摘要:

ANNUAL REPORTSPROGRESS OF’ CHEMISTRY.ON THANNUAL REPORTSA. C. CHAPMAN, F.I.C.J. R. COHEN, Ph.D., B.Sc.H. J. H. FENTON, M.A., Sc.D., F.R.S.W. D. HALLIBURTON, M.D., F.R.S.ON THEA. HUTCHINSON, M.A., Ph. D.W. J. POPE, F.R.S., F.I.C.F. SODDY, M.A.J. A. VOELCKER, M.A., Ph.D.PROGRESS OF CHEMISTRYFOR 1 9 0 5 .ISSUED BY THE CHEMICAL SOCIETY.Qomm'rttee o f @ubIitnfioir :H. T. BROWN, LL.D., F.R.S.A. W. CROSSLEY, D.Sc., Ph.D.WYNDHAM R. DUNSTAN, M.A., LL.D.,BERNARD DYER, D.Sc.M. 0. FORSTER, D.Sc., Ph.D., F.R.S.F.R. S.H. MCLEOD, F.R.S.R. MELDOLA, F.R.S.E. J. MILLS, D.Sc., LL.D., F.R.S.Sir W. RAMSAY, K.C.B., LL.D., F.R.S.A. SCOTT, D.Sc., F.K.S.W. A. TILDEN, D.Sc., F.R,.S.6biilYr :G. T. MORGAN, D.Sc.53 ub-dbitor :A. J. GREENAWAY.3ssistrrnt %I&.- Cbifar,C.H. DESCH, D.Sc., Ph.D.V O l . 11.LONDONGURNEY & JACKSON, 10, PATERNOSTEE ROW.1906RICHARD CLAY ANn SONS, LIMITED,BREAD ST. BILL, E.G., ANT,BVNCIAY, SUFFOLKCONTENTS.PAGEGENERAL AND PHYSICAL CHEMISTRY. By JAMES WALKER, D.Sc.,Ph.D., F.R.S. . . . . . . . . . . 1INORGANIC CHEMISTRY. By P. PHILLIPS BEDSON, M.A., D.Sc. . 30ORGANIC CHEMISTRY-ALIPHATIC DIVISION. By H. J. H. FENTON,M.A., ~ c . D . , F.R.S. . . . . . . . . . . 66ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. By JULIUS B.COHEN, Ph.D., B.Sc. . . . . . . . . . . 101ORGANIC CHEMISTRY - HETEROCYCLIC DIVISION. By JOHNTHEODORE HEWITT, M . A . , D.Sc., Ph.D. . . . . . . 129STEREOCHEblISTRY. By WILLIAM J-~CKSON POPE, F.R.S., F.I.C. . 168ANALYTICAL CHEMISTRY.By ALFRED CHASTON CHAPMAN, F. I.C. . 185PHYSIOLOGJCAL CHEMISTRY. By W. D. HALLIBURTON, M.D., F.R.S. 212By JOHN AUGUSTUS VOELCKER, M.A., Yh.D., B.Sc., F.I.C. . . 238MINERALOGICAL CHEMISTRY. By ARTHUR HUTCHIKSON, M.A., Ph.D. 267RADIOACTIVITY. By EREDERICK SODDY, M.A. . . . . . 295AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGYTABLE OF ABBREVIATIONS EMPLOYED I N THEABBREVIATED TITLE.Amer. Chem. J. . . .Amer. Geol. . . .Arner. J. Pharm. . .Amer. J. Physiol. . .Amer. J. Sci. . . .Analyst . . . .Annalen . . . .Ann. Physik . . .Ann. agron. . . .Ann, Chim. anal. . .Ann. Chim. Phys. . .Ann. Inst. Pasteur . .Ann. sci. Univ. Jassy .Arbb. Kais. Ges. . .Arch. Exp. Path. Pharm. .Arch. Hygiene . . .Arch. Ne’erland.. .Arch. Phann.. . . .Arch,. Xci. biol. St. PetersbiwgArch. Sei. phys. nat. . .Atti It. Acead. Sci. Torino .Atti R, Amd. Lineei .Beilr. chem. Physiol. Path.Ber. . . . . .Ber. Deut. pharm. Ges. .Berlin Klin. Woch. . .B e d . Centr. . . .Bihang X . Svenska yet.-Brit. Med. J. , . .Bull. Aead. roy. Belg. .Bull. Acad. Sci. Cracoio .Akad. Hand.Bull. Assoc. Chim. Suer.Bull. Coll. Agr. T6ky6 .Bull. Geol. Xoc. Amer. .Dist.REFERENCES.JOURNAL.American Chemical Journal.American Geologist.American Journal of Pharmacy.American Journal of Physiology.American Journal of Science.The Analyst.Justus Liebig’s Annalen der Chemie.Annalen der Physik.Annales agronomiques.Annales de Chimie analytique appliqude h l’I~idustrie,Annales de Chimie e t de Physique.Annales de I’Institut Pasteur.Annales scientifiqiies de 1’ Universitd de Jassy.Arbeiten aus dem Kaiserlichen Gesundheitsamt.Archiv fur experimentelle Pathologie und Pharma-Archiv fiir Hygiene.Archives NBerlandaises des sciences exactes et natur-Archiv der Pharmazie.Archives des Sciences biologiques, St.Petersbourg.Archives des Sciences physiques et naturelles.Atti della Reale Accademia delle Scienze di Torino.Atti della Reale Accademia dei Lincei.Beitrage fiir chemische Physiologie und Pathologie.Berichte der Deutschen chemischen Gesellschaft.Berichte der Deutschen pharmazeutischen GesellschaftBerliner Klinische Wochenschrift.Biedermann’s Centralblatt fur Agrikulturchemie undBihang till Kongl.Svenska Vetenskaps-AkademiensBritish Medical Journal.Acaddmie royale de Belgiqne-Bulletin de la ClasseBulletin international de l’Acad6mie des Sciences deBulletin de 1’Association des Chimistes de Sucrdrie e tBulletin of the College of Agriculture, Imperial Uni.Bulletin of the Geological Society of America,A l’dgricnlture, It la Pharmacie et A la Biologie.kologie.elles.(Berlin).rationellen Landwirtschafts-Betrieb.Handlingar.des Sciences.Cracovie.de Distillerie.versity, T6ky6viii TABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENCES.ABBREVIATED TITLE.Bull. SOC. Chin?,. . .Bull. SOC. franc. Min. .Bull. SOC. ind. Mzclhozcse .Centr. Bakt. Par. . .Centr. Min. . . .Chem. Centr. . . .Chem. NGWS 0 .Chnz. Rev. Fett ’ Hurz Ind.Chcm.Zeit. . . .Compt. rend. . . .Compt. rend. SOC. Biol. .Exper. Stat. Record . .Farm. Tid. . . .Fold. Koxlony . . .Gazzetta . . . .Geol. Mag. . . . .Jahrb. Min. . . .Jahrb. Min. Bei1.-Bd. .Jahrb. Rndioakt. Elek. .J. Agric. flci. . . .J. Amer. Chent. SOC. . .J. Amer. Mcd. Assoc. .J. Chern. Metall. MiningJ. Chirn. phys. . , .J. Fed. Inst. Brewing. .J. Geol. . . . .J. Hygiene. . . .J. LarLdw. . . . .J. Med. Research . .J. Path. Bad. . . .J. Pharm. Chim. . .J. Physical Chem. . .J. Physique . . .,J. pr. Chem. . . .J. Roy. Agric. SOC.J. Russ. Phys. Chem. SOC. .J. SOC. Chcm. Ind. . .Landw. Versuchs-Slat. .L’Orosi . . . .Mem. Accad. Sci. Torino .Me;. Xanchester Phil. SOC.SOC. Soulh AfricaJ. Physiol.. . t .J. Eoy. SOC. New ;S026tiWalesMem. R. Accnd. Lincei .Milch Zeit. . . .Milchw. Zentr. . . ,Min. Mag. . . . .Monatsh. . . . .Mon. Sci. . . .Nmvo Cim. . . ,JOURNAL.Bulletin de la SociQt6 chimique de Paris.Bulletin de la Soci6t6 franqaise de Mindralogie.Bulletin de la SociM industrielle de Mulhouse.Centralblatt fur Bakteriologie, Parasitenkunde undInfektionskrankheiten.Centralblatt fur Mineralogie, Geologie und Palaeonto-logie.Chemisches Centralblatt.Chemical News.Chemische Revue uber die Fett- und Harz-Industrie.Chemiker Zeitung.Comptes rendus hebdomadaires des Sdances deComptes rendus des Sdances de la SociQtc? de Biologie.Experiment Station Record.Farmaceiit isk Tidsskrift.Foldtani Kozlony.Gazzetta chimica italiana.Geological Magazine.Neues Jahrbuch fiir Mineralogie, Geologie und Pal-aeontologie.Neues Jahrbuch fiir Mineralogie, Geologie und Pal-aeontologie.Beilage-Band.Jahrbuch fur Radioaktivitat und Elektronik.Journal of Agricultural Science.Journal of the American Chemical Society.Journal of the American Medical Association.Journal of the Chemical, Metallurgical, and MiningSociety of S. Africa.Journal de Chimie physique.Journal of the Federated Institutes of Brewing.Journal of Geology.Journal of Hygiene.Journal fur Landwirtschaft.Journal of Medical Research.Journal of Pathology and Bacteriology.Journal de Pharmacie et de Chimie.Journal of Physical Chemistry.Journal of Physiology.Journal de Physique.Journal fur praktische Chemie.Journal of the Royal Agricultural Society.Journal of the Royal Society of New South Wales.Journal of the Physical and Chemical Society ofJournal of the Society of Chemical Industry,Die landwirtschaftlichen Versuchs-Stationen,L’Orosi.Memorie della Reale Accademia delle Scienze d iMemoirs and Proceedings of the Manchester LiteraryMemoires della Reale Accademia dei Lincei.Milch Zeitung.IKilchwirtscliaftliclies Zentralblatt.Mineralogical Magazine and Journal of the Mineral-ogical Society.Monatshefte fur:Chemie und verwandte Theile andererWissenschaften.Moniteur Scientifique.I1 Nuovo Cimento.l’Acad6mie des Sciences.Russia.Torino.and Philosophical SocietyTABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENCES, ixABBREVIATED TITLE.Csfver K.Vet.-Akad. F6rhPjiiger's Archiv.Pharm. Arch. . . .Pharm. Centr. H . .Pharm. J. . . . .Pharm. Rev. . . .Pharm. Weekblad . .Pharm. Zeit. . . .Phil. Mag. . . .Phil. Trans. . , .Phys. Proc. . . .Phys. Zeit. . . .Proc. . . . . .Proc. Amer. Physwl. SOC. .Proc. Cantb. Phil. SOC. .Proc. Phil. Xoc. Glusgow .Proc. Physio2. SOC. . .Proc. K. Akad. Wetensch.Proc. Roy. Soc. . . .Proc. Roy. Xoc. Edin. ,Proc. Washington Acad. Sci.Qt6art. J . Geol. SOC. . .Rev. intern. Falsif. . .Rec. t?*av. chim. . . .Amsterdam.Rev. Mctallurgic . .Revista Min. . . .Sci. Proc. Roy. Dubl Suc. .Sci. Trans. Roy. Dubl. SOC.Sitxzmgsber. K. Akad. Wiss.Sitxungsber. K. Aknd. Miin-Skand. Arch. Physiol. .Trans.. . . .Trans. Amer. Imt. Jf iningTrans. Faraday SOC. . .Trans. Nova Scotia Inst.?'Tans. Path. Xoc. Lond. .Trans. Roy. Dubl. Soc. .Trans. Roy. Irish Acad. .Trans. Roy. SOC. Canada .Trans. Roy. SOC. S. Aus-Tsch. Min. Mitth. . .U.S.A. Dcpt. Agric. Bull. .U. S. A. Dept. Agric. Rep. .Wien. Xitzungsber. . .Wiss. Abhandl. Phys.-Tech.Woch. Byazc. . . .Zeit anal. Chem, . .Zeit. angew. Chem. . .Zeit. amrg. C h m . . ,Berlin.chen.Eng.sci.traliaReichsanstalt.JOURNAL.Ufversigt af Kongl. Vetenskaps -Akademiens FGrhand-lingar.Archiv fur die gesammte Physiologie des Menschenund der Thiere.Pharmaceutical Archives.Pharmazeutische Centralhalle.Pharmaceutical Journal.Pharmaceutical Review.Pharmaceutisch Weekblad.Pharmazcutische Zeitung (Berlin).Philosophical Magazine (The London, Edinburgh andPhilosophical Transactions of the Royal Society ofProceedings of the Physical Society.Physikalische Zeit schrift.Proceedings of the Chemical Society.Proceedings of the American Physiological Society.Proceedings of the Cambridge Philosophical Society.Proceedings of the Glasoow Philosophical Society.Proceedings of the Phy?iological Society.Koninklijke Akademie van 'Wetenschappen te Amster-dam.Proceedings (English Version).Proceedings of the Royal Society.Proceedings of the Royal Society of Edinburgh.Proceedings of the Washington Academy of Science.Quarterly Journal of the Geological Society.Revue intcrnationale des Falsifications.Receuil des travanx chimiques des Pays-Bas e t de laRevue de Metnllurgie.Revista Minera.Scientific Proceedings of the Royal Dublin Society.Scientific Transactions of the Royal Dublin Society.Sitzungsberichte der Koniglich Preussischen Akademieder Wissenschsften zu Berlin.Sitzungsberichte der koniglich bayerischen Akademieder Wissenschaften in Munchen.Skandinavisches Archiv fur Physiologie.Transactions of the Chemical Society.Transactions of the American Institute of MiningTransactions of the Faraday Society,Transactions of the Nova Scotia Institute of Science.Transactions of the Pathological Society, London.Transactions of the Royal Dublin Society.Transactions of the Royal Irish Academy.Transactions of the Royal Society of Canada.Transactions of the Royal Society of S.Australia.Tschermak's Mineralogische Mittheilungen.Bulletins of the Department of Agriculture, U.S. A.Reports of the Department of Agriculture, U. S. A.Sitzungsberichte der Kaiserlich Akademie dcr Wissen -achaften zu Wien.Wissenschaftliche Abhandlungen der Physikalisch-Technischen Reichsanstalt.Wochenschrift fur Brauerei.Zeitschrift fur analytische Chemie.Zeitschrift fur angewandte Chemie.Zeitschrift fur anorganische Chemie.Dublin).London.Belgiq ue.EngineersX TABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENCES.ABBREVIATED TITLE.Zeit. Biol. . . . .Zeit. Elektrochem. . .Zeit. Farb. Text. Ind. .Zeit. Kryst. Min. , .Zeit. Zand. Yersuch. wtes.Zeit. Nahr. Genussm. . Ost.Zeit. ofentl. Chem. . .Zeit. physikal. Chem. . .Zeit. physiol. Chem. . .Zeit. prakt. Geol. . .Zeit. Ver. deut. Zuckerind.Zeit. Zuckerind. Bohm. .JOURNAL.Zeitschrift fur Biologie.Zeitschrift fur Elektrochemie.Zeitschrift fur Farben- und Textil-Industrie.Zeitschrift fiir Krystallographie und Mineralogie.Zeitschrift fur das landwirtschaftliche VersuchswesenZeitschrift flir Untersuchung der Nahrungs- nndZeitschrift fur offentliche Chemie.Zeitschrift fiir physikalische Chemie, Stochiometrieund Verwandtschaftslehre.Hoppe-Seyler’s Zeitschrift fur physiologische Chemie.Zeitschrift fur praktische Geologie.Zeitschrift des Vereins der deutschen Zucker-Industrie.Zeitschrift fiir Zuckerindustrie in Bohmen.in Osterreich.Genussmittel

ISSN:0365-6217    

DOI:10.1039/AR90502FP001

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

INORGANIC CHEMISTRY.AGAIN we have to record losses in the ranks of the workers ininorganic chemistry; by the death of Cleve, our Society has lost one ofits distinguished honorary Fellows, and chemistry a foremost worker inthe department of the rare earths. Cleve was born at Stockholm onFebruary loth, 1840, received his early chemical training at the Uni-versity of Upsala, where for three years, namely, 1863-66, he dischargedthe duties of ‘‘ Privat-docent ” in organic chemistry. Relinquishingthis post, Clevt devoted some years to travel and to the completion ofhis chemical training, remaining for some time in Paris to study underBerthelot and Wurtz. These years of travel were useful in other ways,and reveal the many-sided scientific man, who was not only a chemistbut also geologist and botanist, I n 1870, Cleve was appointed to thestaff of the Polytechnic a t Stockholm, and in 1574 he became theprofessor of chemistry in the University at Upsala, in which positionhe continued until his death, which took place on June 18th.Cleve’s published work, whilst it shows his activity in differentdepartments of chemistry, both organic and inorganic, is chiefly con-cerned with the elucidationlof the chemistry of the rare earths; inrecognition of the importance of these investigations the Royal Societyawarded him the Davy Medal in 1904.There is still one other asso-ciation with the name of Cleve which recent events have emphasised,and that is to be found in the name cleveite given by Nordenskjijld toa species of pitchblende in which Sir William Ramsay first found asource of terrestrial helium.On January 13th, T.H. Behrens, professor at the Polytechnic Schoola t Delft, died at the age of 63. The name of Behrens is identifiedwith micro-chemical analysis, to the perfecting of the methods of whichbranch of analysis he devoted much labour.The death of G. B. Buckton on September 35th a t the advanced ageof 88 recalls the important investigations made between forty andsixty years ago on several members of that interesting group of sub-stances, the metallo-organic compounds.It is difficult, if not impossible, to give in a few words an indicationof the direction of chemical research in inorganic chemistry during thINORGANIC CHEMISTRY. 31year.The number and variety of the elements themselves and theirnumerous compounds are largely responsible for the miscellany-likeimpression which the contemplation of the titles of the papers pub-lished produces. The exact revision of atomic weights has providedprecise information in the case of some thirteen or fourteen elements.The commercial production of metallic calcium, chronicled last year,has provided the opportunity for the closer study of the chemicaland physical properties of this element. Again, this year, we see an-other rare element pressed into the service of man; the electrolyticdecomposition of tantalum tetroxide has been employed as a means ofobtaining the metal in the form of filaments suitable for the construc-tion of incandescent electric lamps. Such lamps have a useful lifeabout the same as those with a carbon filament, whilst the electricalenergy consumed is about one-half.A considerable number of papersdeal with investigations of the rare earths. The application of physicalmethods, more especially the construction of fusion diagrams by Tam-mann’s method, has very materially extended the knowledge of alloys,and in many instances afforded indications of the nature of the definitecompounds formed by metals with one another. The study of colloidalsolutions of metals and their compounds is another branch of investi-gation to which many chemists have devoted themselves during theyear.Atomic Weights and the ClassiJcation of t?Le Elements.I n a paper entitled “ A Contribution to the Development of thePeriodic System,” Werner has suggested an arrangement of thcelements for which many advantages over the generally acceptedforms may be claimed.I n this table, the elements are arrangedhorizontally in eight periods or series, the periods fall again into foursets of two each; in each set there are the same number of elements.I n the first period, which might be styled the zero-period, there are threeblank spaces, in which possibly “ coronium ” and “ the ether ” may finda place. The second period, a repetition of the first so far as the num-ber of elements is concerned, contains at present hydrogen a t oneextreme and helium a t the other, with a blank space next to heliumrepresenting the position of a lower hornologue of the halogen group.The third and fourth periods contain a like number of elements,namely, eight ; the third begins with lithium, the homologue of hydrogen,followed by glucinum, boron, carbon, nitrogen, oxygen, fluorine, and endswith neon, the next homologue of helium.I n this period, the averagedifference in atomic weights from member to member is 1.85. Thefourth period is constituted of the elements arranged in the order oftheir atomic weights, from sodium to argon, with sodium placed belowBer., 1905, 38, 91432 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.-I1Sa Eu150’5 151’71U239’5- -SC44-1Y89 -0-Yb -173.0- - -lithium, magnesium below glucinum, aluminium below boron, and so on,argon coming into the helium group.The fifth and sixth periods are again constituted of a like number ofelements, more numerous than the preceding periods, and containeighteen elements each.I n the fifth period, the average difference inthe atomic weights of the successive members is 2-47 ; it begins withpotassium, followed by calcium, scandium, titanium, vanadium, chrom-ium, manganese, iron, cobalt, nickel, and copper; after which comezinc, gallium, germanium, arsenic, selenium, bromine, and krypton,these last seven elements forming the natural homologues of the lastseven elements of the third and fourth periods. I n the sixth period, theaverage difference in the atomic weights of the successive members is2.5, and of the eighteen elements required for this period seventeen areknown, the missing member being the homologue of manganese.Thisperiod begins with rubidium and strontium and ends with iodine andxenon.The seventh and eighth periods should, it is shown, consist of thirty-three elements each; and whilst, at present, only three elements of theeighth period are known, namely, radium, thorium, and uranium, theblank spaces in the seventh period are nine in number. The seventhperiod begins with cssium, followed by barium, and between bariumand tantalum room is found for the metals of the rare earths, fromlanthanum to ytterbium, a position in accord with Benedick’s viewZeit. nnorg. Chem., 1904, 39, 41INORGANIC CHEMISTRY. 33mentioned in last year’s Report. The other members of this period aretanfalum and tungsten, the homologues of niobium and molybdenum,osmium, iridium, platinum, and gold, which are placed in association withruthenium, rhodium, palladium, and silver in the sixth period, andfinally, mercury, thallium, lead, silver, and bismuth, which respectivelyfind positions as members of groups 11, 111, IV, and V in the oldertables of the elements.The main features which distinguish Werner’s mode of tabulationfrom that adopted by Mendeleeff are seen to be in the separation of thetwo sections of the elements of Group I1 from one another.Into thisspqe are introduced the members of Group VIII, together with thoseelements of which the sub-groups are composed; in this manner alsothe elements of the rare earths fall quite naturally into position.Further, the nonvalent elements of the argon family are broughttogether into a group, between the strongly electro-negative elements,the halogens, and the electro-positive alkali metals. The blank spacesin the table indicate that additions to the elementary substances maybe expected among the rare earths and in other parts of the seventhperiod, but it is chiefly in the eighth period that elements are lacking ;these vacancies may possibly be supplied by such substances as radioactivetellurium, &c.Although it cannot be claimed that the arrangementunder discussion obviates all the difficulties met with in a systematicarrangement of the elements in order of their atomic weights, still itmay be fairly regarded as affording a clear exposition of the relationsVOL.11. between the properties of the elements and their atomic weights.Some of the difficulties experienced in arranging the elements in theorder of their atomic weights are specially indicated in the foregoingtable by the enclosure of certain of the elements with thick lines.Revision of Atomic Weights.Investigations dealing with the revision of the accepted atomic weightsof some fourteen elements have been published during the year, and ofthese the most interesting is the method adopted by H. B. Dixon andE. C. Edgar for the redetermination of the atomic weight of chlorine bythe direct synthesis of hydrogen chloride. The chlorine employed wasprepared by the electrolysis of fused silver chloride ; it was liquefiedand weighed in a sealed glass globe, from which it was allowedto evaporate into an exhausted combustion globe, in which the com-bination with hydrogen took place, the hydrogen chloride formedbeing absorbed by water in this combustion globe, cooled by melt-ing ice.The hydrogen employed was produced by the electrolysis ofa solution of barium hydroxide, and after drying was absorbed bymetallic palladium in a weighed vessel. The hydrogen driven off byheat from the palladium was conveyed into the combustion globe,filled with chlorine, then ignited by a spark, and burnt at a jet. Thegases were carefully regulated so as to maintain the hydrogen burninguntil nearly all the chlorine was used up ; then the palladium was al-lowed to cool and the hydrogen turned off just before the flame diedout.As already mentioned, the hydrogen chloride was absorbed by thewater in the combustion globe, and the residual gas left in the globewas analysed, the chlorine being determined by breaking ti thin glassbulb containing a solution of potassium iodide, the liberated iodine beingestimated by titration with a solution of sodium thiosulphate. I n eachexperiment, about 11 litres of each of the gases were consumed, theunused chlorine being about 2 per cent. of the volume burnt. Themean value obtained for the atomic weight of chlorine from nine ofthese experiments is 35.463 (0 = 16), which is somewhat higher thaneither Stas's value (35.457) or that calculated by Clarke, namely,35.447. I n their revision of the atomic weights of sodium and chlorine,T.W. Richards and R. C. Wells2 give results which indicate thatthe value 10'7.920 for the atomic weight of silver is more correct;than 10'7.930. With the former of these values for silver then theatomic weight of sodium is 23.006, and for chlorine 35.470, whereaswith the value 10'7-930 for silver the atomic weights of sodium andchlorine become 23.008 and 35.473 respectively.Phil. Trans., 1906, Series A , 205, 169.J. Amer. Chem. SOC., 1905, 27, 459INORGANIC CHEMIBTRT, 35The atomic weight of nitrogen has formed the subject of severaloommunioations ; Hinrichs,l far example, has drawn attention to thefact that the results recently obtained 2 gii-e valuea approaching nearlythe true value, nemely, 14.00. Gray,9 from the determination of thedensity of nitric oxide, carefully purified by liquefaction and subsequentfractionation of the liquid, as also by the complete gravimetric cbnalysiaof this compound, has deduced the value 14.01 as the atomic weight ofnitrogen.I n a recent note, Scott 4 has drawn attention t o the fact thatby the titration of ammonium bromide against silver he had in 1901arrived at the value 14.01 for the atomic weight of nitrogen, and thatthe discrepancy between the value obtained from the experiments madewith ammonium chloride disappears if Richard's value, namely, 35.473,for the atomic weight of chlorine is used instead of the value 35.457.Using the former of these values, Scott's analysis of ammonium chloridegives 14.013 as the atomic weight of nitrogen.From the analysis of the chloride, Richards has obtained for stron-tium the value 87.661 as its atomic weight (C1=35.473), a valueagreeing well with that deduced from the bromide, namely, 87.663.By the analysis of cadmium chloride, Baxter and Hines 6 obtain 11 2.469for the atomic weight of the metal.From the analysis of carefully purified silicon tetrachloride, Beckerand Meyer7 obtain as a mean of eight experiments the value28-21 (0 = 16) for the atomic weight of silicon.Baxter* has again attacked the revision of the atomic weight ofiodine by determining the ratio of silver iodide to silver chloride byconverting the former first into silver bromide, then into the chloride.One series gave the atomic weight of iodine as 126-985, and a secondseries gave 126.984 (C1= 35.473 and Ag = 107.93). A redetermination ofthe ratio of iodine to silver iodide has given results varying from 126.983to 126.989.Kothner and Aeuer 9 have also discussed this subject anddeduced from thf forty-one determinations made by Scott, Ladenburg,Baxter, and themselves a value 126.97 (0 = 16).A special interest attaches to the atomic weight of tellurium, byreason of its position in the natural system of the elements, and onthis subject are two publications ; in one is given the result of thedetermination of the electro-chemical equivalent of this element, fromwhich the atomic weight 12'7.61 is deduced (Ag = 107.93).'0 In thesecond, from the reduction of tellurium dioxide by hydrogen and byCompt. rend., 1905, 140, 1590.Tram., 1905, 87, 1601.Zeit.anorg. Chem., 1905, 47, 145.7 Zeit. anorg. Chem., 1905, 43, 251.9 Annalen, 1904, 337, 362.See Ann. Reports, 1904.Proc., 1905, 21, 309.ti J. Amer. Chem. h'oc., 1905, 27, 222.8 J. Amer. 'Chem. SOC., 1905, 27, 876.lo G. Gallo, Atti R Accad. Lincei, 1905, [v], 14; I, 23, and 104.0 36 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.hydrazine Gutbier 1 obtained for the atomic weight of tellurium thevalue 127.6. I n a paper dealing with the chemical properties andcombining weight of palladium, Amberg has described a trustworthymethod for estimating the chlorine in palladium chloride, and also amethod of precipitating the metal electrolytically from solution of itssulphate.The new electrolytic process has given as the mean ofseveral results 106.7 for the atomic weight of palladium. P a r ~ o n s ~has calculated values for the atomic weights of glucinum and of carbonfrom the results of the determination of the equivalent weight ofglucinum by analysis of the acetylacetonate and basic acetate. Thesecalculations give for glucinum the value 9,112 and for carbon 12-007.Parsons 4 has also criticised Pollok’s conclusion, mentioned in lastyear’s Report, that the beryl from Limoges contains an element of highatomic weight associated with glucinum, a conclusion from whichhe dissents mainly on the grounds that the low proportion of chlorinenoted by Pollok in the separate fractions of chloride may have been dueto the action of moisture on the glucinum chloride, which would entailit loss of chlorine.Atomic Weights and Spc6$c Heats.The law of Dulong and Petit and Neumann’s extension formedthe subject of the presidential address to the Society,5 in whichTilden has given a summary of our present knowledge of “the relationof specific heat to atomic weight in elements and compounds.” Manyadditional data to those already published are given, and it is shownthat influence of temperature on specific heat is greater thanhitherto supposed.Further, as there are no conditions under whichthe law of Dulong and Petit is true of all elements, the mean specificheat of metals between Oo and looo may be taken as the nearest approachto a constant available for practical purposes, the elements of lowatomic weight being regarded as exceptions.It isealso pointed outthat the atomic heats of elements in the gaseous state may possiblybe equal. Experimental results give for hydrogen 2.4, for oxygen2-5-24’, and 2.6 for carbon in carbon dioxide.Rare Ekments.The anhydrous chlorides of lanthanum, neodymium, praseodymium,samarium, and yttrium have been prepared by Matignon 6 by the actionof vapours of sulphur chloride, chlorine, and hydrogen chloride on the3 J. Amer. Chem. Xoc., 1905, 27, 1204 ; also Zeit. anorg. Chem., 1905, 46, 215.Annalen, 1905, 342, 266.J. Amer. Chem. Xoc., 1905, 27, 233.Comzlt. rend., 1905. 40. 1181.Ibid., 341, 235.Trans., 1905, 87, 551INORGANIC CHEMISTRY. 37residues left by evaporation of the metallic oxides with hydrochloricacid. The heats of formation of the chlorides of the first four of theseelements, when produced by the dissolution of their oxides inhydrochloric acid, are given as 80.3, 73.9, 71.6, and 34.2 cals.re-spectively.1 Anhydrous neodymium chloride has been thoroughlyinvestigated by Matignon.2 It is a stable compound not attacked byhydrogen a t 1000°, but is converted by oxygen into the oxychlorideNdOCI, which forms mauve-tinted plates, infusible a t 1000°. Fromthe chloride, the iodide (NdI,) and bromide (NdBr,) have been obtainedby, the action of the corresponding hydracids. The chloride is notattacked by ammonia a t the ordinary temperature, but when heatedwith it forms additive compounds.Heated with acetylene, the chlorideis unaltered, the acetylene polymerises, and carbon is deposited in a formpossessing brilliant reflecting surfaces, which is not graphite. Theprobable existence of an oxide, Nd,O,, is maintained by Waegner.3Matignon and Trannoy 4 describe a series of eight compounds whichammonia forms with anhydrous samarium chloride, of which theformulae and temperatures of dissociation are given. By the applicationof the Demarqay-Drossbach method of separation, Feit and Przibyllahave obtained neodymium, samarium, and lanthanum from monaziteearths, from which source also Feit 0 has obtained preparations ofterbium, for which element the atomic weight 158.6 is deduced.Urbain 7 has by careful fractionation obtained 7 grams of the oxide ofthe element Zg, to which he is of the opinion the name terbium should berestricted.The oxide exhibits an absorption band X = 488, and thesolutions of its chloride give the beautiful green fluorescent spectrumof Lecoq de Boisbaudran's Zg. The oxide when pure is non-fluorescent,but when mixed with gadolinia or with alumina it then exhibitsfluorescence. The value deduced for the atomic weight is 159.2(0 = 16). The oxide is black or brown, according as it is preparedfrom the oxalate or sulphate; its salts are colourless and slightly moresoluble than those of gadolinium.It would appear that much remains to be done to clear up mattersrelating to gadolinium and the elementary substances associated withit. Urbains has succeeded in obtaining pure compounds of thiselement from gadolinium earths by crystallisation of the double nitrateof gadolinium and nickel, and from the conversion of the sulphate,Gd,(SO,), + 8H,O, into the oxide, (Gd,O,), deduced the atomic weight of157.23-157*25 for this metal.Crookes, from observations of the ultra-Compt. rend., 1905, 40, 1339.3 Zeit. anorg. Chem., 1904, 42, 118.Zeit. anorg. Chem., 1905, 43, 202.7 Cmnpt. rend., 1904, 139, 736 ; 1905,141, 521.8 Ibid., 1905, 140, 583.2 B i d . , 1637.4 Compt. rend., 1905, 140, 140.6 Ibid., 26738 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.violet spectrum of gadolinium purified by the Urbain-Lacombe method 1(see Ann. Report, 1904), has concluded that victorium is present as animpurity in the gadolinium. According to the same authority,gthe oxide of europium, prepared by the same method, gives anultra-violet spectrum indicating the presence in it of gadolinium,yttrium, lanthanum, and calcium, whereas Eberhard’s 3 spectrographicinvestigation of the Urbain-Laoombe method for the separation ofsamarium, europium, and gadolinium shows the method to be satisfactoryas a means of obtaining pure europium salts, also samarium free fromeuropium, and gadolinium free from samarium.Gadolinium, accordingto Urbain,4 whether obtained from monazite, xenotine, or pitchblende,exhibits certain new lines in the ultra-violet absorption spectrum.Further, the metal shows the same phosphorescent spectrum as thatattributed by Crookes to victorium, which Urbain does not consider tohave been definitely shown to be different from gadolinium.The high values of the heat of formation of the oxides of the ceritemetals indicate that the metals should prove powerful reducing agents.This indication has been verified by Weiss and Aichel,5 who, by the aidof the ‘‘ mixed metals ” obtained from the residual oxides in preparingthorium nitrate, have reduced many metallic oxides to the metallicstate.I n this way, the following metals have been produced : iron,nickel, cobalt, manganese, chromium, molybdenum, vanadium, tantalum,niobium, tungsten, uranium, and columbium.Wolff,G in detailing the results of the determination of the solubilitiesof double nitrates and double sulphates of cerium and ammonium, hasdescribed the composition and properties of several cerous salts of thefatty acids.Cerous trichloracetate, Ce(C,C1,0,),,3H20, is distinguishedfrom the others by the fact that when its aqueous solution is boiledthe cerium separates out as carbonate and that the salt is not oxidisedby hydrogen peroxide.Meyer and Gumperz 7 are unable to confirm Baskerville’s observationson the composit,e nature of thorium (see Ann. Report, 1904), and theirconclusions are supported by Eberhard’s 8 spectrographical investigationsof thorium preparations from various sources.have discovered a new source of thorium in a rock from South America,which consists chiefly of barium carbonate with a little inactive thoria.An analysis of thorianite, the only British source of thoria, found inCeylon, has been recently published by Dunstan and Blake.lo Thismineral contains some 70 per cent.of thoria, and is possibly isomorphouaBaskerville and ZerbanProc. Xoy. Xoe., 1905, Series A, 74, 420.Zeit. anorg. C‘hem., 1905, 45, 374.]bid., 550.4 Conzpt. rend., 1905, 1413, 1233.6 Zeit. anorg. Chem., 1905, 45, 89.lo Proc. Boy. sbc., 1905, 76, 253.ti Annabn, 1905, 337, 3709 J, Amer. Chern. Xoc,, 1904, 26, 1642.Bw., 1905, 38, 817. 8 ad., 826INORGANIC CHEMISTRY. 39with uraninite; in addition to uranium, it contains the oxides ofcerium, lanthanum, didymium, and yttrium, also zirconia and silica.Helium was found in one specimen of this mineral ; the thorium isradioactive ; inactive thorium is, according to Zerban found in thoseminerals which do not contain uranium.The reduction of thorium oxide when heated in an electric furnacewith amorphous boron has been studied by Jassonneix, and byE.Wedekind and Fetzer.3 The first of these authorities obtained twoborides, namely, the compound ThB,, as a yellow, metallic powder, easilyattacked by acids, and bhe substance ThB,, a reddish-violet, amorphoussubstance not so readily acted on by acids. Thorium oxide is alsoreduced by silicon.During the year, the following observations have been made onzirconium and its compounds ; zirconia is not reduced when heated withmetallic aluminium, and when heated with magnesium in a looselycovered crucible the nitride Zr,N, is formed, together with a substancewhich forms a blue colloidal solution.The nitride is easily oxidisedwhen heated in the air ; it resists the action of alkalis and of acids, butis readily converted into chloride or bromide by the action of thesehalogens (Wedekind).4 Stahler and Denk 5 describe the compoundswhich the zirconium halides form with gaseous ammonia. The iodideforms with liquid ammonia the compound Zr14,SNH3, from which liquidammonia removes ammonium iodide, indicative of the following decom-position : Zr14,SNH3 = Zr(NH2), + 4NH,. The following substances,ZrI,,GNH,Et and ZrI4,4Et,O, have also been obtained. Compounds ofthe type R2,H,ZrC1, are, according to Rosenheim and Frank,, formedwhen alcoholic solutions of zirconium chloride are treated with the hydro-chlorides of pyridine or quinoline.The authors also describe the com-plex sulphates Zr20,(S04K),,8H,0 ; Zr20,(S04Rb),, 1 5H20 ;Zr20,( SO,Cs),, 1 1 H,Oand Zr(SO4K),,3H,O. From the fact that the normal zirconium sul-phate does not exhibit reactions similar to those of the chloride, Ruer 7concludes that it is a dibasic acid having the formula ZrOS04,S04H2,forming salts of the type ZrOS04,S04Ni,, and that the crystalline sul-phate is to be represented by the formula ZrOS04,S04H,,3H,0 and notZr(SO4),,4H,O. Ruer 8 has also specially studied the hydrolysisof zirconium oxychloride and obtained a hydroxide, metazirconicacid, which is related to the ordinary hydroxide as metastannicacid is to stannic acid. It is suggested by van Bemmelen9 thatBer., 1905, 38, 557.Chem.Zeit., 1905, 29, 1031.Ber., 1905, 38, 2011.2 Compt. rend., 1905, 141, 191.Zeit. anorg. Chem., 1905, 45, 385.Ibid., 812.7 Zeit. anorg. Chem., 1904, 42, 87.9 /bid., 45, 83.8 Ibid., 1905, 43, 28240 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the proportion of water in metazirconic acid observed by Ruer isaccident a1 .Considerable interest surrounds the production of tantalum, alreadyreferred to, a description of which has been given by von Bolton.' Avery complete account is given of the physical constants of this metal,which combines extraordinary hardness with great ductility ; the metalmelts about 2250'. Tantalum in the form of wire is used for the construc-tion of incandescent electric lamps ; the red-hot metal decomposes water,combines with sulphur, selenium, and tellurium, and forms alloys withiron, molybdenum, and tungsten, but not with silver.The fact thatwhen heated at a white heat it does not combine with oxygen if the pres-sure be below 20 mm. gives a clue to the explanation of the method ofpreparing the metal, which is effected by heating electrically in avacuum rods made of the compressed oxides. At the high temperatureso attained, the oxide is decomposed and the oxygen removed by con-tinued exhaustion. It has also been pointed out by von Bolton thatthe hardness of the metal tantalum is largely increased by the presenceof its oxide. Ton Pirani3 has also shown that this metal absorbs aconsiderable volume of hydrogen when heated in this gas, and that thehydride is formed when the pentachloride and hydrogen are passedthrough a heated tube.Vanadium and columbium may also be obtained in a similar mannerfrom their oxides, which in the form of compressed powder conductelectricity. Columbium is more ductile than vanadium and melts a t195G0, whilst the latter melts at 1680O.Goldschmidt's process hasbeen utilised in the production of metallic vanadium, yielding a productcontaining '78.2-81 -1 per cent. of the element.* This crude metal, treatedwith chlorine, yields a mixture of VC1, and VOCl,, which can beseparated by fractional distillation. Koppel and Kaufmann alsodescribe a compound of vanadium oxychloride and pyridine,VOCl3,C,NH,HC1, C,H,O,formed by the interaction of pyridine and an alcoholic solution ofthe oxychloride.They were not successful in obtaining the thio-chloride, VSCl,, but by heating vanadium sulphide, V,S,, in chlorinethe compound 4VSC1,,S2C1, is produced, from the ethereal solutions ofwhich brown tablets of the composition 4VSC1,,S,C12,C,H,,0 separate.Vanadium oxychloride is formed when the pentoxide suspended in ether,acetic acid, or alcohol is treated with gaseous hydrogen chloride, thetemperature being kept low to prevent the production of vanadylchloride, VOC1,. With the hydrochlorides of pyridine and of quino-line, vanadyl chloride forms two series of double salts ; one series,Zeit. Elektrochem., 1905, 11, 45. Ibid., 503. Ibid., 555.Zeit. anorg. Chem., 1905, 46, 352.VOC1,,4(RHC1),xH2OINORGANIC CHEMISTRY.41green in colour, and another series, VOC1,,2(RRC1),~H20, the mem-bers of which are blue.1 The first of these is produced with solventssuch as absolute alcohol, glacial acetic acid, or a mixture of alcohol andether, which show but little ionisation, whereas the addition of waterto these solvents results in the production of the blue compounds.Similar changes in colour are observed on the addition of water to thesolutions of vanadyl chloride in alcohol or glacial acetic acid.An instance of the passage of a compound from a higher into alower state of oxidation has been observed by Prandtl,2 who found thatwhen a mixture of vanadium pentoxide and sodium carbonate to whichsome phosphoric acid has been added is fused before the blowpipe andallowed to cool slowly, the mass gave off oxygen.Prandtl and Lustig,3by dissolving vanadium pentoxide in aqueous solutions of seleniousacid, have obtained vanadioselenious acid, 3V205, 4Se0,,H20, fromwhich, by treatment with alkalis, a red and a yellow series of vana-dioselenites are obtained. Gold is dissolved by vanadic acid in pre-sence of hydrochloric acid, and from these solutions it is precipitated asa greyish-violet powder on treatment with an alkali. The followingreaction is, therefore, reversible under the conditions mentioned :Acid.Alkaline.3VOC1, + Au SVOCI, + AuCl,.Selenic and telluric acids behave in a similar manner, and on this reac-tion Hundeshagen 4 has based a method of testing minerals for vana-dium.The Argon Group.Depending on the different behaviour of these gases when broughtinto contact with charcoal cooled by liquid air, a method of separatingneon, krypton, and xenon has been described by Valentiner andSchmidt,5 whilst Ramsay6 has utilised the same property to deter-mine the proportion of neon and helium in the atmosphere, with thefollowing results : neon, 0.0000086 per cent.by weight and 0.0000123by volume; helium, 0*00000056 per cent. by weight and 0.000004 byvolume; the percentage of argon is given as 0.937.An appliance for grinding solids in a vacuum has been devised byMOSS,^ who has applied the same to the study of the gases given offfrom pitchblende and the condition in which helium exists in thismineral.Zeit anorg. Chem., 1905, 45, 345.lbid., 1305.Sitrmngsber. K.Akad. wiss. Berlin, 1905, 38, 816.Proc. Roy. Sac., 1905, Series A, 76, 111.Ber., 1905, 38, 657.* Chem. Zeit., 1905, 29, 799.7 Boy. Dub. SOC. Trans., 1905, 8, 15342 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRYMany of the investigations and the results obtained may con-veniently be classified under the headings of the several groups in theperiodic system of the elements. Judging by the number of com-munications published, the elements and compounds of Groups IV,V, VI, and V I I I appear to have attracted special attention during theyear.G r o u p I.A.-The study of the action of sodamide on a number and variety ofinorganic substances has shown this compound to be very energetic inits chemical properties, reducing the oxides of several metals and alsocertain metallic chlorides to the metals.With some oxy-compounds,such as nitrates of lead and silver, deflagration takes place whensodamide is rubbed with them, whilst when heated with potassiumchlorate it explodes with considerable violence (Ephraim).lLoeb 2 has noted a difference between sodium and potassium iodides ;when crystallised from alcoholic solutions, the latter crystallises withoutany of the solvent, whereas the sodium iodide separates in the form ofcompounds with the solvent ; in this manner the following have beenobtained : NaI,3CH3*OH ; NaI,C,H,*OH, and 5NaI,3C,H7*OH.By the action of sodium polysulphide in presence of caustic soda onsodium hyposulphite,3 both sodium sulphite and sulphate are formed,possibly with the temporary production of a thiosulphite, thus :(1) Na,S,O, + Na,S, + 2NaOH = Na2S,0, + Na,SO, + Na,S + H,O.( 2 ) Na,S,O, + 2NaOH = Na,S + Na,SO, + H,O.A study of the crystalline forms of potassium and thallous salts4 hasrevealed the isomorphism of the perchlorates, neutral sulphates, acidsulphates, and other oxy-salts of these metals.From the determination of the solubility of bromine in solution ofpotassium bromide, Worley5 has adduced evidence in support of theexistence of the tribromide, KBr,.Metallic rubidium and csesium6 can be obtained by heating thefused chlorides with calcium in exhausted glass tubes; the reactioncommences at 400-500° and the heat of the reaction is sufficient tovolatilise the metals.The pentasulphides of these metals are formedwhen the monosulphides are warmed with sulphur and an aqueousalkali hydroxide in an atmosphere of hydrogen ; Rb,S, crystallises inred prisms melting at 223-224'; Cs,S,,H,O forms red crystalsmelting at 2O3O.7 The fluoride and double fluorides of rubidium aredescribed by Eggeling and Meyer.81 Zeit. anorg. Chenr., 1905, 44, 185.3 Binz, Ber., 1905, 38, 2051.Trans., 1905, 87, 1107.7 Bcr., 1905, 38, 123,J. Amer. Chem. SOC., 1905, 27, 1019.Rec. trau. chim., 1905, 24, 65.Hackspill, Compt. rend., 1905, 141, 101.8 .@it, anorg. Chem., 1905, 46, 174INORGANIC CHEMISTRY. 43Rengade 1 has described the production of czesamide, (CsNH,), bythe spontaneous decomposition of caesium-ammonium, a reaction whichis complete at 120'.From liquid ammonia, the amide separates as awhite, crystalline solid ; it is readily oxidised, forming ammonia, and caes-ium nitrite and hydroxide. Potassamide behaves in a similar manner,whereas sodamide is not oxidised. The oxidation of caesium-ammoniumin liquid ammonia, under different conditions of temperature, yields theoxides Cs202, Cs203, and Cs,O,. By the slow oxidation of czesium-ammonium, the hydroxide and amide are formed; when the mixture isheated, the monoxide and amide react, producing caesium hydroxide,metallic caesium, and nitrogen.B.-Naumann and Rucker conclude that the solubility of silvernitrite is influenced by silver nitrate, much as sodium acetate affects thesolubility of silver acetate, a conclusion adversely criticised by Abeggand Pick,3 who find that only a portion of the silver nitrite is ionised.Clarke,4 by heating finely-divided minerals mixed with silver orthallous nitrate in sealed tubes a t the melting point of these nitrates,has shown that the sodium in silicates like analcite may be replaced bysilver or thallium ; thus, from NaAlSi,O,,H,O both AgAlSi,O,, H,Oand TlAlSi,O, have been prepared.Aurous iodide,5 AuI, is formed when iodine acts on gold a ttemperatures ranging from 50' to the melting point of iodine; it is agreen solid and can only be freed from excess of iodine by volatilisingthe latter at 30'.When heated to a somewhat higher temperature, itforms yellow plates, and a t 190' is resolved into its constituent elements.The production of a red hydrosol of gold 6 by the action of carbonmonoxide on dilute solutions of gold chloride (0*002--0*05 per cent. ofgold) may be used as a means of detecting small quantities of carbonmonoxide mixed with air.The melting point of gold is given as 1066~1-106'7~4° by Jaquerodand Perrot from determinations made with thermometers constructed ofsilica and filled with different gases, namely, nitrogen, air, carbon dioxide,carbon monoxide, and oxygen.The authors find that neither hydrogennor helium can be used in these thermometers, as these gases diffusethrough the silica, the diffusion commencing a t 200' with hydrogen,and possibly below 100" with helium. Results obtained with porcelainthermometers filled with nitrogen are also vitiated by diffusion of thegas.A process for the extraction of gold from sea water is describedby de Wilde.8 Van Heteren9 concludes that the allotropism of goldhas not been satisfactorily demonstrated.Compt. rend., 1905,140,1183 and 1536.Ibid., 2571.Conapt. rend., 1904, 139, 733.Arch. Sci. phys. nat., 1905, 20, 128.Chcm. Centr., 1905, 1, 503.Ber., 1905, 38, 2292.Zeit. anorg. Chem., 1905, $6, 191.Donau, Monatsh., 1905, 26, 525.Ibid., [iv], 19, 55944 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Many investigations have been made of the phenomena associatedwith the alloying of different metals with copper, silver, and gold, inmany instances the fusion diagrams indicating the formation of definitecompounds of the metals concerned.Gutbier and Hofmeier 1 obtain various coloured hydrosols of silverby the reduction of silver nitrate solutions containing gum arabic withhydrazine sulphate.Ammoniacal solutions of phenylhydrazine andhypophosphorous acid may also be used to reduce silver nitrate. I n theelectro-deposition of silver from solutions of the nitrate, good coherentdeposits are obtained if the cathode is rotated and the cathodic andanodic liquids separated ; further, by the addition of glue to the solu-tions, smooth, bright, purple or yellow deposits are obtained resemblingthe deposits obtained by Carey-Lea from solutions of organic salts(Snowdon 2).Group 11.A,-Some of the physical constants of metallic calcium have beendetermined by Moissan and Chavanne,3 who describe an amalgam,CaHg,, formed by dissolving the metal in mercury ; it is stable in dry air,is slowly attacked by water, and is useful as a reducing agent.has prepared three distinct alloys of calcium and aluminium, containing23.4, 41.74-45-44, and 80.55-83032 per cent.of calcium respectively.From these alloys, containing a large proportion of aluminium, thecalcium can be separated by distillation under reduced pressure. Alloysare also produced by electrolysing fused calcium chloride, using alumi-nium as cathode. For the purification and sterilisation of drinkingwater, the use of calcium peroxide has been suggested; 0.4 gramsterilises a litre in from fifteen to twenty minutes.5 Monocalciumsilicate in the form of hexagonal crystals has been prepared byBenzian 6 by heating sand and chalk together in a graphite crucible.Laboratory methods for preparing calcium by the electrolysis of thefused chloride, are described by Wohler 7 and by Goodwin.8Strontium-ammonium is formed in reddish-brown crystals by theaction on strontium of dry ammonia a t 60O.9 Barium amide, Ba(NH2),,I0is produced by the action of potassammonium on barium bromide;the last-named compound forms with dry ammonia the compoundBaBr2,8NH,.The phosphorescence of barium sulphide, prepared by the ignition ofthe thiosulphate, is much intensified by the addition of the nitrates ofArndt&it. nnorg.Chem., 1905, 45, 77.Compt. rend., 1905, 140, 122.Chent. Zeit., 1905, 29, 737.J. PhysicaE Ohm., 1905, 9, 392.Ber., 1905, 38, 1472.5 Freyssingi and Roche, Xev.intern. Palsif.> 1905, 18, 49.8 J. Amer. Chem. SOC., 1905, 27, 1403.lo D i d . , 1243.7 Zeit. Elektrochem., 1905, 11, 612.Compt. r e d . , 1905, 140, 1252INORGANIC CHEMISTRY. 45uranium, bismuth, or thorium before ignition ; these substances exert alike influence on strontium sulphide.1 The precipitation of calciumcarbonate from solutions of the nitrate by alkali carbonates has beenthoroughly examined by Meigen,2 who has also determined the conditionsof the change from amorphous carbonate to aragonite and calcite. Astudy of the influence of temperature and concentration of solutions ofammonium, potassium, and sodium chlorides on the action of these sub-stances on the carbonates of the alkaline earths has shown the rate ofaction of the chlorides to be in the order named, whereas the followingis the order in which the carbonates resist the action of the chlorides :barium, calcium, strontium; conimon salt has no action on strontiumcarbonate.3B.-Many examples of the reducing action of magnesium in form ofribbon and powder are described by Faktor,4 amongst others the reduc-tion of solutions of magenta, benzoquinone, potassium ferricyanide,and indigo.Carrick Anderson5 has found the basic carbonates ofmagnesium to be more complex than is usually supposed, the samplesexamined by him corresponding to the formulie20MgC03 ; 2lMg(OH),,BH,O ;14MgC03,10Mg(OH),,75H,0 ; and 19MgC03,20Mg(OH),,65H,0. Allare decomposed completely to the oxide when heated in an openvessel, but at temperatures ranging from 750' to 810° ; the higher thetemperature at which the oxide is formed the more slowly does itdissolve in water. According to Brill,6 the temperature a t which theproducts of dissociation exert a pressure of one atmosphere is in thecase of calcium carbonate -825', and 1155' for strontium carbonate.Magnesium carbonate forms a series of basic carbonates, the tempera-tures of dissociation of seven of which are given.Grube,7 from an examination of the alloys of magnesium and leadconcludes that one compound, PbMg,, is formed, similarly tin formsonly one definite compound, SnMg,, conclusions which are confirmed byKurnakoff and Stepanoff.8 With thallium there are indications of theexistence of the three following compounds : Tl,Mg,, TlMg,, and Tl,Mg,.gMagnesium and aluminium lo appear to form only one definite compound,Al,Mg,, in the form of very brittle, silver-white needles.The alloyscontaining from 5 to 30 per cent. of magnesium are technically knownas magnalium. A second series of alloys form homogeneous con-glomerates of mixed crystals, capable of a high polish, whilst thosecontaining 55 to 68 per cent. of magnesium consist of the crystalsVanino and Gaus, J. pr. Chem., 1905, [ii], 71, 196.2 Chem. Centr., 1906, [i], 1363.Chem. Centr., 1905, [i], 1305.Zeit. anorg. Chem., 1905, 45, 275.Ibid., 46, 177.BUZZ. Soc. chim., 1905, [iii], 33, 13.Zeit. anorg. Chem., 1905, 44, 117.ti Trans., 1905, 87, 257,lo IbM, 45, 225.0 Ibid., 46, 7646 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of Al,Mg, mixed with a soft eutectic. The alloys of magnesiumand aluminium together with other alloys containing the latter metal,when recently filed, decompose water with the liberation of hydrogen,the oxygen being absorbed by the aluminium (Pecheux).lBoth mercurous and mercuric thiocyanates dissolve in potassiumthiocyanate, forming complex double salts.2 Ditte has obtained aseries of double salts by the action of concentrated sulphuric acid andof mercury sulphate in sulphuric acid on mercuric iodide. Whenmercuric oxide is heated with mercurous halides in sealed tubes at1 60-180°, the following oxyhalides are formed : HgC1,HgO; HgBr,HgO;and HgI,3HgO ; they are red solids.The preparation of a series ofheavy liquids by adding alternately mercuric iodide and an alkaliiodide to water until saturated is described by DuboinO5 The specificgravities of the liquids range from 2.98, that of the ammonium mercuriciodide, to 3-46, the specific gravity of the sodium mercuric iodide.The amount of the precipitate formed when a solution of ammoniummercuric chloride is added to a natural water is proportional to thetemporary hardness; no precipitate is formed if the water has beenpreviously boiled.6Group r nA.-Perborates are described by Jaubert,7 also by Bruhat andDubois.8 According to the first author the perborate, Na2B408, 1 OH,O,is obtained by adding boric acid and sodium peroxide to water; bytreatment of this compound with hydrochloric acid equivalent to halfthe sodium contained in it, crystals of the perborate, NaB0,,4H20,separate out.Bruhat and Dubois obtain this compound by the electro-lysis of solutions of sodium orthoborates. The perborates are stable inthe solid state, but their solutions on warming readily decompose withthe liberation of oxygen. The solutions of the perborates containhydrogen peroxide and provide a good method of preparing thissubstance.9A complex series of calcium chloroborates formed by fusing borontrioxide and calcium chloride together is described by Ouvrard.10Wedekind and Fetzer 11 have obtained two manganese borides ; theboride MnB, is formed by heating boron with manganese thermite,1 Compt. rend., 1905, 140, 1535.2 Grossmann, Zeit.anorg. Chem., 1905, 43, 356.3 Compt. rend., 1905, 140, 1162.4 Fischer and von Wartenberg, Chm, Zeit., 1905, 29, 308.6 Compt. rend., 1905, 141, 385.6 Villenet and Cheiiu, Bull. SOC. china., 1905, [iii], 33, 944.7 Compt. rend., 1904, 139, 711.9 Chem. Centr., 1905, [ii], 99.10 Compt. Tend., 1905, 141, 351.Ibid., 1905, 140, 506.l1 BcT., 1905, 38, 1228INORGANIC CHEMISTRY. 47whilst MnB is produced by heating manganese suboxide with boron inthe electric furnace.B.--The double chromium aluminium silicide, Cr,AlSi,, and also thecompound Cr,AlSi,, are formed by heating together chromium,potassium dichromate, or potassium chromofluoride with a large excessof potassium silicofluoride and aluminium. They are dark grey, crystal-line solids, which resist the action of acids excepting hydrofluoric acid,and are attacked by molten alkali hydroxides.Similar tungstencompounds have been prepared.1The solution of aluminium chloride in carbonyl chloride leaves onevaporation the compound 2AlC13,5COC1,, from which, by the gradualremoval of carbonyl chloride, other compounds are produced, untilfinally the double chloride, A1C13,COC1,, is formed, which forms silkyneedles and is not decomposed at 75P. This compound is present incommercial aluminium chloride and is formed when aluminiumchloride is distilled in sarbonyl chloride or when carbon monoxideand aluminium chloride are together passed through red-hot tubes.2Colani 3 has described the production of phosphides, arsenides,antimonides, silicides, and borides of metals by heating a mixtureof a metallic oxide with the nan-metal or its oxide and aluminiumpowder.The mixture is inflamed by a magnesium cartridge ; in caseinfusible products are expected to result from the action, the additionof copper oxide or tin oxide should be made to the aluminium. Theseobservations are confirmed by Matignon and Trannoy.4Prix~g,~ in an investigation of the astion of aluminium carbide, hasfound that up to 1400° the carbide acts as a reducing agent on metallicoxides, both constituenta being oxidised, thus :Al,CJ, + 12MO = 2A1,03 + 3C0, + 12M,whereas a t higher temperatures alloys of aluminium and the metal areproduced and the carbon only oxidised, for example :3CuO + A1,C3 = 4A1, ~ C U + 3CO.These results are explained by the fact that alumina can be reduced bycarbon at high temperatures, whereas at low temperatures carbon mon-oxide oxidises aluminium.The reaction at low temperatures,6A1+ 3CO = Al,C, + A1,0,,is reversed a t higher temperatures.From the manner in which aluminium powder absorbs oxygen atManchot and Kieser, Annalen, 1904, 337, 353.Compt. rend., 1906, 141, 190.a Baud, Compt. rend., 1905, 140, 1688. Ibid., 141, 33.Trans., 1905, 87, 153048 ANNUAL REPORTS ON THE PROGRESS OF CHEMlSTRY.different temperatures, Kohn-Abrest 1 infers the existence of severaloxides of aluminium. Shepherd 2 has, by the study of the curves of thespecific volumes of the alloys of zinc and aluminium, confirmed the con-clusions of Heycock and Neville as to the non-existence of definitecompounds of these metals. The effect of tempering on the copperaluminium bronze, known as '' fortior," is similar to that produced onsteel.The change is due to the production a t 650-750' of a newconstituent which appears in the form of needles embedded in agranular substance. This substance increases in quantity until at 950°it is the only constituent, the change being associated with a doublingof the elastic limit and breaking strain of the alloy. The compositionof commercial varieties of magnalium and other light alloys which havebeen applied industrially has been dealt with. by Barnett.3Group IV.A.-Moissan,4 in repeating his experiments on the production of thediamond, has found that the yield is much increased by the presence ofiron sulphide and of silicon.The same author has shown that the carbonsilicide of the Cafion Diablo meteorite is identical with the syntheticalsilicide, CSi.5 The heat of combustion of the carbon produced by thedecomposition of acetylene is found by Mixter 6 to be 7894 cals., whereasthose of sugar charcoal and graphite are 8057 and 7831 respectively.This carbon is regarded as another allotropic form of the element.Ammonium cyanate and not cyanide is, according to Jackson andLaurie,7 formed by the passage of a mixture of carbon monoxide andammonia over heated platinum or by subjecting the mixture to silentelectric discharge or by sparking the gases.The proportion of incompletely oxidised carbon compounds in freeair has been determined by Wolpert ; the proportion in the air ofBerlin is given as 0.015 volume per 1000 volumes.The action of carbon monoxide on dry silver oxide takes place a t theordinary temperature and is associated with an evolution of heat, thus :Ag,O + CO = Ag, + CO, + 61 -2 cals.I n some instances it is necessary to apply heat to start this reaction,a temperature between 40" and 50" being sufficient.Silver oxide sus-pended in water reacts similarly, but better when dissolved inamm~nia.~1 Compt. rend., 1905, 141, 323.3 J. SOC, Chem. Ind., 1905, 24, 832.7 Trans., 1905, 87, 433.0 Dejust, Corn@. rend., 1905, 140, 1250.J. Physical Chem., 1905, 9, 504.Compt. rend., 1905, 140, 277.Amer.J. Sci., 1905, 14, 434.8 Arch. Hygiene, 1905, 52, 151.Ibid., 405INORGANIC CHEMISTRY. 49The knowledge of titanium compounds has been greatly extended bythe researches of Stahler 1 and of Stahler and Wirthwein.2 As a meansof producing the tetrachloride, rutile or titanic iron ore is conyertedinto the carbide in the electric furnace, and the crude chloride formedfrom it by the action of chlorine; after shaking up with sodiumamalgam, the product is distilled under reduced pressure. By the actionof dry ammonia under different conditions, the compounds TiC1,,8NH3and TiCl,,GNH, are formed, from either of which, on treatment withliquid ammonia, titanamide, Ti(",),, is obtained. Amongst the tervalenttitanium compounds described is a series of sparingly soluble oxalateshaving the following formule : Ti(C20J3, 10H20; Ti(NH,)(C,0,),,bH20;TiK(C204)2, 2H20 ; and TiRb(C204)2, 2H20.B.-Silicochloroform,~ SiHCl,, is produced by cooling the gaseousproducts of the action of hydrochloric acid on copper silicide with liquidair ; it boils a t 33O (758 mm.), melts at - 1 3 4 O , and has a sp.gr. of 1.3438.Its decomposition by caustic soda with the production of orthosilicicacid, sodium chloride, and hydrogen has been utilised in the analysisof the compound. When heated at 800°, it is resolved into silicontetrachloride, silicon, and hydrogen, a reaction which is reversible. Itsreactions with several oxides are described, and with ammonia it givesrise to the formation of silicon nitrogen hydride, SiNH, the analogueof hydrogen cyanide, a compound difficult to free entirely from theammonium chloride simultaneously produced.This hydride is decom-posed by caustic soda, forming sodium orthosilicate, ammonia, andhydrogen. Silicofluoroform, SiHF,, has also been obtained by Ruffand Albert 4 by the interaction of silicochloroform and stannic fluoride ;i t is a gas condensable to a liquid boiling at 80.2O ('758.5 mm.), andforms a solid melting at - llOo. I n sealed tubes, it slowly decomposesat the ordinary temperature into hydrogen, silicon fluoride, and silicon ;the decomposition is accelerated by heat. Silicofluoroform burns in airwith a pale blue flame, its temperature of ignition being somewhathigher than that of the corresponding chlorine compound.It isdecomposed by water and with alcohol yields ethyl orthosilicate,Si(O-C2H5)4, whilst with ether it forms the compound SiH(O*C,H,),,ethyl orthoformate.The production of borides, silicides, aluminides, &c., by the inter-action in the electric furnace of metallic chlorides and elementarysubstances, for example, silicon and boron, is made the subject of apatent by Jiingst and Mewes.5 I n the reaction, a volatile chloride ofsilicon or boron is formed, the metal combining to form a silicide orBey., 1904, 37, 4405. Ibid., 38, 2619.a Ruff and Albert, Ber., 1905, 38, 2222.Bern, 1901, 38, 53. D.R.-P. 157615.VOL. 11. 50 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.boride, thus calcium chloride and iron yield ferrous chloride andcalcium ferride.Hydrated metatitanic acid and some other metallic acids are violentlyattacked when heated with crystalline silicon, titanium trioxide beingformed and hydrogen liberated ; the amorphous variety of silicon doesnot react in this way.l M.Berthelot2 has recorded experiments onthe permeability of silica tubes by the gases oxygen, nitrogen, andhydrogen a t high temperatures. The experiments of Mylius andMeusser3 show that quartz vessels are not attacked by water or diluteacids a t temperatures up to loo', but are acted on by alkalis even atthe ordinary temperature.Pfeiffer4 has found that a freshly prepared solution of stannicchloride in water gives an ethereal extract, from which lightpetroleum precipitates SnCl,OH, H,O( C,H,),O in deliquescent needleswhich decompose at 160'.A similar compound has been obtained fromstannic bromide; further, stannic bromide treated with absolute alcoholyields glistening leaflets of the compound SnBr,(O*C,H,)( C,H,),O.Bellucci and Parravano 5 support their view of the constitutionof stannic acid6 by the isomorphism of potassium stannate withpotassium platinate and plumbate. Perstannic acid is formed whentin dioxide is ground up with hydrogen peroxide; dried at TO', ithas the formula IISn04,2H20, and at 100' it forms H,Sn,0,,3H20.Perstannic acid is decomposed by water ; a potassium perstannate,KSnO,, 2H,O, has been prepared by the action of hydrogen peroxideon potassium stannate; by continued drying it is converted intoK2Sn207, 3H,O. Potassium perstannate forms with water an alkalinesolution which reduces potassium permanganate and sulphuric acidwith a liberation of oxygen; it forms a white precipitate with leadsalts, gradually decomposing with the production of lead peroxide, afact regarded as supporting the view that the compounds are trueperstannates and not substances with hydrogen peroxide of crys-tallisation (Tanatar).7The refining of lead by the electrolytic decomposition of solutions oflead fluosilicates with an unrefined lead as anode, a method nowcarried out commercially, is discussed by Senn.8 The addition ofgelatine solutions is found advantageous, the copper, bismuth, andantimony in the anode remain undissolved, and the anode usedcontains both silica and lead fluoride. It is found impossible toseparate platinum and lead by this process, owing to the formation ofZeit.anorg, Chem., 1906, 43, 370.Zeit. nnorg, Chena., 1905, a, 221.Atti €2. Aecad. Lincei, 1905, [v], 14, i, 457,See Ann. Reports, 1904.Zeit. Elektrochem., 1905, 11, 229,Compt. rend., 1905, 140, 817 and1169.Ber., 1905, 38, 2406.7 Ber., 1905, 38, 1184INORGANIC CHEMISTRY. 51a crystalline compound having the formula PtPb,. Cadmium may alsobe deposited from the solutions of its fluosilicate. The current yield withlead solutions is found to be 98 per cent. of that required by theory.Galena and other native metallic sulphides yield the metals whenheated with sodium nitrate ; red lead is produced when the metal isadded to the fused nitrate containing some potassium chlorate.1 Theformation of an oxyiodide by the absorption of oxygen by fused leadiodide explains, according to Schtscherbakoff the anomalies observedby chemists in the electrochemical behaviour of lead iodide. Thisoxyiodide is formed by the action of steam on heated lead iodide andmore slowly by boiling lead iodide with water.Lead iodide is stablein an atmosphere of carbon dioxide and can be sublimed in it. Theproduction of a definite lead potassium sulphate, K,Pb(SO,),, isdescribed by Belton.3G r o u p T?A.-Nitrogen and its compounds have attracted considerable atten-tion during the year ; Baxter and Hickey suggest the preparation ofnitrogen by passing nitric oxide and ammonia over heated copper orplatinised asbestos, whilst Hulett 5 has described a method whichshould be serviceable in the easy preparation of this gas.Hydrogen isburnt in a carefully regulated stream of air, and the products arepassed over heated copper and copper oxide, and the nitrogen collected inthe usual way. Tower6 has found that at about 2000’ nitrogen canreduce steam, forming nitric oxide and hydrogen.The behaviour of ammonia a t high temperatures and also ofmixtures of nitrogen and hydrogen have been the subject of severalresearches. Perman 7 concludes that ammonia cannot be synthesisedby heat : that i t is produced by the direct union of its elements whenthe gases are “ionised,” for example, by exploding with oxygen, byheating with many metals, or by sparking the mixed gases.8 Amethod of producing ammonia industrially by the interaction of nitricoxide and hydrogen in presence of platinum black has been patentedby the Westdeutsche Thoma~phosphatwerke.~ Yeley lo has shown thatthe liberation of ammonia from aqueous solutions of ammonium saltsMatuschek, Chem.Zeit., 1905, 29, 510.J. Buss. Phys. Clzern. sbc., 1905, 37, 682 ; also Bogorodsky, ibad., 609.Chm. News, 1905, 91, 191.Amer. Chem. J., 1905, 33, 300.J. Anzer. Chin. Xoc., 1905, 27, 1415. Ibid., 1209. ’ Proc. Roy. Soc., 1905, Series A , 76, 167.See also Haber and van Oordt, Zeit. tnzorg. Chem., 1905, 46, 111 ; 44, 341 ;D.R.-P. 157287. lo Trans., 1906, 87, 26.White and Melville, J. Amer. ClzenL. Xoc., 1905, 27, 373.E 52 ,4NNUAL HEI’OHTS ON THE PROGRESS OF CHEMISTRY.heated to boiling is due to the hydrolysis of these compounds and notto dissociation. Hydrazoic acid is formed by the oxidation of hydr-azine by hydrogen peroxide and sulphuric acid.1 The oxidation ofhydroxylamine by Caro’s acid yields nitroxyl, which Angelo andAngelica regard as either NH(OH), or the anhydride, NHO.Silberrad 3 concludes, from the study of the action of zinc ethide onnitrogen iodide, that its constitution is represented by the formulaH,N:NI,, a view supported by the investigation of its metalliccompound^.^The conditions favourable to the oxidation of atmospheric nitrogenin the electric arc have been investigated by Stavenhagen,5 whilstvon Lepel 6 has studied the influence of metallic salts distributed inthe cathode on this oxidation.7 Rossis has noted the production ofnitric oxides by the action on compressed air of incandescent bodies,such as the filament in the Nernst lamp.It is suggested that theyield is sufficient to be of industrial importance in the manufacture ofnitric acid.An interesting method for the production of a mixture of nitricoxide and nitrogen peroxide is that described by Matu~chek,~ dependenton the interaction in aqueous solutions of ferric chloride and sodiumnitrite.R&y1* has continued his researches on the nitrites, discussing theconditions influencing the formation of ten different products of theaction of nitric acid on mercury. This author I1 has also prepared thenitrites of alkali- and alkaline-earth metals which are formed by theinteraction of the chlorides on silver nitrite.The solutions of thesenitrites may be evaporated in contact with the air without undergoingoxidation. These nitrites have a yellow colour, the depth of whichincreases with the atomic weight of the metal. Magnesium nitrite isthe least stable of those of the alkaline earths forming, as magnesiumdoeg in many other cases, a link between the nitrites of zinc andcadmium and those of calcium, strontium, and barium.R&y and Gafiguli 12 have recently described two varieties of silvernitrite, the one having the formula AgNO,, the other the formulaAgONO ; but Divers 13 has shown that the evidence advanced by theseauthors in support of the existence of these two varieties is capable ofanother intermetation.1246781012LBrowne, J.Amer. Chem. Soc., 1905, 27, 651.Bazaetta, 1905, 35, [i], 152.Ibid., 66.Ibid., 2524.See also Scheuer, Zeit. Elektrochem., 1905, 11, 563.Gazzetta, 1905, 35, [i], 89.Trans., 1905, 87, 171.Proc., 1905, 21, 279.Trans., 1905, 87, 55.ti Ber., 1905, 38, 2171.Chem. Zeit., 1905, 29, 31.l1 Ibid., 175.l3 Ibid., 281INORGANIC CHEMISTRY. 53Nitroxyl fluoride (N0,F) is formed by the action of nitric oxide onfluorine at the temperature of liquid oxygen. It is a colourless gas,which attacks the mucous membrane ; it has been solidified and melts a t- 139O, forming a liquid boiling a t - 63.5’. The discoverers of thiscompound, Moissan and Lebeau,l describe its reactions with a numberof substances, the decomposition by water yielding hydrofiuoric and nitricacids, which reaction has been utilised in its analysis. Nitrosyl fi uoride,NOF, formed, according to Ruff and Stauber,2 by the action of silverfluoride on nitrosyl chloride, resembles fluorine and nitroxyl fluoride,but differs from these in its density and action in water.Ruff andGeisel,3 continuing their researches on nitrogen sulphide find the solu-tion of sulphur in liquid ammonia affords a method of preparing thesulphide. The action of sulphur and liquid ammonia resulting in theformation of hydrogen and nitrogen sulphides is a reversible one, theremoval of the former as silver sulphide by means of silver iodide dis-solved in ammonia favouring the formation of the nitrogen sulphide,which can be obtained by evaporating off the ammoniafrom the filtrateleft after the removal of the silver sulphide. The blue colour of thesolution of sulphur in liquid ammonia is attributed to colloidalsulphur.B.-It would appear that the term red phosphorus embraces a numberof modifications; a scarlet variety is described by Schenck; 5 it isdeposited from the solutions of phosphorus in phosphorus iodide,sulphide (P4S3), or tribromide.The scarlet modification is an amor-phous solid which phosphoresces in ozone, but not in air ; it is dissolvedby alcoholic potash, from which solution acids precipitate the hydridePI2H6, and when heated it is converted into the red modification. Thephosphorescence of phosphorus is not, according to Jungfleisch,B due tocombustion of phosphorus, but to the formation of an oxide which ismore volatile than phosphorus, and which, by its spontaneous combus-tion, gives rise to the phenomenon in question.The subiodide ofphosphorus, P,I, is produced by the action of dry iodine on phosphorusdissolved in carbon disulphide; with alkalis, it reacts to form thesuboxide, P,(OH).” Stock and Thiel have prepared the pentasulphideby heating the solution of phosphorus and sulphur in carbon disulphideat 120-130‘ with a trace of iodine. The pentasulphide in appearanceresembles the flowers of sulphur, and exists in two varieties, differingin solubility in carbon disulphide, the less readily soluble form havinga molecular formula, P4Sl0, whilst the other variety appears to have alower molecular weight.Compt.rend., 1905,140, 1573 and 1621.Ber., 1905, 38, 2659.Zeit. Elektrochem., 1905, 11, 117.Zcit. nnorg. Chem., 1905, 47, 190.See Ann. Reports, 1904,Compt. rend., 1905, 140, 444.Ber., 1905, 38, 2719. 7 Boulough, Conzpt. rend., 1905, 141, 25654 Ah’NUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Stock and Siebert describe another mode of formation of the yellowmodification of arsenic, and Lockemann2 has drawn attention to thecatalytic decomposition of arsine by cotton wool, glass wool, or alcohol,an observation of importance in connection with the detection of arsenicby the Marsh test.The halogen double salts of tervaleiit antimony are colourless,those of quinquevalent antimony have a slightly green tint, whilstthe double salts containing quadrivalent antimony are stronglycoloured.The latter are formed by taking a solution of antimonytrichloride, dividing it into two equal parts, one half after oxidationwith chlorine being added to the other portion. Such a mixture containsthe chloride of quadrivalent antimonySbC1, + SbC1, BSbCl,,the proportion depending on the temperature and concentration ofhydrogen chloride. By adding rubidium chloride and hydrochloricacid to such solutions containing SbCl,, Rb,SbCl, is formed as a black,crystalline powder ; the corresponding ammonium and pyridine saltshave been prepared. These and other double halides are described byWeinland and $chmidt,3 who, by treatment of the solution ofantimony trioxide in hydrochloric acid with chlorine, and subsequentlywith hydrogen chloride, have obtained metachlorantimonic acid,HSbCl,, 44H,O, in the form of greenish-yellow, hygroscopic prisms.Theauthors describe a series of ammonia metachlorantimonates, as alsopyridine and quinoline salts of this acid,4 thus :BgSbCl,, BNH,, Cu(SbCl,),, 5NH,, HSbCl,,C,H,N, and HSbC1,,C,H7N.Group VI.A.-The production of oxygen from bleaching powder by the simul-taneous action of a ferrous or manganous salt with a salt of copper,nickel, or cobalt is patented by Jaubert.5‘ Julius Meyer 6 considersthe facts of auto-oxidation are best explained on the assumption thatan unsaturated molecule is added to a molecule of oxygen, one atom ofwhich functions as a quadrivalent atom. The grouping 0:O: is pro-bably more common and more stable than that of two quadrivalentoxygen atoms, just as in the case of nitrogen compounds the groupingN”’:N’ is more common and stable than two quinquevalent nitrogenatoms. Hydrogen peroxide is, therefore, regarded as OIOH,, exist-ing in the unimolecular state only, whereas water in the bimole-cular form is H,O:OH,.The formulz are proposed for the peroxides :Ber., 1905, 38, 966.3 Ber., 1905, 38, 1080.D.R.-P. 157171.Zeit. angew. Chem., 2905, 18, 491.Zeit. anorg. Chem., 1905, 44, 37.J. p. Chem., 1905, [ii], 72, 278INORGANIC CHEMISTRY 55ozone, 0 :O: 0, barium peroxide, 0 :OBa, potassium peroxide, 0: OK,, andsodium hydrogen peroxide, 0:OHNa. McIntosh has continued hisresearches on the basic properties of oxygen and materially extendedthe list of compounds formed by alcohol, ether, and acetone with acidsand acidic elements, the formation of which is most readily explainedby assuming that the oxygen contained in these organic substances isquadrivalent at low temperatures.The production of ozone by theultra-violet light produced by the mercury arc lamp has been investigatedby Fischer and Braehmer,, who find that no ozone is formed at tempera-tures above 270", and conclude that the production of ozone by thesilent electrical discharge is probably due to the action of light, asWarburg has shown that, in the silent electrical discharge both ultra-violet rays and cathode rays are produced.Chromium deposited electrolytically from solutions of chromic acidoccludes about 250 times its volume of hydrogen.3 Colson's researcheson the sulphates of chromium show that a normal green sulphate,Cr,( SO,),, 1 OH,O, is formed by reducing a solution of chromic acid withsulphur dioxide a t 0'.This sulphate is isomeric with violet chromiumsulphate, and by boiling its aqueous solutions a pentasulphate is formed,for which the formula SO, is pr~posed,~ the greenCr : SO,Cr:SO,' sulphate being SO,< I Potassium and ammonium chromoxalatesform isomorphous mixtures ; these complex salts can, as has been pro-posed by Camer~n,~ be derived from Cr(OH), by the step by stepreplacement of the hydroxyl groups by univalent radicles (C,O,M)',thus Cr(C20,K),, OH=Cr(C20,K)2, and so on.The researches ofRiesenfeld, Wohlers, and Kutch on the higher oxidation products ofchromium show that the oxidation of ammonium chromate by hydrogenperoxide yields, according to the proportion of peroxide used, either redsalts or blue salts, and not the substances described by Hofmann andHiendlmaier.7 The red salts are derivatives of an acid H3CrOg, whilstthe blue salts correspond to the acid H,Cr07. I n neutral or alkalinesolutions, the red salts are decomposed to chromates, whilst in acidsolutions blue perchromic acid is first formed, rapidly passing into achromic salt. From the blue ethereal solutions of perchromic acid,Byers and Reid8 have prepared a number of salts of this acid, The1 Trans., 1905, 87, 784, and J.Amer. Chent. Soc., 1905, 27, 1013.3 J. Physical Chem., 1905, 9, 353.4 Compt. rend., 1905, 140, 42, 372, 1451 ; 141, 114, 331.5 Proc. Roy. Soc. Edin., 1905, 25, 727.8 Amer. Chem. J., 1904, 32, 503.Ber., 1905, 38, 2633.Ber., 1905, 38, 1885. See Ann. Beports, 190456 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.potassium salt, KCrO, or K,Cr,O,, is formed as a purplish-black solidby the action of potassium on the ethereal solution at - 209Molybdenum1 can be obtained by the Goldschmidt method, usingfluorspar as flux. The insoluble trichloride, MoCl,, resembles redphosphorus in appearance and reacts with gaseous ammonia at 340° toform a black solid, Mo,(NH,),CI,, which at 760" decomposes and givesthe nitride Mo,N, as a metallic powder.The insoluble tribromide,MoBr3, prepared like the chloride by Blomstrand's method, formsblack needles, and is converted into the metal by ammonia. Thesoluble chloride, prepared by electrolysing the solutions of molybdenumtrioxide in hydrochloric acid, gives on treatment with potassiumfluoride crystalline potassium molybdenum fluoride, KMoF,,H,O.By the interaction of tungsten hexachloride and hydrogen fluoride atlow temperatures, Ruff and Eisner2 have obtained the gaseous hexa-fluoride, WF6, which is the heaviest gas known, being ten times asheavy as an equal volume of air; it is a very active compound, attack-ing glass and metals. The use of tungstic trioxide as a glaze onporcelain is limited by the fact that it becomes opaque at high tempera-tures, but by fusing it at 800' with lead silicate or a mixture of zincborate and silicate Granger has succeeded in obtaining a permanentyellow glaze.&-In molten sulphur there appear to be two varieties of theelement which are only partially miscible, namely, Sb a yellow, mobileform which predominates at temperatures between the melting pointand 160", and S,, a brown, viscous form which constitutes the chiefportion above 160°., Sulphur is soluble in benzyl chloride, andseparates from its solution in this medium in rhombic crystals.5 Theprimary action of alkali hydroxides on sulphur is suggested by Pomeranz 6to be similar a t the outset to their action on chlorine in the cold, and toresult in the production of a sulphide and a hyposulphite. The forma-tion of polysulphides and thiosulphates is due to subsequent reactions.The action of sulphur and sodium hydroxide under the above-mentionedconditions may be represented as follows :S, + 3NaOH = NaHSO, + Na2S + H,O.Solutions containing sulphur and caustic soda bleach p-nitjaniline-red, as sodium hyposulphite does.The composition attributed to thehyposulphite is, it will be noted, at variance with Bernthsen's formula,Rosenheim and Rraun, Zeit. anorg. Chem., 1905, 46, 311.b ' e ~ . , 1905, 38, 742. Compt. mnd., 1905, 140, 935.-1 Smith, PYOC. Bop. SOC. Edin., 1905, 28, 588, 590.Boguski, J. RWSS. Phys. Chern. Soc., 1905, 37, 92.Zeit. Farb. Text. lnd., 1905, 4, 392INORGANIC CHEMISTRY. 57who adheres to the view that the sodium salt is Na2S204,2H,0, and nota double salt of the composition NaHSO,,NaHSO,,H,O.Bernthsen 1has suggested that the name “ hyposulphite ” should be restricted to thesalts R’2S204, and that salts RHSO, and R,SO, should be styled‘‘ sulphoxylites.” Several authors have busied themselves with thepreparation and properties of the hyposulphites, and Billy states thatthe sodium salt is not formed by the action of sulphur dioxide onsodium amalgam in presence of ether or light petroleum unless a traceof alcohol be present. Observations on the oxidation of sodium hypo-sulphite have been made by A. LumiBre, L. Lumihre, and Seyewetz,3and by Binz.*The contact process for the manufacture of sulphuric acid has beenthe subject of several researches ; Kiister has found platinum to be themost efficient catalytic agent and the only one of technical importance ;Bodenstein and Pohl,6 also L u c ~ s , ~ have investigated the equilibriumbetween sulphur dioxide, oxygen, and sulphur trioxide.From the cryoscopic study of the solutions of copper sulphate, Colson 8concludes that the molecular complexity of this compound is (CUSO,)~,and that the composition of the sulphates of bivalent metals in aqueoussolutions is represented by the formula (HSO,M),O ; the sulphates aresupposed to be formed by the condensation of two molecules of sulphuricacid with hydroxides of the formula (OHM),O. Many of the reactionsof such sulphates, for example, their acidic properties, are readilyexplained by these assumptions.Hantzsch and Stuer 9 conclude that the gelatinous product formedwhen sulphuryl chloride dissolved in light petroleum is attacked byammonia is probably ammonium uci-sulphomelide, S,O,N,( ONH,),,sulphomelide being the analogue of cyamelide, formed by the action ofammonia on carbonyl chloride in light petroleum.Sulphomelide formssalts, whereas cyamelide does not ; whilst sulphomelide has the constitu-tion NH:SO<O.SO.NH>O, O*SO*NH and is a pseudo-acid, the aci-sulpho-melide would be OH*NS<g:$$gE{>O, a true acid. Further, it isshown that the trisulphimide described by Hantzsch and Holl is inreality iminosulphonamide, NH,*SO,*NH~SO,*NH,, formed by theaction of water on trisulphimide, thus :NH<S02.NH>so2 SO *NH + 2H,O = NH,*SO2*NH*SO2*NH2 + H,SO,.21 Rcr., 1905, 38, 1048 ; see also Prud‘homme, Bt~ll.SOC. chim., 1905, [iii], 33,3 Bull. SOC. clzim., 1905, [iii], 33, 931.Zeit. tmorg. Chene., 1904, 42, 453.7 Ibld., 1905, 11, 457.Ber., 1905,.38, 1022.129 ; and Bazlen, Ber,, 1905, 38, 1057. Comnpl. rend., 1905, 140, 936.Zeit. Fnrb. Text. Ixd., 1905, 4, 161.ti Zeit. Elektrocicm., 1905, 11, 373.8 Compt. wnd., 1904, 139, 85758 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Iminosulphonamide is a monobasic acid, moderately stable towardsalkalis, forming salts of the type RN(SO,*NH,),, which by an excess ofalkali are resolved into ammonia and aminosulphonates.Double sulphates of uranyl and the alkali metals, for example,K2S0,,U02S04,2H,0, are described by de Coninck and Chauvenet ; 1these compounds are formed by the action under pressure of acid sul-phates of the alkali metals on uranic hydroxide.Magnesium powder, when heated with an anhydrous sulphate, reactswith very considerable energy; in all cases excepting that of the alkalisulphates, sulphur dioxide is produced, frequently sulphur, magnesia, theoxide, sulphide, and thiosulphate of the metal.Sulphur trioxide passedover heated magnesium gives sulphur dioxide, oxide, and sulphide ofmagnesium (Bruckner).2 Colloidal modifications of selenium andtellurium are formed by the reduction of selenious or telluric acids byhydroxylamine or hydrazine in presence of sodium protalbate or1ysalbate.s The precipitates formed by the action of hydrogen sulphideon selenious acid are mixtures of selenium and sulphur.4 Uranylselenide, UO,Se, formed by heating together selenium, potassiumcyanide, and uranium oxide, is described by Milbauer,5 who, by replac-ing uranium oxide by chromium sesquioxide, has obtained potassiumchromic selenide, K,Cr,Se4.Hutchins,G from a careful revision of the preparation and propertiesof the tellurates, concludes that there are no well authenticated cases ofisomorphism amongst the tellurates and sulphates.Group V I LA.-Of manganese there is little to record beyond the borides alreadymentioned.Four manganous sulphides exist according to Olsen andRapalje ; 7 the red and green are anhydrous, a grey variety contains alarge proportion of water, whilst the pink sulphide is a mixture ofthe grey and red.A double chromate of potassium and manganese,K,CrO,,MnCrO,, 2H20, crystallising in red prisms, has been preparedby Groger;* the production of manganese chromates by the action ofsoluble chromates on manganese chloride is rendered difficult by theready decomposition of manganous chromate into chromium manganite,(Cr2( MnO,),), and chromic anhydride. The absorption spectrum ofcarefully prepared manganous chloride has been shown to consist ofBUZZ. Acad. roy. BeZg., 1905, 7, 50, 94, 151, 182.Monatsh., 1905, 26, 675.Gutbier and Lohmann, Zeit. anorg. Chem., 1905, 43, 384.Did., 1904, 42, 450.J. Amer. Chem., 1905, 27, 1157.J. Amer. Chem. SOC., 1904, 26, 1615.8 Zeit. anorg. Chem., 1905, 441, 453.3 Paal and Koch, Ber., 1905, 38, 526 and 534INORGANIC CHEMISTRY.59(1) a broad band h513---X557*5, (2) a less intense band, X4XL--X442.5,and (3) a group of six bands from X410--X695.123.-An examination of the properties of hydrofluoric acid has beenmade by Deussen,2 who from the manner in which it affects the inver-sion of cane sugar places this acid with the weak acids, such aschloracetic acid. Hydrofluoric acid may be titrated by caustic sodaor potash with phenolphthalein as indicator; it interferes with thetitration of ferrous salts by potassium permanganate. I n the separa-tion of alumina from ferric oxide when the former predominates,Deussen recommends fusion with potassium hydrogen fluoride. Theremoval of rust from ironis readily affected by hydrofluoric acid.Ruffand Thiel3 have found in the action of hydrofluoric acid on nitrogensulphide and copper oxide a method of preparing thionyl fluoride. Thefluoride in presence of carbon or of sunlight reacts with chlorine andsilica, forming silicon tetrafluoride and sulphuryl fluoride, and withnitrogen trioxide and traces of moisture it reacts with silica, formingnitrosulphonic acid and silicon tetrafluoride. A series of fluorides ofthe heavy metals has been prepared by Biihm.*RUSS’S 5 researches on the ‘‘ activation ” of chlorine by the simultaneousaction of light and of the silent electrical discharge, the retention ofthis activity, and other facts, indicate that the question is still an openone whether the “activation” is due t o the formation of a modifiedchlorine or to the production of intermediate compounds.Foster,6however, shows that there are no such changes, for example, in density,as would justify the acceptance of the conclusion that a new modificationof chlorine is formed in this way.Levi and Bettoni7 conclude that the Deacon process for themanufacture of chlorine depends on the joint action of hightemperature and the porous materials used in the towers, the coppersalt accelerating the interaction between the hydrochloric acid andthe air by absorbing the water formed in the reaction. A newexplanation of the formation and constitution of bleaching powder isthat brought forward by Tarugi.8 As oxygen influences the formationof a bleaching powder containing the maximum proportion of activechlorine, and hydrated lime left in contact with the air containsperoxide, the formation of bleaching powder may be explained asdepending on: firstly, the formation of oxygen by the action ofchlorine on water ; secondly, the oxygen converting the calciumhydroxide into the compound CaO,, H,O,, which by hydrochloricLambert, Compt.rend., 1905, 141, 357.Ber., 1905, 38, 549.Ber., 1905, 38, 1310.Gazxetta, 1905, 38, [i], 320.2 Zeit. anorg. Chem., 1905, 44, 300 and 408.Zeit. anorg. Chem., 1905, 43, 326.Ibid., 1781.lbid., 1904, %, [ii], 25460 ANNUAL REPORT8 ON THE PROGRESS OF CHEMISTRY.acid formed in the first reaction is converted into Ca02C12, that is,the chloride of the peroxide, the hypochlorites being regarded as thechlorides of the peroxides.Bleaching powder containing 44-09 percent. of active chlorine would have the formula Ca0,C12,H20. Thiscompound is decomposed quantitatively by mercury into calciumperoxide and mercuric chloride.By the action of hydroxylamine on aqueous solutions of metallicchlorides, double salts are formed which can be precipitated from thesesolutions by alcohol; the following will serve as examples of the seriesof compounds : MgCl,, 2NH20H,2H,0 ; CaCl,, 2NH,OH,H,O ;ZnCl,, 2NH20H.1Group V I I I .Experimenting on the reduction of ferric and of ferrous oxide by amixture of equal volumes of carbon monoxide and carbon dioxidewhen ‘‘ dry” and (‘moist,” Boudouard has found the dry gas moreefficient at temperatures up to 800°, but above that temperature andup to 1050O there is little difference between moist and dry gas.Theresearches of Schenck and Heller on the reactions involved in thereduction of iron are of considerable importance. When carbonmonoxide is heated with metallic iron, the pressure observed afterequilibrium is established is extremely small, and apparently all the gasis removed. This arises from the oxidation of the iron and thedeposition of the carbon in the solid form. Pure carbon monoxidecannot oxidise iron ; it is assumed that the iron acts firstly catalytically,decomposing the carbon monoxide into carbon and carbon dioxide,secondly, reducing the carbon dioxide to carbon monoxide with thesimultaneous formation of ferrous oxide ; thus, the end equilibrium istwofold, as represented by the equations :(1) 2c07-.c + GO,.(2) FeO + COZFe + GO,.The partial pressures of the two oxides of carbon and their sum aredependent on the temperature only, or for each temperature there is adefinite partial pressure for each oxide and also a definite totalpressure.It follows that in the blast furnace ferrous oxide will onlybe reduced by carbon monoxide in the presence of carbon if the totalpressure of the carbon monoxide and dioxide is less than the pressure ofthe total equilibrium, whereas, when the pressure of the gas mixtureat the given temperature is greater, the reoxidation of iron andAutonoff, J. I 1 i . m . Phys. Chem. Soc., 1905, 37, 476.Bw., 1905, 38, 2132.’’ Conzpt. rend., 1905, 140, 142 ; also 141, 252INORGANIC CHEMISTRY. 61deposition of carbon take place.The pressure for the total equilibriumhas been determined for temperatures between 400° and 8003 ; firstly, byheating carbon monoxide with finely-di>-ided iron and measuringthe pressure when equilibrium is established ; secondly, by heatingferrous oxide and carbon in a vacuum andidetermining the pressure a tfixed temperatures. Applying this last method with different varietiesof carbon, the authors1 have shown that a t the same temperature thehighest pressures are given by amorphous carbon and the lowest withgraphite, powdered diamond being intermediate between the two.The powdered carbon obtained by decomposing carbon monoxidecomports itself like graphite. Consequently for a given temperature ina blast furnace worked with wood charcoal the gaseous mixture willbe richer in carbon monoxide than in a furnace worked with coke.The fact that iron saturated with carbon expands on solidifying?whereas pure iron behaves normally, is shown by Moissan2 to be animportant factor in the formation of the diamond by his method.Iron is deposited electrolytically most satisfactorily by employing asolution of ferrous and magnesium sulphates, to which a small pro-portion of sodium bicarbonate is added; a skin of ferric hydroxidethus formed on the surface serves to protect the solution from oxidation.Wrought iron is used as anode, and copper, thinly silvered, is used ascathode.3 Of the researches on the question of the rusting of iron, specialmention should be made of the complete and thorough examinationmade by Dunstan, Jowett, and Goulding,4 from which it appears thatiron, oxygen, and liquid water are alone essential to the phenomenon,the carbon dioxide of the air playing but a small part. The ex-planation advanced assumes the production of hydrogen peroxide,although its formation has not been demonstrated.The analyses ofrust produced in different experiments agree satisfactorily with theformula Fe,O,(OH),. Divers contends that the production of hydro-gen peroxide is unnecessary to the explanation of the observationsof the authors.Despite the sensitiveness to air, moisture, and light exhibited byiron carbonyl, Dewar and Jones,6 have succeeded in establishing its com-position as iron pentacarbonyl, Fe(CO), ; the physical constants havebeen determined and in its chemical reactions it has been found tocomport itself like nickel carbonyl.7 By the action of light it is con-verted into the compound Fe,(C0)7, the production of which is explainedBer., 1905, 38, 2139.Trans, 1905, 87, 1548 ; see also Cribb and Arnaud, Analyst, 1905, 30, 225 ;Proc., 1905, 21, 251.Proc.Roy. Soc., 1905, Series A, 76, 558.Cmpt. rend., 1905, 140, 185.a Maximowitsch, Zeit. Elektrochem., 1905, 11, 52.Lindet, Compt. rend., 1904, 139, 859.7 See Ann. Reports, 190462 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by assuming that the pentacarbonyl is partly resolved into the tetra-carbonyl, Fe( CO),, and carbon monoxide, the tetracarbonyl combiningwith iron pentacarbonyl to form Fe,(CO),. Consistently with theseconclusions, nickel carbonyl and iron carbonyl should form FeNi(CO), ;the coloration observed when nickel carbonyl is dissolved in iron carb-onyl is regarded as a confirmation of these views.has obtained a new class of complex iron compounds fromthe solutions formed by the treatment of both ferrous and ferric saltswith an excess of ammonium carbonate. Iron phosphide, Fe,P, is formedby heating calcium phosphate with metallic iron and silica in theelectric furnace.2 Lipschitz and von Hasslinger find that pureferrous sulphide is but slightly attacked by dilute acids, whereas wheni t contains metallic iron the iron sulphide is readily dissolved. Theiron is first dissolved by the acid, and the hydrogen so formedattacks the iron sulphide, forming sulphuretted hydrogen and metalliciron.Consequently the small amount of iron in the ferrous sulphideacts as an accelerator.The physical constants of pure nickel and cobalt have been deter-mined by Copaux; + the pure metals were prepared from carefullypurified oxalates. Cobalt is silvery-white in colour, whereas nickel iscomparatively dull, and both have a specific gravity of 8.8; cobaltmelts a t 1530O and nickel a t 1470O ; Guertler and Tanimann give themelting points of these metals as 1528O and 1484' respectively.Cobaltic fluoride, CoF,, is formed as a green powder by electrolysing asolution of cobalt fluoride in hydrofluoric acid, using a platinumdish as anode; nickel fluoride does not yield a nickelic compound(Barbieri and Calzolari).G When a current of electricity is passedthrough a solution of caustic soda or potash, using cobalt as the anode,a blue solution is formed, which Tubandt 7 regards as containing cobalt-ous oxide in a colloidal form.Tubandt * has also noted the productionof a deep red solution on electrolysing nickel carbonate in presence ofpotassium hydrogen carbonate ; the colour is due to the formation of anunstable nickelic salt. Our knowledge of the cobaltammine salts hasbeen extended by the researches of Werner and his pupil^.^ Thecobaltammines richest in ammonia are of the type [Co(NH,),]X, ;other saturated compounds containing two atoms of cobalt of the typeX,[Co(NH3),NH,Co(NH3),]X2 have been prepared, as also derivativesfrom the same in which two NH, groups are replaced by pyridine,thus : Clz[CoPy(NH,),NHCo(NH,),PylC1,. Dibromotetra-ammineHauserBer., 1905, 38, 2707.Monatsh., 1905, 26, 217.6 Zeit.anorg. Chcm., 1904, 42, 353.Zeit. anorg. Chem., 1905, 45, 368.Ber., 1905, 38, 923, 992, 2009.Gin, D.R.-P. 156087.Compt. rend., 1905, 190, 651.6 Atti X. Accad. Lincei, 1905, [v], 14, 464. * Ibid., 73INORGANIC CHEMISTRY. 63cobalt bromide, [Br,Co( NH3)JBr, is obt,ained as a green, amorphous solidby the action of hydrobromic acid on the carbonate ; the bromidetreated with hydrochloric acid gives the chloride, which by water isconverted into the aquo-salt, [Br(H,O)Co(NH,),]ClBr, forming reddish-violet solutions. This compound belongs to a series intermediatebetween the diaquotetra-ammine salts, [ (H,O),Co(NH,),]Br,, and di-bromotetra-nmmine series, for example, [Br,Co(NH3),]B~,.By theaction of hydroxylamine hydrochloride on dichlorodiethylenediaminecobalt chloride or on chlorohydroxylaminediethylenodiamine cobaltchloride in aqueous caustic potash solutions, hexahydroxylamine cobaltchloride, [Co(NH,OH),]Cl,, is formed, which crystallises in large, goldenleaflets. 1By employing hydrazine hydrate to reduce dilute solutions of salts ofthe platinum metals in presence of gum arabic, Gutbier and Hofmeierhave obtained hydrosols of these metals. The hydrosols may be obtainedin the solid form by evaporating the solutions in a vacuum over strongsulphuric acid. Paal and Amberger have also investigated theprecipitation of palladium by hydrazine hydrate and the production ofthe metal as a hydrosol, which is effected by treating solutions ofpalladium chloride with hydrogen in presence of sodium pr~talbate.~These authors find that the dry hydrosol obtained by evaporating thesolution in a vacuum renders hydrogen sufficiently active to be able toreduce nitrobenzene in alcoholic solutions to aniline, whereas palladiumblack and the hydrogel of this metal have no such power.Gutbier andKrel14 have described a series of ammonium, cEsium, and rubidiumpalladichlorides and palladochlorides of the types R,PdCl, andR,'PdCl, respectively. Wiihler and Kijnig 5 show that there are onlytwo oxides of palladium, namely, palladic oxide, PdO,, which is formedeither by the action of ozone on palladium salts or by the anodicelectrolytic oxidation, and palladous oxide, PdO, which is obtained byboiling faintly acid nitrate solutions with water.The palladic oxide,which is readily decomposed into the lower oxide and oxygen, acts asan oxidising agent and decomposes hydrogen peroxide.Ruthenium is obtained by reducing the oxide, Ru204, with alcoholand finally heating the product in a stream of hydrogen. Gutbier andTrenkner6 have been unsuccessful in their attempts to obtain adichloride and a tetrachloride, but readily obtained the chloride Ru,C16by C1aus's method. These authors have also prepared double salts ofthis chloride with those of rubidium and cesium.Ruthenium bromideWerner and Berl, Ber., 1905, 38, 893.J. pr. Chem., 1905, [ii], 71, 358 and 452.Bey., 1905, 38, 1388, 1394, 1398, 1406.lhiid., 2385.Zeit. anorg. Chem., 1905, 46, 323.Ibid., 46, 16664 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and iodide are also described, as are the compounds which they formwith ammonia, analogous in composition to Joly's Ru,Cl,, '7NH,.Ituthenium dioxide, RuO,, is obtained in the form of blue plates byheating the metal in oxygen, and is also produced by the ignition ofthe sulphate. The sesquioxide, Ru,O,, can be obtained by heating thehydroxide formed by the action of caustic potash on the trichloride.Attempts to obtain the oxides described by Joly and Debray wereunsuccessful (Gutbier and Ramsohoff).lDouble nitrites of osmium with nitrites of sodium, ammonium, silver,and of the nitrites of the metals of Group I1 are described byWintrebert.2 They are for the most part yellow, crystalline solids.Bydecomposing the barium salt, BaOs(NO,),, 4H20, with dilute sulphuricacid, a solution of osminitrous acid, H,Os(NO,),, is formed, which, onevaporation, leaves osmium nitrite as a deep brown powder. Potassiumiridochloronitrite, K121r,C1,,(N02),,4H,0, is formed by evaporatingpotassium iridium nitrite to dryness with dilute nitric acid and dis-solving the residue in a solution of potassium chloride, from which theiridochloronitrite separates out (Quennessen).3 Hussak 4 has describedthe mode of occurrence of platinum and palladium in Brazil. On thevolatilisation of platinum, Hulett and Berger note that the metalbegins to volatilise in air a t SOOO, whereas no volatilisation is observedif oxygen be absent, This observation has led to the suggestion thatan oxide is formed which decomposes a t 800O. Lucas, finds thatplatinum begins to absorb oxygen at 6 1 5 O , and the rate increases up to1000°, from which point it begins to fall. This is only true of platinumcontaining iridium, as pure platinum does not absorb the gas.The alteration in appearance which platinic hydroxide, Pt0,,41120,undergoes when dried is explained by Blonde17 as being due to itsconversion into H2Pt( OH),., I n platinic hydroxide, two of thehydroxyl groups are acidic, whilst another two are basic, consequentlyit forms platinates of the type Pt(OH),,2MOH, where M is an alkalimetal, and with acids salts like the chloride, Pt(OH),,2HCl, which com-pound is formed by dissolving the hydroxide in dilute hydrochloricacid. It gives no precipitate with a potassium salt, but in course oftime passes into chloroplatinic acid. Potassium platinoso-oxalate, whenoxidised by potassium permanganate, forms the platinic oxalate,from the silver salt of which has been prepared the acidcrystallising in amber tablets and detonating violently when heated.K2Pt0(C204),,2H20,H2PtO(C@4)&&0,Zeit. anorg. Chem., 1905, 45, 243.B i d . , 141, 258.J. Amer. Chem. Soc., 1904, 26, 1512. ' Ann. Chim. Ph3s., 1905, [viii], 6, 81.Compf. rend., 1905, 140, 585.Chem. Centr., 1905, [ii], 107.Zeit. EZektrochem., 1905, 11, 182.See Ann. Reports, 1904INORGANIC CHEMISTRY. 65Guillet’s 1 researches on the constitution and properties of steelsshow that up to 2 per cent. aluminium has but little influence on theproperties of steel, further, that up to 15 per cent. this metal dissolvesin the iron, and the solution does not dissolve carbon. The structureof ordinary steels is not affected by tin up to 0.5 per cent., whereaswhen the tin is between 5 and 10 per cent. it dissolves in the iron andseparates in the form of a definite compound ; in such steels the carbonexists as carbide, and there is no graphite present. Titanium up to9 per cent. does not change the structure of steel; the mechanicalproperties are but slightly altered; in steels containing 0.7 per cent. ofcarbon, the breaking strain is much improved by the presence oftitanium. The mechanical properties are but little affected by cobalt ;the perlitic structure is shown in steels containing up to 60 per cent.cobalt.Ternary steels are grouped by Guillet as follows : (1) perlitic; (2)martensitic, including troostitic ; (3) y-iron ; (4) carbide, and (5)graphitic steels. Braune2 has observed that iron heated a t 800° in anatmosphere of ammonia forms iron nitride, which, forming a solidsolution with iron, lowers its melting point and reduces its ability todissolve carbon. By annealing, the nitride can be made to diffuseequally through the iron. The tensile strength increases with theproportion of nitrogen, whilst the ductility falls rapidly. Steel contain-ing 1.15 per cent. of carbon becomes brittle with 0.04-0.045 per cent.of nitrogen. Le Chatelier considers that Braune’s observationsexplain the difference in brittleness frequently observed in steels ofidentical composition. Le Chatelier points out that iron does notcombine directly with atmospheric nitrogen, but in presence of basicslag and of reducing agents this combination takes place. Consequentlythe absorption of nitrogen takes place chiefly in the blast furnace andin the basic-converter, and is probably due to the formation of cyanides,Inferior qualities of iron are, as is well known, produced in furnaces inwhich much potassium cyanide is formed.P. PHILLIPS BEDSON.1 Compt. rend., 1905, 141, 35; 140, 1689; 141, 107.Ibid., 503. Rev. Netallurgie, 1905, 2, 497.VOL. II.

