 1 to 3 per cent. of acetic acid the formation of a thick viscous and fatty skin was observed, consisting of minute globules (micro- cocci), occurring whilst young in contiguous rows, but after a few days changing into an animal glue, through the formation of inter- cellular tissue.An increase in the quantity of acid caused the forma- tion of veins, rays, and spots which extend more and more, whilst the original layer sinks to the bottom. This new pellicle consisted of bacilli, and was less viscous than the first. It, however, became more viscous, and was replaced by a more delicate pellicle of bacilli. The amount of 1 per cent. of acid is sufficient t o stop the production of the micrococci, but in such a mixture the bacilli continue to multiply. No difference has been as yet detected in the power of acetification of these two forms.Thin pellicles should be taken for sowing, as they germinate more quickly than the viscous pellicles. Apparatus for Skimming Milk. By C. STIM~EL (Bied. Cerh,., 1880, 617--618).-The cream is allowed to rise in shallow paus, immersed in cold water, and the milk separated by means of a syphon. J. K. C. Colouring Matter of Rubus Chamaemorus. By C. 0. CECII (J. y r . Cken2. [el, 22, 399--400).-The author noticed that the cotton and woollen bags in which the berries of this plant were subjected to pressure to obtain their juice for making wine were coloured inteusely orange-yellow. The colour imparted was so per- L. T. 0's.130 ABSTRACTS OF CHEMICAL PAPERS. manent and had SO thoroughly penetrated the fibre, that it was nn- affected even by dilute hydrochloric acid.Experiment showed that, the juice of these berries imparted an in- tense orange-red colour to cotton and wool in a few minutes, and somewhat more slowly to silk. The colouring matter appears to be present in considerable quan- tity, and the author is now engaged in isolating it. Its colour will be suitable for dying shades of chamois amber and orange-yellow, and also for harmlessly colouring white wines in imita- tion of sherry. F. c. COCCUS Red. By R. ROTHER (Pharqn. J. Tram. [3], 11, 130).- There being several defects in the usual method for the preparation of coccus red, the author has submitted a new process. Two parts of sodium chloride are dissolved in a mixture of 1 paft of hydrochloric acid and 44 parts water, and 8 parts of cochineal are macerated in the solution for two days ; after which time the solution is decanted and the residue again digested with 32 parts water for two days.This solution is then poured off, and the residue digested with 32 parts water, containing 3 parts sodium chloride in solution ; and after two days the mixture is strained and subjected to strong pressure. The three solutions are mixed, and the clear solution decanted from the sediment. In the decanted liquoe 2 parts alum are dissolved, and 2.5 parts ammonia solution (16 to 18 per cent.) added, and the re- sulting precipitate is collected and washed free from ammonium salts, and finally dissolved in a warm solution of sodium citrate (prepared by neutralising 1 part of citric acid with sodium carbonate).The solution is diluted with water to 28 parts, and mixed with 4 parts alcohol. The principle of this process is first to extract the dibasic carminic acid, then unite it with alumininm, and finally to bring the aluminium salt into solution. The dry compound may be obtained by precipitating the concentrated solution with alcohol, or allowing it to eva,porate slowly. The aluminium carminate obtained by precipitating the acid with alum and ammonia is a dark purple-red powder, soluble in acids to a scarlet solution, and in alkalis to deep purple.. Acid solutions of a, carminate, when diluted with large quantities of water, change from bright scarlet to purple or deep pink ; dilution with alcohol does not produce the same effect. Aluminium carminate is also soluble in aluminium citrate, with a purple colour.Coccus red may also be obtained by treating ammonium carminate with nluminium citrate. By treating some of the crude solution with aluminium hydrate, precipitated with ammonia, no result was obtained. On adding acetic acid to the mixture, a solution was obtained from which alkaline car- bonates failed t o give a precipitate. On adding calcium carbonate, however, a gelatinous greenish-black magna was obtained, slightly soluble in water, soluble in acids to scarlet solutions, and in alkalis to purple. It is slowly decom- posed by ammonium sulphate, and quickly by aluminium sulphate, giving a purple solution, the colour of which is not destroyed by Lime water changes its colour to pink.TECHKICAL CHEMISTRY.131 alcohol. On spontaneous evaporation, a purple crystalline residue is obtained. The filtrate from the calcium salt is of a purple colour, and from it a.nmonia throws down a pink precipitate, leaving a light’ scarlet solu- tion. Earium and magnesium compounds corresponding to the cal- Analysis of Bohemian Tea. By BELOHOUBECE (Bid. Centr., 1880, 703) .-So-called Bohemian tea, the leaves of Litkospermcm qft.., is often used t o adulterate ordinary tea. Compared with Chinese tea, it yields the following figures on analysis :- cium compound could not be obtained. L. T. 07s. Bohemian tea. Cellulose ...................... 5.9 6 Tannin.. ...................... 8.25 Fat .......................... 9.29 Ethereal oil.. .................. Other nitrogen-free organic bodies 26.49 T he’in - Albumin...................... 2454 Water ........................ 9.85 Ash .......................... 20.59 - ........................ Chinese tea. 21.30 13.78 3.76 0-67 24-12 1.76 19.90 9.32 5-34 J. K. C. Preparation of Iodine-iron Cod Liver Oil. By S. D. VOX VALAKNBUEG (Pharm. J. Tmm. [ 31, 11, 209).--1.25 parts of iodine are dissolved in 98.5 parts of cod liver oil by constant shaking and stirring. The solution, having the sp. gr. 0.932-0.937, is poured into a vessel, trhich is hermetically closed aud shaken with 2.5 parts iron until it assumes a purple colour, and contains no free iodine. This is ascer- tained by shaking a portion of the oil with a solution of potassium iodide and starch-paste. The mixture is then allowed to stand for 24 hours, then shaken again, and finally allowed to stand until clear. The clear liquid has the sp.gr. 0.937-0.94, and should contain 1.23 per cent. iodine and 0.27 per cent. iron. In the preparation, air should be excludcd as much as possible, since it causes the quantity of iron to increase, owing to the formation of ferric oxyiodide, French iodine is generally used in preference to English, since the latter, on account of its fineness, forms a tough mass when mixed with the oil, and this can only be broken up with difficulty. I n some cases, a dark-coloured amorphous substance adheres to the bottom of the vessel; it is insoluble in ether, and can he almost completely volatilised. The mixture, although originally containing no free iodine, is found to contain it after standing for 24 hours, owing t o the formation of a sniall quantity of ferric iodide, which, on standing, is decomposed into ferrous iodide and iodine.The violet colour is due to the pre- sence of ferric oxyiodide. The mixture readily oxidises on exposure to the air, losing its colour. Water destroys the mixture, siiice it first dissolves the ferrous iodide, which it afterwards decomposes. L. T. 0’s.132 ABSTRACTS OF CHEMICAL PAPERS. Steeping Hemp. By A. REPU’OUARD (Bied. Cent?.., 1880, 6:30),- The water in which hemp has been steeped produces no evil effects on the health of a district when allowed to flow into running water, but it always destroys the fish, together with certain vegetablegrowths. J. K. C. Hardness and Resistance of Wood. By v.NORDLINGER (Bied. Cenfr., 1880, 600--602).--The resistance of wood is greatest when it has been cut in May or October ; this is especially the case with Foung trees. J. K. C . A Baking Powder. By M. WEITZ (Bied. Cejitr., 1880, 389-390). -The report of an examination of a baking powder which has been selling freely in Berlin. It consists of fine wheat flour, with a small addition of inorganic matter, which, when water is added, disengages gas, and renders the dough porous, acting as a substitute for yeast. This preparation has been found well adapted for the purpose. The gas is carbonic anhydride, and each kilogram of the powder contains 5.1 gram of phosphoric anhydride and 8.7 grams of sodium bicar- bonate. It is very similar to the proportions recommended for baking poxtier by Liebig, except that he recommended the ingredients to be kept separate until required for use.Preservation of Fruit in Winter. By P. SARAUER (Bied. CeiLtr., 1880, 383-3355).-The object of preserving fruit in their fresh state is best attained by keeping them in a cool dark place. The author’s expe- riments were directed so as to ascertain the influence of dry and damp air on the stored fruit. Apples were the subjects of his investigation. They were kept in an ordinary fruit store, part exposed to damp air in the open store, part enclosed in glass vessels, through one of which dry and the other damp air was aspirated. The loss of weight per cent. was : loose samples, 3.42 ; dry air, 7-90; saturated with damp, 0.60. The sample which was in dried air did not show mould so soon, but it shrivelled quickly and ripened, and at the end of the expe- riments tasted less sweet, and showed a larger proportion of decayed fruit. The breaking off or leaving on of the stalk has a considerable effect on the drying out of the moisture; leaving it on promotes a rapid evaporation.The removal of the external coating of wax by means of ether, &c., also promotes rapid evaporation. Wrapping the apples in silk paper was not found to be advantageous, except when the storing place was unusually dry ; the germs of mould attacked the rough portions of the fruit with great avidity through the openings in tbe paper. Packing in straw was also found injurious, the least damp- ness in the straw imparting a musty flavour to the fruit.Dry sand i s recommended strongly above all other means of preserving fruit. The specimens tried by the author would apparently have kept fresh and sn-eet until the July of the following year. The loss of weight was not half that of the loose fiwit; there was no appearance of mould, and the damaged specimens did not infect their neighbours. The chief point in selecting fruit for preservation is to choose those with whole sound skins and with the waxy covering perfect. J. F. J. F.TECHNICAL CHEMISTRY.T e c h n i c a1 Chemistry.125A Photo-electric Regulator for Painted-glass Furnaces. By R. GERMAIN (Coinpi. rend., 91, 688--69O).-The muffle in which theglass is heated is provided with a window of very refractive aluminaglass, so that the red glow within may reach a distant mirror. Thismirror concentrates the rays on a sphere of selenium, and the modifica-tion in the electric conductivity of that substa,nce thus induced actsan a mechanical arrangement, whereby the fire bars are withdrawn,and the fuel allowed to fall out as soon as the right temperature to fusethe enamels is attained. R.R126 ABSTRACTS OF CHEMICAL PAPERS.Disinfecting Power of the Chlorphenols. By C. 0. CECH(J. pr. Chew. [2], 22, 345--347).-1tt has often been noticed that theaddition of bleaching powder to carbolic acid in dressing woundscauses healing to take place more rapidly than when the acid is usedalone. It has been shown by Diamin that phenol and bleachingpowder react on one another, forniing mono-, di-, and tri-chlorophenol,which may be isolated and separated by treatment with a strongacid, and distillation with aqueous vapour.The author, consideringthat these chlorophenols are probably formed when carbolic acid andbleaching powder are used together in dressing a, wound, and exert a,healing power greater than that of carbolic acid alone, attempted toprepare chlorophenols in quantity by the above process; it proveddangerous on the large scale, and direct treatment of phenol by chlo-rine gas was resorted to. A red crystalline mass was obtained, fromwhich white crystals are obtainable by pressure between filter-paper ;after purifying these crystals by precipitation from their alcoholicsolution by water, they were dissolved in alcohol, and the bandageswere impregnated with this solution.These crystals consist of amixture of three chlorophenols, in which trichlorophenol predomi-nates, and is probably the most useful. The chlorophenols presentthe advantage over phenol of being less corrosive and poisonous, andtrichloyophenol probably has most advantage in these respects : itsvalue as a disinfectant remains to be decided by the use of the chloro-Wickerheim's Preservative Fluid. By H. STRUVE and 0. JACOB-SEN (Biecl. Centr., 1880, 613--615).-This fluid is made by mixingtogether 100 C.C. water, 40 C.C. glycerol, 10 C.C. methyl alcohol,3.33 grams alum, 0.40 gram saltpetre, 2 grams potash, and0.66 gram arsenious oxide. I n the place of alum and potash, anequivalent quantity of potassium sulphate is recommended.phenol bandages.E'. c.J. K. C.Action of Soda on Cast-iron. By H. BRUKCK and C. GRXERE(Ber., 13, 725--726).-A cast-iron vessel which was used for fusingsoda a t a red heat, was in the coume of time converted into a friablemass, composed of minute crjst'alline scales of sp. gr. 2 - 9 2 Thecrystals have the composition Be,O,.H:,O, but contain about 1.7 percent. of Mn,O,. w. c. IT.New Method of Fermentation. By M. DELBR~CK and G.HEIKZELMANN (Bied. C'entr., 1880, 622-624) .-As the use of thickmashes for fermentation is attended with the development of too higha temperature, the authors recommend that the process should be com-menced at about 19" or 20' R., and that the temperature of the mashbe kept from rising too high by means of cooling apparatus.Thetime saved in this way is considerable. J. K. C.Mashing of Grapes. By E. MACH and PORTELE (Bded. Centr.,1880, 619-620). In this investigation, a small incision was made ineach grape, and the fleshy core was pressed out, the liquid which ranoff at the same time was kept separate, as also the liquid which coulTECHNICAL CHEMISTRY. 12%be pressed out of the skins. It was found that the first containedthe greatest quantity of acid and cream of tartar, and the least amountof sugar, the liquid running off being richest in sugar, and yielding thestrongest must. J. K. C.Saccharine Matters in the Fruit of the Coffee Plant. ByBOUSSINGAULT (Conzpt. ?*end., 91, 639--642).--The dried fruit of thecoff'ee plant contains :-Mannite, 2.21 ; inverted sugar, 8.73 ; cane-sugar, 2.37.From this it will be seen that the amount of sugarpresent in the fruit is too small to enable it t o be profitably utilised asa source of alcohol, although the readiness with which it ferments hadsuggested that idea to Humboldt.Action of Animal Charcoal in the Sugar Manufacture, ByH. PELLET (Ann. C'l~iin. Phys. [ 5 ] , 20, 89--95).-Alkaline nitratesand chlorides are but little absorbed by animal black, but caustic limeon the contrary is absorbed in largc quantity; the question whichpresented itself was whether lime salts were absorbed to the same ex-tent as lime in the free state. Various solutions were made contain-i n g in different proportions sugar, calcium glucosnte, potash, lime, andalkaline salts ; these having been carefully analysed beforehard, weresubmitted to the action of purified animal charcoal a t a temperature of90-95" for a short time, and after filtration were reanalysed.Theactual results are given in a series of tables, of which the followingmay be taken as a fair summary :-That lime salts can be absorbed in certain proportion by animalblack.That free potash can also be absorbed by the black, and that itspresence considerably augments the proportion of lime salts ab-sorbed; in the latter case a larger proportion of potash itself istaken up.That the presence of free lime does not sensibly modify the actionof potash as far as regards the absorption of lime salts by the black.That free lime is almost wholly absorbed, the presence of sugarbeicg without influence on the action.When there esists simultaneously free and combined lime in a solu-tion, animal black absorbs the same proportion of the free lime,whilst its absorptive power for the saline lime is considerably dimi-nished.The presence of sugar and foreign salts generally affects the absorp-tive power of animal black but little.An investigation into the alkalinity of new charcoal and of charcoalwhich had been used and calcined several times, showed that whilst afresh black had an alkalinity of more than 0.15 per cent.(returned aslime), an old sample contained only 0.05 per cent., or not one-thirdthat in a new one ; as a necessary consequence, therefore, and from aconsideration of the foregoing experiments, a new black should absorba larger proportion of lime salts than an old one ; in actual practicesuch is always found to be the case.Inversion of Sugar during Manufacture.By DURIN (Bied.Cedr., 1880, G18--619).-According to the author, this is due t o theR. R.J. W128 ABSTRACTS OF CHEMICAL PAPERS.oxidation, and consequent acidification of the sugar during the pro-cess of manufacture, and can be avoided by the use of a small quant,ityof alkali. J. K. C.Separation of Sugar from Molasses. Ry J~~NEMANN and C.SCHEIBLER (Bied. Cp77t~., 1880, 687--688).--The method of Junemannconsists i n the precipitation of sugar by means of lime in hot solutionand mashing the precipitate under presslire at 172"; according toScheibler, however, this method presents difficulties which make itunsuccessful in practice. J.K. C.Manufacture of Vinegar by Means of Bacteria. By E. WURM(I'har1n. ?J. Trans. [3], 11, 136-134) .-According to Pasteur, theformation of vinegar from alcohol is due to the vegetation of thebactcrium, Mycodema aceti. Liebig, however, maintained that it isdue to chemical and not physiological action, since no Mycode?-nla aceticould be detected by microscopic examination on a shaving froin thebottom of a vinegar generator which had been in use for 25 years.Mayer and De Knierym, however, distinctly proved that the fermentexists in great quantity on the shavings of the vinegar generator.The author has carried out the manufacture according to the direc-tions of Pasteur, and most satisfactory results have been obtained.200 liters of a mixture of alcohol, water, and vinegar, with mineralsalts, namely, potassium phosphate, 0.01 per cent.; calcium phosphate,0.01 per cent. ; magnesium phosphate, 0.01 per cent. ; ammoniumphosphate, 0.02 per cent., are placed in a large wooden vat well closedwith a woodencover, access to air being obtained through small open-ings a t the side. The mycoderma are sown by means of a woodenspatula. The liquid in the vats is maintained a t 25-30" C., and t'hetemperature of the surrounding atmosphere a t about 30" C. Pasteurlimits the amount of vinegar to 1 per cent., but a liquid so slightlyacid is easily invaded by Saccharomyces mycoderma, which hinders thegeneration of the acetic fungus.Experiments prove that with from0.5-1.2 per cent. of acetic acid present, the Xacchcrronyces mycodernzamultiply exclusively ; with 1.6 per cent. the Mycoderma aceti pre-dominate, and with 2 per cent. the latter alone multiply.The liquid in the vat originally contained 2 per cent. of alcohol, andas this is converted into vinegar fresh quantities are added, unt'il thevinegar has attained the required strength. When the surface of thevat becomes entirely covered with bacteria, the surroundicg tempera-ture being 30" C., that of the liquid rises to 34" C., and a strong odourof acetic acid is apparent. The augmentation of the acid varies from0.2-2.4 per cent. daily. The loss of alcohol in this process is muchless than in the generators with shavings, which in the preparation ofcrude vinegar amounts to 23 per cent., but in the case of strongervinegar 12 to 15 per cent.I n this process, however, there is only lossfrom evaporation at the beginning, it being afterwards prevented bythe layers of fungus. The total loss is from 10 to 15 per ceat., oneportion of which is used by the bacteria in forming their substance,and the other converted into ethyl acetate a t the high temperature ofthe solutionTECHNICAL CHERIISTRT. 129An addition of alcohol should not be made when there is more than0.5 per cent. in the vat, and it should be added in such a way thatthe liquid coming in contact with the fungus does not contain morethan 0.5 per cent. The greater proportion of acid in the liquid, themore nearly should the quantity of alcohol added equal the quantityused up.When the vinegar has reached the required strength, it is drawnoff into vats, where it is clarified and freed from mycoderma.The precautions to be observed are-the sowing of pure bacteria, auniform temperature of 80", and a well regulated addition of alcohol.The chief advantages of this process are its cheapness and the great,economy of space, and it much greater yield.The generation of " vinegar eels " is of great inconvenience, sinceby their motion they destroy the pellicle of the mycodernia, and pre-vent its reforming.If they multiply to any great extent, the tempera-ture of the liquid falls, but by preventing the cooling, the parts ofthe pellicle destroyed may be reproduced, in which case the eels takerefuge in the upper parts of the vessel, and form a ring of viscosityabove the layer of bacteria.In t'his process, however, they haw nottime to multiply so as to become injurious, since the vats are emptiedevery 10-14 days. The mycoderma used for sowing must not comefrom a liquid infected with eels.The microscopic examination of the ferment shows that tbreedifferent forms can be observed. Whether they are from the sameorganism in different stages of development, or three differentorganisms capable of producing acetic acid, remains to be proved.With 1 to 3 per cent. of acetic acid the formation of a thick viscousand fatty skin was observed, consisting of minute globules (micro-cocci), occurring whilst young in contiguous rows, but after a fewdays changing into an animal glue, through the formation of inter-cellular tissue.An increase in the quantity of acid caused the forma-tion of veins, rays, and spots which extend more and more, whilst theoriginal layer sinks to the bottom. This new pellicle consisted of bacilli,and was less viscous than the first. It, however, became more viscous,and was replaced by a more delicate pellicle of bacilli. The amount of1 per cent. of acid is sufficient t o stop the production of the micrococci,but in such a mixture the bacilli continue to multiply. No differencehas been as yet detected in the power of acetification of these twoforms. Thin pellicles should be taken for sowing, as they germinatemore quickly than the viscous pellicles.Apparatus for Skimming Milk.By C. STIM~EL (Bied. Cerh,.,1880, 617--618).-The cream is allowed to rise in shallow paus,immersed in cold water, and the milk separated by means of asyphon. J. K. C.Colouring Matter of Rubus Chamaemorus. By C. 0. CECII(J. y r . Cken2. [el, 22, 399--400).-The author noticed that thecotton and woollen bags in which the berries of this plant weresubjected to pressure to obtain their juice for making wine werecoloured inteusely orange-yellow. The colour imparted was so per-L. T. 0's130 ABSTRACTS OF CHEMICAL PAPERS.manent and had SO thoroughly penetrated the fibre, that it was nn-affected even by dilute hydrochloric acid.Experiment showed that, the juice of these berries imparted an in-tense orange-red colour to cotton and wool in a few minutes, andsomewhat more slowly to silk.The colouring matter appears to be present in considerable quan-tity, and the author is now engaged in isolating it.Its colour will be suitable for dying shades of chamois amber andorange-yellow, and also for harmlessly colouring white wines in imita-tion of sherry.F. c.COCCUS Red. By R. ROTHER (Pharqn. J. Tram. [3], 11, 130).-There being several defects in the usual method for the preparation ofcoccus red, the author has submitted a new process. Two parts ofsodium chloride are dissolved in a mixture of 1 paft of hydrochloricacid and 44 parts water, and 8 parts of cochineal are macerated inthe solution for two days ; after which time the solution is decantedand the residue again digested with 32 parts water for two days.This solution is then poured off, and the residue digested with 32parts water, containing 3 parts sodium chloride in solution ; and aftertwo days the mixture is strained and subjected to strong pressure.The three solutions are mixed, and the clear solution decanted fromthe sediment.In the decanted liquoe 2 parts alum are dissolved, and2.5 parts ammonia solution (16 to 18 per cent.) added, and the re-sulting precipitate is collected and washed free from ammonium salts,and finally dissolved in a warm solution of sodium citrate (preparedby neutralising 1 part of citric acid with sodium carbonate). Thesolution is diluted with water to 28 parts, and mixed with 4 partsalcohol.The principle of this process is first to extract the dibasiccarminic acid, then unite it with alumininm, and finally to bring thealuminium salt into solution. The dry compound may be obtained byprecipitating the concentrated solution with alcohol, or allowing it toeva,porate slowly.The aluminium carminate obtained by precipitating the acid withalum and ammonia is a dark purple-red powder, soluble in acids to ascarlet solution, and in alkalis to deep purple.. Acid solutions of a,carminate, when diluted with large quantities of water, change frombright scarlet to purple or deep pink ; dilution with alcohol does notproduce the same effect. Aluminium carminate is also soluble inaluminium citrate, with a purple colour.Coccus red may also be obtained by treating ammonium carminatewith nluminium citrate.By treating some of the crude solution with aluminium hydrate,precipitated with ammonia, no result was obtained.On adding aceticacid to the mixture, a solution was obtained from which alkaline car-bonates failed t o give a precipitate. On adding calcium carbonate,however, a gelatinous greenish-black magna was obtained, slightlysoluble in water, soluble in acids to scarlet solutions, and in alkalis topurple. It is slowly decom-posed by ammonium sulphate, and quickly by aluminium sulphate,giving a purple solution, the colour of which is not destroyed byLime water changes its colour to pinkTECHKICAL CHEMISTRY. 131alcohol. On spontaneous evaporation, a purple crystalline residue isobtained.The filtrate from the calcium salt is of a purple colour, and from ita.nmonia throws down a pink precipitate, leaving a light’ scarlet solu-tion.Earium and magnesium compounds corresponding to the cal-Analysis of Bohemian Tea. By BELOHOUBECE (Bid. Centr.,1880, 703) .-So-called Bohemian tea, the leaves of Litkospermcm qft..,is often used t o adulterate ordinary tea. Compared with Chinese tea,it yields the following figures on analysis :-cium compound could not be obtained. L. T. 07s.Bohemian tea.Cellulose ...................... 5.9 6Tannin.. ...................... 8.25Fat .......................... 9.29Ethereal oil.. ..................Other nitrogen-free organic bodies 26.49T he’in -Albumin...................... 2454Water ........................ 9.85Ash .......................... 20.59-........................Chinese tea.21.3013.783.760-6724-121.7619.909.325-34J. K. C.Preparation of Iodine-iron Cod Liver Oil. By S. D. VOXVALAKNBUEG (Pharm. J. Tmm. [ 31, 11, 209).--1.25 parts of iodine aredissolved in 98.5 parts of cod liver oil by constant shaking and stirring.The solution, having the sp. gr. 0.932-0.937, is poured into a vessel,trhich is hermetically closed aud shaken with 2.5 parts iron until itassumes a purple colour, and contains no free iodine. This is ascer-tained by shaking a portion of the oil with a solution of potassiumiodide and starch-paste. The mixture is then allowed to stand for24 hours, then shaken again, and finally allowed to stand until clear.The clear liquid has the sp.gr. 0.937-0.94, and should contain 1.23per cent. iodine and 0.27 per cent. iron. In the preparation, airshould be excludcd as much as possible, since it causes the quantityof iron to increase, owing to the formation of ferric oxyiodide,French iodine is generally used in preference to English, since thelatter, on account of its fineness, forms a tough mass when mixedwith the oil, and this can only be broken up with difficulty. I n somecases, a dark-coloured amorphous substance adheres to the bottom ofthe vessel; it is insoluble in ether, and can he almost completelyvolatilised.The mixture, although originally containing no free iodine, is foundto contain it after standing for 24 hours, owing t o the formation ofa sniall quantity of ferric iodide, which, on standing, is decomposedinto ferrous iodide and iodine.The violet colour is due to the pre-sence of ferric oxyiodide. The mixture readily oxidises on exposureto the air, losing its colour.Water destroys the mixture, siiice it first dissolves the ferrousiodide, which it afterwards decomposes. L. T. 0’s132 ABSTRACTS OF CHEMICAL PAPERS.Steeping Hemp. By A. REPU’OUARD (Bied. Cent?.., 1880, 6:30),-The water in which hemp has been steeped produces no evil effects onthe health of a district when allowed to flow into running water, but italways destroys the fish, together with certain vegetablegrowths.J. K. C.Hardness and Resistance of Wood.By v. NORDLINGER (Bied.Cenfr., 1880, 600--602).--The resistance of wood is greatest when ithas been cut in May or October ; this is especially the case with Foungtrees. J. K. C .A Baking Powder. By M. WEITZ (Bied. Cejitr., 1880, 389-390).-The report of an examination of a baking powder which has beenselling freely in Berlin. It consists of fine wheat flour, with a smalladdition of inorganic matter, which, when water is added, disengagesgas, and renders the dough porous, acting as a substitute for yeast.This preparation has been found well adapted for the purpose. Thegas is carbonic anhydride, and each kilogram of the powder contains5.1 gram of phosphoric anhydride and 8.7 grams of sodium bicar-bonate. It is very similar to the proportions recommended for bakingpoxtier by Liebig, except that he recommended the ingredients to bekept separate until required for use.Preservation of Fruit in Winter. By P. SARAUER (Bied. CeiLtr.,1880, 383-3355).-The object of preserving fruit in their fresh state isbest attained by keeping them in a cool dark place. The author’s expe-riments were directed so as to ascertain the influence of dry and dampair on the stored fruit. Apples were the subjects of his investigation.They were kept in an ordinary fruit store, part exposed to damp airin the open store, part enclosed in glass vessels, through one of whichdry and the other damp air was aspirated. The loss of weight percent. was : loose samples, 3.42 ; dry air, 7-90; saturated with damp,0.60. The sample which was in dried air did not show mould sosoon, but it shrivelled quickly and ripened, and at the end of the expe-riments tasted less sweet, and showed a larger proportion of decayedfruit. The breaking off or leaving on of the stalk has a considerableeffect on the drying out of the moisture; leaving it on promotes arapid evaporation. The removal of the external coating of wax bymeans of ether, &c., also promotes rapid evaporation. Wrapping theapples in silk paper was not found to be advantageous, except whenthe storing place was unusually dry ; the germs of mould attacked therough portions of the fruit with great avidity through the openings intbe paper. Packing in straw was also found injurious, the least damp-ness in the straw imparting a musty flavour to the fruit. Dry sand i srecommended strongly above all other means of preserving fruit. Thespecimens tried by the author would apparently have kept fresh andsn-eet until the July of the following year. The loss of weight wasnot half that of the loose fiwit; there was no appearance of mould,and the damaged specimens did not infect their neighbours. Thechief point in selecting fruit for preservation is to choose those withwhole sound skins and with the waxy covering perfect.J. F.J. F

