摘要:

ANNUAL REPORTSON THEPROGRESS OF CHEMISTRYANNUAL REPORTSM. P. APPLEBEY, M.A., B.Sc.H. BASSETT, D.Sc., Ph.D.G. M. BENNETT, M.A., Ph.D.H. V. A. RRIBCOE, D.Sc.F.G. DONNAN, C.B.E., LL.D., F.R.S.J. J. Fox, O.B.E., D.Sc.C. S. GIBSON, O.B.E., M.A.R. W. GRAY, O.B.E., Ph.D., F.B.S.A. J. GREENAWAY, F.I.C.T. A. HENRY, D. Sc.J. T. HEwIm, D.Sc., F.R.S.0. N. HINSHELWOOD, M.A., F.R.S.C. K. INGOLD, D.Sc., F.R.SON THEJ. KENYON, D.Sc.H. KING, D.Sc.T. S. MOORE, M.A., B.Sc.K. J. P. ORTON, M.A., Ph.D., F.R.S.J. C. PHILIP, O.B.E., D.Sc., F.R.S.T. S. PRICE, O.B.E., D.Sc., F.R.S.F. L. PYMAN, D.Sc., F.R.S.E. I(. RIDEAL, M.A., Ph.D.,D.Sc.R. ROBINSON, D.Sc., F.R.S.J. L. SIMONSBN. D-Sc.8. SMILES, O.B.E., D.Sc., F.R.S.8. SUGDEN, D.Sc.J. F. THORPE, C.B.E., D.Sc., F.R.S.PROGRESS OF CHEMISTRYH.BAssETr, D.Sc., Ph.D., D.-&-Sc.,G. M. BENNETT, M.A. , Ph.D., F.I.C.J. D. BEBNAL, M.A.A. C. CHIBNALL, M.A., Ph.D.B. A. ELLIS, M.A.J. J. Fox, O.B.E., D.Sc.F. I.C.F O R 1929.W. N. HAWORTH, D.Sc., Ph.D., F.R.S.E. L. HIRST, M.A., Ph.D.H. HUNTER, D.Sc.S. G. P. PLANT, D.Phil., M.A.J. PRYDE, M.Sc.L. J. SPENCER, M. A,, Sc.D. F.R.S.W. A. WOOSTER.ISSUED BY THE CHEMICAL SOCIETY,Cbitor :CLARENCE SMITH, D.Sc.~ m i s f x n t mitar :A. D. MITCHELL, D.Sc.Vol, XXVI.LONDON:T H E C H E M I C A L S O C I E T Y1930PRINTED IN QREAT BRITAIN BYRICHARD CLAY & SONS. LIMITED.BUNGAY, SUFFOLCONTENTS.PAGEGENERAL AND PHYSICAL CHEMISTRY. By H. HUNTER, D.Sc. . 11INORGANIC CHEMISTRY. By H.BASSETT, D.Sc., Ph.D., D. -6s-S~. ,F.I.C. . . . . . . . . . . . 34ORGANIC CHEMISTRY :-Part ~.-ALIPHATIC DIVISION. By W. N. HAWORTH, D.Sc., Ph.D.,By G. M. BENNETT, M.A., Ph.D.,F.I.C. . . . . . . . . . . . 115By S. G. P. PLANT, D.Phil., M.A. 152ANALYTICAL CHEMISTRY. By B. A. ELLIS, M.A., and J. J. Fox,F.R.S., and E. L. HIRST, M.A., Ph.D. . . . . . 74Part II.-HOMOCYCLIC DIVISION.Part III.-HETEROCPCLIC DIVISION.O.B.E., D.Sc. . . . . . . . . . . 185BIOCHEMISTRY. By A. C. CHIBNALL, M.A., Ph.D., and J. PRYDE,M.Sc. . . . . . . . . . . . 205MINERALOGICAL CHEMISTRY (1928-29). By L. J. SPENCER, M. A.,ScD., F.R.S. . . . . . . . . . . 253CRYSTALLOORAPHY. By J. D. BERNAL, M.A., and W. A. WOOSTEB. 27TABLE OF ABBREVIATIONS EMPLOYED IN THEREFERENCES.Abbreviated Title.A .. . . . .Abs. Theses Mass. Inst. Tech.Ab8. Theses Univ. Chicago.(Sci Ser.) . . .Anaer. J. Bot. . , .Amer. J. Phamn. . .A m r . J. Physiol. . .Amer. J. Sci. . . .Amr. Mi%. . . .Anal. Asoc. Quh ArytntinaAnal. Fis. Quim. . .Anal@ . . . .Annalen . . . .Ann. Bot. . . . .Ann. Chim. . . .Ann. Chim. Appl. . .Ann. Jard. bot. Buitenzorg .Ann. Physik . . .Ann. Physique . . .Ann. Reports . . .Ann. sci. Univ. Jassy .Arch. Phrm. . . .ArhivHemiju . . .Atti I I Cong. Naz. Chim.Atti R. Accad. L&ei , . pura aml. . .B . . . . . .FULL TITLE.Abstracts in Journal of the Chemical Society (until1925) or in British Chemical Abstracts,* Section A.Abstracts of scientific and technical publications, in-cluding abstracts of Doctors’ theses, of the Massa-chusetts Institute of Technology.Abstracts of Theses, University of Chicago (ScienceSeries).American Journal of Botany.American Journal of Pharmacy.American Journal of Physiology.American Journal of Science.American Mineralogist.Anales de la Asociacion Quimica Argentina.Anales de la Sociedad EspanGla Fisica y Quimica.The Analyst.Justus Liebig’s Annalen der Chemie.Annals of Botany.Annales de Chimie.Annali di Chimica Applicata.Annales du Jardin botanique de Buitenzorg.Annalen der Physik.Annales de Physique.Annual Reports of the Chemical Society.Annales scientifiques de 1’Universitd de Jassy.Archiv der Pharmazie.Arhiv za Hemiju i Farmaciju.Atti del I10 Congress Nazionale di Chimica pum edAtti (Eendiconti, Memorie) della Reale AccademiaNazionale dei Lincei, classe di scienze fisiche,matematiche e naturali, Roma.British Chemical Abstracts.* Section B.applicata.Ber.deut. pham. Ges. . Rerichte der deutschen pharmazeutischen Gesellschaft.Ber. . . Berichte der deutschen Chemischen Gesellschaft.Ber. S&hs. ‘A,. WAS. Berichte iiber die Verhandlungen der SlichsischenBer. ungar. pharm. Ges. . Berichte der ungarischen pharmazeutischen Gesell-Bhchem. J. . . . The Biochemical Journal.Biochcm. 2. . . . Biochemische Zeitschrift.Brit. J . RadioE. . . . The British Journal of Radiology:Bul. SOC. Chim. Romdnia . Buletinul Societiitai de Chimie din RomBnia.Bul. SOC. Btiinte CZuj. . Buletinul Societlitii Stiinte din Cluj.Bzcll. A c d .Polonaise . Bulletin Internationale de 1’ Acaddmie Polonaise deaBull. Chem. SOC. Japan . Bulletin of the Chemical Society of Japan.BulZ. Inst. Phys. Chem. Res. Bulletin of the Institute of Physical and ChemicalTOkyP . . . . Research, Tokyo.Bull. Nat. Res. Council . Bulletin of the National Research Counci1,Washington.Bull. SOC. chim. . . Bulletin de la SociBt6 chimique de France.Bull. Soc. chim. Belg. . Bulletin de la SociktB chimique de Belgique.Bull. Soc. Chim. bid. . Bulletin de la Soci6te de Chimie biologique.Bull. 8oc. franq. Min. . Bulletin de la Socibtd franpaise de MinBralogie.Bur. &and. J. Res. . . Bureau of Standards Journal of Research.Canadian Chm. Met. . . Canadian Chemistry and Metallurgy.&sopia 6eskosEov.La. . casopis Geskkho L6kkQrnictva..Akademie der Wissenschaften zu Leipzig.schaft.Sciences e t des Lettres.The year is not inserted in references to 1929riii TABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENUES.A bbreviatdd Title.Centr. Min. . . .Chem.andInd. . . .Chein. Erde . . .Chem. Listy . . .Chem. Met.Eng.. . .Chem. News . . .Chem. Reviews . . ,Chem. Weekblad . .Chem. Zentr. . . .Chem.-Ztg. . . .Chim. et hd. . . .Chinese J. Physiol. . ,C'ompt. rend. . . .Compt. rend. 80c. Biol. .Conn. Agric. Exp. Stn.BUZZ. . . . .Deuf. 2. ges. gericlttl. Mcd. .Econ. Geol. . . .F6rh. I I I nord. Kemistmo'tetFortschr. Min. grist. Petr.Gazzetta . . . .Eiandl. Ing. Vetenskapsnks-akad. Stockholm ..Eelv. Chim. Acta , .Helv. Phys. Acta . .Ind. Eng. Chem.. . .Indian J. Med. Res. . .Indian J. Physics . .J . . . . . .J. Agrie. Rcs. . . .J. Amer. Chem. Soc. . ,J. Arner. Leather Chem.Assoc. . . . .J . Amer. Pharm. Assoc. .J. B a t . . . . .J. Bio,?. Chein. . . .J. Chem. Ind. MoscowJ. Chem. Met. Min. SOC. 8:Africa . . . .J. Chim.physique . .J. Czech. Chern. Cmm. .J. Exp. filed. . . .J. Gen. Physiol. . . .J . GeoZ. . . . .J. Indian Chem. Soc. . .J. lndian Inst. Sci. . .J. Inst. Brewing . .J. Inst. Metals . . .J . Iron Steel Inst. . ,J. Pharm. Chim. . .J. Pharm. Exp. Thr. .J. Pharm. SOG. Japan. .FULL TI-rm.Centralblat,t fur Mincralogie, Geologic, und Palaon-Chemistry and Industry.Chemie der Erde.Chemickd Listy pro V6du a Prfimysl.Organ de la" Cesksi chemicks Spolednost pro VBdu aPrSniysl."Chemical and Metallurgical Engineering.Chemical Nows.Chemical Reviews.Chemisch Weekblad.Chemisches Zentralblatt.Chemiker- Zeitung.Chimie et Induatrie.Chinese Journal of Physiology.Comptes rendns hebdomadaires des SQances del'bcaddmie des Sciences.Comptes rendus hebdomadaires de Sdances de laSoci6td de Biology.Bulletin of the Connecticut Agricultural ExperimentStation.Deutsche Zeitschrift fur die gesammte gerichtlicheMedizin.Economic Geology.Fijrhandlingar 111 Nordiska Kemistmotet.Fortschritte cler Mineralogie, Kristallographie undPetrographie.Gazzetta chimica italiana.Ingeniijrsvetenskapsakadamiens Handlingar, Stock-holm.Helvetica Chimica Acta.Helvetica Physica Acta.Industrial and Engineering Chemistry.Indian Journal of Medical Research.Indian Journal of Physics.Journal of the Chcmical SocietJournal of Agricultural Rescarci.Journal of the American Chemical Society.Journal of the American Leather Chemists' Asso-Journal of the American Pharmaceutical Association.JourDal of Bacteriology, Baltimore.Journal of Biological Chemistry.Journal of Chemical Industry, Moscow.Journal of the Chemical, Metallurgical, and MiningSociety of South Africa.Journal de Chimie physique.Journal of Czechoslovak Chemical Communications.Journal of Experimental Medicine.Journal of General Physiology.Journal of Geology.Quarterly Journal of the Indian Chemical Society.Journal of the Indian Institute of Science.Journal of the Institute of Brewing.Journal of the Institnte of Metals.Journal of the Iron and Steel Institute.Journal de Pharmacie et de Chimie.Journal of Pharmacology and Experimental Thera-Journal of the Pharmaceutical Society of Japan,tologie.ciation.peutics.(Yakugakuzasshi)TABLE OB ABBREVIATIONS EMPLOYED IN THE REFERENOES.ixAbbreviated Title.J. Phys. Badiwm . .J. Physical Chem. .J . p r . C h . . . .J. Proc. Asiatic Bdc. BengalJ . Roy. Soc. W. Australia .J. Buss. Phys. Chem. SOC. .J . Soc. Chem. I?&. . . J. SOC. Chem. Ind. Japan .J. SOC. Leather Trades Chem.Jahrb. Min., Beil-Bd. . .Japan. J. Chem. . .Japan. J. Physics . .Klin. Woch. . . .Kolloidchern. Beih.. .KOlZoid- 2. . . .Lunds Univ. drsskr. . .Mem. Coll. Sci. Kyoto. .Mem. Mancheder Phil. SOC.Mikrochem. . . .Min. Hag. . . . .Monatsh. . . . .Manch. med. Woch. . .Nach. Qes. Wis. Gottingen.Natumoiss. . . .Natuurwetensch. Tijd-s. .New Phyt.Nomk Geol. Ti&k&fl'Nov. Act. Reg. Soc. Upsala.Oesterr. Chern.-Ztg. . ,Pharm. Weekblad. . .Pharm. Zentr. . . .Pharm.-Ztg. . . .Phil. Mag. . . .Phil. Tram. . . .PhysicatRev. . . .Physikal. 2. . . .Plant Physwl. . . .Proc. Imp. A&. Tokyo .Proc. K. Akad. Wetensch.Proe. Lee& Phil. Soc. .Pa pier- Fabr. * .AmsterdamProc. Nat. A d . Sei. , ,Proc. Nova Scotia Inst. Sci.Proc. Physicalfloe. . .Proc. Roy. Dublin SOC. .Proc. Roy. Imt. . .Proc. Roy. Irish Acud. .Proc.Roy. Soc. . . .FULL TITLE.Journal de Physique et le Radium.Journal of Physical Chemistry.Journal fiir praktische Chemie.Journal and Proceedings of the Asiatic Society ofJournal of the Royal Society of West Australia.Journal of the Physical and Chemical Society ofJournal of the Society of Chemical Industry.Journal of the Society of Chemical Industry, Japan.Journal of the Society of Leather Trades Chemists.Neues Jahrbuch fur Mineralogie, Geologie undJapanese Journal of Chemistry.Japanese Journal of Physics.Klinische Wochenschrift.Kolloidchemische Beihefte.Kolloid-Zeitschrift.Lunds Universitets Ars-skrift.Memoirs of the College of Science, Kyoto ImperialMemoirs and Proceedings of the Manchester LiteraryMikrochemie.Mineralogical Magazine and Journal of the Minera-Monatshefte fur Chemie und verwandte Theile andererMiinchene medizinische Wochenschrift.Nachrichten von der Gesellschaft der Wissenschaftenzu Gottingen.Die Naturwissenschaften.Natuurwetenschappelijk Tijdschrift.New Phytologist.Norsk Geologisk Tidsskrift, Oslo.Nova Acta Regiae Societatis Scientiaium Upsaliensis.Oesterreichische Chemiker-Zeitung.Papier-Fabrikant .Phmaceutisch Weekblad..Pharmazeutische Zentralhalle.Pharmazeutische Zeituner.Bengal.Russia.(K6gy6 Kwagaku Zasshi.)Paliiontologie, Beilage-Band.University.and Philosophical Society.logical Society.Wissenschaften.Philosophical Magazine @he London, Edinburgh andDublin).Philosophical Transactions of the Royal Society ofLondon.Physical Review.Physikalische Zeitschrift.Plant Physiology.Proceedings of the Imperial Academy of Japan.Koninklijke Akademie van Wetenschappen te Amster-dam.Proceedings (English version).Proceedings of the Leeds Philosophical and LiteraryProceedings of the National Academy of Sciences.Proceedings of the Nova Scotia Institute of 8cience.Proceedings of the Physical Society of London.Proceedings of the Royal Dublin Society.Proceedings of the Royal Institution of Great Britain.Proceedings of the Royal Irish Academy.Proceedings of the Royal Society.Society (Scientific Section)X TABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENUES.Ahbevialed Z’itlc.Przemyst Chem. . . .&wrt. J. Phamn. . .Rec. trav. bot . N6erlandaisesRcc.trav. chim. . . .Rend. Accad. Sci. Pis. Mat.Nupoli. * . . .Rev. Centr. Est. Farm. Bio-quim. . * . .Xiv. Ital. Ess. Prof. . .Rocz. Chem. . . .SchWeiZ. APth.-Zfg. .Schweix. Min. Petr. Mitt. .815. Papers Inst. Phys.Chem. Res. Tokyo . .Sci. Rep. T6hoku Imp. Univ.Sitzungsber. Preuss. Akad.Wiss. Berlin aSkrifter Norskc Vi&xsiAkad. Oslo . . .Bdiddeut. Apoth.-Ztg. . .Srensk Xcm. Tidskr. . .Tech. Rep. T6hoJc.u Imp.Unity. . . . .Tekn. Tidskr. . . .Tidsskr. Kjemi Berg. . .Trans. Amer. Electrochem.SOC. . . . .Trans. Faraday Soc. . .Trans. Greol. SOC. 8. Africa.Trans. Inst. Pure Chcm.Trans. Boy. 8oc. Canada .Tsch. Min. Petr. Nitt. .Reagents, Moscow. .Ukraine Chem. J. . .77.8. Bur. Stand. Bes. PaperWhs.Veroj’. Siemens-Konx.2.anal.Chem. . . .2. angew. Chem.. . .2. anorg. Chem.. . .2. Elektrochem. . . .z. Krist. . . . .2. Metallk. . . . .Z. Physik . . . .Z.physika1. Chem. . .Z.physwl. Chcm. . .2. wiss. Biol. . . .FULL TITLE.Przemysi Chemiczny.Quarterly Journal of Pharmacy and Pharmacology.Recueil des travaux botaniques NBerlandaises.Recueil des travaux ctiimiques des Pays-Bas et de laRendicoii to dell’ Accademia delle Scienze Fisiche eRevista del Centro Estudiantes de Parmacia y Bio-Rivista Italiana delle Essenze e Profumi.Roczniki Chemji organ Polskiego TowarzystwaSchweizerische Apotheker-Zeitung.Schweizerische mineralogische und petrographischeScientific Papers of the Institute of Physical andScience Reports, TGhoku Imperial University.Sitzungsberichte der Preussischen Akademie derSkrifter udg. af Videnskabsselskabet i Oslo (I. Matem.-naturvid. Klassef.Suddeutsche Apothekerzeitung.Svensk Kemisk Tidskrift.Technology Reports of the T6hoku ImperialUniversity,Sendai, Japan.Teknisk Tidskrift.Tidsskrift for Kemi og Eergvaesen.Transactions of the American ElectrochemicalTransactions of the Faraday Society.Transactions of the Geological Society of South Africa.Transactions of the Institute for Pure ChemicalTransactions of the Royal Society of Canada.Tschermaks mineralogische und petrogaphischeUkrainian Chemical Joiirnal.Research Papers of the US. Bureau of Standards.Wissenschaftliche Veroffentlichungen aus demZeitschrift fur analytische Chemie.Zeitschrift fur angewandte Chemie.Zeitschrift fur anorganische und allgemeine Chemie.Zeitschrift fir Elektrochemie.Zeitschrift fiir Krystallographie.Zeitschrift fur Metal1 kunde.Zeitschrift fur Physik.Zeitschrift fur physikalische Chernie, StochiometrieHOppe-SeVler’S Zeitschrift fur physiologische Chemie.Zeitschrift fur wissenschaftliche Biologie.Belgique.Matematiche, Napoli.quimica, Buenos Aires.Chemicznego.Mitteilungen.Chemical Research, Tokyo.Wissenschaften zu Berlin.Society .Reagents , Moscow.Mitteilungen.Siemens- Konzern.und Verwandtschaftslehre

ISSN:0365-6217    

DOI:10.1039/AR9292600001

出版商:RSC    

年代:1929

数据来源: RSC

摘要:

X TABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENUES.ERRATUM.VOL. 25, 1928.Page Line31 19 delete ‘( S. Gla~stone,~~.

ISSN:0365-6217    

DOI:10.1039/AR9292600010

出版商:RSC    

年代:1929

数据来源: RSC

摘要:

ANNUAL REPORTSON THEPROGRESS OF CHEMISTRY.GENERAL AND PHYSICAL CHEMISTRY.THE output of research in this branch of science has been wellmaintained during the year under review and steady progress hasbeen made. Perhaps the most notable advances of the last yearor so have been in the domain of sub-atomic phenomena and mole-cular structure: we are now observing the confluence of manylines of work, and it is perhaps not too much to say that the elucid-ation of the chemical significance of molecular structure is progressingwith greater rapidity than ever before. The first two sections ofthis Report are devoted to this subject and a few other topics ofinterest are touched on later.The Atom and its Constituent Parts.One of the outstanding features of recent research has been theintroduction, by L.de Broglie,l E. Schrodinger,2 and others, of atheory of wave mechanics according to which a moving particle (inparticular, an electron) behaves as a group of waves whose velocityand wave-length are governed by the speed and the mass of theparticle. For a particle moving in free space, the theory leads tothe equations h = lid1 - v2/c2/m,,v and V = c2/v, where A denotesthe wave-length; v, c, and V represent the velocities of the particle,of light, and of the wave front, respectively; h is Planck’s constantof action; and mo is the mass of the particle at slow speeds. Itfollows that V is greater than the velocity of light, but since thewaves are not considered to carry energy, no contradiction of thedeductions of the theory of relativity is involved.In the neigh-bourhood of matter, the velocity of the wave front is modified and1 Ann. Physique, 1926, 3, 22; J . Phys. Radium, 1927, [vi], 8, 226; A.,a Ann. Phyaik, 1926,70,361,489,734; 80,437; 81,109; Natumu&ee., 1926,1927,807.14,664 ; P h y W Rev., 1926, aS, 104912 ANNUAL REPORTS ON THE PROGRESS OF (3HEMISTRY.the resultant refraction of the wave corresponds to the modificationof the path of the particle when entering the field of force associatedwith the matter.A. S. Eddington3 has raised a question which has aroused veryconsiderable interest. The ratio of hc to e2 is dimensionless, where eis the charge on an electron. The methods of what may now betermed classical quantum physics (as, for example, in Bohr’s theoryof atomic structure and spectra) break up this number into con-stituent factors so that its dimensionless character seems unim-portant ; but in the wave equation for two electrons (or an electronand a proton) the combination hc/2xe2 occurs as the coefficient ofcertain terms. By conceiving a wider principle of relativity, thisauthor determines the numerical value of this ratio as136, the numberof degrees of freedom appropriate to a two-electron system in 16-space.Although there is some uncertainty about this number, yetit is one of hesitation between, say, 10 and 136 and 256, and notbetween 136 and 137; but the accepted values for h, c, and e give137.1 as the magnitude of the ratio. (It is said, however, that a newdetermination of e by Siegbahn has given the value 4-792 x 10-10c.g.s.e.s.u.as against R. A. Millikan’s value of 4.774 x 10-10.) Thatthere is a real uncertainty as to the magnitude of e within thelimits indicated by Eddington’s theory, is pointed out by E.Backlin: who, after examining the values obtained by Millikan,Wadlund, and himself, concludes that it is not possible to decide(on these experimental grounds) between 136 and 137 for the abovefundamental ratio. W. N. Bond,6 on the other hand, doubts thevalidity of Eddington’s result and considers that the evidenceconfirms the classical equation for Rydberg’s constant, vix.,R = 1,0968 x lo5 = (e5/h3)[2x2/c(l + nz/M)(e/m)]. J. H. J. Pooleconsiders that a larger value of 7~ might hold in the intense electricfields within the atom and might be used for the calculation ofhc/2xe2. Other speculations on possible integral relations betweensub-atomic constants have been put forward by V.Rojansky 7 andby E. E. Witmer.8 The former suggests that the ratio of the massof the proton to that of the electron may be 1362/10 = 1849.6, thedenominator and the square root of the numerator being possiblenumbers of degrees of freedom in the theory put forward by Edding-ton. The latter author’s suggestion is that this mass ratio should besimply related to an integer and points out that 1849 = 432 =Nature, 1929, 123, 409; A., 369; see also R. T. Birge, ibid., p. 318;Ibid., 1929,124, 408; A., 1126. Ibid., 1929,123,630; A,, 484.Ibid., p.911 ; A., 861. Ibid., 1929, l24, 180; A,, 973.3 Proc. Roy. Xoc., 1929, [ A ] , 122, 368 ; A., 231.A . , 368GENERAL AND PHYSICAL CHEMISTRY. 1312 + 2 2 + 22 + 32 + 32 + 42 which is half of (2 + 8 + 8 + 18 +18 + 32) which is the atomic number of the heaviest member of thezero group of elements. R. Fiirth 9 points out that this mass ratiois of the same order of magnitude as hc/e2 and shows that the ratiocan be deduced from the quantum and relativity theories. In alater paper l o he deduces the actual masses of the electron and theproton from the fundamental magnitudes of these theories.There is now a considerable amount of direct experimentalevidence in favour of the de Broglie wave theory of the electron.G. P. Thomson,ll by using a stream of nearly homogeneous cathoderays from an induction coil in what is practically his father’sclassical apparatus, has shown that metals such as aluminium, gold,and platinum produce diffraction patterns just as with X-rays, andthat their crystal constants, obtained by applying de Broglie’stheory, agree to 1% with those determined by X-ray analysis.Similar results have been obtained for celluloid,12 copper, silver, andtin,ls and for gold, silver, lead, iron, and nickel,14 although thelast-named gave an unexpected result.Evidence has been obtainedthat the electrons must be accompanied by a train of not less than50 waves in length, and it has been shown l5 that the above experi-mental results may be exactly predicted from an application of theordinary laws of electrodynamics to the motion of an electronconsisting of the usually accepted point charge surrounded by asystem made up of parts which can be set in motion by electricforces and, when in motion, produce the effects of electric currents.This system surrounding the nuclear charge will have a definitevibration period, the frequency of which is proportional to thesquare root of the number of electrified systems per unit of volume,and these vibrations form an oscillating electric field in which thereis no transmission of energy.Both the nuclear charge and thesurrounding system can vibrate and, in the steady state of theelectron, the vibrations are in resonance. The total energy of theelectron is that due to the charge on the nucleus together with thatdue to the oscillating field, a conception which is of importance inconnexion with the calculation of the size of the electron.E.Rupp,16 working along similar experimental lines, has examined thedeflexion phenomena which occur when electrons pass through thinNa.tu?-w&38., 1929,17, 688; A., 1123.lo Ibid., p. 728 ; A., 1209.l1 PTOC. Roy. SOC., 1928, [ A ] , 117, 600; 119, 661 ; A . , 1928, 3, 938.l2 A. Reid, ibid., 1928, [ A ] , 119, 663; A., 1928, 938.13 R. Ironside, ibid., p. 668; A., 1928, 938.l4 Ibid., 1929, [ A ] , 125,352; A., 1209.l5 (Sir) J. J. Thomeon, Phil. Mug., 1928, [vii], 6, 1254; A,, 231.l6 Ann. Phgd;, 1929, [v], 1, 773, 801; A,, 61914 ANNUAL REPORTS ON TBE PROGRESS OF CHEMISTRY.metallic sheets.He finds that with fairly slow-moving electrons,deviations occur from the de Broglie free-space relation, h = h/mv,and accounts for these by introducing a refractive index which isgreater than unity. This is ascribed to the existence of a positiveinner lattice potential, E,, corresponding to the relation p = (1 +E,/V)1’2, where V is the electron velocity in volts. Eo varies from 11to 17 volts, and is positive for all metals, so that p is greater thanunity, decreases towards unity with increasing electron velocity, andfor a given velocity is constant for a given lattice. Rupp’s calcul-ations of the effects of refractive index have been the subject ofcriticism by G. P. Thomson,17 but since the effects are small, thediscrepancies thus brought out are of little moment.L. H. Germer 18has obtained, under suitable experimental conditions, diffractionpatterns of four distinct types from the electron diffraction from asingle crystal of metal. One of these is due to the space lattice ofthe bulk, one to the space lattice of the surface metallic layer, athird to that of a monatomic film of adsorbed gas, and the fourth tothat of a thicker gas film.The problem of the diffraction of an electron wave by a line grating,consisting of a periodic distribution of electric or magnetic material,has been worked out by C. G. Darwin,lg who concludes that nopolarisation can occur with pure electric forces or with some magneticforces. In the case where electric and magnetic fields occur simul-taneously, some polarisation may occur, but the case has not beenworked out in detail.E. Rupp 20 could detect no such effect withcertainty, although there was a slight indication that it mighthave occurred when a beam of electrons of velocity 150 volts wastwice reflected from the (111) face of a copper crystal. C. J. Davis-son and L. H. Germer 2 1 detected no polarisation when an electronbeam was twice reflected from nickel crystal faces at bombardingvelocities from 10 to 200 volts.During the past year, the Royal Society held a discussion22 onthe structure of atomic nuclei in which the progress made in the lastfifteen yems was reviewed. The problem has been attacked inthree ways : (a) by the proof of the existence of isotopes and theaccurate determination of their relative masses, (b) by the artificialdisintegration of atoms by bombardment with a-particles, and (c)by a study of the wave-lengths of the penetrating y-rays which1 7 Phil.Mag., 1929, [vii], 6, 939.1 8 2. Physik, 1929, 54, 408; A., 620.2o 2. Physik, 1929, 53, 648; A., 483.21 Phy8iCal Rev., 1929, [ii], 38, 760; A., 736.82 Proc. Bog. Soc,, 1929, [AJ1 Ws 373; A., 622.PTOC. Roy. SOC., 1928, [ A ] , 120, 631; A., 1928, 1300GENERAL AND PHYSICAL CHEMISTRY. 15originate in the disintegration of the nucleus. The discovery of newisotopes has been much facilitated by recent work on band spectrawhich seem to be superior to the mass spectrograph for detectingthose occurring in very small quantity, but, as band spectra giveonly relative masses of two isotopes, the two methods are supple-mentary.The scattering of a-particles by atoms is that which would beexpected from an inverse-square law of force between the particleand the nucleus for all atoms heavier than copper; with lighteratoms, however, the scattering is abnormal and is explained byassuming that the approaching particle polarises the nucleus andthus gives rise to an attractive force varying as the inverse fifthpower of the distance.The scattering of a-particles by hydrogenand helium is quite abnormal and indicates that the nuclei of theseatoms must be very flat in shape. Scattering experiments show thata-particles cannot penetrate the nucleus of uranium, but the speedof emission of an a-particle from this nucleus shows that penetrationshould be possible.This difficulty is got over by the new wavemechanics, which allows the a-particle, or rather, the wave train withwhich it is identified, to leak through the high-potential barriersurrounding the nucleus, and to emerge with the kinetic energy itpossessed when inside the barrier. On this view, the radius of theuranium nucleus is about 7 x 10-13 cm., and into this small nuclearvolume must be packed 238 protons and 146 electrons. A picture ispresented of the building up of atomic nuclei from protons andelectrons, with an energy loss of 7 million electron volts per proton,so that to divide a mercury nucleus into its constituent protons andelectrons would require an amount of work equal to 1400 millionelectron volts. But this view cannot be reconciled with the facts ofradioactivity, so that it must be supposed that, for the heavier ele-ments, a t least, the main structural unit is the a-particle, whichmust have a greater energy in the nucleus than in the free state.Applying this view to the facts represented by F. W.Aston’s packingfraction curve,24 one gets the following picture-an instantaneousview only-of the nuclei of the various atoms. For the lighteratoms, a highly concentrated and stable nucleus is formed by thebinding of protons, electrons, and a-particles, partly by distortional,and partly by magnetic forces. The formation of this nucleus isaccompanied by the loss of mass (energy) and so the process continuesup to a nucleus with mass 120, which represents the closest packingand maximum loss of mass.Beyond this point, the additionalparticles are less and less h l y held and the structure becomes lessdense towards the outside, until uranium is reached, where the2s See p. 20, 14 Ann. Reports, 1927,24, 1216 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.packing is so loose that the nucleus has as much energy as it can hold.Finally, the whole nucleus is surrounded by a high-potential barrier,which is normally impassable to a-particles (the kinetic energies ofwhich are known) but is occasionally traversed when a particleassumes its alternative wave train identity.A. C. Burton25 regards packing fractions in rather a differentmanner from that preferred by F. W. Aston.He finds the loss'inmass due to packing by subtracting the actual mass found from(1.00778 x mass number) and interprets his results by the help ofthe rule that, if it is found that in any two cases the addition of thesame quantity to the nucleus in passing from one atom to the nextproduces the same extra loss in mass, it can be concluded that theaddition has probably been made in the same way. It is found thatthe packing is particularly close for atoms of mass = 4n. A theoryof packing is developed which interprets the existence of Sir ERutherford's neutrons,26 and the packing loss due to the looseaddition of a neutron is calculated to lie between 0.007 and 0.008.Molecular Xtructure and Molecular Spectra.Three types of spectra are now available which may affordevidence of molecular structure : band spectra in the visible andultra-violet regions, infra-red spectra, and Raman ~pectra.~' Ofthese, the first two are not new, but the study of the last is of com-paratively recent development.The Raman E#ect.-This was first noticed as a disturbing effectduring the examination of several carefully purified substances forlight scattering.The phenomenon took the form of the inclusionin the scattered light of light of altered wave-length. When theincident light was monochromatic, examination of the scatteredlight revealed its spectral nature, consisting of lines in some cases,more or less diffuse bands in others, and, in addition, a more or lessdiffuse continuous spectrum accompanying the lines or bands.The Raman effect is closely allied to the Compton effect, and asimilar explanation has been advanced; the following scheme maybe used to illustrate it :Molecule + Radiation -F+= Molecule -k Radiation(normel) (excited) (altered frequency)Thus, if a quantum, W = hN, falls on a molecule and alters itsenergy level from El to E,, then the energy of the diffused quantum26 Trans.Roy. SOC. Canada, 1928, [iii], 22,111, 379; A , , 372.26 Ann. Reports, 1927,24, 13.27 Trans. Paraday SOC., 1929,25, 781 ; C. V. Raman, Indian J . Physics, 1928,2, 387; C. V. Raman and K. S. Krishnm, ibid., p. 399 Proc. Roy. Soo., 1929,pq, 122.23GENERAL AND PHYSICAL CHEMISTRY. 17is W’ = hN’ = hN - (E, - E l ) , and the corresponding frequencyN’ = N - ( E , - El)/h = N & n, in which the sign of n depends onwhether the energy level of the molecule is raised or lowered.NowE, and El, and consequently n, are quantities characteristic of themolecule, so that n = N - N’ is of great interest in studying problemsof molecular structure.In general, of course, when light acts on matter and is re-emitted,the frequency of the radiation is degraded on account of absorptionof energy by the matter. This is the meaning of Stokes’s law,which is only a particular case of the degradation of luminousfrequencies by matter. The Raman effect falls into line with thisgeneralisation, since the secondary negative lines (frequency N - n)are more intense than the secondary positive lines (frequency N + n).It is thus possible to classify the interactions between materialparticles and radiant quanta as follows :(1) The photoelectric eflect, where the incident quantum is whollyabsorbed : part of it goes to tear an electron out of an atom, andthe rest appears as kinetic energy of the electron.(2) Fluorescence, where part of the energy increases the energylevel of the molecule, and the rest increases its thermal energy.The first part is re-emitted as a quantum of lower frequency whenthe molecule returns to its normal state.(3) The C m p t m eflect, where the quantum encounters a freeelectron at rest, shoots it out with a certain velocity, and is itselfre-radiated a t a correspondingly lower frequency.(4) The Raman eflect, where the quantum encounters a morecomplicated system (ions, atoms, or molecules) and alters its energylevel, being itself re-radiated a t a correspondingly different frequency.The essential difference between fluorescence and the Ramaneffect is thus that for incident light of frequency N , a molecule witha free period n will emit light of frequency n if it fluoresces and ofN &- n in the Raman effect : a Raman spectrum is essentially anabsorption spectrum.Sir C. V. Ramanm has summarised thecharacteristic features of the phenomenon as : (a) its universality-it is observed in gases, vapours, liquids, crystals, and glasses; ( b )its spectral character ; (c) the theoretical explanation, as involvingan exchange of energy between the quantum and the molecule, theidentification of the frequency difference with a characteristicfrequency of the molecule and the consequent utility of the pheno-menon as an aid to the exploration of molecular spectra, especiallyin the infra-red ; (d) the possibility of an increase as well as a decreaseof frequency, but the greater probability of the latter; (e) thestrong polarisation of the re-emitted radiations ; (f) the distinctnessz 8 J.Cabmnes, Tram. Fwaday Soc., 1929,25, 80018 ANNUAL REPORTS ON THE PROURESS OF CHEMISTRY.of the new phenomenon from fluorescence, but its obvious relationto it ; (9) its relation to the Compton effect ; and (h) the incoherentnature of the radiation.In the earlier work on the Raman effect, light from a lamp wasfocused on to the centre of a bulb containing the liquid underexamination and the scattered light was viewed from the side.R.W. W00dF9 however, has indicated methods of excitation whichare much less wasteful of light. The method advocated is to placethe liquid in a long tube illuminated from the side by a mercuryarc with a cylindrical reflector, or by means of a helium tube woundin a close spiral round the tube. Water-cooling may be necessary,and a careful choice of the exciting lamp is essential, since the Ramanradiations are very faint and may be obscured by light scattered inthe classical manner iP the exciting source emits anything in thenature of a continuous spectrum. Suitable filters may, if necessary,be employed.It is, of course, impossible in this Report to mention more than avery few of the results which have already been obtained in thisdirection, but the following selection notes some of the more interest-ing. All Raman frequencies (positive or negative) characterised bythe same change of frequency, & n, are in the same state of polaris-ation whatever the frequency, N , of the exciting radiation, but thestate of polarisation varies within wide limits.30 The Raman effectcan be observed with powders as well as with clear crystals,31 andwith naphthalene, for example, the effect is the same whether thesubstance is solid, molten, or dissolved, although there is a differencebetween the spectrum of the solid and that of the solution in thecase of compounds such as sodium nitrate.32 The Raman spectrumof liquid hydrogen33 indicates that this substance is a mixture oftwo effectively distinct sets of molecules in the proportion 2 or 3to 1, in agreement with the result already obtained from measure-ments of the specific heat of hydrogen gas.34 One of the mostuseful of the features of the Raman effect is that the frequencies ofthe scattered radiation indicate the existence of vibrations inmolecules which are optically inactive or obscure in absorption.Gaps in infra-red spectra had already been inferred : in calcite, forinstance, one such missing fundamental has been postulated with awave-length of 9 p, and it is precisely this one which shows up verystrongly in Raman photograph^.^^ In many cases, it is possible to29 Trans.Paraday SOC., 1929, 25, 792.31 A. C.Menzies, ibid., p. 836.33 J. C. McLennan, ibid., p. 797.34 D. M. Dennison, Proc. Roy. SOC., 1927, [ A ] , 115,483.Q5 C. Schaefer, Tran8. Paraday Soc., 1929, 26, 841.30 J. Cabannes, ibid., p. 813.32 Ibid., p. 838GENERAL AND PHPSICBL CHEMISTRY. 19identify particular frequencies with the vibration of certain chemicalbonds in the molecule. For example, the frequency correspondingto the C-H bond is different in aliphatic and in aromatic compounds,and the degree of polarisation strikingly so; 27 benzene shows bothtypes of bond ; 36 other links have their characteristic frequencies:?and analogy between spectra is more noticeable in homology t6anin i~ornerisrn.~~ Rise of temperature has the effect of diffusingcertain Raman lines and it is supposed that this is due to the increaseof molecular rotation.39 The effect is most noticeable in closedoublets.Since the frequencies concerned in the Raman effect arethe vibration frequencies connected with the return of the moleculefrom an excited state to its normal electronic level, they should,as has already been pointed out, occur as end states in fluorescence.This has been confirmed for benzene.40Band Spectra.-The new theory of wave mechanics has cleared upmany of the complexities of molecular spectra and has led to resultsof very great importance both to the chemist and to the physicist.Unfortunately, the nomenclature is so complex, and the resultsare so detailed, that it is not possible to give an account of thiswork here.A few only of the results can be mentioned and, for therest, the reader is referred to the Report of the Symposium ofMolecular Structure and Molecular Spectra held by the FaradaySociety a t Bristol on September 24th and 25th, 1929,41 whichcontains 40 papers and reports and 3 discussions. A further account,as far as work in the infra-red is concerned, is to be found in “ Infra-Red Analysis of Molecular Structure” by F. I. G. Rawlins andA. M. Taylor 42 which has recently appeared.The inhomogeneity of hydrogen, to which reference has alreadybeen made,& has been deduced from considerations of the alternatingintensities of lines in band spectra as accounted for by nuclearspin.u Calculations show that, owing to minute perturbationsbetween the nuclei, interchange between the two forms of hydrogenis complete in about a month, so that hydrogen, though a mixture,does not consist of two sets of independent components.At absolutezero, there is no rotation, so that all molecules must then be identical.36 A. Dadieu and K. W. F. Rohlrausch, Phy&kal. Z., 1929,30,384; A., 976.37 A. Petrikaln, 2. physikab. Chem., 1929, [B], 3,360; A ., 866.38 A. Dadieu and K. W. F. Kohlrausch, NatumucSs., 1929,17, 366; A , , 866.39 Y. Fujioka, Nature, 1929,124, 11 ; A., 976; Sci. Papers Inst. Phys. Chem.40 C. V. Shapiro, Nature, 1929, 124, 372; A., 1127.41 Trans. Faraday Soc., 1929, 25, 611-949.42 Cambridge University Press.p3 Seep. 18.44 R. S . Mdliken, Trans. Faraduy Soc,, 1929, 25, 634.Rea.Tokyo, 1929,11,205; A., 136120 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.If, therefore, hydrogen is kept at a very low temperature for asufficient length of time, it should become more homogeneous andthus have a different specific heat from that of ordinary hydrogen.This experiment has been made with success.45Thermal-conductivity measurements at low pressures show thatthe transformation of ordinary (mixed) hydrogen into the para-formis incomplete even after a year, but at high pressures (350 atm.) a tthe temperature of liquid air, practically the theoretical quantity ofpara-hydrogen can be obtained in a week. Para-hydrogen is fairlystable for a week a t the ordinary temperature in glass vessels,whilst a t 100 atm. it slowly reverts to ordinary hydrogen in metalvessels, but in the presence of platinised asbestos the change occursat once.Adsorption on charcoal a t the temperature of liquid airgives practically pure para-hydrogen. The pure para-form has avapour pressure of 787 1 mm. a t 20.39" K., the temperature a twhich the ordinary form boils. Its melting point is 13+33"K., asagainst 13-96' K. for the ordinary form.The spectrum of nitrogen presents diffic~lties.~~Since the various band spectra constants depend on the mass ofthe vibrating nucleus, it follows that band spectra, should be of usein detecting the presence of isotopes. Recent work on this subjecthas been summarised by R. T. BirgeF7 and it may be stated that theexistence of mass 1748 and mass 1849 isotopes of oxygen and amass 13 isotope of carbon 50 is now definitely established.It maybe, therefore, that all elements have isotopes, although the agree-ment of F. W. Aston's mass determinations with atomic weights asdetermined by chemical means proves that any isotopes as yet un-detected must occur in very small quantity indeed.A problem of the greatest importance to the chemist is that ofmolecular formation and dissociation. The first part of the problemhas been considered by F. London,51 alone and in collaborationwith W. Heitle~-.~~ The application of the theory of spectra givesresults which also follow qualitatively from the well-known theory ofvalency of G. N. Lewis, but the new point of view has wider possi-bilities on account of its quantitative nature.The second part of46 K. F. Bonhoeffer and P. Harteck, Naturwias., 1929,17,182,321; A., 479;4 6 F. Rssetti, Nature, 1929, 123, 757; Phy8iCal Rev., 1929, 34, 367; Proc.4 7 Trans. Paraday SOC., 1929, 25, 719.2. phy8ikaE. Chem., 1929, [B], 4, 113; A., 982.Nat. Acad. Sci., 1929, 15, 515.W. F. Giauque and H. L. Johnston, Nature, 1929, 123, 318; J . Amer.Chem. SOC., 1929,51, 1436.4@ Idem, Nature, 1929,123, 831.50 A. S. King and R. T. Birge, ibid., 1929,134,127 ; R. T. Birge, ibid., p, 182.51 2. Physik, 1928,50,24. ba IW., 1927, 44, 466GENERAL AND PHYSICAL OHEMISTRY. 21the problem was first attacked from the standpoint of the theov ofspectra three years ago 53 and an improved method has now beensuggested.u It has been observed that sets of vibrational levelsin a molecule often converge to a limit, i.e., the separation of succes-sive levels becomes smaller and smaller towards zero, and it is con-sidered that this limiting point represents dissociation of the mole-cule.When the series can be followed up to, or nearly to, the pointof convergence, the heat of dissociation can then be deduced whenthe energy content of the dissociated atoms is known. When,however, an incomplete set of levels only can be obtained, themethod of extrapolation referred to above may be employed. Itleads to values of the heats of dissociation of nitrogen and oxygenwhich agree well with the accepted value for the heat of dissociationof nitric oxide, and in other hands 66 the method has given valuesfor the heats of dissociation of C-H and N-H groups in good agree-ment with thermal data.Teslu-luminescence Spectra.-Further results of investigations onthis subject have appeared since it was last mentioned in theseReports.6s Many substances of varied chemical type have beene~amined,~' and up to the present it has been found that the onlygroups capable of forming centres of emission under the Tesladischarge are the benzene ring and the carbonyl radical.Thebenzene ring gives a banded spectrum in the ultra-violet, which ismodified by substituent groups, sometimes in a very marked manner,so that occasionally the ultra-violet spectrum is completely sup-pressed and replaced by a glow or a banded spectrum in the visibleregion : sometimes, again, both visible and ultra-violet spectra meobserved.68 The aliphatic aldehydes and ketones emit a con-tinuous spectrum, without bands, in the blue region, and thosearomatic aldehydes which give the Tesla effect emit a bandedspectrum in the same region but do not show the characteristicbenzene spectrum.69 More careful examination 60 of some com-pounds which had previously been reported as not giving Teslaspectra has shown that they do, in fact, show faint emission." Inall the banded spectra obtained, it has been found that a simplewave-number relationship holds between the bands, the series of68 R. T. Birge and (Miss) H. Sponer, PhysieaZ Rev., 1926, 28, 269; A.,1926,993.54 R. T. Birge, Tram. Paraday SOC., 1929,2S, 707.5 5 J.W. Ellis, ibid., p. 888.6 7 W. H. McVicker, J. K:Marsh, and A. W. Stewart, J., 1924, l95, 1743;66 Ann. Repor@ 1923,f?o, 9.1926,127, 999.J. C. Macmaster, A. Russell, and A. W. Stewart, J., 1929, 2401.59 A. Russell and A. W. Stewart, ibid., p. 2407.8o Idem, &id., p. 243222 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.bands, for any one compound, being divisible into groups, themembers of which exhibit a constant difference from their congenersin other groups.’’ Benzene and its simple substitution products havebeen found to emit identical spectra when their vapours are excitedeither by the Tesla discharge or by the short waves from a mercurylamp.61The Nesornorphic States (Mesophases or Liquid Crystals).It is now generally recognised that “ liquid crystals ” are phasesintermediate between the crystalline (solid) and amorphous (liquid)states. G.Friedel 62 considers that there may be two or possiblymore such mesophases between the true crystal and the true liquidso that the order of succession of phases is always : Crystalline,smectic (soap-like), nematic (thread-like), liquid, with increasingtemperature or increasing dilution. It is very well known thatmesophases are exhibited only by molecules which are long andunbranched, and it appears that, in most cases, one of the meso-morphic states is not exhibited. When, however, they both appear,they invariably do so in the above order. This limitation of thephenomenon to substances which possess long molecules is supportedby the observation of W.H. Martin,s3 who finds that the depolaris-ation factor of the light scattered by dust-free p-azoxyanisole is0.85 : the calculated value for a liquid composed of molecules whichcan vibrate only in one direction is 0.86. The transition from onephase or mesophase to the other is always perfectly definite andappears in every case to conform strictly to the phase rule. That isto say, in a one-component condensed system the transition isgoverned by temperature only, in a two-component system, by thetemperature and the composition, and so on. Excellent examplesof these transitions may be found in the work on soap of J. W.McBain and his colleagues,64 who call the crystalline phase the“ curd,” the smectic phase the “ neat soap,” and the nematic phasethe ‘‘ middle soap.”The smectic phase may exhibit a plane homogeneous or a conicstructure : it is birefringent and always positively uniaxial.Themolecular elements making up the structure are arranged with theirlong axes parallel, but are turned around this direction in a randommanner. X-Ray analysis has shown that the smectic structure61 J. K. Marsh, J . , 1923, 123, 820, 3316; (Miss) M. W. Monypeny and A.62 Ann. Phyeique, 1922, [ix], 18, 273; A , , 1923, ii, 223.63 Trane. Roy. SOC. Canada, 1926, [iii], 19,111, 36; A., 1926,16.64 J. W. McBain and A. J. Burnett, J., 1922,121, 1320; J. W. McBain andG. M. Lrtngdon, J., 1926, 127, 862; J. W. McBain and W. J. Elford, J., 1926,421.Russell, J . , 1929, 2436GENERAL AND PECYSICAL CHEMISTRY.23consists of parallel planes at equidistant intervals, and the directionperpendicular to these planes is the only one in which the periodicityof the crystal is imitated-in the case of sodium ~ l e a t e , ~ ~ for example,the distance between the smectic planes has been found by X-rayanalysis to be 43*5A., confirming previous measurements on soapbubbles. A magnetic field has no effect on molecular orientation inthe smectic state (but see below).The nematic state is divided into two types, the true nematicand the choksteric. The former is birefringent and positivelyuniaxial. It shows no sign of parallel plane structure, but exhibits athread-like structure corresponding to the conic structure of thesmectic state.The optic axis alines itself parallel to a magneticfield and perpendicular to an electric field. The cholesteric state,however, differs from the others in being always negatively uniaxial.It is invariably associated with rotatory power and may be assumedeither by an optically active compound or by a mixture of anoptically active substance with a compound in the true nematicstate. Thus, whilst there is a sharp discontinuity between thesmectic and either of the nematic states, the true nematic state maymerge continuously into the cholesteric. A substance in the chol-esteric state may resemble a smectic phase in appearance, showingboth plane and conic forms. Substances in the plane form of thecholesteric state may show enormous rotatory powers up to 180,000"per mm.and this has no relation to the rotatory power of the sub-stance in the molten or dissolved state.We may thus picture the gradual transition of matter by the actionof thermal or solvent forces from the crystal form, with its orderedarrangement of planes in three or more directions, by a sudden jumpto the smectic state with somewhat less order, having its planesordered in one direction only. A second jump leads to the nematicstate, where the only trace of order remaining is the parallel orient-ation of the molecules. A final jump leads to the amorphous orliquid state of molecular chaos.H. Zocher and V. Birstein 66 have recently published accounts ofexperiments on mesophases which in the main confirm G. Friedel'sviews and observations.In the nematic and the smectic state,differences in surface tensibn are responsible for the orientation ofthe elements to the bounding surface. In some cases slight changesin the condition of the surface profoundly modify the orientation ofthe phase : e.g., an acid-treated glass surface induces p-azoxyanisoleto set itself perpendicular to the surface, whereas an alkali-treated6s M. de Broglie and E. Friedel, Cornpi?. rend., 1923, 176, 738.66 2. phy&kal. Chern., 1929,141,413; 142,113,126,177,186; A , , 870,876,1013; 888 also H. Zocher, Phy8ikd. Z., 1927, aS, 790; A,, 1928,22624 ANNUAL REPORTS ON THE PROGRESS OF CHmISTRY.surface induces parallel orientation. The aqueous mesophase ofsalvarsan is nematic, and addition of sucrose or dextrose gives riseto the twisted structure and rotatory power characteristic of theconversion of the nematic to the cholesteric state, although thetwisted structure may often be observed when such optically activesubstances have not been added : when this is the case, however,the direction of the twist is right or left indifferently.Of the oleates, palmitates, and stearates of sodium and potassium,only the first show aqueous mesophases, and ammonium oleatesolutions prepared from concentrated ammonia and oleic acid giveno evidence of an aqueous mesophase.Both sodium naphthenateand cetyl xanthate form a smectic mesophase in aqueous solution,and the birefractive dispersion of the latter is anomalous. G.Friedel has previously stated that lO-bromophenanthrene-6-sulphonic acid formed anhydrous crystals which passed into thesmectic state on the addition of water, to the nematic state onfurther dilution, and finally to an ordinary solution on still furtherdilution, all a t laboratory temperature.These results are nowconfirmed and the additional observation is made that the nematicphase which is formed a t moderate concentrations shows, in con-trast to the nematic mesophasea already known, a negative streamdouble refraction and forms drops with optically positive radii.It is noteworthy that commercial lecithin forms a mesopha,se, whilssynthetic lecithin does not.For compounds, such as p-azoxyanisole, which have a symmetricalmolecular structure, the dielectric and the magnetic anisotropy of thenematic phase are negative, but when the structure is asymmetric,both the dielectric and the magnetic anisotropy are positive.Bythe use of strong electric fields of the order of 10,000 volts per cm.,it is shown that, contrary to Friedel's ~tatement,~' cholesteric phasessuch as that of optically active amyl ethoxybenzylideneamio-a-methylcinnamate are oriented and become doubly refracting.The optical activity is considerably diminished by the field, butremoval of the field destroys the birefringence and restores thenormal optical activity. Smectic mesophases are also influencedby electric fields of sufficient strength. In all the cases studied, themagnetic anisotropy is positive and the dielectric anisotropy negative,even when that of the corresponding nematic phase is positive.A new type of sol having many of the properties of a mesophasehas been described by H.Zocher and K. Jacobsohn.ss Theseauthors have given the name " tactosol " to sols containing non-spherical particles which have the property of spontaneously6 7 G. Friedel, Ann. Phpique, 1922, [ix], 18,273; A,, 1923, ii, 223.6 8 KoWoidchem. Beih., 1929,28,167; A., 606GENERAL AND PHYSICAL OHEMISTRY. 25arranging themselves in parallel order. Vanadium pentoxide,benzopurpurin, ferric oxide, tungsten trioxide, and chrysopheninhave been found to form tactosols. Vanadium pentoxide, on age-ing, separates into a concentrated anisotropic phase-the tactosol-which later is precipitated, and a dilute isotropic phase, which istermed the “atactosol.~’ The process is greatly retarded by theaddition of arsenic acid, whilst the addition of other electrolytesdoes not affect the ageing, although it affects the closeness of packingof the particles.The application of an electric potential differencecauses the particles to arrange themselves with their long axesparallel to the direction of the current, but an alternating currenthas the effect of orienting the particles perpendicular to its direction.In a magnetic field, the particles are arranged parallel to the lines offorce. Tactosols are readily produced by cooling a 2% boiling solof benzopurpurin-4B, or a 1% sol of benzopurpurin-6B. Elec-trolytes have the same effect on this tactosol as on that of vanadiumpentoxide, but a magnetic field causes the particles to arrangethemselves with their long axes perpendicular to the lines of force.Tactosols of tungsten trioxide have disc-like, negatively chargedparticles which consist of a number of parallel platelets having aconstant period or distance apart.This period is diminished byincreasing the electrolyte content of the sol.Intensive Drying.The problem of intensive drying is still the subject of muchcontroversy. Many workers assert that the properties of substancesare altered by intensive drying and they favour, in general, theexplanationGQ that such change in properties is the result of theretardation or even the complete prevention thereby of the establish-ment of the inner equilibrium which is normally rapidly attainedbetween different molecular species in chemically pure substances.Other workers, however, deny that intensive drying causes anychange of properties, and the experimental evidence for theirattitude falls into two classes.On the one hand, there are inves-tigators who have completely failed to observe any change ofproperties of substances after intensive drying, and on the other,there are critics who state that some, at least, of the changes whichare said to be produced by intensive drying can be observed withmaterial which has not been dried a t all.H. B. Baker ‘O has measured the vapour densities of numeroussubstances after intensive drying for periods varying from 2 to 16years, and finds increases in the molecular complexity in all cases.A diminution of about 30% in the latent heat of vaporisation of6g Ann.Rep&, 1927,24,21. ‘O J., 1928, 106126 ANNUAL REPORTS ON THE PROQRESS OF CHEMISTRY.benzene after 3Q years’ drying was also observed. This workerfavours the hypothesis 71 that the action of water in promotingmolecular dissociation is due to its high dielectric constant and, insupport of this view, adduces the experimental fact that benzene,hexane, and carbon disulphide, when not intensively dried, havetheir boiling points raised by application of a voltage of 400 toplatinum plates immersed in them. A. Smits 72 attributed thiseffect, in part a t least, to superheating, and on repeating the experi-ment and determining vapour pressures, failed completely to observeany alteration produced by the electric field.This worker con-cludes that large effects after intensive drying are to be expectedin rapid-distillation experiments, but small or zero effects in vapour-pressure measurements. He regards surface-tension measurementsas untrustworthy criteria of molecular complexity, since the magni-tude of this property may be altered by the removal of dust particlesfrom a liquid during long standing. On reviewing the availableevidence, he concludes that the inner equilibria of solids and gaseshave been fixed by the treatment under discussion, but that, in thecase of liquids, the inner transformations have been retarded but notabsolutely stopped. Drying by means of low temperatures hasbeen employed 73 for various gases, but this process appears, ingeneral, to be ineffective in preventing chemical action or in alteringthe boiling point of ether.The duration of contact with phos-phoric oxide necessary to realise the utmost drying is not more than6 months according to the experiments of W. A. Bone, F. R. Weston,and D. A. Winter 74 with carbon monoxide and oxygen. J. J.M a n l e ~ , ~ ~ as a result of measurements of the refractive index ofbenzene in contact with phosphoric oxide for varying periods oftime, infers that water is removed in two stages, the fist part to beremoved being that which is mechanically admixed, and the last,that which is chemically combined.The effect of intensive drying on the reduction of metals byhydrogen and by carbon monoxide 76 has been investigated. Noeffect was observed with silver and mercury oxides and carbonmonoxide or with copper oxide and hydrogen, but the temperaturerequired to effect reduction of copper and bismuth oxides by meansof carbon monoxide was raised.has failed to observeany change in the dielectric constant of oxygen after intensivedrying.H. L. Riley7 1 (Sir) J. J. Thomson, Phil. Mag., 1893, 36, 320.73 D. MoIntosh, Proc. Nova Scotian In&. Sci., 1928,17, 142; A , , 271.74 PTOC. Roy. SOC., 1929, [A], 123, 286 ; A., 616.76 Nature, 1929,123, 907 ; A., 763.7 6 R. H. Purcell, J., 1928, 1207.J., 1928, 2399.Ibid., 1929, 1026GENERAL AND PHYSICAL CHEMISTRY. 27J. Timmermans 78 found no change in the freezing points andsurface tensions of benzene, p-xylene, and cyclohexane after 36months' intensive drying, and similar negative results on theboiling points of benzene and carbon tetrachloride after 4 years'drying are rep~rted.'~ A series of very careful experiments hasbeen carried out 80 on the density and surface-tension changesoccurring when benzene is intensively dried, measurements beingmade on the bulk of the liquid and on middle, head, and tail frac-tions.The density changes observed were not more than 7 parts in100,000 parts, and the surface-tension changes were smaller and inthe opposite sense to those previously recorded by H. B. Baker.81These authors " still feel it to be inconceivable that any considerablemolecular association or dissociation could occur in a liquid withoutcausing readily measurable changes in density as well aa in surfacetension.. . . Though material changes may yet occur, the con-clusion at this stage is, evidently, that intensive drying has notproduced any change in the density or surface tension of benzenesuch as would justify an assumption of appreciable change in degreeof association or of fractional separation of pseudo-components."H. B. Baker's reply 82 to those who fail to repeat his observationsis that intensive drying manipulation is full of pitfalls for theunwary. Great care is needed in the selection of the glass, to avoidcapillaries in the walls of the apparatus which may fill with water,in cleaning, in drying, in the selection of a lubricant, and in thepurification of materials.Neglect to observe any one of the manyprecautions detailed in this paper may lead to failure. W. A. Bone 83has published a similar note on the precautions to be observed indrying gaseous media.S. Lenher * states that the elevation of $he boiling points ofliquids which have not been intensively dried can be readily observedwhen the heating is carried out in a bath, and that the phenomenonis entirely one of superheating. Benzene was superheated by 10"and, when freed from the liquid temperature was raisedto 106" before boiling occurred. Carbon tetrachloride was super-heated by 30" and water by 12". He considers that the appearanceof bubbles in a liquid is not evidence that theliquid is at its boiling78 Bull. Soc.c h h . Bdg., 1929, 30, 160; A., 991.7B S. Lenher and F. Daniels, PTOC. Nat. Aca&. Sci., 1928, 14, 606; A., 1928,8O H, V. A. Briecoe, J. B. Peel, and P. L. Robinson, J., 1929, 368.82 J., 1929, 1661.83 Ibid., p. 1664.84 Nature, 1929, raS, 907; A., 872; J . Physical Chem., 1929, 33, 1579. *' 8ee also J. W. Smith, W., p. 788.11 89.J., 1922,121, 66328 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.point and insists that vapour pressure is the only admissible criterion.He further points out that the failure of a refluxing drop to coalescewith the bulk of the liquid may quite well be due to a difference ofsurface tension caused by a difference of temperature rather than toa difference of surface tension caused by a variation of composition.All who have observed this phenomenon on a briefer scale in anordinary laboratory distillation will be inclined to agree.Inanother paper 86 he points out that he observed no elevation in theboiling point of intensively dried liquids heated electrically bymeans of a wire in the liquid and not in a bath. W. A. West andA. W. C. Menzies 87 have conducted experiments on the effect ofprolonged heating on the vapour pressures of liquids. They wereunable to observe any lag in the return to the normal value oncooling in the cases of benzene, water, acetone, ether, and aceticacid, and found only a small lag in the case of sulphur, which theyascribe to ditliculty in establishing thermal equilibrium. Theymade the interesting observcttion on acetic acid, which they foundto retain water tenaciously even after very close fractionation, thatwhen heated it evolves a more volatile fraction, which presumablycontains a larger proportion of water.On cooling, this fractioncondenses last and remains for an appreciable time on the surfaceof the bulk of the liquid, and hence gives rise to a, higher vapourpressure. After the liquid has stood for a time, or immediatelyafter it has been shaken, the vapour pressure returns to its normalvalue. These authors consider that this observation may explainsome of H. B. Baker's results. A. Smits has repeated, with vari-ations, his experiments on the vapour pressure of intensively driedn-hexene,B* and has concluded that further work is necessary ifconvincing results are to be obtained.89 In the same paper, herecords results which show that his previously reported increase ofthe vapour pressure of nitrogen tetroxide O0 does not necessarilyindicate a shift of the inner equilibrium, but may be due to theevolution of nitrogen tetroxide and oxygen by the action of nitricacid (dissolved in the nitrogen tetroxide used for the experiment)on the phosphorus pentoxide.It is found that 5 years' intensivedrying of ammonia has no effect on its melting point. Anotherpaper 91 contains a description of a method for removing gasescompletely from volatile substances prior to vapour-pressuremeasurements.86 Proc. Nat. Acad. Sci., 1928,14, 606.8' J . Physical Chem., 1929, 33, 1893.O0 A. Smite, W.de Liefde, E. Swart, and A. Claaamn, J., 1926, 2667; see@l A. Smite and E. Bwart, J., 1929,2724.J., 1927, 949.A. Smite, E. Swart, and P. Bruin, J., 1929,2712.also Ann. Reports, 1927,24, 20GENERAL AND PHYSICJAL CHEMISTRY. 29Periodic Precipitates.A considerable amount of work has been done on the conditionsof formation of periodic precipitates or Liesegang rings. M.Copisarow 92 has shown that, for their formation, the salt-salt orsalt-acid systems may be replaced by a base, e.g., sodium carbonate,caustic soda, bmyta, etc., and a gas or its aqueous solution, e.g.,hydrogen chloride, formaldehyde, or ammonia. The preaence of agel is not necessary for the formation of these rings, since they maybe formed in purely aqueous solution, as when a solution of sodiumcarbonate is carefully run over a solution of calcium chloride.Asimilar observation with calcium hydroxide has been made by W. M.Fischer and A. Schmidt.Qs In this case, another phenomenon mayalso be observed, vix., the formation of trees and streamers. Thisformation is inhibited in the presence of gelatin or agar-agar, andboth phenomena are greatly influenced by temperature. Light hasa directive influence on tree formation, as in more than 70% of thecases the trees spiralled towards the illuminated side of the vessel.When rings were formed in a vessel illuminated on one side, theyseemed invariably to incline towards that side. He concludes thatrings and trees are special cases of the Liesegang phenomenon, theformer being produced under very mild conditions and the latterunder the influence of forced irregular diffusion.Furthemore, theprimary cause of the phenomenon is the periodic deformation orsystematic orientation of a mobile medium which may be either acolloid or h e l y divided suspended matter. The whole mpect ofthe phenomenon is therefore widened and earlier theories are in-adequate to account for it. P. B. Ganguly Q4 has obtained mother-of-pearl-like deposits from an aqueous solution of calcium hydrogencarbonate containing gelatin, and finds that for each concentrationof the salt there is a, definite range of gelatin concentrations whichyield these deposits. N. R. Dhar and A. C. Chatterjig5 concludefrom conductivity and diffusion measurements that salts such assilver chromate and lead iodide in gelatin are present as peptisedsols and not as supersaturated solutions.They, too, conclude thatearlier theories are inadequate.Periodic precipitates in the absence of jellies have also been ob-tained Q6 by suspending capillary tubes containing calcium chloridesolution with their open ends dipping in a saturated solution ofsodium phosphate. Banded precipitates were also obtained with98 J., 1927, 222.g6 2. arwrg. Chem., 1926,169,129; A., 1927,200.Rocz. Cham., 1926,5,404; A., 1927,199. @' J., 1926, 1381.R. J. Doyle and H. Ryan, Pm. Roy. I&h Ad., 1929,88, [B], 436; A.,114430 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.lead nitrate and potassium iodide in the absence of gels, and it wasfound that the distances between successive bands were in geo-metrical progression and that the distance of any band from theorigin was proportional to the square root of the time taken for itsformation.It was also shown that the formation of the bands takesplace, not a t the head of the diffusion wave, but behind it. Thecomplexity of a Liesegang ring formation has been pointed out byM. S. Dunin and E'. M. Schemjakin?' who have carried out diffusionexperiments in tubes 150 cm. long, left in the dark for 18 months.The resultant structures (of silver chromate, silver phosphate, andlead iodide) showed three definite periods, a large-scale periodicity,the ordinary rings, and microscopic rings between the ordinaryrings. It is suggested that the precipitations are controlled by threecritical concentrations.E.S. Hedges and (Miss) R. V. Henley 9* have studied the formationof banded precipitates of silver dichromate and of magnesiumhydroxide in gelatin and of lead iodide in agar-agar. In each case,by mixing equivalent quantities of the reactants in the gel, and thensuperimposing a strong solution of the diffusing electrolyte, it waspossible to separate the chemical reaction from the formation ofprecipitate. Since rings were obtained in these experiments com-parable with those formed by chemical reaction, it follows that theformation of periodic structures is a coagulation phenomenon takingplace after the chemical reaction, so that periodic structures are tobe distinguished from periodic reactions.Periodic structures werealso obtained by the diffusion of an electrolyte other than one of thereactants. The relative amounts of product in the bands and in theclear spaces were determined for a magnesium hydroxide gel (pro-duced from magnesium chloride and ammonia) by chemical analysis.The ratio of magnesium hydroxide in the band to that in the clearspace was about 12 to 1, and the corresponding ratio for theammonium chloride about 1 to 3. J. R. I. Hepburng9 points outthat the work of Hedges and Henley supports the coagulationtheory of Freundlich,l and cites some interesting observations onthe production of rings of basic copper carbonate by their method.With sodium carbonate as the diffusing electrolyte the colour of therings was violet, but with copper sulphate only a single green ringwas obtained.Alternate blue and green bands of copper hydroxidehave also been described.2 The activity product of the ions ofmagnesium hydroxide in a banded gel has been measured8 and97 Kolloid-Z., 1929, 48, 167; A., 879. J., 1928, 2714. @' J . , 1920,213.1 " Colloid and Capillary Chemistry," p. 736.2 D.Namasiv&yam, J . Proc. Ae&aticSoc. BengaZ, 1924,20,367; A., 1927,199.9 R. Fricke andO. Suwelack, 2. p?hyeikal. Chem., 1926, l24,369 ; A., 1927,310GENERAL AND PHYSICAL (YHEMISTBY. 31found to increase for some distance beyond the last precipitate andthen to fall again. It is concluded that the phenomenon is due tothe ordinary processes of diffusion and precipitation, and is notpeculiar to solutions containing substances in the colloidal state.Periodic precipitates have also been observed with sulphides: antigenand antiserum,6 and gold and platinum.6 B.Kisch7 makes theinteresting observation that the width of Liesegang rings can bemodified by means of an electric field. With silver nitrate diffusinginto dichromate in gelatin, diffusion occurs more rapidly and therings are broader and more strongly marked in the direction of thecathode.The formation of a periodic precipitate has recently been demon-strated by E. s. Hedges 8 in a reaction of the simplest possiblecharacter. Concentrated aqueous hydrogen chloride was allowedto diffuse into concentrated aqueous sodium chloride and bands ofsodium chloride increasing in thickness and distance apart wereobtained.Thus the chief features of the Liesegang phenomenonhave been duplicated as a result of a reaction involving no gel,and only two diffusible products. Since, moreover, the bandswere composed of relatively large crystals, adsorption effects musthave been negligible ; these results, therefore, me directly at vasiancewith most of the theories of the formation of Liesegang rings.The Parachor.Work on the parachor has been considerably extended sincethe last mention of this subject in these report^.^ The value ofthe parachor constant for the semipok double bond has been con-firmed, and the method applied to a determination of the structuralformule of some cyclic sulphones.l0 It has also been used l1 in asuccessful attempt to confirm the conclusions of C.K. Ingold andC. W. Shoppee l2 with regard to ring-chain valency tautomerism insome derivatives of phorone. As a result of the work of S. Sugdenand his colleagues, the periodic table of parachors is rapidly fillingup. In the Erst short period l3 there is a sharp minimum in theatomic pazachor at carbon, just as there is in the atomic volume inS. M. Kuunenko, Ukraine Chem. J., 1928,8,231; A., 1928,1187,6 L. Reiner and H. Kopp, KolW-Z., 1927,42,336; A., 1927,932.6 E. C. H. Daviea and V . Sivertz, J . Physical Chem., 1926, SO, 1407; A,,1927, 18. ' K o W - Z . , 1929,40,164; A*, 1382.J., 1929,2779. Ann. Reports, 1927, M,I[i.10 A. Freiman and S. Sugden, J., 1928,263.l1 S. Sugden, ibicl., p.410.l2 I W . , p. 366. l8 J . J . Etridge and 8. Sugden, ibid., p. 98932 mu& REPORTS ON THE PROGRESS OF CHEMISTRY.the solid state. It is also found l4 that there is a regular distributionin the atomic parachors along the periods and down the groups of theperiodic table. The parachor for a semipolar double bond is, aswould be expected, identical with that for the polar bond in fusedsalts.lbThe hypothesis of singlet bonds is of great service in accountingfor the parachors of the higher halides and co-ordinated compoundsof uni-, bi-, and ter-valent metals.lS Postulation of duplet bonds inthese compounds leads to sizes of the electron shells about thecentral atoms which bear no simple relation to the observed parachoranomalies unless it is assumed that the sharing of an electron bringsabout a diminution of about 12 units in the parachor.Now, indeducing parachor constants, the contribution of a single bond isassumed to be zero, i.e., the sharing of an electron is assumed to haveno effect. Since atomic parachors have been calculated frommeasurements on compounds in which the constituent atoms exerttheir normal valencies, this assumption will have no effect whenthese values are used to predict the parachors of other normalcompounds : any error is automatically compensated. The samecompensation is found for compounds containing semipolar doublebonds. For higher halides (such as phosphorus pentachloride) andco-ordinated compounds, however, this compensation does notoccur, and the observed values of the parachors can be accountedfor equally well by the hypothesis of singlet bonds, or by assumingthat duplet bonds exist between the atoms and that sharing gives acontraction of 12 units per electron.A direct test which dis-tinguishes between these hypotheses is provided by data onelementary mercury and mercury diphenyl and on two thalliumcompounds. The experimental figures show that electron sharinghas little or no effect on the parachor. Other workers have shown l7that compounds of quadrivalent selenium differ characteristicallyfrom similar compounds of sulphur : sulphoxides are readily oxidisedto sulphones, but the corresponding selenoxides cannot be similarlyoxidised ; furthermore, unsymmetrical sulphoxides of the typeR,R,S e 0 have been resolved into enantiomorphous forms, butthe corresponding selenoxides have resisted d attempts at resolu-tion. It therefore seemed possible that the octet rule might not holdfor selenium. The results of parachor measurements lend no supportto this view. S. Sugden has compared the zero volumes, parachors,l4 W. J. R. Henley and 8. Sugden, J., 1929, 1068, and other papers of thisl6 S. Sugden and H. Wilkins, ibid., p. 1291. S. Sugden, ibid., p. 316.l7 W. R. Gaythwaite, J. Kenyon, and H. Phillip~, J., 1928, 2280, 2287;series.idern and 0. I(. Edward& ibiiE,, p. 2293GENERAL AND PHYSICAL CHEMISTRY. 33and critical volumes of some gaseous elements and compounds withthe diameters of their molecules as calculated from viscosity data.18It is found that the parachor conforms more closely to the require-ments of an ideal additive function than any of the other properties.The determination of the parachors of substances in solution hasbeen studied by D. L. Hammick and L. W. Andrew.lg Mixturesof associated, of non-associated, and of associated with non-associated liquids were used, and it was found that the parachor is alinear function of the molecular fraction. Anomalous results,however, were obtained with water as solvent. The observedparachors of the lower members of the fatty-acid series have beenfound to be consistently low, whilst the reverse holds with thehigher members of the series.20 S. Sugden’s calculation of atomicand structural parachors has therefore been criticised 21 on theground that the effect of chain branching has largely been ignored.His data have been recalculated using a slightly higher value for themean parachor increment for the methylene group, and betteragreement between observed parachors and those calculated withthe revised coqstants is claimed, especially in compounds of highmolecular weight. With the new values, the parachor becomesmore constitutive in character and is said to afford information as tothe effects of intramolecular and interatomic stresses, for whichallowance is made by the introduction of a strain constant. Themain conclusions drawn by Sugden and his co-workers, however,remain unaffected by the recalculations.HAROLD HUNTER.J., 1929, 1066. ID Ibid., p. 754.u, K. W. Hunten and 0. M a w , J . Amer. Chem. Soc., 1929,51,153; A., 252.z1 S. A. Mumford and J. W. C. Phillips, J., 1929, 2112.REP.-VOL. XXVI.