ISSN:0365-6217    

DOI:10.1039/AR9050200030

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

ORGANIC CHEMISTRY-ALIPHATIC DIVISION.A CONSIDERABLE part of the work done in organic chemistry at thepresent time has for its principal object the elucidation of someproblem in physical, biological, or steric chemistry, and there is everyindication that chemists are taking increased advantage of biologicalmethods and of the principles of physical chemistry in working outproblems of pure organic chemistry; some of the most importantrecent results, indeed, owe their success to the application of suchmethods and principles.Much interesting work has been done in connection with thebehaviour of gases or vapours of carbon compounds under the influenceof heat, of the silent discharge, and of finely divided metals. Althoughcomparatively few papers have appeared on the chemistry of thecarbohydrates, results of considerable importance have been obtainedin this department.The application of Grignard’s reaction showsundiminished popularity as a subject for investigation, and theresearches on polypeptides continue to be actively pursued. Anoteworthy coincidence is the large amount of attention which appearsto have been given to aldehydes and aldehyde-acids.Notwithstanding the exhaustive character of the researches whichhave been made during the last two or three years on the applicationsof G3’ignccrd’s wccction in organic synthesis, a considerable number ofnew observations continue to be published. Many of these havereference more particularly to compounds belonging to the cyclicdivision, but the following may be mentioned as examples of generalapplication of the reagent.It is shown by Tschitschibabinl thatesters of the type RG0,Et may be obtained by the action ofmagnesium alkyl haloids, RMgX, on the esters of carbonic acid. Thethree changes which might be expected t o result from this action arethe following : -OMgX.( OEt), ’ 1. CO(OEt), + RMgX= R*C<+ RMgX = R2C<:ffX + MgXOEt ; HOMgX( O W ,2. RC\3. R2C<gZx + RMgX = R,C*OMgX + MgXOEt,Ber., 1905, 38, 661ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 61and these products on hydrolysis would give esters, ketones, andtertiary alcohols respectively.Experiment shows that the first of these changes is the principalone, the yield of ester on hydrolysis being in some cases as much as80 per cent.OC that required by theory.If esters of ortho-carbonic acid are employed, the changes to beexpected (from analogy with the behaviour of ortho-formic esters)areC(OEt), + RMgX = RC(OEt), + MgXOEtandRC(OEt), + RMgX = R,C(OEt), + MgXOEt.Here again the change takes place principally according to the firsttype, provided the experiment is carefully conducted and the action isnot too prolonged.The replacement of aldehydic oxygen by two univalent alkyl groupshas hitherto been accomplished only in an indirect way; F. and L.Sachsl now show that in certain cases this change can be broughtabout with the agency of Grignard's reaction. p-Dimethylamino-benzaldehyde, for example, when acted on by magnesium methylbromide, yields first (CH,),N*C,H,-CH<~~~Br, and this by furtheraction of the reagent at a higher temperature gives(CH,),N'C,H,* CH<gE:(p-isopropyldimet hylaniline).It is pointed out by Beckmann t h a t organo-calcium haloids,analogous to the magnesium compounds, may be obtained by theaction of ethyl iodide or iodobenzene on finely divided calcium.I nbenzene solution, negative results are obtained, even if a smallquantity of ether is added, but in absolute ethereal solution thechsnge takes place rapidly with formation of an additive compound,CaRI,Et,O. Iodobenzene gives the compound PhCaI, the actiontaking place readily in ethereal solution if EL trace of iodine is added.This compound reacts with benzaldehyde to give a product which, onhydrolysis, yields benzhydrol ; when treated with carbon dioxide andthe product decomposed by water, benzoic acid is obtained.By the action of metallic magnesium on ethylene dibromide,Grignard and Tissier (190 1) obtained only magnesium bromide andethylene ; but Ahrens and Stapler now find t h a t these substancesreact in ethereal solution to produce a crystalline compound whichhas the composition CH,Br*CH,*MgBr( C,H,),O.This product isdecomposed by water, giving ethylene, ether, and magnesium bromide J1 Ber., 1905, 38, 517, a Ibbid., 904. lbbid., 1296, 3259.F 68 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.when shaken with benzaldehyde in ethereal solution, it reacts in themanner of other organo-metallic haloids, giving the compoundC6H,*CH(OMgBr)*CH,*CH,Br(C2H,),0, and this when acted on bywater produces benzaldehyde, ether, ethylene, and magnesium bromide.I n both cases, therefore, the action of water yields all the bromine inthe ionic condition.If a small quantity of iodine is added to theethereal solution of ethylene dibromide, the action of magnesiumgives rise to an oil which, on treatment with benzaldehyde, yields ayellowish-white powder having a composition corresponding to theformula C,H,*CH(OMgBr)*CH2*CH2*CH(OMgBr)*C6H5. The authorsconsider that the constitution of these products is best represented onthe oxonium type of Baeyer and Villiger,l the compound firstand the additive C H Brmentioned being C:H:>'<Mg CH2*CH2Br'compound with benzaldehyde,C2H,>*<B'C2H6 CH(C,H,)*O*Mg* CH2* CH,Br.They further show that dry bromine acts on magnesium in coldethereal solution, giving an oily product, C2H5>O<f:gBr C H ; this reacts2 5with benzaldehyde, furfural, ethyl acetoacetate, ethyl malonate,piperidine, &c., to produce additive compounds.Iodine yields aproduct analogous to that given by bromine, but it is unstable.With metallic calcium, bromine in ethereal solution yields acrystalline product of similar constitution which combines withpiperidine to give an additive product.Tschelinzeff ,2 after discussing the various views which have beenput forward as to the constitution of the ether complexes formed withthe magnesium organic compounds, comes also to the conclusion thatthe formula of Baeyer and Villiger gives the best explanation of thefacts. This author has attempted to throw further light on thequestion, and on the oxonium bases generally, by application ofthermochemical methods.Although, as found by Blaise and Grignard,it is not possible directly to separate the ether in these compounds fromthe organo-magnesium haloid, the conveme process can now be easilystudied, since the individual magnesium compounds, free from ether, canbe isolated. The results obtained indicate that the thermal effect of thechange RMgX + Et>O = gi>O<zgR is always positive, amount-ing to about 12-13 cal. €or the molecular quantities indicated, thesubstances experimented with being ethyl, n-propyl, isobutyl, andisoamyl iodides and ethyl ether.For the purpose of synthesising certain higher alcohols, a newSee Am.Reports, 1904, 56. Ber., 1905, 38, 3664ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 6 9method, which appears to be of general application, has been devisedby Grignard;l it will perhaps be most easily explained by thefollowing illustration. When glycol chlorohydrin is acted on by anorgano-magnesium haloid in the cold, only the hydroxyl group isattacked, thus :ClCH,.CH,*OH + RMgX = RH + ClCH,*CH,*OMgX.This product may now be further acted on by another molecule of anorgano-magnesium haloid in which the halogen and alkyl may either bethe same as or different to those originally employed :ClCH,*CH,*OMgX + R’MgX’ = R’CH,*CH,*OMgX -+ MgX’Cl.By action of water on the latter compound, the alcohol R’CH,-CH,*OHis obtained ; in this way phenylethyl alcohol, for example, can be pre-pared from glycol chlorohydrin.Paal and Weidenkaff have studied the action of Grignard’s reagenton certain amino-acids with the object of obtaining products whichmight serve for the characterisation of these acids when they arise asproducts of proteid hydrolysis. The aliphatic amino-acids are as arule sparingly soluble in alcohol and easily soluble in water, and it isto be expected that the ‘‘ basic ” alcohols which should be formed byGrignard’s reaction would exhibit solubilities of the converse order, andso be easily separated.They find that glycine ethyl ester readily reactswith magnesium phenyl bromide in ethereal solution, giving a productwhich, when hydrolysed with dilute hydrochloric acid, yields diphenyltogether with a substance crystallising in needles, which is easilysoluble in alcohol and sparingly soluble in cold water.The lattersubstance proves to be diphenylhydroxyethy Iamine,OH.C(C6H,),*CH,=NH,.Sabatier and Senderens have recently published 3 a very completesummary of their exhaustive researches on the hydrogenation ordecomposition of various volatile compoonds under the catalyticinfluence of finely divided nickel and certain other metals.The action of hydrogen on volatile carbon compounds in presence ofreduced nickel at temperatures below 250” constitutes a new method ofhydrogenation which is of general application, and may give resultswhich are practically unattainable by the older methods.Ethylenic oracetylenic hydrocarbons may be converted into paraffins, aldehydes andketones yield the corresponding primary or secondary alcohols, aliphaticnitriles and oximes give rise to amines, and various other nitrogen com-pounds can similarly be hydrogenated ; all such changes can, i t is said,Cowapt. mnd., 1905, 141, 44.Ann. China. Phys., 1905, [viii], 4, 319-458.Ber., 1905, 38, 168670 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.be effected more readily by this than by the older processes. Carbonmonoxide and dioxide are directly hydrogenated to methane, andhydrogen can easily be added to compounds having an aromaticnucleus with production of cyclohexanes, cyclic alcohols, and cyclicamines. Actions of the latter type (" special '' reactions), which can beobtained only with difficulty, if at all, by older methods, may easilybe brought about by the influence of nickel and to some extent ofcobalt, but not by copper or platinum.Many remarkable and important changes may also take place whenthe volatile compounds by themselves, without admixture with hydrogen,are subjected to the action of these metals; primary and secondaryalcohols, for example, are resolved, especially in presence of copper, intofree hydrogen and the corresponding aldehyde or ketone.Ethylene inpresence of nickel, at about 300°, yields a mixture of hydrogen, methane,and ethane, and cyclohexane gives benzene and methane.I n addition to this simple resolution, or dbdoublement as the authorsterm it, condensations of various types may take place; directpolymerides may result, for example, benzene from acetylene, or con-densation may occur accompanied by union with hydrogen or other ofthe resolution products.Thus, acetylene gives rise, in addition toother products, to a solid condensed hydrocarbon, (C7H&, which theauthors call '' cuprene."When acetylene mixed with hydrogen is passed over cold reducednickel, heat is evolved and the temperature may rise as high as 150" ;the acetylene entirely disappears and the product has the odour ofpetroleum. By using a column of nickel maintained at about 2000and allowing the operation to continue for twenty-eight hours, theauthors were able to condense a yellow liquid having a beautifulfluorescence, which began to boil a t 45'.I n its density, composition,and all its other properties it closely resembled ordinary Pennsylvanianpetroleum. By passing acetylene alone over nickel heated to 200-300°,a mixture of liquid hydrocarbons was obtained, which appeared greenby diffused light and red by transmitted light. This liquid beganto boil at 60-70", and in composition and properties closely resembledCaucasian petroleum. The authors suggest, as a theory of the naturalformation of petroleums, that at great depths free alkali and alkaline-earth metals may exist together with their carbides, and that by actionof water these give rise respectively to hydrogen and acetylene ; thesegases passing over nickel, cobalt, or iron, in a state of division, at asufficiently high temperature would behave in the manner which theabove experiments indicate.The finely divided metals which were employed in these investiga-tions were obtained by reduction of the oxides in pure hydrogen ; it isnecessary, however, to pay particular attention t o the temperature aORGAKIC CHEMISTRY-ALIPHATIC DIVISION.71which the reduction is effected; nickel reduced from its oxide at a redheat is practically inert, whereas if prepared below 300' its activity isextreme and becomes soon exhausted ; for most purposes, i t is prefer-able to carry out the reduction a t about 350'.Attention is drawn by Collie1 to the fact that the action of thesilent electric discharge on various elements and compounds often runsparallel with that of the action of light in plants; water and carbondioxide are decomposed, nitrogen and hydrogen combine to formammonia, formaldehyde is produced from carbon monoxide andhydrogen, and polymerisation is induced.It has been shown furtherthat under the influence of light hydrogen may be lost from a methyl-ene group in certain compounds, such as alcohol, and that thishydrogen may then combine with carbonyl in carbonyl compounds(thus, benzoquinone in alcoholic solution gives rise to quinol and acet-aldehyde). It appeared, therefore, to be of interest to ascertain thebehaviour of ethylene-a substance most nearly allied to methylene-when mixed with carbon monoxide and subjected to the action of thesilent discharge.Some of the principal results arrived at were asfollows : ethylene a t the ordinary temperature not only unites withcarbon monoxide with production of aldehydes, &c., but also poly-merises, yielding a series of complicated hydrocarbons ; the chief pro-duct has a boiling point approximating to that of the hydrocarbons,C,,H,, ; this also polymerises with loss of hydrogen, giving a substancewith properties something like those of india-rubber and having acomposition closely approaching ( C5HJ2. A hydrocarbon boiling atabout 250° was also obtained, which may be C,,H,o. A remarkablesimilarity evidently exists between some of these products andthose which are built up in a plant ; the changes, moreover, can bebrought about at the ordinary temperature, and, by further oxidationat the ordinary temperature, a series of aldehydes and acids can beproduced.Reference was made in the previous report to the investigations ofBone, Stockings, and Wheeler on the chemistry of combustion ofmethane, ethane, ethyl alcohol, acetaldehyde, and ethylene.Furtherexperiments have since been made by Bone and Andrew 2 on the com-bustion of acetylene, and some of their principal results may besummarised as follows :-The process is essentially of the same type as that involved in thecases of methane, ethane, and ethylene, the oxygen being initiallyincorporated with the hydrocarbon and giving rise to an unstablemolecule which rapidly undergoes thermal decomposition into simplerproducts.When mixtures of acetylene and oxygen are sealed up in glassI Trans,, 1905, 87, 1542.Did., 123272 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.vessels a t atmospheric temperature and pressure and then heated, theybegin to interact at 250", or sometimes below; a t 300", the changeproceeds rapidly and explosive combustion takes place at about350--375O, according to the composition of the mixtures taken. I nthe burning of acetylene there is no preferential oxidation of eithercarbon or hydrogen, nor is there any evidence of the breaking down ofan unstable hydroxyacetylene into carbon and steam, as mas formerlysuggested by Armstrong.I n the slow combustion of acetylene, carbon monoxide and form-aldehyde are produced sirnultaneonsly at an early stage of the process ;these products, the authors consider, are probably due to the decom-position of an unstable initial compound, such asSeparation of carbon occurs in the explosive combustion of acetyleneonly when the reacting mixture contains more than an equivalentmolecular proportion of the hydrocarbon, and is to be attributed t o thesecondary decomposition of the excess of acetylene.I n contact withhot catalysing surfaces, such as porous porcelain, acetylene unites withsteam, giving acetaldehyde ; this change may: take place even inpresence of oxygen, and may therefore cause complications in the com-bustion experiments when such contact is allowed. In none of theexperiments was the formation of any benzene observed.The decomposition of formaldehyde and of acetaldehyde by heathas been studied by Bone and Smith,l and they show that at alltemperatures between 400" and 11 25" formaldehyde decomposesmainly according to the equation H*CHO=CO+H2.At 400' and500°, however, this principal decomposition was accompanied by somemore complex change, involving a preliminary condensation of aportion of the vapour. Acetaldehyde decomposes at 400' into methaneand carbon monoxide, but at 600° notable quantities of free hydrogenwere obtained and some carbon deposited, although the authors havepreviously shown that methane does not decompose below 800'. AtSOO", the proportion of hydrogen is increased, and some acetylene couldalso be detected in the products. I n contact with porous porcelain at450-500", not only is carbon separated, but ethane and carbonmonoxide are also produced together with crotonaldehyde, &c.The fact that formaldehyde may be synthetically formed frommixtures of carbon monoxide or dioxide with hydrogen under theinfluence of the silent discharge has been fully established by earlierinvestigations, and more recently it has been shown by Jahn and byBach that similar changes may be effected by means of hydrogenatedpalladium. With the object of throwing furtber light on the conditionswhich determine the 'production of formaldehyde, Chapman and HoltTrans., 1905, 87, 910. Ibid., 916ORGANIC CHEMISTRY-ALIPHATIC DIVISION.73have subjected various gaseous mixtures to a high temperature bymeans of an incandescent platinum wire, and their experimentsestablish the fact that in the system containing carbon monoxide,carbon dioxide, steam, and hydrogen, formaldehyde is undoubtedlyproduced.Interesting studies on the condition of formaldehyde in aqueoussolution have been made by Auerbach and Bsrscha1l.l The purealdehyde was obtained by subliming trioxymethylene in a stream ofnitrogen, and its strength was estimated by the sulphite method ofLumitze and Seyewetz er by Romijn’s iodine method.Determina-tions of the molecular weight in the cryoscopic way indicated that thevalue depends on the concentration of the solution. By application ofthe lam of mass action to the values so obtained, it is shown thata state of reversible equilibrium probably exists between the singleand the trimeric forms, the same limit being reached under the sameconditions whether gaseous formaldehyde or solid paraformaldehydeis employed.There are some indications that in strong solutionspolymerides higher than (CH20)3 may exist. Rise of temperaturecauses a displacement of the equilibrium in the direction of increase inthe proportion of the single or unimolecular form, the polymeric formsbeing decomposed with absorption of heat.The authors find that when an aqueous solution of formaldehyde isdistilled, the distillate is always poorer and the residue richer in form-aldehyde than the original solution. It is probable that whengaseous formaldehyde is dissolved in water only a small part exists inthe original condition, the greater part being converted into hydratedor polymerised forms.A knowledge of the behaviour of formaldehyde in dilute alkalinesolution is a matter of considerable importance in throwing light onthe function of alkalis in bringing about the condensation of form-aldehyde to sugars, and an investigation in this direction has beenundertaken by H.and A. Euler.2 These authors come to the con-clusion that formaldehyde behaves itself RS a weak acid, the saltsformed with strong bases being considerably hydrolysed in aqueoussolution. They calculate that in a normal solution of the mono-sodium derivahive about one-half exists as such, the remainder beinghydrolysed t o free base and formaldehyde. In dilute aqueous solutionthe ‘‘ salt ” behaves as a binary electrolyte, the change being probablyrepresented by the relation :OH + +H C < ~ ~ + Na + OH = Hc<ZH- + Na + H~O.Arbb.Kais. GIcs., A, 22, 584; from Chenz. Ccntr., 1905, ii, 1081.Bcr., 1905, 38, 255174 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The change which formaldehyde undergoes in contact with bases ismade up of two independent parts, the condensation and the formation offormates and methyl alcohol. The latter change has also been in-vestigated by the authors, and they show that production of sodium orbarium formate by the action of the hydroxides on formaldehydeis a reaction of the second order; with great excess of the aldehyde,it behaves as a reaction of the first order, the concentration of thealdehyde being then practically constant.Calcium hydroxide behavesabnormally in the latter respect, and the authors suggest that a calcium-formaldehyde complex is formed in this case; it appears that thisresult has an important bearing on the observation of Loew (1888)that calcium hydroxide acts much better than barium hydroxide as acondensing agent of formaldehyde to sugars. It is evident from theauthors’ results that the activity of different bases in bringing aboutthe sugar condensation does not stand in direct relation to theirreaction velocity in the production of formates.I n a subsequent communication,l Auerbach takes exception to someof the results of the last named authors. H e considers that it is notpossible that their formaldehyde could have been free from methylalcohol, since they prepared it from commercial formol by distillation(after dilution and neutralisation). The strength of their solution,moreover, was determined by the cryoscopic method, which, in view ofthe above-mentioned observatioiis of Auerbach and Barschall, wouldgive misleading results.Pyruvic aldehyde or rnethylglyoxal was first obtained by Pechmann in1887; isonitrosoacetone was acted on by a 30 per cent.solution ofsodium hydrogen sulphite and the resulting crystalline compound wasdecomposed with dilute acids. In this may a product was obtainedwhich was volatile in steam and which was recognised as methyl-glyoxal by its reactions with ammoniacal silver solution, Schiff’sreagent, tolylenediamine, and phenylhydrazine, the latter yieldingthe dihydrazone, CH,-C( :N,HPh)*CH:N,HPh, melting a t 145’.Thisaldehyde has now been prepared by Harries and Turk in an entirelydifferent way, as follows.Mesityl oxide when treated with ozone in the cold yields the ozonide,C6H100b, as a green, explosive syrup. When a solution of this com-pound is warmed, it yields white crystals of acetone peroxide, and thesolution contains methylglyoxal :+ CH3*CO*CH0 + H202.The aqueous solution reduces Fehling’s solution in the cold and1 Ber., 1905, 35, 2333. Ibid., 1630ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 75yields with phenylhydrazine the dihydrazone referred t o above.When distilled in a vacuum, a considerable part of the aldehyde passesover, and this watery distillate, when again carefully evaporated,leaves a nearly colourless liquid which sets to a glassy mass whenkept over sulphuric acid, Analysis and molecular weight determina-tion show that the latter product is a polymeride of methylglyoxalhaving the formula (C,H,O,),.The di-semicarbazone and the mono-acetal of methylglyoxal werealso isolated, and hydroxylamine yielded the dioxime (methylglyoxime)identical with the product prepared from isonitrosoacetone by V.Meyerin 1882.Since dextrose under the influence of dilute alkalis is known t oundergo various transformations leading to the production of hydroxy-acids, such as lactic acid, it might be expected that in presence ofammonia analogous changes would occur resulting in the formationof alanine or other amino-acids of similar type.Windaus andKnoop,l while working in this direction, have observed that ammoniaitself acts only very slowly on dextrose, but that by employing,instead of ammonia, the strongly dissociated “ zinc hydroxide-ammonia,” reaction takes place, even i n the cold, with production ofan oxygen-free base; the latter, which is formed in considerablequantity, proves to be methylglyoxaline or methyliminazole (either theU- or the P-derivative).This result has an important bearing on the question as t o thenature of the intermediate products which are formed in the transitionof dextrose to lactic acid, It was suggested by Pinkus that theformation of acetol is the intermediate stage, whilst the work of Nef,Wohl, and Buchner gives.support t o the view that glyceraldehyde isfirst formed and that this passes, by loss of water, t o methylglyoxal ;by again assimilating the elements of water, the latter gives rise t olactic acid.The latter view, namely, that methylglyoxal is formed, appears tobe favoured by the results here mentioned, since glyoxalines areknown to be produced by condensation of orthodicarbonyl compoundswith formaldehyde and ammonia.The authors consider that themethylglyoxaline arises in this way in the present case, the changebeing expressed as follows :CH,*$!O H,N R CH38*NH>CH.CH*N + >CH -+ CHOfH,N 0The formaldehyde necessary for this reaction may arise, it is sug-gested, as a primary reversible degradation product of the hexose, orBer., 1905, 38, 1166’76 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.possibly it may have its origin in the decomposition of methylglyoxal.The yield of pure methylglyoxaline from 1 kilogram of dextroseis about 100 grams.Buchner and Meisenheirner,l in discussing the formation of lacticacid from dextrose and of alcohol from lactic acid, favour the opinionthat methylglyoxal is produced as an intermediate stage in the fer-mentation of sugar to lactic acid, and they show that this assumptionis in accord with the fact; that only the inactive acid is obtained,whether cane sugar or dextrose is started with.2 That alcohol may beproduced from lactic acid by fermentation has been shown by Fitz(1880) and Maze (1902).Duclaux in 1886 observed that calciumlactate in presence of air and sunlight gave rise to alcohol, calciumcarbonate, and calcium acetate, and Hanriot (18S6) obtained con-siderable quantities of alcohol by heating calcium lactate with lime.The authors confirm the latter observation, but they show that thedistillate, which was regarded by Hanriot as ethyl alcohol, containsalso isopropyl alcohol.Incidentally, they have also proved that ethylalcohol is formed, although only in small quantity, when invert sugaris heated with a strong solution of sodium hydroxide.Although on the whole there is much evidence in favour of thehypothesis that lactic acid may play an important patt as an inter-mediate stage in the alcoholic fermentation of sugar, it must beremarked that the recent experiments of Slator3 appear to indicatethat “it is improbable that any but small quantities of sugar gothrough the intermediate step of lactic acid in fermentation.”Naleic Semi-aldehyde.-By the oxidation of pyromucic acid withbromine in aqueous solution, Limpricht in 1873 obtained this substanceas an indistinctly crystallisable oil, but its properties were but littlestudied.Fecht * has now improved the method of preparation and madea further study of the compound. Pyromucic acid is oxidised withpotassium hypobromite, and the solution, after saturation with sodiumsulphate, is extracted many times with ether. The product thus obtainedis dried in a vacuum at SO’, and the crystalline mass resulting isdistilled under a pressure of 0.1 to 0.3 rnm. After crystallisationfrom ether and benzene, the semi-aldehyde is obtained in the form offlat needles, which melt at 55’ and boil at 145’ under 10 mm.pressurewith slight decomposition.Phenylhydrazine acetate in the cold gives a yellow, crystallinehydrazone (m. p. 158’), and a white, crystalline oxime is obtained bythe action of hydroxylamine hydrochloride in acid solution. OnBer., 1905, 38, 620.Compare, however, McKenzie, Tyans., 1905, 87, 1379.Proc., 1905, 21, 304. * Ber., 1905, 38, 1272ORGANIC CHEMISTRP-ALIPHATIC DIVISION. 77saturating a solution of the oxime in methyl alcohol with hydrogenchloride in the cold, a large yield of methyl fumarate is obtained, thisresult being due to the Beckmann rearrangement.When the semi-aldehyde is neutralised with sodium bicarbonate andheated with potassium cyanide on the water-bath, it is transformedalmost quantitatively into succinic acid.Maleic Dialdehyde.-Marquis in 1901 observed that when furfuran isnitrated in acetic anhydride solution below - 5", the product treatedwith water and extracted with ether, an oil is obtained which has reduc-ing properties and which reacts with phenylhydrazine to give a crystal-line hydrazone melting at 230'.This reducing substance appears to benitrosuccinaldehyde monacetin, CH O*CH( NO,)-CH: CAc* OH. Whenthe latter is boiled with water, it yields an aldehyde, the phenylhydr-azone of which contains no oxygen. The author now shows 1 that thisis the diuldehyde of muleic acid, CHO*CH:CH*CHO ; with hydroxyl-fH-CH:NOHCH*CH:NOH' amine, it reacts to produce the dioxime,Tartronic Xemi-aldehyde.-From the product of the action ofan aqueous solution of caustic soda on an ether-alcohol solutionof collodion-wool, W.Will in 1891 obtained an acid which haspowerful reducing properties, and which with phenylhydrazineacetate gives the osazone CH( :N,HPh)*C( :N,HPh)*CO,H. Thisosazone was previously obtained by Nastvogel by the action ofphenylhydrazine on dibromopyruvic acid, and it may be regardedeither as the dihydrazone of mesoxalic semi-aldehyde, or as the osazoneof tartronic semi-aldehyde or of hydroxypyruvic acid. Analysis ofthe calcium, strontium, and cadmium salts of Will's acid indicated theformula C,H,O, for the free acid, so that it must be either tartronicsemi-aldehyde, CHO* CH(OH)*CO,H, or hydroxypyruvic acid,CH,(OH)*CO*CO,H.Since the acid is stable towards bromine water and towards alkalis,such as barium hydroxide, Will concluded that it was the keto- andnot the aldehyde-acid.Aqueous solutions of the acid, or its salts,mere fouud to be feebly lzvorotatory, and this circumstance was atthe time supposed to lend further support to the ketonic formula,attention being drawn to the presence of the -CO*CH,*OH group inlaevulose.Since, however, in the constitution of hydroxypyruvic acid there isno asymmetric carbon atom, it was evident that the matter requiredfurther investigation. This was undertaken by Aberson,2 who statesthat by repeated evaporation of the solution of Will's acid the opticalactivity diminishes and finally disappears, although in other respectsAnn.Chim. Phys,, 1905, [viii], 4, 196.Zeit. physikaZ. Chern., 1899, 31, 17‘78 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the properties remain unaltered. He concludes therefore that theoptical activity was due to some impurity containing nitrogen, sincetraces of oxides of nitrogen can be detected in the process of erapora-tion.By heating this inactive acid in sealed tubes with hydrocyanic acid,Aberson obtained a product which, on treatment with hydrochloric acidand tben with barium hydroxide, gave rise t o barium glycerate; thelatter he assumes must result from the decomposition of isotartaricacid, CH,(OH)*C(OH)(CO,H),, and considers that t h i s fact establishesthe ketonic acid formula for Will’s acid, since the aldehydic acidwould under similar treatment yield tartaric acid.Neuberg and Silbermannl have now made a further study of thisproduct and they arrive at a conclusion different from that ofAberson; the work of the latter chemist appears, moreover, to havebeen overlooked.Their results may briefly be summarised as follows :Will’s product was obtained in the manner above indicated, the acidbeing precipitated in the form of lead salt and the latter decomposedby hydrogen sulphide. The acid solution so prepared was feeblylaevorotatory, powerfully reducing, gave precipitates with bnrytawater and with ammoniacal calcium chloride, and with phenylhydrazine yielded Nastvogel’s osazone. In addition t o these pro-perties, they find that the acid yields a characteristic brucine salt whichcrystallises in needles.By acting on a solution of the active acid with excess of potassiumcyanide and hydrolysis of the resulting product, an acid was isolated(by means of its lead salt and acid potassium salt) which proved to bel-tartaric acid, mesotartaric acid being probably simultaneouslyformed, From this result, the authors conclude that Will’s acid is inreality not hydroxypyruvic acid, but the semialdehyde of tar tronic acidor, as they term it, aldehydo-glyceric acid.The configuration of thisacid must evidently be Hdr*OH , Etartaric acid beingCHO60,HC O PH&OHO H ~ H60,HReduction of the aldehyde-acid with sodium amalgam is shown togive rise to Lglyceric acid, from which it follows that the configura-tion Hd*OHCH,*OHis to be assigned to the latter.60,HZeit. physiol.Chem., 1905, 44, 134ORGAKIC CHEMISTRY-ALIPHATIC DIVISION. 79The above changes therefore, in the author’s opinion, represent atransformation from the d- to the Z-series, since cellulose, from itsrelation to d-glucose, must be regarded as belonging to the former.In connection with the question as to the constitution of Will’sacid, it may be mentioned that when glyceric acid is oxidised inpresence of iron, a product is obtained which, with phenylhydrazine,yields Nastvogel’s osazone.1 This differs from Will’s acid in that itgives an intense violet colour with ferric salts in presence of alkaliand must be either hydroxypyruvic or dihydroxyacrylic acid.Mesoxalic semi-aldehyde has been further studied by the writer.2It is easily prepared by the action of mercuric chloride on dihydroxy-maleic acid and is fairly stable in acid solution; alkalis transform itto tartronic acid.When heated for some time, it yields glyoxal, kndwith urea it condenses with evolution of carbon dioxide, givingglycoluril.dfesoxalic dialdehyde has hitherto been known only in the form ofits oxime (diisonitrosoacetone) and its di- and tri-phenylhydrazides.Harries and Turk have recently succeeded in obtaining the freealdehyde in the following way. Crystallised phorone when dissoivedin chloroform and treated with ozone yields a diozonide, C,H,,07, as agreen, explosive syrup; on shaking this with ice-water, it slowlydecomposes and crystals of acetone peroxide slowly separate.Theclear solution which remains after separation of the latter substance,when concentrated under reduced pressure, yields a viscid syrup whichsets to a glassy mass if dried in a vacuum desiccator ; analysis showsthis to be a hydrate of mesoxalic dialdehyde. The water may beremoved by heating for some time to 65’ over phosphoric oxide, and ayellow, brittle mass is then obtained which has the composition of theanhydrous dialdehyde, but which is doubtless a polymeric form, Themonomeric form is volatile in steam and the distillate gives withphenylhydrazine acetate the triphenylhydrazide,C(N,HPh): (CHN,HPh),,which was previously obtained by Pechmann and Jenisch in 1891from acetonedicarboxylic acid and diazobenzene chloride.The authors explain the formation of the dialdehyde and acetoneperoxide from phorone diozonide as follows :(C€T,),C-CH*CO*HC-C(CH,), 01 / \ 1 1 / \ 1 = 2(CH3>,C< I + CHO*CO*CHO.0:o:o 0:o:o 0Henle and Schupp4 have obtained an aqueous solution of mesoxalicdialdehyde by acting with nitrous acid on an ice-cold aqueous solutionFenton and Jones, Trans., 1900, 77, 73.Ber., 1905, 38, 1630,Tram., 1905, 87, 813.Ibid., 137280 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of Pechmann's diisonitrosoacetone, the process being analogous to thatby which Harries obtained succinic dialdehyde from the correspond-ing dioxime :OH*N:CH*CO*CH:N*OH + 2HO*NO = OCH*CO*CHO + 2H2O +2N20.By action of phenylhydrazine acetate in the cold, this productyielded the bisphenylhydrazone of mesoxalic dialdehyde (01 itsisomeride) melting at 1 7 6 O .IL.cevulic aldehyde was obtained by Harries in 1898 from a-dimethyl-furfuran; when this is acted on by hydrogen chloride in methyl-alcoholic solution, lavulinmethylal, CH,*CO * CH,*CH,*CH(OMe),, isproduced, and this, by action of dilute hydrochloric acid, is readilyliydrolysed to the aldehyde. The same author has now succeeded inobtaining this aldehyde in an entirely different way, which is of muchinterest from a general standpoint. When Para caoutchouc is dissolvedin chloroform and treated with ozonised oxygen, a viscid oil is obtainedwhich, after standing in a vacuum desiccator, sets to an explosive,glassy mass.Analysis and molecular weight determinations of thisozonide show that it has the formula C,,H1,O,. If this product istreated with water and distilled in steam, lavulic aldehyde passes over,and may be recognised by its reducing properties and behaviour withphenylhydrazine and hydroxylamine. If the action of steam iscontinued for a short time only and the solution cooled, crystalsseparate which prove to be ltevulic aldehyde peroxide. The decom-position of the ozonide may therefore be represented by the relation :The peroxide is readily decomposed by further action of steam,yielding the aldehyde. By continued action of steam on the ozonide,lavulic acid is formed. The author considers that the reacting moleculeof caoutchouc is t o be regarded as the derivative of an eight-carboncyclic compound, namely, 1 : 5-dimethylcycZooctadiene,CH,* $*CH,*CH,* XHHC* CH,*CH,* C-CH:,'From the foregoing and other results, it is considered probable thatthe caoutchouc hydrocarbons have their origin in the breaking downof carbohydrates in the plant; the pentadienyl residues, C,H,, mayresult from reduction of sugars, especially of pentoses, and may uniteto form the complexes (CI0H1&.1 Compare Pechmann, Ber., 1891, 24, 3259 ; and Bamberger, ihid., 3260.2 Ber., 1905, 38, 1195ORGANIC CHEMISTRY-ALIPHATIC DIVISION.81An experimental connection is seen in the fact that a-dimethyl-furfuran was isolated by the author from beech wood t a r and that amixture of methylated furfurans was obtained by Fischer and Laycock(1889) from the dry distillation of sugar with lime.Laevulic aldehyde,as above shown, results by simple processes of treatment both fromcaoutchouc and from dimethylfurf uran ; the connection betweenlsvulic acid and the carbohydrates is, of course, well known.It is pointed out by Winkler 1 that the commercial (‘ absolute” ethylalcohol not only contains from 1 to 2 per cent. of water, but is usuallycontaminated also with some aldehyde. The ordinary process offractional distillation and purification with lime, barium oxide, orsodium does not yield a product free from aldehyde, and for purposesin which the perfectly pure substance is requisite, as in abaorptio-metric investigations, the author recommends the removal of thealdehyde by silver oxide and caustic alkali and subsequent dehydrationby metallic calcium.It would appear from the author’s observations that the usual state-ments as to the extremely hygroscopic nature of absolute alcohol aresomewhat exaggerated; less than 0.1 per cent.of water was absorbedby 200 C.C. of absolute alcohol when exposed in an open vessel forfifteen minutes.Mathieu2 points out that aldehyde is formed in wines and otheralcoholic liquids by simple contact with air at the ordinary temperature,even without the influence of micro-organisms or porous substances.The oxidation is favoured by the presence of oxidisable substancesand by sunlight.For the identification of minute quantities oE ethyl alcohol, Buchnerand Meisenheimer 3 employ p-nitrobenzoyl chloride, which gives aquantitative yield of crystalline ethyl p-nitrobenzoate melting at 57”.employ the method of decomposition inpresence of metallic copper, which was referred to on p.70, for thedistinction between primary, secondary, and tertiary alcohols ; in theproduct, they identify aldehydes by Schiff’s reagent and ketones bysemicarbazide ; the olefinic hydrocarbons obtained from tertiaryalcohols are recognised by the property of decolorising bromine.Weinland and Schmid5 draw attention to the fact that alkyl haloidsmay readily be obtained by the action of methyl or ethyl sulphateon a metallic haloid in aqueous solution. When, for example, potassiumSabatier and SenderensBer., 1905, 38, 3612.Bull.Assoc. Chim. Suer. Did., 1905, 22, 1283.Bey., 1905, 38, 625.BuZ1. SOC. chim., 1905, [iii], 33, 263.Ber., 1905, 38, 2327.VOL. 11. 82 ANXUAL REPORTS ON THE PROGRESS OF CHEMISTRY.iodide is dissolved in its own weight of water and gently warmed withmethyl sulphate in calculated quantity, a nearly theoretical yield ofpure methyl iodide is obtained. I n the dry state, potassium chlorideand potassium methyl sulphate yield methyl chloride, and methylbromide is also formed, mixed with other products, in a similar wayfrom metallic bromides. Methyl iodide cannot be prepared in thisdry way since large quantities of iodine vapour result. It appears1that Dumas in 1835 prepared methyl chloride by heating dry sodiumchloride with methyl sulphate, but the fact appears to have escapednotice.Methylazoimide, (CH,)N,, has been obtained by Dimroth andWislicenus 2 as a colourless liquid boiling a t 20°, which explodes onlyif heated above 500".It is prepared by acting on an aqueous solutionof sodium azoimide with methyl sulphate.I n preparing alkyl iodides from alcohols by means of iodine andphosphorus, it is often assumed that the proportion of the two lattersubstances should be that corresponding t o the tri-iodide, but it isfound by Walker and Johnson3 that by using the proportion corre-sponding to the penta-iodide a yield of 87 per cent. or more of thetheoretical quantity of methyl iodide may be obtained.Bogojawlensky and Narbutt have studied the influence of variouswater-absorbing metallic salts on the esterification of ethyl alcoholwith various organic acids.They show, for example, that potassiumpyrosulphate increases the yield of ester in the case of both aliphaticand aromatic acids, but the influence of copper sulphate appears to befavourable only as regards aliphatic acids unless a little free sulphuricacid is also present; the latter appears to exert a good influence innearly all cases.For the purpose of removing the water formed during the prepara-tion of esters, Taylor makes use of the principle described by Young,Onamely, the addition of benzene and distillation of the more volatileternary mixture- alcohol, benzene, mat er.Sudborough and Thomas7 describe a simple method for theestimation of acetyl groups, which consists i n hydrolysing the com-pound with either benzenesulphonic acid or with naphthalene-a- or-P-sulphonic acid and distilling off the resulting acetic acid in steam.The distillate is then titrated with barium hydroxide, using phenol-phthalein as indicator. The acids mentioned have the advantage overphosphoric acid that they are relatively stronger and, unlike sulphuricacid, they have no tendency to yield acid'gases such as sulphur dioxide.LOG.cit., p. 3696.Trans., 1905, 87, 1596.Proe. Xoy. SOC. Edin., 1905, 25, 831.Ibid., 1905, 87, 1752.Ber., 1905, 38, 1573.Ber., 1905, 38. 3344.Trans., 1902, 81, 709ORGANIC CHEMISTRY-ALIPHATIC DIVISION, 83The ordinary methods available for bringing about the replacementof hydroxyl by bromine, such as the action of hydrobromic acid or ofphosphorus bromides, may often lead to very unsatisfactory results,especially in the case of aliphatic polyhydric compounds such asglycerol, erythritol, and mannitol.Perkin and Simonsen have nowpointed out that the process may be greatly improved if the hydroxy-groups are first acetylated and the resulting acetate is then treatedwith hydrogen bromidein glacial acetic acid at 150". I n this way, itis generally possible to substitute all the hydroxy-groups by bromine,and the process goes on smoothly without danger of carbonisation, &c.Glycol diacetate and glyceryl t.riacetate give in this way quantitativeyields of ethylene dibromide and s-tribromopropane. Erythritoltetracetate yields s-tetrabromobutane (two modifications) anderythritol tribromohydrin. The tetracetate of penterythritol,C(CH2*O*CH,*CO),, treated in a similar may at 160°, gave s-tetra-bromotetramethylmethane, C(CH2Br)4, together with the acetyl-tribromo-derivative, (CH,Br),C*CH,*O-CO*CH,.Mannitol hexa-acetate gave only the acetylpentabromo-derivative, C,H,Br,(O*CO*CH,),the sixth acetyl group obstinately resisting replacement.The synthetical preparation of glycerides of the higher fatty acidshas hitherto been effected by the direct esterification of glycerol withthe free acid (Berthelot) or by the action of chlorohydrins with salts ofthe acid. Grun2 finds that in many cases it is advantageous t o startwith the sulphuric ester of glycerol o r of the chlorohydrin and to act onthis with a solution of the fatty acid in concentrated sulphuric acid.When glycerol is esterified with sulphuric acid, the action stops a t thestage of the disulphate, even if great excess of acid is used, and theaction of the fatty acids on this producb yields only diglycerides underthe conditions stated.I n this reaction, apparently the two primaryalcoholic groups undergo esterification, so that aa-diglycerides result.Starting, however, with glycerol a-chlorohydrin, the primary andsecondary group are esterified and ap-diglycerides are obtained.If the hydroxyl or halogen in these compounds is replaced by acidradicles which are different from those already contained in thediglyceride, it is possible to prepare the structurally isomeric pairs ofsymmetrical and unsymmetrical triglycerides,CH2( 0 COR) CH(O*COR') *CH,*O*COR andCH2( 0.COR)*CH(O* COR) * CH,*O*COR,and it should evidently be possible to resolve the latter into its opticallyactive components.I n the previous report, attention was drawn to the interestingwork of VotoEek and VondrBGek on the separation of certain sugars inTraw., 1905, 87, 855. Ber., 1905, 38, 2284.G 84 ANNUAL REPORTS ON THE'PROGRESS OF CHEMISTRY.a mixture by successive treatment with diff ermt hydrazines. Theseauthors show further that by the action of a suitably chosen hydrazineon the hydrazone of a sugar it is possible to effect an interchange ofhydrazine-residues in the sense AB, + B, = AB, + B,, provided thenewly formed hydrazone has a smaller solubility.Similarly, onesugar may replace another from its hydrazone, provided the resultinghydrazone is less soluble than the one acted on; it is also possible tobring about '' double decomposition " between two sugar hydrazoneswith the production of that which is less soluble. These reactions,which resemble to some extent the behaviour of salts in solution,suggest the hypothesis that a certain amount of dissociation takesplace when a sugar hydrazone is dissolved. Galactosephenylhydr-azone, for example, reacts with mannose, giving mannosephenyl-hydrazone, galactose being liberated. The phenylmethylhydrazone ofdextrose behaves similarly towards galactose, and the diphenglhydrazoneof dextrose towards arabinose.Double decomposition oocurs betweengalactosephenylhydrazone and dextrosephenylmetbylhydrazone. Thesereplacements take place in water or dilute alcoholic solutions, andare accelerated by slight acidification with acetic acid. I n the caseof the diphenylhydrazones, the change occurs only if acetic acid ispresent.Dierssen in 1903 observed that when starch is hydrolysed by meansof oxalic acid there is formed, in addition to dextrose, a disaccharideapparently identical with Lintner's isornaltose and lsvulose. Thelatter, according to Ost,2 is not a primary product of the hydrolysis,but arises owing to the action of the acid on dextrose. By dissolvingdextrose in a mixture of equal volumes of strong sulphuric acid andwater and allowing the mixture to stand for four months a t theordinary temperature, the author obtained from 5 to 10 per cent.oflsvulose.3The author discusses some of the methods of detecting lsvulosein mixtures and gives preference to that of Dubrunfaut, namely,the separation as calcium lsvulosatc.recommends heating thesolution with a mixture of ammonium molybdate and a little aceticacid to 95'. After three minutes, lavulose produces a beautiful bluecolour, whereas with other sugars the solution remains colourlessduring this period. When the heating is continued for half an hour,arabinose, rhamnose, galactose, mannose, and sorbose produce afeeble green colour, but no blue. Mineral acids must be absent,Ber., 1905, 38, 1093.Compare Fenton and Gostling, Trans., 1901, 79, 363.Ber., 1905, 38, 3317.As a delicate test for lsvulose, Pinoff'L Zeit.angew. Chem., 1905, 18, 1170ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 85otherwise most sugars will give a blue colour under the aboveconditions.The same author has made a further study of various other colourreactions for carbohydrates, such as Tollen’s phloroglucinol reactionfor pentoses and Molisch’s a-naphthol reaction, especially with theobject of ascertaining the influence of conditions on the character ofthe absorption bands given by the coloured solutions produced.A colour-reaction of lactose which distinguishes it from other carbo-hydrates, and which may be used to detect it in mixtures, is given byGraaff .I The substance is heated with diphenylhydrazine and aceticacid, when, if lactose is present, the original brownish-violet colour ofthe mixture changes eventually to blackish-green and finally brown.If 70 per cent.alcohol is added at the green stage, a characteristicgreen solution is obtained. The green colouring matter dissolves alsoin ether o r chloroform.recommend an alcoholic solution ofp-nitrophenylhydrazine for the separation of cane sugar from dextrose,laevulose, and mannose ; these hexoses form hydrazones which arenearly insoluble in water, whereas cane sugar does not react inalcoholic solution. The same reagent may be used for the determina-tion of many aldehydes and ketones, the yield of hydrazone beingalmost quantitative. o-Nitrophenylhydrazine behaves similarly andmay be used for the separation of dextrose from laevulose, thehydrazone of the latter separating more readily from an alcoholicsolution.The compounds first observed by Morrell, which are formed bycertain sugars with guanidine, have been further studied by Morrelland Bellars.3 These compounds, which are hygroscopic, crystallinesubstances, are precipitated when alcoholic solutions of guanidine andthe sugar are mixed together.They have a strongly alkaline reactionin aqueous solution, and their optical activity is generally much lowerthan that of the parent sugar. The rotation angle of the glucosecompound in water in time becomes negative, and that of fructosefalls t o a constant value which is of the same sign as that of theparent sugar.These changes may perhaps indicate a slow transforma-tion of glucose into fructose, like that which was observed byLobry de Briiyn in the action of alkalis, These compounds are decom-posed by the action of dilute acids, but in some cases the extent of thechange is largely dependent on conditions, such as time and con-centration.Experiments of very considerable interest have been carried out byVan Ekenstein and BlanksmaPharnz. Weekblnd, 1905, 42, 685.Bee. Trav. chim., 1905, 24, 33.Proc. Carnb. Phil. XOC., 1905, [xiii], 2, 7986 ANNUAL REPORTS OK THE PROGRESS OF CHEMISTRY.E. F. Armstrong with the view of ascertaining the manner in whichthe activity of various organisms which give rise t o alcoholic fermenta-tion is dependent on, or influenced by, the enzymes which they contain.About twenty selected yeasts were employed and their action wasstudied on four hexoses-glucose, fructose, mannose, and galactose-and on the bioses-cane sugar, maltose, and lactose. The resultsshowed that glucose, fructose, and mannose could be fermented byall the yeasts employed, but that several of these were unable toferment galactose. This power of a yeast to ferment glucose, &c., orits inability to ferment galactose does not depend in any way on thepresence or absence of a particular sucroclastic enzyme; the author isof opinion, in fact, that the occurrence of alcoholic fermentation isaltogether independent of a particular enzyme, whether free or fixed,which is able to induce the hydrolysis of either maltose or cane sugar.The three hexoses which behave alike have already been shown t ohave oue common enolic form, and the author considers that theformation of the enol is the initial stage in the fermentation of thehexoses, and that the breakdown of the molecule commences a tthe terminal carbon atom.Compounds which differ from glucoseonly in the groups attached to the terminal carbon atom (methylglucosides, gluconic acid, &c.) are unfernientable.The conception of reversible hydrolysis of the hioses or disaccha-rides under the influence of enzymes was first indicated by theresearches of Croft Hill in 1898. Since that time, many furtherinvestigations have been made on the subject, but it is pointed out byE. F. Armstrong2 that little has been done to advance any theoryof the process or to arrive at any definite understanding as to thelimitations of the changes involved.Similar remarks apply also tothe action of acids which can likewise act reversibly under certainconditions.The key to the interpretation of these changes must, in this author’sopinion, be looked for in the behaviour of glucose itself in solution.The fact that glucose exists in more than one form was first clearlypointed out by Tanret in 1895 ; he then assumed that three formsexist, but in view of later investigations the number is now admit-tedly reduced to two. These two forms ca.n be completely convertedone into the other i n the solid state; as crystallised from alcohol,glucose consists almost entirely of the a-form, but by heating this forseveral days to 105O it is changed to the p - f ~ r m .~ When either formis dissolved in water (or other solvents), partial transformation intothe other form takes place until equilibrium is established, the pro-portions depending on the concentration and temperature.Proc. Aoy. sbc., 1905, 76, 600. Ibid., 592.3 Tanret, Bull. Soc. chirn., 1905, 33, 337ORGANIC CHEMISTRP-ALIPHATIC DlVlSTUN. 87The process by which a monose is converted into a biose mustbe regarded as precisely similar to t h a t by which a- and P-glucose8are converted into the respective methyl glucosides ; maltose must, infact, be regarded as glucose a-glucoside and isomaltose as glucoseP-glucoside. One would expect then t h a t when glucose undergoescondensation to the biose form it should, if the process is uncon-trolled, give rise t o both maltose and isomaltose in proportionsdepending on their relative stability under the conditions.It is shown that when the condensation of glucose is effected byacids, both maltose and isomaltose are formed. But since hydrolysisunder the influence of enzymes is a selective process, being so con-trolled that it takes place in one direction only (thus, only derivativesof a-glucose are hydrolysed by maltase), it might be supposed that thetendency would be for the enzyme to reproduce that biose which ithydrolyses. As a matter of fact, the main product is a biose, iso-maltose, isomeric with that normally hydrolysed, and it is uncertainat present whether the normal biose, maltose, is produced at all by theaction of maltase.The formation under the influence of an enzymeof a single biose which is isomeric with that which it hydrolyses couldbe accounted for if it is assumed that both are initially produced, butthat one is again hydrolysed as fast as formed, and so all but disappears.If, however, it were shown that only the stereoisomeride of the biosehydrolysed is produced initially, it would be necessary to regard thesynthetical activity of the enzyme as opposed to its hydrolytic activity.An explanation which, in a measure, unites both points of view is thatthe enzyme acts throughout by protecting one or the other positionaccording as it belongs either to the a- or to the p-class of hydrolysts,thereby practically preventing condensation from taking place inmore than one direction.The author’s results show that, under the given conditions, bothmaltose and isomaltose are producible from glucose, the former by theaid of the P-enzyme, emulsin, and the latter by the a-enzyme, maltase.So far it is left undecided whether maltase can give rise to maltose,but experiments are mentioned which at any rate render it probablethat emulsin does not give rise t o isomaltose.The stereoisomeric glucosides are now of considerable importance astest materials in the study of enzyme action, and an improved methodfor their preparation has been published by E.F. Armstrong andCourtau1d.l When solid anhydrous glucose is dissolved in methylalcohol containing hydrogen chloride, it is quickly converted into amixture of nearly equal parts of a- and P-glucoses, which then undergoetherification yielding tho corresponding glucosides. I f the solutionis neutralised before the further slow conversion of @met hylglucosidePhys.Proc. 1905, Jiily 188 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.into the more stable a-form can take place and the solvent is removed,a mixture of the two forms is obtained; by subjecting this mixtureto a suitably active yeast, the a-form undergoes fermentation, and theP-compound is obtained in a pure state. I n this way, about 230 gramsof P-methylglucoside may be obtained from 500 grams of glucose.Maquenne 1 prepares P-methylglucoside by the action of methylsulphate on glucose in presence of caustic potash ; the a-modificationis not produced under the conditions of his experiment.The yield ofP-methylglucoside is equal t o about 20 per cent. of the glucose taken.Ter Meulin2 points out that in determining the nature of a sugarcontained in a glucoside, hydrolysis should be effected by means of anenzyme and not by a dilute acid, since his experiments go to showthat in the latter case the process is carried further. The same authorhas also made experiments illustrating the fact that the enzymehydrolysis of glucosides can be retarded by addition of one of thereaction products ; by enzyme hydrolysis of glucosides in contact withdifferent sugars, under the same conditions, he was able to show thatless decomposition occurs in cases where the added sugar is identicalwith that resulting from the hydrolysis of the glucoside.It has been shown by Purdie and Irvine3 that when a solution oftetramethylglucose in pure benzene containing hydrogen chloride isheated at 105-115° water is eliminated and the rotatory powerincreased.The product, when distilled under reduced pressure, was aneutral dextrorotatory syrup without multirotation, which did notreduce hot Fehling’s solution. Analysis and determination of themethoxy-groups indicate that this product is an octamethylated disac-charide. Hydrolysis with dilute hydrochloric acid gave tetramethyl-glucose apparently as the sole product. It would appear that con-densation had occurred between two molecules of tetramethylglucosein the y-oxidic form, the product being an octamethylglucosido-glucoside.Apparently this is the first example of a synthesiseddisaccharide of the non-reducing type, of which cane sugar andtrehalose are representative.Irvine and Moody 4 in the course of an investigation on alkylatedsugars have prepared and described tetramethylmannose and the isomerictetramethyl a- and P-methylmannosides. The results are on the wholestrictly comparable with those obtained in the study of the corre-sponding glucose and galactose compounds.It has been shown by Cross, Bevan, and Briggs5 that by treatingcellulose with mixtures of acetic anhydride and acetic acid in presenceof increasing quantities of sulphuric acid a series of acetosulphuric1 Bull.Xoc. chim., 1905, [iii], 33, 469.3 Tmm., 1905, 87, 1022.Ber., 1905, 38, 1859.Rec. Trav. chim., 1905, 24, 444.Ibid., 1962ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 89esters is produced. Their formation takes place in a graduated way,and the particular equilibrium attained is dependent on the con-centration of the sulphuric acid present in the mixture. By treatmentwith solvents such as acetone, alcohol, and water, these products canbe approximately separated. One of these esters, which the authorsterm the normal acetosulphate, has the compositionit is insoluble in water, but has the property of absorbing water to aremarkable extent, forming a hydrated jelly. It is soluble in acetoneand in hot alcohol. Saponification with alcoholic potash fails to splitoff the SO, group, the resulting product being a water-soluble cellulosesulphate.The fact that this compound contains four C, residues toone SO, group would appear to afford additional proof that cellulosebehaves in its reactions as a complex containing at least 24 carbonatoms.Owing to the colloidal and hygroscopic character of these esters,their analysis was in the first instance a, matter of some difficulty. I na later communication, however,l the authors show that by pouringthe reaction mixture into amyl alcohol and washing the resulting preci-pitate with the same solvent the product may be dried at looo with-out decomposition. Under these conditions, the compound behaves asa neutral sulphate, but in contact with water the SO, residue assumesthe acid form, reacting with bases as the group SO,H.The calcium,magnesium, and zinc salts have been prepared and analysed.The authors are of opinion that these results confirm the conclusionsat which they previously arrived2 with regard to the simultaneousreaction of nitric and sulphuric acids with the hydroxyl groups incellulose in the ordinary process of preparing cellulose nitrates ; theyexplain also the mechanism of the ordinary practical methods forrendering these esters stable. From the general character of theseester reactions, the authors consider “ that the reacting unit of cellu-lose is not of fixed dimensions, but combines in continuous and pro-gressive proportions with negative groups to form these syntheticalderivatives.I n other words, as in the reactions of solutions it isgenerally held that it is not the molecules which react but the ionisedfractions of these, so in cellulose the complex reacts as a solution, andwhile the stoichiometrical proportions of the interacting groups are,of course, experimentally verifiable, the molecular interpretation of thereactions is certainly not reconcilable with the experimental facts,Positive evidence is available that the colloidal characteristics of thesecompounds, which are maintained undisturbed by the reactions, are anessential condition of chemical constitution and function, and notmerely an incidental ‘ physical ’ property.” 3Ibid., 1901, 34, 2496. Chem. Zeit., 1905, 29, 527.(C,H70,)*SO,(C,H, 0 2 ) 10 ;1 Ber., 1905, 38, 353190 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Le Sueur has shown1 that when a-hydroxystearic acid is heated to270' it decomposes into carbon monoxide, water, formic acid,margaric aldehyde, and the lactide of a-hydroxystearic acid.Asimilar decomposition is now found by the author to occur in thecases of the u-hydroxy-derivatives of margaric, palmitic, pentadecylic,and myristic acids. The yield of the aldehyde in these cases is never lessthan 35 per cent. of the theoretical; the products are white solids andform oximes, semicarbazones, hydroxycyanides, &c., characteristic ofaldehydes. They polymerise on keeping, the resulting compounds beingtrimolecular. These polymerides do not form oximes, semicarbaznnes,&c., and do not reduce potassium permanganate ; when slowly distilledunder reduced pressure, they are reconverted into the original alde-hydes.The above-mentioned action affords, as previously pointedout, a convenient method, not only of preparing aldehydes of thisclass, but also of systematically degrading the aliphatic acids.Garzarolli-Thurnlackh in 1892, by heating chloral and malonicacid in molecular proportions with excess of acetic acid, obtainedy-trichloro-P- hydroxy but yric acid, CCI, CH(0 H) CH,. CO, H , and thiswhen acted on by a concentrated solution of potassium or bariumhydroxide gave rise to malic acid. Doebner and Segelitz 3 find tbatthe yield is improved if pyridine is used in place of acetic acid, andthey have extended the method to the preparation of substitutedmnlic acids.By the condensation of chloral with ethylmalonic acidin presenqe of excess of pyridine, a-ethyl-P-hydroxy-y-trichlorobutyricacid is obtained, and this, when warmed with aqueous (10 per cent.)caustic potash for an hour, acidified, evaporated, and extracted withether, gave a theoretical yield of P-ethylmalic acid,CCl,*CH(OH)*CHEt*CO,H + 5KOH = CO,H*CH(OH)*CHEt*CO,H +3KC1+ 3H,O.The product is less hygroscopic than malic acid and melts at 8 6 O ;when heated at 200°, it gives rise to ethylmaleic acid. It is not identicalwith the ethylmalic acid which Fichter and Goldhaber obtained(1904) by reduction of ethyl oxalacetate with aluminium amalgam ;their product melted at 133' and on heating gave methylcitraconicacid as the principal product.P-Benxylmalic acid was similarly prepared from benzylmalonic acid,chloral, and pyridine.It melts at 155' and when heated to 200" givesphenylitaconic acid ; it is presumed that phenyloitraconic (benzyl-maleic) acid is first formed and undergoes transformation into theisomeride.Only one modification of glutaconic acid has, up to the present1 Compare Ann. Reports, 1904, 62. Tram., 1905, 87, 1888.Ber., 1905, 38, 2733ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 91time, been isolated, although from the generally accepted formula,CO,B*CH,*CH:CH*CO,H, the cis- and trans-modifications are tobe expected. Such forms have, in fact, been shown t o exist in aa-dimethylglutaconic acid and in aaal-trimethylglutaconic acid.’ Aseries of experiments has now been carried out by Perkin andTattersall with the object of preparing a second modification ofglutaconic acid itself,2 and although in this they were unsuccessfultheir results throw an important new light on the problem.Theyshow in the first instance that glutaconic anhydride may be distilledwithout decomposition and they confirm Buchner’s observation that onhydrolysis it yields the same modification of the acid from which itmas prepared and which is therefore the cis-form. It is shown,further, that removal of the elements of hydrogen chloride fromthe ethyl ester of /I-chloroglutarate, C0,Et*CH,*CHCl*CH2~CO~Et,and subsequent hydrolysis gives again only the cis-acid, although asimilar procedure in the case of a substituted aaal-trimethylglutaconicacid yields the trans-form.Prom these and other observations, theauthors consider that the generally accepted formula for glutaconicacid does not always correctly represent its constitution and thatmany of the remarkable properties of the acid would be moresatisfactorily indicated by the symmetrical expressionC@,H*CH*CH2*CH*C02H.This might be regarded as a tautoderic modification of the usualformula, one type being converted into the other during the course ofcertain reactions.Thorpe, who has made a complete study of the methyl derivatives ofglutaconic acid,3 comes to a similar conclusion. He shows that the@-derivatives are identical with the &derivatives, that is, that thepositions a and ul are identical and suggests for glutaconic acid theICHformula C02H*CH CH*CO,H, in which the dotted lines repre- !p ., . ,Hsent a state of equilibrium between the hydrogen and the twoa-carbon atoms.Reference was made in last year’s Annual Report (p. 72) tothe comparatively limited state of our knowledge of the dihydroxy-derivatives of acids of the succinic series other than the tartaric acids,and attention was drawn t o the work of Rosenlew on isomeric dihydr-oxy-adipic acids. and Kiliani and Loeffler 5 have Kiliani and HeroldPerkin and Smith, Tram., 1903, 83, 8, 771 ; 1904, 85, 155.Trans., 1905, 87, 361. Ibid., 1669.Ber., 1905, 38, 2671. ]bid,, 362492 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.recently published further investigations on the dihydroxyglutaricacids. It was shown by Kiliani in 1885 that isosaccharin (preparedby action of calcium hydroxide on milk sugar), when oxidised bynitric acid, yields glycollic acid and an unstable tribasic acid,C3H,(OH),(C02H), (dihydroxypropenyltricarboxylic acid), and thatthe latter on being heated loses carbon dioxide, yielding a dihydroxy-glutaric acid.This product differed in properties from the up-dihydr-oxyglutaric acid prepared from glutaconic acid dibromide, and wastherefore represented as the uy-compound,CO,H* CH(OH)*CH,*CH( OH)*C02H.This constitution is supported in an indirect way by the observationof Ruff, Meusser, and Franz that isosaccharin, when oxidised withhydrogen peroxide in presence of iron, gives rise to a keto-pentose,C5Hl,04 ; in this case, isosaccharin must have a hydroxyl group in thea-position.For the preparation of the above-mentioned tricarboxylicacid, the authors now recommend the oxidation of calcium isosaccha-rinate with strong nitric acid ; by removal of resulting oxalic acid andconcentration in a vacuum, the product is obtained in deliquescentplates or prisms. The constitution of the tricarboxylic acid isevidently represented by the formulaCO,H* C(OH)(C02H) CH,*CH(OH)*CO,H.By boiling the acid calcium salt of this acid with the calculatedquantity of oxalic acid and evaporating the resulting solution, thelactone of ay-dihydroxyglutaric acid is obtained, and from the calciumsalt of this lactone the free acid is prepared in a similar way onallowing the solution to concentrate in a vacuum desiccator.Thisay-acid melts at about 120' and yields a quinine salt containing 4H,O.It is further shown that the up-acid can be obtained from glutaconicacid not only by the bromine method above referred to, but alsoby oxidation with potassium permanganate ; it melts and decomposesat 164O, and is optically inactive.By oxidation of metasaccharopentose with dilute nitric acid at 35O,another up-dihydroxyglutaric acid is obtained, which is dextrorotatoryand melts at 156O.By hydrolysis of the glucoside '' P-digitoxin," Kiliani in 1895obtained a crystalline substance named by him digitoxose, which atfirst sight appeared to resemble glucose ; analysis, however, showedthat it has the composition C,H,,O,.It gives a blue colour withferric chloride and yields an oxime, but no osazone. The constitutionof this substance was for a considerable time a matter of doubt, butthe same author shows now 2 conclusively that i t is an aldose havingthe formula CH3[CH*OH],*CH2*CH0. When oxidised by bromine, ityields the corresponding acid, C6HI2O5, and by oxidation with nitricBer., 1902, 35, 2367, Bid., 1905, 38, 4040ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 93acid i t gives rise to a dihydroxyglutaric acid, which appears t o be oneof the up-compounds.A trihydyoxyadipic acid melting a t 146' was obtained by Kilianiin 1885 by oxidation of metasaccharin by nitric acid; the sameauthor1 has now prepared an acid which is probably a structure-isomeride of this by oxidation of the lactone of digitalonic acid.This new trihydroxyadipic acid melts a t 124' and has the constitutionC02H[CH*OH],*CH2*C02H, that from metasaccharin beingC02H[CH*OH],*CH2*CH( OH) C0,H.Mesoxulic acid may conveniently be prepared by action of mercuricoxide on dihydroxytartaric acid in aqueous solution at 50°,2 and ethylmesoxalate by action of oxides of nitrogen on ethyl malonate a t- 15°.3It is, of course, well known that ammonia, or primary or secondaryamines, can react with formaldehyde even a t the ordinary tempera-ture, giving condensation products with elimination of water.When,however, these bases are heated with formaldehyde to about120-160° in closed vessels, the course of the reaction is different, theresult then being the replacement of amino- or imino-hydrogen bymethyl.The principle of the latter change formed the subject ofa patent by Eschweiler in 1893, but since it appears to have escapedthe attention of chemists the author now gives a supplementaryaccount of the process.* With ammonia, the resulting changes may berepresented as follows :2NH3 + 3CH20 = SNH2-CH, + CO, + H20.2NH3 + 6CH20 = 2NH(CH,), +2C02 +2H20.2NH, + 9cH20 = 2N(CH,), +3CO, +3H20.Hexamethylenetetramine heated with excess of formaldehyde alsoyields trimethylamine, a circumstance which explains the odour ofamines usually observed in the preparation of hexamethylenetetramine.Primary and secondary amines behave in quite an analogousmanner, dimethylethylamine being obtained from ethylamine, tetra-methylethylenediamine from ethylenediamine, methylpiperidine frompiperidine, and so on.This process forms a very convenient andsimple method for the preparation of trimethylamine in quantity ; byheating 50 grams of ammonium chloride with 40 per cent.forrnaldehydesolution in an autoclave to 1 ZOO, Koeppengrams of trimethylamine hydrochloride.Loe. eit., 3621. 2Schmitt, C'ompt. rend., 1905, 141, [i], 48 ; and33, 603.obtained a yield of 70-80Fenton, Trans., 1905, 87, 813.Curtis, Amer. Chem. J., 1905,Ber., 1905, 38, 850. Ibid., 88294 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRYBearing in mind the interesting characters and properties of thetetralkylammonium hydroxides and the extent to which they havebeen employed in chemical and physical investigations, it is somewhatremarkable, as pointed out by Walker and Johnson,l that the freebases have never been isolated in any definite form.The solutionsresulting from the interaction of alkyl iodides and silver oxide yield,it is true, a crystalline mass on evaporation, but the pure productshave not been definitely isolated and analysed. By acting on tetra-methylammonium chloride with potassium hydroxide in methyl-alcoholic solution, these authors obtained a product which by treatmentwith water and distillation yielded a crystalline pentahydrate oftetramethylammonium hydroxide. Concentration of tbe motherliquor from these crystals gave a trihydrate, and by dehydration ofthe pentahydrate a t 35’/18 mm. a monohydrate was obtained.Underno conditions, however, was it found possible to obtain the anhydrousbase, since the monohydrate decomposes with formation of trimethyl-amine before a temperature is reached a t which its water-vapourpressure is appreciable.In accordance with the observations of Kulz (1871) and Baumann(1882), cysteine and cystine were formerly represented by theconstitutional formulseCH3*C(NH2)(SH) CO,H and [CH;C( NH,)( CO,H)*S -I2.But the investigations of Friedmann and of Neuberg in 1902established the fact that the nitrogen and sulphur in these compoundsare associated with different carbon atoms. From Friedmann’s resultsand from the recent synthesis by E. Erlenmeyer, jun.,, there is nowlittle if any doubt that the two compounds are correctly representedby the constitutionCH,(SH)*CH(NH,)*CO,H and [-S*CH,*CH(NH,)*CO,H],.Before the conclusion of these last-named investigations thereremained yet the alternative formulseCH,(NH,)*CH(SH)*CO,H and [-S *C H( CO,H)*CH,*NH,],,and researches were carried out by Gabriel with the object ofsynthetically producing compounds of these constitutions.Theauthor has now succeeded in effecting this synthesis, and thecompounds obtained are named by him isocysteine and isocystine.3 Themethod employed was briefly as follows : dihydrouracil (or P-lactyl-urea), C H , < ~ ~ ~ ~ ~ > C O , was converted into the bromo-derivativeTrans., 1905, 87, 953.Ber., 1905, 38, 630.See A?m.Rcports, 1904, 75ORGANIC CHEMISTKY-ALIPHATIC DIVISION. 95and, by action of potassium thiocyanate, the bromine atom wasreplaced by the CNS group. This thiocyanyl derivative when heatedto 170’ in a sealed tube with fuming hydrochloric acid is convertedinto the hydrochloride of isocysteine. Iodine converts the latter intothe hydriodide of isocystine :2C,H70,NS + I, = C,H,,O,N,S, + 2HI.The free base melts a t 1S5O; it differs from cystine in giving a darkbrown coloration when warmed with copper sulphate in hydrochloricacid solution and a black colour with alkaline lead solutions even inthe cold.According to the investigations of Neuberg, Loewy, and Mayer,it appears that calculus-cyntine differs both physiologically andchemically from protein-cystine, which is derived from hair, horn, &c.It might at first sight seem probable that this difference is to beexplained by the two alternative formuh above mentioned, butalthough it is fairly certain that protein-cystine is correctlyrepresented by Friedmann’s a-amino-P-thio-constitution, the propertiesof calculus-cgstine differ somewhat from those of Gabriel’s syntheticalproduct.Since the latter is the a-thio-P-amino-compound, theconstitution of calculus-cystine cannot be regarded as finally sett1ed.lExperiments of Fischer and Suzuki 2 suggest the possibility that thedifferences observed in calculus cystine may be due to the presence oftyrosine as an impurity. By suspending cystine in absolute methylalcohol and passing hydrogen chloride into the mixture they obtainthe hydrochloride of cystine dimethyl ester, C,H1,O,N,S, ; this andthe corresponding nitrate, sulphate, and picrate are crystalline saltswhich serve for the identification of cystine.Treated in this way,both calculus-cystine and protein-cystine gave identical products.The behaviour of urea when treated with hypobromites and hypo-chlorites has been the subject of quite an extraordinary number ofindependent researches during the last fifty years, and it wouldnaturally be supposed that the nature of the change, apparently SOsimple, must have been exhaustively established. It comes as asurprise, therefore, to learn from Schestakoff that by the action ofsodium hypochlorite and sodium hydroxide at about 5’ urea can bemade to yield hydrazine.This result, which was predicted by theauthor from analogy with Hofmann’s well-known conversion ofamides to amines, would appear to be reached in the followingstages :Compare Neuberg and Mayer, Zeit. physiol. Chem., 1905, 44, 472.Zeit. physiol. Chem., 1905, 45, 405.J. Auss. Phys. Chenz. Soc., 1905, 37, 196 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.(1) NH,.CO’NH, + NaClO = NH,*C(ONa):NCl+ H,O.(2) NH,C(ONa):NCl = NH,*N:C(ONa)*Cl.(3) NH2*N:C(ONa)*C1 + NaOH = NH2*NH*C02Na + NaCI.(4) NH,*NH*CO,Na + H,O = NH2*NH, + NaHCO,.Hydrazine is of course immediately oxidised by hypochlorites withevolution of nitrogen, but by having present a substance which reactswith hydrazine to form a difficultly oxidisable product this decomposi-tion is avoided.For this purpose, a suitable agent was found inbenzaldehyde, which reacts with the hydrazine a t the moment of itsformation to give benzalazine, C,H,CH:N*N:CHC,H,. By additionof sulphuric acid arid removal of the benzaldehyde in steam, thehydrazine is obtained in the form of sulphate. The yield is said to be60 per cent. of that required by theory, and from one litre of urinethe author obtained 30-40 grams of hydrazine sulphate. Substitutedureas similarly yield corresponding hydrazines, benzoylurea, forexample, giving benzoy1hydrazine.l It is somewhat difficult a t firstsight to reconcile the facts here recorded with some of the conclusionswhich have been drawn by previous observers. It was shown, forexample, by the present writer in 1878 that when urea is acted on byhypochlorites in presence of caustic alkali, one-half of the nitrogen isevolved in the free state, the other half remaining as cyanate.Thisresult was easily explained in view of the further observation (1 888)that the transformation of ammonium cyanate into urea is a limitedand reversible reaction, a result which was afterwards confirmed in adifferent manner by Walker and Hambly (1895). The conditionsunder which Schestakoff’s experiments were carried out, however,differed very considerably from those of previous observers in that heused only the calculated quantities of hypochlorite and soda andoperated a t a low temperature.The explanation previously suggested of the hypochlorite action wasthat urea itself is not acted on by the agent, and that the nitrogencomes only from the ammonium group after reversion of the urea hastaken place.Possibly both actions, the oxidation of urea itself andthe reversion, take place simultaneously, but at the lower temperaturethe latter change is too slow t o be very appreciable, and the principalresult is then the oxidation of urea to hydrazine.3Armstrong and Robertson 4 point out that Schestakoff’s result hasan important bearing on the theory that nitrogen in conjunction witha It may be mentioned that E. P. Frankland, who is now working in the Cam-bridge University Laboratory, has carefully repeated Schestakoffs experiments,and is able entirely to confirm the latter’s statements, except that the yield ofhydrazine obtained was very much smaller than that above mentioned.Chem.Centr., 1905, ii, 1703. Fenton, Proc., 1895, 11, 138.Tram., 1905, 87, 1286ORGANIC CHEMISTRY-ALIPHATIC DIVISION. 97carbon has a tendency t o give rise t o three atom rings as a preferredform; they suggest that the reaction in question may be representedas taking place in the following stages :Hofmann’s conversion of acetamide into methylamine being formulatedas :CH3--3 I . CH3 CH, CH3 I +I\ -+ ICO*NH NH*C02H NH, CO*NHBrThe interaction of dry carbon monoxide and ammonia when thegases are heated in presence of platinum has hitherto been representedby the relation CO + 2NH, = NH-;CN + H,O,l but it is now shown byJackson and Northall-Laurie that the main product is ammoniumcyanate, which, as the temperature rises, is converted into urea.Thechange may be brought about not only by passing the gases over aheated platinum spiral or platinised asbestos, but also by ordinarysparking. Similar results are obtained by using the silent discharge,but in this case polymerised cyanogen compounds are also produced.Water, methane, hydrogen, and nitrogen are found amongst thegaseous products, and the authors consider that the initial change maybe UO + 2NH3 = NH,-CNO + H2, and that methane results from theinteraction of carbon monoxide with the free hydrogen.By the action of ammonia on carbonyl chloride, dissolved in lightpetroleum at Oo, there is formed not only urea but also cyanuric acidand cyamelide.2 Melanurenic acid (the monamide of cyanuric acid), asfirst pointed out by Bouchardat, is also produced when the substancesreact in the gaseous state.3It is sometimes stated that cyamelide is produced, together withcyanuric acid, when urea is heated.This, according to H a n t ~ s c h , ~ isnot the case; a substance is produced, however, which at first sightappears closely to resemble cyamelide, but differs from it in beingsoluble without decomposition in boiling water. This substance,which exhibits both basic and acidic properties, is proved to be theureide of cyanuric acid or tricyanocarbamide, (CN),(NH*CO*NHJ,.It is also formed by heating urea with cyanogen bromide t o 150°, orwith cyanuric acid to 1 8 0 O . The same compound is formed whenbiuret is heated, the change being probably in the first instanceNH,*CO*NH*CO*NH, = NH,-CO*NH.CN + H,O, this resulting cyan-urea then undergoing polymerisation.1 Kuhlmann, 1841.a Stner, ibid., 2326.VOL.11. HHantzsch and Stuer, Ber., 1905, 38, 1042,Ber., 1905, 38, 101398 ANNUAL EEPORTS ON THE PROGRESS OF CHEMISTRY.No direct determination of the molecular weight df cyamelide hasyet been made owing t o its insolubility in ordinary solvents, but theauthor comes to the conclusion, by indirect evidence, that it has thesame molecular weight as cyanuric acid, cyamelide and cyanuric acidbeing isomeric and not polymeric. The conversion of cyanic acid tocyamelide is known to be a trimolecular reaction; this fact and alsothe composition of the mercuric derivative of cyamelide which the authorhas obtained indicate (HCNO), as the minimum formula, and manyreasons are adduced for considering that this is likewise the maximum.Cyamelide is more easily decomposed (by sulphuric acid, for example)than cyanuric acid; the fact that in many reactions the oppositeappears to be the case is explained by saying that cyanuric acid is apseudo-acid which is easily convertible into the more reactive true acid.It is shown that cyamelide cannot be regarded as a tricyanogenderivative, neither can it contain the salt-forming group -N:C*OH orthe ‘‘ indirect ” salt-forming group -NH*CO ; these and other consider-ations lead to the conclusion that cyamelide is to be regarded as apolymeride of pseudo-cyanic acid, OC:NH, and not of cyanic acid,KO-CN, its formation being represented as :0HN:C/\C:NH o! !o -+Although the molecular formula for fulminic acid has been some-times expressed as (CHNO),-this formula appearing on the wholeto be the most consistent with the reactions of its derivatives-the question could not be regarded as settled, since there appeared t obe certain facts (for example, the non-existence of acid salt,s and thesynthesis of fulminates from mono-carbon compounds such as nitro-ethane) which were more in accord with the single formula.Wohlerand Theodorovitsl have now made a study of the formation ofmercury fulminate from a variety of carbon compounds by theusual method of treatment with strong nitric acid and mercuricnitrate.They come to the conclusion that mono-carbon compoundsdo not give fulminate by this treatment, and the same appears tobe the case with compounds containing three or more carbon atoms,whereas many of the 2-carbon series yield the pure product, althoughin all cases a very considerable excess of the carbon compound has tobe employed. Since, however, negative results were obtained withglycol, glyoxal, glyoxime, and acetonitrile, the authors conclude thatit 2-carbon chain of a certain structure (for example, methyl groups inBer., 1905, 38, 1345UKGANIC CHEMISTRY-ALIPHATIC DIVISION. 99conjunction with -CH,*OH, -CH<EI, -C<g, or =CH*O-) isnecessary for fulminate formation by this treatment. These resultsappeared therefore to favour the bimolecular formula for f ulminicacid.But Wohler 1 has further made determinations of the molecularweight of sodium fulminate, which can be prepared in a pureanhydrous state by the action of sodium tmalgam on mercury fulminatesuspended in alcohol.The numbers obtained by the cryoscopic method, assuming thatsodium fulminate is ionised to the same extent as ofher salts ofanalogous constitution under similar conditions, correspond closelywith the theoretical value required for the single formula NaCNO.Determination of the equivalent conductivities at 0' of the solution a tdilutions of N/32 and iV/1024 lead to a similar result, sodium ful-minate behaving as the salt of a monobasic acid; in this case, themeasurements could not be carried out a t 25" as in Ostwald's ex-periments, since the solution shows signs of decomposition at thistemperature.By the action of nitric acid on ethyl acetonedicarboxylate, an oil isobtained which, according t o Ulpiani and Bernardini, is the peroxideof ethyl oximinoacetate; the same compound results also from theaction of fuming nitric acid on ethyl acetoacetate. When thiscompound is treated with concentrated ammonia it is convertedquantitatively into a compound having the formula (CHON),. Theseauthors now show that the latter compound is succinamidedinitroso-peroxide. When this is boiled with concentrated ammonia, it givesrise to fulminuric acid and isofulminuramide. The fulminuric acid soobtained is identical with that obtained by Liebig from mercuricfulminate by action of alkali chlorides and is considered by theauthors t o have the constitution NO,H:C(CN)*CO=NH,.Researches on the synthesis of polypeptides continue to be activelycarried on by Emil Fischer and his colleague^.^ Results of consider-able importance have been arrived at, and a large number of newpolypeptides, of very varying types, has been synthesised. It wouldbe quite impossible in the short space here available to give anythinglike a useful account of these later results, which in their present staterefer principally to matters of detail and, in part, belong moreappropriately to the domain of Physiological Chemistry. It ispointed out that a study of the polypeptides offers special advantagesin dealing with certain problems in stereochemistry owing t o the1 Ber., 1905, 38, 1351. Gnxxetta, 1905, [ii], 35, 7.3 Ber., 1905, 38, 605, 2375, 2914 ; Amalert, 1905, 340, 123, 128, 142, 152, 168,172, 180, 190.H 100 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.large number of asymmetric carbon atoms which can be introducedinto some of the higher members. Optically active polypeptides havehitherto been prepared only from active amino-acids, but it has nowbeen found possible to build up members of this class by using opti-cally active o r racemic acid chlorides.An improved method of obtaining amino-acid chlorides, whichis applicable to those of a complex character, has been devised. Thisconsists in heating the acids with a mixture of acetyl chloride andphosphorus pentachloride.The polypeptides when melted yield anhydrides or diketopiperazines,and these by the action of dilute alkalis yield the salt of a highermember; thus glycine anhydride gives the sodium salt of glycyl-glycine when shaken with normal solution of caustic soda; alanyl-alanine can similarly be obtained from alanine-anhydride.It will be noticed from the structural formulae that each diketo-piperazine with a side-chain corresponds to two different polypeptides,thus leucylglycine, (CH,),*CH*CH,*CH( NH,)*CO NH*CH,*CO,H, andglycyl-leucine, NH,*CH,*CO-NH*CH(C,H,)*C02H, each give on meltingthe same anhydride, isobutylqketopiperazine,(CH,),CH*CH2*qH*NH*S0CO-NH-CH,H. J. H. FENTON