ISSN:0368-1769    

DOI:10.1039/CA8814000125

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

133 G e n e r a l a n d P h y s i c a l C h e m i s t r y . Evaporation without Fusion. By L. MEYER (Ber., 13, 1831- 1833). -The author (Ber., 8, 1627), has shown that the conversion of a solid body directly into the gaseous or indirectly through the liquid state is dependent on the pressure. If iodine is melted in an ex- hausted tube, and the heat raised until the maximum tension of the vapour at the melting point is reached, the iodine melts in a black stream along the side of the tube. On cooling, the fluid iodine begins to boil, and then solidifies ; on warming again, the solidified mass of iodiiie exhibits Leidenfrost’s phenomenon. The same is observable with Japan camphor, naphthalene, anthracene, and hexchlorethaxte. Cmr- nelley has defined that pressure below which no amount af heat will melt a substance, as the “critical pressure,” a term analogous to Andrew’s “ critical temperature.” But these definitions are not strictly comparable, for by the pressure on the substance is meant the pressure of its own vapour.In order that these definitions may be compared they must be as follows :- The criticul temperature of a gas is that above which no pressure cuii The critical pressure of a solid is that tension oj its own vapour under which no incyemerit of heat can melt it. Lothar Meyer and the latest Discovery in Physics. By 0. YETTERSSON ( B e y . , 13, 2141-21G). This is a criticism on Lothar Dfeyer’s remarks (Ber., 13, 1831) in reference to the results recently published by Carnelley (Nature, Sept. 8th, 1880) on the critical pressure of substances, and the existence of bodies a t temperatures considerably above their ordinary melting points.In conclusion, it is pointed out t h a t the existence of bodies above their ordinary melting points when heated under low pressures depends on the same prim ciple as the lowering of the melting point by increased pressure, as was predicted by Prof. J. Thomson, and confirmed by Sir W. Thom- son and others. T. C. liqlKfiJ it. V. H. V. Lecture Experiment. By R. EAASS (Bey., l3,2203).-This is an experiment to illustrate the critical pressure of a substance a s recmtly described by Carnelley (Ohem. News, 42, L30). A solid piece of mercuric chloride is introduced into a glass tube closed at one end, and connected at the other with an air-pump ; on reducing the pressure below about 400 m-m.it i s impossible to melt the salt, how- ever strong the heat applied, the solid merely subliming into the cooler portions of the tube ; on letting in the air fusion begins when the pressure has risen to about 450 mm. Note.-This experiment as far as it goes is identical with that VOL. XL. l T. C.134 ABSTRACTS OF CHEMICAL PAPERS. 79 *19 shown by Carnelley at the Chemical Society on Dec. 16th, 1880, and described in a paper received by the Royal Society on Nov. 11th. 155 5 5 Reciprocal Displacement of the Halogens in absence of Water. By M. POTILITZIN (Bull. SOC. Chim. [2], 34, 220-225).- From the author's previous researches (ibid. [el, 27, 303, it -would appear that bromine replaces chlorine in the anhydrous metallic chlorides, and that when equivalent quantities act on one another the percentage of halogen replaced depends on the atomic weight and quantivalence of the metal, and on the temperature.For two bodies in the same system, the percentage of halogen replaced increases with the mass (number of molecules of bromine entering into the reaction). The author has repeated and extended his previous experiments, find- ing that the limit of change between a given system of two bodies, such as BaC1,+Br2, is attained in a few hours at 400" ; in the case quoted from 2-6 hours. By arranging the elements according to Mendelejeff's periodic law in a table showing the percentage of chlorine replaced by bromine in their chlorides, it is seen that in the same vertical series the amount of chlorine replaced is proportional to the atomic weight of the element, and therefore in that series 5 = constant, where A = atomic weight of the metal, and p the percentage of chlorine re- placed : - P R.C1 + Br.LiCl.. . . NaCl .. KC1 ... . . AgCl .. - Mean constant A Y - RCL, + BY^. CaCI, SrC12 BaCl, HgC12 PbC1, 16 9 1 2RC1, + 3Br2. - BiC1, 1 5-38 38.66 R.C4 + 2Br2. I &C16 + 3Br2. - I - I - In comparing elements in the same horizontal series" it is seen that the percentage of chlorine replaced diminishes aa the quantivalence of the element increases, not progressively, but as the square of the valency ; hence __ = constant (4 nearly) where E = the quantiva- lence of the element. A PEz * The horizontal series in the table are not identical with those of Mendelejeff's.6ENERA.L AND PHYSICAL CHEMISTRY.135 Heat of combustion (CO,) =96,960 h. u. (H,O) = 68,360 h. u. ~ of constituents. ’786,840 h. u. From further considerations the author is of opinion that the fixed limit arrived at in these reactions with anhydrous bodies, whether they be accompanied with the evolution or absorption of heat, is a function of the atomic weight, the mass of the acting bodies, and the temperature ; this has been proved to be true for bodies in solution. In discusging the thermochemical results on the separation of acids and bases, the author shows that in cases where the amount of chemical energy developed is but small, it is doubtful whether the calorimetric method can be employed. This applies to these reactions, since in the reciprocal actions of the bodies the rapidity of the formation of the molecules (the rapidity of the reaction) ought to diminish, as the limit of reaction is reached ; this has been confirmed by the results of Malaguti, Guldberg, Harcourt, and others.C~nsequent~ly the work measured by the calorimetric method, as the total transformation of one system into another, is only the work done in the first five or ten minutes of the reaction ; and therefore the thermochemical results are only proportional to the rapidity of the reaction in those first moments ; and the so-called thermal equivalents, although pointing out the direction of the principal reaction, do not measure the affinities, nor foretell or explain the number of inverse reactions accompanied by an absorption of heat.In these considerations may be found an exp1a.n- ation of the divergence between the predicted and experimental thermochemical results. L. T. 0’s. Heat of formation of gaseous benzene. At constaiit At constant pressure. volume. ------ - 18,960 h. U. -20,120 h. U. Heat of Combustion of Benzene. By J. THOMSEN (Rer., 13, 1806--1807).-The author remarks on the importance of heat deter- minations of benzene as the foundation of the aromatic compounds. The heat of combustion of a molecule (72 grams) of benzene vapour was found to be 805,800 heat-units. As the heat of formation is equal to the difference between the heats of combustion of the constituents of the compound and of the compound itself, the following values are deduced :- Heat of combustion of benzene vapour.805,800 h. u. V. H. V. Heat of Combustion of Carbon Compounds. By C. v. RECHENBERG (J. pr. Chem., 22, 1--45).-The following is a summary of the author’s results. In all cases the products formed were C02 (gaseous) and H,O (liquid), and Berthelot’s values for these were adopted in the calculations, viz., C + O2 = CO, = 94 cals., and H2 + 0 = H,O = 69 cals. The combustion of dextrose affords an example of the method of calculation. The process may be resolved into two stages :- (a*) C6H1206 = Cg + Hi, + 0 6 . (6.) c6 + Hiz -I- 0 6 + 602 = 6C0, 6HD. 1 2136 ABSTRACTS OF CHEMICAL PAPERS . 1 gram c . The amount of heat evolved in these two processes is + 709 cals . The heat evolved in ( p ) is. however. equal to the sum of the heat of formation of 6 mols .CO. and 6 mols . of HzO. i.e., 564 + 414 = +978. therefore the heat of (a) must be 709 - 978 = - 269 . Then as -269 represents the heat of decomposition of dextrose into its elements. it must also represent the heat of its formation from its elements . The following table gives tlhe values for the compounds expcri- mented on. “ csl” being the beat necessary to heat 1 kilo . of water 1” c., and c the amount necessary to heat 1 gram :- 1 mol . cal . Dextrose anhydride . , .......... , .. .... 180 Dextrose hydrate .. , , ............. Lactose anhydride . , , ............. .... 180 Mannitol ........................ Dulcitol., ........................ Mjristic acid .................... Stearic acid ...................... Cane-sugar ...................... Maltose anhydride ................Maltose hydrat.e .................. Milk-sugar anhpdride., ............ Milk-sugar hydrate ................ Starch .......................... Erythrodextrin .................. Inulin .......................... Cellulose ........................ Metarabic acid. ................... C6H& .... C6H1406 .... C, 4H2802 .... C18H3602 .... C.H.. ....... CBH1.O. .... C6H.00. .... CeHl.0. .... C6H1005 .... 760 753 2175 2808 +287 +294 +lo7 +126 Oxalic acid ...................... Malonic acid ...................... 8ucciriic acid .................... Tartaric acid ...................... Citric acid., ...................... Phenol .......................... Benzoie acid ..................... Phenylacetic acid .................. Phchalic acid ....................Salicylic acid .................... Metahydroxybenzoic acid .......... Parahydroxy benzoic acid .......... Anthracene ...................... Anthraquinone .................... Naphthalene ...................... C3H304 ...... C.H. O. ...... C4H604 ...... C4H606 ...... c.H.0, ...... C6H. 0 ...... C7H.0. ...... c&3.02 ...... CaHg04 ...... C.H.O. ...... Q7H.03 ...... Cl.Hs ........ C7H.0. ...... CI4H5O2 .... C.4HI. ...... 342 342 360 3 1.2 360 162 162 162 162 162 182 182 228 284 90 104 118 134 148 64 122 136 166 138 138 138 128 178 208 3939 3667 3894 4173 4163 3932 4162 3945 4479 4325 4398 4452 4464 4175 4135 9540 9886 659 1992 2996 1408 2531 7908 6650 7127 4855 5503 5464 5448 9831 9977 7198 709 701 701 1427 1424 1416 1423 1420 726 ’lo1 i 712 721 723 +269 -t 346 +277 +460 +476 +54Q +464 +536 +183 + 208? 1197 +188 +186 59 207 354 211 486 743 811 969 806 759 754 9’52 1258 1’776 1424 i +198 +213 +229 +372 +354 + 2 8 + 5 4 + 5 9 +153 +106 +111 +113 .42 .115 + 168? The conclusion will follow .G . T . A .GENERAL AND PHYSICAL CHEMISTRY. 137 Determination of the Densities of Permanent Gases. By V. MEYER (Ber., 13, 2019-2021).--For the determination of the density of the permanent gases at high temperatures, the author has devised an apparatus which consists of a pipette-shaped vessel (of about 100-200 C.C. capacity) fitted with two capillary tubes a t each end. The apparatus is filled with the gas, which, after acquiring the temperature of the vessel, is expelled by anot'her having no chemi- cal action on it. The expelling gas and the method of performing the experiment is varied according to circumstances; thus if the gas is insoluble in water, it may be expelled by carbonic or hydrochloric acid and measured over water or potash.Before and after an ex- periment the apparatus is filled with air or nitroyen and expelled by carbonic or hydrochloric acid and measured over water, the expelled volumes of air or nitrogen will be equal if the temperature has re- mained constant. By a comparison of the air collected on the one hand, and of the gas on the other (under the same conditions), the density of the gas a t the higher temperature is determined, without necessarily ascertaining the pressure or temperature to which it has been subjected. At higher temperatures a similar shaped apparatus, made of porcelain or platinum, is used, and instead of the capillary tubes the vessel is pa,rtly closed at each end by glass or graphite stop- pers so as to allow a minute annular space between the stoppers and the vessel. By means of this apparatus the author, in conjunction with H.Ztiblin, has established that hydrogen undergoes no change in density a t the highest temperature of a Schloesing's oven. A tsble is given of those gases whose expansion-coefficient is unaltered even at very high temperatures. V. H. V. Volume Constitution of Sulphates, Chromates, and Sele- nates. By H. SCHRODER ( J . pr. Chem. ['L], 22,432--460).-A con- tinuation of the previous paper of the author on this subject (J. pr. Chem. [el, 19, 267 ; this Journal, 1879, Abstr., 768; see also this Journal, 1878, 926).The molecular volumes of the anhydrous sul- phates, chromates, and selenates of potassium, silver, glucinum, and caesium are rn~lt~iples of 5.52, as are also the volumes of the anhydrous sulphates of magnesium, zinc, copper, cobalt, iron, manganese, and nickel. In the case of the sulphates of ammonium, rubidium, and thallium, the molecular volumes must, be doubled in order to become multiples of 5.52. A large number of molecular volumes of sul- pbates, selenates, and chromates containing water of crystallisation are then discussed. It appears that water may have two different molecular volumes, and t>hat the number of molecules occupying me more condensed volume in these salts stands in no direct relation to the chemical composition; it amounts to 1, 2, 2Q, and 3 mols., and cannot be referred to the nature of the acid and base merely, but is most directly influenced by the nature and temperature of preparation.The author points out that the stere, 5-55, must be taken only as a first approximation to the t r u t h ; that the stere of the selenates is slightly greater t'han that of the sulphates, and the stere of an ammo- nium compound slightly greater than that of the corresponding potassium compound. A. J. G.138 ABSTRACTS OF CHEMICAL PAPERS. History of Periodic Atomicity. By D. MENDELEJEFF (Bey., 13, 1796--1804).-1n this paper the author claims priority for the publi- cation of the law of periodic atomicity in answer to Lothar Meyer (Bsr., 13, 259). The author considers that Carnelley (Phil. Mag., October to December, 1879) has added the only new facts to this theory since the original publication in the Jount.Russ. Chem. SOC. The author also st'ates that he is not indebted for his theory to New- lands or Lothar Meyer, but only to Lenssen and Dumas. A freshly- arranged table of elements is given. V. H. V. Periodic Atomicity. By L. MEYER (Ber., 13, 2043-2044).-An answer to Mendelejeffs communications (Ber., 13, 1796).133G e n e r a l a n d P h y s i c a l C h e m i s t r y .Evaporation without Fusion. By L. MEYER (Ber., 13, 1831-1833). -The author (Ber., 8, 1627), has shown that the conversion ofa solid body directly into the gaseous or indirectly through the liquidstate is dependent on the pressure.If iodine is melted in an ex-hausted tube, and the heat raised until the maximum tension of thevapour at the melting point is reached, the iodine melts in a blackstream along the side of the tube. On cooling, the fluid iodine beginsto boil, and then solidifies ; on warming again, the solidified mass ofiodiiie exhibits Leidenfrost’s phenomenon. The same is observable withJapan camphor, naphthalene, anthracene, and hexchlorethaxte. Cmr-nelley has defined that pressure below which no amount af heat willmelt a substance, as the “critical pressure,” a term analogous toAndrew’s “ critical temperature.” But these definitions are notstrictly comparable, for by the pressure on the substance is meant thepressure of its own vapour. In order that these definitions may becompared they must be as follows :-The criticul temperature of a gas is that above which no pressure cuiiThe critical pressure of a solid is that tension oj its own vapour underwhich no incyemerit of heat can melt it.Lothar Meyer and the latest Discovery in Physics.By0. YETTERSSON ( B e y . , 13, 2141-21G). This is a criticism on LotharDfeyer’s remarks (Ber., 13, 1831) in reference to the results recentlypublished by Carnelley (Nature, Sept. 8th, 1880) on the criticalpressure of substances, and the existence of bodies a t temperaturesconsiderably above their ordinary melting points. In conclusion, it ispointed out t h a t the existence of bodies above their ordinary meltingpoints when heated under low pressures depends on the same primciple as the lowering of the melting point by increased pressure, aswas predicted by Prof.J. Thomson, and confirmed by Sir W. Thom-son and others. T. C.liqlKfiJ it.V. H. V.Lecture Experiment. By R. EAASS (Bey., l3,2203).-This is anexperiment to illustrate the critical pressure of a substance a srecmtly described by Carnelley (Ohem. News, 42, L30). A solidpiece of mercuric chloride is introduced into a glass tube closed at oneend, and connected at the other with an air-pump ; on reducing thepressure below about 400 m-m. it i s impossible to melt the salt, how-ever strong the heat applied, the solid merely subliming into thecooler portions of the tube ; on letting in the air fusion begins whenthe pressure has risen to about 450 mm.Note.-This experiment as far as it goes is identical with thatVOL.XL. lT. C134 ABSTRACTS OF CHEMICAL PAPERS.79 *19shown by Carnelley at the Chemical Society on Dec. 16th, 1880, anddescribed in a paper received by the Royal Society on Nov. 11th.155 5 5Reciprocal Displacement of the Halogens in absence ofWater. By M. POTILITZIN (Bull. SOC. Chim. [2], 34, 220-225).-From the author's previous researches (ibid. [el, 27, 303, it -wouldappear that bromine replaces chlorine in the anhydrous metallicchlorides, and that when equivalent quantities act on one another thepercentage of halogen replaced depends on the atomic weight andquantivalence of the metal, and on the temperature. For two bodies inthe same system, the percentage of halogen replaced increases with themass (number of molecules of bromine entering into the reaction).The author has repeated and extended his previous experiments, find-ing that the limit of change between a given system of two bodies, suchas BaC1,+Br2, is attained in a few hours at 400" ; in the case quotedfrom 2-6 hours.By arranging the elements according to Mendelejeff'speriodic law in a table showing the percentage of chlorine replaced bybromine in their chlorides, it is seen that in the same vertical seriesthe amount of chlorine replaced is proportional to the atomic weightof the element, and therefore in that series 5 = constant, where A =atomic weight of the metal, and p the percentage of chlorine re-placed : -PR.C1 + Br.LiCl.. ..NaCl ..KC1 ... . .AgCl .. -MeanconstantAY-RCL, + BY^.CaCI,SrC12BaCl,HgC12PbC1,16 9 12RC1, + 3Br2.-BiC1, 1 5-3838.66R.C4 + 2Br2. I &C16 + 3Br2.- I - I -In comparing elements in the same horizontal series" it is seen thatthe percentage of chlorine replaced diminishes aa the quantivalenceof the element increases, not progressively, but as the square of thevalency ; hence __ = constant (4 nearly) where E = the quantiva-lence of the element.APEz* The horizontal series in the table are not identical with those of Mendelejeff's6ENERA.L AND PHYSICAL CHEMISTRY. 135Heat of combustion(CO,) =96,960 h. u.(H,O) = 68,360 h. u.~ of constituents.’786,840 h. u.From further considerations the author is of opinion that the fixedlimit arrived at in these reactions with anhydrous bodies, whetherthey be accompanied with the evolution or absorption of heat, is afunction of the atomic weight, the mass of the acting bodies, and thetemperature ; this has been proved to be true for bodies in solution.In discusging the thermochemical results on the separation of acidsand bases, the author shows that in cases where the amount of chemicalenergy developed is but small, it is doubtful whether the calorimetricmethod can be employed.This applies to these reactions, since in thereciprocal actions of the bodies the rapidity of the formation of themolecules (the rapidity of the reaction) ought to diminish, as thelimit of reaction is reached ; this has been confirmed by the results ofMalaguti, Guldberg, Harcourt, and others.C~nsequent~ly the workmeasured by the calorimetric method, as the total transformation ofone system into another, is only the work done in the first five or tenminutes of the reaction ; and therefore the thermochemical results areonly proportional to the rapidity of the reaction in those first moments ;and the so-called thermal equivalents, although pointing out thedirection of the principal reaction, do not measure the affinities, norforetell or explain the number of inverse reactions accompanied by anabsorption of heat. In these considerations may be found an exp1a.n-ation of the divergence between the predicted and experimentalthermochemical results. L. T. 0’s.Heat of formation of gaseous benzene.At constaiit At constantpressure.volume. ------- 18,960 h. U. -20,120 h. U.Heat of Combustion of Benzene. By J. THOMSEN (Rer., 13,1806--1807).-The author remarks on the importance of heat deter-minations of benzene as the foundation of the aromatic compounds.The heat of combustion of a molecule (72 grams) of benzene vapour wasfound to be 805,800 heat-units. As the heat of formation is equal tothe difference between the heats of combustion of the constituents ofthe compound and of the compound itself, the following values arededuced :-Heat of combustionof benzene vapour.805,800 h. u.V. H. V.Heat of Combustion of Carbon Compounds. By C. v.RECHENBERG (J. pr. Chem., 22, 1--45).-The following is a summaryof the author’s results. In all cases the products formed were C02(gaseous) and H,O (liquid), and Berthelot’s values for these wereadopted in the calculations, viz., C + O2 = CO, = 94 cals., andH2 + 0 = H,O = 69 cals.The combustion of dextrose affords anexample of the method of calculation. The process may be resolvedinto two stages :-(a*) C6H1206 = Cg + Hi, + 0 6 . (6.) c6 + Hiz -I- 0 6 + 602 = 6C0, 6HD.1 136 ABSTRACTS OF CHEMICAL PAPERS .1 gramc .The amount of heat evolved in these two processes is + 709 cals .The heat evolved in ( p ) is. however. equal to the sum of the heat offormation of 6 mols . CO. and 6 mols . of HzO. i.e., 564 + 414 =+978. therefore the heat of (a) must be 709 - 978 = - 269 .Then as -269 represents the heat of decomposition of dextrose intoits elements.it must also represent the heat of its formation from itselements .The following table gives tlhe values for the compounds expcri-mented on. “ csl” being the beat necessary to heat 1 kilo . of water1” c., and c the amount necessary to heat 1 gram :-1 mol .cal .Dextrose anhydride . , .......... , .. .... 180Dextrose hydrate .. , , .............Lactose anhydride . , , ............. .... 180Mannitol ........................Dulcitol., ........................Mjristic acid ....................Stearic acid ......................Cane-sugar ......................Maltose anhydride ................Maltose hydrat.e ..................Milk-sugar anhpdride., ............Milk-sugar hydrate ................Starch ..........................Erythrodextrin ..................Inulin ..........................Cellulose ........................Metarabic acid....................C6H& ....C6H1406 ....C, 4H2802 ....C18H3602 ....C.H.. .......CBH1.O. ....C6H.00. ....CeHl.0. .... C6H1005 ....76075321752808+287+294+lo7+126Oxalic acid ......................Malonic acid ......................8ucciriic acid ....................Tartaric acid ......................Citric acid., ......................Phenol ..........................Benzoie acid .....................Phenylacetic acid ..................Phchalic acid ....................Salicylic acid ....................Metahydroxybenzoic acid ..........Parahydroxy benzoic acid ..........Anthracene ......................Anthraquinone ....................Naphthalene ......................C3H304 ......C.H.O. ......C4H604 ......C4H606 ......c.H.0, ......C6H. 0 ......C7H.0. ......c&3.02 ......CaHg04 ......C.H.O. ...... Q7H.03 ......Cl.Hs ........ C7H.0. ......CI4H5O2 .... C.4HI. ......3423423603 1.23601621621621621621821822282849010411813414864122136166138138138128178208393936673894417341633932416239454479432543984452446441754135954098866591992299614082531790866507127485555035464544898319977719870970170114271424141614231420726’lo1 i712721723+269-t 346+277+460+476+54Q+464+536+183 + 208?1197+188+186592073542114867438119698067597549’5212581’7761424 i+198+213+229+372+354+ 2 8+ 5 4+ 5 9+153+106+111+113.42.115 + 168?The conclusion will follow .G . T . A GENERAL AND PHYSICAL CHEMISTRY. 137Determination of the Densities of Permanent Gases. ByV. MEYER (Ber., 13, 2019-2021).--For the determination of thedensity of the permanent gases at high temperatures, the author hasdevised an apparatus which consists of a pipette-shaped vessel (ofabout 100-200 C.C. capacity) fitted with two capillary tubes a t eachend. The apparatus is filled with the gas, which, after acquiring thetemperature of the vessel, is expelled by anot'her having no chemi-cal action on it.The expelling gas and the method of performing theexperiment is varied according to circumstances; thus if the gas isinsoluble in water, it may be expelled by carbonic or hydrochloricacid and measured over water or potash. Before and after an ex-periment the apparatus is filled with air or nitroyen and expelled bycarbonic or hydrochloric acid and measured over water, the expelledvolumes of air or nitrogen will be equal if the temperature has re-mained constant. By a comparison of the air collected on the onehand, and of the gas on the other (under the same conditions), thedensity of the gas a t the higher temperature is determined, withoutnecessarily ascertaining the pressure or temperature to which it hasbeen subjected.At higher temperatures a similar shaped apparatus,made of porcelain or platinum, is used, and instead of the capillarytubes the vessel is pa,rtly closed at each end by glass or graphite stop-pers so as to allow a minute annular space between the stoppers andthe vessel. By means of this apparatus the author, in conjunctionwith H. Ztiblin, has established that hydrogen undergoes no changein density a t the highest temperature of a Schloesing's oven. A tsbleis given of those gases whose expansion-coefficient is unaltered evenat very high temperatures. V. H. V.Volume Constitution of Sulphates, Chromates, and Sele-nates. By H. SCHRODER ( J . pr. Chem. ['L], 22,432--460).-A con-tinuation of the previous paper of the author on this subject (J.pr.Chem. [el, 19, 267 ; this Journal, 1879, Abstr., 768; see also thisJournal, 1878, 926). The molecular volumes of the anhydrous sul-phates, chromates, and selenates of potassium, silver, glucinum, andcaesium are rn~lt~iples of 5.52, as are also the volumes of the anhydroussulphates of magnesium, zinc, copper, cobalt, iron, manganese, andnickel. In the case of the sulphates of ammonium, rubidium, andthallium, the molecular volumes must, be doubled in order to becomemultiples of 5.52. A large number of molecular volumes of sul-pbates, selenates, and chromates containing water of crystallisationare then discussed. It appears that water may have two differentmolecular volumes, and t>hat the number of molecules occupying memore condensed volume in these salts stands in no direct relation tothe chemical composition; it amounts to 1, 2, 2Q, and 3 mols., andcannot be referred to the nature of the acid and base merely, but is mostdirectly influenced by the nature and temperature of preparation.The author points out that the stere, 5-55, must be taken only as afirst approximation to the t r u t h ; that the stere of the selenates isslightly greater t'han that of the sulphates, and the stere of an ammo-nium compound slightly greater than that of the correspondingpotassium compound. A. J. G138 ABSTRACTS OF CHEMICAL PAPERS.History of Periodic Atomicity. By D. MENDELEJEFF (Bey., 13,1796--1804).-1n this paper the author claims priority for the publi-cation of the law of periodic atomicity in answer to Lothar Meyer(Bsr., 13, 259). The author considers that Carnelley (Phil. Mag.,October to December, 1879) has added the only new facts to thistheory since the original publication in the Jount. Russ. Chem. SOC.The author also st'ates that he is not indebted for his theory to New-lands or Lothar Meyer, but only to Lenssen and Dumas. A freshly-arranged table of elements is given. V. H. V.Periodic Atomicity. By L. MEYER (Ber., 13, 2043-2044).-Ananswer to Mendelejeffs communications (Ber., 13, 1796)

ISSN:0368-1769    

DOI:10.1039/CA8814000133

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

138 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c Chemistry. Preparation of Hydrochloric Acid Gas. By L. L. DE KONINCK (Zeds. Anal. Chent., 1880, 467-468) .-The author prepares hydro - chloric acid by the action of concentrated sulphuric acid on ammo- nium chloride, the advantage of the method consisting in the regularity of the action, and in the residue of ammonium sulphate being non-crystalline and syrupy. 0. H. Action of Iodine on Phosphorus Trichloride. By C. G. MOOT (Bey., 13, 2029--2031).-On mixing iodine with phosphorus trichlo- ride, the liquid is reddened and a part of the iodine is dissolved. On exposing the liquid to moist air, a golden mbstance separates out ; the author establishes that moisture, and not the oxygen of the air, is necessary for this change. On treatment of a small quantity of phos- phorus trichloride with a large excess of iodine, a solid mass is obtained completely soluble in carbon bisulphide ; on evaporating the solution, fine red hexagonal crystals of the formula PClJ, separate out, which are decomposed by moist air, and split up with liberation of iodine when heated.The author promises a, further account of the properties of the golden substance and of phosphorus trichloriodide. V. H. V. Impurities in Sodium Bicarbonate. By A. KOSTER (Arch. Pharm. [3], 14, 31--33).-Ammonium bicarbonate may occur to the extent of nearly 4 per cent. in sodium bicarbonate prepared by the ammonia process. 0. H. Action of Hydrochloric Acid at High Temperatures on Ultramarine rich in Silica. By P. G. S~LBER (Bey., 13, 1854- 1857).-The author considers that all previous analyses of red ultra- marine were of specimens contaminated with blue ultramarine (R.Hoffmann, this Journal, Abstr., 1879, 108). By the action of hydrochloric acid at high temperatures with access of air, a violetINORGANIO CHEMISTRY. 139 ultramarine is obtained which bears the same relation to the blue and red ultramarines that the green ultramarine does to the white or blue in the series poor in silica. By systematic'washings, the violet can be separated from the un- altered blue. By further treatment with hydrochloric acid, the violet can be converted into the red of commerce, which may be fractionally separated from the violet. The violet portion in the red of commerce is due either to an imperfect action of hydrochloric acid or to the change of red into violet after continuous treatment with water.The violet can be reconverted into the red on heating with water at 130°, or more directly by a drop of soda. In order to obtain a perfect red, the trade product is heated with hyd.rochloric acid until no further change of colour is evident, the sodium chloride removed by washing with slightly alkaline water, and the completely washed product dried below 150". If dried at a higher temperature, the red immediately passes over into the yellow nltrnma rine. Analyses oj' Ultrarnariizes.-a, a blue of greatest purity used for the preparation of the violet and red ; b and c, violet and red of com- rnerce ; d, red from c after all the sodium had been separated out ; and e (yellow), from d after heating for a long time in the air.a. b. c. a. e. Si.. . . 19.07 18.91 19.39 20.51. 21.44 A1 . . 13-04 13.55 13.80 13.99 14-32 Na . . 15.92 14.53 11.29 8.98 8.00 S . . . . 14-09 12.39 12*44 12-14 10.90 0 . . . . 37.88 40.62 43.08 4438 45.14 From these analyses it follows tbat in the conversion of ultramarine- blue into yellow, half the sodium contained in the blue must be re- moved. The authoy considers that on account of the similarity of the analytical numbers of d and e, that e is not a pure yellow. The num- bers for perfect red ( d ) correspond with the formula, Si,A14Na3.S3022, and the conversion of blue into red can be expressed by the following equation :- Si6A14Na6S,0zo + 0, = Si6A14Na3S3022 + Na, + S. Blue. Red. The author proposes to study the action of hydrochloric acid on ultramarines poor in silica.V. H. V. Atomic Weight of Glucinum. By L. MEYER (Ber., 13, 1780 -1 786) .-Acbording to Nilson and Pettersson (this Journal, Abstr., 1880, 792) the equivalent of glucinum is 4.55, and its atomic heat normal if the ahomic weight be taken as 13.65, making glucinum a, triad. The author objects to these conclusions, and considers glucinum a dyad with an atomic weight of 9.10. Firstly, if glucinum had an atomic weight of 13.65, it would have a position in the system of elements between nitrogen and carbon which would not correspond to any of the known properties of the metal; but this consideration is not sufficient to justify any correction of its atomic weight. Secondly,140 ABSTRACTS OF UHEMICAL PAPERS.Nilson and Pettersaon have shown that the specific and atomic heats increase slightly with the temperature like those of iron, hence for glucinum an atomic weight of 13.65 best corresponds with the mean specific heat between 0" and 100". But the author establishes that even adopting Nilson and Pettersson's determinations, glucinum is rather comparable with carbon, boron, and silicon, whose specific heats increase a t first rapidly, then more slowly, until a limit is reached at which they show a normal specific heat. Then glucinum would be a dyad with an atomic weight of 9.1 : for if glucinum has an atomic weight of 13.65, its atomic heat at 157" should be 7.;0, and a t 257" is 8.94, which is far greater than those of iron and silver. Atomic Weight of Glucinum.By L. F. NmoN (Ber., 13, 2035 -2040).-This pager is in answer to that of L. Meyer (Ber., 13, 1780). The author points out lst, that glucinum with the atomic weight of 9.1 departs from the regular series of Mendelejeff's classification by more than 13 75 per cent. from the number required for this system ; thus of all the elements of the first series glucinum is the only one which differs from the neighbouring elements of the second series by not less than 16. 2nd. Although Meyer compares glucinum with boron, silicon, and carbon, with regard to the increase of specific heat with increase of temperature, yet in Weber's researches on these latter elements, neither pure materials, nor eyen compounds of known com- position, were used : for Hamp6 has established that crystalline boron contains aluminium and carbon, and Mixter and Dana have shown that crystalline silicon contains zinc and iron.3rd. The molecular heat of glucina and its sulphate is equal to those of alumina, scandia, gallium oxide and their sulphates (Ber., 13, 1459; Abstrs., 1880, 838), but differs from those of the oxides and sulphates of magnesia, copper, and other dyad metals. The formula G,O, is then in accordance with the laws of Ihlong and Petit and Naumann, and although glucinum has an atomic heat of 5.79 (between 0" and lWo), slightly less than the normal number, yet in this respect it resembles its analogues aluminium and gal- lium. V. H. V. V. H. V. Phosphotungstic Acid. By M. SPRENGER (J. p r . Chem. [2], 22, 418-432).-Phosphotungstic acids have been previously described by Scheibler (Ber., 5, 801 ; this Journal, 1873, 246) who obtained acids of the formulae H15PW11043, 18H20 and HllPWl0&, 8H20, and by W.Gibbs (Ber., 10, 1385 ; this Journal, 18i7, 2, 848), who prepared an acid of the formula 2OWO3, P,05, 81120, aAq. I n the author's experiments, barium tungstate was suspended in water and mixed with dilute phosphoric acid ; the resulting precipi- tate was then decomposed by dilute sulphuric acid in slight excess, such excess being afterwards removed by cautious addition of baryh- water, The solution is evaporated on the water-bath and finally in a vacuum : an acid is then obtained in large well-formed crystals of the regular system, which are efloresceut, readily soluble in water, and have the formula P205, 24w03, 61H,O.The following salts were pre- pared and analysed :-3Ba0, P205, 24W03, 58H2r3 ; 2Ba0, P205,ORGANIC CHEMISTRY. 141 24W03, 59H20; 2Ba0, P,O,, 24W03, 59H20; BaO, Pz05, 24W03, Agio, P,05, 24W03, 60H20 ; of these the silver salts are insoluble in water. Addition of excess of baryta to a solution of the acid causes a precipitate of barium tungstate, whilst on evaporating the solution, a salt, 7Ba0, P205, 22W03, 59*5H,0, crystallises in doubly refracting needles of the rhombic system. 59H20 ; 3 C ~ 0 , PJOj, 24W03, 58HZO; 3Ag.20, PZO5, 24W03, 58H20; A. J. G. Sodium Arsenate. By G. FLEURY (J. Phurm. [ 5 ] , 2, 367-368). -Sodium arsenate containing 14H20 may be prepared by exposing the ordinary commercial salt to a moist atmosphere for 1 2 days a t B temperature of 15-30'.Bismuth Subnitrate. By A. RICHE (J. Phnrrn. [5], 384-387). --Further analyses of specimens of bismuth subnitrate, when com- pared with previous results (this Journal, 34, 841), show that tile commercial article contains lead, varying from 0.34 to 0.03 per cent. lead sulphate. The actual quantity of lead present,, however, is only Besides lead, the subnitrate is found to contain arsenic varying I t is probable that so small a quantity of arsenic passes through the system without being absorbed. Nevertheless, the author urges the use of extra precaution in the purification of bismuth subnitrate. The esmmation of nitric acid shows that it varies from 4.52 to 0.57 per cent. N20, as compared with 16 per cent. according to the codex, proving that the commercial substance has a very different composition from that prescribed.L. T. 0's. Manganese Dioxide containing Antimony. BJ- H. REINSCH (J. p r . C'hem., 22, Ill).-The author found that, on passing sulphu- retted hydrogen into the acid liquid formed in the preparation of chlorine by means of hydrochloric acid, the precipitate contained antimony. He could not ascertain where the manganese dioxide came from. G. T. A. L. T. 0's. d o 0 part. from - 2 - l o o o o o to --L-- l o o o o part of arsenious acid, or about 0.01 per cent.138 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c Chemistry.Preparation of Hydrochloric Acid Gas. By L. L. DE KONINCK(Zeds. Anal. Chent., 1880, 467-468) .-The author prepares hydro -chloric acid by the action of concentrated sulphuric acid on ammo-nium chloride, the advantage of the method consisting in theregularity of the action, and in the residue of ammonium sulphatebeing non-crystalline and syrupy.0. H.Action of Iodine on Phosphorus Trichloride. By C. G. MOOT(Bey., 13, 2029--2031).-On mixing iodine with phosphorus trichlo-ride, the liquid is reddened and a part of the iodine is dissolved. Onexposing the liquid to moist air, a golden mbstance separates out ; theauthor establishes that moisture, and not the oxygen of the air, isnecessary for this change. On treatment of a small quantity of phos-phorus trichloride with a large excess of iodine, a solid mass isobtained completely soluble in carbon bisulphide ; on evaporating thesolution, fine red hexagonal crystals of the formula PClJ, separate out,which are decomposed by moist air, and split up with liberation ofiodine when heated.The author promises a, further account of the properties of thegolden substance and of phosphorus trichloriodide.V. H. V.Impurities in Sodium Bicarbonate. By A. KOSTER (Arch.Pharm. [3], 14, 31--33).-Ammonium bicarbonate may occur to theextent of nearly 4 per cent. in sodium bicarbonate prepared by theammonia process. 0. H.Action of Hydrochloric Acid at High Temperatures onUltramarine rich in Silica. By P. G. S~LBER (Bey., 13, 1854-1857).-The author considers that all previous analyses of red ultra-marine were of specimens contaminated with blue ultramarine(R. Hoffmann, this Journal, Abstr., 1879, 108).By the action ofhydrochloric acid at high temperatures with access of air, a violeINORGANIO CHEMISTRY. 139ultramarine is obtained which bears the same relation to the blue andred ultramarines that the green ultramarine does to the white or bluein the series poor in silica.By systematic'washings, the violet can be separated from the un-altered blue. By further treatment with hydrochloric acid, the violetcan be converted into the red of commerce, which may be fractionallyseparated from the violet. The violet portion in the red of commerceis due either to an imperfect action of hydrochloric acid or to thechange of red into violet after continuous treatment with water. Theviolet can be reconverted into the red on heating with water at 130°,or more directly by a drop of soda.In order to obtain a perfect red, the trade product is heated withhyd.rochloric acid until no further change of colour is evident, thesodium chloride removed by washing with slightly alkaline water, andthe completely washed product dried below 150".If dried at ahigher temperature, the red immediately passes over into the yellownltrnma rine.Analyses oj' Ultrarnariizes.-a, a blue of greatest purity used forthe preparation of the violet and red ; b and c, violet and red of com-rnerce ; d, red from c after all the sodium had been separated out ; ande (yellow), from d after heating for a long time in the air.a. b. c. a. e.Si.. . . 19.07 18.91 19.39 20.51. 21.44A1 . . 13-04 13.55 13.80 13.99 14-32Na .. 15.92 14.53 11.29 8.98 8.00S . . . . 14-09 12.39 12*44 12-14 10.900 . . . . 37.88 40.62 43.08 4438 45.14From these analyses it follows tbat in the conversion of ultramarine-blue into yellow, half the sodium contained in the blue must be re-moved. The authoy considers that on account of the similarity of theanalytical numbers of d and e, that e is not a pure yellow. The num-bers for perfect red ( d ) correspond with the formula, Si,A14Na3.S3022,and the conversion of blue into red can be expressed by the followingequation :-Si6A14Na6S,0zo + 0, = Si6A14Na3S3022 + Na, + S.Blue. Red.The author proposes to study the action of hydrochloric acid onultramarines poor in silica. V. H. V.Atomic Weight of Glucinum. By L. MEYER (Ber., 13, 1780-1 786) .-Acbording to Nilson and Pettersson (this Journal, Abstr.,1880, 792) the equivalent of glucinum is 4.55, and its atomic heatnormal if the ahomic weight be taken as 13.65, making glucinum a,triad.The author objects to these conclusions, and considers glucinuma dyad with an atomic weight of 9.10. Firstly, if glucinum had anatomic weight of 13.65, it would have a position in the system ofelements between nitrogen and carbon which would not correspond toany of the known properties of the metal; but this consideration isnot sufficient to justify any correction of its atomic weight. Secondly140 ABSTRACTS OF UHEMICAL PAPERS.Nilson and Pettersaon have shown that the specific and atomic heatsincrease slightly with the temperature like those of iron, hence forglucinum an atomic weight of 13.65 best corresponds with the meanspecific heat between 0" and 100".But the author establishes thateven adopting Nilson and Pettersson's determinations, glucinum israther comparable with carbon, boron, and silicon, whose specific heatsincrease a t first rapidly, then more slowly, until a limit is reached atwhich they show a normal specific heat. Then glucinum would be adyad with an atomic weight of 9.1 : for if glucinum has an atomicweight of 13.65, its atomic heat at 157" should be 7.;0, and a t 257"is 8.94, which is far greater than those of iron and silver.Atomic Weight of Glucinum. By L. F. NmoN (Ber., 13, 2035-2040).-This pager is in answer to that of L. Meyer (Ber., 13,1780).The author points out lst, that glucinum with the atomic weightof 9.1 departs from the regular series of Mendelejeff's classification bymore than 13 75 per cent. from the number required for this system ;thus of all the elements of the first series glucinum is the only onewhich differs from the neighbouring elements of the second series bynot less than 16. 2nd. Although Meyer compares glucinum with boron,silicon, and carbon, with regard to the increase of specific heat withincrease of temperature, yet in Weber's researches on these latterelements, neither pure materials, nor eyen compounds of known com-position, were used : for Hamp6 has established that crystalline boroncontains aluminium and carbon, and Mixter and Dana have shownthat crystalline silicon contains zinc and iron.3rd. The molecularheat of glucina and its sulphate is equal to those of alumina, scandia,gallium oxide and their sulphates (Ber., 13, 1459; Abstrs., 1880,838), but differs from those of the oxides and sulphates of magnesia,copper, and other dyad metals.The formula G,O, is then in accordance with the laws of Ihlongand Petit and Naumann, and although glucinum has an atomic heatof 5.79 (between 0" and lWo), slightly less than the normal number,yet in this respect it resembles its analogues aluminium and gal-lium. V. H. V.V. H. V.Phosphotungstic Acid. By M. SPRENGER (J. p r . Chem. [2], 22,418-432).-Phosphotungstic acids have been previously described byScheibler (Ber., 5, 801 ; this Journal, 1873, 246) who obtained acidsof the formulae H15PW11043, 18H20 and HllPWl0&, 8H20, and byW.Gibbs (Ber., 10, 1385 ; this Journal, 18i7, 2, 848), who preparedan acid of the formula 2OWO3, P,05, 81120, aAq.I n the author's experiments, barium tungstate was suspended inwater and mixed with dilute phosphoric acid ; the resulting precipi-tate was then decomposed by dilute sulphuric acid in slight excess,such excess being afterwards removed by cautious addition of baryh-water, The solution is evaporated on the water-bath and finally in avacuum : an acid is then obtained in large well-formed crystals of theregular system, which are efloresceut, readily soluble in water, andhave the formula P205, 24w03, 61H,O. The following salts were pre-pared and analysed :-3Ba0, P205, 24W03, 58H2r3 ; 2Ba0, P205ORGANIC CHEMISTRY. 14124W03, 59H20; 2Ba0, P,O,, 24W03, 59H20; BaO, Pz05, 24W03,Agio, P,05, 24W03, 60H20 ; of these the silver salts are insoluble inwater.Addition of excess of baryta to a solution of the acid causes aprecipitate of barium tungstate, whilst on evaporating the solution,a salt, 7Ba0, P205, 22W03, 59*5H,0, crystallises in doubly refractingneedles of the rhombic system.59H20 ; 3 C ~ 0 , PJOj, 24W03, 58HZO; 3Ag.20, PZO5, 24W03, 58H20;A. J. G.Sodium Arsenate. By G. FLEURY (J. Phurm. [ 5 ] , 2, 367-368).-Sodium arsenate containing 14H20 may be prepared by exposingthe ordinary commercial salt to a moist atmosphere for 1 2 days a t Btemperature of 15-30'.Bismuth Subnitrate. By A. RICHE (J. Phnrrn. [5], 384-387).--Further analyses of specimens of bismuth subnitrate, when com-pared with previous results (this Journal, 34, 841), show that tilecommercial article contains lead, varying from 0.34 to 0.03 per cent.lead sulphate. The actual quantity of lead present,, however, is onlyBesides lead, the subnitrate is found to contain arsenic varyingI t is probable that so small a quantity of arsenic passes through thesystem without being absorbed. Nevertheless, the author urges theuse of extra precaution in the purification of bismuth subnitrate.The esmmation of nitric acid shows that it varies from 4.52 to 0.57 percent. N20, as compared with 16 per cent. according to the codex,proving that the commercial substance has a very different compositionfrom that prescribed. L. T. 0's.Manganese Dioxide containing Antimony. BJ- H. REINSCH(J. p r . C'hem., 22, Ill).-The author found that, on passing sulphu-retted hydrogen into the acid liquid formed in the preparation ofchlorine by means of hydrochloric acid, the precipitate containedantimony. He could not ascertain where the manganese dioxide camefrom. G. T. A.L. T. 0's.d o 0 part.from - 2 - l o o o o o to --L-- l o o o o part of arsenious acid, or about 0.01 per cent