ISSN:0365-6217    

DOI:10.1039/AR9292600011

出版商:RSC    

年代:1929

数据来源: RSC

摘要:

INORGANIC CHEMISTRY.IT is becoming increasingly difficult to separate inorganic chemistryfrom physical chemistry, and whatever method of selection is usedfor this purpose, it may be open to criticism. An endeavour hasbeen made to follow the line of division used in former years. Thewriters of all annual reports on chemistry are, however, faced witha far more serious difficulty, namely, the uneven quality of thegreat mass of literature which has to be considered.All who have had much experience of chemical journals knowthat at the present time there are published many papers whichare probably worthless, others simply restate facts which havelong been known, while others, and this is true of many of thosepublished in proprietary journals, should have Ween drasticallycurtailed before publication.Much pub-lished work is valueless because it has been done in a careless andinefficient manner, and although the way in which it is describedor the journal in which i t is published will often suggest this, it isunfortunately not always obvious until one repeats the workoneself.In other cases, long lists of compounds are given withoutany analytical support, and results of experiments without anysupporting data. There is nothing to show to what extent the“ results ” depend on the author’s imagination and to what extenton experimental measurements. Many papers belonging to thesetwo unsatisfactory classes have been referred to in the followingReport, as it is scarcely justifiable to exclude them without strongerevidence than is usually available.It seems time that these matters should be referred toAtomic Weights and Separation of Isotopes.Potassium.-The ratios KBr : Ag and KBr : AgBr gave 39.104 &0.0020 as the most probable value for the atomic weight ofpotassium.Copper.-From analyses of cupric chloride the atomic weight ofcopper was found to be 63.557 independently of its geographicalorigin .20.Honigschmidand J. Goubeau, 2. anorg. Chem., 1928,177, 102; A., 369.T. W. Richards and A. W. Phillips, J . Amer. Chem. SOC., 1929, 51, 400;A., 370INORGANIC CHEMISTRY. 35SiEver mid Barium-Full details of the determinations referredt o in last year's annual report have been p~blished.~Cadmium-Thirteen evaporations of cadmium in a vacuumfailed to show any separation of isotope^.^Boron.-It has been shown that unless boric oxide glass is verycarefully annealed it has too low a density.The variable densitiesobtained by Briscoe, Robinson, and Stephenson cannot, therefore,be justifiably used as evidence of variation in the atomic weightof boron with its geographical source.Cerium.-Analysis of cerium trichloride gave 140.125 & 0.007 asthe most probable value of the atomic weight of cerium.'Uranium Lead and Protoactinium.-The mass spectrum of leadtetramethyl prepared from uranium lead shows only isotopes ofmass numbers 206, 207, and 208, present in the proportions 86.8,9.3, and 3-97',,. With a packing fraction of 0.8 x lo-*, thiscorresponds to a mean atomic weight of 206.19.It is concludedthat the line 207 corresponds with the end product of the diuinte-gration of actiniua. The mass number of protoactinium wouldthen be fixed a t 231, and extrapolation of the packing fractioncurve then gives 231.08 for its exact atomic eight.^Chlorine.-The ratio NOCl : Ag gave 35.4565 for the atomicweight of chlorine.1° A fraction in which the chlorine had atomicweight 35.418 was obtained by diffusion of hydrogen chlorideagainst air at atmospheric pressure through porous pipe-stems.llFractional distillation of carbon tetrachloride showed no separationinto fractions of different densities owing to the presence of differentisotopes of chlorine.12 Fractional distillation of large quantities ofliquid chlorine, conversion of the fractions into ammonium chloride,and determination of the densities of the saturated solutions of thelatter compound also failed to show any separation of chlorineisotopes.13Ann. Reports, 1920, 25, 37.A., 115.0.Honigschmid and R. Sachtleben, 2. anorg. Chem., 1929,178,l; A., 370 ;A. A. Sunier, Abs. Theses Univ. Chicago, Sci. Ser. 1925-1926, 4, 173;A. Cousen and W. E. S. Turner, J., 1928, 2664; A., 22.J., 1926, 70; A., 1926, 219; Ann. Reports, 1926, 23, 49.0. Honigschmid and H. Holch, 2. anorg. Chem., 1928, 177, 91; A.,370:a Ann. Reports, 1928, 25, 301.* F. W. Aston, Ndure, 1929,123, 313; A., 370.lo A. F. Scott and C. R. Johnson, J . Phyeical Chem., 1929, 33, 1975.l1 F. A. Jenkins, Abs. Theses Univ. Chicago, Sci. Ser., 1925-1926, 4, 93;l2 H.G. Grimm, 2. phyaikal. Chem., 1929, [B], 2, 181 ; A., 484.l3 H. G. Grimm and L. Braun, ibid., p. 200; A,, 484.-4., 11536 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Intensive Drying.The minute details of manipulation and procedure essential forsuccess in experiments on intensive drying have been described intwo papers,14 and experimental data on intensively dried liquidshave been reviewed in another.15 A book dealing with "TheEffects of Moisture on Chemical and Physical Changes " has recentlyappeared. l 6Xuperconductors.Tantalum, thorium,17 and gallium l8 have been added to the list ofsuperconducting metals, the phenomenon commencing at 4.36',1*4*, and 1-07" Abs., respectively. It is pointed out that all theknown superconducting elements occupy neighbouring places in theperiodic table.Since the superconductivity of tin at the temperature of liquidhelium is not eliminated when the metal is enclosed in a tightly-fitting sheath of German silver, it is concluded that the phenomenonis a volume rather than a surface effect, and from other experimentsit is concluded that the current is carried by electrons distributedat random and that the disappearance of resistance is due to thefailure of the electrons to give up their energy to the atoms owingto elastic reflexion.1'Compounds of a superconducting metal with a non-superconductormay be superconductors. This is true of the compounds Bi,T1,,Sh,T1,, SbSn, Sb,Sn,, and AuPb,, in which only thallium, tin, andlead are superconductors in the pure state.lS Antimony and zincalso yield a superconducting alloy.2o In exceptional cases, as withccrtain alloys of gold and bismuth, it appears to be possible to getsuperconducting mixtures from two metals neither of which is asiiperconductor.21 Copper sulphide (CuS) has the distinction ofbeing the first ordinary simple compound that has been found tobe a superconductor.22l4 See this vol., p.2T.1 5 J. W. Smith, Phil. Mug., 1929, [vii], 8, 380; A., 1226.16 By J. W. Smith (Longmans, Green & Co., Ltd., 1929).1 7 W. Meissner, Physikul. Z., 1928, 29, 897 ; A., 250; Naturwiss., 1929, 17,18 W. J. de Haas and J. Voogd, Proc. K. Akad. Wetensclt. Anwterdum, 1929,19 E. van Aubel, W. J. de Haas, and J. Voogd, &d., pp.218, 731 ; A .,2o W. J. de Haas, Naturwha., 1929, 17, 85; A., 250.21 W. J. de Haas, E. van Aubel, and J. Voogd, Proc. K . Akad. Wetensch.390; A., 871.32,214,733; A., 496,1135.496, 1136; W. J. de Haas, Nature, 1929,123, 130; A., 385.Amsterdam, 1929, 32, 226, 724; A., 652, 1135; W. J. de Haas, Natumoiss.1929,17, 85 ; A., 250.22 W. Meissner, 2. Physik, 1929, 58, 670; A., 1930, 22INORGANIC CHEMISTRY. 37The superconductivity of thallium in magnetic fields 23 has beenstudied, as also the resistance of various alloys a t the temperaturesof liquid hydrogen and liquid helium.24X-Rays and Chemical Problems.The crystal structure of many compounds and mixtures, bothsimple and complex, has been examined of recent years by means ofX-rays, but it may be doubted whether the conclusions which areoften drawn as to chemical structure are always justified by theobservations. Very few of these papers can even be referred tohere, although in some cases, undoubtedly, X-rays can give usefulhelp to the chemist.Some support has been obtained for the existence of sub-ionsfrom observations on silver subfluoride, which appears to have astructure in which the atomic diameter of silver with respect tosilver and with respect to fluorine is equal to the atomic diameterof silver in the metallic state and in normal combination, respect-ively.25 Copper amalgams appear to be merely mechanical mixturesof the two metals so long as they are soft, but when an amalgamsets there is a change in structure and a definite compound isformed.28 Cobaltous and magnesium orthostannates have beenprepared by precipitating suitable mixtures of cobalt or magnesiumand stannic chlorides with sodium hydroxide and calcining theprecipitates at 900".X-Ray examination shows that the productsso obtained, viz., M211WV04, are true spinels and correspond inevery structural particular with the more usual type of spinelThe nature of the precipitates obtained from mixed salt solutionsis of some interest. Mixed hydroxides have been examined byX-rays and found to consist of solid solutions if the kations of thetwo constituent hydroxides do not differ widely in radius; other-wise the precipitate is a simple mixture. Thus nickel hydroxideforms solid solutions with the hydroxides of magnesium, zinc, andcobalt, but not with those of cadmium or calcium.28 X-Rayexamination has shown the complete miscibility of the oxides inthe systems CoO-MgO, NiO-MgO, and CoO-Ni0.aM%po4.2723 W.Tuyn, Proc. K. A M . Weten8Ch. Anasterdam, 1928, 31, 687; A., 250.24 W. J. de Haas, E. van Aubd, and J. Voogd, Proc. K . Akad. Wetensch.25 H. Terrey and H. Diamond, J . , 1928, 2820; A . , 16.26 H. Terrey and C. M. Wright, PhiE. Mag., 1928, [vii], 6, 1055; A., 16.27 G. Natta and L. Passerini, Atti R. A c d . Lincei, 1929, [vi], 9, 557; A.,Ameterdam, 1929,32, 715; A., 1135.780.28 Idem, Gazzetta, 1928,58,579; A., 1928,1316.2B S. Holgersson and A. Karlsson, 2. anorg. Chem., 1929,182, 225; A., 113038 ANNUAL REPORTS ON THE PROGRESS OF CHE~IISTRY.Zinc oxide and silica begin to react at 775” and the orthosilicate.Zn,SiO,, is always obtained even although the constituent oxidesare used in the proportion required for the metasilicate, ZnSi03.3*“ Titanium cyanonitride,” found in blast furnaces, is of doubtfulnature : X-ray data are said t o support the view that it consistsof mixed crystals of titanium carbide and nitride,31 althoughchemical work shows that it is probably titanium nitride withintermingled graphite .32Considerable X-ray activity continues in connexion with metallo-graphy.Two borides of iron, Fe2B and FeB, appear to occur iniron-boron alloys containing from 0 to 19% of boron.% Chromiumcontaining nitrogen shows the existence of two nitrogenous phases.I n the one the chromium atoms are densely packed in a hexagonallattice, the nitrogen atoms probably being distributed at randomin the hollow spaces of the lattice; this phase varies in compositionup to one approaching that required by the formula Cr,N.Thesecond phase has the sodium chloride structure and correspondswith the compound CrN. In a ferrochrome containing 2.4% ofnitrogen, the latter was mainly present as the hexagonal Cr-PI’phase.34 X-Ray observations on copper-antimony alloys 35 agreewith the equilibrium diagram for the system obtained by Car-enter,^^ but those on the silver-antimony system show thatPetrenko’s equilibrium diagram is incorrect .37Alloys of zinc with iron are closely similar in their crystalline formst o its alloys with silver, copper, and gold : two compounds, Fe3Zn,,and FeZn,, are apparently formed.38Corrosion and Passivity of Metals.Several important papers on the corrosion of metals have beenpublished during the past year.I n the case of atmospheric corro-sion, it is concluded that there is a critical humidity for each metal,determined by the nature of its corrosion products, above whichcondensation will occur on the surface, such condensation probablybeing essential for corrosion. The amount of corrosion of different30 A. Pabst, 2. physikal. Chem., 1929,142,227 ; A., 996.3L V. M. Goldschmidt, Nachr. Qes. U’ias. Gttingen, 1927, 390; Chem. Zentr.,33 E. A. Rudge and F. Arnall, J . SOC. Chem. Ind., 1928,47, 3 7 6 ~ .33 T. Bjurstrom and H. Arnfelt, 2.physikal. Chem., 1929, [B], 4, 469; A . ,34 R. Blix, ibid., 3, 229; A., 747.s5 A. Westgren, G. Hiigg, and S. Erikason, ibid., 4, 453; A., 1139.36 2. Metallk., 1913, 4, 300.37 2. anorg. Chem., 1906,50, 139.38 A. asawa and Y. Ogawa, Sci. Rep. T6hoku Imp. Unic., 1929, 18, 165;1928, i, 1541,2692; A., 18,524.1138.A,, 1130INORGANIC CHEMISTRY. 39non-ferrous metals and alloys under various atmospheric conditionswas determined in several w-ays.39 The corrosion of spirals of pureiron wire in various atmospheres of dry or moist air, oxygen, carbondioxide, and mixtures of the last two has been investigated. A filmof liquid water adhering to the metal seems essential; in this theiron is supposed to dissolve as ferrous hydroxide till the pH is 0.4.The oxygen and carbon dioxide, by oxidation and formation offerrous carbonate, act as depolarisers and so accelerate the corrosion.40Much higher hydrogen pressures are reached in the reaction betweeniron and water than electrochemical data suggest, and it is inferredthat this is due to the decomposition of water by ferrous hydroxidejlWhen air-free water and ferric hydroxide act upon iron filings,hydrogen is evolved, and the ferric hydroxide is blackened owing toconversion into triferric t e t r ~ x i d e .~ ~ Hydrogen peroxide is formedwhen iron amalgam rusts in water, still larger amounts beingformed in presence of alkali; with iron powder (ferrum reductum)the hydrogen peroxide can only be detected when alkali is used.The part played by the peroxide in the rusting of iron is discussed.43The importance of differential &ration and the breakdown of pro-tective films as factors in the corrosion of metals has been emphasisedand dem~nstrated.~~ The importance of oxygen supply in cases ofcorrosion of one metal in contact with a nobler metal has also beenshown.Measurement of the electrical currents between the twometals gives a quick and simple indication of the corrosive propertiesof the soIutions.*5 Potential differences between adjacent portionsof metal play an important part in the corrosion and dissolution ofmetals.46Potential measurements show that, with care, iron can be madeto corrode in a stable and reproducible manner. Time-potentialcurves show that the film present on iron after exposure to airincreases its resistance to destruction by the ele~trolyte.~~ Thepresence of oxide films, often invisible, on many metals has nowbeen demonstrated, in many cases by the separation and isolationof the films; that the presence of such a film is the normal cause3e J.C. Hudson, Atmospheric Corrosion of Metals, Third (Experimental)Report to the Atmospheric Corrosion Research Committee (British Non-ferrous Metals Research Association), 1929 ; B., 684.40 J. F. G. Hicks, J . Physical Chem., 1929,33, 780; B., 521.41 G. Schikorr, 2. Elektrochem, 1929, 35, 62; A., 266.42 A. Schikorr, ibid., p. 65; A., 283.43 H. Wieland and W. Franke, Annalen, 1929, 469, 257; B., 476.44 U. R. Evans, J., 1929, 92, 111 ; A., 270,271.45 F.Tadt, 2. Elektrochem., 1928,34, 586, 591, 853; A., 145, 145, 270.46 W. Palmaer and others, Hand. Ing. Vetenskaps-Akad. Stockholm, 1929,4 7 A. L. McAulsy and S. H. Bastow, J., 1929, 85; A., 270.No. 93; B., 92140 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of passivity is becoming generally accepted.48 The electrolyticformation of protective films and its bearing on the question ofpassivity has been st~died.~QThe theory that the phenomena of passivity are due to valencychanges still survives.60 It has also been suggested that crystalstructure plays a part.51&oup 0.The m. p.-pressure curve of helium has been followed up to atemperature of 42" Abs. where the corresponding pressure is 5600kg./sq. ~ 1 1 1 . ~ ~When a discharge is passed through helium at several mm.pressure between platinum electrodes, the deposit formed on thetube contains large quantities of adsorbed or combined helium.The observed diminution of pressure in the tube corresponded tothe adsorption of 14-34 C.C.per g. of platinum deposited.% F.Paneth and K. Peters describe unsuccessful attempts to preparehelium compounds, and show how the diffusion of helium throughglass can be utilised to prepare neon-free helium. Hydrogen andhelium may be easily separated by causing the former to diffusethrough palladium.Ghup I .One of the most striking results of the past year is the separationof the two forms of molecular hydrogen predicted by the wave-mechanics. These are characterised by symmetrical and anti-symmetrical functions, and the terms para- and ortho- have beenused to distinguish these states, although Sir E.Rutherford wouldprefer to designate them ct and p.564 8 J. Hinnuber, 2. EEektrochern., 1929, 35, 95; A., 270; U. R. Evans andJ. Stockdale, J., 1929, 2651 ; A. M. Haselrink, 2. Elektrochem., 1928,34, 819 ;A., 146; L. C. Bannister, J., 1928, 3163; A., 158; U. R. Evans, J., 1927,1020; A., 1927, 619; Ann. Repwh, 1927,24, 5 8 ; U. R. Evans, Nature, 1929,123, 16; A., 134; F. H. Constable, Nature, 1929, 123, 569; A., 520; L.Tronstad, ibid., 124, 373; A., 1150; 2. physiknl. Chem., 1929, 142, 241;A., 1012.4a W. J. Muller and Ic. Konopicky, Monahh., 1928,50,386; 1929,523,289;A., 146, 1241 ; W. J. Muller and 0. Lowy, ibid., 51, 73; A., 402; W.J. Muller,2. Elektrochem., 1929, 35, 93, 666; A., 270, 1393.R. Miiller, ibid., p., 459; A., 1016.51 J. N. Stranski and Z. C. Mutaftschiew, ibid., p. 393; A., 1016.52 F. Simon, Natu?-wiss., 1929, 17, 256; A., 636; F. Simon, M. Ruhemann,and W. A. M. Edwards, 2. physikal. Chern., 1929, [B], 2, 340; [B], 6, 62; A.,497 ; 1930, 24.53 H. Damianovich, Anal. Fis. Quirn., 1928,28,365; A., 156; Compt. rend.,1929,188, 790; A., 523; H. Damianovich and J. J. Trillat, ibid., p. 991; A . ,523.54 2. physikal. Chem., 1928, [B], 1, 253; A . , 25.5 5 Pres. Address to Royal Society, Nov. 30th) 1929; see Nature, 1929, 124,878INORGANIC CHEMISTRY. 41The specific heat of hydrogen changes with temperature in a waywhich could not be explained by the older theories.This is dueto a gradual change in the proportion of the two forms present.56K. F. Bonhoeffer and P. Harteck 57 have studied the inter-conversion of para- and ortho-hydrogen very fully. The changesare most readily followed by measuring the change in resistanceof a heated wire in presence of the gas, which varies with the specificheat of the latter. Hydrogen in equilibrium a t ordinary temper-atures consists of about 25% para- and 75% ortho-. At liquid-airtemperatures, the equilibrium is very largely in favour of the para-form, and probably would be almost entirely so at liquid-heliumtemperatures. Equilibrium is established very slowly in the puregas phase, but very rapidly when the gas is adsorbed on platinisedasbestos or, still better, on charcoal, especially under pressure.Inthis way para-hydrogen has been obtained practically pure, andwill remain so for a long time at the ordinary temperature in absenceof catalysts like charcoal. The ortho-form has not been obtainedpure. The specific heat of para-hydrogen at low temperatures isgreater than that of ortho-hydrogen. There is a large evolutionof heat during the passage of ortho- to para-hydrogen. The stronglines in the para-hydrogen emission spectrum are the weak ones inthe emission spectrum of ordinary hydrogen. Attempts to separatepara- and ortho-forms of water by fractionation at low temperatureswere unsuccessful, and this is attributed to the high velocity oftransformation of one form into the other.58A.Smits 59 regards the discovery of para- and ortho-hydrogen as anexperimental realisation of certain aspects of his theory of allotropy.The formation of monatomic hydrogen from hydrogen moleculesby collision with electrons of 7-16 volts energy has been studiedby K. E. Dorsch and H. Kallmann.go The reaction 2H = H, hasbeen followed calorimetrically. The action of atomic hydrogenon hydrocarbons seems to be very complex.6266 A. Eucken, Natumuis8., 1929, 17, 182; A . , 497; A. Eucken and K.Hiller, 2. physikal. Chem., 1929, [B], 4, 142; A., 990; K. Clusius and K. Hiller,&bid., p. 168; A., 990.5 7 Natud88., 1929,17, 182, 381 ; A., 479, 732; 2. phyeikal. Chem., 1929,[B], 4, 113; [B], 6, 292; A., 982, 1218; Sitzungsber. Preuss. Akad. Wi88.BerZin, 1929, 103; A., 732; 2.Elektrochem., 1929, 35, 621; A., 1372.68 K. F. Bonhoeffer and P. Harteck, 2. physikal. them., 1929, [B], 5, 293;A., 1218.Phy8ihxd. Z., 1929, 30, 425; A., 982.60 2. Ph$Y8&, 1929,63, 80; A., 483.61 H. M. Smallwood, J . Amer. Chem. Soc., 1929,51, 1985; A., 1016.82 K. F. Bonhoeffer and P. Harteck, 2. physikal. Chem., 1928,139,64; A.,409; H. S. Taylor and D. G. Hill, aid., 1929, [B], 2,449 ; A., 656 ; A. Klemencand F. Patat, ibid., 3, 289 ; A . , 892.B 42 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Under high pressure, hydrogen will displace metallic copper fromsolutions of its salts, but as, in all circumstances, there is anequilibrium between cupric and cuprous salt and metallic copper,the displacement is never complete.s3 The reducing action ofhydrogen under high pressure on pentachlororuthenates has alsobeen studied.64When lithium carbonate and sodium carbonate are decomposedin boiling aqueous solution the amount transformed into hydroxideis proportional to the square root of the time.65 The solubility ofsodium in sodium chloride is said to be 4.2% at 800" and 15-20%at 850", whilst at higher temperatures the metal phase disappears.66By treating sodium dissolved in liquid ammonia with lead iodide,or by extracting an alloy of lead and sodium with liquid ammonia,compounds of the type Na4Pb7 and I)u'a4Yb, are obtained.Allelements of the long periods of the periodic system which are 1-4positions removed from a rare gas and form liquid hydrides willgive such compounds with sodium ; these have the characteristicsof salts, probably have a polysulphide-like structure, and crystallisefrom ammonia in the form [Na(NH3)I],E+ [Xn-(X),]. X-Ray observ-ations show that in the ammonia-free form there is a completechange of structure with formation of an intermetallic phase con-taining no chemical compound.67 NaZn, is formed by the actionof sodium on zinc cyanide dissolved in liquid ammonia.68The precipitate obtained by the action of potassium salts onsolutions of sodium cobaltinitrite has a constant compositioncorresponding with the formula [Co(NO,),]K,Na,nH,O (where n isgenerally 1) so long as the ratio Na/K is above about 25.Asthe ratio falls below this value, the amount of potassium in theprecipitate increases and gradually approaches that required forthe compound [Co(NO,),]K,,nH,O.For a given Na/K ratio theprecipitate is richer in potassium the higher the temperature ofprecipitati~n.~~Rubidium chloride, bromide, and iodide are converted at highpressures into a second modification.7063 V. Ipatiev and V. Ipatiev, jun., Ber., 1929, 62, [BJ, 386; A., 410.64 V. N. Ipatiev and 0. E. Zvjaginstsev, ibid., p. 708; J. Russ. Phys. CILCV~.66 B. L. Vanzetti, Gazzetta, 1929, 59, 219; A., 661; B. L. Vanzetti and66 R. LorenzandR. Winzer, 2. anorg. Cl~em., 1929,183, 121; A., 1229.6s W. M. Burgess and A. Roae, J . ,4?ner. CIienz. SOC., 1929, 51, 2127; A . ,68 L. Bonneau, Bull. SOC. chim., 1929, [iv], 45, 798; A., 1930, 49.'O P. W. Bridgman, 2.Krist., 1928,67, 363; Chem. Zentr., 1928, ii, 317; A . ,SOC., 1929, 61, 823; A., 527, 1029.-4. Oliverio, ibid., pp. 288, 300; A., 887.E. Zintl, Natz~noiss., 1929, 17, 782; A., 1249.1154.140INORGANIC CHEMISTRY. 43Element 87 (ekacaesium) has been searched for by a positive-raymethod in products obtained from pollucite and lepidolite. It wasnot present to an extent greater than 3.5 x 10-7 and 7.3 x 10-6 inthe caesium separated from the two minerals, respectively. 71A number of ammines of cupric nitrite have been obtained.72Pure cupric sulphide has been prepared, as a dark blue substancesoluble in potassium cyanide, by the union of finely divided copperand sulphur prepared at low temperatures ; the mixture was heatedby steam in a bomb tube containing carbon disulphide.73 Thesulphide precipitate obtained by the action of cupric salts onsodium thiosulphate is a mixture of cuprous and cupric sulphidesand free sulphur.74 Cuprous sulphide reacts with ferric sulphate intwo stages; the first, Cu,S + Fe,(SO,), = CuS + CuSO, +ZFeSO,, predominates at ordinary temperatures, but a t highertemperatures it is followed by a second reaction : CuS + Fe,(SO,),=CuSO, + 2FeS0, + S.75 A method of obtaining cuprous sulphatefrom copper and sulphuric acid has been de~cribed.?~ Cuprousiodide has a vapour density at 900-1100" corresponding with theformula CuI, whereas the bromide has the double formula.77 Anumber of comples dicarbosylic acid salts of copper have beenprepared which are said to have the structure Na,[CuX,(H,O),]and to contain copper with a co-ordination number of six.78 Thesolutions obtained by adding sodium hydroxide to solutions con-taining copper or iron salts in presence of various hydroxylic organicsubstances were examined by ultra-filtration and other methods :it is concluded that the dissolved metal is present partly as a colloidand partly as a crystalloid complex in proportions which depend onthe conditions.79 Fehling's solution is considered to be essentiallycolloidal in nature. 8oThe ratio of the hydroxyl- and chloride-ion conceiitrations whensilver oxide has reached equilibrium with potassium chloride solu-tions at 25" is independent of the method of preparation of theoxide s1 and is substantially the same as that found by Noyes andKo.hr.82 A crystalline compound &6[AgI(CNS),] has been obtained'1 K.T. Bainbridge, Phyeical Rev., 1929, [ii], 34, 752; A., 1210.52 H. J. S. King, J., 1929,2593; A., 1930, 47.53 K. Fischbeck and 0. Dorner, 2. anorg. Chem., 1929,182, 228; A., 1250.14 J. HanuL and V. Hovorka, J . Czech. Chem. Comm., 1929,1, 65; A., 410.75 L. Whitby, J., 1929, 60; A . , 283.7 6 J. G. F. Druce and G. Fowles, Chena. News, 1928,137,385; A . , 156.7 7 K. Jellinek and A. Rudat, Z. physikal. Chem., 1929,143,55; A., 1226.78 H. L. Riley, J., 1929, 1307; A., 896.59 W. Bachmann, Kollhd-Z., 1929,47,49; A., 260.80 H. Dumawki and A. A. Chalieev, ibid., p. 121 ; A,, 259.*l R. F. Newton, J . Anter. Chem. SOC., 1928,50, 3258; A., 141.a* A,, 1903, ii, 2014.1 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.by refluxing an acetone solution of sodium thiocyanate with silveriodide ; the compounds K,[AgI(CNS),] and (NH,),[AgI(CNS),]n-ere also prepared.83 Silver dissolves to a considerable extent indilute ammonia on account of the relatively stable Ag(NH,),OHcomplex facilitating atmospheric oxidation.The dissolution getsslower and slower and finally stops after some months, long beforethe ammonia is saturated with respect to silver oxide; it is con-cluded that this is due to the slow formation of silver fulminate orsimilar products, e.g. , Ag,N or Ag,NH, which are gradually depositedon the surface of the meta1.aThe dissociation pressures of aurous chloride and bromide andauric chloride have been determined at various temperatures.Noevidence could be obtained for the existence of gold dichloride orof a double compound between i t and potassium chloride.85 Thesystem gold-chlorine has been investigated up to 1250" at 1 atm.pressure of chlorine ; above 475" the vapour phase contains Au,CI,molecules.s6 The auric chloride molecule is Au,C16 at 25OomS7Group I l .Thecommercial production of the metal on the scale of one ton perannum is about t o occur.88 The metal is produced by electrolysisof a mixed electrolyte prepared from 2BeO,BeF, and bariumfluoride and containing about 45% of the latter. Electrolysis iscarried out at 1400" with a current density of 100-400 amps./cm.Zof cathode area, a graphite crucible serving as anode and a water-cooled iron tube as cath0de.8~ The metal can be plated electro-lytically on to other metals from fused bath~.~O The 2BeO,BeF,required for the above process is obtained from beryl by a method 91which gives nearly a 90% yield of pure product : the finely powderedmineral is heated to 650" far several hours with sodium silicofluoride,the product leached, the resulting Na,BeF4 precipitated with limein slight excess, the beryllium hydroxide obtained is separated fromcalcium fluoride by solution in hydrofluoric acid, the solutionevaporated to dryness, and the residue heated to 150".An accountThere has been much activity in connexion with beryllium.133 A. C . Vournasos, 2. anorg. Chem., 1929,182, 37; A., 1153.8 5 W. Fischer and W.Biltz, 2. anorg. Chem., 1928, 176, 81; A., 31.86 W. Biltz, W. Fischer, and R. Juza, ibid., p. 121; A., 31.5 7 W. Fischer, ibid., 1929, 184, 333.8 8 A. Stock, 2. nngew. Chern., 1929, 42,637.89 K. Illig, M. Hosenfeld, and H. Fischer, Wiss. Ver68. Siemena-Konz.,90 H. Fischer, ibid., p. 8 3 ; B., 723.91 K. Illig, M. Hosenfeld, and H. Fischer, ibid., p. 30; B., 723.K. A. Hofmann and U. Hofmann, Ber., 1928,61, [B], 2566; A., 156.1929, S, ( l ) , 42; B., 722; H. Fischer, ibid., p. 59; B., 723INORGANIC CHEMISTRY. 45has been published of older methods of obtaining andalso a review of the literature dealing with the physical propertiesof the element and much of its chemical behavi0ur.~3 There aretwo crystalline forms of beryllium hydroxide.Monosodium beryl-late, BeO,NaOH,H,O, is the stable solid phase at 30" in contactwith solutions of sodium hydroxide containing above 35% of thelatter.g4 The preparation of beryllium chloride from beryl isdescribed by W. Winters and L. F. Yntema,95 and that of berylliumoxide by H. A. Sloman,96 while J. M. Schmidt 97 has made a detailedstudy of the chloride and of its combination with other chlorides.Hydrated beryllium chloride and bromide have been prepared byV. Gupr and H. Salanskj.!sVery pure magnesium has been made commercially by sublimingthe ordinary meta'l at 600" under a pressure of 0-5-1.5 1~1111.~~The solubilities of magnesium hydroxide 1 and carbonate 2 havebeen examined.The m. p.'s of calcium, strontium, and barium are 810", 752",and 658" re~pectively.~Solubilities have been recorded for calcium hydroxide 4 andcalcium sulphate in water, for calcium carbonate in solutions ofcarbon dioxide, gypsum, and sodium and for calciumphosphates in sulphurous acid.7 The hydrolysis of calcium phos-phate and the adsorption of lime by basic calcium phosphate havebeen examined,* and the existence of two suspiciously complexcalcium sulphoaluminates has been anno~nced.~ The action ofbromine on strontium oxide and its hydrates has been examined in9a K.Illig and M. Hoaenfeld, Wiss. F'enjfl. Siemens-Konz., 1929, 8, (I),26; A,, 1024.K. Illig, &bid., p. 74; A,, 1024.94 R. Fricke and H. Humme, 2. anorg. Chem., 1929,178, 400; A., 399.95 Trans. Amer. Electrochem. SOC., 1929, 55, 205; B., 641.96 J .SOC. Chem. Ind., 1929,48,309~; B., 1043.91 Ann. Chim., 1929, [XI, 11, 361; A., 1024.O 8 2. anorg. Chem., 1928,176, 241 ; A., 38.Og H. E. Bakken, Chem. Met. Eng., 1929,36,345; B., 685.A. Travers and Nouvel, Compt. rend., 1929,188, 499; A . , 388.W. D. Kline, J. Amer. Chem. SOC., 1929,51, 2093; A,, 997.H. Hartmann and G. May, 2. anorg. Chem., 1929,185, 167.L. B. Miller and J. C. Witt, J . Physica2 Chem., 1929,33, 285 ; A., 388.E. P. Partridge and A. H. White, J . Amer. Chem. SOC., 1929, 51, 360;A . , 388.* G. L. Frear and J. Johnston, ibid., p. 2082; A., 997.W. &I. Mebane, J. T. Dobbins, and F. K. Cameron, J . Physical Chetn.,J . R. Lorah, H. V. Tartar, and (Miss) L. Wood, J . Amer. Chem. SOC., 1929,W. Lerch, F.W. Aehton, and R. H. Bogue, U.S. Bur. Stand. Res. Paper,1929,33, 961 ; A., 997.51, 1097; A., 777.1929, No. 64; Bur. Stand. J . Res., 1929,2, 716; A., 66246 AXNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.some detail. l o Strontium thiosulphate and strontium and bariumtetrathionates l1 have been prepared and described.The use of barium perchlorate as a drying agent and absorbentof ammonia is recommended by G. F. SmithY12 and the fractionationof barium-radium solutions has been investigated by Z. T. Walterand H. S ~ h l u n d t . ~ ~Careful studies have been made of the distribution of radiumnitrate between crystalline barium nitrate and its saturated solu-tions at 0" and 25", also between mixed crystals of barium and leadnitrates and the corresponding saturated aqueous solutions.TheBerthelot-Nernst distribution law was found to h01d.l~The dehydration of 3CdS0,,8K20 has been studied by L. Coniglio,n-ho found that 3CdS0,,5H20, 3CdS04,2H,0, and 3CdS0,,H20 areformed as stages between it and the anhydrous salt.15Cadmium peroxides have been prepared by several methods.There are considered to be at least two definite compounds,Cd40,,2H,O and 3Cd0,2H20,.16A number of complex salts of o-phenylenediamine and o-tolylene-diamine with zinc and cadmium halides have been prepared, someof which are octammines. All are brightly coloured compoundsand several exist in two forms which are probably stereois~merides.~~Mercury-vapour pressure and calorimetric measurements havebeen made on a number of amalgams, and several definite com-pounds of mercury with sodium, gold, thallium, and cerium areindicated.There are two definite compounds of ammonia with mercuriciodide, Hg12,2NH, and 3HgI2,4NH, ; their reactions with aqueousammonia leading to Hg,NI and Kg,N41, have been fully investig-ated.19 Contrary to statements of earlier workers, mercuric chlorideand bromide combine with dry gaseous ammonia to yield HgC1,,2NH3and HgBr,,2NH,.20The decomposition of mercurous chloride in concentrated alkalil o H.B. Dunnicliff, H. D. Suri, and K. L. Malhotra, J., 1928, 3106; A , ,l1 R. Portillo, Anal. Fia. QuCm., 1929,27, 236, 243, 351 ; A., 778, 896.l2 Chemist-Analyst, 1929, 18, 18 ; A., 1026.l3 J . Amer. Chem. SOC., 1928, 50, 3266; A , , 132.l4 V.Chlopin, A. Polessitsky, and P. Tolmatscheff, 2. phplsikal. Chem., 1929,l5 Rend. Accad. Sci. Pis. Mat. Napoli, 1928, [iii], 34, 119; A., 279.l6 T. R. Perkins, J., 1929,1687; A., 1164.l7 W. Wahl, F6rh. I11 nord. Hemistm6tet, 1928, 172 ; A., 157.la M. Frangois, Ann. Chim., 1929, 11, 22; A., 524.2o Idem, C m p t . rend., 1929,188, 1500; Bull. Soc. chim., 1929, [iv], 45, 616;157.145, 57, 67.W. Biltz and F. Meyer, 2. anorg. Chem., 1928,176,23 ; A., 31.A., 896, 1250INORGANIC CHEMISTRY. 