ISSN:0365-6217    

DOI:10.1039/AR9050200066

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION.DURING the past year, the contributions to the chemistry of the homo-cyclic division of the aromatic compounds have not been marked byany discoveries of exceptional interest. The advances have followedthe lines of former work, and very little new ground has been broken.The study of the relation of colour to structure, which engaged somuch attention in the past year, has made little real progress. Thewriter ventures to offer the opinion that, in the present state of ourknowledge, any explanation of colour which finds its final expressionin terms of structural formulae, based on chemical changes alone, will beas inconclusive as the derivation of structural formulz from the mereattribute of colour. It is for this reason that the valuable data onabsorption spectra, which are being accumulated by Hartley, Dobbie,Baly, and other workers in this field, will be followed with specialin t erest.1The growing importance of the industry which is best described bythe German "Riechstoffe," and the theoretical value of a correctknowledge of these widely distributed products of vegetable life, isreflected in the increasing attention which is being given to the studyof hydrocyclic compounds.Reagents.Phenylcarbimide, which has been regarded as a trustworthy reagentfor hydroxy-compounds in non-dissociating solvents, has been shownby Dieckmann, Hoppe, and Stein 2 to have forfeited to some extent itscharacter. They find that among 1 : 3-diketones this reagent inpresence of a trace of alkali may form C-carbanilido-compounds,but the reaction is inhibited if the carbimide is pure.On the otherhand, hydroxymethylene compounds and cyclic hydroxy-compounds(hydroresorcinols and phenols) combine to form O-carbanilido-deriv-Since this paragraph was written, an interesting paper by Professor Hartley hasappeared on the subject of colour in its relation to structnre, which is based onobservations of absorption spectra of colourless and coloured substances ( Trans.,1905, 87, 1822). 2 Ber., 1904, 37, 4627102 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.atives, but whereas the cyclic compounds combine in absence ofalkali, the hydroxymethylene compounds do not. They conclude thatthe use of phenylcarbimide as a reagent for determining constitutionof tautomeric 1 : 3-diketones is subject to obvious limitations.Goldschmidt and Low-Beer have also found that the distinctionwhich they formerly drew between 0- and p-hydroxyazo-compounds onthe strength of the phenylcarbimide reaction must be revised.Thepara-compounds, which readily combine with this reagent, were regardedas true phenols, whereas the ortho-compounds, which did not, wererepresented as quinone derivatives.Both series of compounds have now been proved to form carbanilido-compounds, and therefare possess the same structure. It appears,further, that in the special case investigated, that of benzeneazo-p-cresol,the phenylcarbimide molecule attaches itself to the hydroxyl group :CH,The authors conclude from this and other reasons which cannot befairly condensed into a small compass that the hgdrazine formula forhydroxyazo-compounds is no longer tenable, and the same applies toaminoazo-compounds.Finally, Dimroth has demonstrated the un-reliability of phenylcarbimide for ascertaining the structure of diazo-amino-compounds, which Busch and Bergmann for other reasons alsocoriclude must possess the normal constitution.The use of copper as a catalytic agent, referred to in last year'sreport (p. 87), has been extended by Ullmann and his collaborators,*who now show that chlorine in o-chlorobenzoic acid and its derivativesmay, in presence of small quantities of finely-divided copper, bereplaced by phenol, thiophenol, arylamine, and arylsulphinic groups.To give a few examples, potassium o-chlorobenzoate, heated to180-190' with sodium phenoxide in alcoholic solution to which a littlecopper powder is added, gives a 90 per cent.yield of o-phenoxy-benzoic acid :ClC,H,*CO,Xtt + NaG*C,H, = C,ff,*O*C,H,*CO,Na + NaC1.The latter can be readily converted into xanthone :0 0Ber., 1905, 38, 1098.Zeit. Text. Fad. &ad., 1905, 4, 105.Ibid., 675.4 Ber., 1905, 38, 729, 2120, 2211ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 103I n the same way, 2-chloro-5-methoxybenzoic acid with phenol in theone case and aniline in the other yields 2-phenoxy-5-methoxybenzoicacid (I) and 4-methoxydiphenylamine-2-carboxylic acid (11), which canbe converted respectively into xanthone and acridone derivatives :0 NHBy the use of metallic copper, phenoxides and bromobenzene or itsderivatives give excellent yields of phenylated phenols.Hinsberg's method 1 for separating primary and secondary aminesby the aid of benzenesulphonic chloride, which was subsequentlyshown to be untrustworthy, has been modified by the substitution ofP-anthraquinonesulphonic chloride for the former reagent in such away as to render it applicable to the quantitative separation of thebases, but the details of the process are too intricate to be reproducedin a general report.2A very interesting method has been devised by Wislicenus andWren 3 for preparing both arylnitromethanes and stilbene derivativesconcurrently.It may be illusbated in the case of benzyl cyanide,which was previously found to combine with ethyl nitrate in presenceof sodium ethoxide 4 to form the sodium compound of phenylisonitro-acetonitrile :C,H,*CH,.CN + C,H,*O.NO, = C6H5'C(CN):NO*ONa + C,H,*OH.When boiled with caustic soda, the latter loses cyanogen in the form ofsodiiim carbonate and ammonia, and phenylisonitromethane results,which, however, rapidly isomerises to phenylnitromethane.At ahigher temperature, it decomposes and yields stilbene :ZC,H,*CH:NO*ONa = C,H,*CH:CH*C,H, + 2NaN0,.Formaldehyde has been employed in the synthesis of methylnaphthoiby preparing in the first instance dihydroxydinaphthylmethane bycondensing formaldehyde and naphthol and then reducing the productwith zinc dust and alkalis,CH2(CloH6*OH), = CH,*C,,H,*OH + CloH7*OH.5The use of sodamide as a condensing reagent is described onPatents have been taken out during theyear for two new reagents ;Ber., 1890, 23, 2963.Ibid., 1905, 38, 906. Ibid., 670.Ibid., 1902, 35, 1755.p. 108.Zeit. Farb. Text. Ind., 1905, 4, 2651.04 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the Badische Anilin- & Soda-Fabrik 1 prepare manganese disulphate,Mn(SO,),, by the action of electrolytic oxygen on manganous sulphatein presence of moderately strong sulphuric acid. I n acid solution,the reagent possesses the power of oxidising the side-chain of aromatichydrocarbons to aldehyde or acid as required. The other reagent issilicon fluoride, which Sommer 2 uses for the preparation of anhydridesby passing the gas into the heated salt of the acid.Grignard’s Reaction.-To judge from the uninterrupted stream ofmemoirs on the subject, the applications of Grignard‘s remarkablereaction are not yet exhausted.From the long list before us, thoseonly have been selected which offer points of novelty.Dimroth 3 finds that organo-magnesium compounds act on alkyland aryl derivatives of azoimide (azides) in the following way :NRN<N + RlMgX = RNMgXN:NR1;RNMgXN:NRI + H,O = RNH*N:NaR1 + MgX(OH),and thus offer a means of preparing simple and mixed aliphatic diazo-amino-compounds which are not obtainable by Griess’s reaction.Tschitschibabin * has introduced methods for obtaining acid esters andortho-esters by the aid of ethyl carbonate and orthocarbonate. Thefirst reaction passes through the following three phases :1.CO(O*C,H,), + RMgX = R*il(O*C,H5),0MgX.2. R*C(O*C,H,),OMgX + RMgX = R,C(O*C,H,)OMgX + C,H,*OMgX.3. R,C(O*C,H,)OMgX + RMgX = R,CO*MgX + C,H,*O*MgX.On decomposing the product at each stage with water, the firstyields an acid ester, the second a ketone, and the third a tertiaryalcohol. With care, the operation may be arrested at the first stageand gives a yield of upwards of 80 per cent. of the theoretical amount ofacid ester. In preparing the ortho-esters from ethyl orthocarbonate,the rcaction proceeds as follows :1. C(O*C2H5), + RMgX =R*C(O*C,H,), + C,H,*OMgX.2. R*C(O*C,H,), + IcMgX = R,C(O*C,H,), + C,H,*OMgX.The use of magnesium has been ingeniously applied to the prepara-tion of sulphonic acids of the cyclo-paraffins, which, until now, havenot been obtained. Borsche and Lange5 have shown that cyclo-paraffinsulphinic acids, which are first formed by passing sulphurdioxide into the magnesium halogen compound of the paraffin, can beoxidised to the sulphonic acid.Hexahydrobenzenesulphonic acid hasbeen prepared in this way :C6H11MgC1 * [C6H,1S02]2Mg -+ [c,H,1s03]!2Mg*Zeit. Farb. Text. I?zd., 1905, 4, 283.Ber., 1905, 38, 670. Ibid., 561. Ibid., 2766.Ibid., 527ORGANIC CHEMISTRY-HOMOCYCLIC DIVISIOR'. 105Grignardl has contributed a method for synthesising mono- andThe starting point is the chlorohydrin, which poly-hydric alcohols.then passes through the following phases :RMgX + CH,CI*CH,*OH = RH + CH,Cl*CH,*OMgX.RllSlgX = CH,Cl*CH,*OMgX = RlCH,*CH,*OMgX + MgXC1.The product, when decomposed with water, gives the monohydricalcohol RCH,*CH,*OH.With glycerol monochlorohydrin, a series ofglycols has been obtained. The preparation of mixed thio-ethers hasbeen effected by Taboury 2 by the action of alkyl halides on compoundsof the formula RSMgBr, which in turn are prepared by the action ofsulphur on the organo-magnesium compound. He has obtained in thisway a variety of phenyl alkyl sulphides.Bouveault3 has devised a process for preparing aldehydes fromsubstituted formamides which forms the subject of a patent. It maybe formulated in the following way :HCO*NRR1+ R2MgX = HCR2(0MgX)NRR1.HCR2(OMgX)NRR1+ H,O = R2CH0 + NHRR' + Mg(0H)X.The magnesium organic compound is prepared in the usual way,and to the boiling ethereal solution the disubstituted formamide dis-solved in ether is gradually added.The product is decomposed withsulphuric acid and the ethereal solution removed and distilled.The practical difficulty of inducing magnesium to combine with iodo-aniline and its derivatives has been overcome by Baeyer4 bypreviously adding a little iodine to the metal and heating so as toform magnesium iodide. It has thus become possible to obtain avariety of amino-derivatives of triphenylcarbinol by uniting themagnesium compound of the base with benzophenone and its deriv-atives :A further account of Grignard's reaction will be found on p.114.Reductiom.-The reduction of benzonitrile with hydrogen in presenceof copper or nickel, whereby Sabatier and Senderens obtained tolueneand ammonia, has been shown by Frebault5 to yield under modifiedconditions benzylamine and dibenzylamine, whilst toluonitrile givesrise to the corresponding homologous bases. It may be added thata very complete review of the various applications of this importantCompt.rend., 1905, 141, 44.Ibid., 1322.ti Compt. rend., 1904, 140, 1036.Bu71. Soc. chinz., 1904, [iii], 31, 1183.Bey., 1905, 38, 2759106 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.reduction method is given by its discoverers in the AnnaZes de Chimieet Phgsipue 1 for the present year. The electrolytic method for reduc-ing acids which was initiated by Tafel and Friedrichs has beenfurther investigated by Mettler,3 who finds that the aromatic acidsme reduced to alcohols as readily as the esters ; benzoic acid and itshalogen and hydroxy-derivatives give the corresponding benzylalcohols, and the nitrobenzoic acids, the aminobenzyl alcohols.I n thisprocess the nucleus is unaffected.The preparation of arylhydroxylamines by the electrolytic reductionof nitro-compounds suspended in a solution of acetic acid and sodiumacetate contained in a cathode cell is described by Brand.4Biaxotisation.-Those who have had occasion to submit a variety ofamino-compounds to the action of nitrous acid will have experiencedthe unaccountable behaviour which they occasionally manifest.Diazonium salts are usually regarded as typically unstable substances,yet there are many examples which exhibit the contrary property.Meldola and Eynon 5 obtained an aminobenzenediazonium chromatewhich can be boiled in acetic acid and only explodes a t 144-148', andGain 6 has prepared a coloured 3-ethoxydiphenyl-4-diazonium sulphate,HO*C,H,*C,H,(O~C,H,) N, *HSO,, which withstands boiling withdilute sulphuric acid without change.A similar stable diazoniumsulphate of 6-arnino~oumarin,~ as well as a stable diazonium carbonateand nitrite derived from p-aminobenzanilide,* are described by Morganand Micklethwait, and in a patent specification of Bayer & C O . ~ it isstated that 1 : 4-diazohydroxyanthraquinone requires to be heated to170-180° with strong sulphuric acid to convert it into quinizarin.In 1901, Meldola and Eyre observed that when dinitroanisidine isdiazotised it loses a nitro-group, the resulting compound being a diazide.By the action of iodine, the latter is converted into iodonitroresorcinolOMe OMe OMemethyl ether,lO the nitro-group in the para-position to the originalamino-group being eliminated.If, however, the amino-group is in thepara-position to the methoxy-group, no nitro-group is removed butmethyl is displaced, and the resulting compound is a dinitroquinone-Ann. Chim. Phys., 1905, [viii], 4, 319, 433.Ber., 1905, 38, 1745.T?-am., 1905, 87, 2.7 Ibid., 1904, 85, 1235.Zeit. Fad. Text. Ind., 1905, 4, 318.lo MeldoIa and Stephens, Trans., 1905, 87, 1199.Ann. Reports, 1904, 93.Ibid., 3076.Ibid., 5.Ibid., 1905, 87, 933, 934ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION.107diazide.the following product :The compound investigated (2 : 6-dinitroaminoanisole) yieldsOMe O-- 1\ / \ /Similar observations have been made by Orton* in the case of thes-trihalogendiazonium salts of weak acids (the hydroxyl and diazoniuniions may be supposed to be present in solution) when quinonediazide isformed with the elimination of bromine.NHO %I n presence of strong acids, the ordinary change to s-tribromophenoloccurs. Orton, Contes, and Burdett find, however, that the normalreaction may be produced in the first case by exposure to sunlight.have made the curious observation that, bythe action of cuprous chloride in hydrochloric acid on the diazoniumsalts of the isomeric nitranilines and their derivatives, the ordinarySandmeyer reaction is subordinated to the production of diphenylderivatives.o-Nitraniline, for example, gives an excellent yield of2 : 2 -dinitrodiphenyl :Ullmann and FrentzelFew examples of diazoalkylamino-compounds are known, for theproduct of the action of diazonium salts on primary alkylamines givesbisdiazoamino-compounds or compounds containing one molecule ofamine united to two of the diazo-compound. Dimroth4 has succeededin obtaining true triazenes of the formula Ar=N:N*NH*Alk. Inorder to prepare phenylmethyltriazene, C6€€,*N:N*NH,CH,, anilineis diazotised in the usual way, a little excess of nitrite is added, andthe solution carefully neutralised with sodium carbonate. On theother hand, a methylamine solution is prepared also containing sodiumcarbonate, to which ice is added, and the liquid covered with a layer ofether.The diazo-solution is run in and the mixture stirred. TheTrans., 1903, 83, 796. Proc., 1905, 21, 168./bid., 2328. 3 Ber., 1905, 38, 725108 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.triazene dissolves in the ethereal layer, which is separated at the endof the operation and the ether removed by distillation.A series of diazoimides is described by Morgan and Micklethwait,lwho obtained them by diazotising sulphonamides of o- and p-phenylene-diamine in the usual way and precipitating the product with sodiumacetate. The diazoimides of d-camphor-P-sulphonyl- and of benzene-sulphonyly-phenylenediamine have the following formuh :The difficulty experienced in obtaining hydrazines of the anthra-quinone series has now been removed by Bayer & Co.2 by reducing thediazosulphonate instead of the chloride or sulphate.The reactionproceeds quite smoothly and the products can be employed in thepreparation of colouring matters.Condensation.Probably the most interesting development in this field of researchis the introduction of sodamide by Claisen 3 as a new condensing agent.I n the majority of cases, its action is quicker and more regular thaneither sodium or sodium ethoxide. It can be used in the synthesis of1 : 3-diketones and for alkylating ketones. Acetophenone and ethyliodide in presence of sodamide give ethylacetophenone. By the actionof ethylchloroacetate on ketones, glycid-esters are formed.The latterreaction may be illustrated in the case of acetophenone, and probablyproceeds in three phases. I n the first, an additive compound withsodamide is formed, which undergoes condensation with the ethylchloroacetate and is followed by the removal of sodium chloride.1. C,H,*C'(CH3)(0Na)*NH2. 2. C,H,*C(CH,)(ONa)CHC1*C02*C2H5.3. C,H,-C( CH,)CH*CO,*C,H,.\O/I n a paper which follows, Claisen reaffirms with little modificationthe position formerly held by him to explain the ethyl acetoacetatesynthesis, which has been promptly criticised by his old opponentMichaeL4 Both papers, although too long to be summarised, are wellworth perusal ; they tend to show that the problem has not reachedits final solution.The study of condensation of pseudo-phenols with tertiary basesreferred t o in the previous Report (p.101) has been extended byAuwers and Rietz 6 to phenols. Dibromo-p-hydroxybenzyl bromide,T?*ans., 1905, 87, 73, 922.Ber., 1905, 38, 693.Zeit. Farb. Text. Ind., 1905, 4, 286.Ibid., 1922, 2523. Ibid., 3302ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 109for example, unites with phenols to form diphenylmet hane derivativeswith the elimination of hydrogen bromide. The dry substances aremerely heated to 100-150° without the aid of any reagent. Withp-cresol, compounds having the following forrnuke were obtained :BrBr '-' OH Br \-' OH Br( 3 3 3Br CH, Br /\\-/ HO/-\-CH~-/-\ ; HO/-\-CH,-!/-CH,-/-\~H \-/ *The use of alkalis or sodium ethoxide for effecting condensation doesnot seem to lose favour, and the following new applications of themethod may be briefly noted.A series of unsaturated alcohols havebeen prepared by Faworski 1 and his collaborators by condensingphenylacetylene with ketones in presence of solid potassium hydroxide.The reaction is supposed to occur in two phases, the ketone firstuniting with the caustic potash, which then interacts with the hydro-carbon :1. >C:O+KOH= >C<gz.The reaction takes place with aliphatic and aromatic ketones aswell as with cyclic ketones like methyleyelohexanone, menthone, andcamphor. The carbinols so formed lose the elements of water onboiling with sulphuric acid and yield new unsaturated hydrocarbons.The carbinol obtained from acetone gives the hydrocarbon C,,H,, asfollows :CH,*C(CH,)(OH)*CiC*C,H5 = CH,.C( :CH,)*CiC*C,H, + H20.Japp and Knox2 have continued their researches on the behaviourof benzil with ketones, substituting unsaturated for saturated ketones.With wobutenyl ketone, CH3*CO*CH:C(CH3)2, in presence ofpotassium hydroxide, the product is a ring compound (I) which onreduction yields diphenylisopropylidenecycEopentenone (11) :C6H5 C*CH,II >coI.11.and the reaction does not, therefore, differ from that taking place withsaturated ketones. I n another paper by de Xouilpied,3 cyclicstructures containing nitrogen are obtained by condensing phenyl-J. Buss. Phy. Chem. SOC., 1905, 37, 643.Trans., 1905, 87, 673. 3 Bid., 435118 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.glycinoacetic esters with various compounds in presence of sodiuamethoxide or ethoxide.With benzaldehyde, the product is a lactone(I), with ethyl oxalate, it is a ring compound having the followingformula (11) :I. I I.The effect of changing the condensing agent and the temperature isshown in the case of benzaldehyde and acetone, which in presence ofsodium hydroxide solution ordinarily yield benzylidene- and di-benzglideue-acetone. With zinc chloride at 140' in a sealed tube,Lippmann and Fritschl obtained stilbene acetone and similar productswith other aldehydes :FH2*CO*YH,C,H, *c== C*C6H5H. von Liebig 2 has studied the products obtained by fusing togetherbenzil, resorcinol, and anhydrous sodium sulphate, and has isolatedfrom the melt a variety of triphenylmethane derivatives, among whichare compounds having the following formulze :OH/\(C,,H,),@--COIn t ra m o l e c u 1 a r C Jm,ng e.There is perhaps no branch of organic chemistry which is moresuggestive than that which deals with isomeric and other changesoccurring within the molecule.Interaction between molecules hasbeen generally conceived as the basis of chemical change, but underthe same conditions parts of the same molecule may interact, andthe knowledge of the mechanism of such processes cannot fail t o beof the greatest value. The pinacone-pinacoline conversion is thesubject this year of two investigations which have been undertakenwith the object of elucidating this curious process. The change isusually represented by the wandering of an alkyl or aryl groupfrom one carbon atom to an adjoining one and is effected by avariety of reagents.The conversion of h ydrobenzoin into diphenyl-acetaldehyde under the action of sulphuric acid, that .of benzil intobenzilic acid by fused potassium hydroxide, and the formation ofBer., 1905, 38, 1626. J. pr. Chem., 1905, 72, 105ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. I l ldiphen ylace tamide from ben zildi hydrocyanide recently observed byJapp and Knox belong to the same category :(C6H5)27*CN -+ (C,H5)2CH CO'NH,. C,H,*(JOH)*CNC,H;C(OH) *CN C( OH),. CX --3Like the majority of intramolecular changes, the process appearst o be in a sense reversible, for under the influence of hydriodic acidthe pinacoline passes by reduction and subsequent removal of waterinto the symmetrical ethylenic hydrocarbon. Couturier,2 Delacre,3and Werner and Grob have all observed changes of this kind.76H4>C( C,H,)*CO~C,I-E, -+ ~eH4>C(C,H,)=CH(OH)*C,H,C6H4 C6H4Montagce 5 has now shown that 4 : 4 : 4 : 4-tetrachlorobenzpinacone,C,H,Cl c6H4c'>C(OH)*C(OH)<$$$~ ,passes into tetrachloropinncoline, which with caustic potash decom-poses into p-chlorobenzoic acid and the same trichlorotriphenylmethanewhich p-leucaniline yields, and therefore the pinacoline contains allthe chlorine atoms in the para-position.The investigation disposes ofthe theory that an intermediate ring compound is first formed, whichwould necessitate a change inatom :YH y,H,C1C,H,Cl.C-C. C,H,ClI I/'H OH I I ---\/c1the relative position of one chlorinebut whether the change is preceded by the formation of an alkyleneoxide, as suggested by Nef and others, is left undetermined.A preliminary paper by Acree 6 has appeared on the same subject,but no definite results have yet been obtained. Closely related to theabove is the memoir by Fourneau and Tiffenea~,~ which describes theTrans,, 1905, 87, 681.Ber., 1890, 23, ~tf. 769.2ec. tmu. chim., 1905, 24, 105.G'onipt. re7ad., 1905, 141, 662.A m . Chim. Phys., 1892, [vi], 26, 433.Ibid., 1904, 37, 2887.Anzer. Chem. J., 1905, 33, 180112 ANKURL REPORTS ON THE PROGRESS OF CHEMISTRY.action of heat on the three series of aromatic alkylene oxides. Themonosubstituted compounds of the general formula Ar*CK,*CH*CH2\/0give the aldehyde Ar*CH,-CH,*CHO, the unsymmetrical disubstitutedcompounds Ar*C( CH3)-CH, also give the aldehydej -0-1Ar*CH( CH,)*CHO,whilst the symmetrical disubstituted compounds Ar-CH*CH-CH, give\/0the ketone Ar*CH,.CO*CH3.A similar result has been obtained byI(lages,l who finds that 20 per cent. sulphuric acid converts phenyl-methylethylene oxide into hydratropaldehyde.Another interesting example of intramolecular change is describedby Auwers and Keil.2 I n attempting to convert l-dichloromethyl-l-methyl-4-keto-1 : 4-dihydrobenzene into a hydrocarbon by the actionof phosphorus pentachloride and subsequent reduction, they found thato-xylene was produced in the following way :A change of a similar character is recorded by the same observers,who have shown that the hydrocyclic alcohol (I) readily loses waterand probably passes into (11), thus :CH, CHCI, CH, CHCI, CH3I/\\/ \/-+ !I li + II I/\ /\It It\/I \/ \.( /\CH2 CH,*CHCl, HO CH,I.11.although the formation of a bridged ring is not excluded :Ber., 1905, 38, 1969. Ibicl., 1693ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 113It was long since pointed out by Fittigl that the change of Py- t oup-unsaturated acids was reversible, A similar observation is madeby Agejewa2 in the case of P-phenylpropylene, which in presence ofsolid alkali forms an equilibrium mixture with symmetrical phenyl-met h ylethylene :C,H,*CH,*CH:CH, -+ C,H,*CH:CH*CH,.The passage of atoms or groups from side-chain to nucleus is acommon phenomenon, but Orton has made the further observationthat by interchanging the nitro-group in 2 : 4 : 6-tribromonitroamino-benzene the para-bromine atom is displaced :NHNO, NH2Br<)Br -4- Br()Br .\/BrA still more curious observation is the behaviour of the correspond-ing nitroamino-s-trichlorobenzene, which with acetic and sulphuricacids passes into s-trichlorophenyliminotrichlorobenzoquinone, wherebyone chlorine atom changes its point of attachment,c1 c1 c1The displacement of bromine from a hydrocarbon side-chain to theHoering4 has, however, shown that by the nucleus is less common,careful oxidation of anethole dibromide a ketone of the formulais formed.CH30*C6H3Br* COO CHBr *CH3A d d i t i v e Compounds.A series of memoirs has been published by Kohler and hiscollaborators 5 on the behaviour of unsaturated compounds towardsmagnesium alkyl iodides.I n the first, which appeared in 1904,6 itwas shown that reactions with compounds containing the group-C:C*C:O*R (unsaturated aldehydes and ketones) depended on thenature of the atoms or groups associated with the ethylene carbon orCO group. The authors have extended the investigation to un-saturated esters, acid chlorides and amides, and have proved that thenature of the addition is determined by the following rules : (1) I nAnnalen, 1905, 283, 47.Trans., 1905, 87, 389.Amer. Chem. J., 1905, 33, 153, 333 ; 1905, 34, 132 ; Ber., 1905, 38, 12C3.Amer. Chem.J., 1904, 31, 642.VOL. I1 IJ. RILSS. Phys. Chem. Soc., 1905, 37, 662.Ber., 1905, 38, 3458114 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.unsaturated aldehydes (R = H) the urgano-magnesium compound reactsexclusively with the carbonyl group. (2) Ketones (R = CH,) react likealdehydes. (3) Ketones (R = C,H,) form additive compounds in the1 : 4-position, thus :C,H,*CH:CH*CO*C,H, + C,H,MgBr =1 2 3 4 C6H,-CH(C,H,)*CH:C(OMgBr)-C6H5.1 2 3 4(4) I n the case of esters (R=OR), either addition occurs at the1 : 4-position or the alkoxyl group is replaced by an alkyl group ; thefirst reaction occurs with aromatic and the second with aliphaticmagnesium compounds. Negative groups (halogens, phenyl) in thea-position favour addition in the 1 : 4-position. With cinnamonitrile,the addition is restricted to the cyanogen group,C,H,* CH:CH* Ci N + C,H,MgBr = C,H,*CH: CH* C( C,H,)N Mg Br ,but in the a-phenyl derivative no union whatever takes place.Ethyl a-cyanocinnamate (I), which contains both conjugated systems,lC:C*C:O and C:C*CiN, 1 : 4-addition occurs in relation t o the groupC:C*C:O, for the CN group in the a-position inhibits the replacementC,H,CH:$+-V:ONiC O*C2H51.of alkoxyl by alkyl.In the case of ethylcompound is formed (I),benzylidenemalonate, the following additivefrom which, by the action of water, the sub-MgBr RI.11.stituted ester (11) is obtained. The magnesium additive compoundmay further be acted on by bromine (111), acetyl chloride (IV), or byother halogen compounds and a variety of interesting derivatives thusC,H,*CHR*CBr(CO,Et), C,H,*CHR-C0,Et:C(O*CO*CH3)*O*C2H5111. IT.prepared.Bauer 2 has also studied the behaviour of organo-magnesiumcompounds with unsaturated ketones of the typeRCH: CH°CH: CH*CO*R1in the hope of producing a conjugated system of three double bonds,R.CH:CH*CH:CH*CH:CH*Rl, b u t the experiment was only partiallysuccessful, for as a rule the unsaturated alcohol and not the hydro-Annual Report, 1904, 105. Ber., 1905, 38, 688ORGANIC CHEMISTRY-BOMOCYCLTC DIVISION. 115carbon was formed.hexadienol,C,H,*CH:CH*CH:CH*CO*C,H, + C,H:,*CH,.MgCl=Thus, cinnamyleneacetophenone gave triphenyl-C,H,* cH:CH*CH: CH*C(OH)* C,H,* CH2*C6HS.Blaise and Courtotl have found that unsaturated esters can formadditive compounds with magnesium alkyl iodides, and have preparedfrom methacrylic ester, dimethylpropenylcarbinol and methyl-3 -pentanone.The second compound is produced by the following seriesof changes :OEt CH,:C( CH,)*CO,Et -+ CH,*C( CH,) -y<OMgI I C W , I ~ ~ I CH,$JH,*CH(CH,) CO*CH,0%--fLast year's Report (p. 104) contained a passing reference to Posner'sresearch on the combination of mercaptans with unsaturated ketones.The subject has been further studied 2 with the object of discovering ifthe double link in unsaturated ketones is alone responsible for theaddition of the mercaptan molecule. This is answered by Posner inthe affirmative.The absence of additive compounds in the case of stilbene,C,H,*CH:CH*C6H,, and diphenylbutadiene,C,H5*CH:CH*CH:CH*C6H5,is ascribed to the number of phenyl groups which diminish the additivecapacity ; for both styrene, C,H,*CH:CH2, and phenylbutadiene,C,H,*CH:CH*CH :CH2, unite with mercaptans.Posner's experience iscontrary to that of Konigs, who found that phenols unite with olefinesby means of nuclear carbon (I), whereas Posner finds that in the case ofmercaptans addition takes place through the sulphur atom (11).K C,H4*OHI 1H S*C,H,">G-C<S I 1YI. 11.R ~ h e m a n n , ~ who has been engaged in a similar line of research,points out that in presence of sodium ethoxide or piperidine, olefinicketones form additive compounds with one molecule of mercaptan,and has corrected previous observations of Posner in which twomolecules are described as entering into combination.Benzylidene-acetophenone and isoamyl mercaptan give isoamylthiolbenzylaceto-Compt. rend., 1905, 140, 370.Trans., 1905, 87, 17, 461.Ber., 1905, 38, 646.1 116 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.phenone, C,H CH(S*C,H,,)C H,*CO-C,H,. Similar additive productswere prepared from benzylidenedeoxybenzoin, ethyl benzylidenebenzoyl-acetate, and cinnamylideneacetophenone by union with phenyl mer-captan. Triolefinic ketones combine with one or two molecules ofmercaptan, and acetylenic ketones also yield additive compounds.Bauer,l in extending his researches on the behaviour of unsaturatedcompounds towards bromine, shows that the difficulty OF addition isincreased by the presence of cyanogen as well as by phenyl and estergroups in the following order : C6H5 -+ CO,R --+ CN, which is alsothe order determining the dissociation constant ; that is to say, themore strongly negative the groups attached to the ethylene carbon, theless readily does bromine combine.The introduction of nitro-groupsinto the phenyl complex also diminishes the additive power forbromine by increasing the negative character of the nucleus. Zinckeand Miihlhausen2 conclude, from the behaviour of dry hydrogen bromideon aldehydes, ketones, and unsaturated ketones, that additive power isa function of the molecule as a whole and not of individual constituents.Neither a double bond nor a ketone group alone can induce com-bination, which only occurs when, in addition to the ketone group, adouble bond or OH or OR group is present.Benzophenone, forexample, forms no additive compound, whereas pp-dihydroxybenzo-phenone does. This is merely stating in other words that positivegroups increase the additive power for acids, a fact which has alreadybeen demonstrated by Baeyer and Villiger and others. Vorliinder andhis collaborators 3 have made a very comprehensive study of the additivecompounds of a/3-unsaturated ketones with acids and salts and laydown certain theoretical conclusions which cannot be convenientlycondensed. Before concluding our account of the behaviour ofunsaturated compounds, attention should be drawn to the paper ofWieland and Bloch4 who have shown that the formation of additivecompounds of nitrogen trioxide with phenylethylenes having theformula C,H,*CH:CHR are subject to certain conditions. If R ispositive, dimolecular pseudonitrosites are formed (I) :I.If, on the contrary, R is negative, as in unsaturated ketones and alde-hydes, the groups NO and NO, form saturated unimolecular compounds.Thus, benzylideneacetone and benzylideneacetophenone yield noAnn.Reports, 1904, 103 ; J. pr. CJzem., 1905, [ii], 72, 201.Ber., 1905, 38, 466. Annulen, 1905, 341, 80.Bid., 340, 63ORGAXIC CHEMISTRY-HOMOCYCLIC DIVISlOX. 117nitrosites unless a strongly positive group is present in the benzenenucleus as in tbe anisylidene derivatives.Nitrogen tetroxide combines with unsaturated ketones of the typeArC:C*CO*R to form in the first instance compounds of the formula (I)which, however, are very unstable and readily lose nitrous acid,passing into unsaturated nitroketones (11) :Ar*yH--V H*CO*R Ar*CH:$l*CO*K,O*NO NO, NO2I.11.These nitro-compounds can be hydrolysed by an ethereal solution ofammonia into aldehydes or ketones (ketonic hydrolysis) (111), whilstcaustic soda produces acid hydrolysis (IV) :Ar*CHO + CH,(NO,)*CO*R Ar*CH:CH*NO, + RCO*OH111. IV.By the ketonic hydrolysis of anisylidenenitroacetone, nitroacetone,Meisenheimer and Heim find that phenylnitroethylene and sodiumCH2(N0,)*CO*CH3, has been obtained,methoxide react according to the equation :C,H,*CH: CH* NO, + NaOCH, = C,H,*CH( O*CH,)CH: NO ONa.Urn s a t u 9' a t e d H y d r o c a r b o n s.Very little fresh light has been thrown on the constitution of tri-phenylmethyl since the last report was published (p.105). The mostimportant contribution to the subject is undoubtedly that of Tschit-schibabin? which appeared towards the close of the year. The identityof the bimolecular triphenylmet.hy1 with hexaphenylethane was dis-proved by the supposed synthesis of the latter by Ullmann andBO~SUM,~ which was found to be a stable compound of entirely distinctproperties. An investigation into the structure of Ullmann's syn-thetical compound by Tschitschibabin has led to the interestingdiscovery that the substance in question is not hexaphenylethane, butin all probability a compound having the formulaThis structure seems to follow from its behaviour with bromine, whichconverts it into a monobromo-derivative, and from the action of waterand pyridine on the latter compound, which transforms i t into thecarbinol :(C6H5)3C'C6H4'CH(C6H~)2'1 Ber., 1905, 38, 466.3 Ibid., 1902, 35, 2877.Ibid., 1904, 37, 4709118 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Tschitschibabin concludes that Gomberg's compound may still behexaphenylethane, and explains its conversion inti0 the above hydro-carbon by a disruption and reunion of the molecule in the followingway :The only new contribution by Gomberg is a paper in conjunctionwith Cone,2 describing a series of additive compounds of triphenyl-methyl with different esters and hydrocarbons.The former arecrystalline substances having the general formula 2(C6K5),C + 1 mol.of ester, to which the authors assign the following structure :The additive compounds with the hydrocarbons are similarlycomposed of 2 molecules of triphenylmethyl with 1 molecule of thehydrocarbon (ethylbenzene and the three isomeric xylenes).Tri-phenylmethyl combines also with fractions of light petroleum, carbondisulphide, and unsaturated hydrocarbons like amylene, yielding in thelatter case the compound 2(C,H,)3C+C5H,,. It also unites withketones (I) (except acetone), ethers (11), and certain nitriles (III)? bu+Jaldehydes and acetonitrile are indifferent. They all retain theirunsaturated character. The formulze of these compounds is repre-sented as follows :I. 11.At the close of the paper the authors111.review the evidence ofTschitschibabin and the alternative formuke suggested by Heintschel(IV) and Jacobson (V) :[CGH5>(J:/=\/Hc6H5 \===A 1 2IV.V.Most of the arguments based on the unsaturated character of thehydrocarbon and the property of forming additive compounds arereaffirmed in support of the original formula.Ber., 1905, 38, 771. Ibid., 1333ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 119H y d r o c y c l i c Compounds.The number of individual memoirs which have appeared in thecourse of the year on the preparation and properties of this group ofcompounds is very large, but the methods used i n their preparationoffer very little novelty. Some of these methods may be illustratedby reference to the following more important investigations.The reduction of benzene derivatives by the method of Sabatier andSenderens has been employed in the preparation of cyclohexane, cyclo-hexanol and their derivatives,l in the preparation of thymomentholfrom thymo1,Z of the three methylcyclohexanols and hexanones fromthe isomeric cresols,3 of decahydro-P-naphthol and octohydronaphtha-lene,4 and of hexa- and octo-hydr~phenanthrenes.~Another reduction method is illustrated by a paper of considerableinterest by Perkin and Pickles,G containing an account of the fourisomeric tetrahydroisophthalic acids which Baeyer and Villiger wereunsuccessful in obtaining.Two of these substances were formedby the reduction of isophthalic acid by sodium and alcohol, andseparated by utilising the different solubilities of the calcium salfis.The other two were prepared indirectly from them.The series isrepresented as follows :H C0,H H C0,H H CO,H C0,H H\/ \/ \/H,/\H, H2'\Hp H,/\H,\7- H,I/CO,H Hi\&O,H HI H C0,H HI \/ J-&CO,HH3 3 4 3H2 H HA2 (m. p. 168"). A3 (m. p. 244"). cis-A4(m. p. 165"). trans-A4(m. p. 227").No dihydroisophthalic acid was obtained in this way, but onemember was subsequently prepared from 3 : 4-dibromohexahydroiso-phthalic acid (from the bromination of the hexahydro-compound) bythe removal of hydrogen bromide, to. which the following constitutionis provisionally assigned :H CO,H\/1 Freundler and Damond, Compt. rend., 1905, 141, 593.4 Brunel, ibid., 1905, 140, 252.3 Sabatier and Mailhe, ibid., 350 : 141, 20.5 Breteau, Compt.rend., 1905, 141, 942.Leroux, ibitl., 140, 59 ; 141, 46.Trans., 1905, 87, 293, 841120 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Among the synthetical methods may be mentioned the condensa-tion of ethyl isopropylideneacetoacetate and ethyl sodioacetoacetate,described by Merling 1 as a &ketone ester having the formulaH,C/\CH*CO,EtOC(dC*CH3CHCrossley 2 has obtained from 1 : 1-dimethyldihydroresorcin, which isalso a condensation product, 1 : 1-dimethylhexahydrobenzene and 1 : 1-di-methyl-A3-tetrahydrobenzene. The original compound is treated firstwith phosphorus trichloride and then reduced to the alcohol. Withhydrobromic acid, the bromide is obtained, which, on treatment withzinc dust in aqueous alcoholic solution, gives hexahydrobenzene, andwith alcoholic potash the unsaturated hydrocarbon :C(CHJ2 '('*3)2 WH3hH,C/\CH2 H,C/\CH, -~ H,C/\CH,HOG1 1CO -+- ClCi,,)CO H,C(,!CH*OH --+-CH CH2\/CHThe 1 : 1-dimethylhexahydrobenzene is not identical with thehydrocarbon obtained by Zelinsky and Lepeschkin 3 from camphoricacid.The synthesis of a trimethylene derivative is recorded by Perkinand Tattersall by the action of alcoholic potash on a-bromoglutaricester : 4CHBr*CO,Et CH*CO,HCH2<C€€2- C0,Et CH*CO,H' -+ CH,<IOne of the most interesting of the methods recently introduced forobtaining hydrocyclic compounds is an adaptation by Willstatter ofHofmann's method of exhaustive methylation for removing nitrogenRer., 1905, 38, 979.Trans., 1905, 87, 1487.Tram., 1905, 87, 362. 3 Annalen, 1901, 319,303ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 221from the ring in breaking down the alkaloids. Hofmann obtained inthis way unsaturated hydrocarbons of the aliphatic series. The dis-covery of tropilidine by Merling among the fragments of the tropineinolecule and its identification with the cycloheptadiene derived fromsuberone prepared the way for Willstatter’s brilliant achievement ofthe synthesis of tropidine and atr0pine.lWillstatter and Veraguth 2 have now succeeded in breaking up thealkaloid pseudopelletierine from pomegranate rind into an eight-membered carbon ring, cyclooctadiene, CSHI2, by a process similar tothat which gave cycloheptadiene. The position of the double bond isstill undetermined, but the hydrocarbon has probably one or other ofthe following alternative formuh :qH2*CH:yH YH:CH-VH,p 2 p z or (!H2 $H2.CH,* CH: CH CH, * CH: CHI n consequence of the great resistance offered by the substance tofurther dehydrogenation, the authors have not yet succeeded in pro-ducing a cyclooctatetraene, which would possess a peculiar interestfrom its structural analogy with benzene.cycZoOctadiene shows a great tendency to polymerise ; this changeoccurs on heating, with explosive violence, the substance passing intoa well-crystallised dicyclooctadiene.Towards permanganate, thehydrocarbon is very unstable, and it also reacts readily with bromine.I n these respects it differs from Doebner’s omp pound,^ which wasobtained from vinylacrylic acid by distillation with baryta, and onthe structure of which the authors throw considerable doubt.I n thetendency to polymerise, cyclooctadiene resembles Para caoutchouc(p. 126), which Harries represents as a polymeric dimethyl derivativeof the same hydrocarbon.The method of exhaustive methylation which has been found soserviceable in obtaining unsaturated ring compounds with seven andeight carbon atoms has been applied by Willstatter to the preparationof cyclobutadiene from Perkin’s aminocyclobutane by the followingseries of changes :FH,*FH*NH, QH2* QH*N(CH,),*OHCH2*CH, --t CH,*CH, -+1 Aimaleit, 1901, 317, 204 ; 1903, 326, 1.3 Ibid., 1902, 35, 2129, 2538; 1903, 36, 4318.a Ber., 1905, 38, 1975.Ibid., 1905, 38, 1992.Traw., 1894, 65, 950122 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The process does not go smoothly, for in addition to cyclobutene acertain amount of 1 : 3-butadiene is formed by the opening of the ringCH,:yHCH,:CH'Before closing our review of the synthesis of hydrocyclic compounds,reference must be made to the xanthogenic reaction of Tschugaeff forconverting cyclic alcohols into unsaturated hydrocarbons. The processmay be illustrated by the formation of y8-methylcyclohexene fromP-methylcyclohexanol, which has been investigated by Markownikoffand Stadnikoff .1The cyclohexanol dissolved in xylene is first heated with sodium,after which carbon disulphide and methyl iodide are added.Theproduct is a xanthogenic ester which, on heating, breaks up intothe hydrocarbon, methyl mercaptan, and carbonyl sulphide :CH3*C6Hlo*CS*S*CH3 + 0 = CYH,, + CH,*SH + COS.The change from alcohol to hydrocarbon is represented as follows :CH,* CH===CH vH,*CH2-$lH*OHI CH2*CH( CH,)*CH, --t CH,.CH(CH,)~IH,The removal of water from hydrocyclic alcohols can also be effectedby heating with potassium hydrogen sulphate, a method which isdescribed by Perkin in his synthesis of the terpenes (p.123) and byBrunel2 in the preparation of cyclohexane from cyclohexanol.T'erpenes and Camphor.The methods which W. H. Perkin, jun., applied so successfully tothe synthesis of terpineol and dipentene, an account of which appearedin last year's Report (p. 117), have since been extended with slightvariation to the synthesis of similar compounds.Perkin, in con-junction with Pickles, Matsubara, Kay, and T a t t e r ~ a l l , ~ has obtaineda series of menthenols, menthadienes, menthanols, and menthanes.The menthenols and menthanols usually possess the peppermintodour of terpineol, whilst that of the menthadienes resembles thecharacteristic lemon smell of dipentene. One example of the methodemployed in the preparation of these substances must suffice. Thestarting point is the ester of a tetrahydrotoluic acid, which is usuallyobtained by removing hydrogen bromide from a bromohexahydro-Annalen, 1905, 336, 310.Tram., 1905, 87, 639, 661, 1066,1083.a Full. SOC. chim., 1905, [iii], 33, 270ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION.123toluic acid.solution of magnesium methyl iodide yielding A3-pmenthenol (11) :Ethyl A'-tetrahydro-p-toluate (I) reacts with an etherealI. 11.On digesting the latter with potassium hydrogen sulphate, water isremoved and A3'8'9-p-menthadiene is formed (111) :L Y 111.The new terpene differs in many important characters from dipentene,more especially in the fact that it combines with only one moleculeinstead of two molecules of bromine, hydrochloric and hydrobromicacids. This is ascribed to the presence of a conjugated system ofdouble linkings, C:C*C:C, in which bromine is known to unite onlywith the end carbon atoms, forming the group CBr*C:C*CBr.l By asimilar series of reactions to the above, using ethyl hexahydro-p-toluate,p-menthanol (IV) aud As-p-menthene (V) were prepared :Finally, from the latter (V), p-menthane (hexahydrocymene) masobtained by reducing the additive compound of p-menthene with hydro-bromic acid, C,,H,,,HBr, with zinc dust and acetic acid.Similarreactions have been carried out with the esters of hexa-. and tetra-hydro-benzoic acids, hexa- and tetra-hydro-o-toluic acids, and hexa- and tetra-hydro-m-toluic acids.Haller and Martini 2 describe a synthesis of menthene and mentholfrom methykyclohexanone by the use of sodamide. A sodiumderivative is thus obtained, which, with isopropyl iodide, yieldsmenthone, and the latter on reduction is converted into menthol. Bya similar process, P-methylcyclohexanone is converted into homologuesof menthol and menthone, and a series of alkyl derivatives of thujonehas been obtained by using sodamide in the same way.3 A secondsynthesis of menthone and menthol by the action of reduced nickeland hydrogen on pulegone is described by the same authors.4I n the year 1904, Wallach published it very complete investigationon the nature of phellandrene, and pointed out that in addition toordinary or a-phellandrene (found as dextro-enantiomorph in elemiand bitter fennel oil and as laevo-compound in Australian eucalyptus)Ann.Reportu, 1904, 105.Ibid., 1626. Ibid., 1298.Compt. rend., 1905,140, 130124 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.a second or P-phellandrene is present in Phellamdrium aquaticum.The first was shown to have the structure of A2:5-dihydrocymene (I)by the conversion of nitrophellandrene into active menthenone (carvo-tanacetone), whilst /3-phellandrene, which forms the subject of asubsequent investigation by Wallach,l is shown to possess theformula (11) : 7% RH2C CHC//\CH H,C/\CHH,C()CH H , C u C HYH CH YH CHHarries and Johnson2 have now confirmed the formula given toa-phellandrene by the reverse process to that used by Wallach, namely,by converting d-menthenone into phellandrene by the following steps.Menthenone is first treated with phosphorus pentachloride and theresulting chloride converted into chlorophellandrene by boiling withquinoline.The chlorophellandrene on reduction with zinc dust inmethyl alcohol yields a-phellandrene. Another and better method isto reduce menthenoneoxime to AG-menthenamine and to distil theproduct under diminished pressure with phosphoric acid.7H3 7%C CQ"3C-~ HC~)C:NOH -, HC~)CH-NH, --3H,C,,CH, H,C\,CH,YHCH(CHJ2FHCJWH,),p 3H C ~ \ C HH,C!,)CH 8YHCH(CH3),YHCH(CH,),Wallach and Backer 3 have studied the various sources of thujone anddefinitely show that three isomeric ketones exist, which they distinguishas a-, p-, and y-thujones.Wallach and Kohler * throw doubt on Baeyer's formula for eucarvone1 AnnaZen, 1905, 340, 1.3 Annalen, 1905, 336, 247.Ber., 1905, 38, 1832.Ibid., 339, 94ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION.125(11)’ which is obtained from carvone hydrobromide (I) by removal ofhydrogen bromide. Certain anomalies which the substance in questionexhibits are removed if, in place of Baeyer’s bridged ring formula, aseven-ring structure (111) is substituted.Baeyer’s formula will thenrepresent an intermediate phase in the process of preparation.p 3Cp 3Cy = 3CHC/\COHC--C(CH,),--+ HC/, ICH,7” CBr/\CH, CH,I. 11. 111.Tilden and Burrows,l and also Leach,2 have studied the action ofpotassium cyanide on an alcoholic solution of the nitrosochlorides ofcertain terpenes. Pinene and limonene yield nitrosocyanides of theformula C,,H,,( :NOK).CN, which can be hydrolysed, and yield thecorresponding amides and acids.Forster and Fierz 3 have shown that by the action of potassiumcyanate on the hydrochloride of aminocamphor, a carbamide, isomericwith the one obtained by Rupe, is formed, which they term camphoryl-$-carbamide, having the formulaThey find that Rupe’s compound undergoes conversion into the newisorneride by shaking it with sodium hydroxide solution and that theconverse change is effected by dilute hydrochloric acid.They thereforeassign to Rupe’s carbamide the formulaWhilst Rupe’s carbamide gives with nitrous acid camphorylcarbimide,the pseudo-compound forms a nitroso-compound which, on reduction,yields camphorylsemicarbazide. This substance is optically active andcan be usefully applied to the preparation of active carbazones. Thepseudo-carbazide, by the further action of nitrous acid, is convertedinto camphorylazoimide :Trans., 1905, 87, 344. Ibid., 413. Ibid., 110, 722126 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The use of the xanthogenic ester reaction of Tschugaeff has alreadybeen noticed (p.122). A long and interesting memoir is contributedby Tschugaeff on the subject, in which he describes how the reactionmay be applied t o the preparation of pure esters of the alcohols ofthe terpene and camphor series and to the unsaturated hydrocarbonsderived from them.A passing reference was made in last year’s Report (p. 92) to theaction of ozone in breaking down the caoutchouc molecule, which wasthe subject of a memoir by Harries., This investigation has sincebeen extended and from the nature of the products of decompositionHarries proposes the following formula for Para caoutchouc :(The arguments adduced in its favour mould occupy too much spaceto consider in detail, and the reader is referred to the original memoir.The reader’s attention is also directed to an important paper byMoycho and Zienkowski,, in which they bring evidence in favour ofWagner’s formula for camphene from a study of its decompositionproducts :(CH,),.C-QH - CH,CH,*C-CH- CH, I $J*2 ICamphene.Colour und Structure.I n the former report (p. 123), the views of Baeyer and Villiger onthe constitution of the triphenylmethane colours was discussed and itwas then stated that the authors had arrived at the conclusion thatthese colouring matters were to be represented by the quinonoidstructure. A further study of the subject has disclosed a diffi~ulty,~inasmuch as the sulphates of p-trichloro- and p-tri-iodo-triphenyl-carbinols are highly colaured salts (the latter closely resemblesfuchsine) which show no tendency to lose halogen. This seemsscarcely compatible with a quinonoid structure, for the chlorineof the quinone nucleus should be easily detached by the action1 J.Russ. Phys. Chem. Soc., 1905, 36, 988.a Bey., 1905, 38, 1195.3 Annalan, 1904, 340, 1 7 ; Ber., 1905, 38, 2461.Ber., 1905, 38, 569, 1156ORGANIC CHEMISTRY-HOMOCYCLIC DIVISION. 127of silver nitrate solution, and this is not the case. Adopting aview held by Walden and Gomberg, that the yellow solutions withwhich triphenylmethyl chloride dissolves in certain solvents aredue to dissociation, Baeyer introduces a distinction between anionisable and non-ionisable valency by the use of a zigzag line,which marks the ionisable bond. I n the case of the triphenylmethanederivatives, this ionisable bond is called the carbonium bond, and isresponsible for the colour, whilst the other kind of attachment, whichis represented by an ordinary straight bond, produces no colour.Butit must not be supposed that electrolytic dissociation has anything incommon with the new theory, since the parts of a compound which arenot known t o dissociate may be attached by zigzag bonds to denotetheir colour. The following are some of the new formulze : (I) is thesodium salt of phenolphthalein; (11) that of aurin; (111) that ofHomolka's colour base ; and (IV) that of azo-compounds :I. 11.whilst the coloured sulphates of trianisyl- and trichlorophenyl-carbinol appear thus :CH,-O*C H C6H4*OCH, C6H,C1 C H C1CH,. 0 * CIHl>c<- 0. SO,H C6H4Cl>c<" Ok0,HIt may be expedient to draw distinctions between the two kinds ofattachment in order to denote colour or its absence, but one is temptedto ask whether such distinctions embody any new conception orexplanation of the phenomenon.A reference was made in last year's Report (pp. 122, 123) to thenew quinones and iminoquinones obtained by Willstatter and hiscollaborators. This series of interesting compounds has been increasedby the addition of the quinones and quinoneimines derived from p-di-methylphenylenediamine, o-phenylenediamine, p-dihydroxydiphenyl,and ben2idine.l These substances are obtained by the former methodof oxidation i n an inert solvent with silver oxide or lead peroxide.Diphenoquinone, O:C,H,*C,H,:O, crystallises in two modifications,one resembling chromic acid in appearance and the other consistingof colourless needles. The first can be convertsd into the second.The substance is without smell, is non-volatile, and is decomposed byalkalis, acids, and even by water alone. Diphenylquinonedi-imine,Ber., 1905, 38, 1232, 2244, 2348128 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.NH:C,H,*C,H,:NH, crystallises in reddish-brown needles ; quinone-dimethylimine, CH3*N:C6H,:N*CH3, shows a close resemblance toquinone di-imine. I n the crystalline form i t is colourless, but insolution it possesses a yellow colour, which, however, differs incharacter from that of the hydrochloride.Quinonemonomethylimine, CH,*N:C,H,:O, was obtained, but as itexplodes in the free state no analysis could be performed. The authordraws a distinction bet ween the coloured and colourless derivativesby using Baeyer’s carbonium bond. By the oxidation of o-phenylene-diamine in ether, a solution was obtained which appeared pale yellowby transmitted light and reddish-yellow by reflected light, resembling thesolution of pure o-benzoquinone. The solution stains the skin black,and, on evaporation of the ether in a vacuum, the substance changesrapidly. On warming the ethereal solution or on shaking it withhydrochloric acid, two compounds are formed, one of which is thewell-known diaminophenazine and the other o-azoaniline. The latteris probably formed by the polymerisation of the di-imine :J. B. COHEN