ISSN:0368-1769    

DOI:10.1039/CA8814000138

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

ORGANIC CHEMISTRY. 141Organic C h e m i s t r y .Decomposition of Simple Organic Compounds by Zinc-dust. By H. JAHN (Ber., 13, 2107-2118).-The following com-pounds when passed over zinc-dust at a temperature of 300--350", aredecomposed.Etliylic ether gives ethylene and hydrogen, together with small quan-tities of ma,rsh-gas and carbonic oxide.Formic acid gives carbonic oxide, hydrogen, and a small yuaiitity ofmarsh-gas.Acetic acid gives acetone, carbonic oxide, hydrogen, and propyleii142 ABSTRACTS OF CHEMICAL PAPERS.(compare Liebig and Pelouze ; also Berthelot, Ann, Chenz. Pharnz., 81,114 ; also Trommsdorff and Chenevix).Acetic anhydride gives acetone, propylene, carbonic oxide, andhydrogen.Ethyl acetate gives acetone, carbonic oxide, hydrogen, and ethy-lene.Butyric acid gives butyrone, propylene, carbonic oxide, hydrogen,and dimethylbutyrone.Butyrone gives hydrogen, propylene, and carbonic oxide.From theabove, it appears that the action of zinc-dust on both alcohols and acidsis esseutially a contact action ; and in the case of acids may be repre-sented thus :---2C,H,,+1.COOH = CnH2n+l.C0.CnH2,+1 + GO2 + H20 ;the carbonic anhydride and water are subsequently reduced by thezinc to carbonic oxide and hydrogen, whilst the hydrocarbons resultfrom the further action of the zinc on the ketone. T. C.Action of Oxygen on the Bromo-derivatives of UnsaturatedHydrocarbons. By E. DEMOLE (BUZZ. SOC. Chim. [2], 34, 201-207).-The author has already shown (this Journal, 34, 401 and847) that by the action of dr.y oxygen gas on dibromethylene, it isconverted partly into bromacetic bromide and partly into a polymeride.I n this reaction, the author was led to suppose that the C2H2Br2 splitup into CzHBr and HBr, and that these two bodies united, together withoxygen, to form bromacetic bromide, C,HBr + 0 + HBr = C2H2Br20.Finding, however, that by mixing these three gases together, no acidbromide was produced, he arrived at the conclusion that in the firstplace oxygen was substituted for bromine in C,H2Br2, and that then theresulting compound was acted on by the free bromine.This seemsprobable, since by exposing hydrobrornic acid or bromo-compounds tothe air, they are gradually decomposed, with liberation of oxygen. Byapplying this theory to the formation of POCI, and POBr, by directunion of PCl, or PBr, and oxygen gas, it is found that when oxygengas is passed into boiling phosphorus tribromide, explosions occurfrom time to time, with liberation of bromine, and the formation ofphosphorus oxybromide and phosphorus pentabromide, showing thatfirst amolecule of bromine is liberated with the formation of POBr (2)and that the bromine thus liberated finally unites with PBr3 and thePOBr, forming PBr5 and POBr,.That a similar reaction takes place in the formation of bromaceticbromide from dibromethylene is seen by passing a slow current of dryoxygen through dibromethylene at the ordinary temperature for1 2 hours, washing the gas with water, drying over calcium chloride,and finally passing it into bromine.The product consists chiefly ofdibromethylene dibromide (b. p. 190--210"), produced either accordingto the equation C2HzBr2 + Br, = C2H2Br4, or C,H2 + Bri = C2H2Br4,also a solid polymeride of C2H,Br,. In the oxidising flask bromaceticbromide, bromacetic acid, and hydrobromic acid were found, and alsoanother polymeride of C,H,Br, (b. p. 220-230"). The presence ofthe two last-mentioned acids shows that the oxygen replaces notonly bromine, but also hydrogen, the water thus formed decomposingpart of the bromacetic bromide. Since the quantity of hydrobromiORGANIC CHEMISTRY. 143acid foriiied is in excess of that produced by the reaction C2H2Br0.Br +H,O = C2HzBr0.H0 + HBr, it is evident that the bromine itselfreplaces hydrogen.Prom this it seems probable that oxygen, like chlorine and broinine,has the power of brea,king up the double link in the unsaturatedcarbon compounds, but that, unlike the halogen, it does not attach itselfto the free bonds, but leaves the body unsaturated, which, coming incontact with bromine, forms the saturated compound CzHzBra, whilstalso at a higher temperature the oxygen expels the halogen,-C€.Iz.CBrz- + 0 = -CH2.C 0- + Rrz,and these two bodies unite thus: -CHz : C : 0- + Br., =CH2Br.CBr 0.Another example of the liberation of bromine by oxygen is affordedin the formation of pentabromethane from tribrbmethylene by theaction of air.Lennox (this Journal, 13, 206) assumed this body tobe a polymeride of C,HBr,.The formation of the body with free bonds is merely an hypothesis,and requires further proof.Preparation of Sodium Ferrocyanide. By S.TANATAR (Dingl.polyt. J., 237, 234) .-The author found that by digesting pure cyanideof sodium with freshly prepared ferrous oxide in an alcoholic solution,it was readily and completely transformed into sodium ferrocyanide.Soda, unlike potash, does not possess the property of forming cyanogenwhen fused with nitrogenous charcoal.The formation of cyanogen by fusing nitrogenous charcoal withpotash is geuerally explained by the fact that the carbon and nitrogencombine with one another, owing to the presence of free metallicpotassium, or the potttssium combines in the first place with carbon,forming potassium-acetylene, C2K2, which afterwards absorbs nitrogenin the fusion.The question whether cyanide of potassium is produced in all cases,or whether its formation does not take place when the conditionsnecessary for the production of free potassium are absent, was investi-gated by the author, in connectioii with the behaviour of the sodiumcompounds in parallel cases.Nitrogenous charcoal (carbo arLiwznZis exsanguine, from Trommsdorff) was fused with potassium and sodiumcompounds, and various reducing agents. The quantity of the cyanideformed was determined after transformation into ferrocyanide. Itwas found that the sodium compounds also have the property offorming cyanogen, and often act more strongly than the correspondingpotassium compounds. The author concludes that the presence of theiree alkali-metal is not the cause of formation of cyanogen, as in caseswhere these alkali-metals cannot be formed in appreciable quantity,cyanogen was nevertheless produced very largely.The following table shows the production of cyanide and ferro-cyanide of sodium and potassium :-L.T. 0’s14 4 ABSTRACTS OF CHEMICAL PAPERS.10 grams animal charcoal gave-l. Fused with 25 grams K2C03 ..................2. ,, 25 ,, carbonate of sodium and3. ,, 25 ,, KC1 and 5 grams K2C0, ..5. ,, 25 ,, KCl ....................6. ,, 25 ,, KCl and 5 grams CaCO, . .7. ,, 25 ,, KCl and 5 grams Na2C03 . . a. ,, 25 ,, KCI, 5 grams Na&O,, and3 grams CaC03 ........potassium. .............4. 9, 25 ,, NaCl and 5 grams K2C03..Ferrocyanideof potassium.2.15 grams.1-87 ,,1-72 ,,1.81 ,,0.40 ),1.20 ,,1-60 ,,2.00 ,,Ferrocy anideof sodium.9. ,, 25 gramsNa2C03.................. 0.20 grams.10. 7 , 23 ,, NaCl 0.20 .. ..................11. ,, 2.5 ,, NaCl and 5 grams CaC03.. 1.22 ),12. ,, 25 ,, NamC1 and 5 grams Na2C03. . 2.17 ,,13. ,, 25 ,, NaC1, 5 gmms Na&03, and3 grams CaCOB ........ 2-30 ,,10 t,o 15 per cent. of cast-iron borings were added to the mixture ineach experiment.Without the addition of iron to the alkaline chlorides, only traces ofcyanogen were formed.The difficulty of sepnrating sodium ferrocyanide from the melt bycrystallisation considerably influences its preparation on a large scale ;should this, however, be surmounted, the manufacture of this sub-stance would probably supersede that 'of potassium ferrocyanide.D.B.An Isomeric Potassium Cyanate. By A. BANNOW (Rer., 13,2201--2202).-The author has previously (Her., 4, 253) described apotassium cyanate, which differed from ordinary potassium cyanate inmany of its properties, but more especially in the fact that by treat-ment with silver nitrate it gave the silrer-salt of' a dicyanimide,AgC,N,. It is now shown that this difference was due to the presenceof pwacyanogen, and that the two potassium cyanates are otherwiseidentical. T. C.Influence of Isomerism of Glycols on the Formation of theirAcetates. By N. MENSCHUTK~N (Her., 13, 1812--1814).--The initialvelocity and limit of etherification of typical glycols by acetic acid ofvarious classes are compared (1 mol.glycol to 2 mols. of acid).Initialvelocity. Limit.42.93 53-86}49.29 60.07Ethylene glycol,CH2. 0 H . C H, ( 0 U) . OH }Trimethylene glycol,CH,(OH).CH?.CHt.OHPrimary glycols . ORGANIC CHEMISTRY. 145In it ialvelocity. Limit.Primary, secondary Propylene glycol, } 36-43 50.83 glycol { MeCH(OH).CH2.0HPseudobutylene e;lycol, } 17.79 32.79Secondary glycol * ' { MeCH(OH)C.H.OH.Me} 2.58 5.8s Pinacone,Tertiary g1yco1* ' { CMe2( OH) CMe2.0HResorcin,C6H4(OH)27.08 l oFrom this table, it is evident that there is an analogous influence ofisomerism on the etherification of the monohydric and dihydric alco-hols ; this is even more evident in the latter than the former.As the author has shown that tertiary alcohols are decomposed onetherification into an olefine, so these experiments point to a similardecomposition of pinacone. Resorcinol in its initial velocity and limitof etherification resembles not only a tertiary glycol, but also a mono-hydric phenol.V. H. V.By LIEBEN and ZEISEL (Ber., 13, 2032).-The paper is merely a priority claim with regard to the synthesis ofa four-carbon glycerol by Markownikoff, and to a study of the reduc-tion of croton aldehyde to croton alcohol, by Karetnikoff.Synthesis of Glycerol.V. H. V.Lead Glycerides and the Quantitative Estimation of Gly-cerol. By T. MORAWSKI ( J . pr. Chem. [el, 22, 401-418).-Mono-plumboglyceride, C3H6PbO3, is best prepared by dissolving 22 grams oflead acetate in 250 C.C.of water, mixing with 20 grams of glycerol,heating, and then adding 15 grams of potash. On standing for one ortwo days, the clear filtrate deposits the compound in fine needles. Bymixing together basic lead acetahe and glycerol, and adding a solutionof lead oxide in potassium hydrate, a precipitate is obtained of theformula (C,H,03j2Pb3. A third glyceride is obtained as a gummymass by adding alcoholic potash solution to a mixture of basic leadacetate and glycerol ; it has the composition C,,H2,Pb5OL3. Additionof ammonia to a hot solution of lead nitrate and glycerol yields hardcrusts of the compound 2C3H50,Pb(0.PbN03).Pb(OH)N03 ; the samesubstance is also obtained on boiling together lead oxide, glycerol, andlead nitrate solution.Experiments on the estimation of glycerol byevaporation of its solutions with a weighed amount of lead oxide gaveresults which, although promising, show that some sources of errorhave yet to be eliminated.Action of Soda on Glycerol. By A. FERNBACH (BUZZ. XOC. Ohim.[2], 34, 146-147) .-Belohoubek obtained propyl glycol by the actionof soda on glycerol. On repeating the experiment, the author has.obtained only about one-tenth of the yield of glycol stated by Belo-houbek, and finds that by secondary reactions methyl, ethyl, normalpropyl, and isopropyl alcohols are formed, together with olefines con-A. J. G146 ABSTRACTS OF CHEMICAL PA4PERS.taining hexylene, which unites with hydrochloric acid in the cold,yielding diisopropyl chloride (b.p. 115").These results show that by this reaction normal alcohols and theolefines C,H,, C.(C,H,,, )2 are formed. L. T. 0's.A Six-Carbon Glycerol. By W. MARKOWNIKOFF (Ber., 13, 1842--1843 j .-The author has obtained from crotonylmethylcarbinol,CH, CH.CH,.CH2.CHMe.0H (Wurtz, Jahresb., 1864, 515 ; Crow,Alznalen,, 201, 42), a triacetin of a glycerol, C,H,,(OH),, boiling at270-280", and at 192-196" at a pressure of 100 mm. The triacetinis a thick, colourless bitter liquid, insoluble in water; its sp. gr.is 1.087 at 0". On saponification, the glycerol is obtained as an oilyliquid, but owing to the small quantity no analyses were made. Byreduction of allylacetone, Rablukoff has obtained, besides crotonyl-methylcarbinol, a liquid boiling at 254-262", which is probably thepinacone of allylacetone, C3H5.CMe(OH) .CMe(OH).C3H,.By N.MENSCHUTKIN (Ber., 13, 1814-1816).-The author remarks that the perfect analogy which exists inthe etherification of mono- and di-hydric alcohols would lead to theconclusion that in polyhydric alcohols corresponding changes ofchemical structure would give rise to corresponding changes of etheri-fication.I. Ether$catiort of Polyhydric Alcohols with the equivalent itumber ofmolecules of Acetic Acid.-The following table gives the etherificationdata of polyhydric alcohols :-V. H. V.Polyhydric Alcohols.Atomicityof alcohol. Initial velocity.acetic acid. Absolute. Relative. LimitEthyl alcohol . . 1 46.81 70.31 66.57Ethylene glycol. 2 42.64 79.58 53.94Glycerol .. . . . . 3 36.26 78.82 46.00 [45*$]"Erythrol .. . . . . 4 2491 62.16 40.07Mannitol .. . . . . 6 20.56 '77.80 26.42No. of molo. of /----This table shows that as the number of OH groups in the alcoholincreases, the initial velocity and limit of etherification decrease, asalso the capacity for etheritication. The decrease cannot be attributedentirely to an increase of secondary alcoholic groupings, for the samephenomenon is observable in ethyl alcohol and ethylene glycol, both ofwhich contain only primary alcoholic groupings.11. E t h e r 9 c a t i o n of Polyhydrir, Alcohols with Acetic A c i d in equalnumbers of molecules of Alcohol and Acid.-Berthelot has found thatin etherification in equal number of molecules all the polyhydricalcohols had tha same degree of etherification (about, 70 per cent.),which led him to apply etherification as a means of determining theequivalence of a polyhydric alcohol.The author, however, finds thatthis is not the case with all polyhydric alcohols.* The numbera in brackets represent the corresponding determinations ofBerthelotORGANIC CHEMIST HP.Initialvelocity.Methyl alcohol .......... 55.59Glycol ................ 51.88Glycerol. ............... 51.85Erythrol. ............... 53.60- Mannitol ..............Differing from these are the following glycols :Initialvelocity.Trimethylene glycol.. .... 59.53Propylene ,glycol ........ 40.6 7147Limit.69-5969.89 [68.8]70.08 L69.3165-73 [69*5]62-53Limit.75.5958.51The first set of alcohols form a group distinguished by theirequality of etherification, but this is not an invariable character-istic of all polyhydric alcohols.The limits given in the above tablealso point to a diminution of etherification capacity of polyhydricalcohols, since although they contain more equivalents than monohydric,yet the '' effect values " (Wirkungswerth) of polyhydric and mono-hydric aIcohols are equal.111. Etherification with excess of Acetic Acid.-The following tablegives a compilation of results :-Acetic Acid.2 mols. 3 mols. 4 mols. 6 mols.Glycol .... 53.72 43.49 36.80 25.00Glycerol.. .. 55.54 46-00 39.73 31.12Erythrol.. .. 56.00 - 40.07 31-24Mannitol .. - I 38.47' 26-42This table shows that the alcohols in this group are identical intheir etherification, which proves that the etherijicatiort of polyhydricalcohols with free acid is no estimate of the nzcmber of OH groups theycontain.V. H. V.Multiples in the Optical Rotary Powers of Carbohydrates.By T. THOMSEN (Ber., 13, 2168--8169).-The author has determinedthe value of [a]= for the following carbohydrates. The values arereferred in all cases to the group CGHlOO5, which is contained in allthese compounds, or, what is the same thing, to the amount of carbon.Dextrose ........................Wood-gum (Jour. f. Prakt. Chena., 19,Arabinic acid. .....................Arabinose ........................Maltose ..........................Starch in alkaline solution ..........Dextrin ...........................Cane-sugar ........................146) in alkaline solution ..........58.8 = 5 x 11.870.3 = 6 x 11.7-84 = 7 x 12.0-93.9 = 8 x 11.7'121.4 = 10 x 12.1143.5 = 12 x 12.0168 = 14 x 12.0193 = 16 x 12.1The table shows that these values of [ a ] ~ are all simple multiplesof a common factor.T. C148 ABSTRACTS OF CHEMlCAL PAPERS.Sorbin and Sorbite. By C. VINCENT (BUZZ. XOC. Chi~z. [2], 34,218-219).-By allowing the juice of the berries of the mountain ashto ferment for about a year and concentrating the solution, large dark-brown crystals of sorbin were obtained. On working as above, butwith a larger quantity of substance, larg: quantities of acicu1:tr crystalsmere obtained, and these on crystallisat8ion from hot alcohol presentedall the properties of sorbite, giving no colour when boiled with alkalis,as sorbin does.The formation of sor'hin in one experiment and sorbitein the other is probably due to the action ofa certain ferment which isnecessary for the formation of sorbin, and was present in the formerbut absenk in the latter case. This may explain why many chemistshave failed to obtain sorbin from mount.ain ash berries, and hencedoubted its formation from that source.Sorbite is isomeric with mannite and dulcite, and forms withoxalic acid a t 75" sorbite-formamide, with evolution of carbonicInversion of Raw Sugar by Carbonic Acid and someProperties of Inverted Sugar. By E. 0. v. LIPPMAEN (Ber., 13,1822-1 826) .--Former experiments on the inversion of sugar bycarbonic acid have not given concordant results.The author findsthat carboiiic acid gas has no effect 011 raw sugar even after six months,but b y acting upon the sugar with a solution of the gas in water in asea1r.d flask the sugar is entirely inverted. The power of inversion ofcarbonic acid is increased by raising the temperature, and increasingthe pyessure ; the reaction is complete in three-quarters to one hour a ta temperature of 100" in a soda-water bottle.The determinations of specific rotatory power after perfect inversionhave varied according to the different observers, using differentmethods for inversim from -338" to -444.16" ; the author finds -44.19"after inversion with carbonic acid. On warming, the left-handedrotatory power diminishes, becoming nil at a temperature of87.3-91-7".The author has made the following determinationsanhydride. It is a colourless odourless syrup. L. T. 07s.( c = 17.21) :-0". loo. 20". 30". 40". 50". 60". 70". 80".-27.9 -224.5 -21.4 -18 -15.2 -12.0 --8.5 -5.8 -2.6These values agree with those calculated from Tuchsmidt's formula,[aD]t = -(27.6 -0.32t). The author has not succeeded in confirni-ing Maumen&'s view, that inverted sugar contains besides glucose andlevulose a third modification, " inactose," itself present in two modifi-cations. Maurnen A's result may probably be explained by supposingthat the action of lime gives rise to the formation of a glycosate,2CsHI2OG + 3CuO + 2H20, unstable in presence of light, the existenceof which has been demonstrated by the researches of PBligot.V.H. V.Presence of Saccharin in Osmosed Sugar. By E. 0. v. LIPP-MANN (Ber., 13, 1826--1827).-Sugar refiners have found a crjstal-line sugar when raw molasses is subjected to osmose. The authorhas heated these crystals with concentrated nitric acid according toP6ligot's process, and has separated crystals which were proved bORGANIC CHEMlSTRY. 149their chemical propeTties and polarisation coefficient [a Jp = + 93*5", tobe identical with PBligot's saccharin. V. H. V.Saccharin and Saccharinic Acid. By C. SCHEIBLER (Ber., 13,2312-221 7).-Saccharin, the new derivative of the glucoses, re-cently discovered by P6ligot (Ber., 13, 196), has not the compositionC12H22011, as he supposed, but is the anhydride, C6Hi005, of a newacid, C6HIZOE, which the author calls saccharinic acid.Saccharin(m. p. 160-161") decomposes carbonates when boiled with them, andforms saccharinates, from which, however, the free acid cannot beobtained, since at the moment of its liberation it splits up into waterand saccharin. Saccharin is probably a lactone having the constitu-tion CH,(OH).OH(OH).CH(OH).CH.CH,.CO : on reduction withhydriodic acid it gives a neutral oil (b. p. 203-5204" uncorr.) consist-ing no doubt of saccharone, Me.C,H,.CH.CH,.CO.The saccharinates are all exceedingly soluble.'O/'0'The potamium andammonium salts are crystalline, whilst those of barium, calcium, andsodium dry up to thick syrups. T. C.Conversion of Starch into Sugar by the Action of DiluteSulphuric Acid at High Temperatures.By F. ALLIHN (J. pr.Ohern., 22, 46--97).-About 10 grams of anhydrous starch were usedin each experiment, and were acted on for various periods by 50 C.C.of acid containing 0.1, 0.2, 0.5, and 1 per cent. a t temperatures of loo", 108", and 114".(1.) The conversion of starch into sugar by dilute sulphuric acidgenerally takes place more quickly and perfectly the more concentratedthe acid is, the longer the period of the reaction, and the higher thetemperat me.(2.) The quantitv of starch converted into sugar up to 40 to 50 percent. is proportional to the duration of the reaction.(3.) In the later stages the reaction becomes gradually slower, sot,hat a perfect conversion, if possible, nndor the given proportions, canonly be reached by an disproportionelly long duration of the reaction.(4.) The reason of the slowness of the reaction is due chieflv toThe following results were obtained :-the varying capacity of resistance of dextrin to dilute acids.G.T. A.Specific Identity of Inulins and of Natural Levulins. BJ-LEFRANC ( J . Pharm. [ 5 ] , 2, 216--220).-The author establishes theidentity of inulins from all sources, on the ground that they all havethe same rotatory power [a],, = - 40 ; and, for the same reason, con-cludes that all natural levulins are identical, their rotatory power[a]? = - 26. The l e d i n obtained b y heating inulin with water at1OU the author names pseudo-levuZi?L, [ a ] D = - 46.Preparation of Natural Levu1in.-The juice of the artichoke is treatedwith lead acetate, and the filtered solution freed from lead by means ofsulphuretted hydrogen, is finally neutralised with magnesium car-bonate.After filtering, the solution is evaporated to a syrupy con-VOL. XL. 9 r150 ABSTRACTS OF CHEMICAL PAPERS.2.2.37024 *89899 -736'79 $91419.4263sistence, and, when cold, the levulin is precipitated with alcohol. Theprecipitated levulin is dissolved in hot alcohol, treated with animalcharcoal, and the solution left to crystallise. The last traces of levuliuare precipitated from the mother-liquors by ether.Specific Rotatory Power of Lactose. By E. MEISSL ( J . p ~ .Chenz., 22, 97--103).-The lactose used in the experiments was pre-pared by acting on milk-sugar with dilute sulphuric acid and crystal-lising the product from alcohol.The following tables embody the results obtained with a Wild'spolaristrobometer.( p = grams of the substance, q = grams ofwater) :-L. T. 0's.17 + %- ~ - - -48 *428249 -404051 *284751 * 246554 *9350NO.-123*45Sp. gr. a. a t-No.--12345Weightpercent.P.--4-899.921Fi.9818.9135-36Found.'79.958)*3981 -1.581-2682.50Gal.80.0980'4881-1981.1982-48--Found.82.0682.5883.3283-2084-66Cal.82.18R2.5'783.2883'2884-57To find the weight per cent. P of lactose in a solution which rotatesao, the formula '*(la may be used. If the value for [a]= a t1" in P per cent.solution be introduced into this formula we obtain-L . d . [a)100 aL . d .(83,883 + 0.0785 P - 0-209L)- P =If 83,883 - 0.209 t = A, and 0.0785 = B, we get-Found.78.0578.2129.0549.2080.4410Oa "> -k IB.L.d - 2B'rCal.'78.0078-3979.1079.1080.39G. T. A.Found.80.4580.9'781.7181.7282-96* Recryhllised three times from met,hyl alcohol.C d .80.6181.0081.7281-7288.0ORGANIC CHEMISTRY. 151Anhydrous Milksugar. BJ- E, 0. ERDNANN (Ber., 13, 2180-2184).-Milk-sugar can exist in the anhydrous state in three differentmodifications, two of them solid and crystalline, and the third liquid.(a.) This is obtained when an ordinary solution of milk-sugar isquickly boiled in a metal vessel ; the solution after a certain timesuddenly solidifies ta a porous mass consisting of small anhydrouscrystals.These have a low rotatory power which gradually increases,and are very soluble in water.( b . ) This solid modification is obtained by dehydrating ordinarymilk-sugar at 130". It has a high rotatory power, which graduallydiminishes on keeping until it is identical with that of the form (a).It is much less soluble in water than the form (a).( c . ) An unstable liquid modification, obtkined by the gradual trans-formation of the solutions of the two preceding forms on keeping. Itis stable only in the dissolved state, for on crystallisation it changes inthe presence of aateT into ordinary hydrated milk-sugar, whilst ondriving off the water by boiling, it gives hhe anhydrous form (a).A Hitherto Unobserved Property of Milksugar.By hl.SCHMOEGER (Ber., 13, 1915-1931) .-The author has found that milk-sugar not only exhibits bi-rotation (the lvgh rotatory power of afreshly-prepared solution of the crystallised sugar) and normal rota-tion (the rotatory power of the same solution after standing), butthat under certain circumstances it exhibits a third rotation, lowerthan either of the others, to which he applies the term semi-rotation(" Halb-rotation "). Crystallised milk-sugar, C12H22011 + HzO, driedin the air or over sulphuric acid, does not lose weight a t 100" ; butwhen a solution of the crystals is evaporatled to dryness over boilingwater the residue is anhydrous. A solution of this residue in coldwater exhibits in the pnlariscope at first semi-rotation, changing inthe course of a few hours to normal rotation.The normal specificrotatory power of crystallised milk-sugar a t 20" is [&In = 52,53".The ratio of semi-rotation to normal rotation is 5 : 8 (about) ; and theratio of normal to bi-rotation is also 5 : 8. Anhydrous milk-sugar,obtained by evaporating its solution a t loo", when dissolved in hotwater, exhibits normal and not semi-rotation. A solution in coldwater of the anhydride obtained by heating the crystallised sugar to130", exhibits bi-rotation. J. R.NoTE.-h Be?., u, 2130-32, the question of prior&y between theauthor and Erdmann is discussed.T. C.Isopropylene-neurine. By H. T. MORLEY (Ber., 13,lSOS--l806).-On heating on a water-bath a mixture of isopropylene chlorhydrinand trimethylamine, a crystalline mass of trime thylhydroxyisopropyl-ammonium or propylene-neurine chloride, CH,(OH) .CHMe.NMe,Cl,is obtained ; it forms colourless, transparent, deliquescent crystals,which t u r n brown in the presence of air.The platinochloride formsfeathery leaflets. V. H. V.Dimethylhydrazine. By E. RENOUF (Ber., 13, 2169 -2174).-This is a more complete investigation of the dimethylhydrazine first912 152 ABSTRACTS OF CHEMICAL PAPERS.obtained by E. Fischer (Ber., 8,1587), by the reductlioii of the nitroso-compound of dimethylamine.Dimeth!/Znitrosamine, NMe,.NO, is a yellow alkaline oil (b. p.143.5" a t 724 nlm.), having great resemblance to the correspondingdiethyl-compound. It forms the hydrochloride NMe,( NO)HCl, andon boiling with hydrochloric acid splits, up into dimethylamine andnitrous acid.Dimeth?yZlzydruzine, NMe2.NH2, is obtained as a colourless oil (b.p.62.5" a t 717 mm.) bx the reduction of the preceding compound. It isvery hygroscopic, and is easily soluble in water, alcohol, and ether.Its sp. gr a t 11" is = 0.801. It forms two series of salts with acids.The acid hydrochloride, NMe2.NH,.2HCl, is obtiained in crystals bynassing an excess of hydrochloric acid into the alcoholic solut,ion of thebase ; by long-continued heating a t l05O it is converted into the neutralsalt NMe,.NH,.HCl. The platinochloride, (NMe,.NH,.HCl),PtCl,, theneutral sulphate, (NMe2.NH2),H2SO* (m. p.1 0 5 O ) , and the acid oxalate,NMe, NH,. C204H2, are also described.Dimethylhydrazine is decomposed by nitrous acid into dimethyl-amine, nitrous oxide, and water. It combines directly with carbonbisulphitle to form the hydrazine salt of dimethylsulphocarbazinicacid, NMoz.NH.CS.S.NrH3Me2, which is easily soluble in water, anddecomposes on heating; on adding acetic acid to its concentratediiqueous solution, it gives the free dii?zethylsttl~hocartr t z i w i c acid,ND4e-,.NH.CS2H, which cryst,allises in colourless leaflets (m. p. 11 2').Dimethylhydrazine combines directly also with phenyl isocyanate toform a cnrbamide, having the composition CO(NHPh).NH.NMe,.It cryst,allises jn double pyramids (m. p. 1 0 8 O ) , and when boiled withhydrochloric acid splits up into dimethylhydrazine and phenyl ismyanate.On warming dimethylhvdrazine with an alcoholic solution of ethyloxalate, t)lle oxamide, CO(NH.NMe2)2, is obtained in white leafletsm.p.. 220"), easily soluble in water and alcohol; ethyl chloride,bromide, and iodide all act violently on dimethylhydrazine, the chiefproduct being the correspondin? azonium-componnd. Dimethylethyl-azoninm chloride is a very soluble crystalline substance which forms acrystalline platinochloride, (NMe2EtC1.NH2),.PtC14. On reductionwith zinc-dust and acetic acid, it is decomposed into dimethylethyl-amine, ammonia, and hydrochloric acid. Dimethylhydrazine, likeprimary hydrazines, combines with potassium pyrosnlphate to formpotassium dimethylhydrazinesulphonate, NMe2.NH.S03K.Teti-anzeth?jltetruzonR, NtMea, is obtained by oxidising an etherealsolution of dimethylhydrazine with mercuric oxide.It is a pale-yellow oil, which is but little soluble in water, and distils undecom-lmseed a t about 130", but if heated slightly above t 4 s point it explodeswith great violence. I t ssalts are mostly soluble in water and in alkalis ; of these the picrate,Me4N4.CsH2( NO,),.OH, is the most characteristic, and crystallises inyellow prisms which are sparingly soluble in alcohol, but easily solublein water. Tetrazone reduces silver nitrate, and on boiling with diluteacids i t gives dimethylamine, monomethylamine, formic aldehyde, andnitrogen. T. C.It is a, strong base with alkaline reactionORGANIC CHEMISTRY.153Decomposition of Copper Acetate in presence of Water. ByP. CAZENEIJVE ( J . Pharm. [5], 1, 409412).-The author has alreadyshown (t'his Journal, 38, 32) that acetic acid is oxidised by cupric oxideto glycollic acid with formation of cuprous oxide ; a t the same time,small quantities of propionic acid are formed, with liberation ofcarbonic anhydride, due to a secondary reaction. This, however, isnot strictly the case, since by substituting basic cupric acetate €or theneutral salt, the quantity of carbonic anhydride evolved increasesconsiderably without a corresponding increase in the quantity of pro-pionic acid. Its formation is therefore due to the complete combustionof the acetic acid.Ordinary verdigris heated witli water under pressure a t 200" farfrom 1 to 24 hours, showed that first the neutral acetate is formeGwith separation of cupric oxide, and, as the heating is continued,carbonic anhydride is evolved, and the cupric acetate gradually lessensin quantity ; finally the cupric is converted into cuprous oxide, andlarge quantities of calcium glycollate (lime being contained in theverdigris as impurity) and free glycollic acid are formed. The pro-portion of glycollic acid obtained from basic cupric acetate is mucliless than is obtained from the neutral salt.The cuprous oxide is obtained in cubical and octohedral crystals.Some Derivatives of Trichloracetyl Cyanide (Synthesis ofIsotrichloroglyceric Acid).By L. CLAISEN and P. J. ANTWEILEZZ(Ber., 13, 1935-1940).-Hofferichter's statement (J.pr. Chcrn. 20,195 ; this Journal, 1880, Abstr., 35) that when trichloracetyl cyanideis treated with hydrochloric acid it yields a body of the formulaC3HC1303 is found by the authors to be incorrect. The ultimate pro-duct of this action is Strecker's isotrichloroglyceric acid, but byvery careful treatment of the cyanide with hydrochloric acid theamide of the acid is formed as an intermediate product. The entirereaction is expressed by the equations :-CCl,.CO.CN + 2H20 = CC13.C(OH)2.CONR2 ;L. T. 0's.CCI3.C(OH),.CONH2 + HzO = HC1+ NH-Z,Cl+ CCl,.C(OH)z.CO@H.TrichZoracety I Cyanide, C C1,. C 0 .CN.