47chloride solutions has been studied and considered with referenceto the irregularities of the calomel Various reactions ofinfusible white precipitate, HgCI,NH,, and of fusible white pre-cipitate, HgC1,,2NH3, have been compared.22J. M. Walter and S.Barratt 23 have shown that t,he majority ofthe band spectra associated with zinc, cadmium, and mercury arein reality due to traces of impurities such as oxide a,nd chloride.There is no doubt, however, that mercury vapour contains somediatomic molecules.Group I I I .The difficult problem of the structure of the boron hydridescontinues to attract investigators. F. Ephraim 24 considers thatthey can be satisfactorily explained on the octet theory of dis-tribution of the outer electrons, but in his suggested structuressome electrons are shared between three atoms, which will doubtlessbe considered unsatisfactory. W. Hellriegel 25 suggests that thetwo inner electrons of the boron atom are displaced so as to producean octet with the other six in the group BH,.These inner electronsare involved in the union of the two BH, groups to form B,H,.B(CH,), and B(C2H5), exist as such and do not polymerise; theirgreat reactivity towards oxygen is, however, attributed to the samecause as that giving rise to polymerisation of BH,. Structures forall the boron hydrides are put forward. A. Stock and E. Pohland 26have published a paper on the more complex boron hydrides; itis mainly concerned with the physical and chemical properties ofVapour pressure measurements indicate the existence of eightboric acids nB,O,,H,O, where n = 1--tL2' BF,,NH, and its threeethyl derivatives have been prepared as white solids by treating anethereal solution of BP, with ammonia or the appropriate amine.28K2BeF4,A12(S04),,24H20 and K2ZnC1,,Al2(SO4),,24H20 are tworepresentatives of an interesting new type of alum.29 The equil-ibrium 4AlN + 3C = A14C, -+ 2N2 has been studied between 1774"BIOH14.21 T.W. Richards and 31. Franqon, J . PhyshE Chem., 1929, 33, 93G; A.,22 P. Ray and P. Banerji, J . Indian Chein. Soc., 1928, 5, 715 ; -4., 279.23 Proc. Roy. Soc., 1929, [A], 122, 201 ; A., 237.24 Hdv. Chim. Acta, 1928,11, 1094; A., 123.25 2. anorg. Chem., 1929,185,65.26 Ber., 1929, 62, [B], 90; A., 279.27 L. F. Gilbert and (Miss) M, Levi, J., 1929,627; A., 491.2B C. A. Kraus and E. H. Brown, J . Amer. Chem, SOC., 1929, 51, 2690; A.,OD W. R. C . Curjel, Nature, 1929,123, 206; A., 246.887.125048 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and 1909" Abs.30 By the action of aluminium triethyl on water,aluminium hydroxide of composition corresponding to the formulaAl(OH), has been obtained either as a gelatinous precipitate or asa fine granular J.Hoffmann32 has published a long paperon ultramarine, in which are some interesting experiments, novelviews, and a useful summary of theories and literature on thispuzzling substance, or, rather, group of substances. A productresembling kaolin has been prepared by precipitating alumina andsilica together in the correct proportion and treating the driedprecipitate with steam for 12 days under a pressure of 200-260 atm.33 The dissociation pressure of kaolin is a function ofthe water content over the whole range.34The formation of gallium oxalste, basic gallium acetate, and basicgallium ammonium sulphate is described by A.T~hakirian.~~W. Klemm has considered the classification of the rare-earthelements in terms of their electronic configuration, and shows thatthere is within the group a certain periodicity of chemical propertiesas well as of physical ones such as the ionic susceptibility and colourof oxides or ions.36 These considerations showed that ytterbiumdichloride should exist, and it has in fact been readily obtained byreduction of the trichloride with hydrogen at 600-900". Thedichloride is colourless, relatively very stable towards water andammonia, and similar in many respects to strontium chloride.37A full and careful account of the scandium oxalates and doubleoxalates has been given,38 while a detailed study has been made ofsamarium chlorideammonia complexes.39 The oxides of the ceria-earth metals have been studied with special reference to the influenceof temperature and oxygen pressure on the composition.Onlycerium and praseodymium appear to form higher oxides.40 Theanhydrous iodides of the elements of the ceria earths have been30 C. H. Prescott, jun., and W. B. Hincke, J . Amer. Chem. SOC., 1928, 50,3 l P. A. Thiessen and K. L. Thater, 2. anorg. Chem., 1929, 181, 417; A . ,32 Ibid., 183, 37.33 C. J. van Nieuwenburg and H. A. J. Pieters, Rec. trav. chim., 1929, 48,34 Idem, ibid., p . 406; A., 636. 35 Compt. rend., 1929, 189, 251 ; A., 1026.36 2. anorg. Chem., 1929,184,345.3' W. Klemm and W. Schuth, ibid., p .352.38 J. b%ba-Bohm and S. &amovskjr, 6aaopia 6e.skoslov. Ldk,, 1928, 8,211 ; Chem. Zentr., 1929, i, 2399; J. Czech. Chem. Comm., 1929,1,1; A., 1251,541.39 W. Klemm and J. Rockstroh, 2. anorg. Chem., 1928, 176, 181 ; A., 38.40 H. A. Page1 and P. H. M.-P. Brinton, J . Amer. Chem. SOC., 1929, 51,3228; A., 142.1026.37 ; A., 280.42 ; A., 280INORGANIC CHEMISTRY. 49prepared, with the exception of that of europium which could notbe obtained, and their melting points determined.41 Europium di-and tri-halides have been examined.42 Argento- and auro-cyanidesare formed by the tervalent rare-earth metals of the cerium group.43Sodium cericarbonate, Na,[Ce( CO&],12H20, has been obtainedin the form of yellow prismatic crystals isomorphous with thecorresponding thorium salt .44Details have been given of the separation of yttrium of highpurity by the fractional crystallisation of the double carbonates ofthe yttria-earth elements and sodium, followed by a fractionalprecipitation of the crystalline double ferrocyanides with the alkalimetals in presence of a large excess of the alkali-metal salt.Theobject of the ferrocyanide treatment is to remove a small amountof erbium .45Group I V .By an application of the Nernst heat theorem it is found thatfrom 0" to 1100" Abs. graphite is more stable than diamond, whilstthe dimorphism is truly monotropic and not pseudo-monotropic.The heat of transition changes sign at 850" Abs., above whichtemperature diamond changes into graphite with absorption ofheat.46 The position of the equilibrium C + CO, 2CO dependson the character of the carbon and its ~re-treatment.~' The doublecarbonates Na,CO,,MgCO, and Na,CO,,CaCO, and the correspondingpotassium compounds have been prepared, but attempts to makedolomite were unsucce~sful.~~ Carbon sulphidoselenide is formedby the action of carbon disulphide vapour on ferrous selenide at650"; several of its physical and chemical properties have beendetermined.49 Complex cyanates of a number of heavy metals andcontaining hexamethylenetetramine have been prepared ; they areof the general formula [X(H20)2,C,H,2N4](CNO)2 and are morestable and less soluble than the simple cyanates.5041 G.Jantach, H. Grubitsch, F. Hoffmann, and H. Alber, 2.anorg. CJLem.,43 G. Jantsch, H. Alber, and H. Grubitsch, Monatsh., 1929,63 and 54, 305;43 G. A. Barbieri, Atti €2. Accad. Lincei, 1929, [vi], 9, 906; A., 1026.44 L. Lortie, Conapt. rend., 1929, 188, 915; A., 624.45 G. Canneri, AttiR. Accad. Lincei, 1928, [vi], 8, 164; A., 158.46 N. Nagaaako, Bull. Chem. SOC. Japan, 1928,3,209; A., 20.4 7 F. J. Dent and J. W. Cobb, J., 1929,1903; A,, 1237.4a W. Eitel and W. Skaliks, Naturwk., 1929,17, 316; A., 777.4* H. V. A. Briscoe, J. B. Peel, and P. L. Robinson, J., 1929,66, 1048; A.,60 R. Ripan, Bul. SOC. Stiinte Cluj, 1928, 4, 29; Chem. Zen&., 1928,1929, 185, 49.A., 1407.410, 778.2938 ; A., 4150 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The partial solubility of silicon in hydrofluoric acid under certainconditions appears to be due to ~ x i d a t i o n .~ ~ The stability regionsof the several forms of silica have been re-investigated 52 and theresults of Fenner 53 confirmed.A number of important slag equilibria have been studied, namely,those between ferrous sulphide and lead, cuprous, and nickelsilicates, and several similar ones.54By the action of silicon tetrachloride vapour on water, withcareful attention to the acidity, i t has been found possible to preparesolutions of nearly pure mono- and di-silicic acid.55 Si0,,2H20was obtained by hydrolysis of ethyl orthosilicate a t ordinary tem-perature, and from it 2Si0,,3H20 and (SiO,,H,O), were obtainedby desiccation at 13°.56 According to R. Schwarz and H. Richter,57the gel produced by hydrolysis of silicon tetrachloride by water a tO", followed by thorough washing and drying with acetone below 2",has a composition very close to that of a metasilicic acid, (SiO,,H,O),.Titanium tetrachloride similarly treated yields Ti0,,2R20.Asilicic acid prepared, in absence of water, by the action of silicontetrachloride on triphenylcarbinol dissolved in anhydrous etheralso had a water content very close to that of the meta-a~id.~*Titanium sesquioxide and ferrous oxide heated together to 1000"yield a spinel.59 A number of compounds of titanium tetra-chlorideand -bromide with cyanogen bromide or hydrocyanic acid havebeen isolated. 6o Zirconium iodide has been prepared. 61 Zirconiumoxide gels age very slowly, and the process seems to end with Zr02without indication of any definite intermediate hydrated com-pound.62R. Schwarz and H. Giese 63 have examined the perosides oftitanium, zirconium, hafnium, and thorium; those of the firstthree metals behave as peroxy-ortho-acids of the general formula5 1 C. Bedel, Compt. rend., 1929, 188, 1255; 189, 180; -4., 756, 997; A. San-fourche, {bid., 188, 1672; 189, 533; A., 1030, 1251.52 C. J. van Nieuwenburg, Rec. truv. chitn., 1929, 48, 402; A., 637.53 A., 1913, ii, 133.54 W. Jander and K. Rothachild, Metull-U'irtschaft, 1928, 7, 580; Chens.Zentr., 1928, i, 2897; A . , 31.R. Willstlitter, H. Kraut, and K. Lobinger, Ber., 1928, 61, [BJ, 3280;1929,62, [B], 2027; A., 39, 1251.56 P. A. Thiessen and 0. Koerner, 2. anorg.CJLetn., 1929,182, 343 ; A . , 1154.57 Ber., 1929, 62, [B], 31; A., 280.5 8 W. Dilthey and E. Holterhoff, ibid., p. 24; A., 280.59 F. Halla, 2. anorg. Chem., 1929,184, 421.F. Oberhauser and J. Schormiiller, Ber., 1929, 62, [ B ] , 1436; A . , 896.6 * E. Chauvenet and J. Davidowicz, Cornpt. rend., 1929,189, 408; A., 1154.62 A. Simon and 0. Fischer, 2. anorg. CJLein., 1929, 185, 130.63 Ibid., 1928,176, 209 ; A., 39INORGANIC CHEMISTRY. 51M(OOH)(OH),, whilst that of thorium is Th207,4H,0. Potassiumpertitanate and perzirconate are found to be K,Ti08,6H,0 andK,Zr0,,6H20 and are regarded as salts of tetraperoxy-ortho-acids.The conditions necessary to precipitate zirconium completely asphosphate have been examined.s4 The compoundsTh(S0,) (HPO,) ,4H,O, and Th,(SO,) (H,P0,)6 ,8H,O have beenobtained by J.D'Ans and W. DawihLs5Full details of the preparation of pure germanium dioxide fromgermanite and its conversion into the tetrachloride have been pub-lished by L. Dede and W. Russ and by W. Pugh,G7 and C. Jamesand H. C. Fogg obtained a rapid concentration of the germaniumand gallium contained in certain samples of zinc oxide in a simplemanner : a solution of the zinc oxide in hydrochloric acid is renderedbasic by the slow addition of some of the original zinc oxide, themixture is filtered, the residue containing the germanium andgallium is dissolved in acid, and the solution is distilled and treatedin the usual manner to obtain the two elements. The solubilityof germanium dioxide in hydrochloric and sulphuric acids of variousconcentrations has been measured.There is no evidence for theformation of a germanium sulphate, for the solubility falls con-tinuously with increasing concentration of the sulphuric acid, butwith hydrochloric acid the solubility passes through a minimumin 53N-acid and thereafter increases owing to formation of tetra-chloride. Except in very strongly acid solutions, the germaniumdioxide behaves essentially as an acid oxide.69 W. Pugh 70 hasalso studied the hydrolysis of sodium germanate and has deter-mined the first and second dissociation constants of germanic acidto be 2-6 x lo4 and 1-9 x 10-13 respectively. Germanic acid andseveral germanates have also been examined by R. Schwarz.71L. 31. Dennis and H.L. Hunter 72 have at last succeeded in pre-paring germanium dichloride by the action of the vapour of thetetrachloride on metallic germanium at 350"; it is a light yellowsolid with properties very similar to those of the dibr0mide.~32eH,CI, GeH,CI,, GeH,Br, and GeH,Br, have all been obtained by;he action of hydrochloric or hydrobromic acid on GeH, in presenceR. D. Reed and J. R. Withrow, J. Amer. Chem. SOC., 1929, 51, 1311;4., 778.Th(HP0,)(H2P0,)2,2H20,6 5 2. anorg. Chem., 1929,178, 252; A., 411.66 Ber., 1928,61, [B], 2451; A., 158.6 8 J . Amer. Chern. SOC., 1929, 51, 1459; A., 778.6B W. Pugh, J., 1929,1537; A,, 997.71 Ber., 1929,62, [B], 2477; A., 1407.72 J. Amer. Chem. SOC., 1929, 51, 1161; A., 662.73 Ann. Reports, 1928, 25, 53.67 J., 1929, 2540; A., 1930, 47.70 Ibid., p.1994; A., 123752 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of anhydrous aluminium chloride or bromide, and their propertiesare described. 74By studying the change in the diffusion coefficient of the stannateion caused by the gradual addition of acid to strongly alkalinestannate solutions, and also the change in the ultra-violet absorp-tion, it is concluded that a change occurs in such solutions whichis not simply the change from a normal to an acid stannateNa,[Sn(OH)6] + HCl = NaH[Sn(OH)6] + NaC1,but is much more comparable with the conversion of a chromateinto a dichromate and is representable by an equation such as2[Sn(OH),]" + 2H' [Sn,(OH),,]" + 2H,0.75The concentration of chlorine ions and hydrogen ions in aqueousstannic chloride solutions has been determined.In dilute solutionsthese are equal, but in solutions of concentrations greater than0-IM an excess of chlorine ions is present. Complete inhibition ofhydrolysis does not take place even in presence of 4N-hydrochloricacid.76 A number of complex amminated stannibromides ofvarious heavy metals have been prepared by G. Spacu and J.The dissolution of lead and cadmium in their respective fusedchlorides is a chemical process involving the formation of a lowerchl~ride.~S (PbCI),CO,, identical with the mineral phosgenite, issaid to be precipitated as an intermediate stage in the action ofsodium carbonate on lead chloride solution.79 Lead nitrate formswith ammonia a hexammine, a triammine, and a monoammine;lead sulphate yields a tetrammine and a diammine.sOThe equilibrium PbS + H, Pb + H2S has been investigatedat various temperatures between 655" and 1000".81Since sodium plumbate, Na2Pb0,,3H,0, loses all its water simul-taneously at 110" without any liberation of oxygen, it must bederived from metaplumbic acid and does not possess the formulaNa2[Pb(OH)6].82Group V .The nature of active nitrogen and the cause of its after-glowThe knowledge with respect to the subject was7 p L. M. Dennis and P. R. Judy, J . Amer. Chern. SOC., 1929, 51, 2321; &4.,75 G. Jander, F. Busch, andT. Aden, 2. artorg. Chem., 1928,177,345; A,, 281.713 L. Smith and A. Persson, ibid., 178, 155; A . , 29.7 7 Bul.Soc.StiinteCluj, 1928,4,84,110; Chem.Zentr., 1928,ii, 1196; A.,281.T o (Mme.) N.Demassieux, Compt. rend., 1929, 189, 333; A,, 1154.*1 K. Jellinek and A. Deubel, 2. Elektrochem., 1929,3!5, 451 ; A., 1012.are still obscure.1154.W. Eitel and B. Lange, 2. anorg. Chem., 1929,178, 108; A., 411.W. Krings, 2. anorg. Chem., 1929, 181, 309; A . , 1026.A. Simon, 2. anorg. Chem., 1928, 1'77, 109; A., 158INORGANIC CHEMISTRY. 53summarked by C. N. Hinshelwood.83 The rate of decay of theafter-glow and the influence of the walls of the containing vesselupon this have been investigated, as also the effect of small addi-tions of other substances.** It appears to be necessary to assumethe presence of nitrogen atoms, and possibly of metastable mole-cules too, in order to explain the results, although, according tosome authors, no appreciable density of atoms is present.85 2.Bayand W. Steiner 86 state that active nitrogen generally consists of amixture of ordinary and metastable (8-volt) nitrogen moleculeswith ordinary and metastable (2.37- and 3-56-volt) nitrogen atoms,and its properties depend upon the mixture ratio. The presenceof atoms is essential for the after-glow. Active nitrogen, apartfrom complications due to the nature of the walls, is not properlydescribed unless the conditions of excitation are accurately specified.Nitrogen activated by the dark electric discharge unites with thealkali metals to produce azides with some secondary nitride.*'Such nitrogen also readily combines with sulphur a t 80-100" toyield a mixture of several nitrogen sulphides.88 When an arc isstruck in nitrogen between iron electrodes considerable formationof iron nitride, Fe,N,, occurs.89The (reversible) decomposition pressures of boron nitride havebeen determined between 1695" and 2045", and some other nitridesexamined at high temperatures.wNo evidence in support of the suggested existence of active andinactive phases of ammonia could be found by W. H. Stringfell~w.~~Vapour-density measurements have shown that the vapours of(moist) ammonium chloride, bromide, and iodide are completelydissociated even in presence of the solid salt .92 Intensively driedammonium chloride also dissociates completely on vapori~ation.~~83 Nature, 1928, 122, 404; A., 39.84 H.0. Kneser, Ann. Physik., 1928, [iv], 8'7, 717; Physikd. Z., 1928, 29,895; A., 6 ; B. Lewis, J. Amer. Chem. SOC., 1929, 51, 654, 665; A., 624;E. J. B. Willey, Nature, 1929,124, 443; A., 1117.85 P. K. Kichlu and S. Basu, ibid., 123, 715; A., 624; P. K. Kichlu andD. P. Acharya, Proc. Roy. SOC., 1929, [ A ] , 123, 168; A., 624, but see LordRayleigh, Nature, 1929,123, 716; A., 624.86 Naturwiss., 1929, 17, 442; A., 863; 2. Eiektrochent., 1929, 35, 733;A., 1359.W. Moldenhauer and H. Mottig, Ber., 1929, 62, [B], 1954; A., 1247.E. J. B. Willey, J., 1928,2840; A., 39.R. Lorenz and J. Woolcock, 2. anorg. Chem., 1928,178,289 ; A., 29.88 W. Moldenhauer and A. Zimmermann, ibid., p. 2390; A., 1252.s1 J., 1929, 1; A., 281.92 A. Smits and R. Purcell, J., 1928, 2936; A., 128; A.Smits and W. deLange, ibid., p. 2944 ; A., 128 ; R. H. Purcell and W. de Lange, J., 1929,276 ;A., 387.DS W. H. Rodebush and J. C. Michalek, J. Amer. Chem. SOC., 1929,51, 748;A., 63654 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The ternary system NH,-C0,-H20 has been studied at temperaturesabove 60", steel bombs being used for reaction vessels. In theneighbourhood of 80-100" a double compound of aiiimoniumhydrogen carbonate and ammonium carbamate is formed, but thisdoes not exist above 106", which is the m. p. of ammonium hydrogencarbonate. Above 135" all these compounds are unstable and areconverted into carbamide. A space diagram of the ternary systemis given.94The conditions under which monobromoamine can be producedby the action of bromine on ammonia have been examined ; unlikemonochloroamine it does not yield hydrazine with ammonia.95The influence of various factors on the interaction of monochloro-amine with ammonia have been studied. Very small amounts ofcupric, ferrous, and cobaltous ions decrease the amount of liydrazineformed.The favourable influence of mannitol and gelatin on theyield of hydrazine is attributed to adsorption of these ions by thegelatin or mannit01.~~ Chlorination of excess of ammonium ions atthe ordinary temperature yields only NH,C1 when the pH of thesolution exceeds 8.5, practically only NHCl, when the pH is between4.5 and 5.0, and NCI, when the pR is below 4 ~ 4 . ~ ' A method ofconcentrating hydrazine hydrate solutions by distillation withxylene has been des~ribed.~~The conditions have been given under which azoimide and itssalts can be safely and conveniently prepared.99 Molecular hydrogenin presence of colloidal palladium has a very slight reducing actionon azoimide in alkaline solution, but in acid solution reduction toammonia and hydrazine is complete.Nascent hydrogen from zincor iron and hydrochloric acid gives the same resu1t.lAccording to K. Gleu and E. Roell,, when oxygen containing loo//,of ozone is passed into a N-sodium azide solution an unstable orangesubstance is produced which reacts quantitatively as a pernitrousacid, isomeric with nitric acid and having the structure O:N*O*OH.I n a mixed chloroform-carbon tetrachloride solution three reactionsoccur when nitrogen trichloride reacts with nitric oxide a t temper-atures between 0" and - 80"; these can be represented by theequations (a) 2NCl, = N, + 3c1,; ( b ) NOCl + NCl, = N,O -i-94 E.Terres and H. Behrens, 2. physikal. Chem., 1928, 139, 695; A . , 141 ;see also E. Jiinecke, 2. Elektrochem., 1929, 35, 716; A., 1388.95 W. Moldenhauer and M. Burger, Ber., 1929,62, [B], 1615; A., 897.96 M. Bodenstein and Tikchack, 2. physikal. Chem., 1928,139,397 ; A., 282.9 7 R. &I. Chapin, J . Amer. Chem. SOC., 1929, 51, 2112; A., 1026.98 C. D. Hurd and C. W. Bennett, ibid., p. 265 ; A., 282.99 W. Hoth and G. Pyl, 2. angew. Chem., 1929,42,888; A., 1155.2 2. anorg. Chem., 1929,179,233; A., 523.B. Ricca and F. Pirrone, Cazzettu, 1929,59,379; A., 1150INORGANIC CHEMISTRY.562C1,; (c) NCl, + 2N0 = K,O + NOC1+ Cl,. Reaction (a) iscatalysed by the nitric oxide.3When hydroxylamine is prepared by electrolytic reduction ofnitric acid in sulphuric acid solution, a mercury cathode being used,considerable quantitiee of hydroxylamineisomonosulphonic acid arealso formed ; the influence of various factors on the yield of hydroxyl-amine has been e~amined.~ L. Cambi has examined the decompos-ition of hyponitrous acid under various conditions.6 The combin-ation of nitric oxide with oxygen to form nitrogen peroxide followsa termolecular course.6 The conditions which influence the inter-action of nitric oxide and hydrogen sulphide to form water, sulphur,and nitrogen have been investigated,' and so has the equilibriumbetween nitrogen trioxide and its dissociation products, nitric oxideand peroxide.Nit'rogen peroxide and sulphur dioxide react in the liquid stateaccording to the scheme 1.5N,04 + 250, = S2N20g + NO.S,N,O,is a white crystalline solid with the properties of an anhydride ofnitrosylsulphuric acid.9 A substance of the same composition hasbeen prepared by methods which suggest that it has the structureNO*O~SO,*O~SO,*ONO, but the similar compound SO,(O*NO),could not be isolated.1° Pure nitryl chloride, NO,C1, has beenprepared l1 by treatment of gaseous nitrosyl chloride with ozone,cooling the product in liquid air, and removing the oxygen formedaccording to the equation NOCl + 0, = N0,Cl + 0,; it is acolourless gas which condenses at - 15" to a colourless liquid of do'1.37 and f.p. - 145".Nitrogen sulphide, N4S4, in benzene is converted by stannouschloride in 96% alcohol into (HSN),. From the reactions of thiscompound, its structure is considered to be NGH-N=SH H=N-S3N ,whilst N4S4 is N<?=NI?>N.12S-N-SW. A. Noyea, J . Amer. Chem. SOC., 1928,50,2902; A., 158.J. G. Stscherbakov and D. M. Libina, 2. Elektrochem., 1929, 35, 70; A.,Gaszetta, 1929,59, 770.(FrI.) G. Kornfeld and E. Klingler, 2. physikal. Chem., 1929, [B], 4, 37 ;J. Pierce, J . Physical Chem., 1929,33,22; A., 281.E. Briner, G. H. Lunge, and A. van der Wijk, Helv. Chim. Actu, 1928,11,1125; A,, 40; W. Manchot and H. Schmid, Ber., 1929,62, [B], 1261 ; A., 779.10 C. W.H. Jones, W. J. Price, andH. W. Webb, J., 1929,312; A., 411.11 H. J. Schumacher and J. Sprenger, 2. anorg. Chem., 1929, 182, 139; A . ,1155; 2. Elektrochem., 1929, 35, 663; A., 1395.l2 A. Meumen, Ber., 1929,62, [B], 1959; A., 1252.274.A., 887.* E. Abel and J. Proial, 2. Elektrochem., 1929,35,712 ; A., 138356 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.A number of chlorobromides of phosphorus are stated to beformed by the action of bromine on phosphorus trichloride or itsvapour,13 whereas the pentachloride is said to yield with brominethe reddish-brown compound PCI6,5Br,, melting at 25" with de-composition. 14The investigations of A. Petrikaln l5 on the emission and absorp-tion spectra of phosphorus pentoxide and phosphorus trioxideindicate that the band spectrum in the phosphorus luminescencespectrum is due to phosphorus trioxide while the continuous spec-trum is due to the pentoxide.The precautions needed in thepreparation of phosphorus oxide so as to obtain a product con-taining the minimum amount of yellow phosphorus are describedby L. Wolf and H. Schmager Is; further papers dealing with theremoval of these traces of yellow phosphorus have been pub1ished.l'Phosphorus trioxide cannot be prepared by the action of thetrichloride on phosphorous acid or on acetic anhydride or glacialacetic acid. l8 Pure sublimed phosphorus pentoxide rapidly absorbsappreciable amounts of intensively dried ammonia, forming a pro-tective film on the pentoxide. Dichlorophosphoric acid is formedas a recognisable intermediate stage in the action of ice-cold wateron phosphoryl chloride or phosphorus pentachloride.zo Difluoro-phosphoric acid, HPO,F,, is produced 21 when phosphoryl fluorideis hydrolysed by cold dilute alkali hydroxide and is convenientlyisolated as the nitron salt. The ammonium salt is obtained byheating phosphoric oxide with 3 mols.of ammonium fluoride in acopper or nickel crucible a t 135" and extracting the cold productwith alcohol. Many other difluorophosphates have been preparedby double decomposition from the ammonium salt. Difluoro-phosphoric acid resembles perchloric acid to a small extent; wheni t is boiled with very dilute potassium hydroxide, monofluoro-phosphate is formed and can be isolated as the silver salt, Ag,PO,F,from which other salts can be prepared.These salts show analogieswith the sulphates and are very stable in neutral or alkaline solution13 T. Milobqdzki and S. Krakowiecki, Rocz. Chem., 1928, 8, 563; A . , 411.14 W. A. Plotnikov and S. I. Jakubson, 2. physikal. Chem., 1928, 138, 243;16 2. Physik, 1928,51, 395; A., 377.l6 Ber., 1929, 62, [B], 771; A., 662.1 7 (Miss) C. C. Miller, J., 1929, 1823, 1829; A,, 1155; Ann. Report8, 1928,L. Wolf, E. Kalaehne, and H. Schmager, Ber., 1929, 62, [B], 1441; A.,L. Harris and C. B. Wooster, J. Arner. Chem. Soc., 1929, 51, 2121; A.2o H. Meerwein and K. Bodendorf, Ber., 1929,63, [B), 1952; A., 1252.21 W. Lange, ibid., pp. 786, 793; A., 662.J . Russ. Phye. Chem. SOC., 1928,60, 1513; A., 158, 663.25, 56.897 ; W.P. Jorissen and A. Tasman, Rec. trav. chim., 1929,48,324 ; A., 662.1154.INORGANIC CHEMISTRY. 57but are rapidly decomposed in hot acid solution. It has beenestablished that there exists a definite equilibrium H,PO,+HF zH2P0,F+H20.22 The preparation of a number of crystallinephosphates and arsenates (of Mn, Co, Ni, Cu, and Cd) has beendescribed by F. Ephraim and C. Rossetti.= Hypophosphoric acidcan be prepared in good yield by the oxidation of red phosphoruswith alkaline permanganate, or peroxide, or hypochlorite.24 Fromthe fact that the hydrolysis of the acid follows a unimolecularcourse, it is concluded that it is H4P206 and not H,p0,.25Silicophosphoric acid, H8Si(P04),, is extremely unstable, butthermal analysis of the system Na,0-Si0,-P,05 indicates theexistence of the sodium salt melting at 961°.26 The solubilities ofarsenic tri- and penta-sulphides in pure water and in hydrogensulphide solutions at 0" have been determined, and the bearing ofthe results on precipitations of arsenic as sulphide for analyticalpurposes has been disc~ssed.,~ An elaborate investigation of thethioarsenites of sodium, potassium, ammonium, calcium, stront-ium, and barium has been made by H.Wunschendorff.28 Inaddition to salts of the ortho-, pyro-, and meta-acids, others con-taining a still higher proportion of As2S3, such as K2As4S7,2H20and K2As,S,,,3H,O, could be prepared in some cases. There isalways a tendency for the solutions from which these compoundsare formed to decompose into metallic arsenic and thioarsenate,and this prevents the preparation of certain members of the seriessuch as K,AsS, and K4As2S,.The compounds described arecrystalline. Finely divided antimony is soluble in distilled waterin the presence of oxygen, and this may be a source of error in anyanalytical method where deposits of antimony have to be washed.=In the presence of a relatively strong acid, the orthosulphovanadates,R,VS,, give V2S5, but in the presence of hydrogen sulphide theygive RVS, and R.,[H,(VS,),]. This has been confirmed by thepreparation of the compounds NH,VS,,SH,O andby the action of ammonium hydrosulphide and hydrogen sulphideon the orthovanadate. The corresponding guanidine salts andT1,[H2(VS,),],18H,O were prepared from the ammonium salts by(NH4)4[H2(VS3)61,18H,022 W.Lange,, Ber., 1929, 62, [B], 1084; A., 764.2s Helv. Chim. Ada, 1929,12, 1025; A., 1930, 47.24 F. Vogel, 2. angew. Chem., 1929, 42, 263; A., 525; J. Probst, 2. anorg.25 A. Rosenheim and H. Zilg, 2. physikal. Chem., 1928,139, 12; A., 145.28 R. Schwan, 2. anorg. Chem., 1928,176,236; A., 39.2 7 R. Holtje, ibid., 1929, 181, 395; A., 997.28 Bull. SOC. chim., 1929, [iv], 45, 889, 897, 903; A., 1930, 48.29 J. Grant, Arutlyst, 1929, 54, 227; A., 639.Chem., 1929, 179, 156; A., 52558 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.double decompo~ition.~~ Other complex sulpho-salts of vanadiuni(and a few of molybdenum) of different types from the above aredescribed by the same authors.31 Tantalum pentabromide is pre-pared by distilling bromine on to powdered tantalum heated to260-300" in an atmosphere of nitrogen or argon.32 The behaviourof a number of tantalum compounds under various conditions isdescribed in a paper by V.Spitzin and L. Kas~htanov.~~Group V I .The kinetics of the formation of ozone by the action of cathoderays and by electrical discharges have been studied,34 and also thethermal decomposition of ozone at low pressures.35 The influenceof cathode rays on the union of hydrogen and oxygen and onvarious gases such as oxygen, nitric oxide, and carbon dioxide hasalso been in~estigated.~~ Full details have been published byK. F. Bonhoeffer and H. Reichardt of work which showed theformation of free hydroxyl at temperatures above 1300" : 37 it isalso formed in water-vapour discharge tubes.38The behaviour of pure hydrogen peroxide with a number ofcompounds is recorded, together with the f . p.curves of somebinary hydrogen peroxide systems.39 A number of sodium andpotassium phosphates containing hydrogen peroxide of crystallis-ation have been prepared. They differ from true perphosphatesprepared electrolytically inasmuch as ether extracts the hydrogenperoxide, which is also evolved at 130" in a vacuum.4oSulphur tetrafluoride has been prepared, by the action of cobalticfluoride on sulphur at 120", as a colourless reactive gas condensingat - 40" and 1 atm. pressure to a clear mobile There isstill some doubt about the nature of the liquid mixtures of sulphur30 L.Fernandes and C. Orlandi, Atti R. Accad. Lincei, 1928, [vi], 8, 234;A., 525.31 Idem, ibid., 1929, [vi], 9, 409 ; A., 663.32 K. R. Krishnaswami, Nature, 1928, 122, 845; A., 40.33 2. nnorg. Chem., 1929,182, 207; A . , 1253.34 A. L. MarshalI, J. Amer. Chem. SOC., 1928, 50, 3178; A., 155; J. I<.Hunt, ibid., 1929, 51, 30; A., 274.35 E. H. Riesenfeld and H. J. Schumacher, 2. physikul. Chem., 1928, 138,368; A., 146; E. H. Riesenfeld and E. Wassmuth, ibid., 1929, 143, 397; A . ,1242.36 A. L. Marshall, J. Amer. Chem. SOC., 1928, 50, 3197; L4., 155; W. E'.Busse and F. Daniels, ibid., p. 3271 ; A., 155.3; 2. physikal. Chem., 1928,139, 75; A., 396; Ann. Reports, 1938, 25, 341.38 0. I. Lavin and F. 13. Stewart, Nature, 1929,123,607; A., 520.39 G.L. Matheson and 0. Maass, J. Anter. Chem. SOL, 1929, 51, 674; A.,4O H. Menzel and G. Gabler, 2. anorg. Chem., 1928, 177, 187; A . , 278.41 J. Fischer and W. Jaenckner, 2. angew. Chem., 1929,42, 810; A., 1155.523INORGANIC CHEMISTRY. 59chlorides, in spite of a good deal of work on the subject, but thereseems no doubt that three definite compounds exist, viz., S2C1,,SCl,, and sc14.42SbCl,,SCl, is formed by the action of sulphur monochloride onantimony pentachloride, but no evidence could be obtained for theexistence of the compound 2AsC1,,3SC12 given in the literature.mThe action of carbon tetrabromide on sulphur and on selenium hasbeen examined. S2Br2, Se2Br2, and SeBr, are formed among otherproducts.P4 Heating a mixture of paraffin (25 g.), sulphur (15 g.),and asbestos (5 g.) is recommended as a convenient way of preparinghydrogen ~ u l p h i d e .~ ~ The action of hydrogen sulphide on nitricacid and on solutions of potassium chromate has been investigated.46Electrolysis of sodium sulphide solutions yields only polysulphideat low current densities; dithionate and sulphate are formed athigher current densities, but no thi~sulphate.~~ Crystalline com-pounds of the type M,[Fe(CN),NOS] have been obtained by theinteraction of the alkali-metal sulphides with sodium nitroprussidein absolute methyl alcohol.48Sodium and potassium sulphites in aqueous solution are oxidisedto dithionates when warmed with lead dioxide, which is reducedt o triplumbic tetroxide ; manganese dioxide does not react.49D.Vorlander and A. Lainau have made a thorough study of theoxidation of ammonium sulphite to ammonium sulphate by air,the effect of various alterations in conditions and of various catalystsbeing examined.Tri-substituted derivatives of aminosulphonic acid, NR,*SO,*O,form neutral solutions in water without immediately sufferinghydrolysis. Alkali decomposes them more readily, usually intotertiary amine and sulphate. With acids they can form saltsand complex compounds such as [NMe3,SO,H]C1O4,H,O and[NMe,,S0,],KI,15 ,2H,O. Solid aminosulphonic acid probably hasa betaine structure, which would be more in keeping with its high42 M. Trautz, (Frl.) H. Acker, L. E. von Broecker, A. Rick, A. Hoffmann,H. Klippel, and 0.Loth, 2. EEektrochem., 1929, 35, 110; A., 525; T. M.Lowry and G. Jessop, J., 1929, 1421 ; A., 978.43 J. R. Partington, ibid., pp. 2573, 2577; A., 1930, 48.44 H. V. A. Briscoe, J. B. Peel, and J. R. Rowlands, ibid., p. 1766; A., 1155.H. Gfeller and K, Schaefer, Schweiz. Apoth.-Ztg., 1929, 67, 109 ; A., 1253.46 H. B. Dunnicliff and 8. Mohammad, J . Physical Chem., 1929, 33, 1343;A., 1253; H. B. Dunnicliff and C. L. Soni, ibid., p. 81 ; A., 282.47 W. R. Fetzer, J . PhysiCal Clhem., 1928, 32, 1787; A., 154.48 G. Scagliarini and P. Pratesi, dtti R . Accad Lincei, 1928, [vi], 8, 75;Is R. Hac, J . Czech. Chem. Comm., 1929,1, 259; A,, 777.I 1A., 160.J . pr. Chem., 1929,123,351; A., 1930,4160 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.m. p., non-hygroscopic character, and limited solubility than theformula NH,*SO,*OH usually assigned to it.51The rate of decomposition of sodium and potassium persulphatesunder a great variety of conditions has been examined: a uni-molecular course is followed fairly closely.52F. Foerster 53 continues his investigations of the sulphur acids,which he still interprets in terms of the hypothetical SO. Thelatter compound also plays an important part in the decompositionof thiosulphate by acid according to 0. von Deines,54 who statesthat hydrogen persulphide is also produced. Some work on themechanism of the decomposition of thiosulphuric acid has beencarried out by J. Scheffer and F. Bohm.55The formation of thiosulphate by hydrolysis of trithionate hasbeen demonstrated by adding potassium trithionate to a coldsaturated solution of copper acetate, whereupon the double potass-ium cuprous thiosulphate, IZ2S,O3,Cu2S,O3,2H,O, separated in afew days.56 The existence of potassium hexathionate has beenconfirmed by J.R. Partington and A. P. T i ~ l e r . ~ ' Six-memberedring formula? have been proposed for tetra- and penta-thionic acids,but seem improbable as they contain peroxidic 0xygen.5~A number of amminated selenocyanates of heavy metals have beenprepared.59 The oxide formed by the action of ozone on seleniumdissolved in SeOCl, is found to be selenium dioxide.60 By theaction of hydrogen chloride on selenium dioxide two compoundsare formed, vix., Se0,,4HCl, a yellow solid, and Se02,2HCI, a yellowliquid.61 Various methods of preparing selenic and telluric acidsfrom the dioxides by oxidation have been H.D. K.Drew has shown that Vernon's 64 two forms of dimethyltelluron-51 P. Baumgarten, Ber., 1929, 62, [B], 820; A., 663.52 A. Kailan and E. Leisek, Monatsh., 1928, 50, 403; A., 148.53 F. Foerster, E. Haufe, and E. Kircheisen, Z . anorg. Chern., 1928, 177, 17,54 Ibid., p. 13; A., 159.5 5 Ibid., 1929,183, 151; A., 1253.56 A. Hornig, ibid., 1928, 176, 423; A., 40.57 J., 1929, 1382 ; A., 896 ; Ann. Repo~t8,1928,26,58.5 8 J. A. Christiansen, Fdrh. I I I nord. Kerni8t&tet, 1928, 177; A., 122.50 G. Spacu and R. Ripen, Bul. SOC. Stiinte Cluj, 1928,4, 3; Chern. Zentr.,G. F. Hoffmann and V. Lenher, J . Amer. Chern. SOC., 1929,51,3177; A.,T. W.Parker and P. L. Robinson, J . , 1928, 2853; A . , 40.42, 61 ; A., 159.1928, i, 2937; A., 41.2930, 48.62 E. R. Huff and C. R. McCrosky, J . Amer. Chem. SOC., 1929,51, 1457 ; A . ,799 ; F. C. Mathers and F. V. Graham, ibid., p. 225 ; A., 1930,48 ; F. C. Blathersand G. M. Bradbury, ibid., p. 3229; A., 1930, 45.63 J., 1929, 560; A., 546.64 J., 1920,117, 86, 897; 1921,119, 105, 687INORGANIC CHEMISTRY. 