ISSN:0365-6217    

DOI:10.1039/AR9050200101

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION.DURING the last twenty or thirty years the progress of syntheticalorganic chemistry has been so great that at the present time weare acquainted with compounds possessing heterocyclic structures ofgreat variety. Whereas the chief interest in former decades was theproduction of rings of new type, the present tendency is more in thedirection of a closer examination of known ring structures with a viewto elucidating on the one hand the mechanism of ring-formation, on theother that of the transformation of rings, it may be into other rings,made up of a different number of atoms, or differing from the originalring in the arrangement of linkages, the latter change frequentlyaccompanying the production of salts.At the same time, new compounds of familiar type are continuallybeing discovered, either by known processes or by new syntheticalmethods, whilst occasionally new types of ring make their appearance.But, in addition to the work which appeals more directly to thechemist, there is that branch connected more closely with animaland vegetable physiology aiming at the determination of the structureof naturally occurring products, so that now no year passes in whichsome addition is not made to our knowledge of the alkaloids, thesubstances of the uric acid group, and the natural colouring matters.Mechanism of Ring-formation.By far the greater number of cyclic compounds contain five orsix members to the ring.I n the case of substances possessing homo-cyclic structure, the ‘‘ Spannungs-Theorie ” of Von Baeyer 1 givesa plausible explanation of the preferential formation of such com-pounds, and it would appear that the replacement of carbon atoms byatoms of other elements has generally little influence on the greaterstability of five- and six-membered rings.But whilst ring compoundswith a greater or less number of atoms in the ring have been met withamongst homocyclic compounds, so also the same obtains with hetero-cyclic substances. For the solution of problems in connection with theVOL. 11.Ber., 1885, 18, 2277.130 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.possible size of closed rings, substances containing amino-groups seemespecially suitable on account of the great reactivity of nitrogen whenin this condition.Heterocyclic compounds with rings of more than six members havebeen obtained by J.von Braunl alone and in conjunction withA. Steindorff.2 w-Chloro-N-hexylamine and w-chloro-N-heptylamineisomerise to the hydrochlorides of hexarnethyleneimine and hepta-methyleneimine. The first base boils between 120° and 130" andsmells like piperidine, but its formation is not so smooth as that of thelatter substance, a large amount of a polymeride being formed. Thispolymeric hexamethyleneimine appears to be a di-secondary base, andits carbon and nitrogen atoms probably form a 14-membered ring,Compounds with rings of seven members have also been obtained byWolbling and Lieck 4 by the action of hydrazine on P-deoxybenzoin-o-carboxylic acid or its lactone (that is, 3-phenylisocoumarin) andm-tolylisocoumarin respectively.The compounds formed might possesseither of the following structures :but since substances undoubtedly of the second type are produced bythe isomerisation (similar to the Beckmann transformation) of theoriginal condensation products, these must have the seven-memberedring structure.S. Gabriel 5 finds that w-homopropylphthalimide hydrolysed bypotassium hydroxide gives the aminopropyl ester of phthalic acid. Thetransformation is explained by the following scheme :co*NH*CH2>CH2 -+ C6H4<c02Hc6H4<CO-O-CH2 COO O*C,H,*NH,.The intermediate nine-membered ring compound is not simply hypo-thetical, it has been isolated, as has also the corresponding eight-membered ring compound from P-bromoethylphthalimide ; these sub-stances have been characterised by their nitroso-derivatives.Gabriel 6at the same time prepared the nitroso-derivative of hydroxyethyl-Ber., 1905, 38, 964, 2340. Ibid., 3083. Ibid., 3845.]bid., 3853. Bid., 2389. ]bid., 2405ORGANIC CHEMISTRY-HETEROCYCLIC DLVISION. 181carbamic anhydride, notable in that it spontaneously decomposes,largely in accordance with the equationSome new bridged-ring compounds with elements besides carbon inthe nucleus have been discovered in the past year. On account oftheir interesting properties the endoiminodihydrotriazoles discovered byM. Busch deserve mention. Triphenylaminoguanidine, obtained bythe action of leadanilide, or anilineformic acid.,oxide on a mixture of phenylhydrazine thiocarb-and diphenylthiosemicarbazide, condenses withC,H,*NH*NY+ C,H,*NH-C :N*C,H, -3-The second formula, that of 1 : 4-diphenyl-3 : 5-endoanilinodihydrotri-azole, is preferred.The nitrate of the base (called shortly nitron) is soinsoluble that nitrates may be gravimetrically estimated with its help(Zoc. cit., p. 861). I n a later paper, conjointly with G. Mehrtens,2 it isshown that formaldehyde and subsequent oxidation may replace theformic acid ; this leads one to formulate the products obtained fromP-thiosemicarbazides and aldehydes as endothiodihydrotriazoles.RNH*N RN-N RN- NC-SH RCH C*SH RC<G%>CRCHO + It -+ 1 [I -+- I 11\/ NR / H*NRenddminodihydrotriazoles yield quaternary ammonium iodides, andthese give pseudo-bases on treatment with alkalis.RN N RN-N-+RC RC*OH C*NRR'\ /\/NR\/ N RBer.1905, 38, 856. ]bid., 4049.3 J. pr. Chem., 1903, [ii], 67, 201.K 132 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.From thiodihydrotriazoles, endosulphonium iodides may be obtained.RON-N R.N--- N-I- r2 = HI +RCI II\/ \RCH C*S*CH,NRNRAccording to A. Michaelis 1 somewhat similarly constituted bridged-rings occur in the “pyrines,” which result from the action of primarybases on antipyrine chloride.2 F. Stolz,, however, considers theproducts to be imino-compounds.7 6H5N7sH5Nf: sH5N/\CH3*fC1 E*NHRAntipyrine. Antipyrine c ti loride. Iminopyrine chloride./\CH,*RCl SCl CH,-r 70CH,*C=CH --3 CH,*C-CH --+- CH,*C-CH/\7sH5 $? 6H5N N/\CH,*N C:NR /\CH,*N CCH,*C-CH i i orCH,*C=C -+ 11x1 I(Michaelis.) (S tolz.)The bases obtained are usually soluble in water with alkalinereaction, whence Michaelis considers his view of the constitutioncorrect, notwithstanding the fact that he obtained a different substance,starting with antipyrine and finally reacting with p-bromoaniline(R = C,H,Br), from the one which he obtained from bromoantipyrineand final condensation with aniline (R = C6H,).Stolz pointed out thatthe production of the same or different products should decide as to thecorrectness of the first or second (Stolz’s) formula, and Michaelis’sformulation of the free iminopyrine as an internal salt is certainly some-what improbable.The solubility in water and alkaline reaction is farmore probably to be accounted for by an equilibrium in the followingsense :f: 6H5Nf: gH5NA CH;7 Y:NR /\CH,*t*OH fi*NHR -+CH,* C-CH f- H2° + C H 3 0 C ~ r C HAnnalen, 1905, 339, 117.Stolz, ibid., 3279.See also Ber., 1901, 34, 723 ; 1903, 36, 3271ORGANIC CHEMISTRY-HETEROCY CLIC DIVISION. 133The bridging of a five-membered nitrogerlous ring is also assumed byM. 0. Forster and H. Fierz 1 in the anhydride obtained by dehydrationof the hydrazino-compound produced by the reduction of nitrosocam-phor y l-q-carbamide.J. N. Collie’s 2 assumption of a bridged ring in pyrone derivativeshas received considerable attention during the past year, and experi-mental evidence in favour of his theory has been brought forwardby I.F. Homfray.3 The molecular refraction of pyrone derivatives isabnormal, but the calculated and experimentally determined figuresagree fairly closely if the assumption be made that the pyrone com-pounds contain two quadrivalent oxygen atoms, the atomic refractionfor oxygen in this condition being taken as 2-73. Dimethylpyrone, itshydrochloride, its additive compound with alcohol, diacetylacetone anddehydracetic acid are respectively formulated.0 0--,0 0Collie’s views have, however, been criticised adversely by R. Will-statter and R. P~rnrnerer.~ These authors formulate the additive pro-duct with potassium methoxide with an open chain,5 since they findTrans., 1906, 87, 110, 722.Ibid., 1905, 87, 1443.Ibid., 1904, 37, 3740.Ibid., 1904, 85, 971.Ber., 1905, 38, 1461134 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.that when the potassium is replaced by methyl the resulting compoundis the dimethyl ether of bishydroxymethyleneacetone.They conse-quently now regard the potassium methoxide additive product asresulting from the breaking of the ring and its conversion to thedimethyl ether as simply depending on the direct replacement ofpotassium by methyl. A similar structure is accorded to the disodiumderivative obtained from pyrone. The cyclic formulze given to thesecompounds and diacetylacetone by Collie are rejected by Willstatter,in that Collie’s formulae make the two hydroxyls of unequal value,whilst all the evidence is in favour of complete symmetry of structure.F.Carlo Palazzo 1 alone and jointly with I?. Onorato 2 also bringsforward evidence for the symmetrical structure of derivatives ofpyrone. The ethyl dimethylpyronkcarboxylate of Conrad and Guth-zeit,3 like other y-pyrone compounds, gives no additive product withbromine, but it furnishes dibromo- and tetrabromo-substitution pro-ducts, the two methyl groups being symmetrically attacked. Theauthors retain the usual symmetrical pyrone formula for the dimethyl-diacetylacetone originally obtained by Thomas and Lefbvre by theaction of phosgene on the salts of acetylacetone. Collie agrees in thisparticular case with such structure on account of the lack of basicproperties. But the ketone group of the pyrone ring is, in this case,incapable of furnishing an oxime, so that Collie’s assumption of aformula with a bridged ring to explain the impossibility of gettingan oxime from dimethylpyrone seems quite unnecessary.Palazzo andOnorato further draw attention to the fact that some years agoF. Feist and H. Belart 5 prepared a dioxime of diacetylacetone,[CH,*(C:NOH)CH,],CO,which furnishes an anhydride. This requires two oxygen atoms ofsimilar function in the molecule of diacetylacetone which it will beseen are not accounted for in Collie’s formula.Whether the products obtained by the diazotisation of benzene-sulphonylphenylenediamines are cyclic or not, is discussed by G. T.Morgan and F. M. G. Micklethwait.6 The ortho-compound may wellbe formulated in such a manner; the para-compound also forms ananhydride which may have a para-bridged ring or be quinonoid intype; the latter explanation is rather suggested by the fact thatbenzenesulphonyl-m-phenylenediamine gives no diazoimide.The limiting length of a bridged ring has been examined by0.Hinsberg and J. Kessler.7 Some years back,8 Hinsberg andGazzetta, 1905, 35, [ii], 465.Bull. Xoc. chim., 1888, 50, 193.Trans., 1905, 87, 73.Annalen, 1905, 340, 110.Ibid., 476.Ber., 1895, 28, 1817.8 Ibid., 1895, 287, 220.3 Ber., 1886, 19, 19 ; 1887, 20, 152 ; Annalen, 1891, 261, 165ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 135S trupler found that s-dibenzenesulphonyl-o-phenylenediamine reactswith alkylene dihalides, givingSO, C6H5 so2*c6H5N*S02*C6H, / /\C,H,<)CH2 9 C,H,<N-?H2 N-CH, ' and C,H,<~:~~:>CH,.\ S0,*C,H5N*S0,*C6H,s02*c6HSThe present authors have carried out similar experiments in themeta- and para-series in order to see what length of chain is necessary,and to get some idea as to the relative distances of the ortho-, meta-,and para-positions.The compounds obtained in the meta- arid para-series are, however, bimolecular and of the typeC6H,:[*N(S0,*C6H,)*(CH2)n*(C6H5*S0,)N.l,:C6H4 ;thus the compound from s-dibenzenesulphonyl-p-phenylenediamine aridtrimethylene bromide must be represented as containing an eighteen-membered ring.Respecting the arrangement of linkings in closed rings, Hinsbergcomes to the conclusion that since, as Tichvinsky and Wolochowitz 2found, the acetylation of dihydrophenazine yields first a monoacetylderivative-a result he himself confirms-the dihydroazine is probablynot symmetrically constituted, and it is more likely that such a consti-tuted dihydro-compound would arise from an o-quinonoid form of theazine itself.N H N H/\/\/\ -+ I I I/\/\/\I I I I\A/\/ \/I\,\/ NNThe linkings in the pyrrole molecule are discussed by G.Ciamician,3who contrasts the non-basic properties of pyrrole with the salt-formingcapability of its dihydro-derivatives. One can apply a symbol similarto Thiele's representation of the benzene molecule to the pyrrolecomplex, but it necessitates the use of the latent affinity of thenitrogen atom of the ring. If, however, the nucleus be reduced, oneimmediately has the nitrogen atom occupying the position it has in anyother secondary amine and hence capable of forming salts.n -**HCZ=$TH*-* Hfi-5H -+ H2Y-fiH* * * IH2C CH2 or H2C CHI*-*N HHC C H\/ \//'\ AN H'\/ Jj N H /Ber., 1905, 38, 2800.Gazzetta, 1905, 35, [ii], 384.Centralbl., 1905, [i], 1263; from Jour.BUSS., 37, 8.See also Ber., 1893, 26, 1946136 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.h case of prevention of ring-formation is noticed by Carl Bulow.1Ethyl phthalylacetoacetate gives both phenylhydrazone and oxime.The latter may be condensed to an isooxazoline, but the former will not.undergo the pyrazoline reaction. Other cases of hindrance of reactionhave been observed where both hydrogen atoms of the CH, groupin ethyl acetoacetate have been replaced by hydrocarbon radicles.2The opening out of closed rings to open-chain compounds has,as usual, engaged some attention.The behaviour of the benzimid-azoles to continued alkylation and subsequent treatment with alkalihas been studied by Otto Fischer.3 A very interesting openingout of the quinoline nucleus has been discovered by A. Rei~sert.~Pyridine unites with acetyl chloride 5 and benzoyl choride to formadditive products of quaternary ammonium type; these are veryeasily decomposed by water. Quinoline and benzoyl chloride wher,mixed develop no heat; nevertheless, Reissert finds that by shakingquinoline and benzoyl chloride with aqueous caustic soda a somewhatbad yield of a compound is obtained which may be formulated asI or 11.CH CH:CH*CHO CH/\/\CH /\/ /\/\CH1 1 ICH.OH I 1 1 I lCH*CN.N*CO*C,H,\A/ \/\NH*CO*C,H,\/\/N*CO*C,H,I.11. 111.Formula I is favoured by the fact that when the solution of causticsoda is replaced by one of potassium cyanide, a compound of structureI11 is produced; nevertheless, formula I1 has to be taken as correct,the substance reacting quite normally with hydroxylamine, aniline, andphenylhydrazine. Reissert has, in addition, examined the followingcyclic bases in regard to this reaction: benzthiazole, pyridine, andacridine.Similarly, when tetrahydro-a-picoline is benzoylated, an open-chaincompound results.7Ber., 1905, 38, 1906. Knorr, Annulen,, 1887, 238, 166.Ber., 1905, 38, 320.Ibicl., 1603, 3415.Dennstedt and Zirnmermann, ibid., 1886, 19, 75.Minunni, Gazzetta, 1892, 22, [ii], 213.7 A. Lipp and E, Widnmann, Ber., 1905, 38, 2276 and 2471ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 137The fact that tetrahydro-a-picoline reacts with formaldehyde to givea P-substituted piperidine can now be explained, if we suppose thatin solution the substance is, by addition of water, in equilibrium withmethyl-c-ketohexylamine. The latter may then react with form-aldehyde, the ring closing in a different position.( - 3 3 2 CH2H,C/\CH -+ 1320 H,C/\CH,=CO-CH, ~ ~ 5 0 --+H2C!,)C*CH, H,C(N*CH, NH-CH,CH2H,C/) CH GO* CH3H,C(,CH,N*CH,Another case where a new member comes into the ring, studiedby Am4 Pictet,I is involved in the conversion of pyrrole into pyridinederivatives by passage through a red-hot tube.Thus ,!I’-methylpyrrolegives 2-methylpyrrole and pyridine in succession.It is of interest to note that the extra carbon atom which comes intothe ring forces its way between the a- and @carbon atoms and notbetween the a-atom and the nitrogen. This is proved by the conver-sion of 2-benzylpyrrole to 3-phenylpyridine. In a similar way quinolineis obtained from %methylindole, and phenanthridine from methyl-carbazole.Xalt Formation and Pseudo-bases.Quite a t the close of 1904, Martin Freund 2 examined the behaviourof quaternary cyclic ammonium salts towards Grignard’s reagents. Theresulting compounds which are derived from dihydrocyclic substancesare but very feebly basic ; the reaction reminds one of the productionof pseudo-bases.CH, ISimilar changes occur with isoquinoline compounds (cotarnine andhydrastinine salts), and these changes amongst cyclic derivatives findtheir analogue in the conversion of methyl violet into a derivativeof benzyltriphenylmethane.Ber., 1905, 38, 1946.Ibid., 1904, 37, 4666138 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Phenylacridine methiodide and magnesium ethyl iodide give a-ethy 1-N-methylphenyldihydroacridine, which has no basic properties.Acridines themselves (containing tertiary nitrogen) have also beenexamined in their behaviour to alkyl magnesium halides-A. Senier,P. C. Austin, and R. Clark finding that usually two molecules of theacridine unite with three molecules of the Grignard reagent to form,for example,HPseudo-bases have also occupied the attention of H.Decker.2When a methylene group is attached to the same carbon atom asthat vhich forms the carbinol group, the elements of water are easilysplit off; and whilst the salts and true ammonium base may becolourless, the anhydro-bases produced by elimination of water areuniformly coloured.Orange-red. Colourlcss.The first transformation of this type was observed by F. Kehrmannin the quinoxaline series,3 and subsequently it has been shown thatderivatives of pyridine, quinoline, isoquinoline, indoline, xanthone, andthioxanthone exhibit the same behaviour.Employing Thiele’s symbol for conjugated partial valencies, Deckeruses the following scheme to explain the way in which these aresatisfied :When applied to the N-methylacridinium compounds on the onehand and the xanthen and thioxanthen derivatives on the other, theresemblance is most striking.The conversion of five-inembered ring compounds into anhydrebasesTrans., 1905, 87, 1469.Ibid., 1892, 25, 1627.Bcr., 1905, 38, 2493ORGANIC CHEMTSTRY-HETEROCYCLIC DIVISION.139receives a particular application in K. Brunner’s production of sucha compound by the action of magnesium benzyl chloride on trimethyl-indolinone. 1The condition of phenylmethylacridol inJ. J. Dobbie and C. K. Tinkler from/\--C( CH3)2I I IC:CH-C,H, \/\/N*CH3solution has been studied bya spectroscopic standpoint,the absorption spectra of solutions in ether and chloroform beingpractically identical with those of dihydroacridine, and quite distinctfrom those of the original salt.But in alcoholic and aqueous-alcoholicsolutions different results are obtained ; thus in 50 per cent. methylalcohol the absorption spectrum closely corresponds wit,h that of 75 percent. dihydroacridine and 25 per cent. phenylacridine methiodide,addition of water increasing the amount of ammonium compoundpresent.These results agree well with Hantzsch’s idea of pseudo-bases ; it has,however, to be kept in mind that the formulation of so many colouringmatters with an orthoquinonoid structure involving formation ofoxonium salts 3 is not in agreement with Hantzsch’s views. Hantzschhas in fact recently pointed out that, for example, the older formulationof Meldola’s blue with a paraquinonoid ammonium grouping is inbetter accord with the properties of the dye than the orthoquinonoidoxonium salt formation proposed by Kehrmann.Taking the simplestaminophenazthionium salts, two alternatives are possible.Bernthsen. Kehrmann,Kehrmann supports his view here, as with the safranines, by theSince, however, the azo-compounds diazotisability of the amino-group.obtained are of the typeHantzsch argues that the addition of water is a necessary forerunnerof the possibility of diazotisation, and the writer would like to drawattention to the fact that in order to diazotise aposafranine i t isnecessary to work in strongly acid solution:5 Diazotisability is con-ditioned by the group - NH,A rather than the amino-group.Ber., 1905, 38, 1359.Trans., 1905, 87, 269.Kehrmann, Ber., 1899, 32, 2610 ; 1901, 34, 1623 ; Annalen, 1902, 322, 64.Ber., 1905, 38, 2143. Kehrmann, ibid., 1896, 29, 2316140 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Against the view of Kehrmann’s, that cyclic oxazine dyes are saltsof oxonium type, Hantzsch further brings forward the fact that thechlorides of Lauth’s violet, Meldola’s blue, and pararosaniline showno more hydrolytic dissociation than does ammonium chloride. Additionof alkali brings about rapid and radical change in the base of Meldola’sblue; the hydroxyl base of Lauth’s violet seems to have an ephemeralexistence, but is probably transformed into an imido-base of the typeof Homolka’s anhydro-base from magenta,N NMethylene blue gives a far more stable base, the addition of anequivalent of alkali to the salt not being accompanied by any immedi-ate diminution of electrical conductivity, the gradual decrease which doesoccur being easily explained by gradual absorption of carbon dioxideand autocatalytic decomposition with formation of methylene azure.That azoxonium salts in which oxygen plays the part of the salt-forming element are possible, seems incontestable, and Kehrmann 1 hasproduced a colourless pseudo-phenanthrophenazoxonium hydroxide,C2011,,0,N, by the action of o-aminophenol on phenanthraquinone.With acids, violet salts are produced, and the transformations ofthese substances have been carefully studied.The colourless base issupposed to have hydroxyl attached to nitrogen ; a yellow base producedfrom the salts by the action of water has the hydroxyl group attachedto carbon.This yellow form spontaneously isomerises to the colourlessvariety. The changes may be represented schematically in the followingmanner :Ber., 1905, 38, 2952ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 141Spontaneous change.I 1H,SO, --+Colourless. Violet./\I I HN*OH/\I I N\/\/\/\I I I I/‘)/\/\/ I 0\iNon-isolable.\\/Yellow.The immediate hydrolysis of the sulphate by water does not alterKehrmann’s views on oxonium salts generally, and when he subsequentlysynthesises the parent substance of Nile-blue by the action of 4-amino-1 : 2-naphthaquinone on 2 : 5-diaminophenol hydrochloride he does nothesitate to formulate it asH,N* C,,H,<~c~C,H,*NH,.From the colour of the solution in strong acids and the changesaccompanying dilution the existence of tri-acid and di-acid salts mustbe assumed, and one cannot quite follow the author in supposing thatthe ammonium groupings are hydrolysed before the oxonium salt groups.Kehrmann and Gottrau2 have shown that the supposed oxime ofnaphthaphenazone of Fischer and Hepp is really an aminonaphtha-phenazone, the amino-group having entered the naphthalene nucleus ;the oxazone portion is however formulated as a sort of oxoniumphenoxide.Fischer and Hepp 3 confirm the correctness of Kehrmannand Gottrau’s results, but dispute the oxonium formulation ; theycontend against Kehrmann’s formulation of methylene-blue as a thioniumsalt, that methylene-azure also forms salts, and pertinently ask if thesulphonyl group is supposed in this case to have a basic character.Ber., 1905, 38, 3604.Ibid., 2574. 3 Ibid., 3435142 ANNUAL KEPOKl"l' ON THE PROGRESS OF CHEMISTRY.Probably Wedekind and Koch are correct in assigning to santoninnitrate discovered by Andreocci an oxonium constitution, as they havesucceeded in preparing a number of double halide salts of santonin.The formulation of a number of rhodamine salts as of ammonium oroxonium type has engaged the attention of E. Noelting and K.Dziew6nski.3 They find further that the coloured rhodamine salts passinto a colourless form on expulsion of water of crystallisation; for thecoloured variety of base they suggest a betaine structure, for thecolourless the usual diaminofluorane formulation.Difficulties in explaining abnormal properties of salts have arisenwith regard to the alkaline salts of q~inolphthalein.~ This colourlesssubstance dissolves with strong coloration in alkalis, and R.Meyer and0. Spengler are inclined to see an explanation in the production of" carbonium valency."0 0/\/\/\\/\/\/ HOI I I IOHCcoColourless.COColonred.Xyntheses.Besides the work which has been done during the past year on thegeneral mechanism of heterocyclic compounds, many new syntheses havebeen effected and new reactions discovered; an account of thesefollows, the material being classified according to ( A ) the total numberof atoms, and (B) the number and nature of atoms other than carbonin the ring.Pyrrole.Carl Bulow obtains ethyl n-camphyldimethylpyrroledicarboxylatefrom camphylamine,5 and ethyl n-ureidodimethylpyrroledicarboxylatefrom semicarbazide and ethyl diacetosuccinate,6 whilst G.Korschun 7synthesises ethyl 2 : 3 : 5-trimethylpyrrole-4-carboxylate by the actionof ammonia on ethyl a-/3-diacetobutyrate.Pyrrolidine has attracted more attention since the discovery of its2-carboxylic acid (proline) amongst the products of the hydrolysis ofproteids. A new synthesis of pyrrolidine is given by A. Wohl, K.1 Ber., 1905, 38, 421, 429.2 Atti Iz. Acead. Lincei Idoma, 1896, [v], 5, ii, 309.3 Ber., 1905, 38, 3516. Ibid., 1903, 36, 2949 ; 1905, 38, 1318.5 Ibid., 189.Ibid., 2366. Ibid., 1125ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 143Schaefer, and A. Thiele,1 the dicthyl acetal of P-chloropropionaldehydebeing used as the starting-point. The chlorine atom is replaced bycyanogen, the latter group reduced to - CH,*NH,, the benzenesul-phony1 derivative of which loses ethyl alcohol with formation of benz-enesulphonylethoxypyrrolidine,C,H,.SO,*N*CH,*CH,* CH,*CH* 0. C,H,.I I .____The latter compound when reduced by sodium in amyl-alcoholic solu-A hydroxypyrrolidinecarboxylic acid,tion gives pyrrolidine.P;H-CH,~CH(OH)~H~~CH=CO,H,has been synthetically obtained by Hermann Leuchs 2 by the action ofammonia on a-bromo-6-chloro-y-hydroxypentoic acid ; corresponding to thetwo asymmetric carbon atoms, two forms have been obtained which muchresemble the oxyproline obtained by Fischer on hydrolysing gelatin.3For the detection of proline itself, D.Alexandroff 4 recommendsthe picrates ; the racemic form melts a t 135--137O, the active a t153-154".New pyrrolidine derivatives are described by 0. Kuhling and FranzFalk,5 whilst thiopyrrolidone (m. p. 114") is obtained from pyrrolidoneand phosphorus trisulphide.6Indole.G. Mazzara and A. Borgo7 find that indole is monochlorinated inthe 2-position by means of sulphuryl chloride. The substance decom-poses with water, giving oxindole. As piperidine compounds arecapable of conversion into pyrrolidine derivatives by Merling'smethod,8 so may tetrahydroquinoline be transformed into methyl-dihydroindole.J. von Braun and A. Steindorffg find that whenbenzoyltetrahydroquinoline is treated with phosphorus pentachlorideortho-7-chloropropylbenzanilide is produced, which, heated underreduced pressure, furnishes o-allylbenzanilide. I f now hydrogenchloride be added and the benzoyl group removed, ortho-P-chloro-propylaniline hydrochloride is produced, the free base readily con-densing on warming to the hydrochloride of methyldihydroindole,1 Ber., 1905, 38, 4154, 4157.3 Ibid., 1902, 35, 2660.5 Ber., 1905, 38, 1215.7 Gazzetta, 1905, 35, [ii], 320.9 Bey., 1904, 37, 4723.Ibid., 1937.Zeit. physiol. Chem., 1905, 46, 17.Tafel and Lavaczek, ibid., 1392.AnnnZern, 1891, 264, 310144 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.A question never previously definitely determined was whether,when an indole is obtained from an a-aminonaphthalene compound,condensation takes place in the ortho-position 2 or in the peri-position8.Pschorr and Kuhtzl have now settled the matter by showing thatSchlieper’s a-naphthindole 2 and Hinsberg’s u-naphthindolesulphonicacid are ortho- and not peri-derivatives.Martin Freund and Gustav Lebach4 have examined the colouringmatters produced by the action of aldehydes on “methyl-ketol” andother indole compounds. When one molecule of each constituentreacts, a blue dye is produced, but from one molecule of the aldehydeand two molecules of the indole compound the leuco-base of a red dyeis formed.Leuco- base. Colour base (red).Leuco- base./c1Coloured salt (blue).Pyraxoles and Pyraxolones.The reaction of o-ethers of propionylacetophenone with hydro-xylamine and hydrazines has engaged the attention of Moureu andBrachin, 5 the first reagent giving 5-phenyl-3-ethylisooxazole, the latterphenylethylpyrazole,C,H,* :CH-CO*C,H,K xO*C,H,HC- C*C,H, HC--- C*C,H,C,H,*C(l /IN \/ C6H,* Cil ]INNH \/0Fenton finds that phenylhydrazine reacts not only with ethylethoxyoxaloacetate to form ethyl phenylhydrazoneketophenylpyrazolone-Ber., 1905, 38, 217.Ber., 1888, 21, 110.Bull.SOC. chiin., 1905, [iii], 33, 142.Annalen, 1888, 239, 229.Ibid., 1905, 38, 2640ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 145carboxylate,l but that the latter ester may also be obtained fromethyl dihydroxymaleate.2Amongst pyrazolone derivatives, 1 -phenyl-5-methyl-3-pyrazolone hasbeen further examined by Michaelis,3 and 1 -phenyl-4-methyl-5-pyrazoloneby Michael* and St01z.~ E.Mohr finds that water is eliminated fromphenylmethylpyrazolone a t 2 50°, the carboxyl group of one moleculereacting with a methylene group of a second molecule.6 4-Aminoanti-pyrine gives in succession ethylenediamine and piperazine derivativeswith ethylene dibromide and an antipyrine-morpholine with ethyleneoxide.7The monohydrazones from ethyl a-P-diketobutyrate have according toA. Wahl a true hydrazone structure, since by acting with p-nitrophenyl-hydrazine on the monophenylhydrazone of the diketobutyric ester, thep-nitrophenylhydrazone of methylphenylketopyrazolone is obtained.Stolle 9 has examined the compound C,,H,,O,N, (m.p. 145')obtained by Knorr from phenylmethylpyrazolone and ethyl acetoacetate.1°The product first formed probably reacts tautomerically and then ethylalcohol is eliminated, giving a %lactone,C,H,*OH + HCR\c-- C*CH3 ocl II IIN\/\/0 $J*C6H,Scholl's l1 product from hydrazine and excess of ethyl acetoacetate isprobably constituted similarly and has been examined further byLudwig Wolff.l2Iminazoles.A very interesting synthesis of methyliminazole is described byWindaus and Knoop,ls who find that it is produced by the action of anammoniacal solution of zinc oxide on glucose. As in the case ofiminazole itself, the ring is broken by benzoylation,Wislicenus and Scheidt, Ber., 1891, 24, 4210.Trans., 1905, 87, 810.I b i d ., 2104. Ibid,, 3273. Ibid., 2578.Max Luft, ibid., 4044.Ber., 1905, 38, 3023.l1 Ibid., 1894, 279, 242.Ber., 1905, 38, 154.8 BuU. Soc. chim., 1905, [iii], 33, 490.Annalen, 1887, 238, 182.l2 Ber., 1905, 38, 3036.13 Ibid., 1166.VOL. 11. 146 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Pinner finds that phenylglyoxal and ammonia furnish benzoyl-phenylglyoxaline and 3-hydroxy-1 : 4-diphenylpyrazine.1Triaxoles.The diazotriazolecarboxylic acid (C,H,O,N,), obtained by Thiele andW. Manchot,2 was regarded as an internal anhydride by its discovererson account of its stability. Manchot and R. No113 find, however, thata stable derivative is also produced by the diazotisation of ethylaminotriazolecarboxylate, so that obviously the substance must containone of the following groups :--N=N*OH, -NH*NO, or =N*NO.G.Young 4 confirms the constitution of a substance he obtained in1901 conjointly with Oates 5 from 5-hydroxy-3-phenyl-l-methyl-1 : 2 : 4-triizole by heating with phosphorus pentasulphide as c-phenyl-s-triazole,since it may also be obtained in the same manner from 5-hydroxy-3-phenyl-1 : 2 : 4-triazole.I n 1900, Wheeler and Dustin G obtained a compound containing nosulphur from ethyl diphenylthionsemicarbazidate,C,H,*NH-CO*N( C,H,)*NH*CS*O*C,H,,and sodium ethoxide, which from analysis might be either a urazole oran oxybiazoline derivative.that if sodium hydroxide and benzyl chloride be used instead, sulphuris not eliminated, but an undoubted ketodihydrotriazole derivative isformed,Wheeler and J.G. Statiropoulos now findc 6 H ~ 7-8OC C *S*CH,*C,H,,\/ fib c6H,since it can be obtained also by the action of phosgene on diphenyl-benzyl-+-thiosemicarbazide.Fer., 1905, 38, 1531.Annalen, 1905, 343, 1.Trans., 1901, 79, 665.Ann. Chem. J., 1905, 34, 117.‘L Annulen, 1898, 303, 33.4 Trans., 1905, 87, 625.Ann. Chcm. J., 1900, 24, 430ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 147Furficran G~oup.F. R. Japp and J. Wood1 find that phenanthraquinone and aceto-phenone are condensed to 3-acetoxy-2-phenyl-4 : 5-diphenylenefurfuranby acetic anhydride and sulphuric acid. One has to assume that acarbonyl group of the quinone reacts with the methyl group of theacetophenone, and that the intermediate product thus obtainedundergoes the following transformation.Y,H4*Q=QH y6H4* QH *SH*O* C2H30 + C,H,*CO CO*C,H, -+ C6H,*C0 CO'C6H,y6H, g-E* O*C,H30C6H4*C C*C,H,\/0Phenylpropiolyl chloride reacts with the sodium derivative ofacetylacetone, giving a substance which S.Ruhemann and R. Merrimanfind is insoluble in dilute alkaline solutions.2 It is, therefore, probablycyclic, and if dissolved in piperidine and reprecipitated by hydrochloricacid is found to have been transformed into an isomeride. This changemay be represented by the following scheme :?HC,H,*CH:$!-~O C~H~-CH: &yo-3- 5 0 C*CO*CH, -3-\/ C,H,,N*C*CH3C*CH, 3Pyridine Group.Ahrens 3 gives a process for isolating y-picoline from the commercialP-picoline, and his pupils have prepared many derivatives ; whilstFormanek finds that pyridine and formaldehyde yield an unstablealkine, C,H4N*CH,*OH.As usual, a large number of compounds has been obtained by thecondensation of methylpyridines with substances containing carbonylgroups,5 and Konigs and von Bentheim6 show that when aldehydescondense with aa'y-trimethylpyridine, it is the a-methyl groups whichare first attacked, ,4 similar reaction has been studied by R.Franke,who finds that 2 : 5-dimethylpyrazine reacts with one or two moleculesof benzaldehyde, giving compounds C,,H,,N, and C,,H,,N,.Trans., 1905, 87, 712.Rer., 1905, 38, 155.Ibid., 2806, 3699, 3704, 3709, 3715.Ibid., 1383.Ibid., 944.Ibid., 3907.L 148 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.W.J. Sell 1 has chlorinated a-picoline ; the hexachloropicolineproduced is a-trichloromethyl-PP'y-trichloropyridine, since it is suc-cessively convertible into trichloropicolinic acid and @y-trichloro-pyridine.The synthesis of y-methyl-ad-dihydroxypyridine has been effectedby H. Rogerson and J. F. Thorpe,2 starting with a condensation of thesodium derivative of ethyl cyanoacetate and ethyl acetoacetate. Thesubsequent transformation can be expressed diagrammatically asfollows :CO,(C,H,)*CHNa*CN + CH,*CO*CH,*CO,*C,H, -+CO,( C,H,) C( CN)Na* C(OH)( CH,) CH,* CO,* C2H5 -+GO,( C2H5) CH( CN) *C( CH,):CH*CO,*C,H, 5The formation of N-substituted y-piperidones has been studied bya ketone, CH2R*CO*CH3, and benzylideneaniline Charles Mayer ;condense to form a substanceA. Wohl, W.Hertzberg, and M. S. Losanitsch4 obtain reducedpyridine derivatives from the acetal of the P-chloropropionaldehydepreviously mentioned. Two molecules of this substance react withammonia to give a secondary amine, which undergoes internalcondensation on hydrolysis with hydrochloric acid.NH[CH2*CH2*CH(O*C2H5)2]2 -+ NH[CH2*CH,*CHO], -+With alcohol and hydrochloric acid, not only is the aldehyde groupacetalysed, but the elements of hydrogen chloride are added a t thedouble linking, the chlorine atom may be replaced by hydrogen, and apiperidine derivative obtained on reduction with alcohol and sodium.Trans., 1905, 87, 799. Ibid., 1685.Ber., 1905, 38, 4161. 3 BUZZ.SOC. chim., 1905, [iii], 33, 157ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 149The products of the decomposition of dinitrophenylpyridiniumchloride, C5H,N[C,N,(N0,),]C1, have occupied Zincke’s attention ; 1they are open chain compounds of the typeNHAr- CH: CH*CH:CH-CH:NAr, HCl.Their great similarity to the colouring matters obtained fromaromatic bases and furfuraldehyde 2 led Zincke to consider thesesubstances as hydroxyl derivatives formed by the opening of thefurfuran ring, and to be produced according to the equationC,H,02 + ArNH2 + ArNH,,HCl= H,O+ ArNH*CH:CH*CH:C(OH)*CH:NAr,HCl.This view has been confirmed, for, when boiled with acetic acid, onenrylamine molecule is eliminated and an arylhydroxypyridiniumchloride is produced.3CH/AAr C1It is remarkable that the same result should have been attainedalmost simultaneously by W.Konig and W. Dieckmann and L. Beck.5Quilzoline.o-Methylquinoline has been examined by Howitz and Schwenk,G new(8 : 8’ and 5 : 5’-dimethyl-8 : 8’) diquinoyls have been prepared by St.von Niementowski and M. Seifert’7 and the formers has preparedy-hydroxy-a-phenylquinoline-P-carboxylic acid by the condensation ofethyl benzoylacetate with anthranilic acid. Oscar Bally finds thatP-aminoanthraquinone does not undergo Skraup’s reaction in a normalmanner, but reacts with two molecules of glycero1,gThe new substance, which he calls benzanthronequinoline, is aderivative of benzanthrone, the substance produced by the interactionof anthraquinone and glycerol ; the relationship of the two substancesis exhibited by the formuleAnnalen, 1904, 333, 311 ; 1905, 339, 193 ; 341, 365.Stenhouse, ibid., 1870, 156, 199 ; H.Schiff, ibid., 1880, 201, 355 ; and 1887,Zincke and G. Miihlhausen, Ber., 1905, 38, 3824.J. pr. Chem., 1905, 72, 555.Ibid., 1280. Ibid., 762.8 Ibid., 2044. [bid., 194.239, 349.Ber., 1905, 38, 4122150 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.H. Decker finds that many ortho-substituted quinolines will not com-bine with methyl iodide owing to steric hindrance, but that the difficultymay be overcome by employing methyl sulphate, a little more than themolecular quantity of which is added to the base, the mixture beingheated for 25 to 30 minutes at 100’. Even this process of makingquaternary ammonium salts fails with dimethylmesidine, 6-bromo-dimethylamino-2 : 4-xylene, N-methylcarbazole and phenyldinaphth-acridine.The nitration of quaternary quinoline compounds follows thesame orientation rules as with quinoline itself.2J. Howitz in conjunction with M. Badocher3 and Witte4 hascontinued his earlier work on the replacement of bromine by chlorinewhen ma-bromo-p-alkyloxy-N-methylquinolones are heated with hydro-chloric acid. It has now been shown that this labile condition of thehalogen atom is not a function of the alkyl or quinolone groups, sinceseveral bromohydroxyquinolines react in the same manner.E. Besthorn and J. Ibele have made further researches on thefluorescent colouring matter, C,,H1,ON,, obtained from quinaldic acidand acid anhydrides; it may also be obtained from quinaldic chlorideand quinoline.Amongst isoquinoline syntheses, Waldemar Findeklee 6 has appliedthe method of Gabriel and Colman ; starting with 4-methylphthalicacid, he has produced eventually 7-methylisoquinoline and 6-methyl-isatin.Acridine.F.Ullmann and R. Fitzenkam employ meta-aminophenols in acridinesyntheses, 6 and obtain Z’-methyl-3’-hydroxy-9-phenyl-l : 2-naphthacridinefrom 4-amino-o-cresol, benzaldehyde, and @-naphthol. When tetra-aminoditolylphenylmethane reacts with resorcinol, one molecule ofm-tolylenediamine is eliminated and aminohydroxymethylmesophenyl-acridine results.N-CPh2H,O + C7H,,N2 + HO*C,H,< I >C6H,(CH,)-NH2.1 Bcr.: 1905, 38, 1144.7 Ibid., 1900, 33, 980.H. Decker, ibid., 1274.Ibid., 1905, 38, 3787.Ber., 1905, 38, 887.Ibid., 1260. Ihid., 2127.l b i d . , 3542ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 151Finally, the replacement of amino-groups by hydroxyl when heatedunder pressure in sealed tubes has been studied in the case of dihydroxy-dimethylacridine. 1Derivatives of dihydroxyacridone, which results from the condensa-tion of anthranilic acid and phloroglucinol, have been described by W.BaczyLski and St. von Niementowski.2K. Friedlander finds that mesomethylacridine reacts with benz-aldehyde to form a base, C,,H,N*CH,-CH(0H)-C,H,, but ifnz-nitrobenzaldehyde is employed, water is eliminated and a base,C,,H,X*CH:CH*C,H4*N02, corresponding to the stilbazoles producedfrom picolines is obtained.J. T.Hewitt and J. J. Fox find that the production of para-quinonoid oxygen-f ree bases from phenylmethylacridol derivatives, whenan amino-group occupies the para-position to the carbinol group, holdsalso in the case of benzofIavine.kOrthodiaxines.F. R. Japp and J. Wood4 find that the 3 : 4 : 6-triphenyl-1 : 2-diazineobtained previously by Alexander Smith5 may be obtained from cis-dibenzoylstyrene and hydrazine, whilst the latter reacts with dibenzoyl-stilbene and a-benzoyl-/3-trimethacetylstyrene to give tetraphenyldiazineand 3 : 4-diphenyl-6-tert.-butyl-l : 2-diazine respectively.Phthalazines have been prepared by A. Daube,, A. L i e ~ k , ~ and H.Wol bling .8Metadiccxines.Amongst the metadiazines, new syntheses of uracil and pyrimidinecompounds are of foremost interest on account of the near relationshipto naturally occurring products.T. Posnerg has found that whenhydroxylamine is added to up-unsaturated acids the hydroxylamino-group becomes attached to the /3-carbon atom, and does not take upan a-position as previously supposed.10 Thus, starting with cinnamicacid and hydroxylamine, an aminohydrocinnamic acid was obtainedwhich he has now condensed to phenyldihydrouracil and phenyldihydro-thiouracil.S. Gabriel has re-examined the bromodihydrouracil of E. Fischerand G. Roder.12 On heating this substance, it loses hydrogen bromide,See also D.R.-P. 121686.Annalen, 1896, 289, 319.Ibid., 2316.2 Ber., 1905, 38, 3009.Ibid., 707.Ber., 1905, 38, 206.lo Ibid., 1903, 36, 4305.la Ibid., 1901, 34, 5759.3 Tyans., 1905, 87, 1058.Ibid., 3918.8 Ibid., 3925.l1 Ibid., 1905, 38, 636, 1689152 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.furnishing uracil from which 2 : 6-dichloropyrimidine and 6-amino-2-chloropyrimidine have been prepared.Otto Gerngross synthesises 5-methylpyrimidine, starting with carb-amide and diethyl isosuccinate, the hydroxyl groups in the resulting tri-hydroxymethylpyrimidine being replaced by chlorine, and the latterelement replaced by hydrogen. A certain amount of 2-chloro-5-methyl-pyrimidine is also obtained. Besides numerous other derivatives, thetrichloromethylpyrimidine has been employed for a fresh synthesis ofthymine,2 the stages in the process being represented by the followingscheme : M - P R-P' Cl? F]-CH, NzCH, -+ CH,OY C;*CH, -+N=CC1 N=C 0.c HTreat B. Johnson and C. 0. Johns find that in several cases replace-ment of halogen by the amino-group in pyrimidinecompounds may beeffected by heating with aqueous ammonia where Wheeler and Jamie-son 4 had failed when using alcoholic ammonia. The same authors 5have examined 2 : 5-diamino-6-hydroxypyrimidine, which they haveobtained by nitration of Wheeler and Jamieson's 6 isocytosine and sub-sequent reduction ; the diaminohydroxypyrimidines possess consider-able interest as possible products of the hydrolysis of the nucleins.7Further syntheses of mercaptoaminohydroxypyrimidines are describedby T. B. Johnson.8Quinazolines, quinazolones, and diketotetrahydroquinazolines havebeen examined by S.Gabriel and J. Colman,g W. Findeklee,lo B,Pawlewski,ll and F. Kunckell.12Paradiaxines.L. Knorr, H. IIorlein, and P. Roth13 show that Knorr's assumptionof the formation of 137-dimethylpiperazinc hydrochloride by the spon-taneous polymerisation of methylchloroethylamine is correct, and in a,similar way chloroethylpiperidine polymerises to a diquaternary chloride,1 Ber., 1905, 38, 3394. Ibid., 3408.3 Amer. Chem. J., 1905, 34, 175.6 Ibid., 1905, 341, 554.7 Zeit. physiol. Chem., 1903, 38, 176. 8 Amcr. Chem. J., 1905, 34, 191.9 Ber., 1906, 38, 3559. lo Ibid., 3553.11 Ibid., 130. l2 Ibid., 1212. l3 lbid., 3136.Ibid., 1904, 32, 343.Ibid., 1903, 29, 493ORGANIC CHEMISTRY -HETEROCYCLIC DIVISION.153Piperazine has also attracted the attention of F. D. Chattaway andW. H. Lewis,l who find that i t reacts with hypobromous acid in thefollowing remarkable manner :F. IE. Japp and J. Knox show that the substance obtained by Jappand Miller2 from benzil and hydrogen cyanide in alcoholic hydro-chloric acid, and subsequently by Minovici 3 by the action of hydrogenchloride on mandelonitrile, is actually 3-keto-2 : 5-diphenyl-3 : 4-dihydro-1 : 4-diazine ; on distillation with zinc dust the 2 : 5 diphenyl-1 : 4-diazine of Staedel and Riigheimer 4 and L. Wolff is produced.Whilst all hitherto known quinoxalines are derivatives of the com-plex I,N NHI. 11.John B. Ekeley and R. .J. Wells have obtained a substance to whichthey ascribe formula 11, by the action of o-phenylenediamine on mesityloxide.6 The presence of two imino-groups seems certain, as the sub-stance gives both dinitroso- and dibenzoyl-derivatives.F.Ullmann and J.F. Ankersmit describe a new naphthazine syn-thesis,7 a typical example of which is furnished by the formation ofaminophenonaphthazine from @-naphthol and 2 : 4-diaminoazobenzene,C,,H7*OH + C,H,*N:N*C,H,(NH,), =The product is identical with that obtained by Nietzki and Otto8from P-naphthylamine and quinonedichlorodi-imide.P. Barbier and P. Sisley 9 have revived the question as to the consti-Trans., 1905, 87, 951. Ibid., 1887, 51, 29.Ibid., 1876, 9, 563.Ibid., 1905, 38, 2259.Ibid., 1888, 21, 1599.3 Ber., 1899, 32, 2206.5 Ibid., 1887, 20, 432.7 Ibbid., 1811.BwEZ.Soc. chiin., 1905, [iii], 33, 995, 1190154 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.tution of phenosafranine, which was supposed to have been definitelysettled in favour of the symmetrical formula :They have synthesised the unsymmetrical compound by oxidisinga mixture of o-p-diaminodiphenylamine with aniline and show that it ispresent in the phenosafranine of commerce.On examining the electrical conductivity of the salts, it is found thatthe value soon becomes a maximum with the symmetrical compound,but with the unsymmetrical compound goes on increasing and ulti-mately exceeds the value in the other case.F. Sachs and G. Bargellinil find that flavinduline condenses withsubstances containing a reactive methylene group (for example,ethyl acetoacetate, acetylacetone, .kc.), oxidation taking place simul-taneously.N---C14H6gN (C,H,)Br >C,H, + R*CH,-R’ + NaOH + 0 =N > ~ , ~ 3 : CRR’.W6HANaBr + 2H,O + C,,H,<Tyicczines .Amongst substances containing three carbon and three nitrogen atomsin the ring, the derivatives of cyanuric acid are especially interesting.A.Hantzsch and H. Bauer have now proved that the cyanilic acidprepared by Liebig by oxidising mellone with nitric acid3 is identicalwith cyanuric acid instead of being isomeric. The mixed oxygen andnitrogen ethers of cyanuric acid have been examined, and the seriesis now complete. I n each case, methyl attached to oxygen is hydro-lysed on heating with hydrochloric acid, the linking betweennitrogen and methyl not being affected.Hantzsch has also solved themystery attached to the constitution of cyarnelide ; the relationshipsbetween this substance, cyanic and cyanuric acids, and the commonproducts of hydrolysis (carbon dioxide and ammonia) is expressed by thefollowing scheme :Ber., 1905, 38, 1742.Anmlert, 1834, 10, 35.]bid., 1005.Ber., 1905, 38, 1013ORGANIC CHEM ISTRY-HETEROCYCLIC DIVISION. 155Cyamelide is an extremely weak acid ; there is no question of itsbeing a pseudo-acid, and these facts combined with the easy depoly-merisation and hydrolysis make the formulaHN: q-O-y:NH0 * C( NH) 0extremely probable.melide (I)By acting on ammonia with sulphuryl chloride, salts of the ccci-sulpho-I 0-S-0 0--8-0/% MO NI./\HN 011.have been obtained by Hantzsch and Stuer,I but sulphomelide itself(11) could not be isolated.Syntheses of 1 : 2 : 4-triazine derivatives from semicarbazides andbenzil or benzoin have been effected by H.Biltz, Arnd, and Stellbaum.2Tetruxines.A diphenyldihydrotetrazine (glyoxalosotetrazone) has been obtainedby W. Dieckmann and L. Platz 3 by the action of alkalis on chloro-glyoxalosazone. The tetrazines (and hydrogenated derivatives) inwhich the carbon atoms occupy the 1 : 4-position have received moreattention. S. Ruhemann and R. Merriman4 have re-examined thebehaviour of tetrazoline towards methyl iodide and shown that the twoproducts which result areand the corresponding periodide, C,H7N,13.When an alkaline solution of the methiodide is exposed to the air, aviolet coloration is produced, the reaction being compared to the forma-tion of indigotin from indoxyl.If this view is correct, the existence ofBnnnlen, 1905, 339, 243.Trans,, 1905,38, 1768.Ber., 1905, 38, 1022.3 Ber., 1905, 38, 2986156 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.a methylene group in the molecule is necessary, and this receives furthersupport from the fact that tetrazoline condenses with benzaldehydeunder the influence of piperidine,C2H4N4 + C,H,*CHO = H,O + CGH5*CH:C,H2N,,whilst dimethyltetrazoline does not furnish an analogous compound.ethylbromoacetate to yield a bromohydrizino-compound of the structureD. A. Bowack and A. Lapworth1 find that bromine reacts withbenzeneazoacetoacetate or diazo-compounds with ethyl aceto-CBr( :N*NH*CGH5)*C02*C2H,.Under the influence of alkalis, hydrogen chloride is eliminated andtwo molecules condense to give ethyl diphenyltetrazolinedicarboxylate,7 (CO,*C,H,):N*~*C,H,N( C,H,)-N=C C02* C2H5C(:NOH))(NH*OH)(NH,,HBr),Wieland has obtained the amidoxime of azodicarboxylic acid and theammonium salt of di-isonitrosotetrahydrotetrazine.2By the action of alkalis on the hydrobromide of dihydroxyguanidine,Py~ones and Xanthone Derivatives.The pyrones themselves have been referred to a t some length earlierin this Report, and there is not much to add with reference to thesyntheses and characteristic reactions of these compounds.F.Feist and E. Baum 3 confirm the experience of previous workersas to the difficulty of introducing substituents into the pyrone ring,although pyromeconic acid (3-hydroxypyrone) readily gives 2-halogensubstituted derivatives.Maltol (2-methyl-3-hydroxypyrone) andmeconic acid (3-hydroxypyrone-2 : 6dicarboxylic acid) resist bromina-tion, but pyrone may be made to yield 2 : 6-dibromopyrone by warmingpyrone with bromine to which a little iodine has been added ; whilstdiethyl dibromochelidonate is obtainable from bromine and ethylace t onedioxala t e,C,H,*CO,*$XO ~O*G02~C,H,CH,*CO* CH, + 2Br, =C,H,* C02*f-0-;Ci*C0,*C2H5BrC*CO* C-Br 2HBr + H20 +C. Bulow finds that ethyl phthalylacetoacetate gives a coumarinderivative having the formula Cl8HI2O6 when condensed with re-sorcinol,* and conjointly with C.Sautermeister 5 has extended hisTrans., 1905, 87, 1854.Ibid., 474.3 Ber., 1905, 38, 1443.Ibid., 1904, 37, 4715.Ibid., 3562ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 157previous work on the synthesis of Nencki and Sieber's resacetein.' Thesynthesis of the last-named compound was effected by condensation of2 : 4-diethoxybenzoylacetone with resorcinol by means of hydrogenchloride in acetic acid solution, the resulting oxonium salt being nexthydrolysed.o*c1 0 O HFurther compounds of the same class have been prepared byreplacing the resorcinol by phloroglucinol and pyrogallol.The preparation of xanthone derivatives has been rendered easierby the new synthesis of o-aryloxybenzoic acids described by F. U11-maim and M.Zlokasoff.2 These authors find that substances such assodium phenoxide react readily with sodium o-chlorobenzoate underthe influence of copper powder, the chlorine being replaced by anaryloxy-group. Aniline in place of the sodium phenoxide gives adiphenylaminecarboxylic acid which readily condenses to acridone asphenylsalicylic acid does to xanthone.E. Heintschel has studied the synthesis of fluorone derivatives from1 : 2 : 4-trihydroxyphenol,3 two molecules of which react normally withone molecule of m-nitrobenzaldehyde. Similar reactions take place with5-nitro- and 5-bromo-salicylaldehydes, although with the last-namedcompound the reaction also takes a different course, one molecule ofeach component condensing in the following manner :The reactions of oxonium salts are in many cases very similar tothose of quaternary ammonium compounds, and A.Robin finds thatthe oxonium bromide corresponding to dinaphthopyranol reacts withaniline much as rosaniline salts react with metallic cyanide^.^I n the fluorescein group, R. Meyer and H. Pfotenhauer find thatphenolphthalein and quinolphthalein give fluorescein on heating withresorcinol ; the reaction is not, however, reversible, since no phenol-J. pr. Chem., 1881, [ii], 23, 541.Ibid., 2878.Ber., 1906, 38, 2111.Conzpt. rend., 1905, 140, 1644158 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.phthalein is produced by heating fluorescein with a large excess ofphenol.1M. T. Bogert and R. G. Wright have prepared and examined atlength the fluoresceins to be obtained from resorcinol and the nitro-phthalic anhydrides ; the amino-compounds obtained on reduction aremarkedly fluorescent.2H. V.Mitchellhas found that salts of benzeneazocoumarinic acid immediately givethe corresponding azocoumarins on acidification.3Only little has to be added with regard to coumarins.Unc I assije d Compounds.The anhydrides of dibasic acids and y-lactones may call for a fewpassing remarks, as they cbntain the same skeletal structure as furfuran.H. Stobbe4 and his pupils (Leuner, Eckert, and Kullenberg) continuetheir researches on the ‘‘ fulgides,” derivatives of the anhydride of astill unknown butadiene-py-dicarboxylic acid,>o CH,:Y*COCH,:S*COMost of the acids are colourless; the anhydrides are colourless if thehydrogen atoms of the methylene groups are replaced by alkyl radicles,but aromatic radicles as well as the furfuryl group impart a yellowcolour which is deeper the greater the number of hydrogen atomswhich have been replaced.A six-membered ring containing both nitrogen and oxygen (lactone)has been produced by A.T. de Mouilpiedl by condensing ethylphenylglycinoacetate, C6H5*N(CH2*CO2*C2H5),, with benzaldehyde orethyl oxalate. The constitution assigned to the compounds obtained arerepresented by the formuleThe enolic constitution is assigned to the second substance onaccount of its giving no ketonic reactions, whilst ferric chlorideproduces a reddish-violet coloration ; it is precipitated from its etherealsolution by dry ammonia gas, and also reacts with phenylcarbimide.Ber., 1905, 38, 3958.Trans., 1905, 87, 1229.Ber., 1905, 38, 3673, 3682, 3893, 3897, 4075, 4081, 4087.Trans., 1905, 87, 435.J.Amer. Chem. SOC., 1905, 27, 1310ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 159F. R. Japp and J. -Knoxl have examined the two compounds,C15H9ON and C1,H,,O,N, obtained by Japp and Miller3 from one ofthe stereoisomeric cyanohydrins of phenanthraquinone. Both thesesubstances yield salts having the formula C,,HIoO,NNa, which,however, are not identical, the salt of the compound C,,H,ONregenerating the same substance when the sodium is removed. Con-sequently the authors formulate the substances asPhenanthranil. Hy droxydihydrophenanthranil.These constitutions can be made to account for the reactions of thetwo substances, but no notice has been taken of the fact that anthranildoes not result from the anhydridisation of anthranilic acid and mostprobably has the constitution0.Diels and R. van der Leeden have obtained derivatives of a ringcontaining three carbon, one oxygen, and two nitrogen atoms.,Hydrogen chloride acts on the monoxime of diacetyl, giving a salt,C,II,,O,N,Cl, from which the corresponding base, C6Hlo03N3, can easilybe liberated,The explanation of the reaction is given by the equationsI. CH,*CO.C(:NOH)*CH, + HC1= CH,*COCl+ CH,*CH:NOH.11. CH,*CO*C(:NOH)*CH, + CH,*CH:NOH + HC1=H20 + C,H,O,N,Cl,and confirmation has been afforded by the condensation of diacetyl-monoxime and acetyldioxime to the same compound, whilst benzaldoximefurnishes a corresponding substance, C,,H,,0,N2.The condensationprobably takes the course represented by the equation7H3 co QH2C*OH/H O\/0Walter Peters 4 has examined Camp's trimethylenetrisulphone inorder to see if it is a pseudo-acid; a comparison of the degree ofTrans., 1905, 87, 681.Ber., 1905, 38, 3357.Ibid., 1892, 25, 234.Ibid., 1887, 51, 29.Ibid., 2565160 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.hydrolysis of its salts with the electric conductivity of the sulphonehas been impossible, however, owing to the insolubility of the lattersubstance.Compounds of the type of benzophenonesulphane have been preparedby the condensation of diarylsulphone-o-carboxylic acids.F. Ullmannand A. Lehner find that diphenylsulphone-o-carboxylic acid is readilyobtainable by the condensation of the potassium salts of o-chloro-benzoic and benzenesulphinic acids, copper powder being used ascatalyst.Some singular derivatives of o-benzoic sulphinide (saccharin) havebeen described by F. D. Chattaway2 in pursuing his work on nitrogenchlorides :This N-chloro-saccharin gives a dipotassium salt,The first of these two formuls is probably correct, as with excess ofpotassium hydroxide no o-aminobenzoic acid is produced.Derivatives of a new heterocyclic complex, phenothioxin, are describedby F. Mauthner ; 3 the dinitro-compound being obtained by the actionof picryl chloride on disodium monothiocatechol,The reaction is based on G.S. Turpin's oxazine ~ynthesis,~ and thedinitrophenothioxin may be oxidised to a sulphoxide and a sulphone.S. J. M. Auld and A. Hantzsch5 have examined the substanceobtained by J. E. Reynolds 6 by dissolving mercuric oxide in alkalineaqueous acetone. This compound furnishes salts of the typeC6H,,Hg303X2, and therefore probably contains two hydroxyl groupsattached to mercury. Since i t is indifferent to hydroxylamine andphenylhydrazine, the authors formulate its production from the firstformed dimercuric acetone hydrate in the .following manner :Hg*OH Hg*OHHg-OH I I2 HY<Hg.oH = HgO + H,O + HC--Hg-CHCH,-C(OH), CH,*b(OH)*O *(HO)*&-CH3Trans., 1905, 87, 1882.Bur., 1905, 38, 2677.Ber., 1905, 38, 729.Trccns., 1891, 59, 714.Ber., 1905, 38, 1411.Zeit.Chem, 1871, 254ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 161J. Thiele and W. Peter obtain a chloroiodofumaric acid by theaction of iodine chloride on acetylenedicarboxylic acid.1 The iodoso-chloride produced from this contains two, instead of three, chlorineatoms, and hence the acid and the derivative obtained from it by lossof carbon dioxide we formulated respectively asc 1 c-co c1 c co\1 ) >O and I 1 /o H02C*C-I-C1 H*G-I-ClAlkaloids.K. Loffler2 finds that the product obtained by WertheimS bydehydration of conhydrine consists largely of solid, secondary, un-saturated /3-coniceine, whilst y-coniceine occurring in hemlock is,according to J. von Braun and A. Steind~rff,~ a-propyltetrahydro-pyridine, for, when benzoylated by the Schotten-Baumann method,benzoyl-4-aminobutylpropylketone is pr~duced.~ The anomalousbehaviour of 7-coniceine on alkylation is largely explained by theformula proposed.A4ccording to Am6 Pictet,6 some N-methylpyrrolidine is producedwhen nicotyrine is prepared from nicotine with silver oxide,7 but thefate of the pyridine nucleus is unknown.Sparkine has been oxidised by R.Willstatter and W. Marx,S whoconclude i t contains the groupingC > ~ ~ * ~ ~ < , Cand Ahren’s oxysparteine, C,,H2,0N2, is regarded, not as an aldehyde,but as an oxide of the cineol type. I f so, the molecule should containtwo tertiary GCH groups ; this structure is also required by the formulawhich Moureu and Valeur have prop~sed.~ The latter authors, takinginto account that sparteine is a bitertiary amine, and that degradation byHofmann’s method leads to a base, N321,H2s, combined with an assumedequivalence of the nitrogen atoms and bridged rings in the nuclei, are ledto assign (with all reserve) one of the following constitutions to sparteine :CH CH OH CHN N N N \I/Ber., 1905, 38, 2842.Ibid., 3326.Annalen, 1856, 100, 75. Ber., 1905, 38, 3094.Compare Lipp and Widnmann, ibid., 2471. BCr., 1905, 38, 1951.8 Bid., 1905, 38, 1772.Bull. Xoc. chim,., [iii], 33, 1234, 1237, 1244, 1252, 1255, 1266, 1274.7 Ibid., 1894, 27, 2537.VOL. 11. 162 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.I n the quinine group, G. Rohde and G. Schwabl have furtherexamined the isonitroso-derivatives of cinchotoxine and quinotoxine,,and P.Rabe and K. Ritter3 find that meroquinene derivatives arereadily obtained by application of the Beckmann reaction to isonitroso-methylcinchotoxine, cinchonic acid and the nitrile of methylmero-quinene being produced,FH,*yH-QH* CHI CH, YH2* ~H-~H*CH:CH,F(:NOH)*CO YH2 YHz - ?‘,IF +CN 9H2 5!H2C9HfP CH2-N*CH, CJ%* CH,--N*CH,W. Koenig and K. Bernhart * have synthesised an inactive P-ethyl-quinuclidine which so much resembles the active form obtained byreduction of ethyl cincholeuponate as to leave but little doubt thatmeroquinene, cincholeupone, and cincholeuponic acid are to be representedrespectively asQH2*COzH QH2* CO, H YH2* C0,HYH, YH*CH:CH,, $!H, FH*C,H,, $!H2 YH*CO,HCH, CH, CH, CH, CH, CH,PH\ PH\ PH\\NH’ “H’ “H’The action of hydrogen peroxide on strychnine furnishes a strychnine-oxide, C,,H2,03N2 + 3H,O, which A.Pictet and M. Mattisson findbelongs. to the group of oxamines,5 whilst A. Bacovescu and A. Pictethave examined Gal and Etard’s ‘‘ hydrates ” of strychnine obtained by theaction of baryta water.7 The later work of Loebisch and Schoop * andTafel9 did not altogether elucidate the reactions taking place, butBacovescu and Pickt have now established the following geneticrelationships :IIzO or Ba(OH)2 isoS trychnine, -+ ------ Strychnine,(c,H,,oN)<~ + H,O.NaO’C2115 + NaO’CgHsisoStrychnic acidStrychnic acid or strychnol, (dihydrostrychnine),* Ber., 1905, 38, 306. See aIso Ber., 1900, 33, 3217, 3221, 3234.Ibbid., 1G05, 38, 2770.Ibid., 3049.Ibid., 2762. Ibid., 2787.7 BulZ. SOC. chim., 1879, [ii], 31, 98.9 A~cnnlen, 1891, 264, 83.* Monntsh., 1886, 7. 83ORGANIC CHE MISTRY-HETEROCY CLIC DIVISION. 16 3New alkaloids of the aconite series have been discovered by W. R.Dunstan and A. E. Andrews.1 Indaconitine is obtained from " mohri "(Acoiziturn chasmanthum, Stapf), and bikhaeonitine from " bikh "(Aconitum spicaturn). Dunstan and Henry classify the aconitealkaloids, according to whether they yield benzoic or veratric acid onhydrolysis, in the following manner :Aconitine, C,,H,70,N(OCO*CH3)(O*C~3)~(~CO*~6H5).Japaconitine, C,1H,S03N(OCO*CH3)(OCH3)4( OCO* C,H5).Indaconitine, C,,H2702N( OCO * CH,)( O*CH,),(OCO C,H,).Pseudaconitine, C,,H,702N( OCO CH,) (0.CH,),( OCO C,H,[O* CH,],).Rikhaconitine, C21H270N(OCO*CH,)(O*CH,)4(OCO*C,H,[O*CH,],).The alkaloids of opium occupy increasing attention, and the existenceof a preformed oxazine (morpholine) ring in morphine, codeine, andthebaine seems to be definitely negatived. L. Knorr3 arrives at thisresult partially from the great difference in stability shown by thedihydro-P-naphthyl ether of ethanoldimethylamine (from naphthalan-morpholine),4 whilst he has also obtained a dihydrocodeinone isomericwith codeine by reduction of codeinone (C,,H,,O,N, the oxidationproduct of codeine) with stannous ~hloride.~ This dihydrocodeinoneis identical with the thebainone, C,,H210,N, produced when thebaineis heated with stannous chloride and hydrochloric acid at 100' (R.Pschorr).GKnorr and Pschorr have jointly examined the decomposition productsof thebainone and conclude it contains the non-nitrogenous nucleusHO/-*\ OH /-\-I-\ \-/ \ /\-/-The group *CH;CH,*N(CH,)* helps to form another ring, and fromthe proved constitution of papaverine the conclusion is arrived at thatthese three above-mentioned alkaloids contain the nucleus 7N/--\/-\ /\-/ \-//-\-/-'>M. Freund also comes to the conclusion that thebaine does notcontain a morpholine ring, * the reaction of thebaine with magnesiumTrans., 1905, 87, 1620.Ber., 1905, 38, 3143.BET., 1905, 38, 3171.Ibid., 1650.Annalen, 1899, 307, 172.Ibid., 3160.7 Ibid., 3172..?hid., 3234.M 164 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.phenyl bromide suggesting that a ‘c bridge ” oxygen atom has enteredinto reaction.Freund differs from Pschorr and Knorr in the positionhe assigns to the ring containing nitrogen, and suggests for thebaine theformula/CH*CHHCH-C \C-C-CH2*CH2-N(CH3)-CH. >CH---- \C H \ T L C ( \C( 0.C H 3)=CH-/0.CH3 \--o-’Jowett regards pilocarpine and isopilocarpine as being s tereoisomeridesland adduces evidence in support of his view ; of great importance arethe facts that the nitrates of the two bases give identical absorptionspectra and that the change from pilocarpine to isopilocarpine is revers-ible, a small amount of the former base being obtained when the nitrateof the latter is treated with caustic potash. Pinner does not hold withthe stereochemical view of the isomerism, for isomerism is only observedso long as the glyoxaline ring remains intact ; this portion of the mole-cule, however, allows of no stereoisomerism.2More recently, Pinner has prepared a new base, metapilocarpine,C,,H180,N2,by heating the pilocarpine hydrochloride for one to two hoursat 225-235q the product being dissolved in water and then treated with50 per cent.potassium carbonate. From the oil thus obtained, themetapilocarpine is separated by its insolubility in chloroform.3I n connection with work on pilocarpine, Jowett’s synthesis of 1 : 4 : 5-trimethylglyoxaline may be mentioned.*Pseudopelletierine is undoubtedly methylgranatonine,s and R. Will-statter and H. Veraguth have used methylgranatanine for the produc-tion of cyclo-octadiene.6$332-yH-$33, yH2* CH-YH, ?H,*CH:QHCH,-C H-CH2 CH,* CH: CR CH,*CH:CHThe latter is an easily polymerisable hydrocarbon.M.Freund and F. Mayer have reduced the methyldihydroberberineof Freund and Beck 7 to a methyltetrahydroberberine standing in anear relationship to corydaline.80. Fischer and C. Buck are continuing their work on harmaline,C,,H,,0N2, and describe several new derivatives of apoharmin,C,H8N2, and its monocarboxylic acid.9(C H3) OH7H2 T*CH, 7H2 -+ YH2 QH2 -+ YH2 7HZ.Trans., 1905, 87, 794. Ber., 1905, 38, 1510.Trans., 1905, 87, 405.G. Ciamician and P. Silber, Ber., 1892, 25, 1601 ; 1893, 26, 156, 2738 ; 1894,Ber., 1905, 38, 1975.Ihid., 1904, 37, 4673. Ibid., 1905, 38, 2652. L, Bid., 1905, 38, 329.3 Ibid., 2560.27, 2850 ; 1896, 29, 481, 490, 2970ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION.165Uric Acid Group.No new syntheses of importance are to be noted in this group.0. Diels and H. Heintzel have obtained hydantoin by the condensationof the sodium derivative of urethane with glycocoll ; 1 Behrend, Meyer,and Rusche have prepared two substances having the formulafrom glycoluril and formaldehyde ; 2 whilst Bartling shows that a sub-stance obtained by von Vogel on oxidation with nitric acid of a condensa-tion product, C,6H26011N12S3, of isodialuric acid and thiocarbamide is inreality dilituric acid, C,H,0,N3.3 0. Kuhling finds that derivatives ofdialuric acid may be obtained through the condensation of alloxan withc16H1S06N12 and ClSH1806N12ketones.CtiH,*CO*CH3 + CO<co.NH CO*NH>COSome very interesting results have been obtained by W.N. Hartleyin studying the spectroscopy of members of the purine group5 Thesimple ureides exhibit no selective absorption, which, however, occursvery markedly when two simple ureides are united by one or morepolyvalent atoms. The development of bands in their spectra is pro-duced amongst purine compounds if in the ring a C:O group is convertedinto an ethylenic linking and a C*OH group adjoining it ; the selectiveabsorption of purine compounds is more marked the greater the numberof C:O groups in the ring. Moreover, the formation of salts by addi-tion of alkalis intensifies the selective absorption. The author is infavour of the formulaCO*NH >c*N:c<c,.,,>co C*<N H* C( 0 *NH,)NH*CO--for murexide.Natural Colouring Matters.A new indigo synthesis is that of A. Salmony and H. Simonis, whofuse sodium dianilinomaleate with sodamide and a little caustic potasha t 200'.6The yield is not very good.Ber., 1905, 38, 305.Trans., 1905, 87, 1791, 1796,Anmlen, 1905, 339, 1.Ber., 1905, 38, 3003.6 Ber., 1905, 38, 2580.3 Ibid., 37166 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.W. P. Bloxam states that '' B. A. S. F. indigo pure " contains 91-99per cent. of indigotin, which he considers is best obtained in a pure con-dition by sublimation under reduced pressure.lDimethylenetetroxyindigo has been prepared by P. Herz, startingwith nitropiperonal and acetone.2C. Liebermann and G. Hase have examined the condensation pro-ducts of isatin with pyrrole,S on which but little work has been donesince their initial discovery by Victor Meyer.4 Pyrrole blue A has thecomposition C,,H,,O,N,, and pyrrole blue B is C,,H,,O,N,.Amongst the colouring matters of the flavone group, A. G. Perkin'swork on catechin and acacatechin must be mentioned.5 These twosubstances, although closely related, are quite different. On oxidation ofthe tetramethyl ethers the same products, veratric acid and phloroglucinoldimethyl ether, are obtained, so that out of the original five hydroxylgroups the positions of four are determined. The isomerism may well bedue to the place the fifth hydroxyl group occupies in the molecule, andPerkin suggests the formulaeOHHO/\"%H-----/-\OH and I I l(-JH.OH \-/\A/HO CH,OHas probable.A. G. Perkin has also examined cyanomaclurin, C1,H,,O,, a dyestuffof Indian jackwood (Artocarpus integrifoZia).G On fusion with causticpotash, phloroglucinol and /3-resorcylic acid are produced, which,taken in conjunction with the constant occurrence of morin with thedyestuff, renders the following structure probable :0 HOSt. von Kostanecki and S. Nitkowski have synthesised fisetin(3 : 3' : 4'-trihydroxyflavonol), starting with veratraldehyde and themonomethyl ether of resacetophenone ; 7 whilst Marie Breger and vonBer., 1905, 38, 2853.Ibid., 1883'16, 2640 ; 1884,17, 1034.Ibid., 1895, 67, 939 ; 1905, 87, 715.Tcrans., 1905, 87, 974.16S., 2847.Tram., 1905, 87, 398.7 B ~ T . , 1905, 38, 3587ORGANIC CHEMISTRY-HETEROCYCLIC DIVISION. 167Kostanecki describe a second synthesis of apigenin, the initial materialsbeing the dimethyl ether of 2 : 4 : 6-trihydroxyacetophenone andp-anisaldehyde.1 Von Kostanecki and his pupils have also prepared anumber of hydroxylated flavones, flavanones, and flavonols, using sub-stituted o-hydroxyacetophenones and benzaldehydes as initial products.2The methods adopted resemble those described a t some length in lastyear's Report, so that there is no need to enter into d e t a i l ~ . ~It is of interest that chroman,Lhe parent substance of the group, has been prepared by J. von Braunand A. Steindorff.4 o-Amino-y-chloropropylbenzene is diazotised andthe resulting chloropropylphenol heated with an alkali. Chroman isobt.ained as a colourless, strongly refractive oil, boiling a t 214-21 5'and having an odour of peppermint.J. T. HEWITT.Ber., 1905, 38, 931.Ann. &ports, 1904, p. 117.Ibid., 933, 935, 1507, 2177, 2748.Ber., 1905, 38, 850