-Hoff erichter obtained thissubstance by the action of silver cyanide on trichloracetic bromide,but it is more easily and cheaply prepared by boiling together equiva-lent quantities of mercuric cyanide and trichloracetic bromide.Thepure cyanide boils a t 121-122'.The amide oJ'i.sotrichZorogZycei.ic acid, CCl,.C(OH), C0.NH2, is readilyobtained by adding 1 niol. of the cooled cyanide to 2 mols. of wateysaturated with hydrochloric acid a t Oo. In the course of 12 hours, thewhole solidifies to a mass of crystals of the amide mixed with some tri-chlorace tic acid.The pure amide forms a white crystalline mass melting a t 126-127".When heated, even below its melting point, it gradually gives off1 mol. of water and is converted into a white body, CC1302H,N, theconstitution of which is as yet uncertain.IsotrichZoronZycel.ic acid, CC13.C (OH),.COOH, is best obtained byheating the foregoing amide with hydrochloric acid in sealed tubes154 ABSTRACTS OF CHEMICAL PAPERS.It crystallises in short, colourless, non-deliquescent prisms, melting at102", and is soluble in all proportions of water.I t reduces Fehling'ssolution and ammonincal silver nitrate. The ba~ium stilt forms smallprismatic crystals, soluble in water. When heated with potash orsoda, and to aome extent even when neutralised with alkaline car-bonates in tJhe cold, the acid splits up into chloroform and oxalates.J. R.Formation of a- and P-Chlorolactic Acids. By P. MELIKOFE~(Ber., 13, 2153-2155).-The product obtained by the action of hypo-chlorous acid on acrylic acid does not consist of a-chlorolactic acidonly, as previously stat'ed (Ber., 13, 956), but is a mixture of a- and/3-chlorolactic acids.These acids are easily separated by means of thezinc salts, that of the @-acid being insoluble in alcohol, whilst kheother is very soluble.a-Chlorolantic acid, C3H5C103, could only be obtained as a thicksyrup. On reduction with hydriodic acid, it gives @-iodopropionicacid (m. p. 82'). Its zinc salt is a non-crystalline hygroscopic gummymass, easily soluble in alcohol and in water.p-ChZoyolactic acid, C3H6C103, cryst allises in prismatic needles (m. p./8 ) or tables. Jts zinc salt is insoluble in alcohol, and has the corn-position (C3H4C1O3),Zn + 3Hz0. The acid is identical with theP-chlorolactic acid obtained by the action of hydrochloric acid onglycidic acid. T. C.b - 0Propionyl-formic Acid.By L. CLAISEN and E. MORITZ (Ber., 13,2191-2123) .-Proyionyl cyanide, CsH50.CW, is formed, together withother products, by heating propionic chloride with silver cyanide at100". It is a colourless liquid (b. p. 108-llO"), which becomesyellow on keeping, and is decomposed *by water into hydrocyanicand propionic acids.Dipropiongl dicynnide (CsH,O.CN),, is formed together with the pre-ceding compound as a colourless, syrupy liquid (b. p. 210-213",lighter than water. It has a peculiar smell, resembling that .of ethylbenzoate.Propionyl fornzamide, C3H50.C0.NH,, is obtained by the actmion offuming hydrochloric acid on the cyanide. It crystnllises in prismsand leaflets (m. p. 116-117"~, which are easily soluble in water andin alcohol, but less so in ether.Propionyl-formic acid, C,H50.COOH, is formed by the action ofthe most concentrated hydrochloric acid on the well-cooled cyanide.It is a colourless and somewhat syrupy liquid, which is miscible wit11water, alcohol, and ether.It has a peculiar and persistent smell ofpyrotartaric acid. Jt boils without decomposition at 74-78' under Bpressure of 25 mm. The silver salt crystal-lises in concentric or feathery groups of needles, which are onlymoderately soluble in cold but easily in hot water, and are decom-posed on boiling with precipitation of metallic silver. The b a h msalt crystallises in small flat prisms or leaflets with 1 mol. of water.It, is much less soluble in water than barium propionate.Propionyl-formic acid gives a-oxybutyric acid (m.p. 42-43') whenreduced wit,h sodium amalgam.Sp. gr. at 17.5 = 1.20.T. CORGANIC CHEAIISTRY. 155Action of Bromine on Malonic Acid. By E. BOURQOIN (Bull.SOC. C I h . ['L], 34, 215-218).-When 5 grams malonic acid, 10 C.C.bromine, and 12 C.C. water are mixed together, the temperature risesto 50-GO", and a little carbonic anhydride is evolved. The mixtureis then heated a t 120" under pressure for 18 hours, and finally at145", when two layers of liquid are formed. The upper layer consistsof an aqueous solution of t>ribromacetic acid, whilst the 1ower.layer isbromoform. Large quantities of carbonic anhydride and hydrobromicacid are formed in the reaction. The explanation of the formation ofbromoform has not yet been established, but it appears prabable thatsome unstable bromo-acids are produced, which, under the conditionsof experiment, are decomposed according to the equation :-C3H404 + 3Br2 = 2C0, + 3HBr + CHBr3,a reaction analogous to that by which bromethilene broiiiide isobtained from succinic acid.L. T. 0's.Action of Water on Ethyl Malonate at a High Tempera-ture. By E. HJELT (Rer., 12, 1949).-The author finds by direct ex-periment that ethyl malonate, when heated with five times its weight ofwater i n a sealed tube, is resolved a t about 150" into ethyl acetateand carbonic anhydride. A quantity of free acetic acid is also pro-duced by the further reaction of the ethyl acetate with water at thetemperature of the experiment.Itaconic Anhydride.By W. MAREOWNIKOFF (Ber., 13, 1844-1.848).-The author has studied the action of acetic chloride on silveritaconate in ethereal solution, and obtained after purification a sub-stance which crystallises in clear transparent rhombic prisms (m. p.68.5'1, whose aqueous solution gives itaconic acid. The anhydridedistills a t 210" (citraconic anhydride 212'). Anschutz and Petri hadstudied the action of acetic chloride on itaconie acid, but without anydecided result. The author is endeavouring to prepare anhydrides ofisoterephtbalic and terephthalic acids.Behaviour of Glyoxylic Acid with Potash. By C. BOTTINGER(Ber., 13, 1931).-Glyoxylic acid, when heated with potash solution,yields oxalic and glycollic acids, but no acetic acid. This fact is usedliy the author in support of his theory of the formation of uvitic acidfrom pyroracemic acid.J. R.Formation of Uvic (Pyrotritaric) Acid. By C. BOTTINGER. ( B e y . ,13, 1969).-This acid is obtained in large quantity on heating a mix-ture of pyroracemic acid with an equal weigh+ of dry sodium acetateand twice its weight of acetic anhydride a t 140" for 3 hours. Theproduct of the reaction is dissolved in water, and boiled with sodauntil an oil which floats on the surface disappears, whereupon theliquid is acidified with sulphuric acid. The yield is 20 per cent. ormore of the pyroracemic acid taken.J. R.V. H. V.J. R.Synthesis of Tri- and. Tetra-basic Fatty Acids. By C. A.BISCHOFF (Ber., 13, 2161-2165).-The author applies Conrad's (Ber.156 ABSTRACTS OF CHEMICAL PAPERS.12, 752) method of preparing polybasic acids by the use of ethylmalonate to the synthesis of a number of acids.EtheiLyltricarboa!jZic Arid, C2H3( COOH),, obt'ained by the saponifica-tion of the ethyl salt (Full, Ber., 12, 752) crystallises in colourlesaprisms, which are soluble in alcohol, ether, and water.It forms well-crystallised salts, and its aqueous solution decomposes carbonates andprecipitates the lead from a solution of lead acetate. It melts at 158",with evolution of carbonic: anhydride and formation of succinic acid.It is identical with the acid which Conrad and the author obtained(Ber., 13, 601) by the saponification of ethyl acetylenetetracarbonate(compare also Orlowsky, Ber., 11, 1604).2MonochlorsthenyItricnl.2,ozylic Acid, C2H,Cl( COOH),.-The ethyl saltof this acid is obtained, by the action of chlorine gas on ethyl ethenyl-tricarboxylate, as a colourless liquid (b.p. 290" with partial decompo-sition). On boiling with aqueous hydrochloric acid, it gives fumaricand carbonic acids, and on saponification with potash, yields inactivemalic acid identical with that obtained by Lloyd (Ann. Chem,. Phaf-m.,192, 80) from fumaric acid.IsoccZZyZenetetrncarboxy7ic A c i d , C (COOH)2(CH,.COOH),.-The ethylsalt of this acid is obtained by the successive action of sodium ethy-late and ethyl monochloracetate on ethyl ethenyltricarboxylste. It isa, colourless oil (b. p. 199-201" a t 25 mm. without decomposition;b. p. 293-296" a t 725 mm.with slight decomposition). The f'reeacid crystallises in prisms which are soluble in water, ether, andalcohol, and forms well-crystallised salts. It melts at 151", withevolution of carbonic anhydride, and formation of tricarballylicacid.Propen y Ztricar boxy Zic A c i d ( C 0 0 H) &H. CHMe ( C 0 0 H) .-The ethylsalt of this acid is obtained by the action of ethyl a-brompropionateon ethyl sodium malonate. It is a colourless oil (b. p. 178-180"a t 25 mm. without decomposition, and under ordinary pressure a tabout 270" with slight decomposition). The free acid has not yet beenisolated. T. C.Tanatar's Dihydroxyfumaric Acid. By A, KEKUL~ and R'.ANSCH~~TZ (Ber., 13, 2150--2152) .-The dioxyfumaric acid, C4H1O6,obtained by Tanatar (Ber., 12, 2293 ; 13, 159) from the oxidation offumaric acid with pot,assium permanganate, is not a dihydroxyfumaricacid, but is identical with ordinary tartaric acid.Constitution of Tartar Emetic.By F. W. CLARKE and HELENASTALLO (Bey., 13, 1787--1796).-Tho hitherto received hypothesis ofthe constitution of tartar emetic is that it contains a monatomic radical,SbO, acting as a base ; this the authors consider superfluous, and theyregard it as the potassium salt of a ilew acid. Their experiments aregrounded on the decomposition of t h e double barium antimony tar-trate with sulphuric acid. On filtering off the barium sulphate formedthe clear solution becomes turbid, a white precipitate separating out.This separation depends on the temperature and degree of dilution.On evaporating the turbid solut,ion, a hard white substance is leftwhich is easily soluble in water, and can be recovered from its solution.T.CORGANIC CHEMISTRY. 157According to the authors’ view this solution contains an acid which istartar emetic with the potassium atom replaced by hydrogen, a body ofthe empirical formula, CIH,SbO,. On account of the instability of t,hisacid, indirect methods of analysis were used ; its solction was neutral-ised with the carbonates of potassium, barium, zinc, cobalt, andstrontium. With potassium carbonate, the acid gave tartar emetic ;with barium, cobalt and zinc carbonates, the double antimony salts ofthese metals ; with strontium carbonate, a salt whose atom relationsof the metals were in the ratio Sr4 : Sb, not Sr : Xb,.I t was found ondecomposing barium antimony tartrate with sulphuric acid, that prac-tically all the antimony was in the filtrate. This fact, together withthe regeneration of the barium and potassium salts from the acid, pointsto the existence of the compound C4HjSb07. Pbligot has described anacid antimony tartrate of formula C&SbO,, which could be representeda s (C4H5Sb07 - H,O), but on preparing this salt by Peligot’smethod it was found that its solution and that of the authors’ acidwere not identical. It is probable that there exist two isomeric com-pounds of the formula C4H,dbOi.On examining the white precipitate formed in the decomposition ofthe unstable acid, it was found to be orthoantimonious acid-CiHjSbOi + 2Hz0 = SbHJO, + C4H6O6.It is well known that concentrated acids and alkalis thrown down,a white precipitate from tartar emetic solutions ; this is not a “ basiccompound ” as hitherto supposed, but orthoantimonious acid-CaH4SbK07 + HNOs + 2H2O = C4H6O6 + KNO, + SbH,OpI n fact, the nitric acid combines with the potassium, setting theacid C4H,SbO7 free ; this is immediately decomposed, with formatioiiof ort’hoantimonious acid.According to this hypothesis, the result isexplained that, on decomposition of tartar emetic with acid, only apart of the antimony is precipittrted. The authors express the con-stitution of their antimony acid and tartar emetic by the formulteSb”’Ob and Sb”’04K ‘ the neutral tartrate described by Berze-1ius as Sb, 0 , Pbligut’s compound as SbCaHj06, and Knspp’sC H O ” C H O ”C4H406 C a n 60 OHC4H606acid tartar-emetic as SbC4H5O6.OKnecessary to suppose the presence of a group SbO.Ferrous Sucrocarbonate.By C . TANR~~T (J. Pharm. [ 5 ] , 2,469-471).-By substituting cane-sugar for milk-sugar in the pre-paration of “ niasse de vallet,” a syrupy mass interspersed wit,h crystalsIS obtained. The crystals are of a brown colour and opaque ; the anglebetween the lateral faces is 79.40”. They are decom-posed by the neutral solvents of sugar, the sugar going into solutionand ferrous carbonate being precipitated. The sugar acts but feeblyon Fehling’s solution until heated with acid, when i t readily reducesI n ncne of these compounds is i tV.H. V.Sp. gr. = 1.85158 ABSTRACTS O F CHEMICAL PAPERS.itl. The analysis of the crystals corresponds with the formula(C1BH22011)Y( Fe2C0J2. L. T. 0's.On Cholic Acid containing Solid Fatty Acids. By P.LATSCHINOFF (Ber., 13, 1911--1915).-The author has previouslysliown that cholic acid cannot be freed from admixed stearic andpalmitic acids by treatment with ether or alcohol. The present papergives the results of further experiments on the subject. When a mix-ture of 4 parts of cholic acid and 1 part of stearic acid (mixed stearicand palmitic acids melting at 58") is dissolved in aqueous ammonia,and the filtered liquid is acidified with hydrochloric acid, the precipi-tate of cholic and stearic acids thereby thrown down is perfectly taste-less, whereas pure cholic acid is distinctly bitter.The dried preci-pitate is not affected, or is only partially melted at 135-140", and thestearic acid in it shows little sign of volatility at 140", although purestearic acid is freely volatile at that temperature.On cooling a hot alcoholic solution containing cholic and stearicacids in the above proportion, well formed homogeneous prismaticcrystals are deposited, with only here and there a trace of laminae;and after washing thoroughly with ether, the crystals remain per-fectly homogeneous, although they contain a considerable proportionof stearic acid.Equally peculiar is the behaviour of the barium salt of the mixedacids. Barium cholate is easily and completely decomposed by solu-tion of ammonium carbonate: whereas barium stearate is scarcelyaffected by it.But when the barium salt of the two acids mixed inthe above proportion (4 : 1) is digested for 12 hours with a solutionof ammonium carbonate, nearly the whole (95 per cent.) of t'he stearicacid goes into solution.The foregoing facts appear to point t o a kind of combination ofcholic and stearic acids. The combination, however, is of an indefiniteand feeble character, for when mixtures of the two acids are treatedwith ether or carbon bisulphide, the solutions formed contain a verymuch larger proportion of stearic acid than the undissolved residues.When more than 20 per cent of stearic acid is present in the mix-ture, its properties are less completely masked. Taurocholic acidmodifies the properties of fatty acids in a still more marked manner,appearing to form with them compounds easily soluble in water.J.R.Ethylphosphordichloride and its Homologues. By A.MICHAELIS (Ber., 13, 2174-21 76) .-Ethylphospl~ordichloride, PC12Et;,is obtained by heating a mixture of mercuric ethide and phosphorustrichloride (1 : 4) in sealed tubes at 230". It fumes in the air, andhas a peculiar odour, resembling that of apples ; it is decomposed bywater, and the solution, when evaporated with strong hydrochloricacid, gives Hofmann's ethylphosphinic acid, EtPO,H,.EtiLy~hosphoi,tetrach20ride, PEtCI,, is formed, together with a chlori-nated ethane, by the direct combination of chlorine with the precedingcompound. It does not melt when heated in an bpen tube, hut in aclosed tube it melts slowly, with decomposition a t loo", and quickljORGANIC CHEMISTRY.159at 160", forming phosphorus trichloride, ethylphosphordichloride,ethyl chloride, aiid free chlorine.Et~i,yl~hosphoroxychZoride, PE tC1,0, is a liquid, boiling a t about 1 7 5 O ,and is rapidly decomposed by water. I t is isomeric with Menschut-kin's oxethylphosphorchloride, PC1,OEt (b. p. 11 7").Isopro~yZ~hos~hordichloride, PCI2Pr, obtained in a manner similar tothe ethyl compound from mercuric isopropide and phosphorus tric hlo-ride, is a liquid (b. p. 135").The above facts show that mercuric alkyls behave differently to thezinc alkyls as regards their action on inorganic chlorides, for whereasthe latter replace all the chlorine atoms of the inorganic chloride, theformer replace them in stages.T. C.Formula of Benzene. By J. THOMSEN (Bey., 13, 2166-2168).-This is a discussion of the contradictory conclusions arrived at byBruhl and by the author, as to the constitution of benzene. Theformer, from his investmigation of the molecular refraction of bodies,considers that benzene contains three double linkings, whereas thelatter, from his determination of the heat of combustion of benzene(this vol., p. 135) concludes that it does not contain any double linkings,but nine eingle linkings. T. C.Nature of Caucasian Petroleum, By F. BEILSTEIN and A.KURBATOW ( B e y . , 13, 1818--1821)~-1t is known that hydrocarbonsobtained from Caucasian petroleum by fractional distillation have ahigher specific gravity than those of the same boiling point fromAmerican petroleum.Caucasian petroleum. American petroleum.B.p. sp. gx. sp. ,gr.80" 0.717 0.669 (hexane)The Caucasian petroleum has also a 10 per cent. higher lightingpower than the American oil. The authors have examined specimensof the Caucasian oil, and even after nine distillations could not obtainproducts of constant boiling points, nor were they able to extract anyaromatic hydrocarbon on treatment with fuming nitric acid, nor anyolefine by bromine. T t appears that the hydrocarbons of Caucasianpetroleum are identical with the additive h ydrogen-products of thearomatic hydrocarbons described by Wreden (Annalen, 187, 166). Asa confirmation of the view, the authors obtained trinitroisoxylene fromthe portion boiling at 115-120", and from the portion boiling at 95- loo", an oil, hexahydrotoluene, C,H,,, unacted upon by nitric acid.From the portion boiling a t 210-215", a nitro-compound, C6H,,N0,,was prepared, which was not fully inveshigated.Hydrocarbons from American Petroleum.By F. BEILSTEINand A. KURBATOW (Ber., 13, 2028--2029).-The authors have esta-blished the presence of hydrocarbons of the C,H,, series in petro-leum from the Caucasus,' and by the action of nitric acid the probableabsence of hydrocarbons of the C2rH2a+2 series. These results are con-95-100" 0 * 748 0.699 (heptane)V. H. V160 ABSTRACTS O F CHEMICAL PAPERS.firmed by experiments, which sht)w that crude heptane obtained byfractional distillation is converted into pure heptane by the action ofnitric acid.As the crude heptane has a higher specific gravity (*7192)than the purified product (-Ci927), and contains less hydrogen thanthat required by theory, and is attacked by nitric acid, it appears thatAmerican petroleum, like petroleum from the Caucasus, containsaddition-products of the aromatic hydrocarbons. By the action ofnitrosulphuric acid on American petroleum, a small quantity of tri-nitroisoxylzne was formed. Further, by the treatment of the crudepetroleum with nitric acid, besides pure heptane, a nitrogen compoundof formula C7H1,N02 was obtained, the Caucasian petroleum yieldingunder the same circumstances a compound of the formula C,H,,NO,.V. H.V.Action of Dimethylaniline on Ethylene Bromide and Acety-lene Tetrabromide. By P. SCHOOP (Ber., 13, 2196-2200).-Tetrarn eth y ldiamidocliph enyleth nne, NMe2. C6H,.C€€,. C H2. C6Hi.NMe2,is obtained by warming ethylene dibromide for several days withdimethylaniline. It crystallises in fine silky needles (m. p. 50", b. p.over 300"), which are easily soluble in ether, light petroleum, and hotmethjl or ethyl alcohol, but insoluble in water. It forms well cha-racterised salts, which are decomposed at 100": The hydrochlorideand hydrobromide are very soluble in all solvents except benzene,whilst the hydriodide is much less soluble. The compoundC,sH2,N21.2HI + I,,is obtained by acting on the base with hydriodic acid containing freeiodine,The platinochloride, Cl,H,,~2~.2HCl.Pt,Cl~, is sparingly soluble inwater and alcohol, and is decomposed a t 100".The oxnZate, CleHlaN2.2C2O4H2, is crystalline, and is decomposedinto free base and acid when heated with water a t 80".The picrats, C,,H,,N2.2C6H2(No,),.0H, is a bright yellow precipi-tate, which is easily soluble in hot methyl or ethyl alcohol, bnt onlysparingly in ether, chloroform, and light petroleum.The free base onoxidation gives quinone and aldehyde.Octometh y ltetramilxotetra~helly letha~e,(C6H,.NMe2)2.CH.CH.(C6HI.NMe2)2,is obtained by the action of dimethylaniline on acetylene tetrabromide.I t separates from alcohol in columnar crystals (m. p. go", b. p. 3\10'),which are easily soluble in alcohol, ether, wood spirit, and benzene ; lesssoluble in light petroleum, and insoluble in water.The pZatiwoc/Lloride, C34H,2Na.4HC1.2PtC14, is a bright yellow,amorphous precipitate, which is decomposed on drying at 100".The picmte, C34HJ?4.CeH2(N02)3. OH, forms brilliant yellow scale?,readily soluble in hot water and alcohol, but only sparingly in ether.The free base on oxidation with ferric chloride, &c , gives quinone.Both the ethylene and acetylene bases give by cautious oxidationbrilliant dye-st uffe, which are under investigation. T. CORGANIC CHEMISTRY. 161Action of Nitrosodimethylaniline Hydrochloride on thePhenolsulphonic Acids which do not contain the Methyl-group. By J. H. STEBBINS (Bar.! 13, 2178--2179).--The authorextends Meldola's (ihid., 12, 2065) action of nitrosodiniethylanilinohydrochloride on phenols to phenolsulphonic acids.1 molecule ofsodium @-naphtholsulphonate, dissolved in an equal quantity ofglacial acetic acid a t 110", unites directly with 1 molecule of nitroso-dimethylaniline hydrochloride to form a beautiful blue dyestuff. Thepure substance is a bronze-coloured powder, which is easily soluble inwater, and after acidifying dyes silk and wool a fine blue. It hasboth acid and basic properties, forming colourless compounds withbases, and blue with acids. T. C.Condensation of Tertiary Bases by Nitric Oxide. By E.LIYPMAKN and R. LANGE (Rer., 13, 2136-2141).-Nitric oxide re-sembles nitrous acid in its action on primary bases, but behaves verydifferently towards tertiary bases, for whereas nitroso-compoundsare produced by the action of nitrous acid, nitric oxide forms conden-sation-products.Dimethylaniline when subjected to the action of nitric oxide in thecold becomes green after four or 6ve days, and large quantities ofcarbonic anhydride are evolved ; after from six to ten days' action it be-comes red, and subsequently deposits bright red needles (A), amountingto 5- 10 per cent.of the base used. After a continued action for threeor four weeks, a violet dyestuff (€3) and a body consisting of brilliantwhite leaflets (C) are obtained.The bright red needles (m. p. 26.6") hare the composition C9H,,N2,and probably the constitution PhMe2N : N i CH, or possiblyPhN : CH.NMe2. I t is insoluble in water, sparingly soluble in etherand in alcohol, but very soluble in boiling benzene.It dissolves inglacial acetic acid with an intense green colour, and is reprecipitatedtherefrom unchanged on the addition of water. The purple hydro-chloride as well R S the other salts are somewhat unstable compounds.Platinum chloride and mercuric chloride give carmine-red preci-pit at es.The white leaflets (C) consist of tetrnineth~/Zdil?henyldiamiize,PhMe,N NlMe2Ph, which melts a t 173" to a blue liquid. It uniteswith acids to form soluble salts, and is precipitated from its solutionby alkalis; on exposure to the air it assuriies a blue coloiir. Theplatinoclzloride, CI6H2,N,PtCl7, crystdlises in white needles, which areinsoluble in cold water, and &re reduced by alcohol and other organicsubstances.The violet dyestuff (B) greatly resembles the methyl hydrochlorideof trimethylrosaniline described by Hofmann (Rer., 6,3.52), but differsfrom the latter i n its complete insolubility in a solution of liver ofsulphur of sp.gr. 1.16. It appears t o be formed by the oxidation ofa portion of the tetramethjddiphenyldiamine produced in the samereaction, and would therefore: have the constitutionPhMe,N-O--NMe,Ph,'NO2162 ABSTRACTS O F CHEMICAL PAPERS.This is confirmed by the fact that it can be obtained directly fromtet ram ethyldip hen yldiamine .By E. and 0. FISCHER (Rer., 13, 2204-2207).-The authors have on a previous occasion (Ann. Chena., 194, 242),shown that it is probable that only one rosaniline of the formulaC,,H2,N,0 exists, notwithstanding that Rosenstiehl (Bull.Xoc. Chin?.,187’3, 13) has described three modifications having this composition.They now find, and their conclusions are confirmed by a privatecommunication from Rosenstiehl, that their former supposition wascorrect, and that Rosenstiehl’s ortho- and orthopars-rosanilines donot exist. Perfectly pure orthot(o1uidine does not give any rosaniline,as supposed by Rosenstiehl, when melted with arsenic acid andaniline, but is converted into red and yellow azo-dyestuffs.The autliors consider that the three amido-groups in rosaniline andin pararosaniline are all in the para-position, thus :-T. C.Rosaniline.H\/’H=2Pararosaniline. Rosaniline.For the format ion of pararosaniline from paratoluidine proves thaha t least one of the amido-groups is in the para-position, whilst the de-composition of anrine into phenol and dihydhxybenzophenone (Caroand Grmbe, Ber.11, 1348) shows that two of the nmido-groups inrosaniline are in the para-position, since dihydroxybenzophenone isa di-para-compound (Stiedel and Gail, Ber., 11, 746 ; Aim. Chem.Pharna., 194 ; Bressler, Ber., 12, 1462). And finally the third amido-group is also proved to be id the para-position from the relation ofrosaniline to the diamidotriphenylmethane obtained from benzoicaldehyde and aniline. This base when treated with nitrous acid givesdihydroxytriphenylmethane, which under the action of alkalis yieldsdihydroxybenzophenone, and therefore contains two para-amido-groups(Doebner, Ber., 12, 1462).The paranitro-derivative of diamidobri-phenylmethane is obtained by the condeusation of paranitrobenzalde-hyde with aniline, and as this nitro-compound gives leucaniline (0.Fisher and P. Grieff, Bey., 13, 669) on reduction, it follows that thethird amido-group of rosaniline is also in the para-position. T. CORGANIC CHEMISTRY. 163Nomenclature of some Azo-compounds. By K. HEUMANN(Bey., 13, 2023--2027).-The author discusses the varied nomencla-ture of the diazo-compounds, and the confusion which is likely to arisefrom a want of uniformity.1st. There is no sufficient ground for changing t'he names azo-benzene, azotoluene, &c., to azodiphenyl, &c., which should be reservedfor the diphenyl derivatives.2nd.I n substituted azo-compounds the whole number of atoms oratom-groupings, (Cl, NO,, S03H, &c.), entering into the moleculeshould be included in the name and not half the number.. Thus thecornpound C,H,( SO,H)N.N( S0,H) C6H4 should be called azobenzene-disnlphonic acid, and not azobenzenesulphonic acid.3rd. I n mixed and unsymmetrical substituted compounds the wordazo should come between the names of the hydrocarbon-radicals corn-He makes the following suggestions :-bined by the grouping N : N.benzenesulphonic acid. V. H. V.Thus, for instance, phloroglucinol-azo-Hydrocyancarbodiphenylimide. By A. LAUBENHEIMER and R.G~RJNG (Ber., 13, 2155--2159).--This compound is obtained by boil-ing diplienylthiocarbamide (1 mol.) with an alcoholic solution ofmercuric cyanide (1 mol.) until mercuric sulphide is no longer preci-pitated.I n this reaction, carbodiphenylimide is first formed, and thisthen combines with a molecule of hydrocyanic acid to form hydro-cyancarbodiphenylimide, thus :-CS(NHPll), + Hg(CN), = C : (NPh), + HgS + HCN;C : (NPh), + HCN = NPh: C(CN).NHPh.This is confirmed by the fact that the compound may also beobtained by t,he action of hydrocyanic acid on a freshly preparedsolution of carbodiphenylimide.Hydrocyancarbodiphenylimide crystallises in pale yellow needles orprisms (m. p. 137" uncorr.), according to the solvent employed. It iseasily soluble in alcohol, glacial acetic acid, ether, and benzene,sparingly sduble in liqht petroleum, and insoluble in water.Onwarming with strong sulphuric acid it gives a red solution, which re-mains clear when water is added. A few drops of the sulphuric acidsolution added to a large quantity c?f water give, on addition of soda, adeep blue liquid, the colour of which gradnally disappears. Whenhydrocyancarbodiphenylimide is warmed with hydrochloric acid itgives aniline, oxalic acid, and ammonia.By A. HIRSCH(Ber., 13, 1903--1911).-Schmitt and Bennewitz, in 1575, obtainedby the action of crtlcium hypochlorite on paramidophenol a body ofthe composition C6HaONCI, which they (doubling this formula) re-garded as dichlorinated azophenol. The author's investigation of thisbody has led him to the conclusion that it is not a chlorazophenol but0a chlorimide of quinone, C H ' I He obtains i t by adding a strongsolution of bleaching powder to an aqueous solution of paramido-T.C.Quinonechlorimide and similar Substances..*\Nc164 ABSTRACTS OF CHEMICAL PAPERS.phenol hydrochloride, with continual stirring, until the colonr of theliquid suddenly changes from violet to yellow. The magma of crys-tals thereby produced is then agitated with ether, which takes up thechlorimide, and leaves it in the crystalline state on evaporation.Quinonechlorimide forms golden or amber-yellow crystals wit11curved faces, easily cleava-ble in one direction, and probably triclinic.It has a distinct odour of quinone, and like that substance dissolveseasily in ether, alcohol, acetic acid, chloroform, and benzene, andsparingly in cold water.It melts a t 84.7-85" ; under water a t 83".When heated above its melting point i t explodes, but with care canbe partially sublimed. I treacts with water a t 100' to form quinone, ammonium chloride, andoxygen, this last producing brown oxidation-products with thequinone. In presence of reducinq agents (hydrogen sulphide, tin andhydrochloric acid, zinc and sulphuric acid, sodium-amalgam) quinone-ohlorimide gives up its chlorine, and is converted into amidophenol.Sulphurous anhydride likewise reduces it, but the sulphuric acidthereby produced reacts with the amidophenol to form amidophenol-sulphonic acid. Althouqh easily rednced, the chlorimide resists in amarked manner the action of oxidising agents and some strong acids.It dissolves in fuming nitric acid and in concentrated sulphuric acidin the cold, and on adding water is precipitated from the solutionsunaltered ; but if the solutions are heated or allowed to stand for along time the chlorimide is completely decomposed.Quinonechlorimide reacts with hydrochloric acid in the cold to formmono-, di- (?), and tri-chloramidophenol.From the last-named sub-stance the author obtained a crystalline trichlorophenol melting a t54-1-54 5", and boiling without decomposition a t 248.5-249.5"(uncorr.) ; insoluble in water, soluble in alcohol, ether, and benzene.&ui?/ onedichlorodiim ic7e.-Krause (Rer., 12, 47) obtained by theaction of calcium hypochlorite on paraphenplenediamine a body of theformula C6H4N2C12, which, from its close resemblance in properties tothA t described above, the author believes to be quinoaedichlorodi-imide.Naphthoquinonechlorimide.-Ami~onaphthol hydrochloride, whentreated with solution of bleaching powder in the nianner describedabove, yields a body which appears from analysis to be a molecularcombination of naphthoquinone with nnpthoquinonechlorimide.Itforms yellow or pale-brown crystals, dissolves sparingly in water,melts a t 35", and explodes a t 130".Action of Sulphonic Chlorides on Urea. By 8. U. E r m r m RBull. SOC. Chini. [el, 34, 207-2~9) .