61ium di-iodide and dibromide are not stereoisomerides as the lattersupposed. Halides of the a-series are normal in type, non-polar,and have a tellurium atom with a tetrahedral valency distribution.The compounds of the p-series are salt-like complex substances ofthe same empirical formula as the corresponding substances in the=-series, with the probable constitution [Me$Te]+[TeMeX,]-.Themolecular structure of quadrivalent tellurium compounds has beendiscussed by T. M. Lowry and F. L. Gilbert 65 in the light of Drew’sresults.The m. p. of chromium is probably 1920” or a little higher.66The electrodeposition of chromium from aqueous solutions ofchromic acid has been studied by E. Miiller and P. Ekwall67 andby E. Liebreich and V. Duffek.6S The number and nature of thehydrates formed by chromic sulphate have been examined,sg andchromium ethoxide, Cr(OEt),, has been obtained by P. A. Thiessenand B. Kandelaky.?O The kationic complexes containing sixmolecules of antipyrine or of urea for each Cr“’ ion are readilyformed and rather characteristic. Many salts of these complexes,as also of similar ones derived from other bi- and ter-valent metals,have been prepared.71 Study of chromium oxide gels indicatesthat probably a definite compound Cr203,H20 can exist, althoughthe tendency for the gel to attain this state is very sma11.72 Anumber of basic (Al, Zr, Sb, Bi, Fe) and normal (Cu, Cd, Co)chromates have been prepared by S.H. C. B r i g g ~ , ~ ~ and the equi-librium 2Cr04” + 2H’ Z Cr207” + H20 has been studied byE. Carrihre and P. C a ~ t e 1 . ~ ~A molybdoselenic acid and some ammonium molybdotellurateshave been described.75 H. M. Spittle and W. Wardlaw 76 haveprepared a number of complex oxalate derivatives of quadrivalentmolybdenum and, in particular, a series of the formBdMo304 (c204) 3 ,5H20165 J., 1929, 2076; A., 1218.66 C. J.Smithells and S. V. Williams, Nature, 1929, 124, 617; A., 1226.1 3 ~ 2. Elektrochern., 1929, 35, 84; A., 275.138 Ber., 1929, 62, [B], 2527; A., 1402.69 F. Krauss, H. Querengiisser, and P. Weyer, 2. anorg. Chem., 1929, 178,7O Ibid., 181, 285; A., 1027.7 1 E. Wilke-Dorfurt and H. G. Mureck, {bid., 184, 121; A., 1930, 49; E.72 A. Simon, 0. Fischer, and T. Schmidt, &id., 185,107.73 J., 1929, 242; A., 411.74 Compt. rend., 1928,187, 1292; A., 140.75 E. Wendehorst, 2. anorg. Chem., 1928,176,233; A., 40; V. W. Meloche76 J . , 1929, 792 ; A., 678.413; A., 663.Wilke-Dorfurt and K. Niederer, Ib&d., p. 145.and W. Woodstock, J . Amer. Chem. SOC., 1929,51, 171; A., 28262 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.(where B = C,H,N, I<, or NH,).Several salts derived fromquinquevalent molybdenum have been described ; they belong tothree types, R,[MoOBr,], R[MoOBr,], and R[MoO,B~,,~H,O].~~The binary systems composed of alkali (Li, Na, or K) molybdatewith molybdenum trioxide and of the same alkali tungstate withtungsten trioxide have been examined, as well as the systemsLi2W04--Na4W0, and Li,MoO,-K2Mo04. 7sThe growth of crystals of tungsten does not commence below1200" if the powdered metal is heated in a stream of dry hydrogen.I f the latter is moist, growth commences a t 1050", accompanied byloss in weight of the sample. These effects are due to the formationof WO,, which is volatile at 1950". The formation of large tungstencrystals in the reduction of the trioxide is due to the volatility ofthe oxides WO, and W205, which is measurable at 850" and 900"respectively .79An abnormality that occurs in the temperature coefficient ofthe oxidation of tungsten in air between 850" and 960" is explainedby supposing that tungsten oxide exists in two forms which are inThe reduction of tungsten trioxide by mixtures ofcarbon monoxide and dioxide takes place through the intermediateoxides W,O, and WO,. Between each oxide and the next, andbetween WO, and metal, there is a limited series of solid solutions.The constants for the successive stages of equilibrium have beendetermined, and the dissociation pressures of the three oxides oftungsten calculated.81 The dissociation and rolatilisation ofNOS,, WS,, US,, A12S3, and MgS at very high temperatures in avacuum have been examined by Picon.82 A.G. Scroggie givesan improved method of preparing silicododecatungstic acid. 83 Thegradual addition of hydrochloric acid to a solution of an alkalitungstate produces first a polymerisation to liexatungstic acidwithout any intermediate stage; the salts of this acid are identicalwith the paratungstates of the literature. Wit'h addition of moreacid there is formed metatungstic acid, which is probably a dipara-tungstic acid, and in presence of other acids, such as arsenic orphosphoric acids, heteropolytungstic acids are formed. Thechanges H2W04 +H6[W,0,,] --+H,[As,(W,07),] are describedin detail, and have been investigated by means of measurements7 7 F.G. Angell, R. G. James, and W. Wardlaw, J . , 1929,2578 ; A., 1930, 45.F. Hoermann, 2. anorg. Chent., 1928, 177, 145 ; A . , 160.5B G. A. Meierson, J . Ruse. Phys. Chent. SOC., 1928, 60, 1217; A . , 160.J. S. Dunn, J., 1929, 1149; A., 889.2. Shibata, Tech. Rep. TGhoku Imp. Univ., 1929, 8, 129, 145; A., 631.82 Bull. SOC. chim., 1929, [iv], 45, 907 ; A., 1930, 47.83 J . Amer. Chem. SOC., 1929,51, 1067; A., 779INORGANIC CHEMISTRY. 63of diffusion coefficients and of absorption coefficients of visible andultra-violet light. 84Metallic uranium of 99.95% purity has been prepared by heatingU308 with sublimed calcium in an iron tube in a vacuum.85An important paper has been published by L. Pauling 86 in whichhe formulates a set of principles governing the structure of complexionic crystals. These are based on the assumption of a co-ordinatedarrangement of anions about each kation at the corners of anapproximately regular polyhedron.The known structures of manycomplex crystals satisfy these principles, by means of which it isshown that no stable basic silicates of bivalent metals can exist,and that in aluminium silicates of alkali metals there should be atleast one aluminium ion for every alkali-metal ion. In a secondpaper,g7 the molecular structure of the tungstosilicates and relatedcompounds is considered. The 12-hetero-poly-acids are givenstructures which may be represented by the formula(where z = 3, 4, 5, 6 respectively when M = P, Si, B, H2), in which12 tungsten octahedra, slightly distorted and linked by 3 cornersto each other, surround the undistorted MO, tetrahedron.Struc-tures are also suggested for still more complex acids.HZ[Mo4 7 w12°1 8 (OH),, 3Group V I I .F. Pichter has continued his researches on the use of fluorine asan oxidising agent, with results which agree with his view thatoxidation products so obtained are very similar to those obtainedby anodic oxidation. During the past year the results obtainedwith salts of thallium, manganese, copper, and lead,88 with nitricand perchloric acids,89 and with alkaline acetate solutions havebeen published. N. C. Jones also considers that, in the main,fluorine- and anodic-oxidation are similar, but criticises some ofFichter’s views.91 Anhydrous hydrogen fluoride with a specificelectrical conductivity as low as 14 x 10-6 mho has been preparedby heating potassium hydrogen fluoride with rigorous precautionsto exclude moisture.92 According to P.Lebeau and A. Damiens,93a gas containing 70% of F,O is formed by passing fluorine in fine84 G. Jander, D. Majert, andT. Aden, 2. anorg. Chem., 1929,180,129; A., 664.85 E. Botolfsen, Bull. Soc. chim., 1929, [iv], 45, 626; A , , 1253.86 J . Amer. Chem. Soc., 1929, 51, 1010; A., 748.8 7 Idem, ibid., p. 2868; A., 1367.8 8 F. Fichter and E. Brunner, Helv. Chim. Acta, 1929, 12, 214; A., 282.8s Idem, ibid., p. 305; A., 526.81 J . Physical Chem., 1929,33,801; A., 891.92 K. Fredenhsgen and G. Csdenbach, 2. a w g . Chem., 1929,178, 289; A.,Compt.rend., 1929, 188, 1253; A., 779.w Idem, {bid., p. 573; A., 779.41164 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.bubbles through a 2% solution of sodium hydroxide; i t is collectedover water, liquefied, and fractionated (b. p. - 167").Chlorine fluoride, ClF, has been obtained as an almost colourlessgas by the interaction of slightly moist chlorine and fluorine.94Spectrophotometric measurements indicate that, when carbontetrachloride solutions of chlorine and bromine in equimolecularproportion are mixed, a compound BrCl is formed to the extentof about 5070.95 H. J. Schumacher and G. Stieger 96 have describeda method and apparatus for preparing chlorine hexoxide (C1206 or(310,) in considerable quantities by the action of ozone on chlorinedioxide.It is a liquid with a vapour pressure of about 1 mm. at20", at which temperature, however, it slowly decomposes. A veryunstable oxide of bromine (Br3O& is said to be formed by theaction of ozone on bromine at - 5" to The solubilities ofmanganous fluoride have been measured, and a number of chemicalobservations recorded about it a,nd cadmium fluoride.98 The pro-cedure required to obtain pure anhydrous hydrogen iodide has beendescribed.99 The solubility of iodine in solutions of halides has beenmeasured a t 25"; its value depends on two opposing factors : (a)the salting-out effect and ( b ) the tendency to form perhalides. Withiodides, (a) is negligible, but with bromides and chlorides i t is ofconsiderable irnportance.l A chloroiodic acid, HIC14,4H,0, hasbeen prepared by passing chlorine through a suspension of iodinein concentrated hydrochloric acid.At 0" i t forms orange-yellowtabular crystals. Salts such as KClJCl, and MgC12,21C1,,8H20 arederived from this acid and possess an absorption band in commonwith it.2 The phosphate, tri-, di-, and mono-chloroacetates, andthe methanesulphonate of tervalent iodine have been prepared byFouque's m e t h ~ d . ~ A saturated solution of iodine acetate in aceticanhydride was electrolysed with a silvered platinum gauze cathode,94 0. Ruff, E. Ascher, J. Fischer, and F. Laass, 2. anory. Chem., 1928,176,268; A . , 40; idem and F. Luft and H. Volkmer, 2. angew. Chem., 1928, 41,1289; A., 160; 0. Ruff and F. Laass, 2. anorg.Chem., 1929, 183, 214; A.,1226.95 S. Barratt and C. P. Stein, Proc. Roy. SOC., 1929, [ A ] , 122, 582; A.,411.g6 2. anorg. Chem., 1929,184, 272; A., 1930, 48.9 7 B. Lewis and H. J. Schurnacher, 2. physikul. Chem., 1928,138, 462; A.,160; 2. anorg. Chem., 1929, 182, 182; A., 1166; 2. Elektrochern., 1929, 35,648; A , , 1395.g8 P. Nuka, 2. anorg. Chem., 1929,180, 235; A,, 779.99 R. T. Dillon end W. G. Young, J . Amer. Chem. Soc., 1929,51, 2389; A.,1156.J. S. Carter and C. R. Hoskins, J., 1929, 680; A., 501.V. Caglioti, Atti R. Accad. Lincei, 1929, [vi], 9, 663; A , , 780.3 Chem.-Ztg., 1914, 38, 860INORQANIC CHEMISTRY. 65and an amount of silver iodide was deposited equivalent to thecurrent passed., A quantitative study has been made of theoxidation of carbon monoxide by iodine pent~xide.~ The electro-lytic preparation of several permanganates , using anodes of silico-manganese and a platinum cathode separated by a diaphragm, hasbeen described by G.Rapin.6 Although neither manganese dioxidenor mercury will by itself dissolve in cold dilute sulphuric or nitricacid, they dissolve in presence of each other owing to the coupledreaction MnO, + 2Hg + 4HN03 = Mn(N03), + BHgNO, + 2H20(or one giving Hg2S04,Hg,0) which is quantitative.' The prepar-ation, properties, and nature of the oxides of manganese have beeninvestigated. *The crystal structure of rhenium resembles that of osmium.From the lattice constants and the atomic weight, the density ofpure rhenium is calculated to be 2 1 ~ 4 .~ As much as a gram of purerhenium has been prepared from Norwegian molybdenite having arhenium content of 2-4 x 10-6.loWhite rhenium peroxide, Re208, is obtained by heating the met.alor lower oxides in a stream of oxygen below 150" ; near that temper-ature it melts and is converted into a yellow oxide, which is Re20,,not ReO, as previously thought, and gives a strongly acid aqueoussolution. The salts NH,ReO,, NaReO,, and Ba(Re04)2 have beenprepared as white crystals and their solubilities determined. Whenthe first two salts are heated in hydrogen to 400°, ReO, is formedas a black solid; from the solution of this dioxide in dilute nitricacid, barium rhenate, BaReO,, was obtained.llThe crystal structure of potassium per-rhenate, KReO,, has beenexamined.12 It is isomorphous with scheelite.croup VIII.At 715" the solubility of oxygen in iron increases with increasingoxygen pressure to a maximum of 0.11%, above which value theformation of ferrous oxide begins.13 The solubility of iron in car-F.Fichter and s. Stern, Helv. Chim. A&, 1928,11, 1256; A., 41.L. Rodriquez Pire, Anal. Fig. QuCm., 1929,27,192; A., 778.Bull. SOC. chim., 1928, [iv], 43, 1174; A., 36; Compt. rend., 1929, 188,See also J. Roudnick, Bull. SOC. chim. Betg., 1547; 189, 287; A., 891, 1151.1929, 38, 147; A,, 891.a Idem, ;bid., p. 177.* V. M. Goldschmidt, NdUmUi88., 1929,17,134; A., 382; 2. physikal. Chem.,1929, [B], 2,244; A., 493.10 I. Noddack and W. Noddack, 2. anorg. Cherta., 1929,183,353; A,, 1408.l1 Idem, Naturwiss., 1929, 17, 93; A., 411; 2.anorg. Chem., 1929, 181, 1;12 E. Broch, 2. phy8;kal. Chem., 1929, [B], 6, 22; A., 1930,20.l a W. Krings and J. Kempkens, 2. a w g . Chem., 1929,183,226; A., 1230.REP.-VOL. XXVT. CJ. Meyer and R. Kantera, 2. anorg. Chern., 1929,185, 172.A., 102766 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.bonic acid solutions under carbon dioxide pressures of 20-50 atm.has been examined-it becomes almost independent of pressureabove 30 atm.14The presence of minute traces of iron in the salt is responsible forthe red coloration which ammonium thiocyanate assumes whenexposed to light. Ferric thiocyanate is formed by photochemicalosidat,ion. This is reversed in the dark and the salt becomescolourless again.15 Iron pentacarbonyl reacts with mercuricsulphate in 10% sulphuric acid to give Fe(CO),Hg, of which severalreactions are described. By the action of halogens, compounds ofthe type Fe(C0)4X, (X = C1, Br, I) are obtained, and by theaction of mercuric salts, compounds Fe(CO),Hg,HgX, are formed(X = C1, Br, I, OAc, +SO4).l6 When nitric oxide under pressure actson iron carbonyl at 45", a violent reaction occurs with formationof black crystals of unstable iron tetranitr0sy1.l~ If the reaction iscarried out in methyl-alcoholic solution, a black substance is formedwhich contains methyl alcohol and is probably Fe(NO),BMeOH.l8The preparation of a number of further compounds of iron, cobalt,and nickel, containing nitric oxide, with the metal attached tosulphur and apparently univalent, has been described.The be-haviour of these compounds has been compared with that of hypo-nitrites and shown to be different, and it is concluded that theyreally do contain univalent metal and have nitric oxide groupingsattached to the metal by co-ordinated covalencies (donated bynitrogen).lg The fluorides of the metals of Group VIII of theperiodic system have been prepared and their physical and chemicalproperties tabulated.20There are two hydrates of ferric fluoride, vix., FeF,,3H20 andFeF,,4.5H20,21 and ferrous bromide forms hydrates with 9, 6, 4,and 2 molecules of water. The solubility of ferrous bromide inwater has been determined over the range - 60" to + 132°.22The reaction between ferric oxide and hydrogen sulphide has beenexamined between 120" and 830" : FeS, is the principal productl4 E.Muller and H. Henecka, 2. anorg. Chem., 1929, 181, 169; B., 751.l5 C. G. Patten and H. D. Smith, Trans. Roy. SOC. Canada, 1928, (ai), 22,Is H. Hock and H. Stuhlmann, Ber., 1929, 62, [B], 431, 2690; A., 412;l7 W. Manchot and E. Enk, Annnlen, 1929, 470, 276 ; A., 1027.W. Manchot and H. Gall, ibid., p. 271 ; A . , 1027.Is Idem, Ber., 1929, 62, [ B ] , 678; A., 526; W. Manchot and S. Davidson,ibid., p. 681 ; A., 526 ; W. Msnchot and G. Lehmann, Annalen, 1929,470,255 ;A., 1027; W. Manchot, ibid., p. 261; A., 1028.111,221 ; L4., 407.1930, 47.2o 0. Ruff and E. Ascher, 2. anorg. Chem., 1929,183, 193; A., 1254.z1 E. Deussen, Monatah., 1929, 52, 107; A., 1027.22 F.Schimmel, Ber., 1929, 62, [B], 963; A., 665INORGANIC CHEMISTRY. 67betvc-een 120" and 40OoB Between 900" and 1000" magnetite,hzmatite, and iron pyrites will yield nearly all their iron as thevolatile chloride on treatment with chlorine.24 The properties ofthe a- and y-hydrates of ferric oxide have been examined; bothare crystalline and, in a general way, correspond to the mineralsgoethite and lepidocr~cite.~~ Dark brown crystals of ferric ethoxide,Fe(OEt),, separate from a mixed solution of ferric chloride andsodium ethoxide in absolute alcohol.26 Cobalt forms only twooxides, COO and Co304, but below about 100" the former can adsorbmore oxygen to form Co0,n02 without any change in the crystallattice. At higher temperatures this changes into Co,O,,mO, withthe lattice of Co,O,.The dry methods for preparing cobaltic oxidefound in the literature actually give C0,O,,rn0~.~~ According toC. W. Stillwe11,28 the rose-coloured cobaltous hydroxide is thestable crystalline form; the blue varieties are unstable and thecolour is structural. One definite hydrate of cobaltic oxide, vix.,Co20,,H,0, appears to exist .29 Cobaltous aluminate, chromite,ferrite, and cobaltite are true spinels,30 but the nature of CoO-ZnOmixtures depends on the proportion of the two oxides present.31-4 number of cobaltites, RO,Co,O, (R = Cu, Mg, Zn, Mn, Ni) havebeen prepared and are of the spinel type.32 A new series of cobaltouscompounds of the formula R2[CoX4], where X is a halogen and R ispyridinium, quinolinium, or %methylquinolinium, has been pre-pared.% The CoCI," ion was postulated by Donnan and Bassett 34t o account for the blue colour of certain cobalt chloride solutions.Crystals of Co2(S0,),,18H20 have been obtained by the action ofozone on a well-cooled solution of cobaltous sulphate in sulphuricacid.35 Lithium cobaltisulphite, Li3[Co(S0,),],4H,0, has been pre-pared, and also the still less soluble potassium salt,K,[CO(SO,),],~H,O.~~23 L.A. Sayce, J., 1929,2002; A., 1254.ar W. Kangro and R. Flugge, 2. Elektrochem., 1929,35,189 ; A., 664.25 W. H. Albrecht, Ber., 1929, 62, [B], 1475; A., 869; see also G. F. Huttig26 P. A. Thiessen and 0. Koerner, 2. anorg. Chem., 1929,180,65 ; A., 675.27 M. Le Blanc and E. Mobius, 2.physikaz. Chem., 1929,142, 151 ; A., 1028.28 J . PhyekZ Chem., 1929,33,1247; A., 1028.2* G. F. Huttig and R. Kassler, 2. anorg. Chem., 1929,184, 279.30 G. Natta, and L. Passerini, Gazzetta, 1929, 59, 280; A., 870.31 Idem, ibid., p. 620; A., 1930,20.32 S. Holgersson and A. Karlsson, 2. anorg. Chem., 1929, 183, 384; A.,33 E. G. V. Percival and W. Wardlaw, J . , 1929,1505; A., 1028.34 J . , 1902,81, 939.35 E. Brunner, Helv. Chiin. Acta, 1929,12, 208; A., 283.3b G. Jantsch and K. Abresch, 2. anorg. Chem., 1929,179, 346; A., 661.and H. Garside, 2. anorg. Ciiem., 1929, 179, 49; A., 510.140968 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The preparation of numerous amminated complex cobaltic com -pounds has been announced during the past year.Sometimes thestructures suggested for individual compounds do not seem veryprobable, and in many cases, since no analytical support for thecompounds is given, their very existence must be considered doubt-f ~ l . ~ ' The manner in which oxalic and malonic acids act ontetramminocobaltic complexes and analogous compounds has beenexamined by W. S~hramrn,~~ whilst some of the factors determiningthe stability of complex salts have been discussed by F. G. Mann.39Experiments are quoted which suggest that, in the action ofmagnesium phenyl bromide on anhydrous nickel chloride, the veryunstable nickel diphenyl is formed as an intermediate product,which is converted by hydrogen into nickel hydride, NiH,, andbenzene; in absence of hydrogen the products are nickel anddiphenyl.Nickel hydride suspended in ether can hydrogenateethylene slowly, and rapidly causes a mixture of ethylene andhydrogen to unite to form ethane.40 Amine derivatives of cobaltand nickel nitrites have been prepared, and the dissociation pressureof hexamminonickel nitrite has been measured between 15" and115"; the correspondence of the curve obtained with that foundby Ephraim for the supposed pentammine shows the latter to bemerely a mixture of hexammine and tetrammine.41A study of ruthenium chloride solutions has shown that the firstproduct of the action of concentrated hydrochloric acid on rutheniumtetroxide is Ru0,C12, which is rapidly reduced further to rutheniumtetrachloride ; this is unstable in solution, decomposing into eitherthe trichloride or the hydroxytrichloride. From pure solutions ofthe latter can be prepared the " hydrated pentachlororuthenates,"which are thus shown to be hydroxypentachlor~ruthenates.~~ Thehydrates of rhodium sulphate have been examined and czesiumrhodium alum has been prepared43 A number of complex pyridinederivatives of rhodium trichloride 44 and pyridine and ammoniaderivatives of iridium trichloride have been described, some of37 H.L. Riley, J., 1928, 2985; A., 41; S. H . C. Briggs, J., 1929, 685; A.,665; E. G. V. Percival and W. Wardlaw, ibid., p. 1317; A., 898; 5. Kranig,Ann. Chim., 1929, [XI, 11, 44; A., 527; C. Duval, Compt. rend., 1929, 188,176; A., 283; C. Duval and (Mme.) Duval, ibid., 189, 537; A., 1254; F.Job and L.0. Tao, ibid., p. 641 ; A., 1409.38 2. anorg. Chem., 1929, 180, 161; A., 780.3s J., 1929, 651 ; A., 678.40 T . Weichselfelder and M. Kossodo, Bey., 1929, 62, [ B ] , 769; A., 665.41 L. Le Boucher, Anal. Pis. Quirn., 1929,27, 145, 358; A., 781, 898.42 H. Remy and A. Luhrs, Ber., 1929,62, [B], 200; A., 283.43 F. Krauss and H. Umbach, 2. unorg. Chem., 1929, 180, 42; 182, 411 ;44 M. DelBpine, Bull. SOC. a h h . , 1929, [ivl, 45, 235; A., 781.A., 663, 1156INORGANIC CHEMISTRY. 69which exist in cis- and tr~ns-forms.~~ The complex ion, [Rh(CN),]"',is said to be very stable, contrary to previous reports in the liter-ature.& The sole product of the action of fluorine on powderediridium at 260" is the hexafl~oride~~ a very volatile, highly reactive,yellow substance, m.p. 44". Iridium tetrafluoride may be preparedby heating powdered iridiumwith the hexafluoride at 150". Lithiumplatinocyanide forms only one hydrate-the tetrahydrate-whichis said to exist in three differently coloured forms.48 A number ofcomplex platinum compounds have been obtained by the oxidationwith ammonium persulphate of Peyrone's salt and the greenMagnus salt .49Systems and Equilibria.Owing to the importance of phase-rule investigations for inorganicchemistry a list of systems which have been examined during thelast year is here given, in the order in which they appear in theabstracts, as was done in last year's Annual Report.Zinc oxide-water 50 ; calcium oxide-aluminium oxide ; calciumoxide-zirconium oxide ; aluminium oxide-zirconium oxide 51 ;lithium chloride-ammonia 52 ; cupric bromide-hydrobromic acid-water 53 ; ammonium sulphate-sulphuric acid-ethyl alcohol 54 ;ferrous chloride-water 55 ; sodium oxalate-sulphuric acid-sodiumsulphate (or oxalic acid)-water 56 ; iron-zinc 57 ; tungsten-carbon 58 ;ammonium sulphite-water 59 ; aluminium-copper-zinc 6o ; leadnitrate-ammonium nitrate-water 61 ; aluminium nitrate-potassium4 5 M. Delepine and J.Pineau, Bull. SOC. china., 1929, [iv], 45, p. 328 ; A., 781.46 F. Krauss and H. Umbach, 2. anorg. Chem., 1929,179, 357; A., 665.4 7 0. Ruff and J. Fischer, ibid., p. 161 ; A., 527.48 F. E. E. Germann and 0. B. Muench, J . Phyrrical Chem., 1929,33, 415;49 L. Tschugaev and J. Tscherniaev, 2.anorg. Chem., 1929, 182, 159; A.,50 A. Gutbier and H. R. Barfuss-Knochendoppel, ibid., 1928,176, 363; A.,51 H. von Wartenberg, H. Linde, and R. Jung, ibid., p. 349 ; A., 30.52 S. C. Collins and F. K. Cameron, J . Phyeical Chem., 1928,32,1705 ; A., 30.53 S. R. Carter and N. J. L. Megson, J., 1928,2954; A., 30.54 H. B. Dunnicliff, A. L. Aggarwal, and R. C. Hoon, J . Physical Chem.,66 F. Schimmel, 2. anorg. Chem., 1928,176, 285; A., 31.56 E. Elod and E. Acker, ibid., p. 305; A., 32.57 Y. Ogawa and T. Murakami, Tech. Rep. Tdhoku, 1928, 8, 53; A,, 141.58 K. Becker, 2. Metallk., 1928, 20, 437; A,, 141.50 F. Ishikawa and H. Murooka, Bull. Inst. Ph98. Chem. Res. Tokyo, 1928,6o M. Hamasumi and S. Matoba, Tech. Rep. Tdhoku, 1928,8,71; A,, 141.A., 527.1157.30.1928,82, 1697; A., 31.7, 1160; A,, 141.G.Malquori, Atti I I Cong. Naz. Chim. pura awl., 1926, I136 ; Chem. Zentr.,1928, ii, 617; A., 14170 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.nitrate-nitric acid-water 62; potassium chloride-ferric chloride-water ; aluminium chloride-ferric chloride-water 63 ; sodium nitrate-magnesium sulphate-water ; nitrates and sulphates of sodium (andpotassium)-water 65 ; thallons chloride-water-chloride of Cd (orHg", Zn, Mg, Ca, Sr, Ba) 66 ; manganese chloride-cobalt chloride ;cadmium chloride-cobalt chloride ; magnesium chloride-cobaltchloride 67 ; magnesium-zinc ; cadmium-gold 69 ; silver-cop-per 70 ; cobalt-sulphur-oxygen ; nickel-sulphur-oxygen 71 ; ca,lc -ium-sulphur-oxygen 72 ; iron-carbon-oxygen 73 ; ammonium sul-phite-ammonium sulphate-water 74 ; sodium nitrate-sodium chlor-ide-water 75 ; mercuric iodide-potassium iodide-acetone 76 ; cad-mium-lead chloride 77 ; lead acetate-lead chloride-acetic acid-water 78 ; sodium nitrate-sodium sulphate-magnesium chloride-water ; magnesium chloride-ferrous chloride ; cadmium chloride-ferrous chloride *O ; cesium sulphate-cerous sulphate-water 81 ;mercuric chloride-mercuric iodide-water 82 ; sodium nitrate-pot ass-ium nitrate-water 83 ; sodium-calcium 84 ; calcium oxide-zirconium62 G.Malquori, Gazxetta, 1928, 58, 781; A., 142.63 Idem, ibid., p. 891; A . , 267.64 W. Schroder, 2. anorg. Chem., 1928, 177, 71; 1929, 184, 63, 77; 185,153; A., 267; Caliche, 1929,11,154.65 E . Cornec and H.Krombach, ibid., 1928, 10, 396; A., 267.6 6 A. Benrath and G. Ammer, 8. anorg. Chem., 1928,177, 129; A., 267.6 7 A. Ferrari and A. Inganni, Atti R. Accad. Lincei, 1928, [vi], 8, 238; A .,6 s W. Hume-Rothery and E. 0. Rounsefell, Inst. Metals, March 1929,g9 P. J. Durrant, ibid.; A., 398.7o J. A. 4 . Leroux and E. Raub, 2. anorg. Chem., 1929, 178, 257; A..i 1 R. Schenck and E. Raub, ibid., p. 225; A . , 399.i 2 R. Schenck and I(. Jordan, ibid., p. 389; A., 399.i3 E. Jiinecke, ibid., p. 73; A., 399.74 F. Ishikawa and H. Murooka, Bull. Inst. Phys. Cliem. Res. Tokyo, 1929, 8,i 5 A. Chrktien and E. Cornec, Compt. rend., 1929,188, 628 ; A., 400.7 6 (Mlle.) M. Pernot, ibid., p. 635; 189, 326; A., 400, 1145. '' R. Lorenz and M. Hering, 2. anorg.Chem., 1928, 177, 1 ; A., 266; ibid.,1929, 178, 33, 40, 337; A., 400; R. Lorenz, G. Schulz, M. Hering, P. Wolff,and J. Silberstein, ibid., 179, 97; A., 510.i s K. Sandved, J., 1929, 337; A., 400.i 9 G. Leimbach and A. Pfeiffenberger, Caliche, 1929, 10, 447; 11, 61; A.,so A. Ferrari and M. Carugati, Atti R . Accad. Lincei, 1928, [vi], 8, 306; A.,81 I?. Zamboniniand S. Restaino, ibid., 1929,9,131; A., 610.82 (Miss) R. Sugden, J., 1929, 488; A., 610.83 E. Cornec and H. Krombach, Compt. rend., 1929, 188, 788; A., 510.388.Advance copy ; A., 398.399.75; A., 400.400, 1013.500.R. Lorenz and R. Winzer, 2. anorg. Chem., 1929,179, 281 ; A., 650INORGANIC CHEMISTRY. 71oxide 8 5 ; sodium sulphate-water-sulphate of Cu (or Mg, Zn, Cd,Mn, Fe.., Co, Ni) 86 ; sodium nitrate-potassium perchlorate-water 87 ;sodium chloride-potassium perchlorate-water 88 ; sodium nitrate-sodium chloride-potassium perchlorate-water.89CaO-CdO ; CaO-MnO ; CaO-Coo ; CaO-NiO ; CaO-MgO ;CoO-NiO ; CoO-MgO ; CoO-MnO ; CoO-CdO ; NiO-MgO ;NiO-MnO ; NiO-CdO 90 ; sodium nitrate-sodium sulphate-water 91 ; ferric nitrate-nitric acid-water 92 ; potassium nitrate-ferric nitrate-nitric acid-water 93 ; strontium oxide-phosphoricoxide-water ; barium oxide-phosphoric oxide-water 94 ; thalloussulphate-mercuric chloride, bromide, or iodide 95 ; thallous nitrate-potassium bromide 96 ; cadmium-antimony g7 ; chromium-nitrogen ;manganese-nitrogen 98 ; zirconium oxide-thorium oxide 99 ; am-monium nitrate-carbamide 1 ; cupric sulphate-ferrous sulphate-water ; sodium iodate-sodium chloride-water ; sodium andpotassium nitrates and sulphates-water ; aluminium nitrate-ferric nitrate-water ; potassium nitrate-ferric nitrate-water 5 ;lanthanum nitrate-manganese nitrate-water ; lanthanum nitrate-magnesium nit rat e-w at er ; manganese nit rat e-magnes ium nitrate-water ; ammonium hydrogen carbonate-water 7 ; aluminium-85 0.Ruff, F. Ebert, and E. Stephan, 2. anorg. Chem., 1929, 180, 215; A.,g6 A. Benrath and H. Benrath, 2. anorg. Chem., 1929, 179, 369; 183, 296;87 E. Cornec and A. Neumeister, Culiche, 1929, 11, 488 ; A., 650.88 Idem, ibid., p. 492; A., 650.89 Idem, ibid., p. 494; A., 650.90 G. Natta and L. Passerini, Gazzetta, 1929, 59, 129, 144; A., 639.9 1 A.ChrBtien, Compt. rend., 1929, 188, 1047; A., 651.92 G. Malquori, Atti R. Accad. Lincei, 1929, [vi], 9, 324; A., 651.93 Idem, ibid., p. 414; A., 651.94 H. V. Tartar and J. R. Lorah, J. Amer. Chem. SOC., 1929, 51, 1091; A.,95 N. K. Voskressenskaja, J. Russ. Phys. Chem. SOC., 1929, 61, 79; A., 651.96 A. P. Rostkovski, ibid., p. 89; A., 651.97 T. M u r a b d and T. Shinagawa, J . Study Met., 1928,5, 283; A . , 766.9s G. Vrtlensi, J. Chim. physique, 1929,26, 162, 202; A . , 664, 766.S9 0. Ruff, F. Ebert, and H. Woitinek, 2. anorg. Clzem., 1929, 180, 252;&4., 766; 0. Ruff, 2. angew. Chem., 1929,42,807; A., 1161.1 W. J. Howells, J., 1929, 910; A., 766.2 F. K. Cameron and H. D. Crockford, J. Physical Chem., 1929, 33, $09;3 H. W. Foote a.nd J.E. Vance, Amer. J. Sci., 1929, [v], 17,424; A., $67.4 E. Cornec, H. Krombach, and A. Spack, Compt. r e d . , 1929,188, 1250;5 G. Malquori, Atti R. Accad. Lincei, 1929, [vi], 9, 569; A., 767.6 C. di Capua, Gazzetta, 1929,50, 164; A . , 767.7 E. Janecke, 2. EEektrochem., 1929, 35, 332; A., 874.660; 0. Ruff,Z. angew. Chem., 1929,42, 807; A , , 1161.d., 650, 1238.651.A., 767.A., 76772 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.copper-nickel * ; iron-molybdenum ; cupric oxide-sulphur tri-oxide-water 10 ; calcium oxide-carbon dioxidesilica 11 ; aluminium-antimony-silicon ; aluminium-antimony-copper 12 ; sodium andpotassium carbonates and hydrogen carbonates-water l3 ; zincsulphide-zinc sulphate-zinc oxide-sulphur dioxide l4 ; copper-aluminium-tin (or cobalt) l5 ; copper-beryllium l6 ; silver-ger-manium l7 ; cobalt chloride-ferrous chloride ; manganous chloride-ferrous chloride l8 ; Na20-N205-HC1-H20 ; K20-N20,-HCl-H20 ;Na20-K20-N20,-H20 ; Na20-K20-HC1-H20 l9 ; gold-mercury 2o ;iron-vanadium 21 ; calcium and sodium and their chlorides 22 ;silver chloride-potassium iodide 23 ; sodium oxide-boric oxide-sodium chloride ; sodium oxide-boric oxide-sodium bromide 24 ;lithium chlorate-water 25 ; lead chloride-lead fluoride (or lithargeor lead iodide, or silver chloride, or cuprous chloride); mercuriciodide-cadmium iodide (or mercurous iodide) 26 ; sodium hydrogencarbonate-potassium hydrogen carbonate-water 27 ; potassiumcarbonate-potassium sulphate-water 28 ; uranyl formate-formicacid-water 29 ; sodium thiocyanate-water (or methyl or ethylH. Nishimura, Suiyokaishi, 1928, 5, 616; A., 883.T. Takei and T. Murakami, Sci. Rep. Tdhoku Imp~Univ., 1929,18, 135;A., 884.lo E. Posnjak and G. Tunell, Amer. J. Sci., 1929, [v], 18, 1 ; A., 884.l1 G. F. Hiittig and E. Rosenkranz, 2. Elektrochem., 1929, 35, 308; A.,l2 T. Matsukawa, Suiyokaishi, 1928, 5, 596; A., 884.l3 A. !E. Hill and S. B. Smith, J. Amer. Chem. SOC., 1929,51, 1626; A.,l4 M. Trautz and S. Pakschwer, J. pr. Chem., 1929, [ii], 122, 147; A., 884.l5 E. Morlet, Compt. rend., 1929, 189, 102; A., 995.l6 G. Masing and 0. Dahl, Wise. Ver6fl. Siemens-Konz., 1929, 8, (l), 94;l7 T. R. Briggs, R. 0. McDuffie, and L. H. Willisford, J. Physical Cheni.,1 8 A. Ferrari, A. Celeri, and F. Giorgi, Atti R. Accad. Lincei, 1929, [vi], 9,l9 V. I. Nikolaev, 2. anorg. Chem., 1929,181, 249; A., 1010.2O A. A. Sunier and B. E. Gramkee, J. Amer. Chem. SOC., 1929, 51, 1703;21 S. Oya, J. Study Met., 1928, 5, 349; A., 1012.22 R. Lorenz and R. Winzer, 2. anorg. Chem., 1929,181, 193; 183, 127; A.,23 A. P. Rostkowski, J. Ruaa. Phye. Chem. Soc., 1929, 61, 595; A., 1012.24 B. Stglhane, 2. Elektrochem., 1929, 35, 486; A., 1012.25 L. Berg, 8. anorg. Chem., 1929, 181, 131; A., 1145.2fj H. PBlabon and (Mme.) Lande, BUZZ. SOC. chim., 1929, [iv], 45, 488;2 7 IS. E. Oglesby, J. Amer. Chem. SOC., 1929, 51, 2352; A., 1145.28 A. E. Hill and S. Moskowitz, ibid., p. 2396 ; A., 1145.2Q A. Colani, Bull. Soc. chim., 1929, [iv], 45, 624; A,, 1238.884.884.A., 985.1929, 33, 1080; A., 996.782; A., 996.A., 874; I. Plaksh, J. Ruse. Phys. Chem. SOC., 1929,61,621; A., 1012.1012, 1238.A., 1145INORGANIC CHEMISTRY. 73alcohol, or acetone) 30 ; sodium ferrocyanidewater 31 ; lithiumsulphate-water 32 ; lithium thiocyanate-water 33 ; leucite-diops-ide 34 ; nitrates and chlorides of sodium and potassium-water 35 ;sodium nitratesodium chloride-sodium sulphate-water 36 ; alumin-ium chloride-ferric chloride-potassium chloride-hydrogen chloride-water 37 ; sodium sulphide-ferrous sulphide 38; potassium meta-silicate-silica 39 ; chromium-carbon 40 ; sodium and potassiumnitrates, chlorides, and sulphates-water 41 ; copper-zinc 42 ; potass-ium nitrate-magnesium sulphate-water ; silver-zinc 44 ; magnesiumsulphate-sodium nitrate-water 45 ; sodium iodate-sodium nitrate-water 46 ; strontium oxide-sucrose-water.47H. BASSETT.30 0. L. Hughes and T. H. Mead, J., 1929,2282; A., 1375.31 J. A. N. Friend, J. E. Townley, and R. H. Vallance, ibid., p. 2326;32 J. A. N. Friend, ibid., p. 2330; A., 1375.33 V. I. Nikolaev, J . RU88. Phy8. Chem. SOC., 1929, 61, 939; A., 1387.34 N. L. Bowen and J. F. Schairer, Amer. J. Sci., 1929, [v], 18, 301; A.,35 E. Cornec and H. Krombach, Caliche, 1928,10, 153 ; Chem. Zentr., 1929,38 A. Chrhtien, Ann. Chim., 1929, [x], 12, 9 ; A., 1388.37 G. Malquori, Qazzetta, 1929,59, 656; A., 1388.38 L. V. Steck, M. Slavin, and 0. C. Ralston, J. Amer. Chem. SOC., 1929, 51,38 F. C. Kracek, N. L. Bowen, and G. W. Morey, J . Physical Chem., 1929,33,40 R. Kraiczek and F. Sauerwald, Z. anorg. Chem., 1929,185, 193.41 E. Cornec and H. Krombach, Ann. C h k . , 1929,l2, 203; Calkhe, 1928,42 R. Ruer and K. Kremers, Z . anorg. Chern., 1929,184, 193.r a A. and H. Benrath, ibid., p. 359.44 B. G. Petrenko, ibicl., p. 369; G. J. Petrenko, ibid., p. 376; G. J. and45 A. Benrath and co-workers, Cdiche, 1929,11,99 ; A., 1930, 36.46 H. W. Foote and J. E. Vance, Arner. J. Sci., 1929, [v], 18,375 ; A., 1930,47 W. Reinders and A. KIinkenburg, Rec. trav. chirn., 1929, 48, 1227; A.,A., 1375.1388.i, 2740; A., 1388.3241 ; A , , 1930, 36.1867.10, 250; Chem. Zentr., 1929, i, 2741; A,, 1388.B. G.Petrenko, ibid., 185, 96.36.1930, 36