ISSN:0365-6217    

DOI:10.1039/AR9050200129

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

STEREOCHEMISTRY.FROM the point of view of stereochemistry, the past year has beenchiefly interesting because of the great simplification which has beeneffected in the data relating to the configurations of quaternary ammo-nium salts; a year ago evidence seemed to be rapidly accumulatingwhich indicated that the stereochemical relationships of quinque-valent nitrogen compounds were of far greater complexity than has beenfound to be the case in connection with carbon compounds. The furtherinvestigation of the subject has resulted in a revision of certain of theexperimental data, and there now seems nothing to suggest that thestereochemistry of quinquevalent nitrogen and of tetravalent carbon in-volves considerations differing in kind. But whilst it is now probable thatthe study of the quaternary ammonium compounds will not immediatelylead to any profound modification of those principles which form thebasis of stereochemistry, a case has been fairly well established amongstcarbon compounds in which the stereochemical relationships cannot beimmediately reconciled with our present views concerning maleinoid 'andfumaroid isomerism. E.Erlenmeyer, jun., and A. Arnold have previ-ously 1 cited data to show that allocinnamic acid is really an externallycompensated mixture of two components possessing enantiomorphouslyrelated molecular configurations. Erlenmeyer has now extended hisprevious work and seems to have established that cinnamic and allocin-namic acids are each capable of resolution into two components of enantio-morphously related configurations.The author crystallised allocinnamicacid with brucine, separating about one-half of the acid as a crystallinesalt, and then liberated the acid from the latter ; the acid thus separatedmelts a t 58-59' and is obtained in enantiomorphously hemihedral crys-tals, and, from its crystalline form, seems to be identical with the iso-cinnamic acid which Liebermann extracted from the coca plant.Another and more soluble brucine salt was obtained crystalline fromthe mother liquors and yielded a cinnamic acid also melting a t 58-59'.The two brucine salts melted at 151' and 139' respectively and gave[a],, - 24-89' and - 1 3 ~ 9 8 ~ respectively, but the acid separated fromA m . Xeports, 1904, p.132.3 Ber., 1905, 38, 2562, 3496, and 3499STEREOCHEMISTRY. 169each was optically inactive. Although the specimens of allocinnamicacid separated from the two brucine salts have the same melting pointand are optically inactive, Erlenmeyer presumes them to be distinct sub-stances because of the great apparent differences between the brucinesalts from which they are derived. He concludes, further, that he hassucceeded in resolving aEZocinnamic acid into d- and I- components whichshould be represented by enantiomorphously related configurations.On crystallising cinnamic acid itself with brucine, two salts were alsoobtained. One melted a t 135" and gave [a]= = 0.0' in a 1 per cent.solution and +S.S2" in a 6 per cent. solution; the other salt meltedwith decomposition a t 111--113" and gave [.ID - 10.84' in a 1 percent.solution. The acid separated from both salts was opticallyinactive in an 8 per cent. solution and melted at 132-133' or 134'.The examination of the crystals showed, however, that both samples ofacids crystallise enantiomorphously and that one set of crystals is enantio-morphously related to the other. It seems thus clear that bothcinnamic and allocinnamic acids are externally compensated substancesand that each is divisible into two enantiomorphously related com-ponents.I n view of the very far-reaching consequences of these results, involv-ing, if they can be substantiated, a revision of our views as to theconfigurations of maleinoid and fumaroid compounds, it would beinteresting to have information on the following points.First, as towhether, on combining the four Erlenmeyer cinnamic acids with opticallyactive bases, four salts, distinguishable in crystalline form, specific androtatory power, c k . , are obtainable ; and, second, as to whether the solu-bilities of the parent cinnamic and allocinnamic acids are respectivelydifferent from those of the presumed enantiomorphously related com-ponents.The accomplishment by Marckwald 1 of a true asymmetric synthesisby expelling carbon dioxide from brucine methylethylmalonate by heat-when the valeric acid produced was found to contain an excess of theI-isomeride-has led to further work in the same direction. WhilstMarckwald obtained a valeric acid containing only 10 per cent.excessof the I-acid, S. Tijmstra, jun.,2 takes advantage of the fact that theloss of carbon dioxide is the result of a dissociation rather than of adecomposition, and heats the brucine methylethylmalonate in a vacuuma t 120' for a short time, instead of heating a t 170' under the ordinarypressure. The possibility of isomeric change affecting the result isthus diminished and the valeric acid separated from the product wasfound to contain 25.8 per cent. excess of I-valeric acid.The Marckwald method for effecting an asymmetric synthesis has beengeneralised by W. Marckwald and D. M. Paul ; 3 they show that advan-Ann. Reports, 1904, p. 133. Ber., 1905, 38, 2165. l b i d . , 810170 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.tage may be taken of the optical inversion which often occurs on heat-ing optically acti;e acids to convert the externally compensated acidinto one optically active component by directing the optical inversion.Thus, on heating dI-mandelic acid with an equivalent quantity ofbrucine at 150-160" for ten hours and subsequently separating the acidfrom the salt, i t is found to contain an excess of d-mandelic acid.This,therefore, forms a distinctly new example of asymmetric synthesis andone to which the objections formerly raised by Cohen and Pattersoncannot apply.McKenzie 1 observes that all commercial samples of fermentationlactic acid are optically active, some being lz~vo- and others dextro-rota-tory. He has accomplished a true asymmctric synthesis of I-lactic acidby reducing I-nienthyl pyruvate with aluininiuni amalgam-when un-equal amounts of I-menthyl d- and I-lactate are formed-and hydro-lysing the product with excess of alcoholic potash ; the potassiumlactate formed contains a preponderance of I-lactic acid.The work of McKenziez has been extended by McKenzie andThompson in a study of the optical inversion which occurs during thehydrolysis of I-menthyl and I-bornyl dI-phenylethoxyacetates, dl-mande-lates, dl-lactates, and dl-ethoxypropionates. On treating the esters witha quantity of alkali insufficient for complete hydrolysis, it is in severalcases observed that the initial hydrolysis product contains an excess ofthe Z-acid and that on hydrolysing the ester which has survived theinitial partial hydrolysis, t-acid is also found in preponderating quantityin the resulting acid.The interpretation of the observed result, that on partially esterifyingcertain dl-acids, such as dl-phenylethoxyacetic acid, with a I-basehydroxide, such as I-menthol, the unesterified acid is lmorotatory,whilst on hydrolysing the ester produced with caustic potash theZ-acid also preponderates in the regenerated acid, is somewhat asfollows.The velocity of formation of the ester, I-base, d-acid, isgreater than that of the ester, I-base, I-acid; consequently, after theinitial esterification stops for lack of sufficient I-base, the residual acidcontains the Z-acid in excess. The ester which has been formed contains anexcess of the component, I-base, d-acid, and as the latter, being the mostrapidly produced, is in general the most rapidly hydrolysed, it is thefirst component of the mixed esters to be hydrolysed on contact withthe strong caustic alkali. During the initial stage of the hydrolysis,the ester, I-base, d-acid, is preferentially hydrolysed and, since thecaustic potash is still strong, or since the concentration of the hydroxylions is still high, the liberated d-acid undergoes more or less completeoptical inversion.There is now left a preponderance of the ester,l'yans., 1905, 87, 1373.Trans., 1905, 87, 1004.Ann. Reports, 1904, I). 135STEBEOCHEMISTRY. 171I-base, I-acid, and t,his, being hydrolysed by the remaining weakalkali, in which the concentration of the hydroxyl ions is too small toeffect any appreciable optical inversion of the liberated acid, gives riseto a preponderance of the Z-acid in the final hydrolysis product.I nthis piece of work, just as in that of Marckwald and Paul abovedescribed, a true asymmetric synthesis has been effected.Hecombined methyl sulphide, methylethyl sulphide, and ethyl sulphidewith I-menthyl bromoacetate so as to obtain the I-menthyl esters of thecorresponding thetines ; the rotatory powers exhibited by the methyi-ethylthetine ester in various solvents are practically the means of thosegiven by the dimethyl- and diethyl-thetine esters in the same solventsFurther, on hydrolysing the esters and so removing the I-menthylgroup, inactive products were obtained. For these and other reasons,the conclusion is drawn that the two isomeric I-menthyl esters of d- andI-methylethylthetine are produced in equal quantities during thecondensation of the sulphide with I-menthyl bromoacetate.a method for ascertaining whether aparticular acid or base is externally compensated, which depends on thefollowing principle.When an externally compensated acid chloridecondenses with an externally compensated amine, two externally com-pensated acid amides are formed ; if, however, either the base or amineis not externally compensated but potentially inactive, only one ex-ternally compensated acid amide is produced. This method has beenapplied to a number of cases by E. Mohr.3Marckwald and R. Meth4 have succeeded in resolving several ex-ternally compensated acids and primary bases by taking advantage of thedifference between the velocity of formation of an acid amide between ad-base and d-acid, and between the corresponding Lbase and d-acid.Onheating dl-mandelic acid with I-menthylamine, d-mandelic-l-menthyl-amide is formed more rapidly than I-mandelic-Z-menthylamide, theratio of the velocities of amide formation being c = 0.862. Similarly,on heating I-quinic acid with dl-a-phenethylamine, Z-quinic-l-phenethyl-amide is the more rapidly formed (c = 0.878) ; the latter amide, whenliydrolysed by heating with hydrochloric acid, yields pure Z-a-phenethyl-amine of [a,] - 39*51°, together with a-chloroethylbenzene. The latterproduct is inactive, so that its formation is attended by optical in-version ; a number of derivatives of La-plienethylamine were examined.Objections have been raised by Kipping and Hunter to some of thestatements made in this paper.5A very convenient method for the production of resolution ofS.Smiles 1 has attempted an asymmetric synthesis of a thetine.Kipping described recentlyTrans., 1905, 87, 450.J. pr. Chem., 1905, 71, 305.€'roc., 1905, 21, 126.Axn. Reports, 1904, p. 145.Ber., 1905, 38, 801172 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.dl-a-phenethylamine has since been given by J. M. Loven.1 Theexternally compensated base is crystallised with I-malic acid, whena moderately soluble and well-crystallised d-phenethylamine hydrogenI-malate separates and a very soluble acid salt of the I-base remainsdissolved; the base is then separated from the mother liquor andcrystallised with d-tartaric acid, when I-phenethylamine d-tartrate iseasily obtained in a pure state.The properties of the base agreeclosely with those given by Marckwald and Meth.The selective action of enzymes on stereoisomeric, but not enantio-morphously, related substances has been long recognised, but with theexception of Fischer's classical isolation of I-fructose by the fermenta-tive destruction of the d-isomeride contained in synthetic dl-fructose,little has been done in the simple chemical treatment of externally com-pensated substances with enzymes. It has now been shown by E. Fischerand P. Bergell that the pancreatic ferment selectively hydrolyses theoptically active components of certain externally compensated dipep-tides ; synthetic dZ-leucine-Id-alanine is thus partially hydrolysed bypancreatine, yielding I-leucine and d-alanine.Indications of similarselective hydrolysis &ere obtained with synthetical externally compen-sated alanylleucine and leucylleucine. 0. Warburg also finds 3 thatpancreatine acts on externally compensated leucine ethyl ester withproduction of I-leucine, the d-leucine ethyl ester being left unattacked,H. D. Dakin has continued his investigation of the partial or selec-tive hydrolysis of externally compensated esters by lipase. On treatingthe methyl, ethyl, isoamyl, and benzyl esters of externally compensatedmandelic acid with lipase, the d-mandelic ester is hydrolysed and theresidue contains the I-mandelic ester.The hydrolysis of the esters ofexternally compensated methyl-, ethyl-, isoamyl-, and benzyl-mandelicacids by lipase proceeds in a similar manner, the d-acid being liberatedand the ester of the I-acid persisting. Lipase hydrolyses the esters ofexternally compensated methylphenyl-chloro- and -bromo-acetic acids,and ethylphenyl-chloro- and -bromo-acetic acids in such a way that theZ-acid is set free and the ester of the d-acid is unattacked. The lipasehydrolysis of esters of the externally compensated methylphenylmethoxy-acetic acid and ethylphenylethoxyacetic acid proceeds as in the case ofthe mandelic and alkylmandelic esters.After administering dl-tyrosine, dI-leucine, dI-aspartic acid, or db-glut-aminic acid to rabbits by the mouth, intravenously or subcutaneously,J.Wohlgemuth 5 finds that one component is more or less completelyexcreted in the urine, whilst the other, the one which is of naturalJ. pr. Chenz., 1905, 72, 307.Ibid., 1905, 38, 187.J. Physiol., 1905, 32, 199 ; see also ibid., 1903, 30, 253.Ber., 1905, 38, 2064.Ber., 1904, 38, 3103STEREOCHEMISTRY. 173occurrence, is assimilated by the organism. Thus, on administering&-tyrosine, the excreted material consisted of one-half dl- and one-halfd-tyrosine. dl-Leucine and aspartic acid appeared in the urine as thed-compo.nents alone, whilst dl-glutaminic acid was excreted as the Z-com-ponent alone.find that I-hyoscine and dl-hyoscineact similarly on the central nervous system in man and mammals and onthe motor terminations in the frog ; on the salivary glands and cardio-inhibitory fibres, I-hyoscine acts twice as strongly as the externallycompensated base.It is thus concluded that d- and I-hyoscines actequally strongly on the central nervous system, but that whilst I-hyoscineacts vigorously on the secretory or cardio-inhibitory nerve fibres, thed-isomeride has no such action.A. R. Cushny and A. R. PeeblesM. 0. Forster and H. E. Fierz have prepared2 a camphoryl-$->GO,CH-N(NH,)C(0H)-NH semicarbazide which has the constitution C8HI4< Iand is the first example of an optically active semicarbazide. Thissubstance should prove of service in the resolution of externallycompensated aldehydes and ketones, and the more so in that itspreparation offers no great difficulties.The semicarbazide gives[a],, - 8.9' in alcoholic solution and reacts with aldehydes and ketones,yielding semicarbazones which in many cases have very high rotatorypowers ; thus, the camphorylsemi-$-carbazones of cinnamaldehyde andp-benzoquinone give the values [MI, - 2051" and - 3310" respectively.Another method for resolving externally compensated aldehydes,ketones, and acids has been shown to be practicable by C. Neuberg andM. Federer ; they have prepared phenyl-d-amylhydrazine by the actionof d-amylbromide on sodiophenylhydrazine and have applied it to theresolution of dl-arabinose and dl-galactose by converting the latter intothe corresponding hydrazones.I-Arabinosephenyl-d-amylhydrazone isless soluble than d-arabinosephenyl-d-amylhydrazone. Racemic acidwas also resolved by converting it into a mixture of d- and I-tartaricphenyl-d-amylhydrazide, the former being the least soluble.I n view of the results obtained by Neuberg and Silbermann,* Frank-land and Done 5 have again investigated the production and propertiesof d-glyceric acid, preparing the material from externally compens;;ttudglyceric acid by four methods based on fermentation with the Bacillusethaceticws and resolution with the aid of brucine. The rotatory powersof the products obtained are in close agreement and show that Frank-land and Appleyard's earlier results are correct.6 Barium d-glyceratehas the specific rotatory power [ a]D + 1 0 .9 O in aqueous solution, andJ. Physiol., 1905, 32, 501.Bey., 1905, 38, 866, 868.Trans., 1905, 87, 618.Tram., 1905, 87, 826.Ann. Reports, 1904, p. 137.Bid., 1893, 63, 2991'74 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Neuberg and Silbermann's erroneous numbers were due to the use of afaulty instrument .1By subjecting nicotine to very careful purification, F. Ratz has suc-ceeded in increasing its specific rotatory power to a higher va@e thanhas been hitherto obtained, namely, [ alD - 169.54" at 20".Externally compensated bromopropionic acid has been resolved byE. Fischer and 0. Warburg ; 3 on crystallising the acid with cinchonineor strychnine, the salt of the Z-acid separates first, whilst if brucine isused, brucine d-bromopropionate is obtained as the least soluble salt.E. Buchner and R.von der Heide * have resolved trimethylene-iranns-1 : 2-dicarboxylic acid into its optically active components by crystalli-sation with brucine, quinine, and cinchonidine. The acid has [MID + or- 109.8". dl-Trimethylene-1 : 1 : 2-tricarboxylic acid was also resolvedby crystallisation with the same bases and gave [MID + or - 147.5'.Attempts to resolve synthetical trimethylene-cis-imns-1 : 2 : 3-tricarb-oxylic acid were not successful, as would be expected from the con-figuration of the acid.C. Neuberg and M. Silbermann find5 that the hydroxypyruvic acidwhich Will prepared from nitrocellulose is lzevorotatory, and there-fore cannot have the constitution which he assigned to it.It is alde-hydoglyceric acid, CHO-C€I(OH)*CO,H, and on reduction yieldsI-glyceric acid ; the hydroxynitrile formed from it gives I-tartaric andmesotartaric acids on hydrolysis, thus :TO*OH $?O*OHH0.Q.H H*f.'HO H*Y*OH ?H,-OHH* $!*OH H*$?*OH H-$?*OH H*$?.OHCO*OH CO OH CO*OH CO OHI-Tartaric acid. I-Aldehydoglyceric Mesotartaric acid. I-Glyceric acid.acid.As the configuration of I-tartaric acid is as given above, the con-figurations of the I-aldehydoglyceric acid and of I-glyceric acid must bealso as stated. The conversion of cellulose, a derivative of &glucose,into derivatives of I-glyceric acid is similar in kind to the conversion ofd-glycuronic acid into I-xylose and of d-galactose into I-sorbose.The labile dihydro-1 -naphthoic acid produced by direct reduction ofa-naphthoic acid has the constitution C,H,< CH(CO,H).~H, CH or CH---CH(Co2H)*fi" and by treatment with ca8ustic soda is converted CGH*<cH2- CII'I Zeit.physiol. Chem., 1905, 44, 146.3 AnanZen, 1905, 340, 168.Zeit. physiol. Chcm., 1905, 44, 134.2 Monntsh., 1905, 26, 1241.ti LIer., 1891, 24, 400.Bw., 1905, 38, 3112STEREOCHEMISTRY. 175C(C0,H):YHCH,-CH, into the stable A'-dihydro-1-naphthoic acid, CBHI<R. H. Pickard and A. Neville1 have resolved the labile acid bycrystallisation with I-menthylamine, when the salt I-B, d-A isobtained as the less soluble isomeride. A'-Dihydro-1-naphthoic acidmelts at 103", whilst the externally compensated isomeride melts a t93" ; the active acid gave [a],, + 212.9" in chloroform solution and itssodium salt gave the molecular rotatory power [MID + 374.6" in aqueoussolution.The investigation as a time reaction of the conversion ofthe sodium salt of the active labile acid into that of the potentiallyoptically inactive and stable A'-acid when treated with caustic sodashowed that the change takes place as a uniniolecular reaction; thisrcsult, although not decisive, favours the view that the formula firstgiven above correctly represents the constitution of the labile acid.J . Buraczewski and L. Marchlewski 2 have resolved externallycompensated methylmalic acid by crystallisation with strychnine ;strychnine d-methylmalate is more sparingly soluble than the salt ofthe Z-acid.By crystallising formyl-dE-leucine with brucine, E.Fischer and0. Warburg 3 have resolved it into the two optically active components.It is noted that whilst I-leucine of natural origin has a slightly bittertaste, the synthetical dl- and d-leucines have a distinctly sweet taste;dZ-forinylphenylalanine is also resolvable by brucine into its activecomponents.By heating optically active proteincystine,C H (N H2) (C 02H) CH2 S S CH,. CH (N H,) CO,H,with hydrochloric acid at 165", C. Neuberg and P. Mayer4 haveeffected its partial optical inversion. The product consists mainly ofexternally compensated cystine and not of the possible internallycompensated isomeride, because i t is acted on by AspwgiZZus nigev anda d-cystine left in the solution.A comprehensive and valuable compilation, which contains, however,a large quantity of original experimental data, has been presented byP.Walden on the subject of the rotatory power of optically activesubstances. The author reviews skilfully the work hitherto publishedon the various factors which influence the numerical values of the rota-tion constants and illustrates the great effect which the solvent exertson rotatory power by quoting new data for the rotatory powers of ethyltartrate, methyl malate, dimethyl d-bromosuccinate, methyl I-mandelate,and I-amyl alcohol in various solvents. He refers to those changes ofrotatory power with time which are attributable to tautomerism asTmn,s., 1905, 87, 1763.Rw., 1905, 38, 3997.Zcit. physiol. Chenz., 1905, 44, 410.Zeit.physiol. Chmn., 1905, 44, 498.5 Bw., 1905, 38, 345176 ANNUAL REPORTS ON THE PROGRESS O F CHEMISTRY.'' tautorotation " and expresses the view that tautomerism and tauto-rotation occur much more frequently than has hitherto been recognised.From a consideration of new determinations of the rotatory powers ofa number of esters in various solvents, the author concludes that theassociation of the dissolved optically active molecules certainly influencesthe rotatory power, but that this polymerisation or depolymerisation isnot the sole factor determining the change of rotatory power. I n a valu-able table are collected the rotatory powers of twenty-five substancesdetermined in different solvents, showing that the various solvents usedaffect the rotatory powers in a certain order; this order is stated below,and to the name of each solvent given is appended, first, the dielectricconstant, and, second, the association factor.Carbon disulphide, 2.64, 1.0 ; benzene, 2-25, 1.0 ; chloroform, 4-95,1.0 ; ether, 4.52, 1.0; ethyl acetate, 6.74, 1.0; ethyl alcohol, 25.9, 2.7 ;acetone, 20.7, 1.0 or 1.26 ; methyl alcohol, 33.2, 3.4 ; formic acid,57.0, 3.7; water, 82, 3.6.The large changes in value of the dielectric constant indicate theinfluence of the solvent on the rotatory power far better than thesmaller variations in the association factor; the former not only gives atrue measure of the activity of the solvent in influencing the rotatorypower, but also, as is shown by other tables, affords a measure of thechemical activity of the solvent as concerns tautomerising power, disso-ciating power, &c. One of the most important of Walden's conclusions,namely, that a relation exists between the osmotically determinedmolecular weight and the rotatory power of an optically active sub-stance dissolved in a particular solvent, has been since criticisedadversely by T.S. Patterson,l who draws attention to a number ofpoints relating to the rotatory powers and molecular weights of ethyltartrate and of methyl acetylmalate and malate in various solvents andconcludes that no recognisable relation of the kind referred to byWalden exists. It is, for instance, pointed out that although themolecular weight of ethyl tartrate changes rapidly with the concentra-tion in benzene solution, the rotatory power of the ester in this solventchanges but very slightly with the concentration, although the rotatorypower of ethyl tartrate differs considerably in different solvents.that the rotatory powerof menthol attains a maximum value of [MI, - 77.94' a t 58.3" ; a t35-2", the value is - 77-5S0, and a t 100' it becomes - 77-34'.The mole-cular rotatory powers of I-menthyl acetate, d-tartrate, and diacetyl-d-tartrate change more rapidly than this with temperature, but no pointsof maximum or minimum rotation were observed. I-Menthyl d-tartrategives [MI, - 287.2' a t 5.5" and - 264.2' a t 100' ; I-menthyl acetategives [MI, - 157.6' a t 13" and 155.6" a t 98.1' ; Z-menthyl diacetyl-d-T.S. Patterson and F. Taylor have shownBer., 1905, 38, 4090. T r a m , 1905, 87, 33STEREOCHEMISTRY. 177tartrate gives [MI, - 258.9' a t 14.4" and 227.S' a t 99.2". It is shownthat, reasoning by analogy, it is possible to trace the separate effects ofthe several optically active groups on the molecular rotatory powers ofthe esters. have also studied the rotatory powersof Z-menthol, Z-menthyl d-tartrate, and Z-menthyl diacetyl-d-tartrate whendissolved in ethyl alcohol, benzene, and nitrobenzene, and have obtaineddata confirming their previous suggestion that the rotatory powers andthe molecular solution volumes of an optically active substance in aparticular solvent are very closely related factors. Patterson has givena set of values2 relating to the rotatory power of ethyl d-tartrate inchloroform solution and shows that this solvent has a marked effect indepressing the rotatory power of the ester ; the changes in rotatory powerare in general agreement with the changes in molecular solution volumeof the dissolved substance.P. F.Frankland and N L. Gebhard3 have prepared the methyl,ethyl, propyl, butyl, heptyl, and octyl dimethoxypropionates by methyl-sting the corresponding esters of d-glyceric acid, and have studiedtheir optical activity. The dimethoxypropionates are all lzvorotatory,as are also the glyceric esters from which they are derived, but themolecular rotatory powers of the former have much the smaller values.I n both series, the molecular rotatory power attains a maximum valuein the normal series a t the amyl, hexyl, or heptyl ester. The rotatorypowers of the dimethoxypropionic esters diminish with a rise of tempera-ture, whilst the reverse occurs with the glycerates and diacetylgly-cerates.of theeffect of position isomerism on the rotatory power of substitutedZ-menthyl benzoates and confirm the previous conclusion, namely, thatthe introduction of an ortho-substituting group has the greatest influence,and that of a para-substituting group the least effect, on the rotatorypower ; the influence of a meta-substituting group is intermediatebetween that of the other two.I n the present investigation, the groupintroduced was a nitro-group.have prepared a number of estersof P-methyladipic and of y-methyl-a-alkyladipic acids for comparisonwith the corresponding esters of 4-methyl-3-cyclopentanecarboxylic acid,obtained from the former by closure of the open chain.It is noticeablethat ring formation greatly increases the rotatory power, the rotationsobserved for the esters of the methylpentamethylenecarboxylic acidbeing of the order of thirty times as great as those observed for theparent P-methyladipic esters. The introduction of alkyl groups into theThe same authorsJ. B. Cohen and H. P. Armes 4 have continued the studyA. Haller and M. DesfontainesTrans., 1905, 87, 122. Ibid., 313. I b i d . , 864.Ibid., 1190.Compt. rend., 1905, 140, 1205.Ann. Reports, 1904, p. 140.VOL. I1 178 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.l-position diminishes the rotatory power.J. Minguin contributes 1observations of the rotatory powers of the esters of amyl alcohol andborneol with succinic, fumaric, and maleic acids which show that thevalues obtained with the unsaturated acids are higher than those givenby the corresponding esters of the unsaturated acids.Employing the methods previously used, A. Klages and R. Sautterhave prepared the following optically active benzene derivatives :p-CHMe,*C,H,*CH:CH*CHMeEt, [ u]D + 41-89'.p-CHMe,*C,H,*CH,*CH,*CHMeEt, [ + 15.91'.o-E to* C,H,* CH: CH CHMe E t, [.ID + 40.97'.o-EtO*C,H,*CH,-CH,*CHMeEt, [a], + 14.99O.Attempts have been made by D. P. Brace 3 to ascertain whether therotatory power of a substance is affected by the polarised light raytravelling with or against the earth's rotation.Experiments made onoil of carraway indicated that if any change in rotatory power is thusset up owing to the drag of the ether, it is certainly less than one-five-millionth and probably less than one-ten-millionth part.I n an investigation into the effect produced on the rotatory powers ofof d-glucose and d-fructose by the addition of inorganic salts or electro-lytes, E. Rimbach and 0. Weber find4 that the greatest changes ofrotatory power are caused by the addition of zirconium salts or of saltslike borax, which undergo considerable hydrolytic dissociation ; thechanges do not proceed instantaneously, and are accompanied by somedecomposition of the sugar. Under otherwise constant conditions, thespeed with which the rotatory power changes appears to be propor-tional to the concentration of the hydroxyl ions.Most of the observedchanges in rotatory pdwer are to be traced, not to the formation ofadditive compounds, but to the influence exerted on the degree ofbreaking down of the sugar molecule by the added electrolyte. Thisis made clear by the study, as a time reaction, of the effect of causticsoda, sodium carbonate, and triethylamine on the rotatory power ofd-glucose. The effect produced by the addition of salts and alkalis onthe rotatory powers of d-glucose, d-fructose, and mannitol has also beenexamined by H. Grossmann.5 Grossmann and H. Potter 6 have given theresults of an extended investigation of the variations in rotatory powerof tartaric acid caused by the addition of molybdates and tungstates.The influence of addition of a number of organic and inorganic com-pounds to solutions of d-glucose on the rotatory power has also beenexamined by Ina A.Milroy.7Compt. rend., 1905, 140, 946.Ber., 1905, 38, 2312. Compare Ann. &epmts, 1904, p. 137.Phi.!. Mag., 1905, 10, 383. Zeit. physikal. Chem., 1905, 51, 473.Ber., 1905, 38, 1711. Ibid., 3438.7 Zeit. physikal. Chem., 1905, 50, 443STEREOCHEMISTRY. 179E. F. Armstrong, in continuing his studies on enzyme action, hasobtained important results relating to the synthetical formation ofbioses.1 He regards the process by which a-glucose and p-glucose areconverted into the stereoisomeric a- and p-methylglucosides as preciselysimilar to that by which a monose may be supposed convertible into abiose ; and, using the terms a and p to distinguish the glucosideswhich are hydrolysed by maltase and by emulsin respectively, he indi-cates that maltose is a glucose-a-glucoside, whilst isomaltose is pre-sumably the stereoisomeric glucose-p-glucoside.After allowing fuminghydrochloric acid to act on glucose in the cold, removing the acid, anddestroying the residual glucose by fermentation with Xacchccromycesinternaedians, a solution is obtained from which isomaltosazone can beseparated ; on removing the glucose by fermentation with SacchccromycesMarxicmus, which contains no maltase and is therefore without actionon maltose, the solution is found to yield maltosazone.It is thus clearthat during the condensation both isomaltose and maltose are produced,the former being obtained in much the larger quantity. By the actionof maltase extract on glucose, isomaltose is produced, and has beenseparated as isomaltosazone. On treating a concentrated glucosesolution with 2 per cent. of emulsin at 25' for two monthsand then destroying the unaltered glucose by the action of 8.Marxianus, a solution was obtained which yielded maltosazone andwhich underwent fermentation with a yeast containing maltase. Little,if any, isomaltose was produced during this condensation. The con-densation of glucose by means of emulsin thus leads to the syntheticalformation of maltose, but probably not of isomaltose. It is undecidedwhether the condensation by means of maltase of glucose gives rise tomaltose, in addition to isomaltose.A convenient method for preparingpure a- and p-methylglucosides in quantity has been given by E. F.Armstrong and 8. L. Courtauld.2C. Tanret 3 concurs in the view that the modifications of glucose,lactose, and galactose which he previously regarded as the p-forms, andwhich exist in the aqueous solution after the rotatory power has becomeconstant, are equilibrium mixtures of the true a- and p-forms. a-Glucose,a-lactose, and a-galactose change into the p-forms when heated a t loo",and on leaving a-glucose at the ordinary temperature the same changeoccurs very slowly. The a-forms of glucose and galactose are convertedinto the @forms when heated in aqueous solution, and the p-form isslowly but completely changed into the a-form by the action of smallquantities of water at the ordinary temperature.I n the case of thethree sugars named, the quantity-ratios in which the a- and /3-formsProc. Roy. Soc., 1905, 76, Series B, 592.Proc. Physiol. SOC., 1905, [iv].Bull. Soe. chim., 1905, [iii], 33, 337.N 180 ANNUAL REPORTS ON Tag PROGRESS OF CHEMISTRY.are present in the equilibrium mixtures are remarkably similar, namely,0.368 : 0.632, 0.376 : 0.624 and 0-354 : 0.646 respectively. The p-formsof glucose, galactose, and lactose have the specific rotatory powers[aID+ 19", + 51", and + 34.2" respectively in water.lThe interconversion of a- and P-methylglucosides in a methyl-alco-holic solution of hydrogen chloride has been studied as a time reactionby c'. L.Jungius.2 The speed of interconversion is approximatelyproportional to the concentration of the hydrogen chloride, and isgreatly diminished by the presence of water; the dynamical study ofthe reaction does not indicate whether the interconversion is direct asbetween the a- and /3-forms of the glucoside, or whether a third andintermediate acetal form plays a part in the change. The essentialcause of the mutarotation of sugar solutions lies in the change a Z p,and if accompanied by formation of a third hydrated aldehydic formthe concentration of the latter is always small. The velocity of inter-conversion of the methylgalactosides is six to seven times greater thanthat of the methylglucosides, and at 24' equilibrium is reached betweenthe isomeric glucosides and galactosides when 23 per cent.and 38 percent. respectively of the p-form is present.J. C. Irvine and A. Cameron3 obtained the same tetramethyl-p-methylglucoside by methylating P-methylglucoside and tetramethyl-glucose with silver oxide and methyl iodide. Tetramethyl-P-methyl-galactoside, identical with that previously described, was obtained bysimilarly methylating /3-rnethylgalacto~ide.~ The interconversion oftetramethyl a- and P-methylglucosides has been studied in severalsolvents, and in each case the presence of small traces of hydrochloricacid is requisite to the interconversion ; in methyl-alcoholic solution,the isomeric change of either modification into the other attainsequilibrium when 7'7 per cent.of the a- and 23 per cent. of the p-formare present, practically the same proportion as Jungius found in theequilibrium mixture of the a- and P-methylglucosides.J. C. Irvine and A. N. Moodie6 observe that on methylatinga-methylmannoside with silver oxide and methyl iodide in methyl-alcoholic solution or tetramethylmannose by heating with methylalcohol, a crystalline dextrorotatory tetramethyl-a-methylmannosideis the sole product. On treating tetramethylmannose with silver oxideand methyl iodide, a mixture of the above pentamethyl-a-mannosidewith an isomeric and 12evorotatory liquid tetramethyl-P-methylmanno-side is produced. The P-mannoside differs from the a-isomeridein that it is readily hydrolysed by dilute hydrochloric acid or byemulsin.1 Zeit.physikal. Chem., 1905, 53, 692.3 Trans., 1905, 87, 900.Ibid., 52, 97.4 Axn. Reports, 1904, p. 142.Trans., 1905, 87, 1462. Ibid., p. 143STEREOCHEMISTRY. 181G. Heikel finds 1 that in anhydrous pyridine solution galactose givesinitially the value [ a ] , + 170', and that this ultimately changes to+ 55.6'. I n boiling pyridine, galactose gives [ a],, + 31', and this valuegradually changes after cooling to + 59.3'. On acetylating galactosein pyridine solution a t Oo, an amorphous pentacetate, presumably thepreviously unknown a-acetate, is formed ; this gives [ u]= + 71 -8' inbenzene solution. On acetylating at higher temperatures in pyridinesolution, the known P-pentacetate of [a], + 59.2' in benzene solution isobtained, together with amorphous products having [a]= + 28.6' to+ 60.8' ; the formation of the latter substances is taken to indicate theexistence of a third or galactose-y-pentacetate corresponding to the alde-hydic form of galactose.Heikel favours the view that the aldohexosesowe their mutarotation to the existence of two interconvertible stereo-isomeric lactonic forms, the aldose form being possibly produced as anintermediate stage in the interconversion. R. Behrend regards the caseof glucose as probably similar to that of galactose, in that three modifi-cations exist, one having the aldose constitution. He shows that themutarotation of glucose is not due to hydration by investigating, as atime reaction, the change in rotatory power of a-glucose in pyridinesolution a t 0'; the change proceeds as a reaction of the first order,whilst if due to hydration it should proceed as one of the second order.H.E. Armstrong and W. Robertson 3 have prepared and examined anumber of hydrazones derived from camphorquinone, some of whichhave extraordinarily high molecular rotatory powers. Thus, the phenyl-methylhydrazone and the phenylbenzylhydrazone of camphorquinonegive the values [MI, 2430' and 2200' respectively. From a considera-tion of the rotatory powers, the magnetic rotations, and the colours ofthese and allied substances, the authors are led to suggest modificationsin the current mode of representing the constitutions of hydrazones,oximes, and diazo-compounds.They decide that the Hantzsch-Wernerhypothesis relating to the isomerism of tervalent nitrogen compoundscannot be upheld ; Hantzsch has replied to the arguments broughtforward.The study of the stereochemistry of quaternary ammonium deriv-atives has been actively pursued during the past year.Kipping has shown5 that the isomeric a- and p-salts preparedby the combination of d-chloro- and d-bromo-camphorsulphonic acidswith externally compensated and optically active bases do not, as waspreviously supposed, owe their formation to stereoisomerism amongstthe groups attached to the quinquevalent nitrogen atom. The produc-tion of the so-called a- and @salts is due to the occurrence of isomericor tautomeric change in the acid used ; it is concluded that the ions ofAnnnlcn, 1905, 338, 71.Ibid., 105. Trans., 1905, 87, 1272.4 Proc., 1905, 21, 288. Trans., 1905, 87, 628182 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the normal and iso-forms of the d-bromocamphorsulphonic acid have[MID + 280' and -t- 1'7'7" respectively ; the corresponding values for thechloro-acid are + 185.5' and + 233' respectively. Evidence pointingto the existence of normal and iso-forms of ordinary u-bromocamphor ofa similar nature has been also brought forward by Kipping.1has shown that the supposed P-phenylbenzylallyl-methylammonium iodide of Wedekind is really phenylbenzyldimethylam-monium iodide. At present, therefore, the only existing evidence indi-cative of isomerism amongst quaternary ammonium iodides is thatafforded by the production of d- and Z-isomerides of the asymmetricallysubstituted tetralkylammonium salts.The known facts are thereforenow all explicable on the assumption previously made that the fouralkyl groups attached to a quinquevalent nitrogen atom are situated a tthe corners of a square, whilst the acidic group lies at the apex of apyramid erected upon that square, the nitrogen atom being situatedwithin the pyramid.The optically active asymmetric nitrogen compounds originally pre-pared by Pope and PeacheyS have been again examined by A. W.Harvey 4 in order to ascertain whether the specific rotatory powers ofthe two enantiomorphously related phenylbenzylallylmethylammoniumiodides have actually the same numerical values, this point having beenleft in doubt by Pope and H a r ~ e y .~ The d- and Z-iodides now give thevalues [ a]D + 56.2" and - 56%O, agreeing therefore within the limits ofexperimental error. Harvey has succeeded in obtaining the four possiblesalts which can be formed between the d- and Z-bases and d- and Z-cam-phorsulphonic acids in a state of purity. E. Wedekind has preparedsolutions of d-phenylbenzylmethylallylammonium hydroxide from thecorresponding active iodide by Pope and Peachey's method, and findsthat the hydroxide loses none of its optical activity in dilute alcoholicsolution-even at 70" ; the solution on boiling gradually loses its activity,owing, not to optical inversion, but to decomposition. I n aqueous alcohol,the hydroxide has [MI, + 192-6', a value higher than that observed byPope and Harvey (166.4") for the ion of the active base in aqueoussolution.externally compensated isophenylbenzyl-niethylbutylammonium iodide by Pope and Peachey's method bythe use of silver d-bromocamphorsulphonate ; the salt of the Z-baseis the more sparingly soluble and the iodide gives [MID - 3 4 9 O inalcoholic solution.The active iodide undergoes optical inversion veryrapidly in chloroform solution. He has also resolved externallyH. 0. JonesWedekind has resolved1 Proc., 1905, 21, 125.3 Ibid., 1899, 75, 1127.5 Ibid., 1901, 79, 828.7 Ibid., 37, 3438.a Trans., 1905, 87, 1721.Ibid., 1905, 87, 1481.Ber., 1905, 38, 3933STEREOCHEMISTRY. 183compensated phenylbenzylmethylpropylammonium iodide by the useof silver d-bromocamphorsulphonate ; the salt, Z-base d-acid, is theleast soluble, and the iodide prepared therefrom shows [MID - 354O inalcohol, and very rapidly undergoes optical inversion in chloroformsolution.The following homologous series of optically active quaternaryammonium iodides is.now known :Phenylbenzylmethylammonium iodides., - \Ethyl. Propyl. isoPropy1. Allyl. isoButyl. isoAmy1.[RI], ... ... ... 30" 354" 428" 206.4" 349" 478"I n extension of his previous work,l H. 0. Jones has preparedmethyl-Z-amylaniline and combined it with methyl, allyl, and benzyliodides. He finds that in the case of phenylmethyl-Z-amylallylammoniumiodide two isomerides are produced ; these differ in rotatory power andsolubility.The rotatory power of one salt diminishes rapidly in chloro-form solution until it finally approximates to the value of that of theother salt, in which no change was observed. On combining benzyl iodidewith methyl-Z-amylaniline, a mixture of two isomeric a- and P-phenyl-benzylmethyl-Z-amylammonium iodides is obtained, and by convertingthe mixture into the d-camphorsulphonate and crystallising, a separationcan be effected. P-Phenylbenzylmethyl-Z-amylammonium d-camphor-sulphonate and a-phenylbenzylmethyl-Z-amylammonium Z-camphor-sulphonate were ultimately obtained in a pure state and the corre-sponding iodides prepared from them. The a-iodide melts a t 144-145"and has [ Q JD + 65' in chloroform solution, whilst the P-isomeride meltsa t 131-132" and has [ a ] D - 18.8' in chloroform solution ; both iodideschange in rotatory power in chloroform solution until a final value of[ a ] , + 2-75' is attained, owing to dissociation into benzyl iodide andtertiary amine.Results of a similar kind have been obtained by M. Scholtz3 incontinuation of those previously described.* He has prepared stereo-isomeric U- and ,%quaternary coninium salts in the cases of ethylallyl-coninium iodide, benz ylpropylconinium iodide, and benzylbutylconiniumiodide ; on heating benzyl-a-ethylconinium iodide a t 180-1 85",it melts and then gradually solidifies, becoming converted intothe P-isomeride melting a t 208'. The reverse change could not beeffected. The formation of Q- and P-isomerides was also observedduring the preparation of benz ylethylconhydrinium iodide, benzyl-propylconhydrinium iodide, and benzylisoamylconhydrinium iodide ;the isomerides differ in melting point, solubility and rotatory power,and in physiological activity. The occurrence of similar isomerism wasTrans., 1905, 87, 135.Ann. Beports, 1904, p. 146.A m . Reports, 1904, p. 140.3 Ber., 1905, 38, 595, 1289184 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.not observed during the addition of benzyl iodide to optically activeethyltetrahydroquinaldine.It is thus shown that when an optically active tertiary amine con-taining an asymmetric carbon atom combines with an alkyl iodide so asto give a quaternary ammonium salt, which also contains an asym-metric nitrogen atom, two optically active isomerides which are notenantiomorphously related are produced.Wedekind has ascertained that ethylenedikairolinium hydroxide isnot resolved by d-camphorsulphonic acid, but on fractional crystallisa-ation with d-bromocamphorsulphonic acid a fraction may be isolatedwhich yields an optically active ethylenekairolinium dibromide, showing[MI, + 150". Wedekind has thus prepared an optically active com-pound containing two asymmetric nitrogen atoms, just as Jones andScholtz have prepared active substances containing one asymmetriccarbon and one asymmetric nitrogen atom; these are, therefore, com-pounds of a similar type to tartaric acid, which owes its opticalactivity to the presence of two asymmetric carbon atoms.w. J. POPE