-When 1 mol. benzeiiesulphonicchloride and 2 or 3 mols. urea are heated a t loo", hydrochloric acid isevolved, and the mass solidifies. On dissolving the mass in hot w:iterand cooling t h e solution, colourless crystals are obtained of the composi-tion, CGH,.S0.NaH,C20, + H,O. This body may have the con-stitution-Like quinone it colours the skin brown.J. R.I NH.CO.NHORGANlC CHEMISTRY.165in which case i t is analogous to pyrnvil or allantoyn, or its constitu-tion may be similar to that of biuret,CsH5. SO (NH,) .NH. CO.NH.CONH,,which is probable, since with potash solution and copper sulphate, itgives a red celour. At a higher temperature than the a.bove, carbonicanhydride is evolved, and the reaction gives rise to a compound eitherof the constitution-a-NmhthalenesnlDhonic chloride pives with urea the compoundC,,H,SON4H5(CO),L+ HzO, which fGms globular masses. IL. T. 0's.Compounds of Benzotrichloride with Phenols and TertiaryAromatic Bases.By 0. DOEBNER (Ber., 13, 2222-2229).-This isa continuation of the author's previous investigations (Bey., 11, 1236 ;12, 1462 ; '13,610) on this subject.Malachite green, PhCOH.( C6H4.NMez),, obtained by the action ofbenzotrichloride on dimethylaniline, and after purification by means ofthe oxalate, crystallises in colourless warty crystals (m. p. 132"). Itmelts under hot water, but is only sparingly soluble therein; it iseasily soluble in alcohol with a green colour. I n the crystalline state,it is scarcely soluble in ether, but when freshly precipitated it is easilysoluble ; it is also moderately soluble in carbon bisulphide and acetone,easily soluble in hot benzene and light petroleum, but less soluble inthe cold.It combines with acids in several proportions to form salts.Those formed with organic acids, and the neutral salts with mineralacids, are green; its solution dyes animal and vegetable fibres anintense emerald green. Most of the salts are very soluble in water,the picrate being the least soluble. It also forms reddish-yellow acidsalts with mineral acids, which are decomposed by water into thegreen salts. The base dissolves in acids in the cold, forming almostcolourless solutions, and it is only on warming that they assume agreen colour.The picmte, CZ3HNN2.C6H3N30,. crystallises from benzene in glitter-ing golden needles. The oxnhte, 2C23H,~N,.3CzH,04, forms greenprisms, which are soluble in cold and more soluble in hot water andalso in alcohol.3(C23Hz~Nz.HC1).2ZnC1,.2Hz0 (m.p. 130").The nzethyi! iodide compound, C23H26N,0.2MeI, formed by the directunion of its constituents, crystallises in bright green leaflets (m. p. 171-172" with decomposition), which are sparingly soluble in cold, buteasily soluble in hot water. It is but little soluble in alcohol, ether,benzene, or carbon bisulphide.Malachite green and its salts, unlike methyl green, are stable whenheated witch water a t 200", but on heating with concentrated hydro-chloric acid at 250°, it is decomposed, giving b~nzoyldimethylalziline,PhC0.CsH4.NMez (m. p. go"), and other basic products.The base forms a double salt with zinc-VOL. XL. 166 ABSTRACTS OF CHEMICAL PAPERS.When malachite green is treated with fuming sulphuric acid, it givesseveral sulphonic acids, of which the monacid alone has been isolated.It crystallises in green needles with a brownish-red reflection, and isverg soluble in hot water, forming a green solution, but is less soluble incold water.The sodium salt, magnesium salt, ( Cz3H2,NzSO3),Mg.4Aq,and calcium salt (C23Hz3N2S03)aCa.3Aq, are described ; they are allcrystalline compounds. The hexnnit ro-compound of malachite green,formed by the action of fuming nitric acid on the base dissolved inglacial acetic acid, is a neutral yellowish amorphous powder, which isbut sparingly soluble in the usual solvents, and is devoid of tinctorialproperties.The Izydro-base, CYsH,,N,, is obtained by the action of reducingagents on malachite green, and is a colourless compound (m.p. lolo),icleiitical with the base obtained by 0. Fischer by the action of benz-aldehyde or OE benzalchloride on dimethylaniline and zinc chloride(Rer., 11, 2274 ; 10, 799 ; 12, 1685 j , By oxidation it is convertedinto malachite green. The methiodide of this bydro-base,-crystallises in colourless six-sided tables (m. p. 231" with loss of methyliodide).With regard to the action of benzotrichloride on other aromatictertiary bases, it appears that the nature of the radicals combined withthe nitrogen of the aniline, has little or no influence on the tinctorialcharact,er of the resulting compound, whilst this is greatly influencedby the entrance of alcohol radicals into the benzene ring of the aniline,none of the three dimethyltoluidines, for instance, give a dyestuff oncombination with benzotrichloride.Other tertiary bases, not belong-ing t o the benzene series, such as a- and P-dimethylnaphthylamine,behave differently to dimethylaniline, and do not form a dyestuff.1'. c.Parahydroxyphenol and some Aldehydes and Alcoholsderived from Quinol. By A. HANTZSCH (J. pr. Chein. [2], 22,460-47~).-Paralzydrozy~henetol (Quinol monethyl ether),-C&&(OEt) .OH,is obtained by heating paradiazophenetol sulphate with dilute sulphuricacid for two t o three hours. It crystallises from aqueous solution inthin plates of satiny lustre (m. p. 66" ; b. p. 246-247"). On boilingfor a short time with dilute hydriodic acid, it yields quinol.j%hoxy- hydroxy-salicylic aZdehyde, C6H3( OEt) (OH) .CHO [ OEt : OH= 1 : 41, is prepared by slowly ranning chloroform into a mixture ofparahydroxyphenetol and soda solution a t 60".It forms thick, nearlyrectangular prisms with oblique end faces (m. p. 51.5" ; b. p. 230") ;it is almost insoluble in water, but readily in alcohol, ether, chloro-form, $c. It gives an intense violet coloration with ferric chloride,yields crystalline compounds with the alkalis, and reduces ammoniacalsilver solutions. On fusion with potash, it yields parahydroxysalicylicacid. The e t h y l - p u p is retained in this substance with great energy ORGANlC CHEMISTRY. 167heating with dilute halogen acids failing to effect its removal,although they readily withdraw the ethyl-group from parahydroxy-phene tol.Acetoethoaysalicylic aldehyde, CsH3( OBc) (OEt) .CHO [ OBc : OEt= 1 : 41, is prepared from the preceding substance by heating it forseveral hours with acetic anhydride.It crystallises in long needles,which melt at 69", and boil with partial decomposition at 285". Theacetyl-group is readily removed by boiling with alkalis or halogenacids, whilst the ethyl-group remains combined.ParadietlzoxysalicyZic aldehyde, CsHE,( OEt)?.CHO, is prepared byadding ethyl iodide and a little absolute alcohol to the potassiumderivative of ethoxyparahydroxysalicylic aldehyde. It forms fibrousgroups of fine white needles (m. p. 60" ; b. p. 280-285"). On boil-ing with dilute nitric acid it yields nitro-paradic:thoxysulicylic aldehiy de,C6H2(N0,) (OEt),.CHO, crystallising in brittle, thin, yellow needles(m.p. 129-130").Ethox~~urahyd).ozysnZigenoZ, C6H3( OEt) (OH).CH,.OH, is obtainedby the action of nascent hydrogen on hhe corresponding aldehyde. Itforms pale brown tables of rhombic section, which melt a t 8315", andreadily decompose a t a higher temperature into a brownish resinousmass, wbich appears also to be formed on long contact with acids.Paradiethoxysalicylic aldehyde is scarcely athcked by sodium amal-gam. A. J. G.Action of Nitrous Acid on Anethol. By P. TONNIES (Bw., 13,1845--1849).-By the action of sodium nitrite on a solution of anetholin acetic acid, two compounds are obtained, namely, an addition-pro-duct, Me0.C'sH4.C3H5N,03, which gives anisic acid on oxidation, andon reduction with tin and hydrochloric acid a hydrochloride of theformula MeO.C,H,.C,H,.(OH) .NH2HCl.It was not found possible toobtain the corresponding base.Besides the above, a substitution-product is formed, which melts at97", and decomposes a t 240". It possesses the properties of an azo-compound, and on reduction with tin and hydrochloric acid, is convertedinto a crystalline compound, (~~e0.C6H4.C3Hs)2N403, which forms asulphonic acid. Bromine-derivatives of the two last-named com-pounds were obtained. 'I'he aut'hor considers that the substitution-product is composed of two molecules of the addition-product less2 molecules of water thus :2Me0.C6H&.C3H5N2O3 = 2H20 + (MeO.C6H,,C3H3N2O2),.On further reduction o€ the substitution-product with tin and hgdro-chloric acid, the hydrochloride of a base,Me0.C6H4.C3H3( OH) .NH2.HCl,was obtained, and on removal of the hydrochloric acid the correspond-ing base is formed, which probably decomposes with formation of acondensation-product. The author is investigating the analogousaction cjf sodium nitrite on styrene.v. H. v.n 168 ABSTRACTS OF CHEMICAL PAPERS.Arsinobenzoie Acid. By W. LA COSTE (Bey., 13, 2176-2178).-Parabenzar&nic Acid o r Dih~droxylai.si.nohenzoic Acid,The potassium salt of this acid is obtained by oxidising tolylarsinicacid in potash solution (Ann.. Chern., 201, 1257) with potassium per-manganate. On warming this salt with strong hydrochloric acid, itgives fhe free acid. It crystallises in large colourless transparenttables which are only sparingly soluble in water, alcohol, and glacialacetic acid.On fusion with potash, i t gives phenol ; and when heatedalone it loses 1 mol. of water and forms awhobenxoic acid,which is a yellow powder, and analogous to nitrobenzoic acid.acid potassium p r a b enzarsinat e,CGH4( C OOH. ) AsO ( OH) 2.C~HE,. ( AsO~.) COOH,TheCJ& (CO OK) .As0 (OH), + CGH, (C 0 OH) .As0 (OH) 2,erystallises in tramparerit triclinic tables, which on heating to 160-170' lose 2 mols. H20. The silver salt, CsH4(COOAg).AsO(OAg)2, isa white amorphous precipitate, insohble in water, but soluble in nitricaeid. T. C.Phenylamido-acetic Acid. By J. PL~CHL (Ber., 13, 2118-2120).-Bedstein and Reinecke (Anikalen, 136, 169) were unable toobtain aromatic amido-acids analogous to alanine by the action ofhydrocyanic and hydrochloric acids on hydramides.More recently,however, Erlenmeyer and Schauffeln (Ber., 11, 149) have shown thatanishydramide unites directly with 2 mols. of hydrocyanic acid t oform a di-imido-dinitril, which on heating with hydrochloric acidgives anisaldehyde and an amido-acid isomeric with tyrosine. Theauthor has applied these reactions in the case of hydrobenzamide, andfinds that it unites with 2 mols. of hydrocyanic acid to form the di-irnido-dinitril, CHPh (CX).NH.CHPh.NH.CHPh(CN), correspondingwith that obtained from anishydramide. It forms pale-yellow crystals(m. p. 55'), which are easily soluble in ether and alcohol, insoluble inpure water, but somewhat soluble in water containing hydrocyanicacid.On warming the free compound, or better, the hydrochloride,with strong hydrochloric acid and afterwards with water, benzaldehydeagd phenylamido-acetic acid are produced.Synthesis of Cinnamie and Phenyl-lactic Acids from EthylMalonate. By M. CONRAD (Ber., 13, 2129-2161) .-Ethyl chloro-malonate reacts in the cold with an alcoholic solutionof sodium ethylateto form the ethyl salt of sod~um-chloromalolzic a c i d , CClNa( COOEt),,which, on the additionof benzy! chloride, gives the ethyl salt of benzyl-chloromdonate, CH2Ph.CC1( COOEt),. This compound is a colourless oil(b. p, 305', sp. gr. 1.15 a t 19"), and on saponification gives cinnamic acid(m. p. 132"), and benzylhydroxymalonic acid, CH,Ph.C(OH)(COOH),.This latter compound melts at 143" with evolution of carbonic anhy-dride, forming a phenyl-lactic acid, CH,Ph.CH(OH).COOH (m.p.SS"), identical with that obtained by Erlenmeyer (Bey., 13, 303), fromphenylethaldehyde and hydrocyanic acid.T. CORQANIC CHEMISTRY 169On heating ethylic sodium-chloromalonate, it yields the ethyl salt ofa dicarbotetracarbonic acid, (COOH),C : C( COOH),, which crystallisesin monoclinic prisms (m. p. 57", b. p. 328" with partial decomposition),and is insoluble in water, but soluble in alcohol, ether, and benzene.T. C.Cinnamyl Cyanide and Cinnamyl-formic Acid. By L. CLA~SENand P. J. ANTWEILER (Ber., 93, 2123-21'25) .-Cinnamic cldoride,@,H,OCI, obtained by the action of phosphorus pentachloride on cin-namic acid, is a pale-yellow crystalline mass (m.p. 35-36', b. p. =170-171" at 58 nim.). (Compare Cahours, A n i d e n , 70, 44; andRostoski, ibid., 178, 214).Cirmamyl-cyanide, C,H,O. CN, is prepared by heating cinnamic chlo-ride with silver cyanide at 100". It crystallises in pale-yellow prisms(m. p. 114") and less frequently in tables. It is moderately soluble inwarm ether, chloroform, benzene, and carbon bisulphide, but lesssoluble in light petroleum. On boiling with water or potash, its solu-tion gives cinnamic and hydrocinnamic acids.Cinnanzyl-furn2arnit3e, C9H,0.CONH,, is obtained by the action ofconcentrated hydrochloric on the glacial acetic acid solution of thecyanide. It crystallises in yellowish prisms or leaflets (m.p. 1'29-130°), which are only sparingly soluble in cold, but more soluble inhot water and also in ether, chloroform, and carbon bisulphide.CimanLyl-fornzic acid could not be obtained in the pure state, as thecyanide when treated with alkali is mostly converted into other pro-ducts, and gives but a very small yield of the acid.Three Isomeric Amidocinnamic Acids and Carbostyril. ByF. TIENANN and J. OPPERMAE'N (Ber., 13, 2056--2073).-The authorsbriefly refer to former researches on nitro- and amido-cinnamic acidsand the relation of these compounds to members of the indigo-group.The 1 : 2 and 1 : 4 nitrocinnamic acids were prepared and separatedby Beilstein and Kuhlberg's process (AnnaZen, 163, 126) ; the meltingpoint of the 1 : 4 acid was found to be 285-286" (Beilstein andKuhlberg, 265') ; it can be heated to 280-290" for some time with-out decomposition.The pure 1 : 2 acid prepared by saponification ofits ethyl salt melts a t 237" (Beilstein and Kuhlberg 232') ; the 1 : ;3acid was prepared by Schiff's method (Rer., 11, 1782); it melts atThe three nitro-acids were converted into the corresponding amido-acids by reduction with ferrous sulphate in the presence of bariumhydrate, and the barium salt of the amido-acid decomposed by hydro-chloric acid. In the course of preparation of the 1 : '2 and 1 : 4 acid,colouring matters were observed which are probably due to the forma-tion of members of the indigo-group.Ortl~oa7nidociniaainnic acid crystallises in needles (m.p. 158-159'),sparingly soluble in cold, moderately soluble in hot water, alcohol,and ether. I t s solutions give an intense blue-green fluoresceuce.By treatment with concentrated acids, salts of the general formulaCgHgNO,.HR are obtained. The hydrochloride forms hard darkprisms, easily soluble in water. The barium salt crystallises in whitestar-shaped prisms, which appear under the microscope as pointedtables : it contains no water of orystallisation.T. c'.196-197"170 ABSTRACTS OF CHEMICAL PAPERS.Meta-amidocinnamic acid crystallises in long needles (m. p. 180-181') of a golden-green colour, sparingly soluble in cold, more solublein hot water, alcohol, and ether. Contrary to the observation ofLimprichl (Ber., 11,a95), it was found that the hydrochloride OF theacid could be obtained in a crystalline form by reduction of meta-nitrocinnamic acid with tin and hydrochloric acid.The acid salts canbe prepared by the direct action of a concentrated acid on the ineta-acid ; the hydrochloride crybtallises in colourless leaflets ; the nitratein fine colourless ueedles. The barium salt, (C9H,N02)3Ba.2H20, crys-tallises in glistening, colourless leaflets.Meta-amidocinnamic acid crystallises in slender, golden needles(m. p. 175--176"), sparingly soluble in cold, soluble in hot water,insoluble in alcoliol and ether. It is easily decomposed with forma-tion of a red resin. The hydrochloride crystallises in needles ; easilysoluble in water.C'omparison of the Actions of Copper and Zin)c Siilphates, SilverNitrate, and Lend Acetate, on strong Ammonincal Solutions of theThree Isomeric Acids.---Zinc sulphate .. . .Silver nitrate . . . .Copper sulphate . .Lead acetate.. . . . .---Concentrated sul-phuric acid withnitric acidPlatinic chloride , .LOrtho -acid.A white crystallineprecipitate, inso-luble in hot waterWhite curdy pre-cipitate, solublein hot water, andseparating out oncoolingClear green pre-cipitate, darkon-ing on heatingGolden precipitate,which on heatingmelts together asa resin, then dis-solves, and sepa-rates out on cool-ing i n crystallineaggregates---Colonrs the acid adark brownForms a doublesalt, crystnllisingin short pointedneedles.Meta-acid.A white crystallineprecipitate, spa-ringly soluble inhot waterWhite flocculentprecipitate, verysparingly solublein hot waterDark green precipi-tate, undergoes nochauge on heatiiigWhite flocculentprecipitate, whichdissolves withoutchange on heat-ing, separatingout on cooling inneedles---Produces no changeForms a goldencryst,alline preci-pitatePara-acid.A white flocculentprecipitat,e, solublein hot waterWhite curdy pre-cipitate, insolublein hot water; onheat,ing it turnsbrownDirty brown floccu-lent precipitateWhite flocculent pre-cipitate, which dis-solves on heating,separating out ascrystals 011 coolingColours the acid adark brownForms long pointedneedleORQANIC CHERIISTRP.1 7 1The metn-acid is the most stable, and the para is the most easilyCarbostyril, C6&< NH >CO.-The authors have confirmed theobservation of Chiozza (AnnaZen, 83, 117) that carbostyril can be pre-pared only by the dehydration of orthoamidocinnamic acid and notfrom its isomeride.They hare found that the easiest process for theconversion of the ortho-acid into carbostyril is by heating an aqueoussolution of the hydrochloride of the acid with a slight excess of hydro-chloric acid: C6H~(NH2).C2H2.COOH = C , H A < ~ >CO + H20.On purification, carbostyril is obtlained in silky needles meltinga t 196" to form a golden-coloured oil; on further heating itsublimes unchanged. As carbostyril, C,H,< >CO, is analogousdecomposed of tJhe three.CzHzNH2 2NHCzH,to coumai-in, ->CO, the oxygen-atom being replaced by an CzH,imido-grouping, the authors' attempt to convert coumarin by diges-tion with ammonia into carbostyril, mas unsuccessful ; the action ofnitrous acid on carbostyril, however, gave rise to an odour of coumarin,but coumarin could not be isolated from the product. Baeyer andJackson have already observed the analogy between coumarin andcarbostyril and the similarity of properties of orthocoumaric andorthoamidocinnamic acids (this Journal, Abstr., 1880, 406).X~pnrrction of Ortho- f r o m the Miztikre of Ortho- and Parn-nmido-ciiinnnzic A cids.-Of tlhe barium salts of the amidocinnamic acids thatof the ortho is the only one sparingly soluble in vater.This propertycan be used for the separation of the ortho- from the para-acid in themixture obtniced by the reduction of the two isomeric nitrwinnamicacids obtained by the direct nitration of cinnamic acid.V. H.V.Synthesis of Tropic Acid. By A. LADENBURG and L. R~GHEIMIER(Ber., 13, 2041) .-The authors have previously established the connec-tion between hydratopic, atrolact,ic, atropic, and tropic acids (thisJournal, Abstr., 1880, 472). I n order to effect the syntlhesis of tropicacid, the authors first convert acetophenone into dichlorethylbenzene,by the action of phosphorus pentachloride: PhCOMe + PCl, =Ph.CC1,Me + POC1,. This is then heated with an alcoholic solutionof potassium cyanide, the qwess of alcohol distilled off, and the residueboiled with barium hydrate ; on acidifying the product with hydro-chloric acid, an oil separates out, which solidifies on cooling, and maybe purified by recrystallisation.The acid crystallises in small prisms(m. p. 59-62"), and is fairly soluble in hot water. The reaction is asfollo~s:-Ph.CC1~Me + KCN + EtOH = Ph.CSle(OEt).CN +KCl + HC1 and 2Ph.CMe(OEt).CN + Ba(OH)2 + 2H,O =Ph.CMe(OEt).COOH -+ 2NH3. The authors have found thet atro-lactic acid is converted into stropic acid by the action of hydrochloricacid ; the conversion is more easily effected by using ethyl atrolactate.Atropic acid thus obtained resembles in its melting point and oi'herproperties atropic acid obtained from tropic acid. The reactio172 ABSTRACTS OF CHEMICAL PAPERS.described above has solved the problem of the synthesis of tropicacid.V. H. V.Preparation of 4-Hydroxyuvitic Acid. By C. BOTTINGER (Bey.,13, 1933--1935).-This acid may be obtained by reducing a-nitro-uvitic acid in spirituous solution with tin and hydrochloric acid, dis-solving the resulting a-aruidouvitic acid in dilute sulphuric acid, andadding sodium nitrite, the solution being a t last heated to 100".a-Hydroxyuvitic acid crystallises in needles, which melt with decom-position at 278'. The cadmium saZt dissolves freely in hot, sparinglyin cold water. The copper saZt dissolves in ammonia, with pure greencolour. The rnethyZ saZt crystallises from hot spirit in long needles ;it volatilises with steam. J. R.Hydroxynvitic Acid. By 0. JACOBSEN (Ber., 13, 2050-2053) .--The author has described a hydroxyuvitic acid (Anizalei~, 205, 94),obtained by fused mesitol or orthohydroxyniesitylenic acid with potash.This acid gave orthocresol when heated with hydrochloric acid,thus showing that it was the orthopara-acid.The author has sinceobtained a second hydroxyuvitic acid by the action of fused potash ona sulphamineuvitic acid, prepared by the oxidation of ortho- and para-sulphamineniesitylenic acid. But this orthopara-acid is not identicalwith that obtained from mesitol, for it yields not ortho- but para-cresol. Hence the former acid is not ortho-para-, but diortho-hydroxy-uvitic acid.COMPARISON OF PROPERTIES OF THE HYDROXYUVITIC ACIDS.Diorthohydr0xyuvitl:c Acid.Crystallises from hot water inarborescent groups of needles ;more soluble in hot water than incold.Softens at about 230°, withpartial decomposition ; at 275" itis perfectly melted.Can be sublimed unchanged,the sublimate appearing as iri-descent leaflets, which change tolong needles when water is pouredover them.Gives paracresol when heatedwith hydrochloric acid.Its dimethyl ether melts a t79".Ortli o-p aw 72 y droxyuuitic A cid.Is almost insoluble in cold, andonly sparingly soluble in hot water;it separates out from its solutionin small, dark, rhombohedra1crystals.Begins to soft'en a t 280", andmelts with partial decompositionat 290".Sublimes as a loose mass, con-sisting neither of needles norleaflets .Gives orthocresol when heatedIts dimethyl ether melts atwith hydrochloric acid.128".The silver salt of the ortho-pa.ra acid is more soluble than that of theFrom a comparison of the properties it appears that Bottinger'sdiortho-acid ; both acids give a red colour with ferric chlorideORGANIC CHEMISTRY.173P-hydroxyuvitic acid is identical with the author’s ortho-para acid, andthat Bottinger’s a-acid is possibly identical with the author’s diortho-acid (see preceding abstract ) .Constitution of Uvitonic Acid. By C. BOTTIKGER (Bey., 13,2032-2035) .-In a former research the author described, under thename of uvitonic acid, a body obtained by the action of ammoxiaunder certain conditions on pyruvic acid (this Journal, 1878, i, 3 2 ) .The empirical formula, C8HgNOa, was assigned t o the acid, and to itshjdrate from which the salts are derived, a formula CsH,,N06. Frommore recent determinations the author finds that the formulae C,H,NO,and CsHgN06 agree better with the analytical numbers obtained.Underthe microscope the acid appears in the form of six-sided leaflets, andthe aqueous solution gives a violet colour with ferrous sulphate. Itis soluble in h o t alcohol, acetic acid, phenol, glycerol, &c. Of thesalts, the lead salt is the most characteristic ; it is precipitated on addi-tion of lead acetate to a solution of the calcium salt. By dry distilla-tion with soda-lime, the acid gives only a trace of ammonia and a basewhich had all the characteristic properties of picoline. It would appearthat nvitonic acid is a picoline dicarboxylic acid, and probably has a=\N , which resembles the constitutional formula, MeCconstitutional formula of the uritonic acid (of Finck) ?V.H. V.CII1.C-COOHCH:C-COOH\CH.C-COOHMe-C< >CHCH: C-COOHCvitonic acid is formed from amidopyruvic acid in the same way asanilineuvitonic acid, CZOH18N20d, is from aniliuepyruvic acid. Notonly aniline but also other bases, such as orthotoluidine, form similarcompounds. V. H. V.Vulpic Acid. By A. SPIEGEL (Bey., 13,2219--2221).-For the pur-pose of determining the constitution of vulpic acid, the author hasstudied its decomposition-products. Vulpic acid, when boiled withdilute potash (sp. gr. 1-1), gives oxatolylic acid, C16H&, carbonicanhydride, and methyl alcohol.Oxatolylic acid is a monobasic acid,and on boiling with strong potash, is further decomposed into tolueneand ovalic acid (Moller and Strecker, Annulen, 113, 36). I n additionto the carboxyl-group (CQOH), oxatolylic acid contains a hydroxylgroup, for it is not reduced by sodium amalgam, as it would be werethe third atom of oxygen present as a ketone-group ; this is furtherproved by the fact that on treatment with phosphorus pentachloride,i t is converted into the phosphate CFHl5O3.PO3HZ, which crystallisesin colourless, clinorhombic prisms (m. p. 160O). The hydrogen of thehydroxyl, however, cannot be replaced by acetyl, nor is the hydroxyl-group replaced by hydrogen when treated with hydriodic acid, but theconstitutim of oxatolylic acid is placed beyond doubt by the followingsynthetical formationI74 ABSTRACTS OF CHENICAL PAPERS.Nitril of dibenz7~7glyco7liie acid, (CH,Ph),C( OH).CN, is obtained bytiturating 1 mol. of dibenzyl ketone with rather more than 1 mol.of potassium cyanide, and subsequent decomposition of the productwith hydrochloric acid.It crystallises in colourless rhombohedrons,which melt a t 113", and then boil with evolution of hydrocyanic acid,leaving a residue of dibenzyl ketone.DibenzyZglycoZZin acid, (CH,Ph),C(OH) .COOH, is obtained by theaction of hjdrochloric acid on the nitrile a t 140". It is identical inevery respwt with oxatolylic acid. It melts at 156-157" (oxatolylicacid at 154", Moller and Strecker, Zoc. at., 156-157, Spiegel), and onboiling with concentrated potash, gives oxalic acid and toluene.T.C.Bromorthamidoparabenzenesulphonic Acid. By L. W.ANDREW'S (Ber . , 13 , 2 126--2 12 7) .-The bromami do benzenesulp h oni cacids obtained (1) directly from orthobromaniline, (2) from ortho-bromonitrobenzene by conversion into the sulphonic acid and subse-quent reduction, (3) by the reduction of Goslich's (Am,. Chem.Ylzar~iz., 180, 101) bromonitrobenzenesulphonic acid, are all ideiiticaland have the following constitution and properties. Brornorthamido-p ~ ? . a b e n z e n e s u , ~ ? ~ o r ~ ~ c acid, CGH3( Br) (NH?) (S0,H) [ 1 : 2 : 41, crystal-lises in short, brilliant, four-sided, colourless prisms, which remainiinchanged a t a temperature of 170". (Accordiug to Goslich it con-tains 1Q mols.H,O.) The acid is more stable than its salts andcrystallises more readily ; 2.55 parts of the acid dissolve in 100 partsof water a t 21". The b a y i i c m salt, NH,.(CsH3Br.S03),Ba..3H,0,forms compact needles or white warty masses. Six parts of the drysalt dissolve in 100 parts of water a t 17". The potassium salt,C,H,Br(NH,), S03K + H,O, crystallises in yellow six-sided needle#.T. c.Bromorthonitrobenaenesulphonic Acids. By L. W. ANDREWS( B e y . , 13, 2127-21 30).-The author infers that the bromorthonitro-benzenesulphonic acid obtained by Post and Augustin (Bey., 8, 1559)by the action of fuming sulphuric acid on bromorthonitrobenzene, andthe acid obtained by Goslich (Ann. Chem., 180, 98) from parabromo-benzenesulphonic acid and nitric acid, are identical and not isomeric,as Augustin (Innzcg.Biss., Gottingen, 1875, 19) supposed. He hascompared the potassium, barium, zinc, and copper salts of the two acids,and also the acid chlorides, C,H,Br(NO,) .SO,Cl, and the correspond-ing amides, C,H,Br(NO,).SO,NH, (m. p. 176-177" ; Goslich found177" for his acid), and finds them to be identical in every respect.The two acids, therefore, have the constitution C,H,(Br) (NOz) (S0,H)[l : 2 : 41. T. C.Cymenesulphonic Acids. By A. CLAUS (Rer., 13, 2044-2045).The author shows that Spica's claim of priority with regard to thecymenesulphonic acids (this Journal, Abstr., 1880, 890) is incorrect.According to Spica, the barium salt of the second cymenesulphonic isless soluble than that of the well-known a-paracymeneed phonic acid,but according to Cratz and the author (this Journal, Abstr , 1880,632) the barium salt of the second acid is more soluble than that oORGANIC CREIIISTRY.175the well-known acid. Thus the two acids in question are notidentical. V. H. V.Skatole-forming Substance. By E. and H. SALKOWSKI (Ber.,13, 221?-2218).-1t has been previously shown (Ber., 13, 191)that the crude hydroxy-acids, obtained during the putrefaction ofalbuminous bodies, contain a horny white substance, which on heatingabove its melting point is decomposed into skatole and carbonic anhy-dride. This substance is skntolecarboxylic acid, C,H8N.COOH ; i tcrystallises from benzene in minute leaflets (UI. p. 164‘). T. C.Azo-compounds of Paramononitrodiphenyl.By J. ZIMMER-MANN (Bey., 13, 1960-1963) .-AzoayZiphenlJZ.-This body was ob-tained by boiling paranitrodiphenyl with alcoholic potash. Itlcrystallises in brilliant yellowish scales, which melt at 20.i0, and dis-solve sparingly in acetic acid, but not in water or alcohol. Its com-position agrees with the formula-c6H4-c.H5N>0.IC6H4-CsHSNHydrazodiphenyZ, (C6H4.NHPh)2. -This substance is produced bythe action of alcoholic ammonium sulphide on azoxydiphenyl at 100’in sealed tubes. It crystallises from alcohol in small satiny plates,which melt a t 247” and dissolve sparingly in alcohol and glacial aceticacid, and more freely in ether, but are insoluble in water. On stand-ing in the air i$ gradually turns brown, like hydrazo-compoundsgenerally.AzodiphenyL-The author has obtained this body (1) by the actionof sodium-amalgam on nitrodiphenyl in ethereal solution ; (2) by theoxidation of hydrazodiphenyl; and (3) by the dry distillation ofhydrazodiphenyl, whereby it is resolved into azodiphenyl and amido-phenyl, just as hydrazobenzene is split up into azobenzene and aniline.The second of these methods was found to ftnswer best, the oxidationbeing conveniently effected by adding an alcoholic solution of ferricchloride to hydrazodiphenyl dissolved in hot alcohol.The red pul-verulent precipitate thereby produced crystallises from beuzene inorange-red lamins, easily soluble in ether, but insoluble in water,alcohol, and acetic acid. It melts a t 249-250°, and agrees in com-position with the formula-C6&-C6&NC,jHA-C6H,N I * J.R. IDerivatives of Paramidodiphenyl (Xenylamine). By . J.ZIMME RMANN (Ber., 13, 1963-1969). - Diodi~heizyZth,ioaa,.h,rmzde,SC(NH.C6H,Ph),.-When dry monamidodiphenyl, dissolved in abso-lut,e alcohol, is heated with excess of carbon bisulphide and a littlesoda, an abundant evolution of hydrogen sulphide takes pla,ce, andthe liquid deposits crjstals of a compound which is nearly insolublein all liquids. All attempts to recrystallise it having failed, i t wa176 ABSTRACTS OF CHEMICAL PAPERS.purified by boiling with alcohol and repeated washings with ether. Itforms brilliant colourless laminae, melting a t 228", and closely re-sembling dip heny 1 thiocarbamide.D~henyZthiocarbimide, SC : N.C6H,Ph.-Produced by distilling thecompound just described with phosphoric anhydride. It crystallisesfrom ether in long white needles, which melt a t 58", gradually turnyellow in the air, and have the characteristic odoiir of thiocarbimides.This substance is isomeric with Hof rnann's benzenylamidophenylmer-captan (Ber., 12, 2359 ; this Journal, 1880, Ahstr., 885).1Jiphenylurethune.