ISSN:0365-6217    

DOI:10.1039/AR9292600034

出版商:RSC    

年代:1929

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ORGANIC CHEMISTRY.PART I.-ALIPHATIC DIVISION.Space Formulce of Simple Carbon Compounds.SOME early work on the crystalline structure of pentaerythritolseemed to point to a pyramidal grouping of the four CH,*OH groupsround the central carbon atom, in place of the usually acceptedtetrahedral clistribution. Although this conclusion was not sup-ported by the whole of the crystallographic data,3 there appeared tobe sufficient evidence, both in this case and in that of methane, toraise a question of fundamental importance in stereochemicalthe or>-.On the chemical side the constitution of the substance asC(CH,*OH), has been confirmed by its transformation into pp-di-methylpropane-~ty-diol,~ the structure of which is known. Anattempt has been made by J.Boeseken and B. B. C. Felix to decidebetween t,he tetrahedral and the pyramidal configuration by formingcompounds of the type C(<CH~eo>CRR’),, CH -0 which are obtained bythe condensation of pentaerythritol with 2 molecules of an aldehyde,ketone, or ketonic acid. If the configuration is tetrahedral, thecondensation compound must be dissymmetric and capable ofresolution ; but if pyramidal, cis-trans isomerism will be encountered.Experiment showed that it was possible to resolve the acid -C(<CH:.-,>CMe*CO,H), CH *O obtained by condensation of pentaery-thritol \&th ethyl pyruvate and hydrolysis of the resulting ester.This resolution, as is pointed out by A. SemenzovY6 does not byitself establish the tetrahedral structure of pentaerythritol, sinceon examination the pyramidal model of the trans-form of the con-densation product is seen to be dissymmetric.It has been suggestedalso that chemical methods are not suitable for testing the validityof I’CTeissenberg’s principle, owing to the possibility of transformationH. Mark and K. Weissenberg, 2. Physik, 1923, 17, 301 ; A., 1923, i, 1055.See Awn. Reports, 1927, 24, 290.K. Weissenberg, Ber., 1926, 59, [ B ] , 1526; A . , 1926, 934.H. Bincer and K. Hess, Ber., 1928, 61, [ B ] , 537; A , , 1928, 504.Ibid., pp. 787, 1855; 1929, 62, [B], 1310; A., 1928, 616, 1213; 1929,Ibid., 1929, 62, [B], 514; A., 638.791ORGANIC CEEMISTRY .-PART I. 75fo a tetrahedral configuration during the reaction.' In reply,Boeseken and Felix maintain that enantiomorphs of the pyramidaltype would be so labile as to render their isolation most improbable.The accomplished resolution of the sole reaction product, togetherwith the failure to detect any trace of cis-trans isomerides, maytherefore be taken as evidence in favour of the tetrahedral con-figuration. A recent crystallographic examination of the tetra-acetate of pentaerythritol by the X-ray method tends to confirmthis view.*Crystal analysis of solid methane has failed to provide evidence ofthe occurrence of pyramidal molecules and here also tetrahedralsymmetry is enco~ntered.~ There is some evidence that two of theC*H linkings in methane differ slightly from the other two,1° but theinequality, although perhaps sufficient to account for the electricmoment and the infra-red absorption spectrum of methane, ispresumably not great enough to be recognised as a non-equivalenceof valency from the chemical point of view.If the carbon valencies show perfect tetrahedral symmetry, theangle between each pair will be 109" 28', a.nd in certain long-chainaliphatic compounds this value appears to be very nearly preservedin the angles formed by the lines joining the centres of successivecarbon atoms.ll On the other hand, the results of an X-rayexamination of a series of fatty acid salts demand a minimum angleof 11 1 O 46', and it is possible that even in these comparatively simplecases, in which the carbon chain appears to be zig-zag in shape, theangle throughout the chain may be dependent on the nature of theend groups.12 It is probable, therefore, that in almost all carboncompounds a departure from the exact value of the tetrahedral angleis to be expected.13Partly Xubstituted Glycerols.Comment mas made in an earlier Report l4 on the uncertaintyattaching to the structure of the alleged P-monoacyl derivatives ofglycerol.Many additional examples of the wandering of substituentacyl groups within the glycerol molecule have come to light recentlyand, although methods are now available for the synthesis of trueJ. Kenner, Ber., 1928, 81, [B], 2470; A., 171.* (Miss) I. E. Knaggs, Proc. Roy. SOC., 1929, [A], 122, 69; A., 246.9 J. C. McLennan and W. G. Plummer, PhiE. Mag., 1929, [vii], 7, 561 ; A , ,lo G. W. Brindley, Nature, 1929, 123, 760; A., 629.l1 A.Muller, Proc. Roy. SOC., 1929, [ A ] , 124, 317; A., 869.l2 S . H. Piper, J., 1929, 234; A., 383.18 Compare B. V. Nekrassov, J . Ruse. Phys. Chern. SOC., 1928, 60, 19; A.,l4 Ann. Reports, 1927,24, 90.750.1928, 61376 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.p-acyl derivatives,lS the situation regarding the disubstitutedderivatives is still confused, several supposed ap-derivatives havingbeen found to be identical with their ay-isomerides.16 For example,it has been proved that the supposed ap- and ay-diphthalimido-derivatives of glycerol, prepared according to the schemes outlinedbelow, are identical, as are also the monoacetates and monobenzoatesof the c+- and ocy-diphthalimido-derivatives, which have beenprepared by independent methods. On the other hand, differentdibromohydrin p-nitrobenzoates have been obtained, and a similarseries of reactions served to produce different dibromohydrinQH-OY +-- QH*OH YH --+- QHBr + YHBrCH,*OH CH,*OH CH,*OY CH,Br CH,Br(Y = *CO*C6H4DN02) Not identicalpalmitates.The latter substances reacted, however, to giveidentical di-p-nitrobenzoates. In many of these transformationsmigration of an acyl group must have occurred, rendering theallocation of structural formuls difficult and uncertain. Theconclusion was reached by Fairbourne and Cowdrey that the onlyabsolute proof of unsymmetrical structure, in disubstituted deriv-atives of glycerol, is furnished by resolution into optically activeand these authors suggest that in the absence of suchevidence it is reasonable to assume that, when a disubstitutedglycerol exists as two isomerides, these have the structures of theirrespective parent substances, but that in all other cases conversionma,y have occurred.The cyclic acetals derived, from glycerol furnish even greaterpossibilities for complex behaviour.It was thought a t one timethat when an aldehyde, R-CHO, condenses with glycerol, only theap-liydroxyl groups of the latter react, giving a cyclic acetal with afive-membered ring.18 Recent work has shown, however, that inl5 B. Helferich and H. Sieber, 2. physiok. Chem., 1928, 175, 311; A., 1928,734.1 6 A. Fairbourne and G. W. Cowdrey, J., 1929, 129; A., 292; compareH. Hibbert and N.M. Carter, J . Amer. Chem. SOC., 1929, 51, 1601; A., 791.l7 Compare M. Bergmann, 2. physbz. C?bem., 1924, 137, 47; A., 1924, i,932.l8 J. C. Irvine, J. L. A. Macdonald, and C. W. Soutar, J., 1916,107, 337.p 2 B r QH2Br QH2Br QJ32Br GH2\VORGANIC CHEMISTRY.-PART I. 77reality there is a partition of the aldehyde between the aP- andthe ay-hydroxyl groups with the formation of both five-memberedand six-membered rings. In such cases there is not only thepossibility of transformation from one ring form to the other, butalso the added complication that the cyclic acetals of glycerol maypossess geometrical and optical, in addition to structural, isomerism. l9It is obvious, for instance, that (A) can givetwo geometricisomerideswhich are resolvable racemic forms owing to the presence of thetwo centres of dissymmetry (*), and that (B) should exist in twogeometrically isomeric but non-resolvable modifications.In view of this intricacy it is particularly satisfactory to find thatin certain cases a complete solution of the problems presented by thestructural and geometric isomerism of these acetals has beenachieved.If formaldehyde is condensed with glycerol, geometricisomerism corresponding to formuh (A) and (B) becomes impossible(R = H) and two structurally isomeric methylene glycerols shouldexist, one of which ought to be resolvable. In accordance withtheory a mixture of the czp- and ay-methylene glycerols was obtainedwhen trioxymethylene was condensed with glycerol.20 The iso-merides were separated as the benzoyl derivatives and the structuresof the latter compounds were proved by removal of the benzoylgroup, followed by methylation to the corresponding monomethylethers, the subsequent hydrolysis of which gave respectively thea- and the p-methyl ether of glycerol. The reactions involved inthe case of the ay-compound are summarised in the followingformulae. A similar series holds for the racemic ap-compound, thepartial resolution of which was effected by D.H. Peacock 21 severalyears ago.It is to be noted that in the presence of a trace of acid the ctg-acetalreadily isomerises into the ay-derivative, the six-membered ringH. Hibbert and N. M. Carter, J . Amer. Chm. SOC., 1928,50, 3120; A.,47.20 Idern, ibid. 21 J., 1915,107, 816; A., 1915, i, 76778 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.being therefore the more stable under these conditions.In alkalinemedia no evidence of a tendency to isomerise was obtainable.Condensation of glycerol with p-nitrobenzaldehyde 22 givesp-nitrobenzylidene derivatives corresponding to formulze (A) and(B) above (R = C6H,*N0,). I n this case structurally differentisomerides were readily isolated and certain derivatives of these,namely, the benzoates, the p-nitrobenzoates, and the methyl ethers,were found to show the maximum number of isomerides theoreticallypossible, ie., two racemic geometric isomerides containing a five-membered ring, and two geometric isomerides containing a sis-membered ring. The proof of ring structure was again obtained bythe methylation method and depended on the identification of theglycerol monomethyl ether left after removal of the p-nitrobenzylid-eiie group, Both the ap- and the ay-p-nitrobenzylidene glycerolunderwent rapid isomerisation in the presence of 0.01 yo of hydrogenchloride, giving in each case an equilibrium mixture which containedthe two forms in the proportion of five parts of the a[3- to one partof the ay-compound.The utilisation of the methyl ethers of glycerol as referencesubstances for the determination of configuration in the glycerolseries may now be expected to give important information concern-ing the structure of the disubstituted glycerols. Hitherto themethylation method was unavailable in such cases owing to thesupposed impossibility of obtaining the p-monomethyl ether.Anattempt to prepare this substance was made by H. S. Gilchrist andC. R. P ~ r v e s , ~ ~ who utilised the following series of reactions :, I I I CH,Cl CH,C1 CH,*OAc CH,*OHThey identified their product (erroneously) as glycerol a-methylether, alleging that the ay-dichlorohydrin might be interchangeablewith itrs a@-isomeride, or alternatively that migration of a methylether group had occurred. Both these hypotheses must be regardedon many grounds as highly improbable.** A satisfactory solutionof the difficulty has now been provided by the preparation of thetrue ?-methyl ether of glycerol,25 which was obtained by the hydro-A . , 22 H. Hibbert and N. 31. Carter, J. Amer.Chem. SOC., 1928, 50, 3376;23 J . , 1925, 127, 2735; A., 1926, 163.24 J. B. Conant and 0. R. Quayle, J . Amer. Chem. SOC., 1923,45, 2771 ; A . ,1924, i, 7 ; A. Fairbourne and G. W. Cowdrey, Zoc. cit. ; compare H. Hibbert,31. E. Platt, and N. M. Carter, J . Amer. Chem. SOC., 1929, 51, 3644.25 H. S . Hill, M. S. Whelen, and H. Hibbcrt, J. Arner. Chem. SOC., 1928, 50,2238 ; A., 1928, 1213.170ORGANIC CHEMISTRY .-PART I. 79lysis of ay-benzylidene glycerol p-methyl ether, and by the subse-quent proof that the compound isolated by Gilchrist and Purves wa.sin fact the @-ether and not, as they supposed, the ct-derivative.26Useful codrmation is thus given of conclusions reached by H.Hibbert, &I. S. Whelen, and N. M. Carter 27 to the effect that themethyl ethers of glycerol and other polyhydric alcohols are stablesubstances which display no liability to isomerise by migration ofmethyl groups and therefore are eminently suitable for use asreference compounds.Of other methylated glycerols required as reference compounds,the a-monomethyl ether and the apy-trimethyl ether 28 clearly havethe structures ascribed to them, but there is some confusion inthe literature concerning the two dimethyl ethers.A supposeda@-dimethyl ether was prepared by Gilchrist and Purves by theaction of sodium methoxide on glycerol ay-dichlorohydrin. Theseauthors believed that isomerisation took place during the reaction,but a repetition29 of their work has shown that their product isidentical with the ay-dimethyl ether of glycerol prepared byZunin0.~0The reaction between the chlorohydrin and sodium methoxidetherefore follows a normal course without involving isomerisation,and the important conclusion may be drawn that the chlorohydrins,so far from being unsuitable initial materials for the preparationof glycerol ethers, can be made to yield at will either a- or a-ethers.By taking advantage of this discovery i t may be anticipated thatthe true glycerol a@-dimethyl ether required to complete the seriesof reference compounds will be obtainable by the methylation andsubsequent hydrolysis of glycerol a-rnono~hlorohydrin.3~It is of interest that ethers of glycerol occur in nature, forming alink between the fats and the waxes.Batyl alcohol, which occursin the liver of certain elasmobranch fish, along with selachyl alcoholand squalene, has beenlshown to be either the a- or the p-mono-glyceryl ether of octadecyl alcohol, having one or other of thefollowing structures :Treatment of batyl alcohol with hydriodic acid gives crystallineoctadecyl iodide, the identity of which was confirmed by its trans-26 A.Fairbourne, J., 1929, 2232; A., 1422.21 J . Amer. Chem. SOC., 1929, 61, 302; A., 292.28 J. C. Irvine, J. L. A. Macdonald, and C. W. Soutar, Zoc. c i t . ; H. G.2s A. Fairbourne, J., 1929, 1161; A., 1038.30 Atti R. Accad. Lincei, 1897,6, 348; A., 1899, i, 410.31 A. Fairbourne, J., 1929, 2234; A., 1422.Gilchrist and C. B. Purves, Eoc. cit80 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.formation into octadecyl alcohol.The second of the two possibleformulae is favoured by the authors 32 on account of the ease withwhich the diacetyl derivative and the phenylurethane of batylalcohol are formed.Since batyl alcohol is the saturated dihydro-derivative of selachylalcohol, the latter substance, which gives nonoic acid on oxidationwith potassium permanganate, can be represented by a formulasimilar to one of the above but with the oleyl group,CH,. [CH,] ,*CH:CH*C,Hi 6, -in place of C,,H,,.Xtructure of the Quadrivalent Derivatives of Tellurium.Few instances are known in which the existence of isomerismamong quadrivalent compounds of an element requires the postul-ation of a planar distribution of the four valencies and a cis- andtrans-arrangement of the addenda.Up to the present the com-pounds of quadrivalent tellurium and platinum have been the chiefof these, the evidence in the case of tellurium resting mainly on thework of Vernon,33 who obtained two forms of dimethyltelluroniumdi-iodide and of the corresponding base. Similar results wereobtained with the dibromide and the dichloride and two distinctseries of substances were recognised, designated respectively a- andp-, the isomerism of which was explained by means of the cis-transarrangements of groups shown in the plane formulae (I) and (11).(I.) a-Di-iodide. (11.) /3-Di-iodide.Such a case was clearly exceptional and a re-examination of thewhole problem by H. D. K. Drew has resulted in an importantpaper, in which it is shown that corresponding compounds of thea- and p-series are not stereoisomeric but are structurally different.The a-compounds are of the normal type and in these tellurium hasin all probability a tetrahedral valency distribution.Tellurium,therefore) ceases to be an exception to the general rule of the tetra-hedral distribution of valencies. Compounds of the p-series are,on the other hand, complex salt-like substances which are polar incharacter in contrast with the broadly non-polar nature of thea-substances. Similar general conclusions may be held to apply tothe ethyl and other homologues.Vernon’s p-base is a mixed anhydride of formula TeMe,*O*Te&IeO,32 I. M. Heilbron and W. M. Owens, J . , 1928, 943; A , , 1928, 616.33 R.H. Vernon, J., 1920,117,86,889; 1921,119,687; (Miss) I. E. Knaggs34 J., 1929, 660; A . , 649.and R. H. Vernon, J., 1921,119,106ORGANIC CHEMISTBY.-PART I. 81which gives on treatment with hydrogen iodide the easily separablesubstances TeMe,I and MeTeO-OH. The latter is readily convertedby an excess of hydrogen iodide into methyltelluronium tri-iodide,TeMeI,, which in turn readily combines with TeMe,I to give Vernon’sp-di-iodide, TeMe,I*TeMeI,. Experiments with the correspondingbromides and mixed p-dihalides containing both bromine and iodinehave led to the view that the constitution of the salts can be mostcorrectly represented by the general formula Me,Te . . . . . . TeMeX, ,corresponding to the co-ordination formula me,Te]TeMeX,, whereall the halogens and alkyl groups are linked covalentlywith tellurium.Support for this is found in the fact that the p-di-iodide and potass-ium iodide give, in acetone solution, trimethyltelluronium iodide anda substance which is probably the salt [TeMe14]K.On dissociationby moisture the latter yields potassium iodide and-methyltelluroniumtri-iodide.The conversion of the a- into the p-base must involve the wander-ing of a methyl group from one tellurium atom to another and it issuggested by Drew that this may take place through the anhydride,HO*TeMe2*O*TeMe2*OH (A), which gives the p-base as the resultof a molecular re-arrangement similar to the pinacol-pinacolintransformation :- +(A) --+ Me,Te<g>TeMe2 --+ Me,Te-O-TeMeOIn the course of earlier work on the properties of quadrivalenttellurium compounds T.M. Lowry and P. L. Gilbert35 extendedVernon’s observations to the corresponding diethyl derivatives andseemed to favour the view of the non-equivalence of the coplanarhalogen-tellurium valency linkings. They now accept Drew’s mainconclusions, for which they find additional support in the resultsof an extensive series of physico-chemical measurement^,,^ butconsider that the contrast between the a- and p-compounds is notsufficient to identify the P-ealts as necessarily containing always thecomplex ion and the a-salts as invariably monomeric.The Walden Inversion.Although many hypotheses have been advanced to explain themechanism of the Walden inversion, it is unfortunately the casethat none of them will account adequately for all the facts. In oneof the more recent attempts to evolve a general theory a suggestionis made that the result is dependent on the reaction distance B-Y35 J., 1928, 307, 1997, 3179; A., 1928, 349, 1098; 1929, 179.s6 J., 1929, 2076; A., 121882 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY."\C/in the molecule BY which reacts with the inolecule b-C-X togive CabcY.If the length B-Y is large compared with C-X, theninspection of models shows that rearrangement is likely to occurand the reaction will be accompanied by in~ersion.~' It is difficult,however, to account on this basis for phenomena such as the influenceof the solvent.A new method of approach to the problem is being explored byH.N. K. Rordam,38 who has advanced a reaction mechanism whichis susceptible to mathematical treatment and is capable, therefore,of being tested quantitatively. The reacting molecule (I) is sup-posed, in the first stage, to split off the group E.(1.1 +D/ EB.. . . * . q A B.. .:A 43 Owing to the disturbance, oscillation then begins in the directionsindicated by the arrows and the incidence of a Walden inversiondepends on whether the entering ion or radical X takes up itsposition when D is on the right or left of the plane ACB. If the timeof oscillation and the concentrations and activities of the com-ponents be known, it is possible to found a quantitative theory andto predict the amount of inversion which will take place in a givenreaction. With the aid of Bronsted's equation for reaction velocitiesthe equation finally obtained is n = k C x f ~ f i / f ~ z , in which n is thefraction of the reaction product retaining the original configuration,C, is the mean concentration of X at the beginning and the end ofthe reaction, fi, f,, and f l X are the activity coefficients of the oscillat-ing molecule, of X, and of the resulting compound, respectively.The activity coefficients are not known directly, but certain probableassumptions are made concerning them.From the point of view of the oscillation hypothesis two distincttypes of reaction are to be expected.Reactions of type I involvethe splitting of the optically active molecule either spontaneouslyor by the action of some molecule which is neither identical with norcontains the entering radical.This type includes the reactionbetween bromosuccinic acid and the xanthogenates 39 and also allreactions where halogen linked to an asymmetric atom is replacedby hydroxyl or other ions or under the influence of such ions. Toall such reactions the theory indicated above applies, and in all caseswhere sufficiently accurate experimental data are available the37 B. Holmberg, Ber., 1926, 59, [B], 125; A., 1926, 384.38 J., 1928, 2447; 1929, 1282; A., 1928, 1215; 1929, 1041.as B. Holmberg, loc. citORGANIC CHEMISTRY .-PART I. 83agreement between theory and experiment is good. The conceptionof the Walden inversion here advocated leads to the conclusion that,in reactions of type I, that form of the reaction product whichincreases in amount with increasing concentration of the enteringradical possesses the same configuration as the original substance.It may be possible, therefore, to use this method as a means ofdeciding which forms of related substances have similar configur-ations, and, in view of the great importance of the latter problemand the state of confusion in which it has rested, the further develop-ment of Rordam’s work will be awaited with much interest.The second type of reaction considered by this author comprisesthat in which the splitting of the active molecule is caused directlyby the molecule containing the entering radical.Possibly an addi-tive compound is formed and, since in that case the entering radicalmust always be a t very nearly the same distance from the vacantposition on the asymmetric atom, replacement can be expected tooccur only at one phase of the oscillation.Inversion may, or maynot, occur, depending on the structure of the molecules and theperiod of oscillation, but as all the factors have constant values,only one stereoisomeric form of the product is to be expected. Tosuch reactions the theoretical treatment outlined above cannot beapplied. As examples the following may be cited : the replacementof hydroxyl groups by halogen by means of phosphorus penta-chloride, thionyl chloride, or nitrosyl bromide. In certain specialcases (the action of nitrosyl bromide on active amino-compounds)it is possible that a transition stage between types I and I1 is to befound.The more restricted problem of determining at what stage in aseries of reactions a VC‘alden inversion takes place continues toengage much attention.The difficulty here lies in the lack ofmethods for correlating the configurations of different compounds ;for when an optically active substance is transformable a t will intooppositely rotating forms of the same reaction product it is rarelypossible to say more than that a Walden inversion has taken placein one of the reactions. R. Kuhn and T. Wagner-Jauregg40 nowpropose for the elucidation of configuration a novel method whichis not dependent on the comparison of optical properties, and bymeans of which they have worked out the relationships in the seriescomprising tartaric acid, malic acid, and the halogenated succinicacids.They have shown,41 in the first place, that in conformitywith theory but contrary to the work of A. Sonn and W. Rosiiiskg,4240 Ber., 1928, 61, [B], 504; A., 1928, 506.41 Idem, ibid., p. 481 ; A., 1928, 606.42 Ibid., 1925, 58, [B], 1688; A., 1925, i, 133784 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.there are four active chloromalic acids, the configurations of whichhave been ascertained by comparing the physical properties of theracemic forms with those of the r- and meso-forms of the dichloro-and dihydroxy-succinic acids. A similar comparison was institutedwith the corresponding esters. The " meso- "structure (I) isascribed to that dZ-chloromalic acid the properties of which are onthe whole intermediate between those of mesodichloro- and meso-dihydroxy-succinic acids, and the " rac " structure (11) to thedl-chloromalic acid with properties intermediate between those ofr-dichloro- and r-dihydroxy-succinic acids.(p2H 902H YO2H QO2HH*Y*OH H0-Y.H H*Y*OH H0Y.HH*Q*Cl C1.Q.H Cl*(i*H H*?*ClC02H C02H CO,H CO,HI-chloro- d-chloro- d-chloro- I-chloro-d-hydroxy- I-hydroxy- d-hydroxy- I-hydroxy-\ 2 \ v v 1(I.) Chloromalic acid.(11.) Chloromalic acid.The dextrorotatory form of chloromalic acid (I) is thus regardedas composed of a half-molecule of I-tartaric acid and a half-moleculeof d-dichlorosuccinic acid and, since the latter is dextrorotatory(see below), it follows that the sign of rotation of the chloromalicacids is governed by the position of the halogen atom.The relationship of the chlorosuccinic acids to d( +)-malic acid,to which all stereochemical formula are referred, is determined inthe following way.It is supposed that a halogen atom is introducedp 2 H 702H QOZHH*(i*H C1.F-H H- 421H*(i*OH H*Q*OH €€*T*OHC0,H C02H C0,H(1.1 (11.) (111.)into (I), which already contains the hydroxyl group of d(+)-malicacid. The halogen may be introduced in either of two ways, makingthe upper carbon atom either d- or Z-. The compounds so formedmay be referred to as (g) and (A) respectively, where small lettersrefer to the dissymmetric centre to which the halogen is attached,and capital letters refer to the centre to which the hydroxyl groupis joined.Now the first of these chloromalic acids (g) must beintermediate, in the totality of its physical properties, between theCompounds (g), i.e., tartaric acid, and , i.e., d-dichlorosucciniORGANIC CHEMISTRY.-PART I. 85acid. Similarly the second chloromalic acid must lie betweenmesotartaric acid and mesodichlorosuccinic acid . All thecomparisons of physical properties can be made with the racemicforms of the acids. Since the configuration of the inactive chloro-malic acids has been established and the position of the hydroxylgroups in the active chloromalic acids has been determined by theirconversion into malic acids (see above), it is possible to decide atonce whether Walden inversion occurs during the transformationof d-tartaric acid into chloromdic acid.For example, methyl&I-wmochloromalate, which occupies an intermediate positionbetween (IV) and (VI), is converted into methyl r-dichlorosuccinate(VII) on treatment with thionyl chloride. Direct replacement(26) Qc1 HO(VII.)/OH(VIII. )icl OH 1;:PI.1:; IC1W.) (V.1would have involved the conversion of (V) into the meso-form (IV),and it follows that a Walden inversion has taken place. Similarlyethyl d-tartrate (VIII) yields the " rneso "-chloromalic ester (V) bythe action of thionyl chloride in pyridine solution, and here againinversion must have occurred. There is, therefore, a doubleinversion during the passage of d( +)-tartaric acid into laevorotatorydichlorosuccinic acid, which must in consequence belong to theZ-series and should be termed I( - )-dichlorosuccinic acid.Althoughdirect conversion of an active dichloro- into a monochloro-succinicacid could not be accomplished, a comparison of the rotations of theacids and of their esters under various conditions as to solvent andtemperature leads to the conclusion that ( - )-monochlorosuccinicacid is configuratively related to the I( -)-dichloro-acid. Thefollowing cycle of transformations therefore involves inversion duringthe reaction with phosphorus pentachloride but not during that withsilver oxide. It will be noted that with respect to the configurationof (+)-chlorosuccinic acid the results are opposed to those ofG. W. Clough,& whose fundamental postulate is criticised.d( +)-Chlorosuccinic acid-Y%d( + ) -Malic acid 3z I( -) -Malic acid \ I( -)-Chlorosuccinic acid F43 J., 1916,107,1609; 1918,113,626; 1926,1674; A., 1915, ii, 811 ; 1918,ii, 266; 1926, 93786 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.In the same paper many transformations in the maleic-fuiuaricacid series are described, accurate quantitative data being given.It is found, for example, that addition of hypochlorous acid t ofumaric acid occurs mainly (80%) in the tmns-position and thatchloromaleic acid is formed from mesochloromalic acid by a processinvolving trans-elimination of water and molecular transformation.Contrary to the results of E.M. Terry and L. Ei~helberger,~~ sodiumfumarate gives more than 80% of mesodichlorosuccinic acid by theaddition of chlorine in the presence of sodium chloride.Additive reactions at an ethenoid bond have been studied fromthe point of view of energy relationships,45 the examples chosenbeing the hydrogenation of the sodium salts of dimethyl-fumaricand -maleic acids in aqueous solution and the hydrogenation of thestereoisomeric py-diphenyl- As-butenes in various solvents.Homo-geneous addition is the exception rather than the rule and often, bysuitable choice of conditions and reaction velocity, cis- or tram-addition may be made to predominate at will. The course of theaddition process is controlled by the differences in energy of theproducts and of the cis- and trans-initial materials, and by the rateof addition.Returning to the question of the configurational relationships,K.Freudenberg and L. Markert 46 have attempted to determine theconfiguration of the a-bromopropionic acids by comparison of theoptical behaviour of the esters, chlorides, and substituted amideswith the corresponding compounds of d-methoxy-, acetoxy-, benzoyl-oxy- and p-toluenesulphonyloxy-propionic acid. On the assumptionthat analogous compounds of similar configuration suffer correspond-ing rotational displacements when subjected to the same changes,i t is deduced from the experimental results that the laevorotatorya-bromopropionic acid is related to I( -)-malic acid. Similarly, acomparison of optical properties indicates that ( - )-bromosuccinicacid belongs to the Z-series. In conjunction with the work ofR.Kuhn and T. Wagner-Jauregg (see above), these and earlierresults enable K. Freudenberg and A. Lux 47 to regard the followingseries as definitely established : Z( +)-lactic acid, I( -)-halogeno-propionic acids, I( +)-alanine, Z( -)-malic acid, I( -)-halogeno-succinic acids, and Z( +)-aspartic acid. A review of the experimentaldata leads to the conclusion that Clough's method is trustworthywithin particular groups, but may break down when substancesbelonging to different groups are compared.44 J . Amer. Chem. SOC., 1925, 47, 1067; A., 1925, i, 631.45 E. Ott, R. Schroter, and A. Behr, Ber., 1928, 61, [B], 2124; A,, 1928,46 Ber., 1927, 60, [B], 2447; A., 1928, 154.4 7 Ber., 1928, 61, [B], 1083; A,, 1928, 735.1350ORGAXIC CHEMISTRY.-PART I.87Freudenberg and Kuhn agree, therefore, in regarding (+)-halog-enosuccinic acids as configuratively related to the (+ )-hydpoxy-acids, but such a view does not as yet command universal acceptance.It is at variance with Clough’s opinions and as the result of ex-tensive investigations concerning the inter-relationship of nitromalic,aspartic, and malic acids B. Holmberg ** has come to the conclusionthat the dextrorotatory halogenosuccinic acids belong to the sameseries as Z-malic acid, a view which is shared also by P. A. Leveneand H. L. Haller.4g With regard to natural ,!(+)-aspartic acid theopinion of Holmberg coincides with that of K. Freudenberg andA. NO^.^Similar problems are met with in connexion with the relativeconfigurations of optically active secondary alcohols.For instance,dextrorotatory p-octanol is converted into laworotatory halides bythe action of hydrogen chloride, bromide, or iodide or by thionylchloride or bromide. The occurrence of a Walden inversion is notnecessarily implied by this change in sign of rotation and contraryopinions have been held on this point. Basing their views on acomparison of optical properties, R. H. Pickard and J. Kenyon 51believed that (+)-p-octanol was configuratively related to the(+)-p-halides, whereas P. A. Levene and L. A. Mikeska,52 as theresult of somewhat insecure arguments derived from the observedreversal of sign of rotation during the change C8H1,*SH --+C8H,,*S03H (where configurational change cannot occur), con-sidered that the (+)-@-octanol and the (-)-p-halides had similarconfigurations.The problem has now been investigated by two chemicalwhich serve to establish more definitely the configur-ational relationships, the underlying principle being the conversion,by closely similar means, of a derivative of the optically activealcohol into (a) the alcohol or a carboxylic ester of the alcohol, and(b) a halide.It is assumed that (a) and (b) then have the sameconfiguration, since they are produced under similar conditions byreactions of the same type. If the configuration of the derivativeemployed is known, the occurrence of a Walden inversion in one ofthe reactions is at once detectable.The above conditions are realised in the present instance becaused- p-octanol can be converted into d-p-octyl dl-p-toluenesulphinateand p-toluenesulphonate without change in configuration. When48 Ber., 1928, 61, [B], 1885; A., 1928, 1216.49 J .Biol. Chem., 1929, 83, 186; A., 1041.50 Ber., 1925, 58, [B], 2399; A., 1926, 63.52 J . Biol. Chem., 1924, 59, 473; A., 1924, i, 940.53 A. J. H. Houssrt, J. Kenyon, and H. Phillips, J., 1929, 1700; A., 1164.51 J., 1911, 99, 4588 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.treated with potassium acetate, d- P-octyl p-toluenesulphonate giveslzevorotatory p-octyl acetate. This change must involve a Waldeninversion, because d- p-octanol gives a dextrorotatory acetate whentreated with acetic anhydride. A similar conclusion is drawn fromthe fact that the d-p-toluenesulphonate gives with lithium chloridea lzevorotatory p-chloro-octane.The experimental results obtained with d-p-octyl dl-p-toluene-sulphinate are summarised in the following scheme :The formation of I-p-octanol shows conclusively that a Waldeninversion has occurred, since d- p-octyl dl-p-toluenesulphinate hasthe same configuration as d-p-octanol, and the reaction with chlorinemust be regarded as involving a similar inversion.These transformations are of special interest in connexion withthe mechanism of the Walden inversion.Since the p-toluene-sulphinoxy-radical can be represented by the formula (I), it issuggested that the reaction with chlorine proceeds via the inter-mediate complex (11), which dissociates with rupture of the COO-0-c1 i5i X % +bond, leaving a carbonium ion.Inversion may take place beforethe addition of the chlorine ion or, alternatively, if dissociation andaddition occur simultaneously, the latter may take effect on theopposite side of the asymmetric complex.54Inasmuch as the following series of reactions has been carried out,it follows that treatment of the halides with silver oxide mustinvolve inversion, and it is suggested by Houssa, Kenyon, andPhillips that “ far from being a comparatively rare phenomenon,inversion occurs whenever a group attached to an asymmetricd- 1-carbon atom is replaced, unIess a phenyl group is directly linked tothe asymmetric carbon atom or a carboxyl group is present in the54 Compare T. M.Lowry, Deuxidme Conseil de C h i d e Solway, 1926, 40ORGIAXIC CHEMISTRY .-PART I. 89molecule. These disturbing factors may, however, lead to theoccurrence of two inversions during the replacement.”Attention is directed also to a series of papers by P. A. Levene andH. L. Haller, in which the configurational relationships of variouscarbinols are discussed. The subjects treated include the butan-7-01s and pentan-&-~ls,~~ methylethyl- and ethyl-n-propyl-~arbinols,~~z-hydroxyvaleric acid,57 hexan- p-ol and a-hydroxy-n-hexoic acid,58met hylprop ylcarbinol, 59 n-pentan- p-ol,~~ <-met hylheptan- p -01 , 61hep t an-y- ol and octan-8-01. 62In view of the recent tendency to regard replacements of groupsattached to asymmetric carbon atoms as being normally accompaniedby inversion it is of interest to recall the suggestion that the riboseobtainable from nucleic acids may be derived from xylose-3-phos-phoric acid by inversion during hydroly~is.~~ Although theevidence in this particular case is inconclusive,64 certain trans-formations in the hexose series have been described which favour theview that under suitable conditions such an inversion may occur.It is claimed 65 that a-fructose-diacetone-3-phosphoric acid isconvertible into a crystalline anhydrohexosazone which is notidentical with the osazone of Fischer and Zach’s 3 : 6-anhydro-glucose,66 and the suggestion is made that an anhydroallose deriv-ative is formed as the result of a Walden inversion during theremoval of the phosphoric acid group.The same osazone isapparently formed from glucose-diacetone-3-phosphoric acid. Onthe other hand, the phosphoric ester of P-fructose-diacetone gaveordinary glucosazone. Until a better understanding of the mechan-ism of these complex reactions is forthcoming it would be unwise toaccept the results as indicating the possibility of inversion duringthe ordinary hydrolysis of phosphoric esters. Under the usualconditions this is held to be unlikely, and experiments have shownthat the product obtained by hydrolysing the diphosphate of Z-glycericacid is optically pure.67 Inversion is to be expected only when the55 J . Biol. Chem., 1927,72, 691; A., 1927, 643.50 Ibid., 1928,76, 416; A., 1928, 394.5 7 Ibid., 1928,77,655; A., 1928, 737.5 8 Ibid., 1928,79, 475; A., 1928, 1353.59 Ibid., 1929,81, 426; A., 424.60 Ibid., 1929, 81, 703; A., 540.62 Ibid., p.679 ; A., 1266.64 P. A. Levene and R. Mori, J. Biol. Chem., 1929, 81, 215; A., 297.0 5 P. A. Levene, A. L. Raymond, and A. Walti, im., 1929,82, 191 ; A.,6% Ber., 1912,45,466; A., 1912, i, 239.07 S. Posternak and T. Posternak, Hdv. Cbim. A&, 1929, l%, 1168.Ibid., 1929, 83, 117; A., 1038.R. Robinson, Nature, 1927, 120, 44, 666; A,, 1927, 960, 1226.683 ; A. L. Raymond and P. A. Levene, ibid., 1929,83,619; A,, 127890 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY,conditions of reaction are such that the C-0 linking is ruptured, andin this connexion reference may be made to the observations ofJ. Kenyon, H. Phillips, and H.G. Turley 6s on the removal of thep-toluenesulphonyloxy-group from an optically active molecule.According to these authors the direct hydrolysis of the sodium saltof 1-a-p-toluenesulphonyloxypropionic acid with sodium hydroxideproceeds without rupture of the (3.0 bond and without inversion,whereas the interaction of potassium benzoate and ethyl l-a-p-tolu-enesulphonyloxypropionate involves the rupture of this bond andlends to complete inversion.Another case of a Walden inversion in the hexose series is pro-vided by the reported formation of d-idose-monoacetone (11) whenthe monoacetone derivative of 5 : 6-anhydroglucose (I) is treatedwith sodium hydroxide.69 The conversion is only partial, a,ndglucose-monoacetone is produced simultaneously, whilst ammoniaappears to open the ethylene oxide ring almost entirely in onedirection, giving 6-aminoglucose-monoacetone. The inversion maybe presumed to arise from the scission of the ethylene oxide ring a tthe bond which unites the fifth carbon atom to the oxygen of the ring.Xatural Products Allied to the Open-chain Terpenes.8pmZene.