ISSN:0365-6217    

DOI:10.1039/AR9050200168

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY.IN reviewing the progress made during the past year in this branchof applied chemistry i t will perhaps be best to follow the general planadopted in my previous report, and to deal with the subjects underthe following headings :1. Inorganic chemistry, including electro-chemical methods.2. Organic analysis.3. Analysis of foods and drugs.4. Toxicological analysis.5. Apparatus.It will be obvious that in a review covering such a wide and variedfield a proper arrangement of the subject matter is of very greatimportance, arid after much consideration 1 have been led to adopt theabove division as lending itself most readily to methodical treatment,and as being open perhaps to the fewest objections. It isscarcely necessary to point out again that such a sub-division mustnecessarily ba to some extent of an arbitrary character, and in somecases it has of course been found difficult to decide in which of theabove categories certain processes should be included. I n lastyear’s report, I did not find it necessary to make any specialreference to Toxicological Analysis, but in the present one I havethought it advisable to deal with this branch of the subject in aseparate section, since, like Food Analysis, it has objects and methodsof its own.Inorganic Analysis.Owing to the comparatively restricted nature of the qualitativesection of this branch of analytical chemistry, useful discoveries arenecessarily rare, and there is as a rule but little of importance torecord.As an example of the increasing use which is being made oforganic compounds both for the detection and estimation of inorganicsubstances, reference may be made to the suggestion of Alvarezl toemploy sodium l-amino-~-naphthol-6-sulphonate as a more delicateCompt.rend., 1905, 140, 1186186 ANNUAL REPORT8 ON THE PROGRESS OF CHEMISTRY.test for potassium than even platinic chloride. It is interesting to notethat, under suitable conditions, ammonium and magnesium salts arestated not to interfere with this test. Trillat and Turchet 1 have deviseda method for the detection of traces of ammonia based on the productionof a black coloration or precipitat.e due to the formation of nitrogeniodide. I n order t o obtain the best results, iodine chloride in thepresence of an alkali is employed as the reagent, and it is stated that,whilst fully as sensitive as Nessler’s reagent, it possesses the advantageof being available in the presence of certain substances which eithermask or entirely’prevent the ordinary Nessler reaction.Blum 2 callsattention to a source of error which may easily occur in applyingthe ordinary routine procedure for the detection of metals, and whichis often overlooked. He points out that ammonium sulphide is proneto undergo oxidation to sulphate and that traces of barium andstrontium may in consequence be easily precipitated with the sulphidesof groups I11 and V. The importance of this fact in quantitativeseparations will be a ~ p a r e n t . ~ a-Dimethylglyoxime is suggested byTschugaeff 4 as a delicate test for nickel, and it is claimed that whenproperly employed it is capable of detecting one part of that metal in400,000 parts of water, and of affording certain indications whencobalt is present t o the extent of 5000 times that of the nickel.Onthe other hand, Pozzi-Escot points out that certain derivatives of thio-hydantoic acid yield characteristic reactions with cobalt salts and maybe usefully employed for the detection of that metal. Benedict 6 findsthat potassium periodate constitutes a convenient test for manganeseand for cobalt, and shows that by means of this reagent as little as 0.1per cent. of the latter metal can be detected in nickel salts. Conversely,a manganous salt serves as a delicate test for periodates in the presenceof iodates and iodides.Several new reactions of certain of the rarer elements which appearto be well suited for their detection have been studied during the yearand the following seem to be worthy of special notice.Melikoff andEltschaninoff 7 describe a reaction of columbium which is said to becapable of detecting as little as 0.1 per cent. of that element intantalum preparations, whilst Alvarez has investigated certainreactions of rhodium and osmium. In the latter case, the test, whichdepends on the formation of osmium hydriodide, is both character-isticand exceedingly delicate, and, conversely, osmic acid can be used as asensitive reagent for iodides, even in the presence of bromides andchlorides. The diphenylamine test for nitric acid has been further1 Bull.,906. ehim., 1905, 33, 304.5 Ann. Chim. anal., 1905, 10, 147.Zeit. amd. Chenz., 1905, 44, 9.Bcr., 1905, 38, 2530.Anzer. Chem. J., 1905, 34, 581.Compt. rend., 1905, 140, 1254, 1341.Bid., 7.J. Buss. Phys Chem. Xoc., 1905, 37, 99ANALYTICAL CHEMISTRY. 187studied by several chemists, and i t has been usefully pointedout by Frerichsl and by Bay2 that many oxidising agentsother than nitric acid produce the same coloration, and that onlyunder closely defined conditions can the test be regarded as a reliableone for nitrates. in which an attempt is madeto differentiate between nitrates and other oxidising agents is ofinterest in this connection. I n the field of quantitative analyticalinvestigation, perhaps no labour is so valuable and certainly none ismore meritorious than that involved in the re-determination or carefulrevision of important physical constants.As an example of suchwork, attention may be called t o a paper by Worden and Motion4giving the densities of solutions of sulphuric, hydrochloric, and oxalicacids and the corresponding percentage strengths. Every possibleprecaution to ensure accuracy appears t o have been taken, and fromthe tables given the '' correction factors " for standard solutions of theabove acids can be arrived a t with considerable ease, and apparentlywith great accuracy. Another paper dealing with the preparation ofstandard hydrochloric acid by a method based on specific gravitydeterminations has been published by Kuster and Munch5 and maybe found useful by chemists engaged in works.The question of theselection of a standard substance for the preparation of the solutionsemployed in acidimetry is perennial, and has been dealt with duringthe year by Sorensen and Andersen.6 The conclusion arrived at byLunge7 as the result of an investigation undertaken for the FifthInternational Congress of Applied Chemistry, that sodium carbonate isthe best of all hitherto studied substances, is dissented from by theabove authors, who again put forward claims on behalf of sodiumoxalate.8 It is pointed out incidentally that methyl-orange is not soindifferent to carbonic acid as is usually assumed. North and Blakey,gon the other hand, recommend the use of sodium bicarbonate, whichthey claim to have been able to prepare perfectly free both frommoisture and from the normal carbonate. For the estimation ofatmospheric carbon dioxide, Horace Brown and Escombe,lo propose anabsorption method based on a novel analytical principle, andwhich has the practical advantage of rendering unnecessary themeasurement of the volume of air employed in the determination.V.Knorre11 has further studied the application of alkaline per-sulphates to the separation of lead from other metals, and has shownA paper by HinrichsArch. Pharm., 1905, 243, 80.3 Bull. SOC. chim., 1905, 33, 1002.Ber., 1905, 38, 150.Zkt. nngew. Chem., 1904, 17, 225.J. SOC. Chem. bcd., 1905, 24, 395.Zed. anal. Chem., 1905, a, 88.Compt.rend., 1905, 140, 796.J. Xoc. Ch.enz. Ind., 1905, 24, 1T8.Zeit. anal. Chem., 1905, 44, 141, 156.8 Coinpare Sebelien, Chem. Zeit., 1905, 29, 638.lo Proc. h'oy. Soc., 1905, B, 76, 112188 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.that his previous criticism of Dittrich and Hassel’s method wasjustified, and that the precipitated lead peroxide cannot be completelyfreed from copper when that metal is present. Dittrich and Reiselrecommend the use of ammonium persulphate in acid solution as aprecipitant of lead, and claim that it is more rapid and convenientthan the ordinary precipitation by sulphuric acid with addition ofalcohol, and equally accurate. It seems clear, however, in view of theabove criticism by v. Knorre, that the method requires furtherexamination, more especially as t o the possibility of completelyeliminating other metals which may be present.Belton2 callsattention to the existence of a lead potassium sulphate, and suggeststhat its formation is sometimes responsible for high results when leadis estimated as sulphate in the presence of potassium salts. Friend 3has continued his study of the conditions necessary for the correctestimation of hydrogen peroxide in the presence of potassiumpersulphate, and has also studied those which must be observed ifaccurate results are to be obtained in the iodometric estimation ofpermanganate in the presence of persulphate. The estimation ofsulphur in pyrites is another perennial problem, and has been studiedduring the year hy H.S. Pattinson5 and by v. Knorre,G the latter ofwhom finds that the benzidine method suggested by Muller7 anddeveloped by Raschig is applicable when precautions are taken toneutralise the disturbing effects of the iron, and that accurate resultscan be obtained. The more general portion of this paper, which dealswith the estimation of sulphate in the presence of various metals bymeans of benzidine, will doubtless be read with interest by analysts.The iodometric estimation of combined sulphurous acid has been made;the subject of investigation by Ruff and Jeroch* and by Ashley,g bothof whom point out that the reaction is not so simple as has usuallybeen assumed, and that good results are only to be obtained by a verycareful regulation of the conditions.Rupp lo points out in reply to theadverse criticism of Ruff and Jeroch that those authors had notfollowed his instructions, and that his method of titration in thepresence of sodium bicarbonate does, when properly carried out, giveaccurate results. For the estimation of mixtures of chlorides,bromides, and iodides, Wentzki 11 has proposed a new method based onthe fact that alkali iodides and bromides are converted into chlorides bytreatment with mercurous chloride, and that an iodide is converted intobromide by means of mercurous bromide. The results are said to beBer., 1905, 38, 1829.Trans., 1905, 87, 1367.Chcm. News, 1905, 91, 191.Ibid., 738.Chem. I?zd., 1905, 28, 2. 5 J. SOC. Chem. Irid., 1905, 24, 7.7 Rer., 1902, 35, 1587.9 Amer.J. Sci., 1905, [iv], 19, 237 ; 20, 13.10 Ber., 1905, 38, 1903.S Ibid., 1905, 38, 409.l1 ,Yeit, angew, Chem., 1905,18, 696ANALYTICAL CHEMISTRY. 189accurate and the method appears to be susceptible of useful application.Tatlock and Thomson 1 describe a process for the determination of smallpraportions of bromine and chlorine in conimercial iodine, which theystate they have satisfactorily used for several years, and which appearsto possess advantages over the ordinary text-book methods. Jannaschand Jahn 2 have investigated the action of a number of '' reducing "agents on chlorates, bromates, and iodates, and find that a hydroxgl-amine salt is the most convenient reagent for quantitative use. Thissubstance has been previously recommended by S ~ h l o t t e r , ~ and althoughthe paper of Jannasch and Jahil contains much that is not new, it isnevertheless worthy of the attention of analysts. Meisenheimer andHeim4 describe for the estimation of nitrous and nitric acids, eitherseparately or when present together, a gasometric process based onthe evolution of nitric oxide when these acids are decomposed byhydrogen iodide and ferrous chloride respectively.The methodappears to be a very useful one, and, judging from the test analysesgiven, is susceptible of a high degree of accuracy. Simon5 has madethe interesting observation that hydroxylarnine can be accuratelyestimated in its salts by permanganate titration if an excess of sodiumoxalate is first added, the mixture behaving as if it were purehydroxylamine oxalate, and the disturbing effect of the acid radiclesbeing thus eliminated.Another paper by the same author dealingwith the action of permanganate on some hydroxylamine salts may beusefully referred t o in connection with this subject. I n a paper byReichard,7 attention is called to the solubility of lithium silicofluorideand to the possibility of employing that salt for the quantitativeseparation of lithium from sodium and potassium, and a method isdiscussed for the estimation of the three metals when present together.An accurate and simple method of quantitatively separating tin fromantimony is still a desideratum, and the method proposed by Vortmannand Metzl,s and depending on the precipitation of the antimony assulphide from a solution strongly acidified with phosphoric acid, willdoubtless be submitted to a thorough examination.Lidholm describesa method for the quantitative separation of silver and lead whichappears to yield very good results, and which depends on the reductionof the silver salt to the metallic condition by means of quinol. Thegravimetric estimation of bismuth as phosphate has been studied byStaehler and Scharfenberg,lo who show that under proper conditionsthis method not only gives accurate results for bismuth alone, but isJ. S'oc. Chcm. Incl., 1905, 24, 187.Zeit. anorg. Chem., 1904, 38, 184.Compt. m i d . , 1905, 140, 724.C7mn. Zcit., 1905, 29, 861.Be?.., 1905, 38, 566.Ber., 1905, 38, 1576.Ber., 1905, 38, 3834.Ibid., 659.8 Zcit.anal. Chew., 1905, 44!, 525.l o Lbid., 3862190 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.applicable to the separation of that metal From copper, cadmium,mercury, and silver. I n connection with this paper, which is deservingof tlie careful attention of analysts, a communicat.ion on the samesubject by Salkowski A most strikingexample of the way in which synthetical organic substances may beutilised in inorganic analysis is furnished by the observation of Buschthat the nitrate of diphenyl endo-anilodihydrotriazole is so sparinglysoluble in water that the base (known in commerce under the nameof “nitron”) may be employed for the gravimetric estimation ofnitric acid. Several acid radicles interfere with the application of thisreagent, but these can, as a rule, be easily eliminated, and as aqualitative test it is interesting to note that a reaction can be obtainedin solutions containing as little as one part of the nitrate in 60,000 partsof water.This interesting method has been investigated by G ~ t b i e r , ~who reports very favourably on it, and it is certain to be subjected torigorous examination by many other chemists.have again investigated the composition of theammonium phosphomolybdate formed by carrying out the precipitationunder certain defined conditions, and find that a compound of constantcomposition can be obtained in which the ratio of molybdic acid totriammonium phosphate is always slightly in excess of 12 mole-cules to 1. Jannasch has continued his able work on the quanti-tative separation of metals, and, in conjunction with his colleagues,has during 1905 studied more particularly the use of hydroxyl-amine and hydrazine for this purpose.In collaboration with Ruhl,Cohen, and S~hilling,~ he has found that many separations may beeasily and accurately effected by ammonia in presence of hydroxyl-auine, although it is difficult in some cases, as has been pointed outby Friedheim and Hasenclever,G to see in what way the new methodis superior to those in common use. It should be mentioned, too, thatthese observers question the possibility of effecting accurately someof the separations referred t o below. According to Jannasch and hiscollaborators, iron may be completely separated by the above reagentsfrom manganese and magnesium ; aluminium and chromium frommanganese, zinc, nickel, and magnesium ; copper from aluminium,chromium, and iron; iron from zinc, and thorium from uranium. I nsome cases, a single precipitation suffices, but in others a second isnecessary, and as a rule the estimation of the metal remaining insolution does not appear to be rendered appreciably more difficult bythe presence of the hydroxylamine.This base and hydrazine are alsowill be read with interest.Bitxter and GriffinBer., 1905, 38, 3943.3 Zeit. angew. Uhenz., 1905, 18, 494.J. pr. Chem., 1905, [ii], 72, 1-37.lbid., 861.Amer. Chem. J., 1905, 34, 204.Zeit. anal. C’hem., 1905, 44, 593ANALYTICAL CHEMISTRY. 191recommended by Jannasch and von Mayer 1 for the separation of goldfrom a number of met&, including those of tbe platinum group.Thepaper dealing with the latter subject is only a preliminary communi-cation, but the results appear to be of a very useful character, andthe further contribution which is promised will be looked forward towith considerable interest by all who are specially concerned with theanalytical chemistry of the so-called ‘( noble ” metals. Several pro-cesses, both gravimetric and volumetric, for the estimation of zinchave been submitted to a critical and comparative study by Nissensenand Ketternbei1,g and the paper containing the authors’ conclusionsand results is well worthy of attention. As another instance of usefulrevision work, attention may be called to a paper by Fernekes andK o c ~ , ~ giving the results of the comparative examination of a numberof volumetric processes for the estimation of copper.Kolb andAhrle4 call attention to the employment of certain organic acids asprecipitants for thorium, and especially recommend m-nitrobenzoicacid, a substance which has already been used by Neish5 for separ-ating thorium from cerium, lanthanum, and didymium. I n this con-nection, attention may be directed to a paper by Grossmann,F whoeffects a separation of the cerite earths from thorium and zirconiumby means of sodium sulphite, the last-named metals forming solubledouble sulphites on the addition of an excess of the precipitant. I na paper by B~5ard,~ the various gravimetric and volumetric processesfor the estimation of vanadium are criticised, and a new process basedon the precipitation of the vanadium by a-nitroso-P-naphthol is de-scribed.Two interesting and suggestive papers have been publishedby Glasmann dealing with the volumetric estimation of molybdenumand vanadium by titrating their reduced solutions with permanganate.The chief interest attaching to these communications centres in thefact that vanadium pentoxide is reduced to dioxide by zinc and hydro-chloric acid, but to trioxide when magnesium is substituted for thezinc. This fact supplies a striking illustration of the impossibility ofregayding ‘( nascent ” hydrogen as a definite chemical reagent andone which is independent of the source from which it is derived.There can be no doubt that in all such reduction phenomena the“ potential ” at which the hydrogen is formed at the metallic surfaceis an important factor, and as this is to some extent dependent on thenature of the impurities present and the proportions in which theyoccur, it is more than probable that differences will be noted not onlybetween different metals, but also between various specimens of theBer , 1905, 38, 2129, 2130.J.Anw. Chenz. Soc., 1905, 27, 1224.Anv. C l ~ f m . mid., 1905, 10, 41.Chem. Zeit., 1905, 29, 951.Zcit. nnycw. Chem., 1905, 18, 92.Zcit. aizorg. Chewz., 1905, 44, 229.BcT., 1905, 38, 600, 604.’ J. AwW. (%?na. Soc., 1904, 26, ’780192 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.same metal-that is, of course, assuming that these are not of a highdegree of purity.That this is at least a partial explanation of theso-called ‘‘ insensitiveness ” of zinc when used in the Marsh-Berzeliusflask for the detection of traces of arsenic has been shown by theauthor of this report, in conjunction with-H. D. Law, in a preliminarynote,l and the study of the reduction of molybdenum and vanadiumcompounds from this point of view is now being undertaken. Forthe estimation of the heptamolybdates, Glasmann has described anaccurate iodometric method which appears to be applicable also to theandysis of polytungstates. V. Knorre has applied the benzidinemethod t o the estimation of tungsten either in its compounds or intungsten steel, and finds that good results can be obtained. Thisappears t o be a useful process, and affords another example of the ser-vices which organic compounds are capable of rendering t o inorganicanalytical chemistry.This indeed constitutes one of the most promis-ing ifields of research a t the present time. Two papers by R o s ~ , ~dealing with cupellation and parting in gold ore assaying, will be readwith interest by all who devote themselves to this branch of analysis.Cantoni and Chautems5 have based on the volatility of a methylester of arsenious acid a method for separating arsenic from antimonywhich appears to be susceptible of useful application in toxicologicalinvestigations. The method is very similar in principle to that alreadysuggested by Friedheim and Michaelis for separating arsenic fromcertain other elements.Seemann’ has made a comparative andcritical study of the various methods which have been suggested forthe estimation of silica and fluorine and for their separation, andrecommends for the latter purpose the precipitation of the silica bymercuric ammonium carbonate. For the estimation of the fluorine,he finds that the methods of Fresenius, Brandl, Oettel, Carnot, andOffermann are all capable of giving good results. Schuchs hasalso investigated the various methods for the estimation of fluorineand favours those of Offermann and of Hempel and Schifferer. Theanalysis of natural silicates is frequently beset with many difficulties,and the errors inherent in the text-book methods when applied t o suchproducts are often far from inconsiderable.Jordis and Ludewigdeal with this subject in two papers which will be studied with interestby all chemists who have t o make such analyses, and in which theydiscuss a number of sources of error and indicate the precautionsAnalyst, 1905, 30, 306. Ber., 1905, 38, 193. Bid., 783.AT&. Sci. phys. nat., 1905, [iv], 19, [4], 364.Ber., 1895, 28, 1414.8 Zeit. Imad. Vcrsuch. Wes. Ost., 1905, 9, 531.Zeit. anorg. Chena., 1905, 45, 362 ; 47, 180.4 J. Chem. Jfetall. Mining SOC. S. Africa, 1905, 5, 165 ; 6, 36.7 Zeit. anal. Cheiiz., 1905, 44, 343ANALYTICAL CHEMISTRY. 193which must be taken if accurate results are to be obtained. For theseparation of silica from tungsten trioxide, as, for example, in theanalysis of silicotungstat es, Friedheim, Henderson, and Pinagelrecommend the volatilisation of the tungsten by heating to redness ina current of dry hydrogen chloride, a method which is said to givevery exact results, Spielmann describes the methods he has adoptedfor the analysis of graphitic silicon a.nd siloxicon.The siloxiconresults are interesting, as this substance, which is of some technicalimportance, does not appear to have been previously subjected to adetailed analysis.Although some very useful work has been done during theyear in the field of electro-chemistry as applied to chemicalanalysis, last year's rate of progress has scarcely been maintained.Every worker in this branch of analytical chemistry knows howgreatly success depends on the nature and arrangement of theapparatus employed, and it may not be out of .place therefore to callattention to a very useful paper dealing with electro-analyticalmethods by Puschin and Trech~insky,~ even although this appears tocontain very little that is really new.Perkiu and Prebble 4 aridRoot deal with the electrolytic estimation of cobalt; Lam andPerkin 6 with the estimation of antimony ; Jene with the estimationof zinc, and Spitzer8 with the electrolytic separation of copper andzinc from cyanide solutions. Chilesotti and Rozzi have studiedthe conditions necessary for the electrolytic estimation of molybdenumin solutions of molybdates. The employment of rotating electrodeshas marked a great advance in electro-chemical procedure, and anumber of estimations and separations which could not formerly becarried out electrolytically are now capable of being performed withease, rapidity, and accuracy.By the use of a rotating anode,DavisonlO has obtained very good results in the estimation ofcadmium and in its separation from magnesium and iron. The samemetal has also been submitted to a detailed electrolytic study byFlora,ll who, however, employed a rotating cathode in his experiments.R. 0. Smith l2 has obtained rapid and good results in the estimation oflead by using a rotating cathode, and of mercuryl3 by means of arotating anode. Kollook and E. F. Smith14 find that a number ofmetals can be very conveniently and rapidly estimated electrolytically1 Zeit.anorg. Chern., 1905, 45, 396.3 J. Rtcss. Phys. Chem. SOL, 1905, 37, 392.4 Trans. Faraday SOC., 1905, 1, 103.6 Trans. Farnday Sot., 1905, 1, 262.8 Zeit. Elektrochem., 1905, 11, 345, 351.9 Gazzetta, 1905, 35, i, 228.11 Amer. J. Xci., 1905, [iv], 20, 268.18 Ibid., 1270.J. SOC. Chem. Ind., 1905, 24, 654.J. Physical Che.m., 1905, 9, 1.Chem. Zeit., 1905, 29, 803.lo J . Arner. Chcm. SOC., 1905, 27, 1276.l2 J. Aazer. Chenz. Sos'oc., 1905, 27, 1287.l4 Ibid., 1255.VOL. 11. 194 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by using a rotating anode in combination with a mercury cathode. Inthis way, accurate results were obtained in a few minutes in the caseof zinc, copper, nickel, cobalt, chromium, and iron.Organic Analpis.There is as a rule but little of importance t o chronicle in the domainof qualitative organic analysis, many of the published papers dealingwith the detection of special substances which are frequently of butlittle practical importance, and being devoted to the description ofcolour reactions which often depend for their success on the purity ofthe substance to be tested for, a condition which is not easily observedin ordinary laboratory practice.Thus, Gutkin describes certaincolorations which are produced by the combined action of concentratedsulphuric acid and furfuraldehyde on a number of alcohols and otherhydroxylic compounds, whilst Alvarez records certain colour reactionsgiven by polyphenols and their isomerides. Aloy and Laprade2recommend the use of a neutral solution of a uranyl salt as a usefultest for the phenolic group, a reaction being obtained in all casesexcept when several negative groups are also present in the compound.For the purpose of distinguishing between primary, secondary, andtertiary alcohols, Sabatier and Senderens describe a simple methodbased on the catalytic decomposition of the alcohols b s heatedmetallic copper and the recognition by special tests of the resultingproducts. Scudder * has usefully compared the delicacy of the variousmethods which have from time to time been proposed for the detectionof methyl alcohol, especially in the presence of a large excess of ethylalcohol, and appears to favour the resorcinol test.I n regard toreactions of the carbohydrates, it will only be necessary to refer totwo communications, one by R.and 0. Adler on the furfurylanilineund other tests, and the second by Shermaq6 who has very carefullyworked out the conditions under which the Barfoed test must beapplied if it is to yield definite and useful indications. In connectionwith tests for special substances, reference may perhaps be made to apaper giving a characteristic reaction of ‘‘ stovaine,” by Zernik,7 andto one by Riedel 8 dealing with the identification of lecithin, as thesesubstances are of somewhat general interest. Green has publisheda most useful paper dealing with the identification of colouringJ. Pharm. Chim., 1905, [vi], 14.Ibid., 263.PJiiger’s Archiv, 1905, 106, 323.Amer. Sch. Mines Quarterly, 1905, 26, 169.Apoth.Zeit.,.1905, 20, 174.J. SOC. Dyers Col., 1905, 21, 236.Bzdl. SOC. chim., 1905, [iii], 33, 860.J. Amer. Chem. Soc., 1905, 27, 892.Ibid., 02ANALYTICAL CHEMISTRY. 195matters on animal fibres, which cannot fail to be of great assistance t ochemists who are concerned with this troublesome and complicatedbranch of analytical chemistry. For the estimation of certain organicdyes capable of yielding colourless leuco-compounds, Knecht andHibbert 1 recommend titration with titanous chloride, and show thatin a number of cases accurate results can be obtained. Dennstedt 2calls attention to the simplified method of elementary organic analysiswhich was first described by him in 1902.a He gives an account of adevice intended to prevent the formation of explosive gaseous mixturesin the combustion tube and points out that his process not only givesgood results with many organic compounds which are known to bedifficult of combustion, but also that it is applicable to a number oftechnical products which are very troublesome to deal with by theordinary method.It seems probable that before very long electricitywill replace gas in many laboratories as a source of heat in organiccombustion operations, and in the second of the papers by Dennstedtabove referred t o a special form of the Heraeus electric furnace isrecommended. Blount 4 has also called attention to the convenience ofelectric furnaces in many laboratory operations. In this connection apaper by Morse and Taylor 5 may be referred to, in which an electricalmethod for the combustion of organic compounds is described, whichis stated to possess several marked advantages over the ordinaryprocess, A method for enabling organic combustions to be performedautomatically is detailed by Pregl,6 who states that when using it nopersonal attention is necessary during the actual combustion process.Pringsheim and Gibson have modified the sodium peroxide process asdevised by the first-mentioned author for the estimation of halogeusin organic compounds in such a way as to render tLhe operation muchsimpler and less tedious.They find that accurate results .are obtainedby its employment in the case of refractory substances which are onlydecomposed with the greatest difficulty in the Carius method, and itseems clear that sodium peroxide is destined to be somewhat widelyemployed in the future in elementary organic analysis.For theestimation of sulphur, halogens, and phosphorus by the alkalineignition method, Sadtler recommends the use of a method involvingthe employment of two crucibles, the one within the other, whichrenders the method applicable to certain more or less volatilesubstances for which the simpler process is not available, and GarrettJ. Soc. Dyers Col,, 1905, 21, 3 ; and Ber,, 1905, 38, 3318,2 Chenz. Zeit., 1905, 29, 52 ; and Zeit. anyew. Chem., 1905, 18, 1134.a Zeit. anal. Chem., 1902, 41, 525.6 Amer. Chem. J., 1905, 33, 591.' Analysc, 1905, 30, 29,Ber., 1905, 38, 1434.' Amer.Chew%. J., 1904, 31, 386. Ibid., 2459.J. Anzcr. C?wm SOC., 1905, 27, 1188.0 196 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and Lomax have adopted a very similar method for the estimation ofsulphur in petroleum and bituminous minerals.It will be remembered that some difference of opinion has existedas to the applicabilityof the Kjeldahl method to the estimation of thenitrogen in such substances as creatine, creatinine, and lysine, bothSorensen and Pedersen and Gibson having maintained, contrary tothe statement of Kutscher and Steudel and others, that good resultscould be obtained. This matter has been further investigated bySorensen and Andersent who find that the above-mentioned andallied substances can be divided into two classes, those capable ofyielding a cyclic compound containing four carbon and one nitrogenatoms, and those containing or capable of forming rings with five carbonand one nitrogen atoms, such as pyridine, piperidine, and lysuric acid.Tho former can be accurately analysed by the ordinary Kjeldahlmethod, whilst the latter give low results, but yield the whole of theirnitrogen as ammonia when the process as modified by Gunning orArnold is employed.The bearing of these observations on theanalysis of substances containing or consisting of the decompositionproducts of proteids will be apparent. Flamand and Prager 5 de-scribe a modification of the Kjeldahl method which renders i tapplicable to the analysis of azo-, azoxy-, and hydrazo-compounds.For the estimation of nitrogen in amino-acids, Stangk has proposed agasornetric process based on the decomposition of nitrosyl chlorideby the amino-acids and the measurement of the evolved nitrogen,I n the case of glycocol, leucine, tyrosine, glutamic acid, and asparticacid, the results are very satisfactory, but it is unfortunate that underthe same conditions ammonium salts, gelatine, urea, and certain othernitrogen-containing compounds which of ten accompany the amino-acids in plant and animal products also yield some of their nitrogen.Betaine and some of the alkaloids do not, on the other hand,appreciably affect the accuracy of the method.For the estimation ofacetyl groups, Sudborough .and Thomas 7 propose a direct methodwhich is very simple and which is stated to give good results in anumber of cases.I n this connection, attention may be drawn to thecomplete paper on the same subject by A. G. Perkin* to the abstractof which brief reference was made in last year’s report. hasstudied the formation of tribromophenol bromide in Koppeschaar’sbromine method for estimating phenol and shows how the errors dueto this secondary reaction can be avoided. Leach and Lythgoe l o haveLloyd1 J. SOC. Chem. Ind., 1905, 24, 1212.3 J. Amer. Chem.. SOC., 1904, 26, 105.‘ Zeit. physiol. (%m., 1903, 39, 513.Zeit. physiol. Chem., 1905, 44, 429.6 Zeit. physiol. Chem., 1905, 46, 263.* Trans., 1.905, 87, 107.9 J. Awzer. Chem. SOC., 1905, 27, 7, 16. lo Ibid., 964.Bey., 1905, 38, 559.Proc., 1905, 21, 88ANALYTICAL CHEMISTRY.197based on the great differences in the refractive indices of ethyl andmethyl alcohols a very useful refractometric method for the detectionand estimation of the latter in the presence of the former. I nthis connection, attention may be directed to a paper by Fendler andMannich,l who claim that by distillation, oxidation, and the ap-plication of the morphine test as little as 0.5 per cent. of methyl alcoholin spirit preparations can be detected. It is worthy of note that theresorcinol method of Mulliken and Scudder has, with some modifica-tion, been officially adopted for the same purpose in the new editionof the United States Pharmacopeia.The assay of solutions of formaldehyde is a matter of some com-mercial importance, and both Williamshave devoted attention to the accurate estimation of that substance.The first-named author has investigated the best known processes andrecommends those of Romijn and of Blank and Pinkenbeiner ac-cording to the strength or purity of the solution under examination.Haywood and Smith have studied the latter process in detail andindicate the conditions which must be observed if uncertain resultsare to be avoided, whilst Fresenius and Griinhut 4 also review thevarious methods and arrive at substantially the same conclusions asWilliams.Instead of titrating the excess of alkali in the Blank andFinkenbeiner process, Frankforter and West 5 propose a gasometricmethod based on the measurement of the hydrogen formed in thereaction, which appears t o be capable of giving good results,alt,hough it does not possess any obvious advantages over the oldertitrimetric method.Messinger’s iodoform method for the estima-tion of acetone has been criticised by Vaubel and Scheuer,gwho recommend that the excess of iodine should be titrated witharsenious acid instead of thiosulphate, but Keppeler states that thelatter substance is capable of giving quite satisfactory results if stepsare taken to prevent the conversion of any of the t,hiosulphate intosulphate. The above papers are of special interest, inasmuch as theydirect attention to a matter of very considerable importance t o theanalyst in many connections, namely, the action of iodine on alkalis,a subject which has already been somewhat exhaustively dealtwith by Foerster and Gyr.8 Schultze has made a comparative study ofthe best known methods which have been proposed for the estimationof glycerol in soaps, fats, distilled glycerine, and other technical pro-and Haywood and Smithvers.Ges. deutscher. Natztrforseher ZG. Aerxte, 1905, Sept.J. Amer. Chem. SOC., 1905, 27, 596.Zed. anal. Chem., 1905, 441, 13.Zeit. angew. Chent., 1905, 18, 214.Zeit. Elektrochmn., 1903, 9, 1.Zeit, land. Versuch, Oest., 1905, 8, 155 ; and Chew. Zeit., 1905, 29, 976.Ibid., 1183.Ibid., 464.5 J. Anrcr. Chem. Xoc., 1905, 27, 714198 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ducts, and arrives at the conclusion that Zeisel nnd Fanto’s iodineprocess and the modified dichromate method of Richardson and Jaffb arethe most reliable.Shukoff and Schestakoff have proposed an extrac-tion method for the estimation of glycerol which has the merit of beinga direct process and which is stated to give good results.has tested this and speaks well of it. A number of papers onthe analytical chemistry of certain fatty oils has appeared during theyear, many of which, although useful, are scarcely of sufficient import-ance to justify special reference to them. Fendlers has examineda sample of sperm oil of undoubted genuineness, which, contrary tothe statements of several observers, yielded over 1 per cent. of glycerol.Should this result be confirmed, it is clear that the presence of suchproportions of glycerol cannot be taken t o indicate adulteration withfatty oils, as has been maintained by Benedikt and Ulzer.Rakusin 4gives the specific gravities and optical activities of a large numberof vegetable oils, and Lythgoe 5 has determined the more importantoptical properties of castor, cod-liver, and Neat’s foot oils. Fischerand Peyau 6 have investigated the Halphen reaction for cotton-seedoil and have come to the conclusion that the phytosterol test isthe only reliable one for detecting that oil in lard, inasmuch assamples of cotton-seed oil can be prepared which do not respond eithert o the Halphen or to the Becchi test. A paper by Suzzi 7 deals withthe use of mineral oil as a diluent in examining certain drying oils bythe Maumend test, and is devoted t o showing that olive oil is much tobe preferred for such purposes.Richardson and Hanson 8 have dealtwith the valuation of lubricants in a paper which contains somenew points, and which will be read with interest by chemists who areinterested in the examination of those materials. For the volumetricestimation of reducing sugars by Fehling’s solution, Ling and Rendlerecommend the use of ferrous thiocyanate as an indicator. Thata solution of this substance when properly prepared does constitntea most useful indicator is the experience of many who have triedit, and its employment very considerably increases the accuracy of thevolumetric method. Baker and Dick lo have submitted the osazonemethod of Grimbert for the detection of small quantities of maltose inpresence of dextrose to a critical examination, and find that even whenimproved i t is not capable of detecting maltose with certainty whenthe proportion of that substance’falls appreciably below 15 per cent.LandsbergerZeit.angew. Chem., 1905, 18, 294.Chem. Xea. Fett. Ham Ind., 1905, 12, 150.Chem. Zeit., 1905, 29, 555. J. Buss. Phys. Chem. SOL, 1905, 37, 442.ti J. Amer. Chem. Xoc., 1905, 27, 887.6 Zeit. Nahr. Genzc’ssm., 1905, 9, 81.8 J! SOC. Chem. Ind., 1905, 24, 315.’ Boll. Chim Farnt., 1905, 44, 301.Analyst, 1905, 30, 182, lo Ibid., 79ANALYTICAL CHEMISTRY. 199of the mixed sugars. They find that the best results are obtained bytaking advantage of the selective fermentation brought about bySuccharornyces Marxiccnus. This yeast has been applied to theestimation of the.free sugars in starch-glucose syrups by von Raumer,1who calls attention to the marked effect produced on the so-calleddextrins in these products by the ordinary top-fermentation yeastfrom German breweries, and to the consequent inaccuracy of theresults obtained by fermentation methods in which such yeast hasbeen used.A paper such as this is very useful a t a time when thereis a tendency t o employ ‘‘ biological ” methods in the analysis of sugarproducts without any attempt to check the purity or even to ascertainthe precise chemical properties of the living ‘‘ reagent ’) employed..Ellett and Tollens2 have endeavoured to devise a method for theestimation of methylpentosan in presence of pentosans by separatingby means of alcohol the mixed phloroglucides obtained in the distillationmethod.Although the results are not altogether satisfactory, thsprocess constitutes an advance and may perhaps serve as the founda-tion of an accurate method. Van Ekenstein and Blanksma3 havedescribed methods for partially separating dextrose from lzevulose byconverting these sugars into their respective o-nitrophenylhydrazones.o-, m-, and p-Nitrophenylhydrazines can be used for the estimationof a number of aldehydes and ketones, and it seems probable thatthese substances will be found to be of further service in the analysis,qualitative if not quantitative, of sugar mixtures. An ever-increasingamount of attention is being paid to the chemical examination ofessential oils, and the number of papers dealing with this importantbranch of analytical chemistry and published during the past yearis very large.As a rule, however, the authors merely record thecomposition and analytical ‘‘ constants ” of new products or describenew forms of adulteration, and whilst such communications are oftenof the highest importance to those analysts who are concerned withthe testing and evaluation of essential oils they rarely contain matterof sufficient originality to justify special reference in a report whichhas necessarily to be kept within narrow limits. Much useful work ofthis character has been, as usual, carried out in Schimmel’s laboratoriesand is described in their half-yearly reports. Conduch64 finds thatmany aldehydes condense with isohydroxycarbamide, forming well-defined crystalline compounds, which should in some cases be ofservice in the detection and identification of some of the aldehydicsubstances occurring in essential oils.Romeo 5 has described a newiiiethod for the estimation of citral in lemon oil, depending on theZeit. Nalzr. Gemsfin., 1905, 9, 705.Rec. trav. chim., 1905, 24, 33.Chem. and Druggist, 1905, 77, 408.J. Landw., 1905, 53, 13.Conzpt. rend., 1905, 140, 434200 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.reduction of acidity which occurs when citral is absorbed by a solutionof potassium sulphite or bisulphite to which an excess of the acidsulphite has been added. The test analyses are good, and it is inter-esting to note that the results obtained by this method, when appliedto several samples of oil of lemon, support the contention of thosechemists who have consistently maintained that the 7 per cent.standard so long adopted by the Messina analysts is much too high.This appears t o have also been recognised by the authors of the newedition of the United States Pharmacopceia.I n this connection, apaper by Sadtlerl on the neutral sulphite method for estimatingaldehydes and ketones will be read with interest. It is noteworthythat the method of Romeo and the similar one of Sadtler are criticisedadversely by Schimmel2 on the ground that it is exceedingly difficultto get an exact end-point in titration. Bert6 hasalsoproposedanindirectpolarimetric method for the estimation of lemon oil aldehydes, whichappears likely t o be of use in the analysis of terpeneless lemon oils.Winton and Bailey4 describe a further modification of Hess andPrescott's method for the analysis of vahilla extract, whichappears to permit of the more accurate estimation of the coumarin.The employment of highly refined pine resin oil and other products ofvery similar composition to turpentine itself for the adulteration of thatsubstancehasin many cases enormously increased the difficulty of detect-ing sophistication, and the ordinary text-book methods which have beenfor so long in use are often quite inadequate.Fractional distillationunder reduced pressure followed by a careful chemical and physicalexamination of the various fractions must frequently be resorted to ifdefinite indications are to be obtained.Of several papers on thissubject which have appeared during the year it is only necessaryto mention two, both of which may be referred to with advantage.The first is by Valenta,5 who deals chiefly with the detection of rosinspirit and pinewood oils, and the second by Utz.6 The adulteration ofshellac with rosin has now reached such serious proportions that apaper by Langmuir,7 dealing very fully with the detection of suchadulteration, will be studied with much interest by all who are calledon to examine shellacs or the varnishes prepared from them. Themethod proposed in 1903 by Webers for the analysis of india-rubber andindia-rubber goods, which depended on the formation of a compoun'd ofcaoutchouc with nitrogen peroxide, has been further examined byHarries9 and by Alexander.10 Neither of these authors has been ableJ.Aneer. Chem. Sot., 1905, 27, 1321. Report, Oct./Nov., 1905.Chem. Zeit., 1905, 29,805. J. Amer. Chem. Soc., 1905, 27, 719.Chem. Zeit., 1905, 29, 807.Chenz. Rev. Fett. Barx I n d . , 1905, 12, 99.J. SOC. Chem. IrtTnd., 1905, 24, 12.Ibid., 1905, 38, 87.* Ber., 1903, 36, 3103.lo Ibid., 181ANALYTICAL CHEMISTRY. 201to confirm Weber’s statement as to the composition of the product,and it would seem therefore to be a somewhat risky process toemploy for the estimation of caoutchouc, although it appears to becapable of giving useful results in some cases. No year passeswithout a number of new alkaloidal colour reactions being described.Whilst some of these are often useful, the utility of many is fre-quently considerably diminished by the fact that the indications aremasked or rendered very uncertain by the presence of such traces ofimpurities as are usually present in the isolated alkaloids obtained inordinary laboratory practice.Reichard, who has manifested greatactivity in this department of analytical chemistry, describes newreactions for quinine and cinchonine,l for sparteine, nicotine, andconiine,2 and for aconitine,3 whilst Alvarez 4 also records a new testfor the last-mentioned alkaloid. The estimation of morphine, moreespecially in connection with the assay of opium, is a matter whichhas engaged the attention of numerous chemists, and the number ofprocesses put forward a t various times is very large.During thepast year, papers on this subject have appeared by A. &, A. Petit,6who deal with the method recommended for adoption as official in thenew edition of the French Codex and who agree with Dott andHesse as to the retention by morphine of 1 molecule of water ofhydration, even after prolonged drying a t looo; by Lenton,6 whodescribes a modification of the B.P. process, and by Mallinckrodt,jun., and Dunlap.7 The last-named authors, in a paper which dealsat some length with the chemistry of meconic acid and the meconates,describe a calcium ammonium meconate which appears to be formedduring the assay of opium by the U.S. Pharmacopaeia (1890) method.The chief importance of this observation to the analyst lies in the factthat this salt neutralises one-fourth as much acid as morphine itself,and that its presence consequently vitiates the titration results forthat alkaloid.Several papers on the estimation of quinine haveappeared, but these do not contain much that is new or of importance.Reference may perhaps be made in passing to the suggestion ofDuncan: that calcium hydroxide should be used in place of ammoniaas a precipitant for the alkaloid and for titration of quinine sulphatesolutions, as more accurate results are obtained. Keller’s method forseparating strychnine and brucine, and depending on the destructionof the latter alkaloid by sulphuric acid, has been studied by H o ~ a r d , ~1 Pharm.Zeit., 1905, 50, 314, 430.Pharm. Centr.-H,, 1905, 46, 309 ; 48, 385.Ibzd., 46, 479.J. Phnrm. Chim., 1905, 21, 107.Pharm, J,, 1905, 74, 652.Pharm. J., 1905, 74, 438.4 Compt. rend., 1905, 140, 1540.7 J. Anzer. Chem. SOC., 1905, 27, 946.9 Analyst, 1905, 30, 261202 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.who finds that if care be taken to keep the temperature sufficientlylow, good results are obtained and that any such modification of theprocess as that recently proposed by Gordin is not necessary. Thomas 1describes a method for estimating alkaloids which involves theirseparation by the ordinary potassium bismuth iodide reagent, andstates that when applied to the estimation of belladonna alkaloidsgood results were obtained.For the estimation of the activeprinciples of alder bark and cascara sngrada, Warin 2 describes acolorimetric method which appears to be useful.Stane‘k has continued his study of the potassium tri-iodide methodf o r the estimation of betaine, and finds that under proper conditionsit may be usefully applied to the examination of industrial sugarproducts. The procedure to be adopted for the separation of betainefrom other co-precipitated nitrogenous substances is described, andthe work appears appreciably to advance our knowledge of theimpurities present in certain products of the sugar factory. H. Wis-licenus 4 has further investigated the applicability of his highlyporous (‘‘ spongy ”) alumina to the analysis of tanning materials, andclaims that more concordant results are obtained than by the hide-powderprocess.This claim appears, however, to Paessler to need furtherconfirmation, and he suggests that the method should be submittedto a more thorough and searching investigation. I n this connection,it is of interest to note6 that the Commission appointed by theInternational Association of Leather Trades Chemists to investigate thecandle-filter method of Parker and Payne has reported in favour ofsubstituting such a filter for paper in the analysis of tannin solutions.Both the above matters are dealt with by Weiss,8 who criticisesWislicenus’ method adversely, and does not altogether approve theuse of a candle-filter. This paper also contains a criticism of Parkerand Payne’s titration method and a description of the author’s chromedhide-powder process as practised at the Vienna Research Institute,Trotman and Hackford9 recommend the use of strychnine as aprecipitant of tannic acid, This suggestion marks a distinct advancein the analysis of tannin-containing materials, inasmuch as it involvesthe substitution of a definite chemical reagent for the indefinitematerials a t present employed.The further development of thiswork will be watched by all leather chemists with very considerableinterest.Ber. Deut. phnrm. Ges., 1905, 15, 85.J. Pharm. Chim., 1905, 21, 253; 22, 12.Zeit. Zuckcrind. Boh,m., 1905, 29, 410.Zeit. anal. Chem., 1905, 44, 96.Collegium, 1905, 46.Ibid., 301.Ibid., 1904, 249.8 Der Gerbcr, 1906, 31, 260, 275.9 J. floc. Chenz. Ind., 1905, 21, 1096ANALYTICAL CHEMISTRY. 203Analysis of Food and B m g s .Of all the articles which are, or may be, submitted to public analystsunder the provisions of the Sale of Food and Drugs Acts, milk is un-questionably the most important from the point of view of the well-being of the community, and a very special interest attaches thereforeto any investigation bearing either on its composition or on its analyticalexamination. I n reviewing the work of the past year in connectionwith this food product, a foremost position must be assigned to a paperby T. E. Thorpel on the analysis of samples of milk referred t o theGovernment Laboratory in connection with the Sale of Food andDrugs Acts, Such samples have, of course, invariably undergone moreor less decomposition when received, and it has naturally been ofimportance to determine whether that fact prevents a correct inferenceas to the character of the milk or interferes with a determination ofthe degree of sophistication to which it may have been subjected.Thecommunication in question deals very fully with the nature of themore important chemical changes occurring during the souring ofmilk, and contains an account of numerous experiments made for thepurpose of ascertaining the relation existing between the decompositionproducts present in any sample and the original milk constituentsfrom which they had been formed. As a result of this importantwork, it has been found possible to ‘ I reconstitute ” the original samplewith a remarkable degree of accuracy, and to obtain results in theanalysis of sour milks which agree very closely indeed with those givenby the same samples when in a fresh condition.I n connection withthe decomposition of milk and the est,imation of ammonia formed bythe decomposition of the proteids, reference may be made to a paperby Berg and Sherman.2 Another paper of importance to food analystsis Richmond’s annual communication on the composition and analysisof milk.3 I n this he states that the average percentage of fat in morethan 33,000 samples analysed during 1904 was found to be 3-74 percent., and of non-fatty solids 8-94 per cent. It is interesting to notein this connection that Billitz * finds almost exactly the same averageproportion of non-fatty solids (8.81 per cent.) in 187,610 samples ofLombardy milk analysed during the years 1892-1902 inclusive, butgives as the average fat percentage 3.55 per ceirt., which is a littlelower.Richmond’s paper above referred to contains some usefulinformation in reference to the estimation of milk fat by the Gerberprocess, and the attention of analysts may be directed to another com-Trans., 1905, 87, 206.3 Analyst, 1905, 30, 325.J. Amer. Chem Xoc., 1905, 27, 124.4 Milchw. Zentr., 1905, 1, 113204 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.munication by the same author and Goodson,l which indicates theimportance of submitting the amyl alcohol used in centrifugal methodsof fat estimation to a more searching examination than has hithertobeen considered necessary.Watts and Tempany find that certainconstituents of milk exert a retarding in3uence on the inversion ofcane sugar by means of citric acid, and that for the estimation of thatsugar in condensed milks and similar products it is necessary to pro-long the inversion period considerably beyond that originally recom-mended by Stokes and Bodmer. Owing to the comparatively largeproportion of the glycerides of volatile fatty acids in cocoa-nut oil, theemployment of that fat for the manufacture of margarine and for thedirect or indirect falsification of butter has very considerably increasedthe difficulties of the analyst. I n my previous report I called attentionto the methods of Muntz and Coudon and of Polenske for its detectionand estimation, methods based upon a differentiation of the volatileinsoluble from the volatile soluble fatty acids obtained in the Reichert-Meissl process.Experience of these methods has shown that they arecapable of yielding exceedingly useful indications in many cases ofadulteration in which the ordinary methods of butter analysis wouldhave been of little use, but a good deal of work still remains to be donebefore the problem can be considered to have been satisfactorily solved.The method of Polenske has been subjected to examination by H e s ~ e , ~who calls attention to several details of procedure which must be observedif uniform results are to be obtained, It is also pointed out that the" new butter value " is somewhat considerably affected by changes in thefeeding of the cows which scarcely affect the Reichert-Meissl value a tall.A very useful contribution to this subject comes from Kir~chner,~who has described for the estimation of butter-fat and cocoa-nut oil inmargarine a modification of the process first published by K. Jensen.5This is based on the different proportions in which octoic and butyricacids occur in the Reichert-Meissl distillates from the above fats, andon the comparative insolubility of silver octoate in water. It appearsthat this process has been for some time in regular use in a t least onewell-known continental laboratory, and it has been favourablyreported on and more fully worked out by 0. Jensen.6 It seems notimprobable that an extended investigation of the solubilities in waterof the silver salts of certain of the volatile fatty acids, separately andmixed, on the lines already followed by 0.Jensen7 would be ofconsiderable value in connection with the analysis of adulteratedbutters. The method of Jensen and Kirschner is, however, based onf Analyst, 1905, 30, 77.Milchw. Centr., 1905, 1, 13.Farm. Tid., 1903, 385.Zeit. Nahr. Genussin.., 1905, 10, 265.Ibid., 119.Zeit.. Nahr. Genussna., 1905, 9, 65.LOG. citANALYTICAL CHEMISTRY. 205certain well-defined differences in the chemical composition of theabove-mentioned fats, and further investigations on these lines aresure to be forthcoming, and will be studied with considerable interestwhen they appear.As a further contribution to the subject,Wauterslhas recorded the different appearances of the crystals of cocoa-nut oiland butter-fat as observed by means of the microscope with and with-out polarised light, Hoton2 has published a further paper dealingwith the application of the different solubilities of various glyceridesin acetic acid to the analysis of butter, and shows that usefulindications can be obtained. It does not, however, appear to besusceptible of application to the detection of cocoa-nut oil. For therecognition of small quantities of sesame oil in butter, Sprinkmeyerand Wagner 3 recommend an apparently useful procedure in which theSubstances giving the fjaudouin colour reaction are concentrated, andwhich is said to be capable of detecting as little as 0.1 per cent.ofsesame oil with certainty. The attention of food analysts may bedirected to a paper by Wesson and Lane4 on the analysis of lard. Itis true that this contains little that is novel, but it summarises veryusefully the methods which are capable of giving the most reliableresults, and contains an account of one or two which are better knownin America than elsewhere. Emmett and Grindley have shown thatthe lard obtained from pigs fed on cott,on-seed meal responds to anumber of the general tests for vegetable oils, and gives the moreimportant special reactions of cotton-seed oil. They also isolatedfrom such lards crystals resembling those of phytosterol, but Tolmsn,who has been working on the same subject,6 has been unable toconfirm this.The nature of the substance giving the red colorationin the very useful test bearing his name has been investigated byHalphen,7 who arrives at the conclusion that it is an unsaturated acid,and that the colour is not due, as has been asserted by Raikow, to theformation of a thio-derivative. Proctors has described a new andapparently exact method for the estimation of saccharin based on thefact that both the ortho- and para-benzoylsulphonimides liberateiodine quantitatively from a solution containing iodide and iodate ofpotassium. The increasing use of chemical substances for the pre-servation of articles of food, and the necessity of keeping a rigidcontrol over this practice in the interest of public health, has renderedthe detection and estimation of such substances an important part ofthe daily work of the food analyst.For the detection of formaldehyde in milk, new reactions have beenBull.Xoc. chim. Belg., 1905, 19, 6.Zeit. Nahr. Gewussm., 1905, 10, 347.J. Amer. Chem. Soc., 1905, 27, 263.Bzdl. Soc. chim., 1905, [iii], 33, 108.Xev. intern. Falsif., 1905, 18, 20.J. SOC. Chem. Id., 1905, 24, 714.Ibid., 589.Pram., 1905, 87, 242206 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.described by Utz,l Bonnet, jun.,2 N i ~ o l a s , ~ and others; but whilst asa rule great sensitiveness is claimed for these, it seems doubtfulwhether they possess any clear advantage over the well-tried methodof Hehner, or the similar one in which the sulphuric acid is replacedby hydrochloric acid.They may, however, be useful in certain casesas confirmatory tests. It may be noted that Lyons4 has modifiedHehner’s formaldehyde test in order to make it applicable to othersubstances than milk, and claims that by using beef peptone as theproteid material one part of formaldehyde in 4,000,000 can be detected.I n a paper on the colorimetric estimation of salicylic acid in food-stuff s,Harry and Mummery 5 describe a process which avoids the difficultyoften experienced in obtaining a good colour with ferric chloride, andwhich is particularly applicable to certain fruit pulps and other pro-ducts which contain appreciable quantities of tannin and similar sub-stances capable of giving colour reactions with the iron solution.Formany purposes, this method appears to mark a great advance on theordinary direct extraction with ether and light petroleum. Archil andcudbear are not infrequently used for the purpose of colouring articlesof food in cases where the use of coal-tar dyes is prohibited. Tolman6points out that these and other lichen colours may easily be mistakenfor the coal-tar dyes, and describes a method for distinguishing be-tween them. Several papers have appeared during the year dealingwith the analytical examination of vinegar, and of these referencemay be made to those of Froehner,7 Pastureau,* and Rossi9 The first-mentioned author records some analyses of wine vinegar, and pointsout that the presence of lactic acid in such vinegar affords a usefulindication of its origin and serves to differentiate it from vinegarsderived from other sources.The detection by Pastureau of appreci-able quantities of acetylmethylcarbinol in several samples o grainvinegar is interesting, but it may be doubted whether his suggestionof its bacterial origin is the correct one. Rossi calls attention to thefact already pointed out by Schidrowitz,lo that free sulphuric acid canbe directly titrated in vinegar, using methyl-orange as indicator, ifalcohol or acetone are first added. I n a paper by Windisch andRoettgen,ll attention is called to the appreciable volatility of lacticacid with steam and to the error thus introduced into the estimationof the volatile acids in wine by distillation, This property of lacticacid is also dealt with by Utz,l2 and is clearly of considerable import-Chem Zeit., 1905, 29, 669.Compt.rezd., 1905, 140, 1123.Analyst, 1905, 30, 124.J, Amel.. Chem. SOL, 1905, 27, 601.Pharwa. J., 1905, 75, 443.J. Aqner. Chem. Soc., 1905, 27, 25.J. Piznrm. Chirn., 1905, [vi], 21, 593.lo Analyst, 1903, 28, 233.la Chein. Zcit., 1905, 29, 363.7 Zeit. Nuhr. Genussrn., 1905, 9, 361.‘J Zeit. Ntchr. G B ~ I S S I I Z . , 1905, 9, 608.l1 Zeit. Xaiw. Gcmcssm., 1906, 9, 70ANALYTICAL CHEMISTRY. 207ance in view of the fact that, as a general rule, the non-volatility oflactic acid is assumed in analytical procedure. In the estimation ofglycerol in wines, Rocques 1 recommends the use of a mixture of alcoholand ethyl acetate for extraction, a mixture which, while dissolvingglycerol readily, is said to exert very little solvent action on theother wine constituents.A modification of the alcohol-ether methodhas also been proposed by Laborde.2 The estimation of the so-calledhigher alcohols in potable spirits is an analytical problem beset withmany difficulties, and one which has certainly not been as yet satis-factorily solved. Schidrowitz and Kaye have very usefully under-taken a critical examination of several of the better known methods,and give the preference to the Allen-Narquardt process as being themost reliable. Beckmann's nitrite process is adversely criticised, butit is to be noted that Beckmann* has now modified his original method,which may consequently be capable of yielding more accurate results.A great advantage of the Allen-Marquardt process, however, consistsin the fact that the actual oxidation products of the higher alcoholsare obtained and can be used for purposes of examination or identifi-cation. Numerous papers dealing with the analysis of drugs havebeen published during the year, but these, whilst often very useful,are scarcely of sufficient general interest or importance to justifyspecial reference in this Report.I n view of the increasing importanceof adrenaline as a therapeutic agent, attention may be called to apaper by Abelous, Soulih, and Toujan 5 on the colorimetric determina-tion of that substance and its estimation in suprarenal glands.Bourcet describes a test which is capable of detecting as little as 2per cent.of antipyrin in pyramidone (dimethylamino-antipyrin), whichappears useful in view of the somewhat frequent adulteration of thelatter drug with the much cheaper antipyrin.A new gravimetric method for the estimation of pyramidone is alsogiven by Astruc and Phgurier,7 depending on its precipitation withpicric acid, and one for the approximate estimation of both drugs whenpresent together by Patein.* I n my previous report I had occasionto refer to the question of the detection of adulterants in cod-liveroil, a subject which, during the present year, has received someattention. Parry has published the tabulated results of the analysisof forty samples of known genuineness, and his numbers should beof value to analysts who are called on t o examine this oil.The methodsfor estimating the metallic iron in ferruru redactum, including that ofAnn. Chim. anal., 1905, 10, 306.AnaZyst, 1905, 30, 190.Compt. rend. Xoc. Biol., 1905, 301.Ann. Chim. anal , 1905, 10, 302, 392.tl Chon. andBruggist, 1905, 66, 491.Ann. Chim. and, 1905, 10, 340.Zeit. A'uhr. Genwssm., 1905, 10, 143.Bull. h'oc. chim., 1905, [iii], 33, 572.J. Phwnz. C ' h i i ~ , 1905, Lvi], 22, 5 208 ANNUAL REPORTS ON THE PROGRESS OF CHEMlSTRY.the German Pharmacopceia, are criticised in a paper by Christensen,lwho recommeiids a process based on the reduction of ferric to ferroussalt, whilst Barmwater advocates the employment of a gasometricmethod.Toxicologica I Ann Zysis.In this branch of chemical analysis there are only a few communica-tions to which special attention need be directed.The importantquestion of the destruction of organic matter as a preliminary to thedetection and estimation of inorganic poisons has received attention atthe hands of several investigators. It is clear that in some cases, moreespecially when arsenic and antimony have to be estimated, the employ-ment of boiling concentrated sulphuric acid, as in Kjeldabl's nitrogenprocess, presents marked advantages over the methods in general use,and both Norton and Koch and Grigorbeff 4 recommend this procedure,either with o r without the addition of nitric acid.For the estimation of arsenic in toxicological work, Mai 5 recommendsthe adoption of an electrolytic method, the organic matter beingcarbonised and partly oxidised by treatment with mixed nitricand sulphuric acids, and the arsenic separated from the dry carbonace-ous mass by distillation with hydrochloric acid in the usual way.Thearsenical distillate is then transferred to an electrolytic apparatusof special construction and the evolved gas passed through a knownvolume of standard silver nitrate solution, From the amount ofunreduced silver, the arsenic can be calculated. I n the case of minutetraces, the mirror method must, of course, be employed. Frerichs andR~denberg,~ who have worked on khe same subject, describe a modifiedelectrolytic cell which is said to enable the complete reduction of thearsenic to be effected inmuch less time than in the apparatus of the above-mentioned authors.It is morthyof note that in nearly all recent workon the electrolytic estimation of arsenic the use of platinum cathodeshas been abandoned, owing to the far greater sensitiveness andefficiency of cathodes constructed of zinc or lead. I n this connection,mention may be made of a paper by Virgili 8 containing an account of acritical examination of the magnesium pyroarsenate method forestimating arsenic. Among much which is perfectly well known toevery properly trained analyst, there are some observations which1 Zeit. a?zd Chem., 1905, 44, 535.3 J. Arner. Chem. Soc., 1905, 27, 1247.Yiertelschy. ger. Med. ofentl. Sanitatszoesen., 29, 74.Zeit. Nahr. CT'en~~ssm., 1905, 10, 290.Mai and Hurt, Zeit.Nahr. Genicssnz., 1905, 9, 193.Ibid., 541.7 Arch. Phnrnz., 1905, 243, 348. Zcit. ccnccl. Chem., 1905, 44, 492ANALYTICAL CHEMISTRY. 209merit the attention of chemists who have occasion to employ thisprocess. Since hydrogen peroxide is not infrequently made use of as anoxidising agent in analytical procedure, the observation of Grimbertthat commercial solutions of this substance often contain appreciablequantities of arsenic is deserving of note. W. Thomson 2 has investi-gated the occurrence of arsenic in the human body and its secretion byt,he kidneys and finds that the urine of people living in districts where,owing to industrial operations, the atmosphere is contaminated witharsenic, contains appreciable traces of that substance.The presence oftraces of arsenic in the urine, lungs, and hair is therefore, in suchcircumstances, devoid of much significance. Schumm describes anelectrolytic method €or the estimation of small quantities of mercury inanimal organs, which appears to be susceptible of useful application.A gold foil cathode is used and the mercuryis easily obtained in themetallic condition for weighing and identification.A p p cc r u t zc s.In the foregoing pages of this report, reference has incidentally beenmade in several cases to certain improved analytical appliances, and ithas not been thought necessary to draw attention to these again.The following list contains references only to those .new pieces ofapparatus which have been described in recognised journals, and whichappear to meet a real want and to be of general utility.It may notbe out of place to refer here to two papers on quartz glass apparatus byBerthelot,* and to one by Mylius5 on the same subject, since therecan be no doubt that this material will in the future find usefulapplication in analytical procedure. A paper by Brill6 on someexperiences in the use of the micro-balance is also of interest.‘ I A compact apparatus for testing gases.”‘‘A modified Orsat gas analysis apparatus.”R. Fieber (Chem. Zeit.,J. E. Babb (J. Amel..Also A. Bement (J. Amer. Chern. Soc.,K.1905, 29, SO).Chem. SOC., 1905, 27, 156).1905, 27, 1252).Voigt (Chenz. Zeit., 1905, 29, 691).“Tube apparatus for drying in a current of carbon dioxide.”J. Phnrm. Chim., 1905, 21, 385.Mem. Proc. Nanchester Phil. Soe., 49, 1.3 Zeit. anal. Chem., 1905, 44, 73.Compt. rend., 1905, 140, 817, 821.Zeit. nnorg. Chem., 1905, 44, 221.Ber., 1905, 38, 140.VOL. 11. 210 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRP.“ A n improved Hempel gas analysis apparatus.” A. H. White andE. D. Campbell (J. Amer. Chem. Soc., 1905, 27, 732).‘‘ Use of nickel vessels in analytical practice.” L. L’HBte (Ann. Chinz.anal., 1905, 10, 253).‘‘ An improved colorimeter for general use.” 0. Schreiner (J. Amer.Chem. Xoc., 1905, 27, 1192).“ A portable gas analysis apparatus.” B. Neumann (Chem. Zeit.,1905, 29, 1128).(‘ Gas regulators for thermostats.” T. M. Lowry (Trans., 1905,87, 1030).‘‘ A burette for delivering the amyl alcohol in Gerber’s method offat estimation.” C. Kippenberger (Zeit. amyew. Chena., 1905, 18,1025).“ A n apparatus for heating substances in a vacuum a t a constanttemperature.’’ W. R. Hodgkinson and A. H. Coote (Chem. News, 1905,91, 194).“Two modifications of the Topler pump.” A. Stock (Ber., 1905,‘‘ An automatic mercury pump with shortened column of mercury.”‘‘A simple Bunsen burner.” F. Allihn (Chem. Zeit., 1905, 29, 34).‘’ A new form of Eggertz tube for the determination of carbon in‘( A practical mechanical mortar ” (Chem. Zeit., 1905, 29, 56).‘‘ Gas-holder with constant flow.” Mario Betti (Chem. Zeit., 1905,‘‘ Potash apparatus for the rapid absorption of carbon dioxide.”6‘ New automatic pipette.” Greiner and Friedrichs (Zeit. ungew.“Improved suction filter.”38, 2lS2).L. Cbbelohde (Be?.., 1905, 38, 2657).steel and iron.” H. Schumacher (Chem. Zeit., 1905, 29, 35).29, 219).G. Schiiler (Chew. Zeit., 1905, 29, 569).Chem., 1905, 18, 465).J. Katz (Chern. Zeit., 1905, 29, 489).Electrically heated carbon tube furnaces.” R. S. Hutton andW. H. Patterson (Chenz. News, 1905, 91, 272, 285).‘‘A new apparatus for the continuous supply of gases.” EmilGeisel (Chem. Zeit., 1905, 29, 726).‘‘ An apparatus for heating crucibles by means of electricity (electricoven) uLder reduced pressure.” E. Haagn (Chem. Zeit., 1905, 29,1209).g L A new apparatus for supporting crucibles during ignition intendedto secure greater heating efficiency.” A. Kette (Chem. Zeit., 1905, 29,1208).The above are not always the exact titles given by the authors,but have been in some cases slightly altered so as to indicate moreclearly the nature of the apparatus in questionANALYTICAL CHEMISTRY. 21 1In concluding this report, the author would once again remind hisreaders that exigencies of space have compelled him to refer only tothose communications which appeared to him to be of the greatestvalue, either from the point of view of their practical importance orof their general scientific interest. The difficulty of making such aselection from the vast and ever-increasing amount of publishedmatter has been very great, and the limits assigned t o this reviewhave naturally precluded reference to a considerable number of papers,many of which unquestionably embody useful observations.ALFRED C. CHAPMAN,P

ISSN:0365-6217    

DOI:10.1039/AR9050200185

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY.As the report which I prepared last year on Physiological Chemistrywas the first of the series, I seized the occasion to preface my summaryof the year’s work by some general remarks, comparing, for instance,the condition of this branch of knowledge a t the present time withwhat it was twenty years ago, and noting the general lines on whichit has progressed. I n this year’s report it is of course unnecessary togo over that ground again, but a study merely of the number ofthe abstracts appearing month by month in the Society’s Journal andof their titles will indicate that there is no halt in the increasingattention which physiologists are bestowing on the chemical side oftheir science, and will show that many of the papers are concernedwith working out and elaborating the details of most of the subjectsalluded to in my report of last year.I have next to chronicle the appearance of two new journals devotedto biochemistry.One of these has been issued in America, and isunder the editorship of Dr. C. A. Herter and Prof. J. J. Abel. Theearly numbers of volume I of this journal hare,already been published.The other, edited by Prof. B. Moore and Dr. Whitley in this country,emanates from the University of Liverpool, and its first number ispromised at an early date. One regrets from some points of view theever-growing number of scientific journals, but it appears to be in-evitable that with the increase of specialisation in science it shouldoccur, and one cannot but rejoice that biochemistry is a t last to berepresented in scientific literature by special journals written inthe English language.I n dealing with the large mass of material at my disposal, it is againnecessary that I should make a selection, and I shall endeavour tochoose those researches for comment which deal with broad questions,rather than those concerned with mere detail.Proteid Chemistry and Pvoteid Metabolism.Emil Fischer and his colleagues are continuing their important workon the polypeptides, but it is evident that much remains to be donebefore it is possible to apply the mass of knowledge thus accumulatinPHYSIOLOGICAL CHEMISTRY, 213to the elucidation of the structure of the proteid molecule and to anattempt to synthesise albumin.As an instance of the kind of laboriouswork this involves, one may allude to the papers issuing from the penof Abderhalden,l who, in the examination of numerous proteids, hasprepared the various cleavage products and shown how different suchare both in kind and in amount in the different members of the proteidfamily.The physiological action of the cleavage products and the exactmanner in which they are utilised in the body form a wide field forfuture investigation. One small gap in our knowledge in this directionI was enabled to fill through the kindness of Prof.Emil Fischerhimself. It is well known that the effect ‘‘ peptone ” has in lesseningthe coagulability of the blood is mainly due to the primary proteoses itcontains. W. H. Thompson some years ago pointed out that thesame admixture is responsible f o r another physiological effect, whichgenerally runs parallel with this, namely, the lowering of arterialblood pressure on intra-vascular injection ; the further proteolysis iscontinued, the less do these effects manifest themselves.The crystallinecleavage products of proteolysis do not have any such physiological-eff ect(C. G. L. Wolf),2 and negative results were also obtained with thesamples of polypeptides sent to me by Prof. F i ~ c h e r . ~ The combinationsof molecular groups necessary to produce such effects must thereforebe more complex than the polypeptides.This, however, is only a small point; a much more important andgeneral question is the utilisation of the cleavage products when theyare administered by the alimentary canal.Evidence is steadily accumulating which confirms Loewi’s statementthat, in animals, weight, health, and nitrogenous equilibrium can bemaintained for a considerable time by feeding them on the crystallinecleavage products of proteolysis.This is what one would expect ifthe action of the digestive ferments on the proteid constituents offood is normally carried beyond the peptone stage. The major partof the proteid ingested is now believed to undergo this extremecleavage, and, that being so, the various proteids of the body mustbe formed synthetically from comparatively simple materials.It has not been possible as yet to discover these cleavage productsin the blood-stream when they are administered by the alimentarycanal ; the synthesis is therefore provisionally considered to occur inthe absorptive epithelium of the alimentary tract.This localisation ofZeit. physiol. Chenz., 1,905, 45, 473, 479 ; Abstr., 1905, i, 846 ; and numerouspapers appearing in the current volume (vol. 46) of Zeit. physiol. Chem., some ofwhich have been abstracted. Abstr., 1905, i, 954 ; ii, 838, 839, 840, 843.J. Physiol., 1905, 32, 171 ; Abstr., 1905, ii, 264.Halliburton, J. Physiol., 1905, 32, 174 ; Abslr., 1905, ii, 265214 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the place of proteid synthesis cannot, however, be taken as fully provedyet, for some experiments by Schryverl have not confirmed thehypothesis, Leathesl also attempted to discover if it is really thecase by examining the blood leaving isolated loops of intestine, in theinterior of which the cleavage products had been placed.These loopswere perfused with defibrinated blood, but under these experimentdconditions no absorption whatever occurred ; one hopes that theexperimental difficulties will in time be overcome,There is something very attractive in a theory which assumes acomplete breakdown of the food-stuffs previous to their being builtinto living tissue. It is less difficult to understand how the livingorganism can construct from the fragments the tissues peculiar toitself and maintain its chemical individuality, although the food takenmay vary widely in composition.has published a very striking experiment in con-firmation of this view.He collected the blood of a horse, separatedout the various proteids of the plasma, and estimated in each the yieldof certain cleavage pr0duct.s (glutamic acid and tyrosine) whichresulted from hydrolysis. He then fed the horse so that it formednew blood, but the only proteid given was glisdin, a vegetable product,which is remarkable for its high percentage yield (36.5) of glutamicacid. But in the regenerated blood proteids the percentage yield ofglutamic acid was not increased at a l l ; they exactly resembled theproteids previously present.It is a far cry from the highly specialised organism of the horseto the protoplasm of the simple mould known as Aspergillus niger ;nevertheless, the same general rule holds ; the proteid matter presentyields, on hydrolysis, glycine, alanine, leucine, glutamic and asparticacids, but aromatic products, such as tyrosine and phenylalanine, werenot discovered.The mould was then cultivated on media of widelyvarying composition, but the proteid formed in the living protoplasmremained constant in composition, and is independent of the composi-tion of the nutritive medium.3What then, if this is the case, would be the fate of food proteidsintroduced directly into the blood stream without the intervention ofthe alimentary digestive processes! This is a question to whichMendel and Rockwood Ifthe preliminary cleavage in the gastro-intestinal tract is absolutelynecessary, one would anticipate that a foreign food proteid (such as edestinAbderhaldenhave been attempting to find an answer.Verbal comniunicatioiis to the Physiological Society.Zeit.physiol. Chenz., 1905, 46, 193 ; Abstr., 1905, ii, 850.3 Abderhalden and Rona, Zeit. physiol. Chcm., 1905, 46, 179-186 ; Abslr., 1905,i, 954.Awzer. J. Physiol., 1904, 12, 336; dbstr., 1905, ii, 45PHYSIOLOGICAL CHEMISTRY. 215from hemp seed, or excelsin from Brazil nuts) administered by intra-venous or intraperitoneal injection mould not be assimilated, but wouldbe cast out of the body in one or more of the excretions. But Mendeland Rockwood found that they mere not eliminated in either urine orbile. In some cases, a proteose was found in small quantities in theurine, but the greater part of the proteid administered mas retained inthe body, especially if the injection was slowly performed.Rapid injec-tion causes toxic symptoms, as one would anticipate. No doubt futureattempts will be made to ascertain more exactly what happens t o theretained proteid and the exact mode of utilisation which it undergoes.The fact that proteids are retained after this method of administra-tion and apparently used in the body does not really militate againstthe theory that proteids under normal conditions are more or lesscompletely broken down in the alimentary tract. Clinical experiencewith feeding per rectum indicates the possibility of a direct absorptionof prbteid without previous digestive changes. We have here one ofmany instances of the adaptability of the.body to altered circum-stances ; a t a critical moment, various portions of the body are capableof rising to the occasion and performing unusual feats, or of taking onthe action normally performed elsewhere.The usual form in whichthe body gets its proteid is by building i t up from simple crystallinematerials, but if these are not available, it can still get proteid byabsorbing the large molecules of the albumin presented to it, It ismore than probable, however, that cleavage is absolutely necessary forassimilation, and here the enzymes present in the tissue cells step in ;they are capable of occasionally taking the place of the pancreatictrypsin and intestinal erepsin and doing their work. The presence ofa proteose in urine in some of Mendel and Rockwood’s experimentspoints in this direction, and this view is supported also by Vernon’s1recent discovery that every tissue of the body has an ereptic action, andthat in some tissues this power is even greater than in the intestinalcavity and mucous membrane.In last year’s Report I mentioned the appearance of ProfessorChittenden’s book, entitled Physiological Economy in Nutrition. Inview of work published more recently, which forms a corollary to hisconclusions, it is necessary to enter more fully into the contentions ofthis really important book.The long established idea that a man requires a minimum of 15 to18 grams of nitrogen (that is, about 100 grams of proteid) in hisdaily food has been questioned by a number of observers, but the con-clusion that a man can do with less has not been advanced con-J.Physiol., 1904, 32, 33; Abstr., 1905, ii, 100; also J. Physiol., 1905, 33, 81 ;See also Cathcart on the splenic enzyme (J. Physiol., 1905, Abstr., 1905, ii, 841.32, 299 ; A6str., 1905, ii, 404)216 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.vincingly, because the experiments have been made either over tcoshort a period or on too few individuals. The figure quoted is basedroughly on the usual diet of the meat-eating nations, and it is arguedthat habit and instinct alike are safe guides in determining thisnumber, and that the effect of such a diet in the maintenance ofhealth and equilibrium has been abundantly proved through centuriesof experience. It is the number which forms the basis of the usuallyaccepted dietaries of Voit and Ranke.I n other nationalities, it is true, a different figure has been arriveda t as the result of experience and instinct ; the prevalence of dyspeptictroubles and uric acid disorders in our midst also should make ushesitate before we conclude that our own diet has reached the stageof perfection.It is alleged that in such nations as the Japanese, orin groups of persons like vegetarians, and in many rural populationswhere low wages render meat a rarely obtained luxury, health and.equilibrium are equally well maintained as in the ordinary flesh-eatinginhabitants of our large cities. Those who hold that the number15 to 18 is the correct one have explained the different numberarrived at by the nations of the Far Ezst as a racial difference pro-pagated by long centuries of inheritance, or have tried more or lesssuccessfully to show that the diet of such people comes nearer toVoit's standard than had been supposed, or that they are not properlynourished.Such explanations will not bear scrutiny when applied to the care-fully conducted and rigorous experiments carried out by ProFessorChittenden on himself, his colleagues, his students, and on athletesand soldiers.These experiments lasted in all cases for months, andin some for more than a year. The proteid intake was reduced tohalf, and sometimes to less than half, the number regarded as normal.After a variable initial drop in body weight, the deprivation wasapparently followed by no untoward results. Bodily equilibrium wasmaintained ; the health remained perfect or improved ; the muscularforce in athletes was usually increased ; mental acuity was un-diminished, and desire for richer food soon disappeared.Chittenden argues from such results that his scanty proteid diet isthe normal one, and that the average meat eater is the man who isabnormal.He says : '' When we recollect that these 18 grams ormore of nitrogen in the urine reach the final stage of urea, &c., only bypassing through a series of stages each one of which means the usingup of a certain amount of energy, to say nothing of the energy madeuse of in digestion, absorption, &c., we can easily picture to ourselvesthe amount of physiological labour which the daily handling by thebody of such amounts of proteid entails.It needs very little imagina-tion to see that a large amount of energy is used up in passing oPHYSIOLOGICAL CHEMISTRY. 217these nitrogenous waste products from organ to organ, or from tissueto tissue, on the way to elimination, and we can fancy that liver andkidneys must at times rebel at the excessive labour they are calledupon to perform.” He then goes on to point out how many of thenitrogenous katabolites (especially of the uric acid group) are toxic, andthe evil results due to their accumulation. He therefore advocates arevolution in our ordinary dietary, and his arguments for temperancein proteid intake are advanced in a temperate and scientific manner.Liebig was the first to divide foods into flesh forming and heatforming, that is, into those which repair the tissue waste and thosewhich are not so intimately assimilated into the protoplasm, but arentilised as sources of energy.The latter function is the oneperformed by the fats and carbohydrates, and the former is moreparticularly the duty of the proteids. This idea is reflected in thepopular use of the term nutritious; it is used almost synonymouslywith nitrogenous, and the notion that non-nitrogenous foods, althoughthey form the greater part of our daily diet, are not nutritious and arenext door to useless is carefully fostered by the advertisers of patentfoods. It is now known that the proteids are not only flesh formers, butalso that they play the other r6Ze in nutrition, and act as a eource OFenergy.The complete breakdown of proteid matter which occurs inthe gastro-intestinal tract has in fact a double signification. It enablesthe body to construct from the cleavage products the proteids peculiarto itself, and it further enables the body to get rid easily of thenitrogenous moiety of the proteid which is not wanted for tissueformation. It in fact protects us from the evils of the too greatamount of proteid most of us eat. This portion is never reallyassimilated, but is rapidly converted into urea and so rendered harm-less, and is quickly cast out by the kidneys. The non-nitrogenousmoiety which remains is then utilised for energy and heat productionjust as if it was a fat or carbohydrate.This a t any rate is the viewwhich has been urged with conspicuous ability by Otto Folin in aseries of papers to be subsequently noticed.Ever since the historical experiment performed by Fick andWislicenus iu their ascent of the Faulhorn, it has been known thatnature works in a wonderfully economical way in reference to proteidwaste. The increased excret-ion of nitrogenous waste during muscularwork is insignificant as compared with the large and immediateincreased output of carbon dioxide. If, therefore, we are to limit ourproteid intake t o the comparatively small supply necessary to repairour lost tissue, it will be seen at once that we must come down toChittenden’s standard or even below it.1s it, however, wise for all men to act immediately on Chittenden’sadvice? This is an all-important question, and one feels som218 ANNUAL REPORTS ON THE PROGRESS OF CHEMIS‘TRY.responsibility in attempting to answer it.We may, however, freelyadmit that the majority of well-to-do people eat too much proteid.There are not many who limit themselves even to Voit’s minimum, andin those who are prone to digestive and uric acid diseases one cannotbut feel that improvement in body and mind will be the result of moretemperate habits. But any change in the practice of years and ofgenerations should be accomplished gradually, not suddenly. Thosewho are young and vigorous may remember that the liver is thelargest organ we possess, its function is to turn nitrogenous metaboliteswhich may be harmful into urea, which is harmless and easily disposedof, and may gain comfort from the reflection that the organ is adequatein health t o deal with large quantities of material.If all of us were to reduce immediately our diet to the Chittendenlevel, we might be living perilously near the margin; any unusualstrain, such as privation o r a severe illness, would then find us withoutany reserve of nutrient energy, and we should probably suffer moreseverely in consequence.The poor around us have had .~zoZens volensto subsist on a diet very like Chittenden’s, but their nutritive conditionis not such as to make people who can afford a more liberal tableinclined to follow their example. I n countries like India, where thevegetarian native population is diluted with the meat-eating whiteraces, it is the former who are more readily attacked by disease andmore easily succumb to its effects.I n the modern treatment of consumption, the open air cure iscombined with a steady process of overfeeding; in certain cases ofnervous breakdown, an important part of the “rest cure” is theproviding of abundant and appetising meals.One can hardly doubtthat much of the benefit noticeable in both classes is due to thereserve energy provided enabling the body more fully to grapple withthe disease.Now let me take up the work carried out by Otto Folin,l t o whichI have already alluded, He does not appear to have seen that somecaution is advisable in accepting Chittenden’s conclusions to the full,but he has, nevertheless, published a series of three important papers,full of pregnant suggestions.The question of What is a normal diet? is intimately bound upwith another, and that is, What is a normal urine? The text-bookstatements of the composition of this fluid are all derived from theexamination of the urine of people accustomed to the Voit dietary;but if the diet of the future is to contain only half as much proteidas in the pmt, the urine of the future will naturally show a nitro-genous output of half of that which is now regarded as normal.Inpeople on such reduced diets, Folin shows that the decrease in urinary1 Amer. J. Physiol., 1905, 13, 45, 66, 117 ; rlbstr., 1905, ii, 183, 268PHYSIOLOGICAL CHEMISTRY. 219nitrogen falls mainly on the ixrea fraction, and in some cases the ureaexcreted accounted for only 66 per cent.of the total nitrogen. Theother nitrogenous katabolites of the urine alter comparatively littleabsolutely, but relatively their ;mount rises ; of these, the endogenouspurine, and more particularly the creatinine, remain remarkablyconstant in absolute amount in spite of the great reduction in theproteid ingested.The laws governing the composition of urine are the effect of morefundamental lams governing proteid-katabolism. Voit’s old theorystated that katabolisrn occurs only in ii circulating proteid.” Thesmall amount of living proteid ” which dies is dissolved, and so isadded to the (‘ circulating proteid.” Pfluger’s theory, mhic h displacedVoit’s, states that all proteid is first transformed into living materialbefore katabolism occurs. The view taken by Folin is that neither ofthese extreme views is correct, but that nitrogenous katabolism is oftwo kinds ; one is immediate and inconstant ; it varies with the food,and leads to the formation of urea and inorganic sulphates, but not ofcreatinine or “neutral sulphur.” The other is smaller in amount,constant in quantity, and is largely represented in the urine bycreatinine, “neutral sulphur,” and to a less extent by uric acid andethereal sulphates, and possibly a certain amount of urea.The latterform of metabolism may be termed tissue or endogenous, whilst theother is exogenous. Endogenous metabolism sets a limit to the lowest!eve1 of nitrogenous equilibrium attainable ; the proteid sufficient tomaintain it is indispensable.Whether the amount exogenouslymetabolised can be entirely dispensed with is a t present questionable,but the balance of evidence is believed to show that it can be verylargely replaced by non-nitrogenous food ; the nitrogen of this part ofthe proteid is easily split off by hydrolysis without oxidation, andthus a non-nitrogenous residue is left which is available for calorificpurposes, The formation of ammonia and amino-acids which occursso largely in the intestine, owing to tryptic and ereptic activity, isfrom this point of view regarded as a preliminary means for gettingrid of the excess of nitrogen taken in. Any extensive formationfrom the cleavage products of Voit’s circulating proteid to befollowed immediately by decomposition into urea is regarded as quiteas improbable as the corresponding formation and decomposition ofPfluger’s organise d pro toplasm.Urea is absent, or nearly so, from the muscles, and its representative,creatine, is eliminated not as urea but as creatinine. The fact thatmuscular work does not increase proteid katabolism is remarkable ifcurrent views of the nature of that katabolism are correct, but i tbecomes intelligible if proteid katabolism, in so far as its nitrogen isconcerned, is independent of the oxidations which give rise to heat, o220 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.to the energy which is converted into work.Whether severe workwill have an effect on the endogenous metabolism cannot be shown byinvestigating urea excretion ; determinations of creatinine and neutralsulphur are necessary for a study of that question.It is hardly necessary to dwell on the importance of work like this,and of the new ideas which arise out of i t ; other physiologists areentering the field so opened up, and Noel Paton1 has already hadtime to publish a paper on some of the points raised.On the wholehe agrees with Folin, but certain differences of detail are noted ; forinstance, in the dog, creatinine excretion is not so constant as in man.2He also expresses a doubt whether any hard and fast line can bedrawn between endogenous and exogenous proteid metabolism, andurea is probably an end-product in both cases.Some of Folin'sresults may be explained by variations in the activity of the liver, forit is there that urea-precursors are transformed into that substance.Of all diets, proteid is the most effective in stimulating hepaticactivity, as gauged by the amount of bile secreted. Hence, on a dietpoor in proteid, the liver may be sluggish, and therefore unable t oconvert much of the waste nitrogen into urea, whereas on a diet richin proteid the conversion will be more complete. Exactly similararguments apply t o the sulphur; the amount which is completelyoxidised must also depend on hepatic activity.The current views on the importance of urinary creatinine mustobviously be modified if we are to regard it with Folin as theprincipal measure of endogenous proteid katabolism.Hitherto it hasbeen believed that the greater part of the muscular creatine is ulti-mately discharged as urea, and that the greater part of the creatininein the urine came directly from the flesh taken in as food. Severalpapers have appeared on the subject. Thus, Czernecki performeda research on Bhe question whether guanidine is the parent substanceof creatine and creatinine, but his results were not very conclusive.The relation of the methyl groups of lecithin to that of creatininesuggested to W. Koch4 feeding experiments with lecithin added toa creatine-free diet; he found that the creatinine excreted was increased,but concludes that proteid-katabolism is the main factor involved insupplying most of the nitrogen of the creatinine molecule.Mendeland Closson arrive at the same conclusion. They found theexcretion of this substance quite noteworthy in vegetarians andJ. Physiol., 1905, 33, 1 ; Abstr., 1905, ii, 734.2 W. Iioch, on the other hand, states that it is as constant in the dog, and theoutput per kilogram is nearly the same as in man (Amer. J. Physiol., 1905, 15, 15).3 Zeit. physiol. Chena., 1905, 44, 294 ; Ahstr., 1905, ii, 467.Abstr., 1905, ii, 182 ; also Amer. J. Physiol., 1905, 15, 15.Proc. Amer. Physiol. h'obc., 1904, xix ;Anter. J. Physiol., 13 ; Abstr., 1905, ii, 186PHYSIOLOGICAL CHEMISTRY. 221those on a low proteid diet, and in those whose food is free fromcreatine there is a tendency to parallelism between the total nitrogenoutput and the excretion of creatinine.There is thus already con-firmatory evidence in favour of Folin’s views.Cystinurim-This is a subject which follows naturally a considera-tion of normal metabolism, because of all the abnormal variations inintermediary metabolism that which results in the occurrence ofcystine in the urine is by far the most interesting.Loewy and Neuberg 1 opened the discussion by their assertion thatthe cystine of urinary calculi is not identical with that obtainedfrom proteid decomposition ; proteid cystine is a-amino-p-thiolpro-pionic acid, whereas calculus cystine is p-amino-a-thiolpropionic acid.The special interest of this isomerism arises from the fact that; t h i sis one of the rare instances of a P-amino-acid arising during animalmetaboliam.In a patient who came under their notice, the cystineexcreted was unexpectedly found to be proteid cystine. Acting onthe supposition that the case was not merely one of anomalous proteidmetabolism, but one in which there was a general breakdown of amino-acid metabolism, the urine was searched for other amino-acids, but with-out success ; diamines were also absent.2 The anomalous nature of themetabolism was, however, shown when amino-acids were administeredby the mouth; tyrosine, leucine, and aspartic acid, instead of beingbroken down in the body, were excreted almost quantitatively in theurine ; the same occurred with proteid cystine (given in 6 gram doses),whereas a normal man will burn 8 grams with the formation ofsulphates and thiosulphates.On the other hand, the remarkable factwas noticed that calculus cystine was completely burnt with a corre-sponding increase in sulphates and neutral sulphur. After feeding onlysine, cadaverine (pentamethylenediamine) appeared in the urine,and putrescine (tetramethylenediamine) appeared after the adminis-tration of arginine.The interest of the case is this : if proteids are normally broken upinto simple crystalline products, why did not this patient excrete themunchanged, as he did when they were given by the mouth 8 Thistells against the theory of complete proteolytic breakdown in theintestine, although it is quite possible that cystine is specially looselycombined in the proteid molecule.The remarkable conclusions reached in this work of Loewy andThis is probably due to enzyme action.Zeit. physiol.Chem., 1904, 43, 338 ; Abstr., 1905, ii, 103.The presence of the diamines, putrescine and cadaverine, in the urine of cystin-uria is by no means constant. Thus, Bodtker describes two cases in which theywere present (Zeit. physiol. Cham., 1905, 45, 393) and Simon (ibid., 357) one casein which they were absent. Abderhalden and Schittenhelm (ibid., 468) describe acase where both lencine and tyrosine occurred in the urine (Abstr., 1905, ii, 741)222 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Neuberg had, at any rate, one good effect; it stimulated others torepeat their experiments, and with the result that, within the shortspace of a few months, nearly every one of their conclusions has beenshown to be incorrect.The earliest to enter the lists was Rothera,lwho was unable to make out any chemical difference between the twoforms of cystine, and who also showed that in normal persons bothare physiologically broken down and oxidised to sulphate, whichappears in the urine quantitatively. H e further showed that cholicacid does not diminish the excretion of sulphates, as it might if cystinewere converted into taurocholate. The same conclusion is reached byE. Fischer and Suzuki;2 they could detect no difference betweencystine prepared from calculi and that prepared from horse-hair, andthey show that Meuberg’s contrary result is explicable by admixturewith tyrosine. A third set of critics appeared in the persons of0.Folin and A l ~ b e r g , ~ and on the chemistry of cystine they hold thesame opinion as Rothera and Fischer. The experiments they recordin connection with a case of cystinuria do not corroborate the views ofLoewy and Neuberg on the nature of the metabolism in this disease.I n the early part of the investigation, when their patient was on aVoit diet, the ‘‘ undetermined nitrogen ’’ in the urine increased. Ittherefore appeared probable that amino-acids might account for this,and that Loemy and Neuberg’s generalisations on the nature of thedisease were correct, and that the failure of these observers to discoveramino-acids in the urine was only an error of analysis. But this in-terpretation was shattered by the results obtained when a fat andstarch diet was substituted for the one first used, for the undeterminednitrogen remained stationary.If aspartic acid was added to this diet,the nitrogen excreted rose to an amount beyond that which theaspartic acid would account for, and the increase was due to urea, notto undetermined nitrogen ; the patient was therefore able t o convertthe nitrogen of aspartic acid into urea. If pure cystine was added tothe diet instead of aspartic acid, the elimination of neutral sulphurwas not increased ; that is to say, in so far as cystine is absorbed, it isnot excreted as such but as ordinary sulphates. There is thus noinability t o katabolise normally the usual products of proteolysis, andthe cystine which is eliminated is not absorbed as such from thealimentary tract ; it comes from other and larger sulphur complexes ;it is this and the sulphur from the tissues which the cystinuric personis unable to convert into sulphates.J.Physiol., 1905, 32, 175 ; Abstr., 1905, ii, 267.Zeit. physiol. Chem., 1905, 45, 405 ; Abstr., 1905, ii, 786.Amer. J. Physiol., 1905, 14, 5 4 ; Abstr., 1905, ii, 544PHYSIOLOGICAL CHEMISTRY. 223Ferments and Co-ferments.The discovery of such enzymes as arginase, which act on simplecrystalline substances, has led to a series of interesting papers. Thus,Schittenhelm 1 concludes that three distinct ferments take part in thetransformation of nucleic acid into uric acid, namely, (1) a nucleasewhich hydrolyses the nucleic acid to purine bases; (2) guairzase andadenase, which have deamidising functions, and lead to the conversionof guanine into xanthine and adenine into hypoxanthine respectively ;and (3) an oxidccse which in presence of oxygen converts hypoxanthineinto xanthine and xanthine into uric acid. These are widely dis-tributed in different tissues.At the same time there is in tbe extractsof certain tissues a ferment which has the power of breaking downuric acid, and this is named uricalase or the uricoEytic firment ; amongthe final decomposition products are glycine and urea. Walter Jones,to whom the discovery of guanase belongs, publishes very similarviews.2have investigated the action oftrypsin on a number of synthetical polypeptides. Some of these are,and others are not, hydrolysed; but it appears too early yet to saywhat is the cause of the difference.Passing next to the influence of one ferment on another, a paper byBayliss and Starling gives a description of experiments which confirmtheir original contention that enterokinase is a real enzyme; pro-vided sufficient time is given, it is able to convert an unlimited amountof trypsinogen into trypsin, and there is no evidence that trypsin isequivalent to a combination of kinase and trypsinogen.We have thus firmly established the view originally put forward byPawloff, that enterokinase is a ‘‘ ferment of a ferment.” This view ofthe way in which the pancreatic enzyme is activated in the smallintestine has now replaced the older theory of Schiff (and supportedamong others by Herzen and Bellamy), that the spleen forms somesubstance necessary for the transformation of trypsinogen into trypsin.If any favouring influence is produced by the addition of a splenicextract to pancreatic juice, 0.Prym has conclusively shown that itmay be simply explained as a result of dilution and bacterial activity,the antiseptics used by the earlier observers mentioned not havingbeen efficient ones.Zeit. physiol. Chm., 1904,- 43, 228 ; 1905, 45, 121, 152, 161 ; Abstr., 1905,Zeit. physiol. Chem., 1904, M, 1 ; 1905, 45, 84 ; Abstr., 1905, ii, 333, 644.J. Physiol., 1905, 32, 129 ; Abstr., 1905, ii, 273.PJEiiger’s Archiv, 1905, 107, 599 ; Abstr., 1905, ii, 404.Emil Fischer and Abderhaldeni, 108 ; ii, 644, 645.‘’ Sitzwngsber.K. Akad. Wiss. Berlin, 1905, 290 ; Abstr., 1905, ii, 383224 ANNUAL REPORTS ON TGE PROGRESS OF CHEMTSTRP.The whole question of co-ferments is, however, in a rather unsettledstate just now. As announced in last year’s Report, Cohnheim madethe striking announcement that the pancreas facilitates the combustionof sugar in the muscles, and it seemed probable that we were to beprovided with an intelligible explanation of pancreatic diabetes. Theactive substance responsible for the action in question is dialysableand not destroyed by boiling, and in these properties resembles theco-ferment of lipase described by Magnus. These expectations havenot been fulfilled, for Claus and Embden have been entirely unable tocorroborate Cohnheim’s results.It appears that the existence of co-ferments has been hastily assumedin other cases also, and that the simpler explanation of the effect ofdilution is much more probable,The word co-ferment may be of course extended to include thehydrochloric acid of the gnstric juice or the calcium which is essentialto the activity of rennet and fibrin-ferment, but it is doubtful whetherthose who coined the word meant to include such inorganic allies offerments in the expression,It, however, appears likely that some at any rate of the so-calledco-ferments are inorganic; as a rule they are not affected by heat.This is the case in the co-ferment of yeast juice described by Hardenand Young3 They found that the rate of alcoholic fermentation isgreatly increased by the addition of boiled and filtered yeast juice.Buchner and Antoni* confirm this observation, and find that thepresence of phosphates in the boiled juice accounts for the increase inactivity.I understand that Harden and Young, as the result offurther work, have arrived a t exactly the same conclusion, and thattheir paper on the subject is already accepted’ for reading a t the RoyalSociety.The substance secretin, which Bayliss and Starling found to be thechemical stimulus for pancreatic secretion, may in a still wider sense beconsidered to come within the category of the co-ferments, and likethem its chemical composition is still unknown. The very importantdiscovery that a chemical stimulant is formed within the upper part ofthe intestine as a result of the action of the gastric acid, and that thismaterial is conveyed in the blood stream to the pancreas, has lednaturally to a search for analogous substances in other situations, andBeitr.chem. Physiol. Path., 1905, 6, 214, 343; Abslr., 1905, ii, 179, 404.Compare also the view advanced by Leo (Zeit. physiol. CJLem., 1905, 46, 286 ;Abstr., 1905, ii, 838) that hydrochloric acid is the effective agent in gastric digestion,and that the part played by pepsin is that of an ainboceptor to anchor the acid on tothe proteid molecule.Proc. Physiol. Soc., 1904, i ; J. PJzysiol., 32 ; Abstr., 1905, ii, 109.Zeit. physiol. Chem., 1905, 45, 136PHYSIOLOGICAL CHEMISTRY. 225Edkinsl has already adduced some evidence to show that the flow ofgastric juice is favoured by the production of a gastm’n, and thatsalivary digestion provides a chemical cause for the secretion of thenext juice in order. Like secretin, it is not destroyed by boiling.Starling2 has in the Croonian lectures, which he has entitled “Thechemical correlation of the functions of the body,” given a conciseaccount of the numerous researches which he and his colleagues havecarried out on the chemical messengers which bring about correlationof function between different organs of the body.The general namebestowed on them is hormone. Some, like secretin, stimulate increasedactivity and katabolism, others involve increased assimilation andgrowth. Under the latter head fall the internal secretions of thethyroid and generative organs, Some preliminary experiments indicatethat it is an internal secretion of the fetus, which leads to the growthof the mammary gland.Blood CoaguZtction.-The number of papers on this very controversialsubject has not been so great as usual this year.The general questionis discussed in a further contribution from the pen of Leo Loeb,3mainly as a result of his investigations on the clotting of the bloodof invertebrates: it is very similar to that of vertebrate blood. Inboth, two substances are important, namely, the tissue coagzclins andsubstances present in the blood itself. The coagulins are within cer-tain limits specific. The substances in the blood are only specific inso far that those from vertebrate animals have no influence on in-vertebrate blood.It is probable that the material extracted bothfrom the cellular elements of the blood and from tissues like muscleact directly on the fibrinogen of the blood plasma, but the conditionsfor their action are different ; for instance, the acceleration by calciumsalts is moremarked with the coagulins than with the material fromthe blood corpuscles. In certain circumstances, a combination of thetwo substances is more active than the sum of their individual activi-ties; that this is due to the influence of tbe coagulin in convertingprothrombin into thrombin is only one of several possibilities.Some discussion as to the meaning of the fibrino-globulin whichappears in the coagulation process has taken place between Huiskamp *and Heubner.5 The view taken by the former is that it is presentbefore clotting takes place.The only other paper worthy of mention is an interesting one byC.J. Martin,G who finds that snake venom produces clotting becauseAbstr., 1905, ii, 735. Proc. Boy. SOC., 1905, 76 B, 376 ; Abstr., 1905, ii, 730.Zeit. physiol. Chem., 1905, 44, 182 ; 46, 273; Abstr., 1905, ii, 499.3 Beitr. chem. Physiol. Path., 1905, 6, 260; Abstr., 1905, ii, 330.6 Zeit. physiol. Chem., 1905, 45, 355 ; Abstr., 1905, ii, 725.(i J. Physiol., 1905, 32, 207 ; Abstr., 1905, ii, 411.VOL. 11. 226 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.it contains true fibrin ferment. The small quantity of venom neces-sary to cause coagulation is remarkable, although it varies in differentvenoms.There is, further, some specificity in the ferments; theserum of a horse immunised against one venom contains an anti-ferment against the clotting ferment in that venom, but not necessarilyin other venoms.A very simple time relationship was found in investigating thereaction velocity of fibrin Ferment, namely, that the amount offerment and the coagulation time are inversely proportional. Asdifferent enzymes are investigated, more and more of them are fallinginto line in obeying this simple law instead of the law of squareroots enunciated by Schutz.l0psonins.-The consideration of ferments leads us next in logicalorder to the immunity question, and that subject is rapidly acquiringa literature of its own. I propose to deal only with one part of it,which has risen into special prominence during the foregoing year.The methods of defence the body possesses against invasion bymicro-organisms are numerous, and different bacteria are dealt with invarying ways.I n some cases, the bacteria are killed by the bacterio-lysins of the blood, but the varieties so dealt with are limited innumber, I n other cases, the toxins produced by the bacteria areneutralised by antitoxins, and in other cases still the bacteria aredirectly attacked and devoured by the white corpuscles or phagocytes.I n connection with phagocytosis, great differences are noticeable ; thishas been partly explained by what is called chemotaxis ; some bacteriaproduce chemical substances which act like magnets, attracting theleucocytes to their neighbourhood (positive chemotaxi8) ; in other cases,such substances are not produced, or even negative chemotaxis mayoccur, so that the phagocytes are repelled. Recent observations byA.E. Wright, which haveresulted in the discovery of opsonin8, are ofgreat importance in this connection, and make our knowledge ofpositive chemotaxis more exact. They form a striking illustration ofhow the leucocytes and body fluids co-operate and how elaborate are themeans the body possesses for combating bacterial invasion. Theword opsonin is derived from a Greek word which means “ t o pre-pare the feast.’’ Bacteria from a pure culture are in many cases dis-tasteful to the leucocytes, but if the bacteria have been previouslysoaked in serum, especially if that serum has been obtained from theblood of an animal immunised against that special bacterium, then theleucocytes devour them eagerly ; in other words, something has beenadded to the bacterium to make it piquant, and each kind of bacteriumapparently requires its own special sauce or opsonin.Compare Bayliss on “The Kinetics of Tryptic Action” (Arch, Sci, biol.St,Petemburg, 1904, 11, Suppl. 281 ; Abstr., 1905, ii, 267)PHYSIOLOGICAL CHEMISTRY. 227It is in connection with tuberculosis that the opsonin question hasbeen mainly worked out. Without going into the details of thetechnique, the following is an instance of how practical investigationsare carried on. Microscopic films are made of blood which has beenpreviously mixed with an emulsion of tubercle bacilli. The bacilliingested by, say, fifty leucocyfes are then counted, and an averagestruck. If this is done after admixture with (1) an abnormal serumand (2) a normal serum, the average per leucocyte in the first casedivided by that in the second is called the opsonic index.I n eighty-six healthy people examined by Bulloch,l the index was 0.97, theextremes being 0.8 and 1.2. I n tuberculosis of the skin (lupus), theaverage was 0.75 in 150 cases. I n 75 per cent. of these, the indexwas below the lowest normal limit, 0.S ; in twenty-seven cases it wasbelow 0.5, and in three cases as low as 0.2. It was found that if theindex is well below the normal, treatment by the Finsen light is oflittle or no benefit.The ultra-violet rays have but little penetrativepower, and probably exert no potent effect on the bacilli themselves ;its healing properties are due to a reaction set up in the tissues andto the congestion which follows exposure to the rays. If the bacilli arebathed in a fluid rich in opsonin, that is, if the opsonic index is high,theythen will fall ready victims to the crowd of leucocytes brought tothe spot by the congestion.I n a more general form of tuberculosis (phthisis) it mill be sufficientto take one example of the sort of work in progress. Meakin andWheeler2 found great variations in the opsonic index even in thesame case, especially during the early stages of the disease. It thenbecomes fairly stationary, and if it is then unity or thereabouts theprognosis is better than when it is low.Considering the vast amount of work which issues from the PasteurInstitute, it may seem remarkable that opsonins were not discoveredearlier.But, as a matter of fact, the favouring effect of the additionof immune serum on the phagocytic action of leucocytes has beenknown in that institution and chronicled in its Alznales for some timepast. The attitude of mind adopted by Metschnikoff and hisdisciples bas always been to attribute to the leucocyte an overmaster-ing r8Ze in all problems of protective mechanism ; and thus they haveconsidered that the favourable action of the serum is one mainly onthe leucocytes, and not so much on the bacilli, Metschnikoff inventedthe word stimulim as the name for the substance in the serum whichstimulates the leucocytes to increased phagocytosis.It is probablethat both factors must be taken into account. Leishman 3 has madeTrans. Path. SOC. London, 1905, 56, 334 ; Abstr., 1905, ii, 844.Brit. illecl. J., 1905, ii, 1396 ; Abstr., 1905, ii, 845.Trans. Path Xoc. London, 1905, 56, 344 ; Abstr., 1905, ii, 844.Q 228 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.experiments with serum from cases of Malta fever and typhoid fever.This increases the phagocytic activity of the leucocytes on the specificbacilli of these diseases. He concludes that the main effect is astimulating one on the leucocytes themselves and is not due to theaddition of an opsonin t o the bacilli. The principal ground for thisconclusion is that Wright’s hitherto described opsonins are destroyedat a temperature of 60°, but the substances Leishman describes arethermostable and are not affected by exposure to this temperature forfifteen minutes, The possibility, however, still remains that someopsonins are more resistant t o heat than others, and even Metschnikoffhimself appears inclined to accept this view.Carbohydrcct e Metabo Zism,The principal question attacked this year has been diabetes, and theprincipal writer Pfluger ; several of his papers are characteristicallycontroversial.He and his colleagues, Schondorff and Wenze1,lexamined some hundreds of urines, and conclude that many forms ofso-called transitory glycosuria (including those produced by anastheticsand by surgical operations) do not exist.The contrary conclusionreached by others is attributed to untrustworthy tests for sugar.Most reliance should be placed on the polarimetric test and WormMiiller’s modification of the copper reaction.on pancreatic diabetes; the firstof these is mainly comment on Luthje’s conclusions on the proteidorigin of sugar. Pfluger thinks it really originates from fat, and i nhis second paper explains in a very ingenious way why he stillcontinues t o doubt its origin from proteid, even although the dogs heexamined were fed exclusively on that substance. Those inirerested incontroversies should read the original papers.Coming from the same laboratory, one next notes a useful piece ofwork by K.G r ~ b e . ~ He finds the glycogen in the liver is uniformlydistributed in the organ; this is by no means an unimportant point whensmall pieces only are analysed as samples. He also describes a newmethod of artificial perfusion of the liver which can be applied to theorgan in, situ without any pause occurring after the cessation of thenatural circulation. If dextrose, dextrin, or laevulose be added to thedefibrinated blood used in perfusion, it is shown conclusively for the firsttime that the carbohydrate added to the blood becomes less as theglycogen stored in the liver increases.He has also published two papersPjliiger’s Archiv, 1904, 105, 121 ; Abstr., 1905, ii, 44.2 Pjluger’s Archiv, 1904, 106, 168 ; Abstr., 1905, ii, 100.3 Pjliiger’s Arehiv, 1904, 106, 160 ; Abstr., 1905, ii, 99.Pjluger’s Archiv, 1905,108, 115; Abstr., 1905, ii, 469.P$uger’s Archiv, 1905, 107, 483, 490 ; Abstr., 1905, ii, 334PHYSIOLOGICAL CHEMISTRY. 229Three papers on allied subjects come from America.Lusk andMandell comment on a case of severe diabetes; the dextrose :nitrogen ratio was 3-65 : 1 on a meat diet. This is the same ratioseenin phlmidzin diabetes in dogs, and indicates a rapidly fatalresult.Underhil12 finds that piperidine and other alkaloids, as well asnarcotics, produce hypergly cEmia, and glycosuria, not by speciallyacting on the pancreas or any other organ, but simply by thedyspnmathey cause by acting on the respiratory centre. Adrenaline diabetes,however, does not fall under this rule.The number of factors which come into play in the causaticn of adiabetic condition is still further accentuated by the third paper,which is by J.J. R. Macleod and J. D01ley.~ Eckhard found thatpuncture of the medulla oblongata did not cause glycosuria whenthe splanchnic nerves were cut, and so argued that impulses reachedthe liver by these nerves. Glycosuria does not follow stimulation ofthe peripheral end of the cut nerves, but it does occur if the cervicalpart of the spinal cord is stimulated; hence the somewhat un-warranted supposition had to be adopted that the impulse under-goes some change as it passes through the upper cervical ganglia,I n the present research, nicotine was injected to block the impulse atthe ganglia; puncture was thus found t o produce little or noglycosuria, and glycogen did not disappear from the liver.Stimula-tion of the central end of the vagus, however, produces glycosuriawhether nicotine had been administered or not, and application ofnicotine locally to the stellate ganglia during excitation of the vagusrenders the urine sugar-free. Still it is unwise to draw importantconclusions from these experiments, since the procedure adopted oEtencaused a lowering of blood pressure, and that in itself causes the sugart o disappear.Gaseous Metabolism.The respiratory processes are capable of two lines of study,namely, those which are concerned with the phenomena of externalrespiration and with internal or tissue respiration respectively.I may refer readers who desire to obtain a full account of theexternal respiratory processes to an article by Christian Bohr inNagel’s Handbuch der Physiologie now being issued ; it contains amongother things a succinct account of the author’s own researches, whichhave extended over many years.A further contribution to this work onthe absorption coefficients of blood and blood-plasma for gases has beena Proc. Amer. Physiol, SOC., 1904, xxxvi ; Amer. J. Physiol., 13 ; Abstr., 1905,J. Amer. Mecl. ASSOC., July, 1904 ; Abstr., 1905, ii, 187.ii, 187.Proc. Physiol. Soc., 1905, lxiii ; J. Physwl., 32 ; Abstr., 1905, ii, 544230 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,issued during the year.l Leonard Hill and his colleagues2 haveadded some more details to their previous work on caisson diseaseand the gases set free in the body after rapid decompression from highatmospheric pressures,One of the most important pieces of new work, however, is thatcarried out by J.S. Haldane, who is well known as an expertin connection with the air in mines. He and Priestley3 haveintroduced a new method of obtaining normal alveolar air; it con-sists in collecting a sample of the expired air at the end of inspirationand another a t the end of expiration ; the mean of the two gives thecomposition of alveolar air. This is much simpler than Pfluger’scatheterisation method, and has the further advantage that it can beapplied t o the human subject.Under constant atmospheric pressure in man, the alveolar aircontains a nearly constant percentage of carbon dioxide in the sameperson. In different individuals, this percentage varies, With vary-ing atmospheric pressures, the percentage varies inversely as theatmospheric pressure, so that the carbon dioxide pressure remainsconstant.The oxygen pressure, however, varies widely under thesame conditions.These observations and the next to be immediately describedfurnish the chemical key to the cause of the amount of pulmonaryventilation, and play an important part in conjunction with therespiratory nervous system in the regulation of breathing. For therespiratory centre is not only affected by impulses reaching it by thevagi and other afferent nerves, but it is also very sensitive to any risein the alveolar carbon dioxide pressure, a rise of 0.2 per cent.beingsufficient to double the amount of alveolar ventilation during rest.Changes in the oxygen pressure within wide limits have no suchinfluence ; the normal chemical stimulus t o respiration is thereforepresence of carbon dioxide, snd not diminution in oxygen. If theseIimits are exceeded, as when the oxygen pressure in the inspired airfalls below 13 per cent. of an atmosphere, the respiratory centrebegins to be excited by want of oxygen, and the alveolar carbondioxide pressure begins to fall. The changes in the alveolar carbondioxide pressure are normally proportional to the tension of that gasin the arterial blood, and it is by that channel that the changes in1 Skand. Arch. Physwl., 1905, 17, 104; Abstr., 1905, ii, 729.2 Proc.PhysioZ. Soc., 1905. vi, vii ; J. PhysioZ., 33 ; Abstr., 1905, ii, 728.3 J. Physiol., 1905, 32, 225 ; Abstr., 1905, ii, 400. A second paper by Haldaneand Fitzgerald (J. Physiol., 1905, 32, 486; Abstr., 1005, ii, 539) is mainlystatistical. Confirmatory observations on the principal point raised are publishedby Hill and Ham (Proc. Physiol. SOC., 1905, v ; J. Physiol., 33 ; Abstr., 1905,ii, 728)PHYSIOLOGICAL CHEMISTRY. 231the lung alveoli are transmitted to the respiratory centre. Duringwork, the alveolar carbon dioxide pressure increases slightly, and thepulmonary ventilation is consequently increased. Apnoea is the namegiven t o the cessation of breathing which temporarily follows excessiveventilation of the lungs, as when one takes a number of deep breathsin rapid succession.It depends on a fall of the carbon dioxidepressure in the respiratory centre to below the threshold excitingvalue, the oxygen pressure a t the same time being sufficiently highnot to excite the centre. The old idea that apnoea is due to overoxygenation of the blood has been abundantly disproved, and Headand others have gone to the other extreme in assuming that apnea ispurely nervous in origin. Some years ago, Fredericq showed thatapnoea can be produced in animals with both vagi cut, and he mootedthe idea that fall in the tension of carbon dioxide is its chemicalcause. Haldane does not allude to this in his papers, but he never-theless confirms Fredericq’s-opinion, and considers that it is unnecessaryto assume the existence of a vagus apnaa in man a t all under normalconditions.The whole paper is replete with interest and should be read infull; it contains many other matters which need not be discussed inthis report, such as new determinations of the volume of tidal air andof the I‘ respiratory dead space.”Passing now to questions of internal respiration, it is necessary toallude t o two researches, one on nerve, the other on the kidney.The question whether nerves participate in respiratory activity hasbeen answered in the affirmative by Baer, Frijhlich, and others in con-firmation of Waller’s long-expressed opinion that carbon dioxide is pro-duced during the activity of nerve-fibres.By means of a n apparatuscalled the micro-respirometer, Thunberg has succeeded in actuallymeasuring the respiratory exchange in small objects like nerves.Theinstrument has also been utilised in measuring the gaseous interchangesin small animals like worms and snails.The work on the gaseous metabolism of the kidney has been carriedout by Barcroft and Brodie.2 The experiments were made on dogswhich had been subjected to evisceration, an operation they surviveabout eight hours. Diuresis can be produced by the injection of urea,phloridzin, or of salts like sodium sulphate. This is accompanied by alarge increase in oxygen absorption. The oxygen absorbed is the bestmeasure of the work of the kidney, for the carbon dioxide formed isnot evolved simultaneously ; still, over a large number of experimentsthe volumes of oxygen absorbed and the carbon dioxide excreted areSknnd.Arch. Physiol.,1905, 17, 133; Abstv., 1905, ii, 728.Centr. Physiol., 1904, 18, 553 ; Abstr., 1905, ii, 44.2 J. Phy$iol., 1904, 32, 18; 1905, 33, 52; Abstr., 1905, ii, 99, 737232 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.approximately equal. This suggests, although it does not exactlyprove, that the substance of the kidney is broken down in the organ it-self. Diuresis is not necessarily accompanied with increase in blood flow,and this is never so great as the acceleration of urine-flow ; when it ispresent, the diuresis outlasts it.The work of concentration, as calculated from the freezing points ofblood and urine, accounts for only a small fraction of the energy trans-formed by the kidney.In so far as urine of the same freezing point asthe serum would represent Ludwig’s glomerular filtrate, the experi-ments yield no support to his theory, for the source of energy for theproduction of such urine should be the heart and not the kidney, yetit is in these circumstances that the kidney is most active as gaugedby the gaseous exchange. I n some cases, urine of smaller molecularconcentration than the serum was obtained, and this divergence isgreatest when the flow of urine is most rapid. The experiments lendlittle or no support to the theory of reabsorption of water in the kidneytubules, a theory recently revived by the work of Cushny.and others should beconsulted.They consider the main cause of certain forms of diuresisis accelerated blood flow, and in other forms it is a hydrsmic conditionof the blood.Adremaline.I n this relation, a series of papers by’loewiThe chemical constitution of adrenaline and the synthesis of certainsubstances allied to it were fully entered into in my report of lastyear. It will be sufficient to add now, that the physiological action ofthese and other synthetical substances has been fully worked out byDakin,2 and later by Loewi and Hans M e ~ e r . ~ The formula given forDakin’s final product is that which Jowett assigns to adrenaline ; butthere are certain differences between the new base and adrenaline, forinstance, the former is optically inactive. Tts salts, however, show allthe reactions of those of adrenaline, and its physiological activiiy is asgreat ; less than a millionth of a gram will raise the blood pressure.The intermediate ketone (Friedmann’s adrenalone) is not much morepowerful physiologically than the chloroacetylcatechol from which it isprepared.Inorgarzic Salts.The number of papers published on inorganic salts is numerous;most of them relate to questions of physical chemistry, and seek toexplain vital phenomena such as rhythm and nerve activity on an1 Arch.exp. Path. Pharm., 1905, 53, 15, 33, 49; Abstr., 1905, ii, 739.2 Proc. Physiol. SOC., 1905, xxxiv; J. Physsiol., 32; Abstr., 1905, ii, 410.3 Arch, exp Path, Pharm., 1905, 53, 213; Abutr., 1905, ii, 846PHYSIOLOGICAL CHEMISTRY.233electrolytic basis. Researches of this kind leave the subjects treated,however, in a hypothetical state, and for this reason, as well as for wantof space, my allusions to these papers must be more of the nature ofa catalogue than is wholly desirable. The following are a selection ofthe most important.Overton 1 publishes a very important series of experiments withvarious salts on the frog’s sartorius. Among the many points raisedit will be sufficient to mention one, namely, that the harmful action ofpotassium ions is like that caused by curare. I mention this onebecause it is also taken up by Locke,2 who points out certain differ-ences between the action of the two substances.records experiments on heart strips, and the resultsobtained do not bear out Howell’s views.The principal main con-clusion drawn is that it is the anion, not the cation, which stimulates.One must, however, point out that the practice of performing experi-ments on strips of the heart, so common in America, although it leadst o results of interest, is not well calculated to discover the causeof the cardiac rhythm in the intact organ during life.J. Loeb4 has continued his experiments on the antagonism of saltsin reference to the growth of fundulus eggs, but W. A. Osborne5points out that the so-called antitoxic action of bivalent cations issusceptible of a simpler explanation than that given by Loeb.A. B. Macallum 6 is still prosecuting his useful work on the micro-chemical detection of inorganic elements. His cobalt nitrite reagentfor potassium shows that element to be present in cell protoplasm,but more abundantly in intercellular material ; in striped muscle,it is limited to the dark bands, and in pancreatic cells t o the granularzone.It is absent from nerve cells and from the nuclei of all cells.In nerve fibres, it occurs in curious patches external to the axiscylinder, especially a t the nodes.The second paper quoted deals with the well-known reduction stainwith silver nitrate so much used in histology. The conclusion reachedis t h a t this is not due to a reduction of a silver-proteid compound,but to inorganic chlorides, Intercellular material is specially richin chlorides, and the reaction may be employed to determine thedistribution of chlorides in histological specimens.The normal nucleiof animal and vegetable cells contain no chlorides at all.BenedictPJtiger’s Archiv, 1904, 105, 176 ; Abstr., 1905, ii, 46.Proc. Physiol. SOL, 1904-1905, x x i i ; J. Physiol,, 32 ; Abstr., 1905, ii, 270.dmer. J. Physwl., 1905, 13, 192; Abstr., 1905, ii, 330.Pfluger’s Archiv, 1905, 107, 252 ; Abstr., 1905, ii, 400.Proc, Physiol. S’oc., 1905, x ; J. Physiol., 33 ; Abstr., 1905, ii, 746.J. Physiol., 1905, 32, 95 ; Abstr., 1905, ii, 270. Prod. Roy. SOL, 1905, 76 B,217 ; Abstr,, 1905, ii, 736234 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.J. S. Macdonaldl amplifies one of Macallurn’s conclusions. Hiswork was directed to obtaining a physical explanation of the electricalchanges which occur in nerves.He found by the use of certain stainsthat granules which are deposited a t the seat of an injury are stainableby “neutral red.” The colour differs according to varying con-ditions; for instance, a cooled fibre is alkaline, a warmed one acid.Attempts to alter the reaction by activity failed. The granules areprobably stained coagula of proteid, and the appearances are similarto those described by Macallum in his potassium reaction. By Mac-allum’s method, potassium salts may be detected wherever an injuryoccurs, and the patchy appearance Macallum describes is attributed toinjury of the axis cylinder at those spots. Not only are potassiumsa1t.s liberated from the axis cylinder, but the amount found leads toa salt solution of great concentration at the injured spot, as measuredby the extraordinarily concentrated solutions necessary t o balance theinjury current so produced.The Pathology of Cuncer.This is the only subject of a pathological nature upon which I willpermit myself to dwell.It is a question fraught with interest to all,and at numerous centres research and money are being expended withno unwilling hands in attempts to grapple with this scourge ofhumanity. It must be confessed that up to the present the diseasehas baffled all attempts to unravel its causes, and hope for the healingof sufferers seems as far off as ever. The surgeon’s knife, if appliedat a sufficiently early stage, is the only remedy, but that cannot alwaysreach deep and hidden structures, and if the tumour is accessible, itis a mere matter of chance whether every particle is even thenremoved.It may be that some of those who have subscribed of their wealthtoward Cancer Research may be disappointed at the paucity of theresults obtained after so many years of labour.But there will beothers who realise that money cannot buy everything, and willsympathise with failure, especially if they have any idea of thedifficulties which beset biological and pathological researches ingeneral, and those relating t o cancer in particular.If a number of eager and capable investigators were set to find outthe cause of an infectious disease, one cannot doubt that the search,although it might be difficult, would be attended with ultimatesuccess, for such workers would have the previous researches ofProc.Physiol. Soc., 1905; xxxvii; J. Physiol., 32; Abstr., 1905, ii, 405PHYSIOLOGICAL CHEMISTRY. 235others to guide them in the investigation of other diseases of thesame order, and the micro-organism, either animal or vegetable, wouldthus be brought t o light.It does not runon the same lines as any other pathological condition, and allattempts to work at it by the older methods have yielded negativeresults. One is therefore groping i n the dark looking for a new andinvisible path along which to progress. One fact which the researchof recent years has demonstrated is that the various bacteria andprotozoa from time to time described as the active agents in cancerare merely accidental concomitants, or the erroneous interpretation ofmicroscopic appearances.The parasitic theory of cancer-causation iskilled, and serum treatment on immunity lines has so far failed.A special stumbling-block is met with at the outset in the difficulty,and often impossibility, of transmitting t h e disease to animals, or ofproducing it in them. Hence at once the field of experimentation islimited.I n addition to this negative conclusion, there is at any rate onepositive finding of some interest, and it may ultimately be shown to bemore important than it appears to be at present. Such discoveries a tany rate encourage further work, and show that the problem maynot be so hopeless as it seems at first. The discovery in question wasnot made by pathologists or even by medical men, but by those whodevote their lives to the calmer atmosphere of biology.Farmer andMoore showed that the actively multiplying units of malignant growthsgo through the process of cell-division in an unusual manner, or, t o usethe technical expression, the mitosis of their nuclei is heterotype.The same unusual behaviour of the cell nuclei is seen in certainstages of the formation of the generative elements. It thereforeappears that the cancer cell is either a cell of embryonic type or thatit has reverted to embryonic habits.l The cause of such reversion andthe explanation why such reversion should generate a malignantdisease is still to be discovered.We now come to see what chemistry has done to help in the matter.Many years ago, the statement was made that in cancer of thestomach the hydrochloric acid of the gastric juice disappeared, andthis fact was urged as a useful means of diagnosis between malignantdisease and a simple ulcer.Although the absolute statement hasbeen doubted from time to time, there is no longer any hesitation inaccepting it as proved that, if the acid does not entirely disappear, itThe most recent paper on the subject is by Farmer, Moore, and Walker (Trans.Path. h'oc., London, 1905, 56, 377), and deals especially with the behaviour of leuco-cytes in malignant growths.But malignant disease appears to be one sui gene&236 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.is at any rate much reduced in quantity. B. Moorel has furthershown that this is not merely a local effect on the stomach wall, buttbe same reduction or abolition of the gastric acid occurs in cancer ofother organs, even although the stomach itself is not affected, andthat it is due to diminished concentration of hydrogen ions in theblood plasma. It is, however, extremely doubtful whether amaintenance of the normal concentration would counteract the effectsof cancer, but that, of course, cannot be asserted until the experimentis tried, and a t present there is no means available for trying it, forthe administration of acid below the limit of acid-intoxication merelycalls forth protective ammonia production from the oxidation ofprot eids.Another line of research consists in the chemicsl examination of theh n o u r s themselves. Carl Neuberg 2 draws attention to certainabnormal fermentative occurrences in the growths, and believes thatsuch influence as radium possesses on carcinomatous tissue is byaltering the ferment actions. By autolysis of liver-cancer, freepentose makes its appearance, whereas in normal liver tissue this doesnot occur. The high percentage of pentose in cancerous tissue isregarded as being due to its richness in nuclei.s. P. Beebe has published a series of papers on the composition oftumours. The first 3 relates to their inorganic constituents, but theexperiments are confessedly too small in number for conclusions t o bedrawn regarding the differences between benign and malignantspecimens. The next 4 relates to proteids, and special search was madefor nucleo-histon; this proteid does not appear to be a common con-stituent of tumours unless they occur in connection with lymphatictissue of which nucleo-histon is a. normal constituent. The third,written in conjunction with Shaffer,5 deals with the pentose questionraised by Neuberg. I n cancer of the breast, they found the amountof pentose higher than in normal breast tissue, and it is sometimesextremely high in cases of chronic scirrhus, where nuclear proliferationis not a marked feature, so that Neuberg’s suggestion of a nuclearorigin is hardly confirmed.I n the tumours of the liver examined, the amount of pentose didnot markedly differ from that found in the normal organ; thepentose content of normal tissues varies considerably ; they concludethat many more observations are needed before any theory on therelation of cancer and pentose can be considered satisfactory.Proc. Xoy. Soe., 1905, 76 B, 138; Abstr., 19C5, ii, 741.Berlin klin. Woch., 1905, 118 ; Abstr., 1905, ii, 338.Amer. J. Physiol., 1904, 12, 167 ; Abstr., 1904, ii, 755.Amer. J. Physiol,, 1905, 13, 341 ; Abstr., 1905, ii, 408.Anzer. J. Physiol., 1905, 14, 231 j Abstr., 1905, ii, 742PHYSIOLOGICAL CHEMISTRY. 23’1Many more observations of all kinds me equally necessary beforeour knowledge of cancer is sufficient to enable us to formulate anyworkable hypothesis of its cause, and still more to effect its cure. Thefragments of research just described may in the future form portionsof the picture; as yet even the outline is not discernible, but therecan be little doubt that chemists will play their part with others inthe final composition. W. D. HALLTBURTON