-Paramidodiphenyl in ethereal solution reactsbriskly with ethyl chlorocarbonste, even in the cold, in the followingmanner :-2CsHAPh.NHZ + EtO.COC1 = CGHaPh.NHZ.IIC1 + CsHJ'h .NH. C 0 OE t .The second of these products (diphenylurethane) crystallises Promether in colourless microscopic needles, which melt at 100" and soonturn brown in the air.C6H4Ph.NH. CH,. C 0 OH .-0 b tained byevaporating an ethereal solution of amidodiphenyl (2 mols.) andmonochloracetic acid (1 mol.), and boiling the amidodiphenyl mono-chloracetate thus formed with wster. It crystallises from hot waterin colourless laminze, which dissolve easily in alcohol and ether.EthyZ Salt of Phenylp?iev y Zene-gZycocine, C6H,Ph.NH.CHZ.COOEt.-Formed on heating amidodiphenyl with ethyl monochloracetate. Itcrystallises from weak spirit in matted white needles, melting at 95".ForrnyZamidoclil,henyZ, C6H4Ph .NH.COH. -0 btabed by digestingamidodiphenyl with ethyl formate i n sealed tubes a t 100". It crystal-lises in small colourless needles (m. p. 172O), and dissolves in alcoholand ether, but only very slightly in waJer.Beizzo~/Zan~idodi~heny I, C6H,Ph.NHBz.-Formed by the action ofbenzoic chloride on amidodiphenyl. First prepared by H.Luddens(this Journal, 1875, l258), whose statements respecting it are con-firmed by the author, who, however, found the melting point t o be230", and not 226" as stated by Luddens.P7i eny Zpheny Zen e-g Zy coc in e,J. R.a- and P-Naphthylphenylamine. By J. STREIFF (Ber., 13, 18.51-18.54) .-a-Naphthylphenylarine, CloH7.NHPh, was prepared byhcating aniline (1 mol.) with naphthylamine hydrochloride (1 mol.).The author finds the melting point t o be 42" (Girard and Vogt 60").The hydrochloride of the base forms colourless prisms, and the picratca brown warty mass. a-Acetylnaphthylphenylamine (m. p. 115"), anda-benzoylnaphthylphenylamine (m.p. 15'2") were obtained by theaction of acetic and benzoic chlorides on the base. a-l?ribromoizaph-thyZphenyZawzine, prepared by the action of bromine on the base, formscolourless crystals (m. p. 137") soluble in benzene, alcohol, and chloro-form. a-Dinitrona~hthy~~lienylamine, prepared by nitrating an aceticacid solution of the base, fbrms, after purification, a brown-redcrystalline powder (m. p. 77"). A barium salt of a-naphthylphenyl-aminetetratsulphonic acid was prepared.~-Na~hthyZ~hei~ylarrLine (Merz and Weith, Ber., 13, 1298 ; Abstr.ORGANIC CHEMISTRY. 1771880, 813). By t,he action of bromine on the base, p-dibrornonnphtyZ-phenyZrcmine is obtained ; it forms white needles (m. p. 140') ; by excessof bromine it is converted into tetrabromouaphthylphenylamine,forming pale-coloured needles (m.p. 198"). The author prepared atrisulphonic acid of p-naphthylphenylamine. V. H, V.Reactions of Naphthol. By C. GRAEBX (Ber., 13, 1849-1851).Merz and Weith (Ber., 13,1298 ; Abstr., 1880,813) have observed theformation of phenyl-6-naphthylamine and 6-naphthylamine by theaction of a dehydrating agent on mixtures of ,@-naphthol and anilinehydrochloride, and of p-naphthol and ammonia respectively. Butphenol under the same conditions gives neither diphenylamine noraniline. Phenol and naphthol show an exactly analogous difference ofreaction with acids. Naphthol when heated with dilute sulphuric acid(1 : 1 ) is readily converted into its corresponding ether; and theauthor proposes to study the various effects of temperature, concentra-tion, and mass on its formation.From &naphthol, P-naphthyl ether irobtained after purification as white leaflets, melting a t 105", and dis-tilling unchanged a t higher temperatures ; with picric acid, it forms 9,compound crystallising in orange-yellow leaflets ; but phenol underthe same conditions gives no trace of phenjl ether. Similarly@naphthol with gaseous hydrochloric acid a t 200-240", or withaqueous solution (1.16 sp. gr.) a t 200" is converted into P-naphthylether. V. H. V.Action of Commercial Trirnethylamine on @-Naphthol. ByA. HANTZSCH (Bey., 13,2053-2056).-By the action of commercial tri-methylamine on ,ll-naphthol, besides B-naphthylamine, there is formedabout 90 per cent.dimethyl-6-naphthylamine. The ethiodide of thisbase forms silky leaflets, sparingly soluble in cold, more soluble in hotwater and alcohol. By the action of moist silver oxide, the corre-sponding trimethyl-6-naphthylammonium hydrate is obt,ained as analkaline, but not very corrosive liquid ; by dry distillation, it is decom-posed into methyl alcohol and the pure base dimethyl-P-naphthylamine(m. p. 46", b. p. 305"), its salts are sparingly soluble ; the platinochlor-ide is with difficulty soluble in alcohol ; wit,h bromine and nitric acid,the base forms bromo- and nitro-compounds. V. H. V.Derivatives of Naphthol. By G. KOELLE (Ber., 12, 1953-1956).-The following compounds have been prepared by theauthor :-a-D~naphthyZiizethyZene ether, CH2(CloH70),, obtained by heating inthe water-bath a solution of ,&naphthol in caustic soda with methyleneiodide and alcohol.The product crystallises from alcohol in fragilesilky needles, melting at 133-134".,@-Dinupkthylethylene ether, CzH4( C,oH70)2, and P-NaphthfyZbromethy1ether, CzH4Br.CloH60, formed simultaneously by the action of /3-naph-thol-sodium on ethylene bromide. The former crgstallises in whiteshining laminae,' insoluble in alcoliol, water, and ether, but sparinglysoluble in glacial acetic acid and benzene: it melts at 217". Th175 ABSTRACTS OF CHEMICAL PAPERS.latter is soluble in alcohol, and crystallises therefrom in fine laminae,which melt a t 96".P-Naphtl2ylan2idoeth2/1 etker.--(3-Naphthylbromethylene ether whendigested with alcoholic ammonia, yields a body which forms withhydrochloric acid a cry stallisable salt agreeing with the formulaCl,H,0.C,H4(NH2).HC1 + H20, and forming with platinic chloridelong needles of the formula, { Cl,,H~O.C2H4(NH2).HCl),PtC1,.Thefree base has iiot yet been obtained pnre.P-Napl~thylaiLi!idoeth?/l ether, CloH70.C2H+NHPh, formed by theabtion of boiling aniline on .P-naphthylbromethyl ether, crystallisesfrom alcohol in laminze, which melt a t 7 5 O , and forms crysiallisablesalts with acids.cc-Di.1iaplztlz~llethylene ether may be obtained in the same manner asthe ,%compound described above, although less easily. White crystal-line lamina, melting at 125-126'.Biebrich Scarlet. By R. NIETZKI (Rer., 13, 1838--1840).-Bythe action of P-naphthol on diazo-azobenzene, a brick-red powder,(3-naphtholtetrazobenzene, is formed, which crystallises out from sol-vents in brown leaflets with a greenish metallic lustre (m.p. 195"), Ithas the constitutioiial formula C,H,.N,.C,R,.N2.C,,H70. By similarreactions, (3-naphtholt etrazobenzene-snlphonic and disnlphonic acidsmay be obtained, the sodium salts of which crystallise in deep redneedles, and form the constituents of the dye known in commerce as( L Biebrich scarlet.'' By the action of zinc-dust or sodium amalgamon an alkaline solution of the sulphonic acids they are decomposedinto amidonaphthol and amidazobenzenesulphonic acid. By heating6-naphtholtetrazobenzene a t 60-100" with fuming sulphuric acid,both the naphthol and benzene groupings are sulphonated with forma-tion of a blue dye. The author shows that dyes which are sulphonstedonly in the benzene grouping dye a dark green, whilst those sulpho-nated only in the naphthol, or both in the naphthol and benzenegroupings dye a pure blue.J.R.V. H. V.p-Naphtholdisulphonic and Dihydroxynaphthalene-disul-phonic Acids. By P. GRIESS (Ber., 12, 1956--1960).-Two, andapparently only two, disulphonic acids of P-naphthol exist. Both areformed when &naphthol i s treated with two or three times its weightof concentrated or, better, fuming sulphuric acid at 100-110". Theymay be separated from each other, and from the monosulphonic acidformed a t the same time by taking advantage of the very unequalsolubility of their barium salts.The acid forming a sparingly solublebarium salt is distinguished by the author as ,@-naphthol-z-disulphonic,whilst that forming an easily soluble barium salt is called 6-naphthol-(3- disul phonic acid.P-Naphthol-a-clisi~l~honic acid, CIOH~(OH) (HSO,),, obtained by care-fully precipitating the base from an aqueous solution of the bariumsalt with sulphuric acid, crjstallises in white silky ncedles, whichdeliquesce in the air. It dissolves very easily in water and alcohol, butnot in ether ; tastes strongly acid, and is completely carbonised a t ahigh temperature. The barium salt, CIoH,(OH) (SO3),I3a + 6H20ORGANIC CHEMISTRY. 179crystallises in needles, which are moderately soluble in hot, sparinglyin cold water, and nearly insoluble in alcohol.The sodium salt crys-tallises in greenish masses of small needles, which dissolve very easilyin water, but only sparingly in spirit, even when very weak. Theaqueous solution precipitates basic lead acetate, but not silver nitrate.~-N~~~llthol-p-disulyhoiiic acid, obtained in the same way as the pre-ceding, resembles it closely, but the crystals are more highly deli-quescent. The barium salt crystallises with 8H20 in very small whiteprisms, which are extremely soluble in cold water, but only verysparingly in weak spirit. The sodium saZt forms white rhombic tablesor prisms, very easily soluble in water and moderately soluble in weakspirit, differing markedly in this respectl from the correspondingB-a-salt. Its solution likewise precipitates basic lead acetate.The salts of both the foregoing acids exhibit, i n aqueous solution,a, blue-green fluorescence, which is intensified by addition of ammonia.Both the a,cids react with diazo-compounds to form very beautifulcolouring matters, some of which are valuable as dyes, the 6-a-acidyielding for the most part deep-red or violet, whilst the @-@-acid yieldsgenerally orange or bright red colours.These colouring matters arethe subject of various patents in England and Germany.C ,,H4( OH) (H S O,),.-T hisacid is obtained by heating dihydroxynaplithalene with twice itsweight of concentrated sulphuric acid in the water-bath, and is puri-fied by crystallising the barium salt in the usual manner. It formswhite needles or lamine, very easily soluble in water and alcohol, butnot deliquescent.The barium saZt crystallises with d mols. of water invery small granules or microscopic lamin=, which dissolve verysparingly even in boiling water. It is not affected by hydrochloricacid.This acid likewise yields with diazo-compounds yellow, red, andviolet colouring matters, which, however, are not generally so beau-tiful as those obtained with the P-naphtholdisulphonic acids.Picene, a new Hydrocarbon from Peat-tar. By 0. BURG (Bey.,13, 1834--1837).-On submitting peat-tar to fractional distillation,after separation of the light paraffin, there is left a t the last stage ahard golden-brown mass. On recrystallking this from petroleum, thehydrocarbon, picene, CZ2Hll, is obtained in sulphur-yellow leaflets.Picene crystallises from cymene in a second form of white glisteningleaflets (m.p. 345" corr.), having a blue fluorescence. Picene is inso-luble in most menstrua, but dissolves sparingly in boiling acetic acid,chloroform, and benzene. The author considers that picene is probablyidentical with the hydrocarbon, parachrysene (m. p. 310-320°),obtaiued by Rasenach (Ber., 6, 1401 ; this Journal, 1874, 259), fromcoal-tar, and with Graebe- Walter's hydrocarbon from American petro-leum.Picewe-quinone, Cz2HlzOZ.-Picene is converted into picene-quinoneby oxidation with chromic acid mixture, and after purification fromacetic acid is obtained as an dark orange-red crjstalline powder insolu-ble in water, soluble in alcohol, benzene, and chloroform.Dibromopicene, C,,Hl,Br2.-By the action of bromine on picene,Dil~yc.lrox~na~~htlzaZer~edisu~ 11 onic acid,J.R180 ABSTRACTS OF CHEMICAL PAPERS.suspended in chloroform, it is converted into tribrompicene, whichcrystallises from xylene in white interlaced needles, insoluble in water,chloroform, and benzene, but easily soluble in boiling xylene and itshigher homologues. V. H. V.By P.CAZENEUVE and JMBERT (BUZZ. SOC. Chim. L23, 34, 209-210).-Bymixing crystallised chloral hydrate and camphor, a colourless viscousliquid is obtained with a diminution in temperature. It has apiquant taste, and an odour resembling those of chloral hydrate andcamphor. It is soluble in alcohol and chloroform, insoluble in waterby which it is decomposed ; if, however, the water previously con-tains some chloral hydrate in solution, the liquid is not decomposed.At 19" it turns the plane of polarisation40" to the right. Pure alco-hol decomposes the liquid, the solution having the same rotatory poweras camphor, but if the liquid be dissolved in alcohol containing a largeproportion of chloral hydrate, the rotatory power of the solution isconsiderably less than that of camphor.These results lead the authorsto the conclusion that the liquid is an unstable molecular compoundsimilar to those of alcohol, acetic acid, and nitric acid with camphor.L. T. 0's.Acetyl-derivatives of Bsculin and Zsculetin. By H. SCHIFF(Ber., 13, 1950-1953) .-The substance formerly described by theauthor as triacetzsculetin is now found to be diacetaesculetin, a freshexamination of the original preparation having confirmed Liebermannand Knietsch's analysis of the body (Ber., 13,1590).The discrepancybetween Schif's first result and that now arrived a t is explained bythe fact that he formerly estimated the acetyl by boiling the compoundwith water and magnesia. He has now discovered t'hat under thesecircumstances Esculetin itself forms a soluble compound with mag-nesia: it follows, therefore, that the amount of ncetyl found was toohigh.For the same reason, the substance formerly described as hexacet-ssculin is to be regarded as the pentacetyl derivative.Combination of Chloral Hydrate with Camphor.J. R.Calycin. By 0. HESSE (Ber., 13, 1816--1817).--From Calycitcmchqsocephalum, a yellow lichen which grows on the oak, birch, and fir,the author has extracted a crystalline substance, which he termscalycim It forms red prisms (m.p. 240°), soluble in hot petroleum,ether, alcohol, chloroform, &c. The formula was found to be C,8H1203.When heated with concentrated potash calycin is decomposed int,oa-toluic and oxalic acids, C18H,20, + 3HzO = 2C,H,02 + C,H2O4.Calycin stands in near relation to vulpic acid, but it is an anhydridewhich is converted into calycic mid by heating with potassium orsodium carbonates. On decomposing the barium salt with hydro-chloric acid, calycic acid is obtained as a golden-yellow resin, soluble inwater and ether, but it cannot be separated from the latter withoutpartial regeneration of calcyin.Optical Rotary Powers of Santonin-derivatives.By J. CAR-NELUTTI and R. NASINI (Ber., 13, 2208-2211).V. H. VORGANIC CHEMISTRY.----Metasantonin (m. p. 136"). ...Metasantonin (m. p. 160.5") . .Santonin ..................Metasantonide ..............Santonide .................Parasantonide ..............Santonic acid ..............Methyl santonate.. ..........Ethyl santonate ............Normal propyl santonate ....Ally1 santonate.. ............Isobutyl santonate ..........Parasantonic acid,, ..........Methyl-parasantonate ........Ethyl-parasantonate ........Propyl-parasantonate ........Santonyl chloride ..........Santonyl bromide ..........Santonyl iodide ............Specificrotation.[.ID.+ 118 *76 + 118.76+ 744 -61+ 897 *25- 171 '37 - 223 -46- 70 '31 - 52 *33-45 -35 - 39 *34 - 39 -54- 41 '63- 98 -51 - 108 '91-99.98-91.27 + 13 -14 - 100 -53 - 99 -21Molecularrotation.100 '&ID _M_--+ 292-15 + 292 *15- 421 '57 - 549 *71 + 1831 -74 + 2207 *23 - 185 '62 - 145 *48 - 132 *42- 120 '38 - 120 -20 - 133 *22- 260 -07- 302 *77- 291 '94- 279 *29+ 3 i *12 - 328 *73 - 371 '05Sp. gr.of thembstame.1 -16491 -19751 *18661 '0461 -19671 -19571 -2511 -16671 -14811 -11851 *14341 -11811 -26841.17771 *1531 - l a 81 -16441 '46461 -3282Molecularvolume.211 -17205 '43207 *32235 *96205 -56205 -74211.04238 '27254 -33273 -58265 *88289 -77208 -13236 * 05253.26267 * 29242 *62223 '27281 *59The following conclusions, among others, are drawn from the aboveresults :-( 1.) The anhydrides, except santonin and santonide, aredextrorotary, whilst the acids are 1aevorotarT.(2.) Krecke's law ofsimple multiples in the molecular rotations holds good in the case ofthe santonins, but not in the case of the remaining compounds.(3.) The rotatory powers of some of these compounds, notably those ofsantonide and parasantonide, are greater than those of any other knownsubstance.The normal propy Z snntonate was prepared by passing hydrochloricacid into a solution of santonin in normal propyl alcohol; underdiminished pressure it distils at 220°, and is a thick colourless syrup.Isobutyl santonate crystallises in needles (m.p. 67"). Ally1 sadonntecrystallises in leaflets (m. p. 54-55'). Propyl parasantonate in colour-less prisms (m. p. 113"). T. C.Thapsia Garganica. By L. SOUBEIRAN (J. Pharm.. Trans. [ 5 ] ,1,495-496) .-The results obtained with the resins of Thapsia garqnnicaand cleka, or " false thapsia," confirm those of Blanchet (this Journal,38, 718). L. T. 0's.Synthetical Pyridinetricarboxylic Acid. By C. BOTTINGER (Ber.,13, 2048--2050).-By the oxidation of uvitonic acid with potassiumperrnanganate or chromic acid mixture, pyridinetricarboxylic acid isformed. It can be separated from the unoxidised uvitonic acid bysolution in water, and purified by conversion into its barium salt,which is decomposed with sulphuric acid. Pyridinetricarboxylic acidcrystallises in colourless, transparent, glistening tables, which loseYOL.XL. 182 ABSTRACTS OF CHEMICAL PAPERS.their water a t loo", melt at 244", and become slightly brown at 220".When heated with soda they evolve an odour of pyridine. The acid issoluble in cold and hot water, and the solution gives a violet colourwith ferrous sulphate, with silver nitrate a gelatinous, with leadacetate a white, and with copper acetate a greenish-blue precipitate.With barium acetate the acid gives a bulky amorphous precipitate,which on warming is converted into slender needles, of the for-mula C8H,Ba3N06 + H,O. The salt decomposes on heating, withevolution of pyridine. I t is not decided whether this pyridinetri-carboxylic is isomeric or identical with that obtained by Hooge-werff and van Dorp (this Journal, Abstr., 1880,406).(Cf. Skraup, ihid.,1879, 656.) V. H. V.Synthesis of Quinoline. By C. BOTTINGER ( B e y . , 13, 2165-2166).-Quinoline is obtained together with water on subjecting anintimate mixture of the hydrochloride of aniluvitonic acid and soda-lime to dry distillation. 1 gram of the hydrochloride gives 1 gramof quinoline platinochloride. This reaction shows that aniluvitonicacid must be nearly related to the quinolinecarboxylic acids.T. C.Quinoline. By A. CLAUS and P. HIMMELMANN (Ber., 13, 2045-2048) .-By heating equal parts of quinoline (prepared synthetically)and benzyl chloride in sealed tubes a t a temperature of loo", a solidmass is obtained, from which the pure quinoline-benzyl chloride,C,H7N.C7H7C1 + 3H20, may be extracted in the form of large, colour-less, transparent tabular crystals.The platinochloride forms darkgolden needles, or a bright golden powder; both forms are verysparingly soluble in water. Quinoline-benzyl chloride forms a doublecompound with mercuric chloride. By the action of pdtash in thecold, or ammonia on warming, an oily base separates out, insoluble inwater, but easily soluble in ether ; this base is very unstable in lightand air, and probably has the empirical formula C,H,(C,E,)N. Thesame compound is obtained by the action of silver oxide on quinoline-benzyl chloride.In order to study better the unstable base, the authors treated itsethereal solution with hydrochloric acid to convert the base into thehydrochloride, but the hydrochloride so obtained was identical withthe addition-product of quinoline and benzyl chloride. These facts arenot in accordance with the accepted view of quinoline, for if quinoline-benzyl chloride has the following structural formula-H HI l lHC C CHa, benzylated quinoline of analogous structure is possible with thORGANIC CHEMISTRT.183C,H, grouping replacing a hydrogen-atom; but on the other hand,it cannot be supposed that in the formation of a hydrochloride of thisbase there is retransposition of the C,H, group from a carbon toa nitrogen-ahom.By the action of niscent hydrogen on quinoline a dark goldensubstance is obtained (m. p. 95"), easily soluble in ether and alcohol,insoluble in water, and crystallising with acids.The authors havealso studied the action of aldehyde and amines on quinoline. Asexperiments on the alcoholic halogen-compounds of quinoline obtainedfrom quinine bases, are in direct contradiction with the experimentsquoted above, the authors propose to carry on a parallel research withquinoline not prepared by a synthetical process.By A. CLAUS ( B e y . , 13, 2184-~~~?).-F~oKLI his experiments, the author concludes that cinchonidineand homociiichonidine are the Sam9 alkaloid in different conditionsof purity. T. C.Ethyl Derivatives of Cinchenidine. Ry A. CLAUS and 14.DANKEN~AUM (Ber., 13, 2187--2191).--The cinchonidine employed inthe following investigation had the composition CzoH,aN,O, and crystal-lised in large compact crystals (m.p. 205-) ; its neutral sdphnte con-sisted of a fine, thin, and almost gelatinous, network of needles. Theethiodide, C,,H,,N,O.EtI, crystallises in anhydrous needles, which meltwith decomposition at 249" (compare also Rer., 11, 1821). Ciizcho?zi-dine naethiodide, CzoH24Nz0.MeI, is very similar to the ethyl-compound,and crystallises in anhFdrous colourless needles (m. p. 245-255" withdecomposition). The ethiodide dissolves in strong hydrochloric acidon warming, and forms an intense yellow liquid, which solidifies oncooling to a mass of yellow needles (cinchonine ethiodide hydrochlo-ride ?), which, however, are not very stable. The correspondinghydriodides are obtained by the action of cinchonidine methiodide onethyl iodide. The diiodl_rl~~yl-coi?lpo~~na.s of ciizchoiiidiiae are best ob-tained by heating the moniodslkyl-compound with an excess of themoniodo-paraffin in sealed tubes.Their colour varies between yellowand red, and even violet, and they crystallise with 1 and sometimes2 mols. H,O. Iodethyl-iodmethylcinchonidine and iodmethyl-iodethj-1-cinchonidine are isomeric, and not iden tical. Eth y Zcinchonidine,C,,H,,EtN,O, is obtained by treating cinchonidine ethiodide withpotash solution. It crjstallises in transparent, needles (m. p. go"),which quickly become red on exposure to light ; i t is insoluble inwater, but easily soluble in benzene, chloroform, &c. Its salts areso soluble in water that they cannot be obtained in the crystallinecondition.The platinochloride, C2,H2,EtN,0.HC1.PtC14.H,0, is abright yellow crystalline precipitate, which is soluble in hydrochloricacid, and in a large quantity of boiling water.Ethylcinchonidine combines directly with the moniodo-paraffins.Ethylcinchonidine ethiodide, C2,H,,E tN20EtI, crystallises in largecolourless needles, and begins to melt with decomposition a t 257".Ethy Zcinchonidine methiodid e, C2,H2,E "0. MeI, is a similar compound,and is isomeric with methylcinchonidine ethiodide, C20H23MeN20.EtI.V. H. V.Alkdoi'ds of Peruvian Bark.0 184 ABSTRACTS OF CHEMICAL PAPERS.Ethylcinchonidine ethiodide on treatinent with potash gives a newbase, which is isomeric and not identical with diiodethylcinchonidiae.Methyl Derivatives of Hornocinchonidine.By A. CLAUS andR. BOCK (Ber., 13, 2191-2194).-The homocinchonidine, C19H22N20,employed fused a t 203--205'.C ,gHz2Nz0 X e I ,is formed by the direct combination of methyl iodide with the freebase both in alcoholic solution. It crystallises in slender colourlessneedles (m. p. 248"), and resembles the corresponding compound ofcinchonidine in all its properties.C19H,zN20.2MeI,is obtained by the action of methyl iodide on the preceding compoundin sealed tubes at 100". It crystallises in large prisms, which arespayingly soluble in alcohol and insoluble in ether.Homocinchonidiize nzetlzylchloride crystallises in slender silky needles,which contain 1 mol. H,O. The anhydrous compound melts at 158"( uncorr.).Methyl-homocinchonidine, C19H,,MeNz0 +.HzO (m. p. 75-76' un-corr.), is obtained by the action of potash on homecinchonidine meth-iodide. CPystallises in almost colourless tables, which assume a redcolour when exposed to light. The anhydrous compound could notbe obtained in the crystalline state. Its salts are very soluble inwater. The platinochloride, C19H21MeH,0.2HC1.PtC14.3Hz0, is a brightyellow crystalline precipitate, which is decomposed on boiling withwater.Methyl-1Lomocinchonidine ntcthiodide, C~gH,,MeNz0.MeI.2Hz0, ob-tained by the direct combination of its constituents, crystallises incolourlesa prisms. T. C.Phenylhomocinchonidines. By A. CLATJS and C. B~TCKE ( B e y ,13, 2194-2196) .-Two isomeric phenyl-h-cinchonidines are obtainedby heating the neutral hydrochloride of h-cinchonidine with aniline(1 mol.: 1 mol.) at the boiling point of the latter.a-Phen yl-h-cinckonidine, C19Nz,PhNz0, is the product obtained whenthe action is stopped at the end of five or six hours. It is moresoluble in ether than the P-compound, and consists of a thick oil. The/3-co~zpound is formed if the action is not shopped until after 60 hours'heating, It is a brown non-crystalline powder, which is insoluble inether. Neither modification, nor the saltls prepared from them, couldhe obtained in the crystalline state. The platinochlorides of both areyellow precipitates, C19H,,PhNz0.2HCl.PtC14.2H,0. The a-phenyl-h-cinchonidine combines with methyl iodide to form phenyZ- homocincho-iiidine dinzethiodide, a reddish-brown brittle resin soluble in water.Neutral quinine and cinchonine salts also give phenylated deriva-tives when heated with aniline, whilst brucine and strychnine salts donot form such compounds.T. C.Homocinchonidine methiodide,Homocinchonidine dimethiodide,T.C.Relation of Echitamine to Ditai'ne. By 0. HESSE ( B e y . , 13,1841-1842) .-The author (Anizulen, 203, 144) has shown t'hat thORGANIC CHEMISTRY. 185ditajlne of Harnack is only impure echitamine. He has observed noformation of glucose by the action of hydrochloric acid on echitaminehydrochloride, but on filtering off the concentrated salt and testingwith Fehling’s solution, an abundant precipitate of cuprous oxide wasthrown down.This was not due to glucose, for the reducing sub-stance was entirely precipitated from the hydrochloric acid solutionby phosphotungstic acid.Echitamine is probably a nitrogenous base, and may perhaps beclassed with aspidospermine and geisospermine. V. H. V.A New Crystalline Decomposition-product of AlbuminousSubstances. By A. DANILEWSKY (Ber., 13, 23 32--2136).--h crys-talline compound having the composition, Czl&N1,08, is obtained onsubjecting peptone, egg albumin, casejin, blood-fi brin, or syntoninto the action of pancreas ferment. It is scarcely soluble in cold water,and quite insoluble in cold alcohol and ether, but is more soluble inhot water or hot dilute alcohol, from which it may be again separatedin the form of microscopic prisms or needles. In its chemical reac-tions it partakes of the properties of both tyrosine and inosite ; i t is,however, distinguished from both these bodies by its smaller stabilityon long heating with water. From its general character it appears tohave the following constitution :-CgH,,NO, + C6H,,06 + CJI,NO = C31H,,N,Oe + 2HZO.Tyrosine. Inosite. Amidophenol.This is confirmed by the fact that on long boiling with dilute sul-phuric acid, it splits up into a compound, C15H,,N@8(=*CgHtl,lNOs +C6H,@6 - HzC)), exhibiting the reactions of both tyrosine and inosite,and a crystalline basic substance, probably amidophenol, which forniaa, well crystallised hydrochloride and platinochloride. T. C.Metahaemoglobin. By A. JADERHOLM (Zeitschr. f. B i d , 16, 1-23).-Hoppe-Seyler in 1865 first gave the name metahzmoglobin tothe product of the spontaneous decomposition of the blood colouringmatter, and in IS75 pointed out that probably no definite bodyexisted, but that it represented an intermediate stage in the decompo-sition of haemoglobin into htematin and prote‘ids.The results of the author’s investigations show-in his opinion-that metahaemoglobin exists as a definite body, differing from hsmo-globin in its spectrum and its behavioar with reducing agents, andfrom haematin in its behaviour with reducing agents and alkalis,although its spectrum resembles that of the latter in acid solution.After referring to Sorby’s researches and quoting his opinioir thatmetahemoglobin is a, peroxyhemoglobin, the author proceeds to ex-amine the spectrum of metahaemoglobin in detail, and repeats hisformer assertion, that a pure and perfect metahemoglobin spectrumlike that of hzematin in acid solution exhibits four absorption-bands-one band in the red, two weaker ones in the green, and nearly in theposition of the bands of oxyhemoglobin, and a fourth at the beginningof the blue, and extending to Fraunhofer’s line F. He then point186 ABSTRACTS OF CHEMICAL PAPERS.out how these bands were one by one recognised and attributed tometahEmoglobin by Hoppe-Seyler, Sorby and Preyer-for referencehe numbers them I, 11,111, IV-No. IV the broad absorption-band inthe blue is very feeble and difficult to see. He deems it highly im-portant to decide whether Nos. 11 and I11 belong to metahaemoglobinor not. Hoppe-Seyler denies this (Zoc. cit.), and expresses the beliefthat they are the oxyhaemoglobin bands. This the author discussesa t length,MetahEmoglobin has, according to the author, another spectrumnot mentioned by Hoppe- Seyler. When met8ahaemoglobin solution ismade alkaline, it turns from a yellowish-brown to red, and then thespectrum exhibits only three bands, a weak one in tlhe orange near theD line, and two in the green in the position of the oxyhaemoglobinbands, the first and second being connected by a decided absorption.The relations of these spectra to that of four-banded hzematin arethen pointed out, and the author expresses the opinion that the twobodies are closely related, but nct identical, on account of their dif-ferent behaviour towards alkalis and reducing agents ; and from thefact that metahaemoglobin when treated with reducing agents yieldsthe oxyhaemoglobin spectrum, the author is inclined to agree withSorby, and regard it as a peroxyhaemoglobin. Hoppe- Segler’s objec-tions to this theory (Zeitschr. j . PhysioZ. Chem., 1877-78) are ex-amined and attention drawn to the fact that various oxidising agentswill convert oxyhaemoglobin into metahaemoglobin, e.g., potassiumpermanganate, and nitrites (Gamgee) .Experiments by Hoppe-Seyler on (1) the effect of passing a streamof hydrogen for some hours through a solution of haemoglobin. (2.)Exhaustion of a solution of haemoglobin by the Sprengel-pump.(3.) The action of palladium saturated with hydrogen, are thenexamined, and the results of a repetition of the experiments with palla-dium given, and the author finds in every case that the resultingmetahzemoglobin behaves with reducing agents exactly as metahaemo-globin prepared in any other way. He then describes his apparatusfor acting on the solutions of blood to colouring matter with variousreagent’s without admitting the air. He obtained as the result ofoperating mith palladium-hydrogen a pure metahzemoglobin solution,which on treatment with a trace of yellow ammonium sulphide, gavethe bands of h~moglobin a t once. The importance of excluding theair is dwelt upon, and a series of experiments mith palladium hydrogencontrolled by a second apparatus, in which no hydrogen was used isgiven with measurerrients of the spectra. These experiments theauthor considers render Hoppe-Seyler’s conclusions untenable. Fromfurther experiments with palladium, the author concludes that itsaction is an indirect oxidation, and is of opinion as the general resultof his observations that metahEmoglobin is a peroxyhaemoglobin .(A table of spectra accompanies the paper.) TT. N