ISSN:0365-6217    

DOI:10.1039/AR9050200212

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

AGRICULTURAL CHEMISTRY AN D VEGETABLEPHYSIOLOGY.WHEN summing up, a year ago, the record of “ Progress in agriculturalchemistry in 1904,” it was pointed out that there was no one out-standing feature which marked the year’s work and which could bedesignated as a great discovery in the sense that this term is appliedto that which is at once startling and far-reaching in its results, Theyear 1905 can, however, claim to be associated with a discovery which,whatever be the practical outcome in its application to agriculture, isof a most highly interesting nature, and which marks the working outof ideas which have existed ever since Cavendish, in 1784, showed thatthe oxygen and the nitrogen of the atmosphere could be made to uniteunder the influence of the electric discharge.Many have been theefforts to bring this discovery into practical working and to lay theatmosphere, with its unlimited atore of nitrogen, under contribution toagriculture, the main needs of which, as shown by Lawes and Gilbert,consist in the adequate supply of nitrogen in a form in which it can betaken up by the living plant. This has now been effected by thediscovery of a method of producing calcium nitrate from the nitrogenof atmospheric air, and, so far as agricultural chemistry is concerned,it forms the most striking item in the year’s progress.As in 1904, interest has turned mainly on the “nitrogen question,”and this not alone in the direction just indicated, but in other wayswhereby either nitrogen-containing materials may be brought to theservice of the plant, or where the bacteriological conditions may be soarranged that the plant may itself be able to utilise the nitrogen of theair as it circulates in the soil.The researches in this direction havecentred in the further examination of the two principal mattersmentioned in last year’s report, namely, cyanamide and inoculatingmaterials known under the general term nitragin.” Within the lastfew weeks the statement has also been put forward of a furtherdiscovery regarding the way in which, not leguminous plants only, butcereal and other agricultural crops, make uae of atmospheric nitrogen,but of this the details are not yet to hand.In further pursuit of inquiry on the utilisation, by cereals, oAGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY.239nitrogen stored up by leguminous crops, experiments on green-manuringhave been continued. These investigations, conducted in the one casein the field and in the other by pot-culture methods, have led tothe noting of differences which raise considerable question as to how farthe one plan of inquiry is comparable with the other.Investigation in regard to soils has hardly turned in any freshdirection, but further useful work has been done on the solubilityof soil-constituents in different solvents and on the oxidation of soil.The subject of lime in soils and the influence which lime exercises hasreceived much attention, alike as regards its occurrence in relation tomagnesia and other soil-constituents, and in reference to its rate ofremoval from the soil under known conditions.Further work has been done on the influence of small applications ofthe less common materials which may be concerned with plant nutri-tion, these embracing such substances as manganese, zinc, iron, chlorine,&e.I n plant physiology, the most important contributions ha3.e beenthose of Horace T. Brown and F. Escombe on the physiological pro-cesses which go on in the green leaves of plants. The preponderatinginfluence of “variety” in cultivated plants of the farm has beenemphasised by field experiments carried out in the case of wheat byA. D. Hall, and by T. B. Wood and 8. H. Collins with root crops.Further investigations by E. J. Russell into the losses which farm-yard manure undergoes in making and storing have gone to prove theaccuracy of former work on this subject.These several points will be dealt with in detail further on.Among matters of general interest mention may be made of the con-tinued activity of the Rothamsted Experimental Station, and of theissue, by the Director, A. D.Hall, of The Book of the Eothamsted Ex-psriments,l in which is given, in a very clear and, at the same time,popular way, a summary of the work of this renowned experimentalstation since its inception, in 1843, by Lawes and Gilbert. The mainfeatures of the work are admirably summarised and brought up todate, while their bearing on agricultural practice of the present dayis set out in a comprehensive and definite manner.The visit of the British Association to South Africa furnished anoccasion for the introduction and discussion of the various problemsexercising the minds of workers in agricultural science at the presenttime, and specially in relation to that great country and its agriculturalpossibilities.From India one hears with interest of the expansion of the work ofagricultural inquiry, this being now fostered both by GovernmentDepartments and private individuals, as well as by commercial indus-tries.The Government of India has decided on the establishmentThe Book of the Rothamsted Zxperiments, by A. D. Hall (John Murray), 1905240 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.at Pusa, in Lower Bengal, of an Agricultural Research Station andLaboratory, connected with which will be an experimental farm, 800acres in extent, and also an Agricultural College.This has been theoutcome of a munificent donation by Mr. Henry Phipps of .&20,000, towhich a further sum of 210,000 has since been added by Mr. Phipps.Further, the Indian Tea Association have resolved to institute a tHeeleaka, near Moriani, Assam, an experimental station where thevarious problems connected with the culture of the tea plant can beinvestigated. Both these spheres of inquiry, begun, as they have been,under favourable auspices and with capable men to carry them out, bidfair to be productive of much benefit and to call for more workers inthe near future.While these advances have to be recorded, it is a matter for regretto note the cessation of the Guinness Research Laboratory, the recordof the work conducted at which formed so prominent a feature in thereview of last year’s progress.It was confidently expected that fromthis Institution would proceed a regular series of results of investiga-tion of the highest importance, a hope which was fostered by the issue,in 1904, of the first part of the transactions, under Dr. Horace Brown’sdirection,From the continent has to be recorded the retirement, after a serviceof more than forty years in this position, of Dr. F. Nobbe, ofTharand, from the editorship of the journal Die LandwirtschafttlichenVersuchs-Stationer, his place being now taken by Dr. 0. Kellner, ofMockern.On May 18th, 1905, died Dr. A. Hilger, of Munich, who, since 1878,had been editor of the Jahresberiaht ubar Agrikultur-Chemie.This,happily, is the only great loss by death torecord in agricultural sciencethroughout the year.The Nitrogen Question.(a) Imm.dation of Leguminous Crops.This operation, as being the direction in which the problem of theutilisation of atmospheric nitrogen has in more recent years beenmainly attacked, will be dealt with first. I n last year’s report mentionwas made of the improved methods, by Hiltner, of Munich, on the onehand, and by G. Moore, of the U.S.A. Department of Agriculture, onthe other, of preparing materials for the purpose of inoculatingleguminous crops so as to enable them to take up and utilise the freenitrogen of the atmosphere. The year 1905 has seen the first trial,alike on the Continent, in America, and in our own country, of thesepreparations, and, although the inquiry is far from complete, yet asthe outcome of the year’s experience, some general conclusions may bAGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 241drawn as to the likelihood of either method of inoculation becoming arecognised part of agricultural practice.I n Great Britain, the Board of Agriculture interested itself largely inthe inquiry, and, having obtained supplies of the inoculating materialdirect from Germany and America, proceeded to distribute these tovarious agricultural colleges where experimental work was conductedand also to the Woburn Experimental Station of the Royal AgriculturalSociety of England.Suggestions were also made as to the lines onwhich the inquiry might be conducted. I n all, thirteen different insti-tutions took part in the work, and the results are shortly to be published.Where the inquiry was carried out in its entirety, the experiments wereconducted in three different ways : (a) with sterilised soil ; ( b ) with ordi-nary soil by pot-culture methods ; (c) under ordinary farming conditionsin the field. I n some instances there was an extension of the scope bythe use of sterilised sand as well as of sterilised soil. The generaloutcome of the work was that while in a certain number of casesthere was some indication of benefit having been derived from theinoculation methods, there were many more instances in which eithernegative or else unfavourable results were obtained.The element ofconsistency between the apparently successful results was missing,and where, for example, at one station barley seemed to be bene-fited, peas were not, while a t another station peas were improved,but beans not. At the Woburn Experimental Station, the onlyinstance of benefit derived was in the case of the Melilotus crop, withthe American inoculation, the other trials having produced little morethan negative results, although carried out on sterilised soil, on unsteril-ised soil which had not borne a leguminous crop for twenty years, andon an ordinary fertile soil. I n one series, conducted at the MidlandInstitute, Kingston, near Derby, successful results were obtained whensterilised sand was used, but these were not reproduced when sterilisedor when ordinary soil was employed.Of the experiments on farm soilunder ordinary conditions, it must be said that with one or two excep-tions they failed to show any beneficial outcome from the treatment.It may, of course, be argued that these soils were, through previousgrowth of leguminous crops, already supplied with the organisms whichthe inoculation was intended to provide, and hence had no further needfor these. It is only fair, also, to mention that in several cases theinoculating materials had been obtained some time previous to theirbeing actually used, and so they might have suffered from not being asfresh as was desirable. As between the German preparations ofHiltner and the American ones of Moore, what there was to choose wasin favour of the German method.Altogether, as the outcome of the inquiry in this country during1905, it cannot be held that there is anything to encourage the beliefVOL. 11.242 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.that inoculation for leguminous crops has reached a stage at which itcan be recommended for adoption in general agricultural practice.Turning to experiments conducted elsewhere, F. T. Shutt 1 reportsfrom Canada the results of a number of experiments carried out invarious parts of the Dominion with both the German and the Americanpreparations. The German preparations, tried over a series of years,gave no clear evidence of benefit accruing, and the vitality of thecultures was found to be very uncertain unless these were used quiteshortly after their preparation.More recently, the new Americancultures for red clover and alfalfa were employed, but did not showclear benefit in any case. Shutt points out that, as regards, at least,Ontario and the Eastern Provinces of Canada, the necessity for inocula-tion is not nearly so great as was at one time thought, but that, whereclover has been found to fail, this is to be attributed to deficiency orexcess of moisture, or to unsuitable mechanical condition of soil, ratherthan to the absence of nitrogen-assimilating germs. He notes that inan extended agricultural tour he found the presence of root nodules onclover to be universal. A. D. Hall2 indicates that much turns on thevirulence possessed by the sub-cultures used for inoculation, and that thismay be greatly modified by growing on particular media, by a high tem-perature, or even by long-continued growth under laboratory conditions.Inoculation is much more likely to be required where new land is beingbrought under cultivation than where leguminous crops have been pre-viously grown.The question of the successful growing of lucerne onSouth African soils calls for consideration in this connection. J. Gold-ing 3 directs attention to the necessity of realising, as far as possible,the conditions under which the organism works in the nodule, and tothe difficulty of reproducing under artificial conditions the actual pro-cess of fixation as it occurs in the nodule.His observations have ledhim to regard as very desirable the removal of the soluble products ofgrowth during the assimilation process, so that the conditions obtainedin nature; can be produced. This he has effected by the use of a porousChamberland filter-candle fixed in the culture vessel, and. has found amore favourable assimilation of nitrogen to result through the removalof the soluble products of growth, a function probably fulfilled undernatural conditions by the host-plant.Whether longer experience may lead to the production of inoculatingmaterials practically useful in agriculture still remains an openquestion, but it would seem at least fairly certain that, up to the-Canada Department of Agriculture, Annual Report on, Experimental Farms," Recent Developments in Agricultural Science," Brit.Assoc. Reports, Section B,J. Agric. Sciefzce, 1, Jan., 1905, p. 59.Ottawa, 1905, p. 165.S. Africa, 1905AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 243present time, there has been something in the method of preparation ofthe cultures which has resulted in the partial or complete destructionof their efficacy, and there is certainly not as yet any clear evidence tojustify a recommendation of their use in agricultural practice.(b) Cyanamide.I n last year’s report, an account was given of the manufacture ofcalcium cyanamide and its sale under the name (‘ Kalkstickstoff.”Further trials with it were made in 1905. At Rothamsted,A. D. Hall 1 tried it in comparison with ammonium sulphate for mangels,swedes, and mustard, but the results were of indefinite character, andthe most that could be said was there was nothing to indicate thatcyanamide was, unit for unit of nitrogen, worth more than ammoniumsulphate.Cyanamide cannot be used as a top-dressing, as loss of ammonia thentakes place, nor can it be mixed with superphosphate or similar manures,since the mixture gets very hot.W. Zielstorff,2 in conducting pot-experiments with mustard, found that when the cyanamide was sownwith the seed its value as compared with sodium nitrate was 88.4 : 100,whereas if applied ten days previous to the sowing of the seed the valueincreased to 92.8 per cent. Zielstorff also ascertained that cyanamideleft practically no residue for a second crop to benefit by.E. Haaelhoff 3 showed that germination was injuriously affected ifoalcium cyanamide were present in the proportion of 0.025 gram to100 grams of soil, but that harm might be avoided by application ofthe cyanamide well in advance of sowing of the seed.C.von Seelhorst and A. mu the^-,^ in comparing calcium cyanamidewith ammonium sulphate, found that in the case of a sandy loam themanurial value was about equal in the two cases, but that when usedin sand-cultures, calcium cyanamide was injurious to vegetation, probablybecause of the presence of calcium carbide.F. Lohnis 5 experimented with several different micro-organisms inorder to see what effect they would have on calcium cyanamide. Hefound that Bacterium Kirchnevi, B.lipsiense, B. megatherium, B. vulgarevaT. Zopj, and others liberated ammonia from cyanamide a t the ordinarytemperature and that aeration took no essential part in the process.R. Perotti,6 having previously shown that for calcium cyanamide to actJ. Agric. Science, I, Jan., 1905, p. 147.Bied. Centr., 1905, 34, 217.Jahrb. Landw. Versuchs-Stat., Marburgj 1904-5.J Landto,, 1905, 53, 329.Centr. Bakt. Par., 1905, [ii], 14, 309;Chem. Centr., 1905, 2, 1507.I:, 244 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.as a fertiliser it must undergo decomposition in the soil, experimentedwith it in conjunction with peat, and he then found that hydrolyticdecomposition took place more rapidly ‘than in aqueous solution, andthat there was no appreciable loss of nitrogen.From this he was ledto suggest the use of peat along with calcium cyanamide for the morerapid decomposition of the latter, and to advise the use of peat withfertilisers containing calcium cyanamide.I n general, as regards the use of calcium cyanamide, it may be saidthat the evidence so far points t o i t being beneficial, although hardlyto the same extent as ammonium sulphate, whilst its practical successin the future must depend entirely on the cost price at which it can beproduced as compared with ammonium sulphate supplying an equalamount of ammonia.(c) Calaiwm Nitrate.Undoubtedly the subject which has given rise, during the year 1905,to the greatest interest so far as agricultural science is concerned, isthat of the discovery of a new method of utilising atmospheric nitrogen.This has been effected by Birkeland and Eyde’s process, which hasbeen fully described by 0.N. Witt.l Briefly, this consists in the pro-duction of nitric acid through the combination of the elements of theair under the influence of electricity generated in a furnace of greatintensity. The nitric acid is then transformed into calcium nitrate bypassing it into lime water, and subsequent manipulations result in theproduction of a salt which can be used directly on the soil as a fertiliser.That small quantities of nitric acid are formed under the influence ofatmospheric electricity has long been known, but these amounts are fartoo small to be of any agricultural importance.I n face of the con-clusions arrived at by Lawes, Gilbert, and Pugh, that plants are unableto avail themselves of the uncombined nitrogen of the air, and that itis in the form of nitrates that they take up nitrogen, recourse hasbeen had to the use of sodium nitrate and other nitrate-yieldingmaterials and to the cheaper production of these. I f the atmospherecould be made to produce these nitrates in sufficiency it is clear that anunlimited source of supply would be ready a t hand. The presentdiscovery, which may be described as Cavendish’s experiment on alarger scale, and carried out under more favourable conditionsas regards electrical energy, has been achieved by Birkeland andEyde at Notodden, Norway, where water power of enormous extent isavailable.Atmo?pheric air is led into a specially constructed electricfurnace, in which it is heated to a very high temperature under theinfluence of an electric arc spread out into disc-like shape by the actionof powerful electro-magnets ; oxides of nitrogen are formed from the airChem. Ind., 1905, 28, 699AGRICULTURAL CHEMlSTRY AND VEGETABLE PHYSIOLOGY. 245thus introduced, and these are conveyed into a series of towers inwhich they are condensed in water and the liquors allowed to concentrate,the weak acid being used over and over again in the towers untila strength of about 50 per cent. is attained. The gases are then ledinto milk of lime, and after that over dry lime, whereby calcium nitriteis mainly formed. By treatment with nitric acid, a calcium nitratecontaining about 13.2 per cent.of nitrogen is obtained as a salt, whichcan then be employed direct as a fertiliser of the land. One objectionto the product, namely, its hygroscopic nature, has been overcome byR. Messel, who, by mixing the calcium nitrate so obtained with calciumoxide, or with calcium sulphate, and calcining the mixture, has obtaineda, basic calcium nitrate, ( 2Ca0,N205), which is non-hygroscopic andwhich, when powdered, can be readily applied to the land. It would, ofcourse, be possible to obtain sodium nitrate in place of calcium nitrateby using sodium carbonate instead of lime, but the calcium nitrate ispreferred both on account of the cheapness of the lime and becauseof the agricultural benefit which the use of lime will in many casesconfer, more particularly when soils are deficient in this necessaryconstituent.Practical trials have been made already with the calcium nitrate,and these would seem to indicate that it is just as effective as sodiumnitrate, supplying the same amount of nitrogen.- Indeed, there is noreason why this should not be the case.T. Schloesing carried out pot-culture experiments with maize, in which the use of calcium nitrate andcalcium nitrite was compared with that of sodium nitrate and nitriterespectively, and the calcium salts were shown to be equally asefficacious as the sodium ones. Also E. S. Bellenoux experimented withcalcium nitrate and sodium nitrate in the field on crops of potato andsugar beet, and found that the calcium salt gave in each case the betterresult.The calcium nitrate in these experiments, however, had notbeen obtained by the electric process above described, but from sodiumnitrate and calcium chloride, whereas in T. Schlcesing’s experimentsthe electrically-produced salts were used.I f calcium nitrate can be obtained by the electric process at a priceat which, as regards its percentage of nitrogen, it can compare favour-ably with sodium nitrate, it is clear that enormous benefits are athand so far as agriculture is concerned. So far we have but littleinformation to guide us as to what the cost of manufacture is, and itis still early, therefore, to build great hopes on the prospects. Theprovision of water-supply adequate for the production of electric powera t a cheap rate is evidently the determining factor, but, from ascientific point of view, the discovery of this new process constitutesone of the most important advances of the century.It is to beCmnpt. rend., 1905, 141, 745, 746. Ibid., 140, 1190246 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.hoped, however, that in the case of an undertaking possessing suchfar-reaching possibilities nothing will be allowed to interfere with itsdevelopment on strictly scientific lines, and with its furtherance forthe benefit of agriculture.(d) Direct Utilisution of Nitrogen by Plunts.Following on the foregoing development, there comes, just a t theclose of 1905, the announcement of a further discovery by T.Jamieson,of Aberdeen, which is, in effect, that he has found that not leguminousplants only, bu? cereals, grasses, and plants in general have the power,by the medium of certain structures on their leaves and leaf-stalks, oftaking in and utilising directly the nitrogqn of the atmosphere. Thisprocess is said to be only exercised by the leaves and leaf-stalks intheir youngest state. Up to the present the details of the work arenot to hand, and therefore it is impossible to criticise them or to domuch more than merely record the facts as stated. At the same time,we can hardly be prepared, despite recent subversions of some of ourviews based on the earlier work of Lawes and Gilbert, to accept off-hand a statement so contrary to the conclusions of past experience,or to think that the existence and functions of these special organshave hitherto escaped the notice of plant physiologists.(e) Pixation of Nitrogen without Xymbiosis.G.S. Fraps,l in giving the result of experiments on soil bacteria,mentions that free nitrogen is assimilated by them without symbiosisand that the greatest activity occurs in an alkaline solution containingglucose, potassium phosphate, sodium chloride, magnesium sulphate,and ferric chloride, calcium carbonate being also. present. Nearly allthe nitrogen was fixed in the first week of the experiment, and asmall amount only in the second week. The replacing of glucose bystarch did not increase assimilation of nitrogen, and the activity wasreduced when magnesium sulphate was omitted.E. B. Voorhees andJ. G. Lipman 2 concluded from experiments conducted with cow-peasthat non-symbiotic fixation of nitrogen was most active in open soilscontaining fairly large amounts of organic matter but having only alow percentage of nitrogen. The soils gained nitrogen during thegrowth of the cow-peas, and fixation of nitrogen was believed tocontinue after their removal and during the growth of subsequentcrops of millet. When organic matter was present in the soils,nitrogen-fixation went on actively, but if large amounts of a leguminouscrop were incorporated with the soil no gain of nitrogen was shown.Agi-ie. Expt. Stat. N.C., Report of Chemist, 1902-3, p. 40.J. Ainer. Chem. Soc., 1905, 27, 556AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY.247The question as to how the organism Axotobacter c?uroococcum, dis-covered by Beyerinck, effects its work of nitrogen-fixation is stillsurrounded with uncertainty, Beyerinck himself now inclining toattribute its power to the presence of certain other organisms livingpractically in symbiosis with it. It is clear, however, that this organism,which exists freely in most cultivated soils, can, in a medium contain-ing phosphate and other nutrient salts, but no nitrogen, fix nitrogenactively if 1 or 2 per cent. of a carbohydrate be present. Thus, A. D.Hall 1 found, with a Rothamsted soil, that, when mannitol was used,for every gram of this compound 19 milligrams of nitrogen were fixed,In considering where the supply of carbohydrate is to come from, hetakes the case of land allowed to run wild and compares it with arableland under regular cultivation but unmanured.The latter has shownpractically no gain of nitrogen and hence absence of nitrogen-fixation,but the land allowed to run wild has, by the annual return of carbohy-drate matter to the soil, supplied what the Axotobacter requires, and theincrease of nitrogen has, in consequence, been very large, and thisalthough leguminous plants were found by botanical examination to bepractically absent. He concludes that the fixation of nitrogen mustbe a process depending on the oxidation of the carbohydrate matter,this supplying the needed energy. I n this connection, it may be pointedout that Henry 2 has shown that the fallen leaves of forest trees bringabout fixation of nitrogen during their decay.The activity ofAzotoEacter has further been shown by A. Koch to be dependent on thepresence of calcium carbonate in the soil, and this has been confirmedat Rothamsted, the development of the organism being found to bemuch more feeble in soils which have not been chalked than in thosethus treated.Keutner has found that Axotobacter chroococczcm and ~ ClostridiumPasteurianum are widely distributed in sea water ; they are present onalgae and on plancton organisms, and Axotobacter will still show thepower of fixing nitrogen in an 8 per cent. solution of sodium chloride.Soil Organisms.G. S. Fraps 4 distinguishes four groups of organisms in soil, three ofwhich successively convert organic nitrogen into ammonia salts, nitrites,and nitrates, and a fourth which produces nitrites or nitrates directlyfrom organic nitrogen.The nitrifying of an organic nitrogenousmaterial like cotton-seed meal would, according to Fraps, be carried out1 Brit. Assoc. Report, Section B, S. Africa, 1905, and J. Agyic. Science, 1, May,2 Bied. Centr., 1904, 33, 795.4 Agric. Exp. Stat. N.C., Report of Chemist, 1902-3, 9.1905, p. 241.Chem. Centr., 1905, i, 395248 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by a different group of organisms to that which nitrifies ammoniumsulphate. He found that ammonium sulphate was nitrified morequickly than either ammonium phosphate or chloride.A. Stutzer and W. Rothe1 carried out experiments with eightvarieties of soil micro-organisms, and these showed that ammoniumsulphate was a better food than sodium nitrate, also that the presenceof calcium carbonate and ammonia favoured the production of organicnitrogen compounds by various soil microbes.F. Lohnis 2 came to thesame conclusion, regarding nitrogen in the form of ammonium salts asbeing more readily assimilable than nitrates, and he found that variousnitrogen-assimilating bacteria, such as Bacillus radicicoka and B. radio-bacter, could assimilate nitrates, while B. agreste did not fix nitrogen, butassimilated nitrates vigorously. B. $?uoi*escens, on the other hand, causednitrates to disappear, and mainly by denitrification. Lohnis 3 also cameto the conclusion that denitrification in soils can be but inconsiderableowing to the amount of air present, and that nitrification is generallymore active than the processes opposed to it, inasmuch as theconditions favouring nitrification are more generally present in soils.attribute the reduction of nitrates to thehydrogenproduced, along with carbon dioxide, in the breaking down ofcarbohydrates and organic acids. Clostridium gelatinosum, a soilorganism, was found to be active in converting nitrates into ammoniaand partly into proteids.Gaspare Ampola5 considers that denitrification in soil can bealmost wholly avoided by not applying nitrates until the organicsubstances have been decomposed and the denitrifying bacteria thusreduced to inaction.He found that calcium nitrate offered greaterresistance to denitrifying oiganisms than did sodium nitrate.R.Perotti 6 gives a new method for the isolation of nitrifying micro-organisms; this being a modification of Omeliansky’s plan. Blocks ofcommercial magnesium carbonate are used and fitted into Petri dishesor in test-tubes. The upper surface is polished smooth and the undersurface is hollowed out to allow of the nutritive solution being used.After sterilisation of the block and nutrient solution, the liquidcontaining the micro-organisms is poured over the surface of the blockand the whole kept at 28-30°. The surface of the block after a timeshows small regular excavations, the magnesium carbonate being herecoloured yellow, and the bacteria can then be examined microscopically.J.Stoklasa and E. VitekBied. Centr., 1905, 34, 433.Ibid., 1904, 13, [ii], 706.5 Gametta, 1904, 34, [ii], 301.Centr. Bakt. Par., 1905, 14, [ii], 582.Ibid., 1905, 14, [ii], 102.6 AtliIZ. Accad. Lincei, 1905, 14, 1, 228AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 249Assirnilability of Nitrogen Compounda by Plants.Following closely on the foregoing, comes the consideration of therelative assimilability of different forms of nitrogen compounds byplants. L. Lutz1 finds that amides are the most readily assimilablecompounds, and, working with Aspergillus niger, Aspergillus repens,and Penicilliwnt glaucum., he obtained higher numbers than withRaulin's solution containing ammonium salts. The next best wereamines, and then nitrites.From this he deduced that the simpler themolecule the better source of nitrogen will it be for plants. On theother hand, 0. Treboux 2 considers amino-acids and amides suitable forthe lower green plants, but that the value of amino-acids is much lessfor the higher plants. He holds that nitrites are satisfactory inalkaline solutions, but poisonous in acid ones, although this effect isonly noticed when a certain concentration is reached. Nitrates, heconsiders, have an equal or greater nutritive valu? than nitrites, whilstammonium salts are better than either, and would seem to be the bestform in which to apply nitrogen for chlorophyllous plants.Gs.een-manuringAt the Woburn Experimental Farm,3 the subject of green-manuringhas been further investigated, and mainly in reference to the questionas to whether in actual practice advantage is to be derived from thegrowing and ploughing-in of a leguminous green crop as against a non-leguminous one.As mentioned last year, no better corn crop wasobtained when following tares ploughed-in than when coming aftermustard similarly treated, although it was found that the taressupplied more nitrogen to the land. To give this time to becomeavailable, a second corn crop (barley) was taken in 1904 after thewheat crop following the green-manuring. The results of the two yearswere :1903.Theat.Produce per acre.1904.Barley.Produce per acre.After tares ploughed-in, mineralmanures used ...........................After mustard ploughed-in, mineralmanures used ..........................After tares ploughed-in, withoutmineral manures .....................After mustard ploughed-in, withoutmineral manures .....................c 7 Corn.Straw.Bushels. Cwt. qr. Ib.,17'8 18 1 2637'9 37 0 818.1 19 0 827'4 27 3 167 ~~Corn. Straw.Bushels. Cwt. qr. lb.18.5 11 0 419.7 11 2 1418.3 9 3 1318.7 12 0 21Compt. rend., 1905, 140, 665.J. Boy. Agric. SOC., 1905, 66, 198. Compare ibid., 1903, 64, 335.Chm. Centr., 1905, i, 619250 ANXUAL REPORTS ON THE PROGRESS OF CHEMISTRY,From this it will be seen that even with a second corn crop theadvantages of ploughing-in a leguminous crop as against a non-legumi-nous one have not been brought out. This investigation is beingcontinued and, simultaneously, experiments in pot-culture with the soilof the field where the practical trial was carried out are now inprogress.It is a point of the greatest importance that the results ofscientific inquiry which are obtained in the laboratory should besubmitted to practical test in the field under the conditions of ordinaryfarming, as in that way alone can they become of more than theoreticalinterest or confer a real benefit on agriculture.Errors attending Pot-culture TPork..I n the course of watching the progress of pot-culture experimentscarried on in conjunction with field experiments on one and the samequestion, it has become increasingly evident that there are in pot-culture investigations' a considerable number of precautions that have tobe observed, the neglect of which may lead to the forming of quiteerroneous conclusions, and that there are many disturbing elements anyof which may vitiate an experiment, and which have to be carefullyeliminated.With the extension of the pot-culture system and themass of results now put out, it is not too much to say that these callfor stricter examination than has perhaps been bestowed in the past,and it is very certain that pot-culture experiments need not onlyduplication but also repetition before they can be fully accepted.0. Lemmermannl points out that diminished growth of plants in potsis not due so much to the limited space at their disposal as to thenutritive conditions attaching to the volume of soil, and that theamount of water is frequently the most import'ant factor. At theWoburn Experimental Station, experience has shown that in preparingdifferent soils for pot-culture work they have to be differently treatedaccording to their nature, and that no hard and fast lines can be laiddown, but that experience alone can decide such points.With a dampor wet soil, it is impossible to fill it into pots so as to get the particlesin a sufficient degree of fineness to allow of equal consolidation andaeration, and want of agreement between duplicate pots will certainlyresult. With a fine dry soil, in which the particles pack closelytogether, there is also difficulty, as the whole sets into a mass, and it isimpossible to ensure a uniform distribution of moisture.Want ofagreement between duplicates is sure to arise from this cause. Theway in which soil is filled into pots will, again, make great differences,and is in many cases responsible for variable results. The right amountof compression to give, and how to avoid the formation of distinctJ. Lnndw., 1905, 53, 173AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 251layers, each different in character and along which the water may runor collect, are matters to which great attention must be given in pot-culture, and in which only experience can be the guide. Regularityand method in water supply, the avoidance of rapid change of tempera-ture, and many other points have to be considered, and experience atWoburn has shown that while duplication of experiment is absolutelynecessary, triplication is still better, followed by repetition in a succeed-ing year.The differences between the results of pot-culture experimentsand those of field trials can, in the great majority of cases, be tracedprimarily to the difficulty of reproducing in pot-culture the conditionswhich exist in the field, and to the non-observance of necessaryprecautions, or failure to check results by duplication and repetition,Oxidation in Soils.E. J. Russel1,l a preliminary account of whose work was given lastyear, has set out the results of his examination of a number of soilsfrom different parts, including Rothamsted and Woburn, and hasshown that his method of determining their rate of oxidation as ameasure of their I‘ bacterial activity ” has given results in harmony withthe experience and records of the respective productive power of thesoils.The rate a t which oxygen is absorbed increases with rise oftemperature, the amount (up to a certain point) of water, and theamount of calcium carbonate. These being the conditions that favourfertility, the rate of oxidation may be used as a measure of thefertility, and, it is suggested, of the activity of the micro-organisms.Sterilisation of Soil.F. Nobbe and L. Richter applied ether and hydrogen peroxide tosoil in which peas were growing, but this failed to exercise anysterilising influence on it, the result of application being favourablerather than otherwise. Other experiments with oats grown in potsfailed to show any sterilisation when ether, benzene, carbon disulphide,and chloroform were used on the soil.C. Schulze3 grew oats andmustard in normal soil and in soil sterilised by heating at 12P.Variable results were obtained according to the nature of the originalsoil. Thus, sterilisation had least injurious effect in the case of richgarden soil, and less in meadow than in arable soil, mustard beingmuch more sensitive than oats. The injurious effect of sterilisationwas found to be entirely removed by applying calcium carbonate.J. Agric. Science, 1, Oct., 1905, 261.Landw. Versuchs-Stat., 1904, 60, 433.Bied. Centr., 1904, 33, 748252 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.AvaiZa6ilit y of #oil-constituents.H. Ingle,] a short notice of whose work was given last year, has putout the results of his inquiry into the condition of a soil which hadbeen extracted with a 1 per cent.solution of citric acid (Dyer’s method),and finds that on subsequently growing plants in it there is arestoration, in available form, of potash and phosphoric acid to greaterextent than that in which they originally existed. Hence Dyer’smethod does not give accurately the relative fertility of different soils,as it leaves out of account the relative rapidity with which the avail-able plant food is being renewed by the natural processes of weatheringand decay.J. Konig2 compares the amounts of potash and phosphoric acidsoluble respectively in cold hydrochloric acid (sp. gr. 1.15) and in1 and 2 per cent.solutions of citric acid, and finds that the results arevery irregular when taking ten different soils. From this he arguesthat the nutritive constituents occur in very different forms. Hefurther compares the results of pot experiments on barley with anexamination of the soil used, but extracted with 2 per cent. citric acid.The citric acid was found to have dissolved much more potash andphosphoric acid than was taken up by the barley plant.Root Xecretions.D. N. PrianischnikoK3 when experimenting on the assimilation ofphosphoric acid, found that gramineous plants like rye and wheatcould hardly avail themselves of the phosphates supplied in crudemineral phosphates, whilst lupins did nearly as well as when bonephosphate was applied.If this difference of behaviour were, he says,found to be proportional to the production of carbon dioxide by rootrespiration, it would support the contention that the dissolving actionof roots is due to carbon dioxide alone, and does not depend on thepresence of any free organic acids.J. Stoklasa and A. Ernest* have estimated the amount of carbondioxide in soils which is produced in the respiration of bacteria,moulds, a l p , and by the roots of plants, the quantity from the last-named source being about sixty kilograms per hectare per diem. Theauthors consider the action of roots, especially the young roots, on themineral substance of the soil to be due to the carbon dioxide evolvedand not to organic acids. P. Kossowitsch5 (who has shown thatTraw., 1905,-87, 43.Landw. Verszcchs-Stat., 1905, 61, 371.Centr. Bakt. Par., 1905, 14, [ii], 723. 3 Bied. Centr., 1905, 34, 741.5 Bied. Centr., 1905, 34, 367AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 253organic acids are not secreted by roots) also finds that the amount ofcarbon dioxide given off by the roots of mustard is very considerablein relation to the ash constituents of the plant. He is uncertain asto whether the carbon-dioxide only acts on the soil or whether it hasother functions as well.Plant Food removable from #oils by Water.I n America, the examination of soils by the methods described inlast year’s report has been continued,*and the Bureau of Soils of theU.S. Department of Agriculture has issued the results of furtherinvestigations by F.H. King,1 chief of the division of Soil Manage-ment, in addition to which this investigator has issued other papers ofhis own.2 He deals mainly with the amounts of plant food which arereadily recovered from field soils by taking the first four feet of thesoil and washing it for three minutes with distilled water ; he thencompares the amounts of potash, lime, magnesia, phosphorus, andnitrogen removed with the amounts of these constituents which cropswould remove. Applying this method, he shows that the three-minutetreatment would remove enough nitrogen to provide that needed by atwo-and-a-half ton per acre crop of clover hay, enough potash for two,and enough phosphoric acid for five such crops. King next considersthe relation of crop-yields to the amounts of plant-food materials whichare removed from the soils by successive washings with distilled water,and concludes that there is a remarkable concordance between thecrop-yields and the potash recovered as soluble salts, whilst, if thetotal salts recovered in the washing be taken, it will be found thatlarger amounts are recovered according as the crops have given thehigher yields.Nitrates removed from Avable XoiEs.R.Warington 3 has made a useful and full survey of the productionand loss of nitrates in the soil, this being drawn from a study of typicalplots of the Rothamsted experiments. After accounting for thenitrogen removed in the subsoil drainage water and in the crop, heshows that there remains a considerable surplus of nitrates which havebeen formed in the surface or added as manure, but which is notaccounted for.He investigates the probable causes of this disappear-ance, and, after allowing that a certain small proportion may disappearthrough denitrification, shows that there must be other reasons for theloss. I n spring, there was stored up in the surface soil a large amountof nitrates for the use of the wheat crop, and yet the drainage water’ “ Investigations in Soil Management,” I!. H. King, Madison, Wis., 1904.U.X. Dept. Agric. Bureau of Soils, Bull. No. 26, 1905.Trans. Highland Agric. Soc. of Scotland, 1905, 148254 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.showed a diminished amount of nitrates, this disappearing almostentirely in the first week of May.Moreover, the crop, although havingthis store at hand, did not at harvest contain more than one-half theamount. And in reply to the question as to what becomes of thisnitrogen, Warington hints at an actual loss of nitrogen taking placein the growing plant itself.Action of Nitrates and Ammonium Salts on Soil.The relative action of sodium nitrate and ammonium salts in regardto the condition in which they leave the soil to which they are severallyapplied has received considerable attention of late. P. Kossowitschstates that when nitrates are used the plant takes up more acid thanbase, and that an alkaline substratum is produced which, if notneutralised, might cause injury to the development of the plant.Whenammonium salts, on the other hand, are used, an acid substratum isproduced, and this needs neutralising by the presence of calciumcarbonate, for example. This is borne out by the results obtained a tthe Woburn Experimental Farm,2 where the continued use of ammoniumsalts on a soil originally containing very little lime has brought aboutan acid condition of the soil and complete sterility. On the applica-tion of lime, the acidity was neutralised and fertility a t once restored.I n 1904, the difference between the barley crop of limed and unlimedplots where ammonium salts had in each case been used continuouslywas as much as twenty-four bushels per acre. Similarly, it may benoted that on this same soil sodium nitrate continuously applied,although not producing sterility as quickly as ammonium salts, is clearlybeginning to show exhaustion of the soil and diminished produce bothwith wheat and barley.A. D.Hall 3 deals with this same question and shows, from theexperience of soils at Rothamsted, the importance of calcium carbonatein acting as a base towards the acids produced by bacterial activity.He has measured the rate of removal of lime from unmanured arableland, and shows that this amounts to 800-1000 lbs. per acre yearly ina soil containing 1 per cent. of calcium carbonate. This loss is furtherincreased by the use of ammonium salts, but is diminished by usingnitrates or dung, the former conclusion accordingly bearing out theresults already obtained at Woburn. The restoration to the soil, bythe growing plant itself, of the bases of the neutral salts on which itfeeds, or the formation of bases by the action of certain bacteria in thesoil on organic salts, Hall points out can alone explain that soils con-taining only a very little calcium carbonate can retain their neutralBied.Centr., 1905, M, 378. J. Roy. Agric. SOC., 1905, 66, 197.a Brit. Assoe. Report, S. Africa, 1905, Section BAGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 255reaction and maintain their fertility. When, however, excess is reached,as in the case of the Woburn soils, sterility will ensue.Organic Matter in So&A. Mayer 1 finds that the humic acids of brown sandstone containless carbon than those of grey sand. He considers that these acidsareoxidised to insoluble ferric salts when ferric oxide is present.E.Blanck,2 in giving complete analyses of a number of black soils fromEast Prussia, states that these contain much less humus than do theblack soils of Russia. A new and rapid method of determining theorganic matter in soils has been introduced by J. H. Pettit and T. 0.Schaub,3 this consisting of a modification of Parr’s method of com-bustion with sodium peroxide, and subsequent determination of thecarbonate formed. Magnesium is used to start the reaction, and theresults obtained are practically identical with those given by combustionwith copper oxide.Colloids in Soils.B. Sjollema 4 estimates approximately the amount of colloids in soilsby treating them with a solution of niethyl-violet (0-1-0.2 gram in500 c.c.).The colloids are dyed, but not the quartz. The use ofdifferent dyes enables further distinction to be made between variouscolloids. Sjollema also describes a means of isolating the colloid sub-stances of soils.Lime und Magnesia in Soils.Mention has been made of work bearing on the importance of havinga sufficiency of calcium carbonate present in soils, as also of A. D.Hall’s estimate of the rate of removal of lime from soils. Th. Dietrich,5working on Hessian soils, found the application of lime (either as burntlime, marl, or dolomite) $0 be beneficial on sandy land and sandy loams.Calcium silicate could not, however, be used in place of calcium car-bonate.0. Loew and K. AS^,^ continuing their work on the ratio of lime tomagnesia in soils in order to produce the best results, state that theratios previously given (1 for most cereals and 1 : 3 or 4 for leafy crops)only hold good when the lime and magnesia are present in the soil inLandw.Yersuch-Stat., 1904, 60, 475.l b i d . , p. 407.J. Amer. Chem. Soc., 1904, 26, 1640.J. Jandw., 1906, 53, 67 and 70.Bied. Centr,, 1904, 33, 814.Bull. Coll. Agr. TGkyd, 1905, 6, 336256 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.equally available forms, as, for example, carbonates. I f calcium werepresent as carbonate and magnesium as sulphate, the ratio would be verydifferent, and more like 7 : 1.Loew,l in another paper, says that an excess of lime is in most casesrendered harmless by being converted into oxalate, but that an excessof magnesium will retard growth.On the other hand, Fr.Gossel,2 in experiments carried out on waterand soil-culture, obtains no confirmation of Loew’s theory as to therebeing any need of a fixed relation between lime and magnesia, butthinks that the influence of lime is. determined principally by thecharacter of the soil.Phosphates.F. Mach3 maae experiments on the solubility of iron, aluminium,and calcium phosphates in water, water containing hydrated silica,water with humic acid, and in a saturated solution of carbon dioxide.All were dissolved to a slight extent with water, and water containhghydrated silica dissolved aluminium phosphate still more. But waterwith humic acid was two to three times as powerful, whilst a saturatedsolution of carbon dioxide dissolved twice as much calcium phosphateas did plain water, although it was not effectual on either ferric oraluminium phosphates.G.Gray 4 has investigated the retrogression of soluble phosphates inmixed manures in which bone dust, basic slag, lime, and other materialshave severally been used with superphosphate. I n a mixture of super-phosphate and bone dust retrogression is small and proceeds but slowly,none taking place until about twelve days have passed. The citrate-soluble phosphate is increased at the expense of the insoluble phosphate.With basic slag, more than 50 per cent. of the soluble phosphoric acidreverts within three hours to the insoluble form, 77 per cent.in twenty-four hours, and 85 per cent. in six days. With slaked lime, 94 per cent.becomes insoluble within three hours, and the whole within twenty-fourhours, the dicalcic phosphate being formed. When superphosphate andkainite are mixed, there is but slight retrogression, this not exceeding7 per cent. in eighteen days and being due mainly to the salts ofmagnesium present in the kainite.Potash and Soda.Schneidewind and Ringleben’s 5 conclusions in favour of the use, on asoil poor in lime, of pure potassium salts in preference to kainite as aBied. Centr., 1905, [ii], 412.Chem. Centr., 1904, ii, 1164.Trans. Australasian Assoc. Adv. Science, 1905, 157.Landw. Jahrb., 1904, 33, 353.Ibid., 1904, [ii], 1157AGRICUT,TURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY.257manure for potatoes have been confirmed a t the Woburn ExperimentalStation,l where better crops of potatoes were obtained by using 1 cwt.of potassium sulphate per acre than with 4 cwt. per acre of kainite, andthis whether sodium nitrate or ammonium sulphate was used (alongwith superphosphate). The soil is a sandy loam deficient in lime.H. C. Prinsen-Geerligs,2 in working on the influence of potassium andsodium salts as manures for sugar cane, found that potassium could notbe replaced by sodium, for on a soil as free as possible from potassiumthe plants would not grow, although watered regularly with sodiumchloride solution. The sugar cane was found to take up very littlesodium in its normal growth, the chlorine in it being combined mainlywith potassium.I f the soil was treated with sodium chloride, potashwas liberated and rendered available as plant food.P. Wagner 3 and others showed that potassium salts containing muchchlorine caused considerable increase in barley and beet, and especiallyin the leaves of mangels and potatoes. H. Suchting 4 states that theharmful influence of sodium chloride on potatoes is due to the chlorineand not to the sodium, inasmuch as sodium carbonate in moderationdid not injure the crop. Sodium is equally distributed through theplant during the vegetative period, but towards the end of this itaccumulates in the leaves.Furmyard Zunure.E. J. Russel1,j in conducting a feeding experiment in which linseed-cake with other foods was given to bullocks, analysed the dung whenremoved from the feeding boxes in which it had been made.The lossof nitrogen in making the dung was 14.6 per cent., this value being infair agreement with Voelcker and Hall’s6 results (15.8’7 per cent.)recently obtained. I n trying to ascertain how the loss of nitrogen ofurine could be avoided, E. Bohme,7 by the use of gypsum (10 per cent.),reduced this loss to 7 per cent. in 250 days, whilst the urine by itselflost 56 per cent. of its nitrogen in that time. One per cent. of sulphuricacid gave a loss of 5.5 per cent. only, and by using 2 per cent. ofsulphuric acid the whole of the nitrogen was retained.Influence of (‘ Rurer )’ Constituents of the Soil.The work on this subject has been continued at the WoburnExperimental Station, by Loew and others at Taky6, and by otherinvestigators on the Continent, At Woburn,s the influence ofChem.Centr., 1905, i, 897.Landw. Versuchs-Stat., 1905, 61, 397.J. Xoy. Agric. Xoc., 1902, 63, 88.8 J. Roy. Agric, Soc., 1905, 66, 206.1 J. Boy. Agric. SOC., 1905, 66, 203.3 Bied. Centr., 1905, 34, 435.ti Report 8.E: Agric. COX, Wye, 1905.7 Bied. Centr., 1905, 34, 300.VOL. 11. 258 ANNUAL 1tEPOEtTS ON THE PROGRESS OF CHEHISTRP.manganese and iron sulphates on wheat and barley has been studied,both by soaking the seed, before sowing, in solutions of the salts, andby direct application of the salts in solution to the growing crop. I nthe case of wheat, the soaking of the seed improved the germination solong as the strength of solution did not exceed 2 per cent., but increaseof yield was only obtained from soaking in a 2 per cent.or 5 per cent.solution of ferrous sulphate. By direct application to the growingplant, manganese sulphate up to 8 cwt. per acre and ferrous sulphate upto 1 cwt. per acre increased the yield. I n the case of barley, soaking ofthe seed did not injure germination, but produced no benefit, whilstsolutions of both manganese and ferrous sulphates, more particularly thelatter, produced some increase of crop.These experiments with manganese have been confirmed lately byothers carried out on oats by G. Bertrandl on a soil which contained0.05'7 per cent. of manganese. Two plots were selected and receivedthe usual fertilisers, but to one of them manganese sulphate at therate of fifty kilograms per hectare was added.This plot gave anincrease of 22-5 per cent. in the total crop over the plot receiving nomanganese. Bertrand made analyses of the oat grain, and theseshowed that the grain from the manganese plot contained less moistureand slightly less nitrogen than that from the other plot, and it also hada higher bushel-weight.E. Haselhoff2 investigated the action of sulphur dioxide, zincoxide, and zinc sulphate on soils and plants. Sulphur dioxide wasrapidly converted into sulphuric acid and did not injure soils, Zincoxide (0-2 per cent.) had a slightly stimulating effect on wheat, butzinc sulphate was extremely injurious. The same observer found that0.1 gram of ammonium thiocyanate (in 8-5 kilograms of soil) actedinjuriously with oats, wheat, and mustard, whilst 0.2 gram almostentirely prevented any yield, the quantity proving injurious even whenapplied twelve weeks before the seed was sown.L. L. Harter 3 showedthat magnesium sulphate, magnesium chloride, and sodium sulphateall act as stimulants to wheat when used in dilute solutions, but thatsodium carbonate and sodium chloride will not. Also that traces ofzinc will kill the root tips in twenty-four hours. Lastly, Y. Yamano 4ascertained by pot-experiments on barley and flax that moderateamounts of aluminium salts have a stimulating effect on plant develop-ment. I n water-cultures, 0.2 per cent. of alum, however, actedinjuriously after three weeks, whilst 0.8 per cent.killed the plants in afew days.1 Compt. rend., 1905, 141, 1255.2 Bied. Centr., 1905, 34, 24 and 31.3 EX. Dept. Ayric., 1905, Bur. Plant I r d , Bull. No. 79.Bull. Coll. Agr. TOkyO, 1905, 6, 429AGRICULTURAL CHEMISTRY AND VE GETABLE PHYSIOLOGY 259Germination.The question has been asked whether it is possible for germinationto take place in absence of air. According to experiments by T. Taka-hashi,l rice-accustomed to grow in swampy ground-will grow inwater alone, in absence of air and without sugar being added.W. Windisch and K. Schonewald 2 controvert Nilson's theory thatgermination of barley depends on the activity of bacteria on thesurface of the corns. They show that barley can be completelysterilised by treatment with mercuric chloride solution in alcoholand yet not lose its vitality, the subsequent germination being quitesatisfactory.P. Becquerel3 has investigated the action of liquid air on seeds,coming to the conclusion that their power of resistance to low tem-peratures depends on the amounts of water and of gas present in thetissues.I f the protoplasm has, through drying, reached its maximumof concentration, it can resist the action of low temperatures, and doesnot freeze, but retains its germinating power ; when, however, a certainamount of water and gas are present, the protoplasm and nucleus becomedisorganised by the cold.Assirnikc6tion.Cr. Bernard,* while not denying that the decomposition of carbondioxide by plants may come from the action of ferments, shows thatwhen chlorophyll and extracts of plant tissues are mixed, no evolutionof oxygen takes place in sunlight.If bacterial decomposition sets in,gaseous products are obtained, but not oxygen. F. F. Blackman andG. Matthaei5 have given the factors which control assimilation ofcarbon dioxide by leaves as being (1) intensity of illumination, (2) ten-perature of leaf, (3) pressure of gas in surrounding air. The endeavouris made to interpret the variations which occur in the amount ofassimilation in terms of these three factors. Leaves of different plantsare found to vary with increased temperature, and there does not seemto be any optimum intensity of light for assimilation. A. Kanitz,6working on the same subject, shows that up to 37" the rate of assimila-tion increases regularly with the temperature, but after 3 7 O the ratiodiminishes rapidly.The principal contributions to the subject of the assimilation ofcarbon dioxide by green leaves consist, however, in the series of papers byBull.Coll. Agr. !Z%ky6, 1905,6, 439.Compt. rend., 1905, MO, 1652Proe. Boy. Soc., 1905, 76, Series B, p. 402.Zeit. Ehktrochent., 1905, 11, 689.Woch. Brau., 1905, 22, 200.Ibid., 509.s 260 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTKY.Horace T. Brown and F. Escombe,I presented to the Royal Society.These have special reference to the rate of assimilation and to the inter-change of energy between the leaf and its environment. sk new methodof determining the rate of assimilation is described, and the results arecompared with those obtained by Sachs’ weighing method.The rate ofassimilation is measured by passing a known volume of air over a leaf sur-rounded by an atmosphere containing a normal but ascertained amountof carbon dioxide, and by subsequently ascertaining, by analysis, whatincrease of carbon dioxide there has been. The authors criticise Sachs’method and point out sources of error in i t which led him to place therate of assimilation much too high. The results they now obtain by thedirect method of estimation are considerably lower than Sachs’ figures.One source of error would seem to lie in the adding-as Sachs did-ofthe hourly gain of weight during the day to the hourly loss during thenight in order to arrive at the result.Brown and Escombe also pointout that experiments such as these cannot be carried out in full sun-shine, but must be made either on dull days or by moderating thesunshine by a thin canvas screen. They further discuss the differencesbetween experiments made on detached leaves and those on attachedleaves freely exposed to the air, and show that the rate of assimilationis much greater with the detached leaves. I n considering the‘‘ energetics ” of the leaf, many factors have had to be determined, forexample, the total incident radiation, its absorption by the leaf, thethermal emissivity of the leaf-lamina, &c., and details are given as tohow these have been severally estimated. It is shown, from experi-ments with a sunflower leaf, that of the total incident energy only0.66 per cent.is used in the work of actual assimilation or productionof new material.J. Friedel,% working on chlorophyllous assimilation, found that thiscan take place when the atmosphere contains no oxygen. On exposinga leaf of Euonymusjaponicus to light in a tube containing only carbondioxide and nitrogen, carbon dioxide was absorbed and oxygen evolved.G. Plancher and C. Ravenna3 discuss the evidence in favour of theformation, in the early stages, of formaldehyde in the manufacture ofstarch by chlorophyllous plants, but on distilling extracts of leaves theyobtained no indication of the presence of either free or combined form-aldehyde in the green tissues. P. Maze and A. Perrier4 found thatsugars, glycerol, and methyl and ethyl alcohols retarded the germinationof maize seeds, but did not prevent the growth of the young plants.Sugars were assimilated in the light, also glycerol, but the latterhindered development.Whilst methyl alcohol helped the activity,ethyl alcohol was harmful, probably owing to production of aldehyde.Compt. rend., 1905, 140, 169.Ann. Imt. Pastew, 1904, 18, 721.1 Proc. Roy, Soc., 1905,,76, Series B, 29.3 Atti R. Accad. Lincei, 1904, 13, [ii], 459AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 261Different plants varied generally in regard to their behaviour toalcohols.The effect of growing plants in an atmosphere rich in carbon dioxidewas ascertained by E. Demoussyl to be an increase in the amount ofdry matter in the plant.Plant Constituents.E.Charabot and GI. Laloue2 find that in an annual plant theessential oil migrates from the leaves to the flowers along with thecarbohydrates. After fructification, the essential oil returns to theleaves.E. Schulze 3 has determined the amount of non-proteid nitrogenoussubstances in plants. I n seeds, this varies very greatly, being highestin leguminous and lowest in cereal and oily seeds. Etiolated plantswill contain either asparagine or glutamine, asparagine being found inthe case of leguminous seedlings and in cereals and grasses, whilstglutamine occurs in etiolated plants of sunflower, white mustard, rape,cress, radish, &c. ; glutamine, however, does not exceed 2.5 per cent. inthe dry matter, but the proportion of asparagine may be as high as25 per cent.I n roots and tubers, the conditions are much the sameas in etiolated plants, and asparagine and glutamine are the mostabundant amides. Many other amides are noted as occurring indifferent roots and tubers.The proteids of wheat have been investigated by T. B. Osborneand I. F. Harris,4 and Kutscher’s view that the proteid soluble inalcohol consists really of two proteids is rejected. The authors con-sider it to be a single substance and give to it the name (‘ gliadin ” ; itcontains an amount of glutamic acid much in excess of that obtainablefrom any other proteid, and possibly on this account special importanceattaches to it when considering wheat as a food. The same authorshave examined the methods of fractional precipitation of proteins byammonium sulphate, and come to the conclusion that whilst it affordsin many cases a useful means of separation, it cannot be used fordistinguishing vegetable globulins from vegetable albumins.T. B.Osborne, with L. B. Mendel and I. F. Harris,5 have investi-gated the nature of the proteins of castor bean, and especially in regardto the toxic substance k i n , believed by Stillmark (who isolated it) tobe a globulin, but the protein nature of which has been questioned byother investigators, notably Jacoby. The authors show that the castorbean seed contains (1) a considerable quantity of a crystallisableCompt. rend., 1904, 139, 883. Ibid., 928.Amer. J. Physiol., 1905, 13, 35, 3 J.Landzo., 1904, 52, 305.5 Ibid., 14, 259262 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.globulin, (2) a much smaller amount of a coagulable albumin, and (3)proteoses. The toxic properties ascribed to ricin are to be associatedwith the coagulable albumin of the castor bean, and the investigationaffords no reason for denying the identity of ricin with the coagulablealbumin of the seed.The increase of proteid formation during the ripening of seeds hasbeen investigated by W. Zaleskil and by G. Vegetablealbumin was not found in white lupin seeds when they first began toform, but when they were mature the nitrogen in this form was 2.5per cent. of the total. Legumin similarly, although absent a t first, inthe ripe seed gave nitrogen up to 10 per cent.of the total.C. von Seelhorst and Fresenius,3 by carrying out pot-culture experi-ments on oats in which variable amounts of water were supplied,ascertained that as the moisture increases the proteid nitrogendiminishes less than the total nitrogen, but that the digestible proteidnitrogen diminishes more than the total proteid nitrogen. Hence, in adry season one would expect the feeding value of oat straw to be higherthan in a wet season.L. du Sablon4 explained why assimilation in the case of evergreensis relatively feeble but continues all the year, by showing that themaximum of reserve substances is attained at the beginning of spring,whilst the minimum is reached about July or August. With caducoustrees, on the contrary, the maximum is in the autumn.B.Schulzeb shows the difference between rye and wheat in regard tothe time a t which they assimilate nitrogen and phosphoric acid. Ryeby the end of winter will have taken up nearly one-half of its fullsupply of nitrogen, whilst with wheat assimilation of nitrogen takesplace mostly from the beginning of April to the time of seed formation.Phosphoric acid is taken up by rye mostly in spring, and with wheatfrom spring to flowering time. A certain amount of potash is takenup by both plants during winter, but the greatest assimilation is at thetime of greatest production of carbohydrates.The last paper written by H. Wilfarth (he died on Nov. 27, 1904),the former colleague of Hellriegel, was in conjunction with H. Romerand G.Wimmer, and had reference to the assimilation by plants oftheir nutritive substances at different stages of their growth. Barley,spring wheat, peas, and mustard were found to assimilate most of theirnutritive substances by the time of flowering, but with potatoes thiswent on until the crop was ripe. Further, the mineral constituents inthe case of the barley, wheat, peas, and mustard were, with the excep-tion of phosphoric acid, returned to more or less extent to the soil, butChem. Centr., 1905, i, 1606.J. Landw., 1905, 53,527.Bied. Centr., 1905,$34, 602,a Compt. rend., 1905, 1M, 1417.Compt. rend., 1905,140, 1608.Landw, Yersuchs-#tat., 1905, ($3, 1AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 263this was not the case with potatoes.Starch increased up to the ripen-ing period in all the plants except mustard, its place in the latter beingtaken by fat.Enzymes.J. Stoklasal has isolated from the sap of the beet-root, potato, andpea an enzyme which produces alcoholic fermentation and the forma-tion of lactic acid in dextrose solutions. This enzyme he terms“ lactolase,” and considers it now definitely settled that the process ofanaerobic respiration in the plant cell is an alcoholic fermentationaccompanied by the formation of lactic acid, the anaerobic metabolismbeing identical with fermentation by yeast. A6robic respiration heholds to be a secondary phenomenon.I n the case of the ripening seeds of peas, W. Zaleski has investigatedthe nature of the proteolytic enzymes present, and states that it isuncertain whether the ripening seeds contain only one ferment of 8tryptic nature or whether they contain several, including trypsisitself.Glucosides,Considerable attention has been directed to the poisonous propertieswhich certain seeds, generally of imported origin, and used occasionallyas food for cattle, are known to possess a t times.Among these are thecoloured seeds of the wild Phaseolus Zunatus, which are variously knownin commerce as (( Rangoon beans,” ‘‘ Java beans,” &c. W. R. Dunstan 3has investigated these and finds the seeds to contain a cyanogeneticglucoside, which undergoes hydrolysis, forming hydrocyanic acid as oneof its products. This glucoside Dunstan has isolated, its formula beingC,,H,70,N, and he gives to it the name “ Phaseolunatin.” He furtherseparated the hydrolytic enzyme of Phaseolus Eunntzcs, which he thinks isprobably emulsin. It is worthy of notice that the glucoside is notfound in the plant after cultivation, the seeds of the cultivated plantbeing white, and not poisonous a t all.Other workers have similarly found cyanogeiietic glucosides in theexamination of other plants.Thus, F. Power and F. Lees 4 found in theseeds of Gynocardia odorata a new glucoside which they call “gyno-cardin,” and they further separated the enzyme ‘‘ gynocardase.” L.Guignard,5 as also E. Bourquelot and E. Danjon,5 separated from theleaves of Sambucus n i g m a glucoside which, when acted on by emulsin,yielded dextrose, hydrogen cyanide, and an aldehyde.Guignard believedthe glucoside to be amygdalin. Subsequently, Guignard 6 ascertainedChern. Centr., 1905, i, 265. Ibid., 1606.Tram., 1905, 87, 349.Ibid., 448,3 Proc. Roy. Soc., 1905, 72, Series B, 285.5 Comnpt. rend., 1905, 141, 16, 59, and 236264 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.that the leaves of the red currant yielded a little hydrogen cyanide atall periods of vegetation, although other species of Ribes did not. I nthe leaves of 5Tbalictrzcm apuilegifoliurn, L. van Itallie found a gluco-side resembling phaseolunatin ; this was not found, however, in otherspecies of Thalictrum.InJuence of Vuriety.A. D. Ha11,2 when dealing with the question of ‘‘ strength ” in wheat,and the various efforts which are being made to introduce into this countryu wheat of equal yielding value to English varieties, but the grain ofwhich possesses the ‘( strength ” of Canadian and other varieties, drawsattention to the importance attaching to “variety.” While climate, soil,season, and manuring may all exercise a certain modifying influence,this is at best small when compared with the intrinsic characteristicsimpressed on the plant, and which constitute what we term ‘‘ variety.”T. B.Wood and R. A. Berry3 have, for instance, shown the varia-tions which occur in the chemical composition of mangels, and S. H.Collins 4 has done the same in respect of swedes ; but in each case thepredominating factor was that attaching to variety. Hence improve-ment, alike in cereals and in root-crops, has to be looked for in thebreeding of new varieties by careful selection. Hall, in the paper justreferred to, shows the difficulties of determining in what the “bakingvalue” of wheat lies and how it is to be estimated, for, whilst the use ofnitrogenous manures sends up the percentage of nitrogen and drygluten as a rule, the baking value is generally deteriorated.Thedetermination of total nitrogen or of gluten obtained by washing outthe starch does not give the baking value, nor is this obtained byascertaining the percentage of gliadin (nitrogen soluble in alcohol), or therelation of gliadin to glutenin. I n Canada, both Synder and F. T.Shutt 5 have worked at the same question, but without being able todifferentiate accurately, by chemical means, between different grades ofwheat.Water.For the purification of water supplies, G.T. Moore6 has adopted amethod of treating water with copper sulphate in the proportion of 1 to5,000,000. The growth of algs is prevented by this, sewage bacteriaare destroyed, and the total number of bacteria very greatly reduced.Experiments by H. Kraemer confirm the efficiency of the treatment,J. Pharm. Chim., 1905, [vi], 22, 337.Brit. Assoc. &ports, S. Africa, 1905, Section B.J. Agric. Sci., 1, May, 1905, 176.Ibid., Jan., 1905, 89.Cent?.. Ezp. Farm, Ottawa, Bulletiu No. 50, 1905.Amer. J. Pharm, 1904, 76, 553 and 574AGRICULTURAL CHEMISTRY AND VEGETABLE PHYSIOLOGY. 265and it is stated that the small amount of copper in solution in the wateris too little to do any harm to consumers.Kraemer in experiments withcopper foil placed in water found that Bacillus coli and B. typhosuswere completely destroyed.E. Bonjean 1 carried out experiments on sterilising water withhydrogen peroxide, and was able to sterilise a litre of Seine water with0.291 gram of hydrogen peroxide in six hours. If, however, nascenthydrogen peroxide was used, only 0.06 gram was required, and didthe work in four hours.Magnesium, when added to water containing micro-organisms, wasfound by F. Dienert2 to kill the bacteria after two to three days,although pure magnesia under similar conditions was unable to destroythem.W. G. SavageY3 in seeking for bacterial evidence of the contaminationof tidal rivers, found that the examiuation of the mud was more reliablethan that of either the water or samples of oysters, inasmuch as thetwo latter only show recent contamination, whereas Bacillus typhosus orB. coli retain their chapacters for a long time in tidal mud. Typhoidbacilli also survive for a t least two weeks in tidal mud.Milk.F. J. Lloyd4 has brought to a conclusion his investigation into thecauses of “flavour” in dairy products, the primary object being toascertain what it was that produced the so-called “nutty” flavour incheese and butter. Although the work failed to solve the mystery,many points of interest were brought out in the course of the research.It was shown, for example, that the lactic bacillus was able to continueits existence after its activity as an aerobic microbe had ceased.Further, the evidence pointed to the conclusion that an enzymedeveloped from the bacillus was the chief factor in the conversion ofmilk-sugar into lactic acid. E. von Freudenreich and J. ThoniY5 whileholding that the lactic acid bacteria have most to do with cheese-ripening, were unable to decide which of them were the most favour-able. If artificial rennet alone was used, the ripening was not satis-factory, but by using suitable bacteria along with artificial rennet theripening proceeded normally.J. Arthaud-Berthet 6 isolated several varieties of Oidium Zactis andstudied their action. I n cream, i t is one of the most likely causes ofrancidity of butter, and in cheese frequently causes a peculiar sicknessknown as “graisse.” L. van Slyke and E. B. Hart 7 show that the4 Report t o Board of Agriczclture, 1905.Compt. rend., 1905, 140, 50.J. Hygiene, 1905, 5, 146.Centr. Bakt. Pm., 1905, 14, [ii], 34..I Amer. Chem._Soc., 1905, 27, 679.Ibid., 273.Cow@. rdnd., 1905, 140, 1475266 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,principal cause of what is known as “mottled” butter is excess oflactic acid, as when this exceeds 5 per cent. casein lactate only ispresent, and not calcium casein or free casein. J. Goldingl whoinvestigated the nature of a peculiar ‘I taint ” which was imparted tomilk after passing through a tinned-copper cooler from which the tinwas much worn off, found that copper is readily acted on by fresh milk,small quantities of the metal going into solution. Milk thus con-taminated acquires a peculiar flavour which appears to be due to thedevelopment of micro-organisms in the presence of copper. T. E. Thorpe 2has investigated the changes which take place in samples of milk keptfor varying periods of time in closed bottles, and shows that by usinghis process for the analysis of sour milks the original composition of themilk can-in all but very exceptional cases-be ascertained withsufficient accuracy.J. AUGUSTUS VOELCKER.1 J. SOC, Chem. h d . , 1905, 24, 1285. Trans., 1905, 87, 206