ISSN:0368-1769    

DOI:10.1039/CA8814000141

出版商:RSC    

年代:1881

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY.P h y s i o 1 o g i c a1 C h em i s t r y .187Decomposition of Pease in the Intestine of Man. By M.RUBNER (Zeits. f. Biol., 16, 11$-128).-The author referring to hisprevious researches on the digestion of various food-stuffs, remarksthat although the question is a very important one, it has not hithertobeen thoroughly investigated. Strumpell and Woroschiloff madeexperiments in this direction, but the diet used was not purely legu-minous, and he is of opinion, from previous investigations, that theadmixture of other food-stuffs has an important influence on thedigestion of the leguminoseae. The experiments described in thepresent paper were begun in the belief that the leguminoseae, althoughrich in nitrogen and an exceedingly cheap food, were probably veryindigestible.Pease were chosen as being most to the taste of thesubject of the experiment. These were decorticated and cleansed fromall impurities. Objection is taken to pea-meal on the ground that itcontains the husk which would vitiate the experiment. The dailyration of pease was cooked for two or three hours until quite soft,passed through a fine sieve, and taken at three meals ; salt at discre-tion, and a litre of beer completed the diet.The numbers of the experiments are in continuation of those pre-viously made by the author.Composition of the Peas.Dry substance ........ 87.05 per cent.Containing nitrogen. ... 3.91 ,,Fats.. ................ 1.35 ,,Ash.. ................ 3.05 ,,Ezperirnent 20, 16th and 17th June, 1079.Daily Ingesta.Peas, Peas, Carbo- Totalfresh.dry. N. Fat. hydrates. Ash. NaC1. dry food.959.8 835.6 32.67 11.28 587.9 26.05 18.7 854.3Daily Excreta (n2 ean).Faeces. Urine, N UricWet. Dry. N. Fat. Ash. C.C. of urine. acid.927.1 124.0 9-09 8.5 16.05 1277 21-54 1.0588Composition of Feces.Nitrogen.. .......... 7.33 per cent.Pats.. .............. 6.87 ,,Ash.. .............. 12.93 ,,There was, therefore, a daily loss of188 ABSTRACTS OF CHEMICAL PAPERS.Dry substance ...... 14-51 per cent.Nitrogen .......... 27-82 ,,Fats .............. 75.35 ,,Carbohydrates ...... 6.9 7 ,,Ash .............. 35.82 ,,NaCl .............. 3-10 ,,The fseces and urine had a strongly acid reaction, and the latterdeposited large quantities of urates on standing.The results of thisexperiment were so much against pease as a food, that the authordetermined to try a smaller quantity, considering it possible that theinere mass of the diet affected its digestion ; tho amount was thereforereduced to 600 grams, and the result fully justified the assumption.Eqeriment 29, 17th and 18th July, 1879.Daily Iugesta.Peas, Peas, Carbo- Total dryfresh. dry. N. Fatt. hydrates. Ash. NaC1. substance.Grams 600 511.1 20.37 7.03 357.0 15-89 14.2 335.3Daily Ezcreta (meam).Wet. Dry. N. Fat. hydrates. Ash. C.C. of urine.260.1 488.5 3.57 4.49 12.9 8-15 1400 17.60Composition of Fcwes.Nitrogen .......... 7.35 per cent.Bats .............. 9.26 ,,Ash .............. 16.80 ,,Dry substance ......9.1 per cent.Nitrogen. ........... 17.5 ,,Carbohydrates ...... 3.6 ,,Ash ................ 32.5 ,,NeCl .............. 1.0 ,,Faxes. Carbo- Urine, NThere was, therefore, a daily loss of-Fat ................ 63.9 ,,The anthor then goes on to state, that the diet was theoreticallyample in all its constituents for the individual experimented upon.He then raises the question as to whether the albuminoids of the?leguminoseae are more or less digestible than those of wheat, andcompares the result of experiments with pease with experiments onmaccaroni :-Per cent.Food. N of food. N of faxes. N lost.Maccaroni.. ...... 22.7 2.5 11.2Pease.. .......... 20.41 3-6 17.5which is in favour of the albuminojids of wheat.be summarised as follows :-The results of a further experiment with beans are given, and maPHY SIOLOQICAL CHEMISTRY.189Daily Loss.Dry substance ........ 15.03 per cent.Fats.. . . . . . . . . . . . . . . . 8.51 ,,Carbohydrates ........ 15.39 ,,Ash.. ................ 22.82 ,, w. N.Effects of Alumina Salts on Digestion. By H. A. MOTT(Analyst, 1880, 5, 16@-161).--The results are described of feedingdogs with biscuits made with alum baking powder and also with meatmixed with precipitated hydrate of alumina, phosphate of alumina,and burnt alum respectively. Vomiting was occasioned in almostevery case, and looseness of the bowels, followed by constipation. Nosuch effects resulted from the use of cream of tartar baking powder.The artificial solution of fibrin by gastric juice in presence of theabove-mentioned aluminium compounds was incomplete, and the solu-tion of coagulated albumin was entirely prevented.Dogs fed on food containing the aluminium compounds for fourdays were killed, and alumina was found in thg blood, heart', liver,spleen, and kidneys.F. c.Researches on Tissue Change in Five Children Aged fromTwo to Eleven Years. By CAMERER (Zeits. f. Biol., 16, 24-41).--The author's investigations comprise six series of experiments of fourdays each, made between September, 1878, and August, 1879 ; four ofthe children have already been the subject of experiment (Correspon-denzblatt cles Wurt arztlichen Vereins, 46, 11 ; and Zeits. f. Bid., 1878).The results of observations on the body-weight, urine, and faeces, andanalyses of the foods, are given in 14 tables, to which it is onlypossible here to refer on some points.The increase of body weightwhich may to a certain degree be regarded as an expressionof the rateof growth, is somevhat irregular. In the case of the oldest child (agirl born April lst, 1878) the daily increase of weight calculated fromobservations made in September and November, 1878, and January,March, April, July, September, and October, 1879, was on an averageas follows :-15.6 grams, -2.4 grams, 2.5 grams, 5-3 grams, 22.1 grams, 0.0 gram,42 grams. The reason of this irregulasity is, no doubt, the variationsin the rate of flesh and fat formation which occur both in childrenand in adults.The mean of all observations give the daily increase of weight perkilo. of original weight for the individual children as 0 4 gram.(eldest), 0.31, 0.27, 0.36, 0.52 (2nd year), 0.36 (3rd year).The mean daily urea excretion was : 15.1, 14.9, 7.0, 5.9, 8.4 gramsfor the respective children, with some rather important variations ;calculated as excretion per kilo.of body weight the 24 hours' ureagives as a mean, 0.64 gram, 0.66 gram, 0.81 gram, 0.83 gram, 1-12gram. The urea excretion of the younger children is greater thanthat of the older. The greater part of the nitrogen of the food wasaccounted for in that of the urine and faeces, e.q., 96.2, 95.7, 99.5, 94.4,and 93.3 per cent. w. N190 ABSTRACTS OF CHEMICAL PAPERS.Importance of Lime to the Animal Organism. By E.VOIT(Zeits. f. B i d , 16, 55--lls).-The plan of the author’s investigationwas to observe the effect of the withdrawal of lime from the food.The importance of putting the animal on a strictly normal diet isinsisted on, and the author draws attention to the fact that this is apoint to which sufficient regard has not been paid by experimenterson this subject. The control over the condition of nutrition lies eitherin the accurate determination of the ingesta and egesta, or in com-parisons with a test animal fed on precisely the same diet both as toquantity and quality and amount of lime contained in it, and which inweight, breed, and other points differs as little as possible from theactual subject of experiment. The researches were first of all madeon growing animals in which the rile of certain calcium salts isundoubtedly important.An experiment is communicated by the author, made upon pigeonsby Dr.Tucrek. The chief experiments were made upon dogs of alarge breed.For the fird experiment three pigeons of the same brood and threeweeks old mere used : (u) was killed at the beginning of the experi-ment, ( b ) and (c) were fed on wheat washed in water, and ( b ) withspring water with pieces of mortar in it, (c) on distilled water only ;( b ) died on the 13th day from unknown causes, (c) was killed on the30th day and was found to be well developed, only the bones appearedto be a little less capable of offering resistance than normal. Thebody weight had risen from 171.7 grams to 286.7 grams.With thewheat 0.362 of lime was taken in, of which 0.356 gram was found inthe excreta; the bird therefore assimilated only 0.012 gram.A puppy of smallbreed, four weeks old, was fed on flesh-meal and bacon exclusively.The animal, on this diet, increased in weight and size, and on the 85thday exhibited no abnormality. At this time the first symptoms ap-peared, namely,-disturbances of locomotion, having their origin indefective formation of the skeleton ; later marked signs of rachitis,swelling of the epiphyses, crookedness of the extremities and of thespinal column. On the 162nd day of the experiment the animal waskilled. The muscles appeared well developed and all the organsnormal, except the bones, which all exhibited well-marked signs ofrachitis.For the third experiment the author selected three puppies 19 daysold from the same litter.For the first 20 days they were fed onmilk, then for five days on a mixture of four parts flesh and one ofbacon. (A) was killed a t once, (B) and (C) fed for a further periodon the same mixture, (B) had spring-water and bone-ash sprinkledin it, (C) ,had distilled water only. (B) remained normal to theend of the experiment, (C) early lost its liveliness and appetite, andsoon exhibited symptoms of rachitis. On the ‘29th day both dogswere killed. (B) was in every respect normal, (C) exhibited abnor-malities only in its osseous system. The bones had the same lineardimensions as those of (B), but were altogether more pliant andshowed the characteristic swelling of the ends.Microscopical inves-tigation indicated rachitis and not osteo-malacia. The body-weightsThe chief investigations were made with dogsPHYSIOLOGICAL CHEJIISTRT. 191were at the beginning of the experiment-(A) 3,025 grams, (B) 3,235gmrns, (C) 3,275 granis ; at the end (B) 4,510 grams, (C) 4, $10 grams.The growth of the animals was not prejudiced by the want of limein their food so long as that did not interfere with their appetite.The general results of' these experiments agree with those of Weiskeand Roloff.Further researches were then made 011 the weight of the organs andthe amount of dry substance they contained. The result obtained wasthat the increase of weight and growth of the dog (C) accorded in allrespects very closely with that of the dog (B) ; the liver being the onlyexception, the increase being, in the case of dog (B), 47.5 gra'ms, dog(C) 80.5 grams. The increase of weight of the skeleton, including car-tilages, was-(B) 225-6 grams, (C) 284.9 grams.The dry weights ofthe organs show this relation ; the bones are an exception, those of thepathological dog were considerably richer in water, viz., 71.9 per cent.against 64.9 per cent. in dog (B), and 66.2 per cent. in dog (A), thedry weight increase of the skeleton being in (B) 93.7 grams, and in(C) only 52.6 grams. The results of the analyses of the ash of theorgans are given in a series of tables ; they tend to the following con-clusions :-That the blood of a young animal coritains more lime saltsthan that of an adult ; that the iron in the organs and blood of thedog (C) was less than in (B) ; the blood of (B) contained 5.44 percent.haemoglobin, that of (C) only 4.53 per cent.The investigatioa of the bones gave t h e very unexpected result thatthe lime salts reckoned from the dry substance in (C) were not less,but a little gyeater, than in (B); e.g., for the dense parts of thehumerus, CaO in (B) 32-77' per cent., (C) 34.62 per cent. ; cancellousparts, (B) 29.23 per cent., (C) 30.96 per cent., and so also for thescapula ; the bones were, however, not analjsed in the fresh state, butafter maceration, and the author thinking that this might in somedegree account for the result, made some experiments on the bonesof a pigeon, which entirely confirmed the opinion.The author also investigated the quantity of lime necessary for thegrowing animal, and how far it was expressed in the food, and hecomes t o the conclusion that for human beings the transition froman exclusive milk diet to a mixed diet may result in a considerabledeficiency of lime salts, unless the very variable quantity of lime takenin the drinking water be taken into account, which, as one of the ex-periments here described, shows may be sufficient for the purposes ofthe animal.A purely flesh diet is the poorest in lime, as Forster hasshown. The author points out that the adult dog on' a flesh dietexcreted more lime salts than it ingested. (Per1 has also deter-mined this in his experiments on a dog in nitrogenous equilibrium---the ingested lime was 0.1215 gram and the excreted 0.3575.[SeeCed. f. d. 1Cfed. Wiss., 1875, 532.1).With regard to rachitis in children, the author agrees with thegenerally-accepted idea that the prescription of lime in cases in whichthere is disturbance of the digestive powers-and these are the mostnumerous-cannot be of use. W. NI92 ABSTRACTS OF CHEMICAL PAPERS.Urine after. Administration of Quinine and Morphine. By A.BORNTRAGER (Arch. Pharm. [3], 14, 118--120).-Urine, after adminis-tration of quinine, turns the polarised ray from 0.3 to 0.4 to the left.The author could not discover any morphine in the urine of a personwho daily took large doses of the alkalo'id, whilst if this was subcuta-neously injected, morphine reactions could readily be obtained fromthe urine.0. H.Formation of Urea in the Animal Organism. By E. DRECIIREL(J. pr. Chew. [a], 22, 47G--488).--The various theories that havebeen suggested in relation to the formation of urea from nitrogenousfood are discussed, and it is shown that most of the reactions that havebeen suggested require conditions with regard to temperature, &c.,other than those existing in the animal organism. The author haspreviously shown that salts of caybamic acid are formed by the oxidationof glycocine, &c., in alkaline solution at the ordinary temperature, andhe considers it probable that ammonium carbonate is the immediatesource of urea, into which it can be converted by removal of theelements of water. The process of elimination must be such as to becapable of occurring in aqueous solution and a t a temperature notexceeding that of the animal body, and may consist either in thedirect removal of water or in the successive elimination of hydrogenand oxygen. This latter may be effected under the conditions above-mentioned in the following manner :-A solution of ammonium car-bonate is submitted to B galvanic current whose direction is rapidly re-versed by a self-acting commutator ; the electrodes being thus renderedalternately positive and negative produce successive oxidation and re-duction, and iu about eight to ten hours the ammonium carbamate isfound to be converted, with but slight loss, into urea. A. J. G

ISSN:0368-1769    

DOI:10.1039/CA8814000187

出版商:RSC    

年代:1881

数据来源: RSC

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192 ABSTRACTS O F CHEMICAL PAPERS.A n a l y t i c a l Chemistry,Apparatus for the Estimation of Nitrogen in Organic Com-pounds. By FLAVART ( J . Pharm., 1,503-504) .-This apparatus, whichis made of copper, is employed for the estimation of nitrogen in desic-cated urine by means of Willand Varrentrapp’s method. The plan re-commended by Washburne ( B d . SOC. Chim., 1876, 490) of evaporatingthe urine to dryness with plaster of Paris and oxalic acid is adoptedi n this case, but the precaution of drying the soda lime is unnecessary,since all risks of cracking from moisture coming in contact with thehot parts of the flask are avoided. L. T. 0’s.Apparatus for the Collection of Nitrogen in ElementaryBy YV. STAEDEL (Zeils. Anal. Chew., 1880, 452-455).-Simple Aspirator.By F. Lux (Zeits. Anal. Chern., 1880, 455-Analysis.Very similar to others recently described in the Berichte.4S7).-Slight modification of Bunsen’s filter-pumpANALYTICAL CHEMISTRY. 193Solution of Bromine as a Reagent. By L. L. DE KONTNCK (Zeits.Aizd. Chem., 1880, 4C;8).--Uromine-water being too dilute, and asolution of bromine in hydrochloric acid too acid for many purposes,the use of a 10 per cent. solution of potassium bromide as solvent forbromine is recommended for oxidation of As2S, into H,As04 for pre-cipitation of manganese and for detection of nickel in presence ofcobalt. 0. H.Flavescin, a New Indicator. By F. Lux (Zeits. A m l . Chew.,1880, 457-467) .-Having observed that commercial spirit frequentlyassumes a strong yellow coloration on addition of alkali, the authorfound the reaction to be due to the presence in the spirit of certainextractive matters which had been taken up from the wood of thespirit casks.He obtained these matters-to which he gives the namejlnvescin, (from j h e s c e r e , to turn yellow) by heating chips of oa,k a t220-260" and passing over them a current of moist air. The dis-tillate thus obtained, containing tarry matters and acetic acid, isfiltered, shaken up with ether, and the ethereal solution evaporated.The residue forms a tenacious, transparent, yellowish mass, soluble inwater, alcohol, and in ether, yielding practically colourless solutions,which become yellow on the addition of alkalis or their carbonates,but not by bicarbonates, the yellow coloration being destroyed byacids, even carbonic acid.Lux proposes flavescin as an indicator in alkalimetric titrations, fordetermination of caustic alkalis and bicarbonates in the presence ofmonocarbonntes, and for the estimation of carbonic acid in all itssolutions and combinations.0. H.Analysis of Gunpowder. By A. WAGNER (Zeits. Anal. Chem.,1880, 443-444) .-Fresenius states that the residue obtained after ex-traction of the nitre from gunpowder cannot be dried a t 100" withouta slight loss of sulphur. Wagner, on the contray, finds that no suchloss can be observed a t or below 100". Above that temperature theresidue suffers a notable diminution in weight.Determination of Sulphur in Pyrites. By G. LUNGE (Zeits.Anal.Chem., 1880, 419--431).-The author has carefully investigatedthe method of determining sulphur in pyrites, described by him in hisManual of Soda Manufacture, especially with a view to ascertainhow far the various sources of error inherent to the method, and whichhave been pointed out by Fresenius, would counteract each other.These sources of error are the solubility of barium d p h a t e in freehydrochloric acid and in ferric solutions, and the contamination of t h ebarium precipitate with ferric oxide. The author finds that consider-able quantities of iron always pass into the precipitate, such contami-nation being avoidable only by addition of large quantities of acid,considerable loss by solubility of the barium sulphate then ensues.Asa rule the errors very nearly counterbalance each other, the resultsbeing somewhat too low, but sufficiently accurate for commercial andtechnical analyses. He now recommends the removal of the iron byprecipitation with ammonia., previous to the precipitation of the sul-0. H194 ABSTRACTS OF CHEMTCAL PAPERS.phuric acid by barium chloride. If the ferric precipitate is v d lwashed with boiling water, it is invariably free from sulphate.Lunge prefers the oxidation of pyrites in the moist, way to fusionwith nitrate and carbonate, since the lakter method yields the w7de ofthe sulphur as sulphate, even in the presence of lead and barium,whilst the former gives the available sulphur only. 0. H.Quantitative Determination of Phosphorus and Silicon inIron and Steel.By A. E. HASWELL (Din$. pQhJt. J., 237, 314-316) .-This method depends on the completeness with which phosphoricacid is precipitated by inolybdate of ammonium in a solution of coppernitrate, strongly acidified with nitric acid ; ultimately weighing aspyrophosphate of magnesia, in the usual manner. Its simplicity andthe rapidity of its execution, compared with the other methods, notonly form a material point, but it has the advantage over the methodof digesting the borings in a solution of double chloride of copper andammonium, and redissolving the precipitated copper with an excess o fthe double salt, that it produces a t once a concentrated solution,wherein the phosphoric acid may be determined, apart from tlhe factthat a smaller quantity of the above reagent is used, hence the loss ofphosphoric acid, if any, is diminished.Estimation of Phosphoric Acid.By B. PEITZSCH and others(Zeite. Aizal. Ghem., 1880,444-452) .-A solution of sodium phosphatewas analysed in 12 different laboratories. The results obtained bysimple evaporation and ignition varied from 128.4 to 129.8 mgrms.PzO, in 25 c.c., whilst the figures obtained by precipitation with rnolyb-die solution and magnesia mixture fluctuated between 127% and135.7 mgrms. The authors find that the results are invariably too highif the magnesiati chloride mixture be added quickly to the ammoniacalsolution of the molybdic precipitate. I f the magnesium solution isadded drop by drop, with vigorous agitation, correct results are obtained,even if a, very large excess be employed.The magnesia precipitatemust be heated for five minutes with the blowpipe, after incinerationby means of the Bunsen flame.Detection of Zinc in Toxicological Cases. By R. OTTO (Arch.Pharn?. [ 3],14, 100-102) .-Chappuis has a.wertained (Jour. Pharm.Chirn., [4], 27, 403) that the whole of the zinc is to be found in thehydrogen sulphide precipitate, and not in the ammonium sulphideprecipitate, if the strongly hydrochloric acid solution obtained afterthe destruction of the organic matter is first neutralised by means ofammonia, and then slightly acidulated with hydrochloric acid previousto treatment with hydrogen sulphide.R. Otto confirms this observation, and recommends remo-ring theexcess of hydrochloric acid by evaporation instead of neutralisation :no trace of zinc then enters the hydrogen sulphide precipitate.D.B.0. H.0. H.Qualitative Separation of Cobalt from Nickel. By F. REZCHEL(Zeits. Anal. Chenz., 1880, 468-469).-The ordinary methods ofdetecting cobalt in presence of much nickel, namely, precipitation witANALYTICAL CHEMISTRY. 195potassium nitrite, or by means of chlorine, require much time. Thefollowing simple method of separation is founded on the difference insolubility of the hydrates in concentrated potash solutions. Thehydrates are precipitated by dilute potash. From solutions containingthe metals the precipitate is collected, heated with concentrated potash,and the solution, which in presence of traces of cobalt is deep blue,filtered through asbestos. 0.H.By E. FISCHER (Ber.,13, 1778--1780).--The process proposed by Schneider and F p e forthe separation of arsenic in toxicological analyses by distillation withhydrochloric acid is inexact. The author recommends the addition offerrous chloride as a reducing agent before distilling with hydrochloricacid, the arsenic is thus separated as a trichloride from the othermetals of the sulphuretted hydrogen group, including tin and antimony.The arsenic in the distillate is estimated either as the trisulphide, orby titration with iodine solution ; the metals in the residue are separatedfrom the iron, and estimated by known methods. To ensure successi t is necessary that the distillate should pass over into hydrochloricacid, and that no trace of nitric acid should be present.Separation and Estimation of Arsenic.V.H. V.Detection and Estimation of Arsenic. By E. R'EICHARDT( A ~ c h . Pharm. [3], 14, 1--23).-The author recommends, as far saferand simpler than Marsh's method, that first described by Lassaigne,consisting in the action of arsenic hydride on silver niti-ate. The silversolution should be strongly acid with nitric acid, aqueous or ammoniacalsolutions only partially affectiag the decomposition of arseniurettedhydrogen. 0.001 mgrm. of arsenious anhydride, still furnished a plainrea,ction, and the author could thus readily detect arsenic in the urineof persons suffering from chronic poisoning through arsenical wallpaper.The vessels used for generating the gas should not hold morethan about 30 c.c., the gas itself being produced from zinc and hydro-chloric acid. If the current be very slow, the whole of the arsenicis found in the silver solution, but not as arsenious acid only, asusually stated, but partially as arsenic acid, and to a very small extentin the silver precipitate. Although antimony, as is well known, alsoproduces a blackening of the silver solution, it remains almost entirelywith the zinc in the gas-generating bottle.For the deternziszation of the arsenic, the author adds a slight excessof bromine-water to the silver' solution, after the whole of the arsenichas been collected in it, the end of the reaction being readily visibleby the settling of the precipitate.From the filtered liqnid the arsenicis precipitated as ammonium magnesium arsenate-The quantitative experiments quoted by the author are very satis-factory, but the method appears only adapted for the determination ofminute amounts of arsenic. 0. H.New Method for the Estimation of Arsenious in Presence ofArsenic Acid. By L. MAYER ( J . pi*. Chem., 22, 103--105).--Arse-nious acid reduces ammoniacal silver solutions a t a boiling heat, accord-ing to the equation, As203 + 2Agz0 = AszO5 + 2Ag,. The reduce196 ABSTRACTS OF CHEMICAL PAPERS.silver must be washed with warm ammonia and water containing alittle sal ammoniac before weighing. As the arsenious is thus con-verted into arsenic acid, the latter may also be estimated.No otherbody capable of reducing an ammoniacal solution of a silver salt mustbe present. The method gives exact results. G. T. A.Analysis of Bismuth Subnitrate. By E. BAUDRIMONT (J.Pharm. [ 5 ] , 368--373).-The principle involved in this method is thatof precipitating a given weight of bismuth subnitrate with a knownvolume of a standard soda-solution, and estimating the excess of alkali.The alkaline solution contains 7.407 grams NaHO per litre, of whicheach C.C. = 0.01 gram N205, the acid, which is standardised to thealkali contains 9.074 grams H,SO, per litre. 1 gram of the subnitrateis dissoved in 100 C.C. water, and treated with 20 C.C. alkali and 30 C.C.water, and boiled for ten minutes. The total volume is made up to100 c.c., and the precipitated oxide filtered through a dry filter-paper.Iu a given volume of the filtrate the excess of alkali is determined, andfrom these data the amount of N,06 calculated.The bismuth is esti-mated by drying and weighing the precipitate, or by igniting a freshppor$ion of the subnitrate. On igniting commercial bismuth subnitrate,a white or yellowish mass is obtained, instead of the orange residue ofbismuth oxide ; tbis is probably due to the presence of bismuth phos-phate. The author is investigating the subject. L. T. 0’s.Determination of Ash in Coal and Coke. By A. WAGNER(Zeits. Anal. Chew., 1880, 432-434).--Experiments are given to showthat complete incineration of coal and coke can be conveniently ob-tained only b r the use of the muffle or of the blowpipe, whilst the heatof the Bunsen flame is insufficient.Estimation of Organic Carbon in Potable Waters.By A.SJIETHAM (Analyst [lSSO], 5, 156-159) .-The author acidifies 1 litreof the water with phosplioric acid, evaporates t o about 50 c.c., andtransfers to a, small tubulatecl retort, the neck of which is connectedwith three absorption tubes, the last of which contains baryta-water.By means of an aspirator, air freed from carbonic anhydride is drawnthrough the tubulure of the retort and the apparatus ; 20 C.C. of clearbarytn-water is then filled into the first absorption-tlube, the second isalso charged, and the liquid in the retort is boiled until steam entersthe first absorption-tube ; if this causes any turbidity, the boiling isfurther continued until the carbonic anhydride is completely expelled,and the baryta-water is then replaced by fresh.As Soon as the retort has cooled, 1 gram of potassium dichromate,1 gram of pot,assium permanganate, and 20 C.C.of sulphuric acid of1.4 sp. gr. are introduced ; the distillation is then slowly proceededwith until only 20 C.C. remain in the retort; the carbonic anhydrideshould be entirely absorbed in the first tube, the second serving as atell-tale, and the third to guard against carbonic anhydride from theair. The barium carbonate precipitate is filtered off and washed, withdue precautions against exposure to the air: it is then dissolved inhydrochloric acid, and the barium precipitated, and weighed as sul-ph at e.0.HANALYTICAL CHEMISTRY. 197The points requiring attention are the perfect expulsion of carbouicanhydride from the water before beginning the oxidation process, theperformance of blank experiments with the reagents used to ascertaintlheir purity or the slight correction necessary, and the completewashing of the barium carbonate produced without allowing absorp-tion of carbonic anhydride from the air. The distillation shouldproceed slowly, and the steam should be condensed in the first leg ofthe first U-tube.The results obtained from known quantities of various organic sub-stances were satisfactory; but urea yielded only 80 per cent. of itscarbon unless distilled again with further addition of‘ sulphuric acidand permanganate.Abstra~tor’~ Note.-The author leaves out of consideration the effectproduced by nitrates during the evaporation with phosphoric acid :oxidation of the organic matter present would take place to some ex-tent, and render the carbon estimation too low.F. c.Determination of Carbon in Water Residues. By F. PEREIPI’S(Analyst [1880], 5, 124--126).-The author suggests a simplifiedprocess for determining carbon in water residues ; it is a modificationof Dittmar’s process, suggested by Perkin’s plan for decomposingnitrogen oxides, and also absorbing sulphurous anhydride evolvedduring the combustion of a nitrogenous organic substance.A rather narrow combustion-tube is drawn out at one end, andcharged with a mixture of potassium chromate and dichromate, andcopper oxide, space being left for the introduction of the platinum boatcontaining the water residue behind this mixture.After the boat hasbeen inserted, the end of the tube is connected with potash-bulbs, itsanterior drawn-out end being joined to two U-tubes, the first of whichcontains calcium chloride, and the second soda-lime, protected fromloss of moisture by a small guard-iube of calcium chloride. The com-bustion is carried on in a stream of air drawn through the apparatusbvan aspirator, care being taken not to heat the front part of the tubestrongly. The apparatns can be used repeatedly for successive com-bustions at short intervals without being charged afresh.After charging the combustion-tube, the tube and its contentsshould be ignited in the air-stream until, when the air is passed throughbarytn-water, no turbidity is produced : it is then ready for use.The results are fairly concordant when the same sample is re-peatedly analysed.B ~ S ~ T ~ C ~ O T ’ S Note.-This method is open to the objection that itleaves undetermined the organic nitrogen contained in the waterresidue, which is really for sanitary reasons of greater importancethan the carbon determination. F.C.Detection of Methyl Alcohol in Ethyl Alcohol. By CAZENWVEand COTTON (J. Pha.rm. [ S ] , 2, 361--367).-Ethyl alcohol is onlyslowly oxidised by potassium permanganate, whereas methyl alcoholis instantly attacked. On this property the authors have based amethod for the detection and estimation of methyl alcohol in ethylalcohol by noticing the time required for the formation of a brownVOL.XL. 198 ABSTRACTS OF CHEMICAL PAPERS.oolour when a given volume of potassium permanganate solution(1 in 1,000) is added to a given volume of alcohol, and also the depthof colour which varies from a yellow to mahogany brown, according tothe quantity of permanganate added.The following table gives the coloration produced by permanganatesolution (1 in 1,000) added to ethyl alcohol, containing different pro-portions of methyl alcohol : temperature 20" :-Alcohol.Ethyl alcohol . . . . . . . .Ethyl alcohol and 10 percent. methyl alcohol(me th ylat ed spirits)Ethyl alcohol and 8 percent. methyl alcoholEthyl alcohol and 5 percent. methyl alcoholEthyl alcohol and 3 percent.methyl alcoholEt,hyl alcohol and 1 percent. methyl alcoholTime.Instant ofaddingAfter 5 mins.,Y 10 Y,9 , 15 Y Y$ 9 20 Y YInstantly . .Instantly ,.4 seconds ..15 ,, ..(Instantly. *l.5 minutes1 c.e.reagent.Rose colourYellowishYellow roseYellow, wit8hrose shadeYellowYellow . . . .--roseYellow .. ..Yellow .. ..Yellow .. . .Pink, withshade ofyellowYellow~ ~~~~5 C.C.reagent.-.-Rose colourMahoganybrownYellow ofburnt sugarYellow ofburnt sugaiMahoganybrownMahoganypink10 C.C.reagent.MahoganybrownMahoganybrownMahoganybrownShould the alcohol contain other organic substances which arereadily acted on by potassium permanganate, it should be diluted withwater to separate the resins, and distilled to free it from sugar, &c.L.T. 0's.Wine from Raisins. By REBOUL (J. Pharm. [ 5 ] , 2, 117-121and 201-207) .-The author discusses in detail the difficulties attend-ing the detection of the presence of wine from raisins in wines madefrom the natural grapes, and has prosecuted the following research,with a view to establish a satisfactory means of attaining thatobject.The method (Moniteur VirticoZe, Jan. 17, ISSO), which is founded onthe left-handed rotatory power of the wine from raisins, is to be re-jected, since it does not hold good for all such wines, '' vin de Vourla"turning the plane 1" to the right; and moreover some wines pre-pal-ed from the natural grape are laevorotatory, the rotatory power of" vin de Bon Secours " (Marseille) being - 26".That of P.Muller based on the presence of Sa,ccharomyces cerevim inthe dregs of natural wines adulterated with glucose or wine fromraisins, has not found confirmation in the hands of the author, whANALYTICAL CHEMISTRY. 199Grams re-ducing sugarper litre.has failed to detect these germs in the wines of Thyra, Vourla, andCorinth, but found the species Sacclmcernyu.One distinguishing feature of the mincs from raisins, but whichmust be accepted with some reserve, is the large proportion of gumwhich they contain in comparison with the natural wines; vin deVourla containing 1.9 in 1,000, vin de Corinthe 2.4 in. 1,000, whereasthe wines of Ande, Hbrault, Burgundy, contain only 1 in 1,000, andChablis 0.6.However, vin de Var contains 2.03, and some othersstill more. still if the amount of gum exceeds 2 in 1,000 adulterationmay be suspected.A still more decisive characteristic is the large amount of reducingsugar which the wines from raisins contain, being, according to thelength of time the wine has been kept, from 5 to 3 times that usuallycontained in ordinary wine as is seen in the table:-Wines from naturalgrapes.Wines from raisins5-4 months after manu-facture.Vin de Corinthe ........Vin deThyra (1). .......,, ), (2).. ......Vin de Tourla (I) ......,,. ), (2) ......I---10 *419 -0611 -008 -2019 -00Vin de Tar ............Vin de Fr6jus ..........Vin de Chablis.. ........Vin de Corse (1) ........ .. . . (2) ........Vin de Tallone (1975). ...Vin de Sollacaro (1877) . .Vin d'Olmento (1877). ...Chams re-duoing sugarper litre.2 . 82 -62 *71 *51 . 73 -27.38.5The two last examples of natural wines from Corsica show anexception to the law, as do also some Italian wines; but should thequantity of reducing sugar rise above 8 parts per litre, the wine is tobe suspected.Another means which serves to distinguish between the two classesof wines is the ameunt of solid extract they contain ; that in, winesfrom raisins varying from 39 to 30.5 grams per litre, and containingonly about one-tenth of its weight of ash, whilst in natural wines it isonly about 10 grams per litre.Special care is required in estimating the quantity of gum presentin the wine, the following process being adopted by the author:-100 C.C.of wine are evaporated until the weight of residue is 7-8grams, which is allowed to stand for 24 hours, when nearly all thecream of tartar sepaaates out. It is filtered, and the residue washedfour times with 5 C.C. alcohol (40-42 per cent.). To the filtrate100-110 C.C. alcohol (92 per cent.) are added, stirring the liquid allthe time to prevent the formation of viscous masses. After standing24 hours, the gum separates out, adhering to the sides of the vessel,the liquid is filtered, and the gum washed with 25 C.C. alcohol (85 percent.), and dissolved in water. The hot solution is filtered, and thefiltrate evaporated at loo", until its weight is constant.On ignitionthe amount of ash is determined..The results furnished are200 ABSTRACTS O F CHEMICAL PAPERS.Per litre of-----------Vin de Corinthe ..............Vin de Thgra ................Tin de Vourla.. ..............Crude gum. Ash.grams. grams.3 *05 0.643 -96 1-383 *32 1-50Gum.grams.3 *705 .964 '72grams.2 '412.581 *32grams.0.551 so02 -69The wines of Ande, Hhrault, and Burgundy contain about 1 gramper litre ; exceptions are shown in the following cases :-Per litre ofVin de Sollacaro (18'77) ........Tin du Var (plastered) ........ Vin d'Olmeto (18774 ...........Crude gum. 1 Ash.I-- --Gum.grams.2.154 *962 -03It may be generally stated, however, that a greater proportion ofgum than 2 in 1,000 is characteristic of wine from raisins.The ash, about half the weight of the crude gum, consists chiefly ofpotassium sulphate, and some calci am phosphate.The rotary power of the gum is -22*8", and compared with thatof the reducing @ugar.as 1 : 6.5 about.The estimation of cream of kartar was made by a special methoddevised by the author, since that of Pasteur was found to yield resultsmuch below the true .amount.100 C.C. of the wine are treated in themanner described for the estimation of the gums, t'he cream of tartarthus obtained, after washing with alcohol, is dissolved in hot water,and the solution titrated with baryta-water (1 C.C. = 0.0015 CIH5KOB).The quantity of cream of tartar reiriaining dissolved in the 8 grams ofwine is very small, amounting to about @012 gram.The check ex-periments prove the value of this method, the results of which com-pared with those obtained 'by the ordinary method are as follows :-Vin der Corinthe ............Vin de Thjra.. ..............Tin de Vourla ..............Vin ciu Var (plastered). .......Vin de Come . . . . . . . . . .Vin d'Olmeto (1877). .........Vin de Sollacaro (1877) ......Tin de Bons Secours (1829) . .Grams of cream of tartarper litre.The abovemethod.3 6753 -821 7 83 .643 .401.343 -561 -47Ordinarymethod.3 -102 -300 *962 -1---0.9ANALYTICAL CHEMISTRY 201Tables are given of the rotatory powers of the two classes of wine,from which it is concluded-(L.) That the wines from raisins.do not always turn the plane ofpolarisation to the left.(2.) That whereas, for the most part, the wines of the South aredextrorotatory, pet exceptions are furnished in the cases of the winesof Corsica, Ssllacaro, Olmeto, Sainte Lucie (1873), Tallano (1866),and Bon Secours (1829).(3.) When the alcoholic fermentation is not complete, and sugar isleft in the wine,. the lzvorotatory power increases with age, and some-times the rota.tory power may change from right to left, since in amixture of glucose and levulose, the glucose is the first to undergofermentation.In the other constitumts of the wine no very marked differenceoccurs between the two classes. L. T. 0’s.Estimation of the Insoluble Fatty Acids in Butter.By J.WEST KNIGHTS (Analyst, 1880 [5], 155--156).-The author hasadopted a method for separating the insoluble from the soluble fattyacids of butter depending on the insolubility of the barium or calciumsalts of the former, the corresponding salts of the latter being readilysoluble. It is claimed for the new process that it obviates the diffi-culty experienced in washing t’he fatty acids with watter, and in trans-ferring them without loss to a vessel in which they can be dried andweighed. The barium salts were found most convenient to manipulate,since barium oleate shows less tendency to adhere to the sides of thevessel or to unite into a plastic mass than calcium oleate. The directweighing of the barium salts was given up, partly from the difficultyof precipitating them free from carbonate, and also because theirunited weight would not give comparable rcsults for different kinds offat, the basicity of the fatty acids present being different.The method is carried out as follows :-From 1 to 3 grams of clari-fied butter fat is saponified by heating it on the water-bath with twicejts volume of alcoholic potash, and occasional addition of a few dropsof boiling water for twenty minutes. The solution is diluted to300 C.C.with cold distilled water, and is completely precipitated withliarium chloride solution, the precipitate is filtered off, washed withwarm water and transferred to a long stoppered tube one inch indiameter throughout, and of 250 C.C. capacity ; the tube is graduatedfrom below upwards, and furnished with a stopcock a t the 50 C.C.mark. Tlie precipitate is rinsed into this tube with water, and hydro-chloric acid is added : 100 C.C.of ether is then poured in, and the tubeis well shaken and allowed to stand until the two liquids sepa,rate. Ifthe aqueous solution rises above the 50 C.C. mark it is run off throughthe stopcock by inclining the tube, unbil the ether solutiori extendsbelow the stopcock when the tube is erect. If the contents of thetube before the introduction of the ether rises above the stopcock,50 C.C. only of ether are added a t first, and after shaking and allowingto stand, some of the solution is drawn off as directed above, and theremaining ether is then added and mixed by shaking.Tlie volume of ether solution is then noted, about 1 C.C.is run off s202 ABSTRACTS OF CHEMICAL PAPERS.as to fill the delivery tube, and a measured quantity is receivedinto a tared flask, the ether is distilled off, and the residue of fattyacids weighed. The results are concordant and satisfactory.F. C.Estimation of Fatty Acids in Oils. By CARPENTIN (J. PAarni.[5], 1, 501-502).-50 C.C. of oil and 100 C.C. of alcohol are placed ina flask with a few drops of turmeric solution and well shaken. Asolution of soda (40 grams per litre = 282 oleic acid) is dropped intothe mixture until the alcoholic solution assumes a red colour, and itis then well shaken until the red colonr disappears from the alcohol,taking up a fresh portion of acid froiii the oil.More soda solution isadded, the mixture again shaken, and the process continued until the redcolour of the turmeric is permanent. Since the operation is casriedon in the cold, and the alcohol takes up less than part of the oil,there is no danger of saponification.This method may be employed for testing the acidity of alimentary,lighting, and lubricating oils. L. T. 0's.Analysis of Heavy Mineral Oils, of Resin and Fatty Oils, andof Resin in Oils of Commerce. (Part IT). By A. R~XONT(J. Pharm. [ 5 ] , 2, 136-140 and 213-216. (Part I, this Journal,38, 683) .-Qualitative Analysis.-T he specific gravity of the oilaffords one of the best clues to its composition. An oil of sp. gr.less than 0.900 is certain to contain mineral oil: a sp. gr. of 0%j00-0.975 shows the oil to be a more or less complex mixture, whilst aresin oil has a specific gravity above 0.975.The oil is treated with distilled carbon bisiilphide free from sulphur,whereby in all cases a clear solution is obtained, unless an alkali basbeen added to oil containing oleic acid, when the soap formed remainsundissolved.The residue is collected, washed with carbon bisulphide,and tested for soap. The carbon bisnlphide is distilled from the filteredsolution, and 1 C.C. of the residue is treated with 4 C.C. alcohol a t 85" ;a clear solution indicates the presence of fatty acids. This solution ismixed with 50 C.C. of alcohol, added by degrees. A clear or slightlyclouded liquidwhich becomes clear on adding a few drops of hydrochloricacid, indicates the presence of oleic acid, pure or mixed with resin.A sp.gr. 0.908 shows the oil to consist of oleic acid. A higher sp. gr.is due to the presence of resin, which may be confirmed by its actionon polarised light. If the turbidity remains after addition of hydro-chloric acid, and on standing oily drops separate out a t the bottom ofthe liquid, some oil insoluble in alcohol is present.As is often the case, 4 parts of alcohol are insufficieiit t o dissolve1 part of the oil ; it is then necessary to agitate a larger quantity ofthe latter with its own volume of alcohol, and evaporate the alcoholicsolution and test the residue.Saponilficntioit.-20 grams of oil are heated at 100-llOo, andtreated with 105 C.C. soda solution, sp.gr. 1.324, and 10 C.C. alcohol,and evaporated nearly to dryness. 150 C.C. water are then added andthe mixture boiled for half an hourAXALPTICAL CHEMJSTRY. 203I. An emulsion is thus produced, and if on adding water a clear oilfloats on the surface a mineral or resin oil is present. On decantingt,he aqueous solution, and adding sulphuric acid to it, if the oil ismineral oil, no precipitate is produced. On the other hand a precipi-tate collecting in viscous brown drops shows the presence of resin oil.This may be confirmed with the polariscope; a sp. gr. below 0.960indicates a mixture of mineral and resin oil.Another means of detecting a mixture of mineral and resin oil is tocarefully fractionate the oil into about 5 parts, and take the specificgravity of each fraction, which will be found to differ from those ofthe corresponding fractions of the pure oils.The reaction with stannic chloride (this Journal, 38, 683) mayalso be applied, and if the violet colour is not very distinct in theoriginal oil, the reaction should be tried with the separate fractions.11.A pasty soap is formed which is soluble in water. Thesolution is neutralised with hydrochloric acid, and the fatty acidswhich separate out are melted ; after cooling, a portion is treated with4 parts of alcohol. (a.) If the solution is clear, it indicates pure fattyoil, or what is rarely the case, a. mixture of fatty and resin oils. Thespecific gravity is an indication of the purity. Baudouin has compiledtables of the specific gravity of the fatty acids of the different oils attemperatures of 30", and in order to compare the specific gravity of anoil a t to with the table, it is only necessary to add or subtract from theweight of a litre of the oil at to, 0.64 gram x t, according as to is higheror lower than 30".The specific gravity of the fatty acids of linseedoil is 0.910, for the other oils it varies from 0.892 to 0.900. It thespecific gravity indicates the presence of a resin oil, a portion of theoriginal oil is heated with alcohol, the alcoholic solution evaporated,and the residue tested with the polariscope.( b . ) A turbid solution is obtained, remaining so on addition of hydro-chloric acid, oily drops separating out ; this indicates the presence ofmineral or resin oil.If solid flakes separate out, the presence ofearth nut oil is to be suspected, since the fatty acid it contains issoluble in a small portion of alcohol, but is precipitated by excess.The flakes of arachidic acid (m. p. 73") are soluble in soda.111. A semi-pasty mass is obtained, and on boiling with water oilydrops separate out, floating on the surface; mineral and resin oils art'present. I n this case the aqueous solution is decanted, and the soapprecipitated with common salt. The filtered liquid has a pale colour,and on adding hydrochloric acid, an odour of fatty acid is evolved, anda slight turbidity is produced, indicating the presence of a neutral oiladded to a non-saponifiable oil. If the solution is dark coloured.andon adding an acid a resinous odour is evolved, and a voluminous pre-cipitate formed, the oil contains resin.Quantitative Analysis.-If the oil is not completely dissolved inca,rbon bisulphide, the solution is filtered, and 20 grams of the residue,left on distilling off the bisulphide, are treated with 15 C.C. causticsoda solution, sp. gr. 1.324, and 15 C.C. alcohol 90-95" ; after heatingon a water-bath for half an hour, the mixture is allowed to stand, andthe alkaline solution decanted. The saponified oil is treated withboiling water, dried, and weighed. Any oil adhering to the side o204 ABSTRACTS OF CHEMICAL PAPERS.the vessel in which the washing takes place is dissolved in ether, andafter evaporation of the solvent, the residue is weighed separately.The alkaline solution is boiled to free it from alcohol, and the soapprecipitated with sodium chloride (free from magnesium) , carryingdown with it the last traces of non-snponifiable oil.The solution de-canted from this and neutralised with hydrochloric acid, gives a floccu-lent precipitate of resin which is collected and weighed. The soap iswashed twice with salt solution, pressed between filter-paper, andallowed to stand for one or two hsours in contact with 100 C.C. carbonbisulphide, when the nnsaponifiable oil is dissolved, coloiiring theliquid yellow ; this is decanted, arid the soap similarly treated untilthe carbon bisulphide is no longer coloured. The carbon bisulphide isdistilled, and the residue of unsaponifiable oil weighed ; it sometimescontains small quantities of aoap dissolved in it, in which case itis treated with a little water and warm carbon bisulphide, the formerdissolves the soap and is separated.The unsaponifiable oil mayconsist of mineral or resin oils, pure or mixed ; a method of separatingthem is stiil wanting.The soap insoluble in carbon bisulphide consists of the sodium com-pounds of resin and fatty acids. These are converted into the bariumcompounds and treated with alcohol of 85", which partially dissolvesthe resinous compounds ; a small quantity of barium oleate goes intosolution. The insoluble soap is dissolved in water and treated withcaustic soda to saturation, when the soap of the fatty acids separatesout, carrying down part of the imperfectly separated resin soap ; theremainder is left in solution, and on saturating with sulphuric acid,a precipitate of resin is formed which is collected and weighed.Thesoap is dissolved in water and precipitated with barium chloride, theprecipitate dried over a water-bath, and macerated with 36-60 C.C.boiling alcohol 85" : the residue is collected and washed with boilingalcohol until free from resin soap ; it is then decomposed, and the fattyacid collected and weighed.The alcoholic washings are evaporated to 50 c.c., and treated withhydrochloric acid ; the precipitated resin is collected and weighed.L. T. 0's.Estimation of the Alkaloids in Quinine Wine. By C.SCHACHT (Avclz. Pharrrz. [3], 14, 81--96).-The author dilutes 100grams of the liquid to be analysed with double its bulk of water, andadds 150 C.C.of saturated solution of picric acid. The voluminousprecipitate, after settling, is washed with picric acid solntion, treatedwith ammonia, and the alkaloids taken up by shaking with a mixtureof chloroform and absolute alcohol (41 : 1). After removal of thesolvents, the alkaloid residue is acidulated with dilute sulphuric acid,the colouring matter precipitated by partial neutralisation withammonia, and %he alkalo'ids separated by soda, dried at 1'20" andweighed. 0. H.Rapid Estimation of Atmospheric Carbonic Anhydride. ByM. KAPOUSTIN (Bull. Xoc. Chim. [ a ] , 34, 219).-Atmospheric carbonicanhydride may be rapidly estimated by agitating the air with a soluANALYTICAL CHEJTTSTRY. 205tion of soda in alcohol of 90 per cent., and adding the exact quantityof water required to dissolve the precipitated sodium carbonate.Limits of Error in Analyses of Combustion Gases.By A.WAGNER (Zeits. And. Chew ., 1880, 434-443) .-A controrersial paperdirected against the " Heizrersuchs-station " a t Munich. The authorpoints out that it is extremely difficult to obtain average samples, sincethe composition of the gases varies much mithin the duration of theexperiment. 0. H.Quantitative Determination of Albumin by Cupric Hydrate.By G. FASSBENDER (Bey., 13,1821-182'2).-The author has examinedthe method proposed by Stutzer (Ber., 13, 251) for the separation ofalbumin and other proteids from amides and alkalo'ids by cuprichydrate in the analysis of foods.In white of egg, white and blackbread, sweet turnips, lupins, &c., this separation is complete. Bythis process the author has found other nitrogen compounds besidesalbumin in substances of animal orig.in as dry blood and so-called fish-guano. The cnpric hydrate used IS best prepared by precipitatinga solution of copper sulphate (1 : 50), after addition of -005 vol.glycerol with a slight excess of sodium hydrate. AEter filtration, theprecipitate is washed with a, 10 per cent. gljcerol solution, and keptin a closely-stoppered bottle.Analyses of Black and White Mustard. By C. H. PIESSE andL. STANSELL (Anahyst, 1880, 5, 161- 164).-The authors examinedboth the whole seeds and the three qualities of farina obt,ained there-from by crushing and sifting.The s u ~ J ~ u r .was precipitated as barium sulphate after oxidation withstrong nitric acid.Nityogen was estimated by combustion with soda-lime, the fat beingfirst removed by light petroleum, and the combustion made with thedried residue freed from fat. This preliminary treatment obviatedthe formation of large quantities of tar. The total nitrogen minusthat contained in the potassiuni myronate was multiplied by 6.25 toobtain the weight of the albumino'ids.Myosin and albumin were extracted by prolonged treatment wit,hcold, and finally with hot water; they were jointly estimated byevaporating a portion of the extract, ar,d the albumin was determinedin another portion after being coagulated by boiling.The fat was extracted from the dried crushed seeds by light petro-leum, and the undissolved residue after being dried and weighed wasboiled successively with hydrochloric acid, soda solution, and hydro-chloric acid, being washed each time with boiling water ; i t was thenfinally washed with alcohol, dried, and weighed as ceZlulose.The volatile oil, consisting of ally1 isothiocpanate, is formed from thebrown mustard on addition of water, but admixture of some whitemustard causes a greater yield t o be obtained.The mixture wasallowed to stand with ten times its weight of cold water for about fiveor six hours, this time giving the maximum prcduction of the oil, theamount of which decreases by longer standing. The oil is distilled offL.T. 0's.V. H. V206 ABSTRACTS OF CHEMICAL PAPERS.into strong ammonia as long as the escaping steam has a pungentodour ; and the mixture of ammonia solution and distillate is put byin a closed vessel until the oily drops have disappeared ; the liquid isthen boiled for a few minutes, and the thiosinamine in solution isweighed after evaporation in a platinum dish and drying at 100". Ittsweight, multiplied by 0.85344, gives the weight of ally1 isothiocyanate,or, if multiplied by 3.5775, the weight of potassium myronate fromwhich it is derivable.Detailed analytical results are given of brown and white mustard,both for the whole seed from different sources and the three qualitiesof farina, of which the following numbers are averages :-~Moisture ..............Fat....................Cellulose ..............Sulphur. ...............Nitrogen ..............Albuminoyds. ...........Soluble matter.. ........Volatile oil ............Ash, total.. ............Ash, soluble.. ..........Myrosin and albumin ....Potassium myroilate ....Whole seed.--White.8 *6626 *539 -690 -964.5128.214 *9126 *830 -074 -630 -65 -Brown.8 *5225 549 -011 *284 '3826 *505 *2424 '220 *4'74 981 -111 *69Farina.White.6.0435 *165 *791 -2'74.7329 -566 7033.940 '034.280 *44 -Brown.4 -8337 -052 *801 -434-7528 *716 -4631.941 -444 *930 -925 .15The differences shown by the different qualities of the farina of thewhite seed are as follows:-The fat in the superfine is about 2 percent.higher, and in the seconds 2 per cent. lower than the niimber inthe table which corresponds to the fine quality ; the cellulose in secondsreaches 9.34, and in superfine is only 3.90; the albuminoids andsoluble matters are each about 3 per cent. lower in the seconds than theaverages given above. I n the brown seeds, the differences are not somarked, but, the albuminoyds in the seconds are about 3 per cent.below the average. The process of manufacture removes the huskand concentrates the constituents with the exception of the celluloseand water which are diminished in amount. The white seeds yield novolatile oil, and differ from t'he brown also by containing less sulphurand more soluble matter. The aqueous extract of white mustardyields a blood-red coloration with ferric chloride, a reaction scarcelyapparent with the extract of the brown seed ; further, the extract ofwhite seed smells in a few hours strongly of snlphuretted hydrogen ;that of the black smells only of the pungent mustard oil.The ash gave the following average percentage composition : thenumbers in columns 3, 4, 5 being calculated after charcoal and sandbave been deducted :TECHNICAL CHEMISTRY. 207Potash ..........Soda ............Lime. ...........Magnesia ........Iron oxide ......Sulphuric acid . .Chlorine ........Phosphoric acid . .Silica. ...........Sand.. ..........Charcoal ........White.20 -080 -1911 -409 -331 *lo7 -110 -1133.871 -061 -8813 -98Brown. White.21 *410 -3513.5'710 -041-065 *560.1537 -201 -411 -387.5723 3 10-2313.4911 -131 *308 *480 -1340.221 -25 --Brown.White seedWay andOgston, 1850.23.590 *3814.9511.061 *I66 -120 *l64@ *991 *55 --25 -780.3319-105 -900 *392 *19trace44 -971.31- -The ash was obtained by incineration below redness. It consistsmainly of potassium, calcium, and magnesium phosphate ; there isalso a trace of chlorine, but no carbonate. There is no differencebetween the two kinds sufficient to enable them to be distinguished byanalysis.Thiosinanaine is an oily substance at loo", but gradually solidifieswhen cold ; it is soluble in hot water, and separates from the solutionin t u f t s of monoclinic crystals. It is only partially oxidised whenboiled with strong nitric acid. Silver nitrate and mercuric chlorideyield white curdy precipitates soluble in excess of thiosinamine :platinic chloride yields an orange-yellow precipitate, soluble in hotwater, insoluble in cold water and in thiosinamine, and, like the twoformer precipitates, soluble in alcohol.Mayer's reagent (HgI, + KI) gives a dirty white precipitate whichcoheres to oily drops, slowly in the cold, but rapidly when heated.Nessler's solution yields a yellow precipitate, and picric acid precipitatesstrong solutions. F. C

ISSN:0368-1769    

DOI:10.1039/CA8814000192

出版商:RSC    

年代:1881

数据来源: RSC