ISSN:0365-6217    

DOI:10.1039/AR9050200238

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY.IN preparing this report the writ,er has folIotved on the whole themethod of treatment adopted in that of last year, for as the materialunder discussion consists in the main of a number of entirely discon-nected facts, the construction of a continuous narrative appearedneither easy nor indeed advisable, and has accordingly not beenattempted. The object in view has been rather to present in somedetail points of general interest, and to touch-lightly, or not a t all,on matters of little moment, or likely to appeal to none save specialists ;it is hoped, however, that nothing of great importance has been over-looked or omitted.Generul and Physical Chemistry of Mi!nerats.Salt Deposits.-During the year, J. H. van't HoEl and his pupilshave added seven more to the long series of papers on the I' Formationof Oceanic Salt Deposits." I n number XXXIX, the transformation ofGlauber's salt, Na2S0,, 1 OH,O, into thenardite, Na,SO,, which takesplace normally a t 32-4", is shown to occur a t lower temperatures ifother salts are present. The limits of the existence of tachhydrite,CaCI2,2MgC1,,12H20, are set forth in number XL.The temperatureof formation of potassium pentacalcium sulphate, K,Ca,(SO,),,H,O,is the subject of number XLI, that of glauberite, Na,SO,,CaSO,, ofnumber XLII. The investigation, so far as calcium compounds a t25" are concerned, is brought to a conclusion in number XLIII, andthe composition of all constant solutions when saturated with theparticular calcium salt with which the solutions are in equilibrium istabulated.Tbe investigation of boron compounds and of the part played bycalcium salts a t higher temperatures is now being begun.Number XLIVdeals with the limit of existence of tachhydrite a t 83", and numberXLV with the occurrence of tinkal, Na,B,O,,lOH,O, and of octahedralborax.The study of this important work has been greatly facilitated bySitzunpber, E, Akad, Tim Berlin, 1904, 1518 ; 1905, 232, 305, 478, 712, 913,1086268 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the publication by van’t Hoff 1 of the first part of a connected accountin book form of his researches, in which salt deposits consisting of thechlorides and sulphates of sodium, potassium, and magnesium arefully dealt with.This account has been supplemented by a longpaper recently published in the Zeitschrift f u r anorganische Chemie,ip which calcium compounds are It is therefore nowpossible to obtain readily a complete conception of the progressso far made towards the solution of the complex problems of saltdeposits.Constitution of tibe FeZspars.-One of the most important contri-butions which has yet been made ’to our- knowledge of the mutualrelations of molten silicates is contained in a paper by A. L. Day andE. T. Allen3 on the “Isomorphism and Thermal Properties of theFelspars.” Employing refined modern methods of high temperaturethermometry, the authors have traced the cooling and heating curvesof albite and anorthite, and of mixtures of these substances corre-sponding to certain of the plagioclases.Microcline and borax havealso been included in the field of observation. The melting pointswere determined by the changes in the cooling or heating curvescaused by evolution or absorption of heat, I n the case of the plagioclases,the various members studied were prepared artificially. After a pre-liminary examination of a1 bite, microcline, and borax, which broughtto light the important part played by viscosity in retarding crystal-lisation and in obscuring the phenomena, it was found that artificialanorthite melted sharply at 1532’ and crystallised readily. Purealbite, on the other hand, could not be persuaded t o crystallise a t all,and had no definite melting point. The intermediate members of theplagioclase series gave intermediate results.Thus, the mixtureAb,An, crystallised tolerably readily, and had a fairly sharp meltingpoint at 1500°, while Ab,Anl was almost as intractable as pure albite.The specific gravities of these crystalline artificial felspars were alsodetermined, The most important conclusions arrived a t are asfollows : (1) if the melting points of the plagioclases are plotted asordinates and the compositions as abscissae, a nearly linear relation isobtained. These felspars are solid solutions and form an isomorphousseries belonging to type I of Bakhuis Roozeboom’s classification.(2) The isomorphism is confirmed by a study of the specific gravities.(3) In the case of albite and microcline there is no definite meltingpoint, the amorphous molted mass remaining of the same order ofZur Bildung der ozennischen Snlzablngerungen. Braunschweig : Vieweg u.Sohn.Zeit. anorg. Clbem., 1905, 47, 244-280.1905. Pp. 85. Price 4 marks.a Amer. J. Sci., 1905, [iv], 19, 93, See also Pub. 31 of the Carriegie Institute,WashingtonMINERALOGICAL CHEMISTRY. 269viscosity as the rigidity of the crystals through a considerable rangeof temperature. The absorbed heat of fusion was distributed overthis interval. (4) Viscous, poorly-conducting melts do not giveconstant solidifying points.Mutual Relations of flused Silicates.-The important work ofJ. H. L. Vogt was referred t o in the report for 1904, and towards theclose of that year the second half of his book entitled “Die Silik-atschmelzlosungen” appeared. I n i t are given the data on whichwere based many of the conclusions he had already announced, as wellas a full discussion of many points, either new or but lightly touchedon in the first portion.The subjects dealt with include : the meltingpoints of minerals ; the cooling curves of the silicates, their total andlatent heats of fusion, specific heats, and radiation exponents ; energyisobars ; points of transformation below the melting points ; experi-mental proof of the depression of the melting point in silicate meltscontaining several components; types of mixed crystals in the meta-silicate series ; the composition of certain eutectic mixtures ; deter-mination of molecular weights ; supersaturation and resorption ;relations between viscosity, time of crystallisation, and size of crystals ;glass as a solid solution ; felspar and quartz ; theory of silicate meltsand technical applications. The general posit?on adopted may besummed up in the statement that van’t Hoff’s law of molecular meltingpoint depression, Ostwald’s law relative to the formation of labilecompounds, Nernst’s laws of the diminution of solubility by a commonion and of the heterogeneous equilibrium of two liquid phases possess-ing limited solubility, Bakhuis Roozeboom’s laws concerning thesolidifying points of mixed crystals of two substances, and the law ofelectrolytic dissociation, due to Arrhenius, all hold for these silicateme1 t s.Further, he believes that silicate melts at the ordinary pressure arecrystalloidal mutual solutions of tolerably simple compounds whichcrystallise out on cooling. As a rule, the compounds do not polymerise.All molten silicates are mutually soluble to any extent, but betweensilicates and sulphides limited solubility prevails,Vogt’s views are only partially shared by C.Doelter, who thinks thatthe former is inclined to press the theories of physical chemistry inthis new sphere further than is warranted in the present state ofknowledge. This difference of opinion has led to a good deal of dis-cussion,l but whatever view may be taken as to the arguments em-ployed, there can be no doubt as to the interest aroused in the subject.Doelter’spresent position is set forth in a long paper communicated totheViennese academy,2 partly experimental and partly theoretical in char-See Centr.Min., 1905, 144, 148, 361.Sitxtmysber. K. Akad. Wiss. Wien, 1905, 114, 529290 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.acter. On the experimental side, the paper deals with the viscosity ofminerals in the neighbourhood of their melting points, which he hasmeasured by observing the depths to which a platinum rod will pene-trate the subhtance previously heated to a definite temperature. Hisresults for the fclspars confirm in the main the observations of Dayand Allen, and he has also examined elzeolite, leucite, diopside, augite,hedenbergite, and acmite. The melting point of a silicate is, he thinks,best defined as the point of transition from the crystalline to theamorphous condition, and he calls attention to the fact that this pointis not necessarily identical with the point of liquefaction, which may belooo or more above the transition point.The uncertainty as to whatvarious authors have meant by the melting point when dealing withthese substances is probably the cause of many of the discrepanciesin the published values. Doelter further points out the necessity ofdistinguishing between the power of crystallisation possessed by a sub-stance and the velocity with which it crystallises, and shows how thecrystallising power may influence the order of separation of com-pounds from complex mixtures such as igneous rocks.Constitution of the Zeolites.-The work of F. W. Clarke and of G.Steiger has shown that the bases in many zeolites can be replaced byammonium when the minerals are heated with ammonium chloride insealed tubes, and the latter1 has lately found that on fusion with thenitrates of silver or thallium these elements can also be introduced intothe silicate molecules. Thus, from analcite, NaA1Si20,,H,0, the com-pounds AgAlSi,O,,H,O and TlAlSi,O, were prepared.I n the case ofchabazite and stilbite, the ratios of the substitution compounds werefound to agree closely with the ratios 1 : 2 : 2 for the monoxide base,alumina, and silicic acid respectively, and, although in thomsoniteincomplete substitution occurs, the ratios are nevertheless fairly wellpreserved. The experiments on chabazite proved of special interest,for the preparations were found to contain notable quantities of nitratewhich could not be removed by washing.The compounds obtainedfrom natrolite, scolecite, and mesolite indicate that all three mineralsare derived from the trisilicic acid, H,Si,O,,.A paper on the same subject has recently been published by F. W.Clarke.2 It contains an account of some experiments on sub-stitution by barium and strontium in the zeolites made by H. C.RlcNeil, as well as a theoretical discussion of the work of bothMcNeil and of Steiger. Analcite is shown to yield the compoundsBaA12Si,0,, and SrA1,Si,012 as well as those mentioned above, and a,sodium stilbite has also been prepared. In the case of chabazite, theaction of barium chloride is to produce complete substitution, but it2 Proc.Washington Acad. Sci., 1905, 7, 257.Bull. U.S. Geol. SZLTV., 1905, 262, 75MlNERALOGICAL CHEMISTRY. 271seems probable that a series of reactions takes place, the bariumchabazite first formed being afterwards decomposed. Although thepresence of chlorine and of NO, in substituted stilbite and chabazitecan be explained on the assumption that chlorides or nitrates areoccluded as such by the preparations, Clarke points out that it ispossible that new compounds have been formed, analogous to sodaliteor marialite, into which chlorine and NO, have entered as integralparts of the molecule. It may be mentioned here that experimentsof a somewhat similar character on the action on kaolin of the chloridesof barium, strontium, sodium, and lithium have been made by Z .WeyberglVater in Zeolites.-Very various opinions have been held as to thepart played by water in zeolites.Some workers have regarded it aspresent partly as water of constitution, partly as water of crystallisa-tion, and have constructed elaborate formuh on the basis of thisassumption. Others, basing their conclusions in the main on thecontinuous and reversible changes in the optical characters which takeplace when zeolites are heated, have held that water is in no wayessential to the existence of these substances in the crystalline state,but that its part in the crystalline network is very much that of waterheld in the pores of a sponge. Others, again, have been inclined toregard zeolites as solid solutions. An important contribution to thissubject, both from the experimental and from the theoretical side, hasbeen made recently by F.Zarnboninie2 Using as material specimensof heulandite and of thomsonite of known composition, he has sethimself to determine the phenomena of dehydration and reabsorptionpresented by these minerals under various conditions, and to trace theresulting changes in the optical properties. To this end he has deter-mined at short intervals of time the loss of weight when the finely-powdered zeolites were dried : (1) over sulphuric acid in a vacuum atthe ordinary temperature, (2) in a current of dry air a t various tempera-tures, (3) in a current of moist air a t various temperatures. He findsthat over sulphuric acid a certain definite maximum loss is slowlyattained.The process can be represented by a continuous curve, andin the case of a heulandite containing 16.6 per cent. of water themaximum loss amounted to 6.06 per cent. From a, study of thedehydration curves obtained when currents of dry and moist air arerespectively employed, he finds that moist air removes water moreslowly than dry air. The difference in effect is apparently due to thetension of aqueous vapour present, and varies with the temperature.As regards reabsorption, he finds that the water given off oversulphuric acid or on exposure to a moderate degree of heat is rapidlyCentr. Min., 1905, 138, 646, 717.Mem. €2. Accad. Lineei, 1905, 5, 344272 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.taken up again when the zeolite is placed in moist air.If, however,the substance has been heated above a certain temperature, about300' in the case of heulandite, the rate of reabsorption is muchdiminished and may be reduced to zero, even if the point of com-plete dehydration has not been attained. Further, he finds that abovea certain temperature the duration of heating has a great retardinginfluence on the velocity of reabsorption when the substance is after-wards exposed to moisture. A similar effect is produced bya series ofsuccessive dehydrations if carried out at temperatures near that atwhich the diminution in the velocity of reabsorption begins. On theother hand, a series of successive dehydrations (followed by exposureto moisture) at moderate temperatures does not appear to influence theabsorption or emission of water.A study of the optical characters ofheulandite has shown that the mode of dehydration has an influence outhe result. Cleavage flakes dehydrated by exposure to a temperatureof 100' f o r from three to eight hours not only presented appearancesdifferent to those exhibited by flakes kept in a vacuum over sulphuricacid for twenty-four hours a t the ordinary temperature, but always re-gained their original optical characters when exposed to moist air,which the latter failed to do. As the result of these experiments,Zambonini concludes that the view is untenable which regards thezeolites as hydrated salts, although they doubtless present many pointsof resemblance to such substances.Moreover, he believes thatalthough the view that zeolites me solid solutions receives somesupport from their dehydration curves and from their optical behaviour,yet it fails to explain all the facts. H e therefore prefers to regardthem as analogous to the hydrogels studied by van Bemmelen, for, likethe zeolites, the state of hydration of these substances depends on thetemperature and on the concentration of the gaseous phase. Moreover,above a certain temperature the phenomena of dehydration are notreversible, and prolonged heating renders them incapable of reabsorbingwater.The dehydration of heulandite has also been studied by A. A. Ferro,lwho used a specimen from Montecchio Maggiore. He determined theloss of weight experienced by the mineral when kept in a desiccatorover calcium chloride and also when heated to various temperatures inair.Like Zambonini, .he finds that the loss attains a maximum inboth cases if sufficient time is allowed. When the mineral is kept inthe desiccator, the maximum loss amounts to from 6#9 to 7.1 per cent.,and can be quickly made good by exposure to moisture. Further, hepoints out that heulandite which has been kept in air absorbs waterwhen exposed to a saturated atmosphere a t a slightly elevatedtemperature, and loses it again when once more placed in air. SinceAtti 3. Accad. Lincei, 1905, 14, ii, 140MINERALOGICAL CHEMISTRY, 273the water retained when equilibrium is reached, either over calciumchloride or on heating to 100-104°, amounts to approximately 3 mols.,Ferro concludes that heulandite contains 3 molecules of water moreintimately connected with the molecule than the rest, which may betermed hygroscopic water.The Silicic Acids.-The importance of the preparation and study ofthe various silicic acids as an aid to our knowledge of the constitutionof the naturally occurring silicates has lately been insisted on byE.Jordisl and by G. Tschermak.2 While the former has occupiedhimself chiefly with the investigation of the conditions necessary forthe preparation of pure silicic acid, the latter has attacked the problemfrom the mineralogical side, He points out that the silicates areprobably salts of various acids derived from orthosilicic acid byremoving from n, - 1 to 25-2 - 1 molecules of water from n molecules ofH4Si04.We thus obtain a series of acids such as H4Si04, H6Si20,,H,Si,O,,, H,SiO,, H4Si206, and so on. Some of these are polymerides,for example, H,Si,06 and H2Si0, ; of others, isomerides can exist.If the natural silicates are salts of these acids, then on decomposingthem with hydrochloric acid the corresponding silicic acid should beset free. To determine whether this is so or not, he proceeds asfollows. A small quantity of the silicate is digested with hydrochloricacid at a temperature not exceeding 60' until decomposition is complete.This may take many days or 0ven weeks. The silica obtained iswashed by decantation until free from chlorine and then allowed todry in the air in a weighed dish.The .weight of the dish andcontents is determined a t intervals of twenty-four hours until itbecomes constant, when the amount of silica present is found byigniting the residue. The results when plotted give the dehydrationcurve. On inspection, this is seen to consist of two parts, one portioncorresponding to the drying process, the other t o the decomposition ofthe silicic acid. The change in the course of the curve marks thepoint when dehydration is complete and decomposition is just beginning.It is difficult to determine the position of this point by direct observ-ation or inspection of the curve, but it may be calculated with a fairdegree of accuracy by means of observations taken on each side of it.Finally, as an aid to the better definition of the acids, their specificgravities were in some cases determined.The main results of the workare as follows. The acid obtained on decomposing silicon chloride bywater is orthosilicic acid, H,SiO, (sp. gr. 1.576). The same acid isobtained from natrolite, Na,H,Al,Si,O,,, and from dioptaie, H,CuSiO,,which are accordingly acid salts of orthosilicic acid. Hemimorphite,See also an earlier paper 011 the sameZeit. anorg. Chcm., 1905, 44, 200.Zeit. physiknl. Chenz., 1905, 53, 349.subject, Sitzz6n~~sber. K. Akad. Wzss. Wien., 1903, 112, i, 355.VOL. 11. 274 ANXUAL REPORTS ON THE PROGRESS OF CHEMISTRY.H2Zn,Si0,, behaves similarly, and is therefore also derived fromorthosilicic acid. The application of the method to olivine yieldedno certain result.From anorthite, CaA 1,Si,OS, metasilicic acid, H,SiO,(sp. gr. 1*813), was obtained. Leucite, KA1Si20,, yields a polymerideof metasilicic a .id, H,Si,O,, which differs from metasilicic acid in itsappearance and also in its behaviour towards methylene-blue. Asimilar result was obtained with serpentine, which is therefore to beregarded as H( Mg,0H),Si,06. From garnet, epidote, misite, andprehnite, the acid ’H4Si308 (sp. gr. 1.910) was obtained. Theseminerals must therefore be regarded as silicoaluminates. Prehnitcis the acid salt Si30s,Ca,A1,0,,H2. I n garnet, all the hydrogen isreplaced by calcium, in epidote and zoisite its place is taken by thegroup AlOH. Albite, NaA1Si,08, yields an acid, H,Si,O,, which isstable when exposed to air.I n concluding this section, attention may be called to the ‘‘ Treatiseon Metamorphism,” by C.R. van Hise, published as Memoir 47 ofthe United States Geological Survey towards the close of last year,which will be found to be a rich storehouse of information on manyimportant branches of mineral chemistry. C. Doelter’s work entitled‘‘ Physikalisch-chemieche Mineralogie ” (Leipzig : J. A. Barth, 1905)will also be found of value.A r t i f i c i a l Pormution of Minerals.Diamond.-The study of the mode of occurrence of the diamondsfound in the Callon Diablo meteorite has led H. Moissan 1 to repeat someof his early experiments on the artificial formation of this substance,and to perform some new ones. Noticing that the diamonds werefound in fissures which appeared to be connected with the presence ofnodules containing sulphur, silicon, and phosphorus, he tried the effectof adding these elements to the molten iron from which carbon wasto separate on cooling. The results showed that the presence ofsulphur improved the yield.In. the case of silicon, the yield alsoappeared to be improved, but the quality of the diamonds was poorer.The influence of phosphorus was unfavourable. His final conclusionsmay be summed up as follows : diamond is the variety of carbon whichhas been liquefied under high pressures; carbon heated t o a hightemperature under atmospheric pressure vaporises without becomingliquid and solidifies as graphite.Similar ideas have guided W.Crookes2 in some recent work onthe same subject. He has pointed out that there is reason to believethat the physical constants of carbon are approximately as follows:Ann. C l ~ h . Phys., 1905, [viii), 5, 174.Proc. Roy. Soc., 1905, 111 76, 458MINERALOGICAL CHEMISTRY. 215boiling point, 3870' abs. ; melting point, 4600' ; critical temperature,5800° ; critical pressure, 2320 atmospheres. From these values themelting point pressure of 16.6 atmospheres can be calculated. If thediamond is the result of the crystallisatiop of liquid carbon, it is clearthat pressure is an all important factor in its formation. Now as theexperimental conditions for the simultaneous production of hightemperatures and high pressures were realised in A. Noble's workon the explosion of cordite in closed cylinders, W.Crookea hasexamined the residues in the cylinders for diamonds, and his searchhas been rewarded by success.C. V. Burton,' on the other hand, has suggested that carbon maycrystallise as diamond under atmospheric pressure at temperatureslying between 550° and 7009 He has found that an alloy oflead with about 1 per cent. of calcium holds some carbor, in solution.On passing steam over the alloy a t a low red heat, no graphite wasproduced, but microscopic crystals were found in the residues, whichfrom their shape, high refractive index, and chemical behaviour seemedto be diamonds. On performing the experiment at a full red heat,no such crystals could be detected, but graphite was obtained.Fmon trite.-In the course of his work on the constitution andgenesis of the native sulphates of iron, R.Scharizer 2 points out thatferronatrite, Na,Fe,S,0,,,6H20, and sideronatrite, Na,Fe2S40,,,7H20,are probably both derived from [(HO)Fe],[HS04],,6H,0, the acid ferricsnlphate ; thus sideronatrite is [(KO)FeJ2[NaSO4],,6K2O End ferro-natrite is [(NaSO,)Fe],[ NaS0,],,6H20. This view is confirmed by thefact that a substance having the composition of ferronatrite wasobtained by mixing acid ferric sulphate and sodium hydrogen sulphateand allowing them to act on one another in the presence of moistair. Experiments on the production and transformation of sideronatritesupport the constitution given above rather than that represented bythe formula 2Na,S0,,Fe,S209,7H20.Radioactive Minerals.Several papers dealing with radioactivity and containing matter ofmineralogical interest have appeared during the year.I n the firstplace, R. J. Strutt has described experiments made to determine theamounts of uranium, radium, thorium, and helium present in monazite,pitchblende, aeschynite, gadolinite, and a number of other minerals.Uranium was estimated by the ordinary chemical methods, radium andthorium by means of their emanations, whilst helium was determineddirectly. The conclusions he arrives a t are as follows : (1) the amountNature, 1905, 72, 397.€'roc. Roy. SOC., 1905, A 76, 88.2 Zeit. Kryst. Min., 1905, 41, 209.T 276 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of radium in a mineral is proportional to the uranium present.Incidentally he has shown that uranium occurs in some minerals, forexample, monazite, not previously known to contain it.(2) Thoriumis always accompanied by the uranium-radium combination, a factwhich leads to the suggestion that thorium is producing uranium.(3) Helium only occurs in quantity if thorium is present, and is there-fore probably produced more by thorium than by radium. (4) Thoriumminerals vary much in emanating power. The conclusion thatthe amount of radium contained in a mineral is proportional to theuranium present has also been reached by B. B. Boltwoodl afteran examination of 22 samples belonging to 12 species of minerals con-taining from 0.3 to 74 per cent. of uranium. He believes thaturanium is the parent of radium and that thorium has no part in itsproduction j he has not, however, been able to obtain direct evidence ofthe change of uranium into radium.Like Strutt, he has detecteduranium in monazite and, noticing the persistent occurrence of lead inthese minerals, suggests that this element may result from the breakingup of uranium, He has followed up this idea in an important paper *on the ultimate disintegration product of the radioactive elements, inwhich he insists on the necessity of distinguishing between the primaryminerals, which occur embedded in pegmatites and other rocks, andthose of secondary origin, produced by the alteration of primary com-pounds or found in many mineral veins. To the first class belong thepitchblendes of Norway, North Carolina, Texas, and Connecticut, aswell as aeschynite, euxenite, fergusonite, samarskite, thorite, andthorianite. I n the second class must be placed the pitchblendes ofCornwall, Saxony, and Bohemia, as well as gummite, autunite, andothers.It is to the study of the composition of the primary mineralsthat we must look for evidence as to the existence of possibledisintegration products. The secondary minerals may be too recent forthe productv to have accumulated in sufficient quantity for us to detectthem. Studying the matter from this point of view, Boltwood findsthat lead is present in all primary minerals which contain more than2 per cent. of uranium. Further, since Hillebrand has found lead inall the uranium minerals he has analysed, Boltwood is confirmed inthe view that lead is one of the final inactive disintegration products ofuranium.The common association of uranium and thorium he inter-prets as supporting the idea that thorium is also a result of thedisintegration of uranium : the opposite position to that adopted byStrutt. The small quantities of barium and of bismuth present inradioactive minerals are, he thinks, also to be attributed to disintegra-tion, the former being possibly derived from actinium, the latter fromthorium. The presence of hydrogen and of water in some of thesePhil. Mag., 1906, [vi], 9, 599. Amer. J. Sci., 1906, [iv], 20, 253MINERALOGICAL CHEMISTRY. 27 7minerals has long been a puzzle to mineralogists. It seems impossibleto believe that water can have penetrated them from without, for manyof them are compact enough to retain helium, and they are, moreover,often associated with anhydrous minerals such as apatite and magnetite.Boltwood points out that this difficulty vanishes if we admit that thehydrogen is also due to disintegration.The presence of argon isaccounted for in the same way. Further, he shows that a comparisonof a number of analyses of pitchblende made by Hillebrand revealsa rough proportionality between the amount of uranium and theamounts of lead, rare earths, and helium for specimens from the samegeneral locality, and a closer relation between the quantities of UO,and of helium. For specimens from the same actual locality, the con-tent of rare earths increases with the amount of lead present, and theproportion of helium, as compared with lead, is greatest in those whichhave the highest specific gravity.It should, however, be noted that theproportions of helium and of rare earths and lead are not the same inthe pitchblendes of Connecticut and of Norway, the relative quantity ofheligm being smaller in the latter than in the former. This discrep-ancy may perhaps be explained by the greater geological age of theNorwegian pitchblendes. That helium and rare earths are absent fromthe secondary pitchblendes of Saxony and Bohemia is quite in accord-ance with theory. From a study of other minerals, Boltwood findsthat the proportion of helium with respect to lead and uranium is highin dense compact substances of low emanating power, such as monaziteand samarskite, and also in minerals such as thorianite found in theoldest geological formations, and that the minerals with the greatestproportion of thorium are in general the most hydrated.That monazitecontains uranium has also been confirmed by F. Zerban,l who detectedthe element in all the monazite sands he examined, and also to theextent of 0.02 per cent. of U,08 in a good crystal from Norway. I nconclusion, we may mention that E. Rutherford and B. B. Boltwood2have found that the quantity of radium associated with 1 gram ofuranium in a radioactive mineral is equal to 7.4 x 10-7 gramsapproximately. This result was arrived at by comparing the effect onan electroscope of the emanation from a radium bromide solution ofknown strength and from a specimen of pitchblende from Spruce Pine,North Carolina, containing 74.65 per cent..of uranium.Ne w M i n era Is.Beckelite.-This mineral is a calcium cero-lanthano-didymo-silicate.It is found in brown grains, or in little isotropic octahedra ordodecahedra embedded in the albite of a dyke rock, consisting ofBer., 1905, 38, 557. AWT. J. Sci., 1905,:[iv], 20, 55278 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.albite and nepheline with magnetite and. zegirine, which occurs in theelzeolite syenite (mariupolite) of the Mariupol district, on the sea ofAzov. The cleavage is cubic, and the specific gravity 4-15 approxi-mately. It is soluble in hot hydrochloric acid, and yields the follow-ing results on analysis :SiO,.ZrO,. A1,03. Mn,O,. Yt,03+Er203. Ce203. L%O,.17'13 2.50 0.30 0.07 2.80 28-10 13.60Di203. CaO. K,O. Na,O. Ignition loss. Total.18 -00 15'46 0.39 0.78 0.99 100.12Traces of iron and magnesium were also detected. These numbersgive the formula Ca,(Yt,Ce,La,Di),(Si,Zr),015. J. Morozewicz,1 thediscoverer of the mineral, points out that by writing this in the formCa3(Ce,La,Di)2Si3012,(Cle,La,Di)203 the analogy with the garnets isexhibited. It can also be written as follows : CaR2Si20,,Ca2Si04,R20,,where R = Ce,La,Di. The mineral may be distinguished from pyro-chlore by its cleavage, lustre, and index of refraction, and also bythe fact that it remains soluble in hydrochloric acid after ignition.It has been named in honour of Professor F.Becke.Bowmanite is bne of the many new minerals recently discovered byR. H. Solly2 in the dolomite of the Binnenthal. Up to the present,only a few small, honey-yellow crystals have been found. Theycrystallise i n the rhombohedra1 system, and have a perfect basalcleavage. Optical examination has shown that the mineral is pseudo-symmetric. It appears to be essentially a phosphate of lime andalumina with small amounts of iron and water.Doughtyite.-This name has been tentatively proposed by W. P.Headden3 for a hydrated basic aluminium sulphate of the formulaA12(S04)3,5A12(OH),,21H,0, found at Doughty Springs, Delta Co.,Colorado.Giorgiosite.-This name has been given by A. Lacroix* to a basicmagnesium carbonate found as a fine powder composed of minutespherules on saline crusts obtained by Fouqud in 1866 from a fissurein the lava of Aphroessn, Santorin.With it is associated a white,flocculent, isotropic material. The amoclnt of these substances avail-able was too small to admit of analyses being made, but as the pro-perties of the latter are comparable with those of the freshly precipi-tated white magnesia of pharmacy, its composition is probably similarto that of hydromagnesite, SMgCO,,Mg( OH),,SH,O. The spherulesappear to be identical with the product obtained when the precipitateBull. Acad. Sci. Cracovie, 1905, annee 1904, 485.2 Nin. Mag., 1905, 14, 80.3 Proc. Colorado Sci. SOC., 1905, 8, 55.4 Bzcll. SOC. frang. Mi%., 1905, 28, 198.See also Compt. rend., 1905, IM, 1308MINERALOGICAL CHEMISTRY. 279of white magnesi L is boiled for s )me time with its mother liquor.This product has been shown to be 4MgC0,,Mg(OH),,4H20, and thisis accordingly the probable formula of the new mineral.Hibschite occurs incrusting a green titaniferous melanite found incalcareous inclusions in the phonolite of the Marienberg near Aussig ;it crystallises in isotropic octahedra. From two analyses, one of themelanite alone, the other of melsnite mixed with hibschite, a formulabas been arrived at by F. Cornu identical with that of lamsonite,H4CaA12Si2010.Hutchinsonite.-A few small crystals of this orthorhombic mineral,showing numerous faces and a good cleavage, have been obtained byR. H.Solly2 from the dolomite of the Binnenthal. An analysis byG. T. Prior revealed the interesting fact that the substance is athioarsenite of thallium, lead, silver, and copper containing nearly30 per cent. of thallium.Junosite.-A greenish-yellow efflorescence found on graphitic schistat the iron mine of Vashegy, Komitat Gomijr, Hungary, has beenanalysed by H. Bockh and K. The substance, which is prob-ably the result of the decomposition of pyrites, crystallisee in minute,orthorhombic plates with good basal cleavage (sp. gr. = 2.51 to 2.548).The formula is Fe2(S0,),,9H,0 and the mineral is therefore dimor-phous with coquimbite (rhombohedral, sp. gr. 2.105) and closely alliedto quenstedtite, Fe2(S0,),,10H20.KZeinite.-A. Sachs 4 finds that small, yellow, hexagonal crystalsfrom Terlingua, Texas, have the composition 3Hg0,HgC12.Themineral has a perfect basal cleavage.Lengenbuchite is a thioaresnite of lead with small amounts of silver,copper, and antimony, found by R. H. Solly5 in thin, blade-shapedcrystals in the dolomite quarry through which flows the Lengenbach,a tributary stream of the Binnenthal.Mccrrite is another of the new minerals described by R. H. Solly 6from the Bionenthal dolomite. Only a few small crystals have so farbeen found, and these belong to the oblique system and are very richin faces.Moissanite.-H. Moissan found green, hexagonal crystals of carbonsilicide together with the various forms of carbon in those residuesfrom the solution of 53 kilograms of Cafion Diablo iron in hydrochloricacid which resisted the attack of hydrofluoric and sulphuric acids.Afurther study of these crystals* leaves no doubt as to their identityIts sp. gr. is 7,441.The chemical composition has not yet been determined.Tsch. Min. Mitth., 1905, 24, 327.3 Fold. Xodony, 1905, 35, 139.Xitzungsber. K. Akffid. Wiss. Berlin, 1905, 1091.5 Nin. Mag., 1905, 14, 78. Ibid., 76. Compt. rend., 1904, 139, 773.8 Compt. rend., 1905, 140, 405. See also Ann. Chim. Phys,, 1905, [viii]. 5, 174&!in. Mag., 1905, 14, 72280 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.with carborundum, and G. F. Kunz, therefore, proposes that thenaturally occurring compound should be called moissani te.Paracehian.-In the crystalline schists of Candoglia, Val del Toce,veins and nodules rich in quartz, diopside, calcite, pyrite, and otherminerals are found together with calcareous fragments consistingalmost entirely of calcite and pyroxene.Intimately associated withthese veins and fragments occur pale yellow granules of a bariumaluminium silicate. The optical properties and chemical compositionof this mineral have been carefully studied by E. Tacconi,l whoseanalyses lead him to assign to it the formula Ba,A1,Si80,. This sug-gests comparisons with barylite, Ba4A14SiP024, and celsian, BaA1,Si,08.From the €ormer,jt is clearly distinguished by its lower specific gravity,3.325, that of barylite being 4.03, and from the latter by its very poorcleavage (celsian has two perfect cleavages and a sp. gr.3.37). As,however, the optical characters of the mineral closely resemble thoseof celsian, Tacconi is doubtful whether it should be considered anentirely new species, and, therefore, following the suggestion of L.Brugnatelli, has named it paracelsian.Purpurite occurs in small, irregular masses in the tin-bearingpegmatite and in the neighbouring schist at the Faires tin mine, Eing'sMountain, Gaston Go., North Carolina. It has also been observed onspecimens from the lithium-bearing pegmatite dykes of Hiriart Hill,Pala, San Diego Go., California. The mineral has probably resultedfrom the oxidation of lithiophilite, the lithium being almost entirelyremoved and the iron and manganese oxidised and recrystallised withphosphoric acid and water.The mineral is of a rich deep red orreddish-purple colour, and appears to crystallise in the orthorhombicsystem. It is soluble in hydrochloric acid with evolution of chlorine,the iron and the manganese being present as ferric and manganic saltsrespectively.Fe,O,. Mn,O,. P,O,. H,O. CaO. Na,O. Insol. Total.15-89 29-25 47-30 5'26 1'48 0'84 0.52 100.54The following results were obtained on analysis :A trace of lithium was detected, and on heating to 105' the loss ofwater amounted to 3.31 per cent. Assuming the isomorphism of ferricand manganic oxides, L. C. Graton and W. T. Schaller have deducedthe formula 2(Mn,Fe)P04,H20.8mithite.-An analysis by G. T. Prior has shown that this mineralhas the simple formula AgAsS,. It was found by R. H. Solly3associated with other rare thioarsenites in the dolomite of theBinnenthal.The small red crystals exhibit numerous faces and belongto the oblique system.Rend. Reale Islit. Lombardo, 1905, [ii], 38, 636.Amer. J. Sci., 1905, [iv], 20, 146. 3 Min. Mag., 1905, 14, 74MINERALOGICAL CHEMISTRY. 281Tq-echrnunnite also occurs in the Binnenthal do1omite.l Like hutchin-sonite and smithite it is a red mineral, but from these the minutecrystals may be distinguished by their symmetry, as they crystallise inthe rhombohedra1 system. The composition of the mineral has not asyet been ascertained.StaZplzochZoyan.-This substance has been discovered by F. Kretsch-mer 2 in the iron mines of Gobitschau, near Sternberg, Moravia. Itis a product of the metamorphism of thuringite and occurs inshining yelIow scales, thus suggesting the name, which is derivedfrom U T L X T V ~ S , glittering, and ~ X ~ p d s , yellow.It is decomposedby hydrochloric acid, and was found to have the following composi-tion :Si02. A1,03. Fe,O,. MnO. CaO. MgO. P,O,. H,O. Total.33.30 4-37 44.33 0-34 1-22 1.73 0.37 14.10 99-76These numbers lead to the formula H,,(Al,Fe),o(Ca,Mg)Si90,6.Tych,ite.--This exceedingly rare mineral occurs associated withnorthupite, MgCO3,Na2CO,,NaC1, which it closely resembles in form andappearance, at the Borax Lake, San Bernardino Co., California. It wasdiscovered by the chance that a small octahedron selected for examina-tion from a parcel of northupites failed to react for chlorine, but masfound to contain sulphate.Following up this observation, S. L. Penfieldand G. S. Jamieson3 tested some thousands of northupites, but wereonly able to detect three more crystals of the new mineral. I t s acci-dental discovery finds expression in the name tychite, from d x y , luck.Thinking that the composition of the mineral might resemble that ofnorthupite, Penfield and Jamieson attempted to prepare it artificially.In this they were successful, for on adding magnesium sulphate to asolution of the carbonate and sulphate of sodium, and heating themixture for five days on a steam-bath, a crystalline precipitate wasobtained. The physical characters of the precipitate agreed withthose of the natural crystals, and as its composition was found to be2MgC0,,2Na2C0,,Na,S0,, this is probably the formula to be assignedto tychite.Penfield and Jamieson further point out that northupiteand tychite both take some time to form when their constituents arebrought together in solution, and that whereas the former is readilydecomposed by boiling water, the latter is almost insoluble. Thisbehaviour suggests that these substances probably possess a complexmolecular structure which may perhaps find expression in a constitu-tional formula in which four carbon atoms are joined with four oxygenatoms to form a ring. The isomorphism of the two compounds canonly be accounted for by the mass effect of the large number of sodium,oxygen, carbon, and magnesium atoms, which overpowers the morpho-Min. Mag., 1905, 14, 75.Centr. A%., 1905, 203.3 Amcr. J. Sci., 1905, [iv], 20, 217282 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.tropic influence of either the two chlorine atoms or the sulphategroup.A New Zeolite.-In the pegmatite veins of the granite of San Fieroin Campo, Elba, small, eight-sided crystals occur which G. D’Achiardi 1thinks may perhaps be a new species of zeolite. He finds that thecrystals are complex twins and that they have the following com-position :SiO,. Al2O,. CaO. SrO. MgO. K,O. Na,O. H,O. Totd.61-41 11.15 5.52 1-14 trace 3‘31 2‘06 13-51 98-10These percentages do not quite accord with those given by anyknown zeolite, although they resemble to some extent those of someheulandites in spite ol a considerable difference in the amounts ofalumina and alkaline oxides.The two minerals, however, differwidely in habit. D’Achiardi deduces the following formula from hisresults : (Na2,K2,Ca),A1,Sil,0,,,1 4H20.Mineral Ann Zyses.Many mineral analyses have been published during the year. Ofthese, some have thrown light on the composition of rare and im-perfectly described species and varieties, others, although referring towell-known minerals, are interesting becaus? the determination ofthe chemical composition has been accompanied by a careful studyof the crystallography and optical characters of the material analysed.The most important of these investigations will be given below underthe name of each species arranged alphabetically.Amphibole Group.-An analysis of the amphibole from the syeniteof Biella has already been published by Cossa. It is remarkableas showing a high percentage of ferric oxide and alumina and littlemagnesia, resembling in this respect the analysis made by Flinkof so-called diastatite from Nordmarken.F. Zambonini,? who haslately made an elaborate study of the minerals of the Biella syenite,has re-examined the amphibole, and his numbers, which differ a,good deal from those obtained by Cossa, are given below :SiO,. TiO,. A1,03. Fe,Os. FeO. MnO. CnO. MgO. K20. Na,O. H,O. Total.51.32 0’84 6’11 3’28 7’39 trace 13’59 16-17 0.36 0.91 0.30 100.27Zambonini represents the substance as composed of the follow-ing molecules : 5Mg2A1,Si20,, ; 3FeFe2Si,012 ; 2(Na2,K2, H,),Si,O,, ;32(Mg,Ca),Si,012 ; 5Fe,Si,O,,, and points out that the composition can-not be satisfactorily explained on Scharizer’s view that amphibole isxCa~Mg,Fe)3Si,012,y(R’2R’’)3R’’2Si3012, because it contains too muchsilica.The geometrical constants also differ considerably from1 Proe. Verb. SOC. Toscana Sei. Nat., 1905. Jap. 15.2 Zeit. Kryst. illin., 1905, 40, 231MINERALOGICAL CHEMISTRY. 283those of other amphiboles and fail t o support the view expressedby Brogger that the angle p increases with the amount of ironaud manganese present. A specimen of the rather rare variety ofhornblende called edenite, which contains much alumina, but littleor no ferric oxide, has been analysed by A. Rocctti1 with thefollowing results :SiO,. Al,O,. Fe,O,. MgO. CaO. Nn,O + K20.Ignition. Total.49'25 13'82 trace 20'95 11'91 2-80 0.91 99'646 (R",R,)O, Al,O,,GSiO,.The mineral is found as grains and crystals embedded in limestonesassociated with the gneissic rocks of Piano dei Chiotas, in theMaritime Alps.A well developed crystal of black hornbEende from Lukow, Bohemia,shown by microscopic examination to be free from inclusions, has beenanalysed by F. Hanusch a t the request of J. E. Hibsch.2 The resultsare as follows :The composition may be expressed by the formulaSiO,. TiO,. F. Al,O,. Fe,O,. FeO. MnO. CaO.39'60 2.50 0.10 18.51 5.50 2.26 0.74 1257MgO, K,O. Na,O. H,O. CO,. Total.14.11 1.87 2.58 0'26 0.07 100.67Aragotite.-H. G. Hanks3 has examined a specimen of this rarehjdrocarbon from the Aetna quicksilver mine, Napa Co., California.On analysis, E.Huetlin found 98-10 per cent. of carbon and 9.17 percent. of hydrogen.Ardenlzite.-This silicate is interesting because it con t ains arsenicand vanadium. AS the formula hitherto assigned to it is verycomplicated, and as the state of oxidation of the vanadium has neverbeen satisfactorily made out, W. Prandtl4 has investigated thesubstance afresh. He concludes that arsenic and vanadium are bothpresent in the quinquevalent state, and writes the formula1 OSiO,,(As,V),0,,5(Al,Fe),O,,l O(Mn,Mg,Ca,Fe)0,6Hz0,basing it on the following analytical data :SiO,. As,O,. V,O,. A1,0,. Fe,O,. MnO. MgO. CaO. FeO. H,O. Total.27-77 9'91 0.81 25.25 0.53 22'70 5.20 1-44 0.65 5-24 99-50Atopite has been found in small, yellow octahedra on manganeseores from the mines of Miguel Burnier, Minas Geraes, Brazil.Ithas been examined by E. H u s Y ~ ~ , ~ who finds that its formula is(Ca,Mn,Na,),Sb,O:, like that of the specimens from Lgngban, inSweden.Awccruite.-The naturally occurring alloys OF iron and nickel haveXevhta Min., 1905, 32, 12. a Tsch. Min. Mitth., 1905. 24. 271. , ,3 J. Roy. Micros. Soc,, 1905, 673.5 Centr. Min., 1905, 249.Zeit. Kryst. Min., 1905, 40, 392284 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.been the subject of investigations by G . C. Hof€mannl and by G. S.Jamieson.2 The former has given the name souesite to a specimenfound in the auriferous gravels of the Fraser River, British Columbia.The latter has examined material from Josephine County, Oregon, andfrom the Smith River, California.On comparing his results withthose of Hoffmann, as well as with fhe published data for similarmaterial from Awarua Bay, New Zealand, from the Elvo River, Pied-mont, and from Josephine County (so-called josephinite), Jamieson findsthat this alloy has not a definite composition, the amount of nickelvarying from 67.63 per cent. up to 77.17 per cent. He thereforerightly deprecates the use of the names josephinite and souesite, andurges that the name awaruite should be alone retained.BZende.-C. Rimatori 3 has continued his quantitative and spectro-scopic investigation of Sardinian blendes. Fifteen specimens wereexamined, and cadmium found in all up to a maximum of 1.23 percent, Seven be-longed to the variety called marmatite, and one of these contained5.81 per cent.of manganese, the largest quantity hitherto reported.Two contained both gallium and indium and six others indium alone;in one of these, 0.0243 per cent. of indium was found.CaZi,fornite.-This name was given by G . F. Kunz to a remarkablecompact variety of vesuvianite found in Siskiyou Co., California.Similar material was subsequently obtained from Fresno Co.,California.The analytical data have been interpreted by F. W. Clarke andG. Steiger as leading to the approximate empirical formula2 H,0,2 A1203, 7Ca0,6Si02 or A1,Ca7 (SiO,),( A19H)( A102R,)H. Ifpart of the water is extraneous, the following much simpler formulamay hold : A12Ca7(Si0,),(A10H)2, and this fairly represents a goodmany other analyses of vesuvianite.Clarke and Steiger furtherpoint out that while A12Ca,(Si0,)5(A10H) is a good expression for theaverage composition of the species it does not fit the extremes, andfrom a study of more than forty analyses they suspect that vesuvianiteis a mixture of the four following molecules : A12Ca7(Si04),(A10H), ;Al,Ca7(Si0,),(A10,H,), ; A1,Ca7(Si04),H4 ; A1,Ca7(Si04),Ca,, the firstand third usually predominating, About one-seventh of the calcium isreplsced by magnesium, and in wiluite the group BOH probably occurs.Carnotite.-This radioactive uranium mineral has been tested forhelium by E. P. Adams.5 As he failed to find any, he concluded thatCopper was present in several, bismuth in two.Amer. J.Sci., 1905, [iv], 19, 319.Ilbid., 1905, [iv], 19, 413.Atti R. Aecad. Lincei, 1905, 14, i, 688.But1 U.X. Geol. Xzwu., 1905, 262, 72..0 Jmer. J. ,Ses%i., 1905, [iv], 19, 321MINERALOGICAL CHEMISTRY. 285helium, if ever present, had escaped owing t o the permeable characterof the mineral.Chs.ysoberyZ.-A crystal from Maskinonge Co., Quebec, has beenanalysed by N. N. Evans 1 with the following results :Sp. gr. BeO. Al,O,. Fe203. Total.17-78 76.76 6.07 100.61 3-52Some if not all the iron was probably present as FeO; no calcium ormagnesium were found.CoZzcmbite.-W. P. Headden has analysed specimens of thismineral (I) from Cation City, Colorado, and (11) from Black Hills,South Dakota, with the following results :Cb,O,. Ta,O,. WO,. SnO,.FeO. MnO. Ignition. Total.I. 56.48 22-12 0'45 0'11 8.07 12'45 0-15 99.83.11. 54.64 25-62 - 0.15 6-80 12.61 - 99-82,Copper-pitch Ore.-A dark brown, pitch-like mineral from Amzalar,Roumania, has been analysed by Th. Nicolau.3 The theory thatcopper-pitch ore is a mixture of chrysocolla and limonite is notsupported by the results, and although no simple formula can becalculated the mineral must be regarded as homogeneous, a conclusionalready reached by Lindgren and Hillebrand.Dognacskaite.-The composition of this bismuth coilper sulphidehas hitherto rested on an analysis by Maderspach. A t the request ofA. Otto, an analysis has been published by Koechlin showing a muchsmaller quantity of bismuth, corresponding to the formula of wit-tichenite, Bi,S3,3Cu2S.As, however, the specific gravity of dognac-skaite is 6.79 to 6.72 and that of mittichenite is 5, and as, moreover,the former mineral has a good cleavage and the latter nono,F. Neugebauer5 has made a fresh analysis of carefully selectedmaterial. From his reaults, he deduces the formula Bi,Cu2S7 or2Bi2S3,Cu2S, and thinks that the individuality of dognacskaite as aspecies may be considered t o be established.Dumortierite has been the subject of an elaborate investigation byW. T. Schaller,G who has not only collected the results of otherworkers, but has determined the crystallographic and opticalproperties of the mineral, and made three very careful analyses.The results of these are given below; I and I1 refer to a specimenfrom near Dehesa, San Diego Co., California, 111 t o material fromSkamania Co., Washington.Amer.J. S'ci., 1905, [iv], 19, 316.9 Ann. Sci, Univ. Jassy, 1905, 3, 103.ti Tsch. Min. Mitlh., 1905, 24, 323.Proc. Colorado Sci. Soc., 1905, 8, 55.Tsch. Mi%. Mitth., 1905, 24, 117.Amer. J. Sci., 1905, [iv], 19, 211 ; see also Bull. U.S. Geol. Sum, 1905,262, 91286 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.SiO,. A1,0,. Ti,O,. Fe20B. H20. B20,. Total.I. 28.58 63'31 1 '49 0'21 1 '53 5-21 100.3311. 28.78 63-30 1 *40 0.25 1-51 5-53 100.77IIJ. 28-51 59.75 0*95* 2.48 2.12 5.54 100-03* Titanium calculated as TiO, ; 0.68 CaO also present.The first two analyses agree exceedingly well with the formula8A1,03,B,03,H,0,6Si02. I n the case of the third, the agreement isnot quite so close, but this analysis is of less value than the othertwo as the material was known to be contaminated with andalusiteand titanite (leucoxene) as well as with traces of pyrite.Schallerpoints out that an analysis by Ford of a specimen from Arizona iscompletely in accord with his formula, although Ford's results for theCalifornian and New York minerals are less perfectly in harmonywith it: the same is true for the analyses made by Whitfield andRiggs. By writing the formula thus, (Si0,)3A1(A10),(BO)H, itsanalogy with andalusite is exhibited, and its alteration into muscoviteexplained.&nurgite.--The following is an analysis by W. P. Headden1 ofcrystalline enargite from the Powers Mine, Willis Gulch, Gilpin Co.,Colorado :S.As. Sb. Cn. Pb. Fe. Zn. Total.29'35 16-17 3.77 48'40 1-83 0.30 0.19 100-01E'idote. -The crystallographic, optical, and chemical properties ofgood crystals of epidote from Inverness-shire have been carefullystudied by H. H. Thomas and W. Pollard.2 The mineral is aninteresting member of the epidotes with a low percentage of ferriciron, and falls naturally into the series. I n composition, it is verysimilar to the epidotes from Huntington, Mass., the Zillerthal, andVal Maigels.FeZspaT Group-In addition to the important investigation of Dayand Allen referred to above, we may note the following points.G. Melczer 3 has determined with great care the crystallographicconstants of an albite from Nadabula, shown by qualitative examinationto be pure.He finds a : b : c = 0.6350 : 1 : 0.5578; a = 94'6', p = 116'36$',y=87'52'. The extinction on 010 is 20'30', on the base 3'5' to4'30'.An albite from Nurra, Sardinia, has been examined by C. Viola,4 andan analysis made by H. Steinmetz (I, below). Viola thinks that the limeis due to impurities and regards the mineral as a mixture of 10 moleculesof albite with 1.3 molecules of orthoclase. He has determined theI t s formula is Ca4A14(A10H),(Si04)G.Proc. Colorado Sci. Soc., 1905, 8, 55.illin. Mag., 1905, 14, 109.Zeit. Kryst. Alin., 1906, 40, 57'1.BOX A. Corn. Geol. d'ltalin, 1905, [iv], 6, 106MlNERALOGICAL CHEMISTRP. 287indices of refraction and the extinctions and finds that, whilst theformer indicate a nearly pure albite, the latter belong rather to anoligoclase-albi t e.An orthockuse from Biella, geom etrically and opticallynormal, has been analysed by F. Zamb0nini.l Some very pure whitecrystals gave the results quoted under I1 below. At the samelocality occur crystals of oligocluse. Zambonini has also measuredthese, and finds that their constants are the same as those of theVesuvian oligoclase determined by vom Rath ; he quotes an analysis byC. Montemartini (111, below), and points out that on Tschermak'stheory the mineral consists of 7Ab + 3An.SiO,. P,05. A1203. Fe203. CaO. MgO. K20. Na,O. Ignition. Total.1. 67-16 - 17.57 - 4'52 - 1.07 9-51. - 99.8311. 64-61 trace 18.75 trace 0'83 trace 14-46 0.81 - 99.46111. 63'51 - 22.40 - 3'38 0.08 1'24 8-66 0.48 99.75Fibroferrite.-W.P. Headden has found that aggregates ofgreenish-white, acicular crystals from Green River, Utah, have theformula Fe20,,2S0,, 1 OH,O.Ei'edZei-ite is an oxychloride of lead found in ancient slags a tLaurion. A. de Schulten3 has recently determined its composition tobe Pb0,2PbC12,H,0. It is therefore related to penfieldite, Pb0,2PbC12,and to laurionite, PbO,PbCI,,H,O, which both occur a t the samelocality.Glaucodote is found in imperfect crystals at the StandardConsolidated gold mine, Sumpter, Oregon. A crystal has beenmeasured, and the material analysed by W. T. Schaller.* As theratio of cobalt to iron is approximately 3 to 2, the formula may bewrit ten Co,Fe, As,S,.G'yyolite occurs with pectolite and datolite a t Fort Point, SanFrancisco.W. T. Schaller has analysed the material and deducesthe formula 5H20,4Ca0,6Si0,, thus confirming the view taken byF'. W. Clarke. The mineral is probably oblique and related toheulandite.has published the following analysis~y 5. V. Peppel of a nearly pure huebnerite, AlnWO,, found in largebrown crystals a t Dragoon Summit, Arizona.Huebnevite.-W. H. HobbsSiO,. wo,. MnO. FeO. Total.1-10 75.10 22.87 0.81 99'88Kentrolite. -Specimens of this rare mineral have recently beendiscovered by D. Lovisato,7 near Ozieri, Sardinia, where i t occurs inZeit. Kryst. Min., 1905, 40, 251.Cornpt. rend., 1905, 140, 315.lbid., 124.AtSi Iz. Accacl. Lincei, 1905, 14, i, 696.PTOC. Colorado Sei. Soc., 1905, 8, 55.Bull. US. Geol. X Z G ~ ., 1905, 262, 132.ti Anzcr. Geol., 1905, 36, 179288 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.little brownish-red spherules and aggregates. An analysis byC. Rimatori gave the following results :SiO,. PbO. CuO. Fe,O,. MnO,. CaO. MgO. H20. Total.17-71 60.02 trace 1.55 18.87 0.33 trace 1.79 100.27In composition, the Sardinia mineral somewhat resembles thatfrom Lgngban, but in its appearance and mode of occurrence it is morelike the specimens from Chili.MeZiZite.-The study of a slag has led F. Zamboninil to analysemelilite from Capo di Bove, and to criticise the formula proposed forthis mineral. His results agree closely with those already publishedby Damour. Very various views as to the nature of melilite havebeen maintained, thus Des Cloizeaux has calculated the formula12R”O,2R”,O,,9SiO2, and Groth has arrived a t a somewhat similarexpression, (Ca,Mg),(A1,Fe),Si5019. Vogt, on the other hand, regwdsmelilite as an isomorphous mixture of gehlenite, R,R”’,Si,O,,, withgkermanite, an artificial substance of the formula K”4Si3O1,.Bodlander, however, has pointed out as a necessary consequence ofVogt’s view that the ratio of the oxygen in the silica to that present8 s R”O must vary between the limits 1-33 and 1.5.Discussing hisown analyses and those of others in the light of Bodlander’s criticism,Zambonini finds that this ratio is always much smaller than thatrequired by Vogt’s hypothesis. If, however, it is assumed that thealumina and ferric oxide are present as gehlenite and the correspond-ing quantity of this mineral is subtracted, Zambonini finds that silicaand oxides of the type R”O are always present in the exact proportionsrequired to form a metasilicate.Melilite may accordingly be regardedas a mixture of gehlenite, R”,R’”,Si201,, with n molecules of ametasilicate, R”Si0,. It may also be represented as an isomorphousmixture of R”Si0, with an aluminate of the type R”R”’0,; this is theview held by Bodlander and preferred by Zambonini. A thirdpossibility is to write it RR”’2Si,08,nR2Si0,. If this lastexpression is adopted, Des Cloizeaux’s formula becomes2 RR”,Si,08, 5R”,SiO,.OZivine.-The investigation of a gabbro containing both olivine anda rhombic pyroxene suggested that it would be interesting todetermine the relative proportions of the iron and magnesiumcompounds present in these two minerals when they occur together.J.Schiller 2 has therefore analysed the olivine and the bronzite frombombs found at Eapfenstein, near Gleichenberg.The olivine consists of 90.2 per cent. of Mg,Si04 and 9.8 per cent. ofFezSiO,. If, in working out the results for the bronzite, the water,lime, and titanium oxide present are omitted, and ferrous oxide and2 Tsch. Min. Mitth., 1905, 24, 309. Zeit. Kryst. Ifin., 1905, 41, 226MINERALOGICAL CHEMISTRY. 289magnesia considered as equivalent, we arrive at the followingcomposition : 86 per cent, of Mg,Si,O,, 3.9 per cent. of MgAl,SiO,,3.2 per cent. of MgFe,SiO,, and 6.9 per cent. of Fe,Si,O,. Here alsothe ferrous silicate and the magnesium silicate are in the ratio 1 : 9.There is, therefore, no essential difference between the proportions inwhich the ferrous compounds and the magnesium compounds occur inthe two minerals.A consideration of the work of others leadsSchiller to conclude that when olivine and rhombic pyroxene occurtogether in rocks free from felspar, the ferrous and magnesiunicompounds exist in about the same molecular ratio in each. When,on the other hand, they occur in rocks which contain felspar, theolivine is always the richer in the magnesium compound.Prehnite.-Specimens from Lower California and from Biella have,been analysed by W. T. Schaller 1 and by F. Zambonini respectively.I n both cases, the composition is well expressed by the formulaH,Cn2A1,Si,0,,.Pyroxene Group-The optical characters of good crystals of diopsidefrom the eozoon limestone of C6te St.Pierre, Canada, have beendescribed by H. Preiswerk.3 The mineral has been analysed byF. Hinden, and may be regarded as a compound of 96.25 per cent. ofCaMgSi,06, 1.92 per cent. of PeMgSi,O,, 1.51 per cent. of MgAl,SiO,,and 0.32 per cent. of MgFe,SiO,, although the actual numbersobtained show an excess of basic oxides as compared with silica (I below).Crystals OF black augite from Canale Monterano, near Rome, havebeen measured and analysed by F. Zambonini ; his results are givenunder I1 below.SiO,. TiO,. A1,03. Fe,O,. FeO. MnO. CaO. MgO. Na,O. H,O. Total.I. 53.70 - 0.95 0.32 0.65 - 25.45 19'04 - 0-47* 100'5811. 50.88 1-02 5-36 1'21 4.67 trace 22'96 13.78 0.50 0.34 lOO'f2* Ignition loss.Tengerite.-In an account of the locality a t Barringer Hill,Llano Co., Texas, from which have come fine specimens of many rareradioactive minerals, W. E.Hidden has described the occurrencein gadolinite of white, semi-globular concretions which may perhapsbe tengerite. As the composition of this species had not previouslybeen determined, the following analysis was made by W. F.Hillebrand :Yt group. Ce group. Fe,O,. BeO. CO,. H,O > 105". H,O t1053 SiO,. MgO40'8 7'0 4'0 9.7 19'6 14.1 3.2 0.4 1.2"* Includes alkalis and loss.No definite formula can be calculated, but the presence of glucinumfl Zeit. Kryst. iMi.n., 1905, 40, 262.a Ib'bid., 498. Bid., 52. Amer. J.Sci., 1905, [iv], 19, 429.Bull. U.S. Geol. Stcrv., 1905, 262, 128.VOL. 11. 290 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.in the form of carbonate is remarkable, and may perhaps indicate theexistence of a new glucinum mineral mechanically mixed with a basichydrous carbonate of the rare earths of the yttrium group.Teetradynzite. -The composition of cleavage masses of this mineralfrom Whitehorn, Fremont Co., Colorado, has been found by W. F.Hillebrand t o agree well with the formula Bi,Te,. I n this connection,we may notice that K. Monkemeyer has made a careful study of thecooling curves of mixtures of bismuth and tellurium taken in variousproportions. These experiments lead to the conclusion that Bi,Te, isthe only compound of the two elements which can exist, and this viewwas confirmed by a study of the sections cut from the solidified masses.Thos.iccnite.-The leading characteristics of this interesting mineralmere given lust year ;] a more detailed description has recently beenpublished by W.R. Dunstan and G. 5. Blake,3 who give the followinganalysis :Thoz. UOP UO,. Ce02. PbO. Fe,O,. CaO. He. Insol. Total.78-86 6-03 9-07 1.02 2.59 0‘46 1’13 0.39 0.20 99-75The number quoted for helium was calculated on the assumptionthat the whole of the gas evolved from the mineral consisted of thatelement. Lanthanum and didymium are included under cerium. Atrace of phosphate was detected. This analysis differs somewhatfrom those previously published. Taken together, they show that themineral consists essentially of thoria, oxide of uranium, and varyingquantities of ceria.The exact part played by the uranium cannot besaid to be as yet precisely made out. Possibly it was originally allpresent as UO,, in isomorphous admixture with the thoria.Thorianite is slightly less radioactive than pitchblende, a mineralwith which it is evidently closely related. From the residues leftafter fusing about 250 kilograms of thorianite with potassiumhydrogen sulphate, 0. Hahn 4 has isolated a highly radioactive productdiffering markedly from radium. The rate of decay of the emanationfrom this substance was found to be identical with that of thethorium emanation. Further work5 has led Hahn to the conclusionthat a new element, ‘‘ radiothorium,” is contained in these residues.Thuringite.-In last year’s report, reference was made to Zalinski’swork on thuringite.Attention may now be called to F.Kretschmer’s 6 observations on specimens from the iron mines ofGobitschau, where it occurs associated with its decomposition productslimonite and the new mineral stilpnochloran. An analysis byS. Vogl shows that it is very similar to the thuringite from Zirmsee,Zeit. anorg. Chem., 1905, 46, 415.Ibid., 115.Centr. &fin., 1905, 195.dull. U.S. Geol. Surv., 1906, 262, 57.3 Proc. Roy. Soe., 1905, series A, 76, 253.6 Per., 1905, 38, 3371MlNERALOGICAL CHEMISTRY 291and if Tschermak’s theory of the composition of the mineral isaccepted it may be expressed as consisting of 4 molecules of ainesitewith 3 molecules of strigovite.Y’itanite.-In spite of much analytical work, the composition of thismineral still offers difficulties.Attention has been called to some ofthese by F. Zamboninil in the course of his work on the minerals ofBiella. A t this locality, titanite occurs in good crystals which weremeasured and in grains which mere found to resemble in compositionthe variety described by Groth from the Plauen Grund. Nosatisfactory formula could, however, be deduced from the followinganalytical data :SiO,. TiO,. Fe,O,. FeO. A1,0,. (Yt,Ce),O,. JInO. CaO. MgO. H,O. Total.30.89 30.55 5.77 trace 2-81 3.07 0-40 26.09 0 2 5 0‘86 100’72The ordinarily accepted formula, CaTiSiO,, also fails to representthe composition of the dark brown crystals from Urotva, Transylvania,described by Th.Nicholau,2 who bas published the two followinganalyses :TiO,. SiO,. CaO. MnO. A1,0,. Na,O. Total.42-24 31.10 24-30 2-09 0’64 0’06 100’4342.65 31-03 24.19 2.34 0.55 trace lOOT6Zeolite Group.-A specimen of heulanclite from the Biella syenitehas been found by Zambonini3 to contain considerably less silica andmore alumina than is usual in this mineral. Its formula isCa2A1,Si,0,6, 1 OH,O. Zambonini has also examined the chabazitefrom the same locality, and points out that it too has an abnormalcomposition, being exceptionally rich in lime and poor in alkalis, Theanalytical numbers do not support Streng’s hypothesis that thechabazites are mixtures of CaAl,Si60,,,8H,0 with CaAl,Si,0,,4H20.Chabazite has also been analysed by A.Bygdh5 The two specimensexamined came from Gellivare, Malmberg. The first may beapproximately represented by the formula R0,A120,,4Si02,6H,0, thesecond by 2R0,2A120,,9Si0,,1 3H,O. To stiZ6ite from the samelocality, Bygd6n assigns the formula 2RO,2Al20,,1 3Si02,1 4H20.I n concluding this section, we may notice that J. Schilling6 hascompiled a useful table showing the specific gravities, percentages oftantalum and of niobium and the localities of all the minerals con-taining tantalum of which analyses have as yet been published.Zeit. Kryst. Mi?&., 1905, 40, 239.8 Zeit. Kryst. Min., 1905, 40, 266.6 Bull. Geol. Instit. U?~iv. Upsala, 1905 (for 1902-1903), 6, 92.6 Zeit. anyew. Chem., 1905, 18, 883.Ann.Sci. Unh. Jassy, 1905, 3, 169.LOC. cit., 263.u 292 ANNUAL REPORTS ON THE PROGRESS OF CHEMXSTRY.M e t e o r i t e s .The death of Professor E. Cohen in the early part of the year hasremoved from this field of inquiry one of its most active cultivators.Among the latest of his publications may be noticed a catalogue of themeteorites in the collection at Greifswald. A catalogue by G. Dewalque 2of the meteorites preserved at Ghent, Gembloux, Lidge, Louvain, andMaredsous is also worthy of mention.The work on meteorites of most general interest which has recentlyappeared is contained in a paper by F. Rinne,3 in which the com-position and structure of meteoric iron are compared with those ofiron and steel, the subject being treated from the point of view ofphysical chemistry and the phase rule.The paper opens with a verylucid description of the phenomena of solidification presented by castiron and steel, and of the composition and mutual relations of ferrite,martensite, cementite, and pearlite. The changes which may occur afterthe metal has solidified are set forth with equal clearness. Havingcalled attention to the fact that the meteoric irons contain compoundssimilar to those found in technical iron, Rinne points out that far-reaching transformations may take place in meteorites long after thealloy composing them has become solid. Thus, nickel-iron is theequivalent of ferrite, cohenite (Fe,Ni,Co),C of cementite Fe,C,schreibersite (rhabdite) of Fe,P, troilite of PeS, and just as martensitemay break up on cooling into ferrite and the mixture of ferrite andcementite known as pearlite, so also in nickel-iron similar changesmay occur.Now, iron and nickel being closely related elements, theymay be expectgd to form mixed crystals, and there is reason to believethat their behaviour on solidification can be represented by a curve ofthe second type of Bakhuis Roozeboom’s classification,of the magnetic and other physical properties of the alloy leads to theconclusion that on further cooling differentiation of the solid takesplace into crystals rich in iron and crystals rich in nickel, the seriesbeing interrupted by a gap or lacuna, the differentiation following acourse which can be represented by a curve of Bakhuis Xoozeboom’sfifth type.A chemical compound of iron and nickel may also possiblyexist. A study of this curve leads to the following classification of thealloys of nickel and iron : (1) group below the lacuna. This includesalloys containing up to 7 per cent, of nickel, and to these the namekamacite has been given. In this groupThe study(2) Group of the lacuna.Mitlh. naturwiss. Yer. Neu- Yorpommewc and Riiyen, 1905, 36, (1904)) 1.3 Ann. Xoc. Gkool. Belg., 1905, 32, bl 15.a Neries Jahrb. &?in., 1905, i, 122.Compare F. Osmond and G. Cartaud, Compt. rend., 1903, 137, 1057MINERALOGICAL CHEMJSTRY. 293three sub-classes may be distinguished : (a) knmacite is crystallisedwith the eutropic mixture of karnacite and taenite (nickel-iron rich innickel) known as plessite, (6) plessite is found alone, ( c ) plessite andtaenite both occur.(3) Group above the lacuna. This contains thealloys rich in nickel, so-called taenite. Assuming the existence of acompound containing 68 per cent. of nickel, this group may be furthersubdivided according as the alloy contains more or less nickel than isrequired to form the compound. (4) Dystektite group. This consistsof a definite chemical compound, assumed to be Ni,Fe, and is heldby Rinne to be represented by awaruite. It should be noted,however, that the work on this substance referred to above rendersthe existence of a definite compound somewhat doubtful. I n con-cluding his paper, Rinne calls attention to the wide field of researchpresented by meteorites when studied from this point of view, andexpresses his belief that the knowledge we already possess as to theinfluence of carbon, phosphorus, and sulphur in modifying the structureand properties of iron will afford the clue to the part played bycohenite, schreibersite, and troilite in the constitution of meteorites.Evidence that differentiation has really taken place after solidifi-cation is found in the fact that in some meteoric irons the relation ofthe kamacite to the troilite is such as to leave no doubt that theformer crystallised after the latter had become solid. As troilitemelts at goo", this observation shows that the crystalliFation ofkamacite can take place at a temperature far below the melting pointof the alIoy.Among the individual meteorites examined, the following may benoticed :T?Ae Billings Meteorite.-This iron was found in southern Missouriand has been described hy H. A. Ward,l and analysed by H. W.Nichols.Caiion Diu6Zo.-The investigation by Moissan 2 of the residueobtained on dissolving 53 kilograms of this iron in hydrochloric acidhas already been referred to. It is interesting to notice that thecrater of Coon Mountain, Arizona, twelve miles south-east of CanonDiablo station, is believed by D. M. Barringer and B. C. Tilghman tqhave been produced by the impact of an immense meteorite of whichthe specimens of CZion Diablo iron once formed R part.Barrabu, Cowra, ccnd Mount Dyrrimg.-Careful analyses of theseAustralian meteorites have been published in full detail by J. C. H.M i n g a ~ e . ~ The first contains 93.50 per cent. of iron and 5.54 percent. of nickel. The second consists mainly of 85.26 per cent. ofAiner. J. S'ci., 1905, [iv], 19, 240.Ann. Chim. Phys., 1905, [viii], 5, 174.3 Bec. Geol. S'urv., N.X. Wales, 1904, 7, 305294 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.iron and 13.23 per cent. of nickel. That of Mount Dyrring is ofpallasite type, but much rusted.1Zvittis.-A. Lacroix 1 has called attention to the similarity in com-position of this meteorite with that of Pillistfer. Both containenstatite but no olivine.to be anoctahedrite of medium coarseness. It contains large inclusions ofschreibersite and some graphite, but no troilite.8heZburne.-This meteorite, which fell near the village of Shelburne,Grey Co., Ontario, in 1504, has been examined by L. H, B~rgstrom,~who 6nds it to be a chondritic stone consisting mainly of olivine andenstatite.Mount Vernon.-W. Tassin4 has determined this to be a pallasiteof the Krasnojarsk type. It consists essentially of nickel-iron con-taining olivine and varying amounts of troilite. The nickel-ironalloy, the taenite, schreibersite, troilite, chromite, and olivine wereseparated and their composition ascertained.Bull. Soc. frccq. Min., 1905, 28, 70.Field Columb. Jhs., Pub. 101, 1905, 3, 1.Trctas. B. Astrononz. SOC. Cmiada, 1905 (for 1904), 69.Proc. United States Nut. Mus., 1905, 28, 213.Rodeo.-This iron has been shown by 0. C. FarringtonA. HUTCHINSON

ISSN:0365-6217    

DOI:10.1039/AR9050200267

出版商:RSC    

年代:1905

数据来源: RSC