-Progress continues to be made in the study of thehydrocarbon squalene, which occurs, along with sterol, selachylalcohol, and batyl alcohol, in the unsaponifiable matter from theoils of elasmobrancli fish.The formulation of squalene as a dihydro-triterpene, C,,H,,, may now be considered as settled,', since underall methods of attack the substance yields products which aretypical of those to be expected in the terpene series.Constant-boiling mixtures of mono- and di-hydromonoterpenes are obtainedwhen squalene is heated nnder diminished pressure in a current ofnitrogen. The action of ozone yields a hexaozonide, which isdecomposed by water, giving lsevulic, succinic, and formic acids,6 8 J . , 1926,127, 399; A., 1925, i, 507.69 H. Ohle and L. von Vargha, Ber., 1929, 62, [ B ] , 2435; A., 1279.70 I. M. Heilbron, W. M. Omens, and I. A. Simpson, J., 1929,873; A., 789;I. M. Heilbron and A. Thompson, &id., p. 883 ; -4., 790ORGANIC CHEMISTRY .-PART I. 91acetone and its peroxide, formaldehyde, carbon dioxide, Izevul-aldehyde peroxide, and a complex peroxide of methylheptenone.Oxidation in acetone solution by solid potassium permanganategives succinic acid, methylheptenone, and dihydro-#-ionone. Theseresults prove that the carbon skeleton 9 ispresent in squalene.The production of formaldehyde and acetalde-hyde, in the oxidation of the hydrocarbon by chromyl chloride,reveals the presence of both the >C:CH, and the CMezCHMegroups, as does also the formation of carbon dioxide, formaldehyde,formic acid, and succinic acid in the same decomposition (see above).It is suggested, therefore, that the squalene exists as a mixtureof a t least two isomerides, to which the formulae (I) and (11) areascribed.c*c:c*c*c*C:c*c*c*c:Very satisfactory confirmation of these views has been obtainedby hydrogenating squalene to a point corresponding to the deca-hydro-derivative and submitting the product to ozonolysis.Itappears that the hydrogenation is selective, giving isomeric deca-hydrosqualenes along with some squalane (dodecahydrosqualene)and products less hydrogenated. The substances isolated after thetreatment with ozone include the following : methyl isohexylketone, hexahydro-#-ionone (CHMe,-[CH,]3-CHMe*[CH2]3*COf\ile),a ketone C,,H,,O (probably 3 : 7 : ll-trimethylhexadecan-15-one),y-methyl-n-valeric acid, 4 : 8-dimethylnonoic acid, and an acidC,,Ha402 (probably 3 : 7 : 11-trimethyltetradecoic acid). Theisolation of the first two of these substances establishes the presenceof double bonds at (a) and ( b ) in (I) and the formation of the acidC1,&402 is readily explicable. It is more difficult, however, toaccount for the formation of the other two acids and for the ketoneC1,H3,0, and it seems most unlikely that either (I) or (11) couldyield these substances either directly or indirectly under the givenexperimental conditions.The authors are forced to conclude thatsqualene exists also in a third stable form (111) :~H*[CH,],-CMe:CH*CH,~CH:CMe,CMe*[CH2]2*CH:CMe*[CH2]2GH:CMe*[CH2]2*CMe:CHMe (111.) --- O,,H,,O, ketone----- j.Consideration of the acids and ketones produced leads to the ideathat the addition of hydrogen proceeds from the terminal group+---- C,,H,,O, acid- - 92 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.CMe:CHMe, which is common to all three isomeric forms, since onlyin this way is it possible to explain the absence of ketones of highermolecular weight than hexahydro-tj-ionone from (I) and of acidsmore complex than 4 : 8-dimethylnonoic acid from (111).Bixin.-Considerable interest is being shown in the chemistryof bixin, a natural colouring matter obtained from the seeds ofBixa orelhna and similar in many ways to crocetin and carotin.The formula C,4H,70,*OMe now appears to be e~tablished,'~ althoughsome workers still favour the formula C,6H,,04.72 According toP.Karrer the special properties of bixin and crocetin and manyother natural products are due to the presence of a series of con-jugated double linkings. Bixin very readily yields m-xylene whenheated, but the pre-existence of a benzene nucleus in the moleculeis most unlikely and the aromatic derivative is probably formed byscission and rearrangement of the conjugated double bonds.73 The - ~-presence of a five-membered ring, CH<mE(?=, has been suggestedCH-C-in order to account for the intense colour, but this assumption doesnot seem to be necessary, and from a study of the dibasic acidnorbixin, C,,H,,O, (obtained from bixin by alkaline hydrolysis),Karrer and his collaborators have obtained evidence in support ofthe structure CO,Me*CH:[CH*CMe:CH*CH:],CH*CO,H for bixin,suggested by Kuhn on the basis of Karrer's work on the structureof ~ r o c e t i n .~ ~ It will be seen that the molecule is composed of fourisoprene and two glyoxylic acid residues. Bixin readily undergoesisomerisation, probably geometric in nature.Carbohydrates.That free sugars are not open-chain compounds but are cyclicin structure, corresponding to the pyranosides or simple glucosides,has been made evident by previous work.It is none the less impor-tant to supplement this evidence by the isolation of a true open-chain aldehyde form of a sugar and to institute a comparison of itsproperties with those of a heterocyclic normal sugar. This has beenachieved 76 by the preparation of the crystalline '2 : 3 : 4 : 5 : 6-penta-acetyl glucose, which has a rotation nearly zero and gives apositive test with Schiff's reagent.Studies of the mutarotation of galactose and of the change of71 P. Karrer, A. Helfemtein, Rose Widmer, and T. B. van Itallie, Helv. Chim.72 F. Faltis and F. Viebiick, Ber., 1929, 62, [ B ] , 701 ; A,, 575.i3 R.Kuhnand A. Winterstein, Helv. Chim. Acta, 1928,11, 427, 716; A.,74 F. Faltis and F. Viebiick, loc. cit.75 P. Karrer and H. Salomon, Helv. China. Acta, 1928, 11, 513; A., 1928,i 6 M. L. Wolfrom, J . AWT. Chern. SOC., 1929,51, 2188; A., 1043.Acta, 1929, 12, 741 ; A., 1075.1928, 644, 869.644ORGANIC CHEMISTRY.-PART I. 93volume of an aqueous solution of this sugar furnish evidence of thepresence of more than the two pyranose forms.77 It seems probablethat the two y- or fursnose varieties exist side by side with the a-and P-galactopyranoses in water. In boiling pyridine the @-ga1act.o-furanose appears to be present in the proportion of 23%. Measure-ment indicates that the mutarotation velocities of glucose, tetra-methyl glucose, and lactose in water are similar, but in the presenceof hydroxyl ions the reactions are catalysed a t very different rates.When glucose is degraded into simpler compounds the changemay proceed in either of two ways : 78 (1) non-oxidation processesare characterised by the formation of C, chains and are precededby 8 rearrangement of glucose into the labile furanose form.Thisprocedure includes processes which give rise to methylglyoxal,acetaldehyde, and products based on these substances; (2) theprocesses depending on primary oxidation of glucose probably occurthrough the pyranose form, and this proceeds most readily atC,, C,, and C, and usually with acid reagents. An endeavour toimitate by chemical reagents the fermentation processes of a hexoseor its phosphate has led to the study 79 of the graded oxidation of a@-fructose sulphate in the form of its diacetone derivative.Withincreasing amounts of oxygen supplied from potassium permangan-ate, the substance yields a dextrorotatory intermediate product,CMe <0*(?(0H)*CH2*0*s03K, which is at its maximum when 6O*CH*CH(CO,K), - -atoms of oxygen are supplied. In addition, 15% of the originalfructose derivative remains unchanged, 15% is oxidised to carbondioxide and sulphuric acid, and about one-third is converted into4 mols. of carbon dioxide and 1 mol. of the glycollic acid derivativeC02K*CH,*O*S0,K. Hydrolysis of the above complex intermediateproduct with N-hydrochloric acid a t 100" for Q hour yields acetone,sulphuric acid, methylglyoxal (75y0), glycollic acid, and carbondioxide. It would appear that the above intermediate product firstloses its acetone residue and breaks down into the sulphuric ester ofdihydroxyacetone, which then gives methylglyoxal and sulphuricacid.The mechanism of the fermentation process envisaged byNeuberg as proceeding by the intermediate formation of C, residues77 C. N. Riiber, J. Minsaas, and R. T. Lyche, J., 1929, 2173; A., 1427;T. M. Lowry and G. F. Smith, J . PhyaicaZ Chem., 1929,33,9; A., 272; H. H.Schlubach and V. Prochownick, Ber., 1929, 62, [B], 1602; A., 912; T. M.Lowry and G. L. Wilson, Tram. Faraday Soc., 1928,24, 683; A., 36.'13 K. Bernhauer and J. Nistler, Biochern. Z., 1929, 205, 230; A., 643; K.Bernhauer, ibk?., 1929,210, 175; A., 1167; M.Honig and W. Ruzicka, Ber.,1929,62, [B], 1434; A., 910; F. Fischler, K. Tiiufter, an4 S. W. Souci, Bkhem.Z., 1929, 208, 191 ; A., 912 ; K. Bernhauer and K. Schon, 2. phy8i0Z. Chem.,1929,180, 232; A., 366.7D H. Ohle and J. Neuscheller, Ber., 1929,62, [B], 1651; A,, 91394 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRYORGANIC CHEMISTRY .-PART I. 95Although a corresponding correction for all sugar forms was impliedand has been used in the formulation of both the pyranose and thefuranose type, yet a recent paper in the Berichte is devoted to asimilar explanation applied to glucofuranose. 84 Doubtless this willserve a useful purpose in placing emphasis on the inadequacy of theFischer convention (IV) as a complete mode of formulation ofy-glucose.Employment of either of the expressions (V) and (VI)will become more general as is the case with (11) and (111).HO*CH,HO*C*H :------ 7 H * + F l H*Y*OH 1 ,H*Y*OH 6 H*Y*OH 6 HOHO*(i*H 1 H 0 . c ~ H~>CHCH HO.7.H ----A 1H $ZH H-Y-OHCH,*OH 013(VI.) ___ - -- W.)\- ~_______ (IV.1a-Glucofuranose.The latter two exprcssions illustrate the spatial proximity of OHgroups a t C, and C, and serve to account for the conversion of 3- into6-monoacetyl glucose derivatives such as the monoacetone com-pounds, a reaction which involves the wandering of the acyl residue.HO*5!H2 CH,*R-O-YH, 9 HO*C*H 0 HO*C*HCH,*C-O H HO H I<ij?+ - kj)?i IO-CMe,H \ I O-CMe2A similar change has been observed with benzoyl derivatives, butin the methyl derivatives this property is not exhibited.A reinvestigation of the methylated sugars derived from glucose-monoacetone and glucose-diacetone has yielded results confirmingt'he five-atom ring forms of these acetone compounds as opposed totheir formulation as four-atom ring sugar complexes. They areto be represented on the basis of the above formulation of ac-gluco-furanose and, in their formation from ordinary glucose by theagency of mineral acid and acetone, the pyranose structure suffersconversion into the furanose type.S5 Many conflicting data associ-84 K.Josephson, Ber., 1929, 62, [B], 317, 1913; A., 428, 1278; AnnaZen,1929,472, 217; A., 1044; Svensk Kern. Tidskr., 1929, 41, 99; A., 912.s5 C. G. Anderson, W. Charlton, and W. N. Haworth, J ., 1929, 1329; A.,1044; C. G. Anderson, W. Charlton, W. N. Haworth, and V. 5. Nicholson,ibid., p. 1337; A., 104496 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ated with their methyl derivatives in comparison with those ofa-fructose-diacetone are removed. In the above and earlier papersthe possible existence of a second form of glucose-diacetone wasforeshadowed and the formula advanced. A compound whichconforms to this isomeride has now been isolated, but, unfortunately,it is a liquid. A number of its transformation products have beeninvestigated *6 and of interest is the crystalline sugar designated5-methylglucose, which has an unexpectedly high specific rotationfor a glucofuranose. The authors' evidence for the orientation ofthe methyl residue is not yet convincing.Meanwhile the isolation of glucose-acetone carbonate (VII) andits transformation into simple crystalline glucofuranose (or y-glucose)derivatives may be considered to have placed the chemistry ofy-sugars on a new basis.The new products which have beenisolated are the glucofuranose carbonate (VIII) and its crystallineanilide and osazone, along with the crystalline isomeric forms ofCX- and fi-ethylglucofuranoside (y-ethylglucoside) (IX and X).H O ~ H H O ~ HOH OHThe last two glucosides possess the constitution formerly appliedby Fischer to the normal alkylglucosides, and the product (VIII)is the first authentic crystalline derivative of y-glucose having afree reducing group.The relationship between sugars of the furanose and the pyranosetype is signified by the synthesis from Z-trimethyl arabofuranose ofthe two lactones related to gluco- and manno-pyritnose. This iseffected by ascent of the series,88 potassium cyanide and methyl86 R.Ohle and L. von Vargha, Ber., 1929, 62, [B], 2425, 2435; A , , 1278,1279.87 W. N. Haworth and C. R. Porter, J., 1929, 2796.8 8 W. N. Haworth and S. Peat, ibid., p. 350; A , , 426ORGANIC CHEMISTRY .-PART I. 97chloroformate being used for the preliminary formation of thenitrile, followed by hydrolysis to the acid and lactone. The featureof this synthesis is that the C, position is the only point for theattachment of the new six-atom ring when the synthesis is com-pleted and this now becomes C5 in the I-lactones of mannose andglucose which are isolated.0H-OMe H-CH2*OMeMeO-Supplementary evidence to that previously adduced for theoccurrence of two types of sugar ring is provided by the correlationof a number of the methylated lactones which have already beenserviceable in the elucidation of sugar constitutions. For instance,the five-atom ring lactones derived from gluco- and manno-furanosederivatives are interconvertible by epimerisation in aqueouspyridine; similarly also the methylated lactones from xylo- andlyxo-furanoses.Among six-atom ring forms, the methylatedlactones from tetramethyl gluco- and manno-pyranose are inter-convertible and so ako are the lactones from trimethyl xylo- and1 y xo - pyranose . strengthen the constitutionalproofs of the various ring structures which have been investigated,and at the same time provide alternative methods for the isolationof a desired lactone.The development of a novel form of stereoisomerism in the sugargroup is made evident by the conclusion that there exist threevarieties of triacetyl methylrhamnoside which have an identicalstructure.Existing theory accounts for only two such forms,a and p, and the third variety is characterised by its possemion ofexceptional properties. The three acetyl residues are eliminatedsmoothly and normally from triacetyl a- and p-methylrhamnosides(pyranosides), but the third form loses only two acetyl groups byhydrolysis with alkali. The recalcitrant acetyl group is found to besituated at C, in the chain, that is, adjoining the @-methyl residue ofthe rhamnoside.This anomaly, which extends also to the tetra-acetyl methylmannosides, is interpreted 90 aa furnishing evidence ofthe interlocking of the groups at C,, C,, and C, ; and as a workinghypothesis it is suggested that this form of the stabilised monoacetylW. N. Haworth and C. W. Long, J., 1929, 345; A., 426.O0 W. N. Haworth, E. L. Hirst, and E. J. Miller, ibid., p. 2469.REP.-VOL. XXVI. DThese observation98 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.p-methylrhamnoside is due to the congestion of the addenda andto a stabilised phase of a non-planar ring.AUnobstructed form.eBInterlocked form.An extension of these experiments may lead to interesting inform-ation on the existence of strainless ring forms of various types.The oxygen of the C:O group of the acetyl residue may (altern-atively to the CH, group) be considered to be enclosed by the OMeand OH groups at C, and C,, and this conception may more easilyaccount for the resistance to hydrolysis of the acetyl group at C,.A new classification of the methyl pentoses is rendered possibleby the discovery that chinovose, the sugar residue in chinovin, isidentical with isorhamn~se.~l Reduction of chinovose yields asugar alcohol, the benzylidene derivative of which is the same asthat prepared by a similar procedure from isorhamnose.A synonymof isorhamnose is isorhodeose, but it is proposed to alter the nornen-clature of the methyl pentoses according to the plan of VotoEek andto name them from the hexoses to which they are related.Thusisorhamnose (isorhodeose) will be known as d-glucomethylose .Rhamnose and fucose are, however, so commonly known that it isdesirable to retain their names rather than to hide them under thenew nomenclature as mannomethylose and galactomethylose. On$he other hand, new methyl pentoses have been isolated, amongwhich are gulomethylose, talomethylose, and altromethylose, andit is preferable to adopt a systematic terminology which has referenceto the parent hexose. d-Glucomethylose (isorhamnose), along withaltromethylose, has been prepared by the reduction of a newunsaturated compound derived from galactose- diacet one-modifiedby the introduction of an ethylene group connecting C, and C,.Attachment of hydrogen at these positions in the unsaturatedgalactoseen furnishes both of these methyloses.Synthetic CZucosides.-Synthetic methods leading to the formationof a-glucosides are of importance, since only the formation ofp-glucosides can be effected with facility by a procedure which isK.Freudenberg and K. Reschig, Ber., 1929 62, [B], 373; A., 427.9 1 E. VotoEek and F. RBc, J. Czech. Chem. Comm., 1929, 4, 239; A., 682ORGANIC CHEMISTRY .-PART I. 99well recognised. The conditions under which a-glucosides may beprepared have received careful investigation. With the employ-ment to this end of the two reagents, 2-trichloroacetyl-3 : 4 : 6-tri-acetyl p-glucosidyl chloride and 3 : 4 : 6-triacetyl p-glucosidylchloride, a yield of 80% or more of a-glucosides has been achieved.92These methods may find an application in the synthesis of naturallyoccurring hexosides, and especially is it to be hoped that methodswill soon be available which will lead to the formation of a-galacto-sides.Meanwhile an extension of the technique in the preparationof p-galactosides is provided by the synthesis of derivatives contain-ing quinol, menthol, and borneol residues.%Alizarin- p-glucosides have been prepared containing (a) oneglucose residue, (b) a gentiobiose residue, (c) a cellobiose residue;these are severally well-defined crystalline compounds.g4 Neither(b) nor (c) appears to be identical with ruberythric acid, the synthesisof which has been the objective in the preparation of theseglucosides.The rates of hydrolysis of a-methylglucoside, tetramethyl a-methyl-glucoside, and trehalose have been determined polarimetrically .The critical increments provided by these results 95 are regarded asmore trustworthy than those of velocity coefficients, since thelatter ratios vary with the temperature at which hydrolysis iseffected. Figures are computed which furnish a measure of thestability of the above compounds, and these are of real utility.Anexplanation of the ease of hydrolysis of sucrose is discussed, and theauthor advances evidence in support of the hypothesis that theprocess of the mutarotation of sugars does not involve a rupture ofthe oxide ring as is commonly supposed.Disaccharides.-A new and abundant source of that interestingrare sugar, turanose, has been discoveredg6 and its physical con-stants redetermined.It is probable that this disaccharide will nowreceive the careful study which its importance demands, and that anew constitutional study will be undertaken. The structurealready allocated suggests that turanose may conceivably give thesame osazone as gentiobiose, which has not been shown to be thecme. The new method for the isolation of gentianose 97 which isreputed to furnish a yield of 24% is of importance inasmuch as thistrisaccharide is the chief source of gentiobiose. The latter hasO2 W. J. Hickinbottom, J., 1929, 1676; A., 1167.93 A. Robertson, im., p. 1820; A., 1167.94 G. Zemplh and A. Muller, Ber., 1929, 62, [B], 2107; A., 1281.95 A.E. Moelwyn-Hughes, Tram. Paraday SOC., 1929,25, 81 ; A., 406.O 6 C. S. Hudson and E. Pacsu, Science, 1929,69,278; A,, 1046.s7 M. Bride1 and M. Desmest, J. Phurm. Chim., 1929, [viii], 9, 466; A.,866100 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.hitherto not been obtainable in other than meagre yields fromgentian root, although its value for the purpose of synthetic work inthe natural glucoside series is apparent.Useful processes for the isolation of a-alkylbiosides have beenrecorded.gs For instance, cellobiose octa-acetate is transformedinto or-ethylcellobioside acetate by sublimed ferric chloride dis-solved in ethyl alcohol, and the same procedure serves for thepreparat'ion of the maltoside from maltose oct,a-acetate. Analternative method involves the initial formation of acetobromo-cellobiose.The introduction of triphenylmethyl residues into a series of di-and tri-saccharides has furnished the interesting generalisation thatone such residue enters each primary alcohol grouping.Thenumber of such residues introduced into maltose, sucrose, andraffinose is respectively two, three, and three, in agreement with therequirements for these sugars on the basis of their recently estab-lished structural formulae.99The series of fluoro-, chloro-, and bromo-melibiose hepta-acetateshas been isolated,l and their physical constants, now made available,are compared with those of the corresponding maltose derivatives,and a regular relationship between these two bioses is established.The author utilises trans-strainless models for the hexose units and,although unaware that similar models have been suggested by otherworkers, has succeeded in tracing certain contrasts in the moleciilarconformation of a-bioses and p-bioses.This confirms the recognitionof the a-configuration of melibiose at the biose junction, a conclusionwhich was reported in previous years.2 Suggestive ideas bearingon the conformation of cellobiose and cellulose are made and thesereceive support from the X-ray diffraction spectra. This preliminarywork should lead to further results of considerable interest.111 an attempt to repeat the synthesis of sucrose communicatedlast year by Pictet and Vogel, other authors have not succeededin isolating the sugar or its octa-acetate.Pictet and his colla-borator have now published fuller details of their work, but similarexperiments, in which materials of different but authentic originhave been employed, have led to the isolation of a crystallineisosucrose which is not identical with su~rose.~ These results mean98 G. Zemplh, Ber., 1929, 62, [B], 985, 990; A., 683.99 K. Josephson, Annulen, 1929, 472, 230; A., 1045.1 D. H. Brauns, J . Amer. Cbem. Soc., 1929,51, 1820; A,, 913.2 Ann. Reports, 1927, 24, 78; 1928, 25, 104.3 G. Zemplh and A. Gereces, Ber., 1929, 62, [BJ, 984; A., 683.4 Ibid.,p. 1418.5 (Sir) J. C. Irvine, J. W. H. Oldham, and A. F. Skinner, J. Amer. Chem. SOC.,1820, 51, 1279 ; A., 683ORGANIC CHEMISTRY.-PART I. 101that the Pictet-Vogel synthesis can only be accepted with reserveuntil their results can be imitated by other experimenters.Polysaccharides.Inu1in.-A review of the literature discloses the existence of alengthy series of pfoducts, based on fructose anhydride, rangingfrom the simplest' member to inulin itseK6 These products,isolated from different sources, have been regarded as intermediatestages in the polymerisation of the fructose unit to the most com-plex stage, and in the process of purifying inulin from water the lesscomplex varieties may be separated by reason of their greatersolubility.Two of the simpler members of the series have beenidentified 7 as sinistrin-A, (C6HI00J2, and sinistrin-B, (C6H1005)4.The former has been converted by methylation with methyl sulphateinto a compound closely resembling methyl inulin and yielding3 : 4 : 6-trimethyl fructofuranose on hydrolysis as does trimethylinulin itself.Conversely it would appear that under a variety ofconditions inulin is transformable into simpler complexes.It has previously been reported that the molecular weight ofinulin in liquid ammonia is in agreement with the formula(C6H100S)2, and the same molecular weight has now been determinedfor inulin dissolved in molten acetamide.8 The isolation of thepolymerised product from t'he latter mixture is said to yield aninulan which is freely soluble in water and has the composition(C6H100s)2. When preserved, it gradually becomes as insoluble incold water as inulin, from which it can no longer be easily dis-tinguished. Facts of a similar nature were commented on in thelast Report, where it was stated " whether this diminution corre-sponds to dissociation or decomposition is a problem remaining forfuture decision." This comment has been misinterpreted byH.Pringsheim as being a criticism of the facts which have beenreported .The synthetic formation of a fructose anhydride is recorded asproceeding from the condensation of fructose with acetone in anacid m e d i ~ m . ~ The product passes into hexamethyl difructoseanhydride on methylation and gives rise on hydrolysis to the sametrimethyl fructofuranose as obtained by Haworth and Learner fromtrimethyl inulin. The isolation of an anhydro-fructose of differentH. H. Schlubach and H.Elmer, Ber., 1929,62, [B], 1493; A., 915; A. C.Thayaen, W. E. Bakes, and B. M. Green, Biochem. J., 1929, 23, 444; A.,866.H. H. Schlubsch and W. Florsheim, Ber., 1929,62, [B], 1491 ; A,, 914.* H. Pringsheim, J. Reilly, and P. P. Donovan, im., p. 2378; A., 1282.H. H. Schlubach and H. Elmer, Ber., 1928,61, [B], 2358; A., 51102 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.optical sign is, however, reported 10 as obtainable from inulin, andthis again yields a hexamethyl difructose anhydride differingsomewhat in physical constants from that described above. It issuggested that inulin contains anhydro-fructose residues of differenttypes in the ratio of 4 : 1. This conclusion seems to be balanced bythe observation that glucose may occur as a product of hydrolysisof inulin, and the isolation of traces of this hexose as the penta-acetylglucose is recorded.11 It is recognised that this occurrence ofglucose may be traceable to a Lobry de Bruyn transformation offructose.The fundamental point of view from which all these observationsmay be considered is that inulin undergoes change with remarkablereadiness to give substances of lower molecular weight, and thatcaution must be exercised in endeavours to reach a conclusion onthe molecular complexity of this polysaccharide.12 The essentialmode of linking which occurs in inulin has already been determinedand it is seen that the mutual union of adjoining residues of thefructose units must occur through the groups at C, and C,.This being so, inulin may be regarded merely as a substitutedvariety of polymerised ethylene oxide.The latter, as has long beenknown, is readily transformed into polymeric forms of the type-O=CH,*CH,*O*CH,*CH,-, etc. In place of pairs of methylenegroups separated by oxygen links, the inulin residue is substitutedat one of these positions by groups which form a fructofurnnose ring,I I II Irepresented by @ in the expression -O*CH,=@*O*CH*,?-. It must'be conceded that, if the polymeric forms of ethylene oxide areconstituted on the principle of the exercise of ordinary covalencybonds between adjoining units, as is believed by Staudinger (seefollowing section on polymerisation), then there is no reason todeny the application of a similar principle for the linking of adjoiningunits in inulin.It is self-evident that the completed molecule of apolymeric form of ethylene oxide is represented by a cyclic structureof the type- CH, CH, [O*CH,*CH,],-O-CH,-(iH,CH,*CH,*O*[CH,~CH,*O],*CH,*CH,*OIn this the chains may be considered to lie fairly close together inspace and to form a kind of flattened loop. Precisely this type oflo R. F. Jackson and S. M. Goergen, Bur. Stand. J . Res., 1929, 3, 27; A.,1280; J. C . Irvine and J. W. Stevenson, J . Amer. Chem. SOC., 1929, 61, 2197;A., 1046.l1 H. H. Schlubach and H. Elsner, Ber., 1929,62, [BJ, 1493; A., 915; A. C.Thaysen, W. E. Bakes, and B. M. Green, Biochem. J., 1929,23,444; A., 856.l2 H. D. K. Drew end W. N. Heworth, J., 1928,2690; A., 1928, 1360ORGANIC CHEMISTRY .-PART I.103structure can be advanced for inulin, and it will be seen that, byadopting this hypothesis, the fructofuranose rings will occur sideby side in pairs and in a plane vertical to that of the ethylene oxidechain. The scission of the oxygen links would then be expected tolead to groups of (C6Hlo05)n, where n is even and has ordinarilythe limiting value 2.la)I ’ I’ 0.6 *CH,*[ O-@-CH,],-O-@-CH,I I t ’ 1 ‘ I 1 f- (4ILooked at from (A), the end view of *such a model for inulin willshow the elevation including the two frucfofuranose groups at (a)and (b), and pairs of such units will be perceived at regular intervalsthroughout the model.This interpretation is an extension of the work of Haworth andLearner and has not hitherto been advanced quite in this way.Xtarch.-The.most reasonable hypothesis on which to found aconception of the constitution of starch is that this is composed ofconjugated maltose units joined by covalent links.13 Furthersupport for this view is furnished in a critical paper l4 which dis-cusses the polarimetric values of starch and compares these withthe values which would be expected if only a-glucosidic links joinedthe contiguous pyranose units.The values are such as to suggestthat the latter hypothesis is the correct one. The assumption thatstarch is composed of simple and uniform units of small molecularweight which are “ associated ” in the complex is considered mostimprobable. Greater variations occur in the lengths of mainvalency chains of starch than is the case with cellulose.Thekinetics of starch hydrolysis with acids indicates that the action hasthe same order of magnitude in the initial and subsequent stages andproceeds at nearly the same rate as the hydrolysis of glucosides.Experiments corresponding to those reported last year arerecorded on the formation of triacetyl starches and molecular-13 Haworth, “ The Constitution of Sugars,” London, 1929, p. 84.1 4 K. H. Meyer, H. Hopff, end H. Mark, Ber., 1929,62, [BJ, 1103; A,, 799104 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.weight determinations of these products indicate a minimum valueof (C,H,O,Ac,),,, but even this value may be due to the occurrenceof depolymerisation in the course of acetylation.15Glycogen.-A solution of glycogen in resorcinol does not exhibitthe Tyndall effect and is regarded as a molecular and not a colloidalsolution : the reverse is the case for aqueous solutions.Preliminarycryoscopic measurements l6 point t o a comparatively low molecularweight in the former solvent. Conditions for the complete acetyl-ation and methylation of glycogen have been established and thetriacetyl and trimethyl derivatives are described and compared withthe corresponding products from starch. Deacetylated glycogenacetate apparently retains the properties of the original poly-saccharide. The trimethyl glycogen yields exclusively 2 : 3 : 6-tri-methyl glucose on hydrolysis and it is emphasised that duringmethylation of glycogen there is evident no stage of arrest corre-sponding t o the introduction of only two methyl residues. It issuggested that glycogen 1' and starch have great similarity in struc-ture and that the former is probably characterised by smallermolecular dimensions.CeZZuZose.-Objection is raised to the opinion of Hess that therotatory power of a solution of cellulose in Schweitzer's reagent isdue to a complex formed between copper and every glucose unit ofths cellulose complex, and the use made of this view in determiningthe molecular weight of cellulose is adversely criticised .I* Equallyinsecure is the later hypothesis that the structural unit of celluloseis a biosan, since independent attempts to isolate the biosan acetat,ehave shown l9 that this is probably a still highly complex breakdownproduct of cellulose and is not homogeneous.The isolation ofhydrolysis products in apparent agreement with the formuh(C6H1005)3 and (C,H,,O,), is reported, but it is emphasised that thecourse of the hydrolysis of cellulose is not in harmony with theconception of a cellulose constitution based on small associatedunits.20The velocity of hydrolysis of cellulose by hydrochloric acid hasbeen studied both in the absence and in the presence of alkali15 Y. Tsuzuki, Bull. Chem. SOC. Japan, 1928,3, 276; 1929, 4, 153; L4., 175,16 P. Brig1 and R. Schinle, Ber., 1929, 62, [B], 99; A., 299; R. 0. Herzog1 7 W. N. Haworth, E. L. Hirst, and J. I. Webb, J., 1929, 2479.18 D. Macgdlavry, Rec. trav. chim., 1929,48, 18,492; A., 262, 763; K.Hess,19 K. Freudenberg, Ber., 1929,62, [B], 383; A., 430; J. R. Katz and P. J. P.20 R. Willstlitter and L. Zechmeister, Ber., 1929, 62, [B], 722; A., 544.1168.and W. Reich, ibid., p. 495; A., 544.ibid., p. 489 ; A., 763.SamweI, Annalen, 1929, 474, 296; A., 1277ORGANIC CHEMISTRY .-PART I. 105chloride.21 With dilute acid the ultimate product is hydrocelluloseand a linear relationship exists between the rate of hydrolysis andthe hydrogen-ion activity of the solution, but a higher reactionvelocity is given when the neutral salt is present. A new determin-ation of the translation lattice of cellulose hydrate 22 has furnishedresults in agreement with a cell content of eight C,H,,O, groups asagainst the recent view of the presence of only four such groups.Interpretations placed upon recent X-ray measurements of celluloseare discussed in the following section on polymerisation.XyEan.-The constitutional relationship of xylan and cellulose isestablished by a study 23 of dimethyl xylan, which is now availablefor the first time as a homogeneous product.This is formed by twomethylation treatments of Esparto xylan and proof is adduced ofthe presence of methyl residues in the 2- and 3-positions, since a2 : 3-dimethyl xylose is isolated by hydrolytic cleavage. It issuggested that the structural formula ascribable to xylan is identicalwith that given last year to cellulose, except that the side-chainCH,*OH groups in the latter are absent from xylan.Polymerisation.The slow progress made until recently in the elucidation of thestructure of highly polymerised natural substances is to be attri-buted in large measure to the experimental difficulties which con-front the investigator in this field.The polysaccharides, caoutchouc,and the proteins are difficult to purify, give colloidal solutions, andlack almost all the properties which have hitherto been utilisedsuccessfully in structural determinations.The two main lines of thought concerning the structure of suchcompounds are differentiated by the views taken of the mechanisminvolved during polymerisation. This process is regarded by aomeworkers as depending almost entirely on the forces of auxiliaryvalency, which may be regarded as being either of a general natureor exerted in the form of definite co-ordinate linkings of the typedescribed by N.V. Sidgwi~k.~* M. Bergmann,26 for example, holdsthe view that the polymerised substances are composed of a funda-mental unit (Grundkorper), the constituent atoms of which arebound together by co-valent bonds. The chemical structure issuch that the whole of the available valency forces is not employedin the formation of these co-valent linkings. The unit, therefore,2l E. Hunter, J., 1928, 2643; A., 1928, 1334.22 I(. Weissenberg, Naturwiss., 1929, 17, 181; A., 493.23 H. A. Hampton, W. N. Haworth, and E. L. Hirst, J., 1929, 1739; A.,24 “ The Electronic Theory of Valency,” Oxford (1927).2s Ber., 1926, 59, [El, 2973.1167.D 106 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.possesses strong residual valency, and is capable of associating withother similar units to form an organised whole, the general structureof which is crystalline and may be determined by the method of X-rayanalysis.The fundamental unit is not to be regarded as an ordinarysubstance owing to the fact that it cannot be isolated, any attemptto separate it from solution being foiled by the strong associatingpower of the unsatisfied auxiliary valency. The latter forces may,however, be so altered in solution that it is possible to obtain valuesof the molecular weight of the dissolved substance correspondingto that of the fundamental unit. Such changes are reversible andthe degree of association varies with solvent, temperature, and otherexternal conditions.It follows that the associated solid substancesare to be regarded as, in a sense, only apparently highly polymerised.Arguments in favour of these views are drawn from the results ofX-ray analysis. It can be shown by this method that the sub-stances in question are crystalline with small elementary cellscontaining simple structural units, which are regarded on the abovehypothesis as the true molecular units. Further experimentalevidence is provided by the marked dependence of the molecularweight of the dissolved substances upon the nature of the solvent,and by the frequency with which values are observed correspondingt o those required by the monomeric structural units. Cellulose,for example, appears to dissolve in an ammoniacal copper oxidesolution as a glucose anhydride,26 and a cellobiose anhydride wasobtained by M.Bergmann 27 which on isolation had the propertiesof a highly polymerised substance. Such observations were inter-preted by K. Hess in the sense that cellulose is an associated glucoseanhydride possessing certain special properties. Some workers havefavoured a biose anhydride as the fundamental unit for cellulose.28The results of molecular-weight determinations are, however,notoriously difficult to interpret in the case of highly polymerisedsubstances and it appears to the Reporters that little reliance canbe placed on the observed values pending a more thorough investig-ation of the cryoscopic and ebullioscopic behaviour of colloidalsolutions.According to the above views, residual valency plays the mostimportant part in polymerisation, but there are many workers whocannot find in this extension of Werner’s ideas a satisfactory explan-ation of the physical and chemical properties of highly polymerisedcompounds.They consider, on the contrary, that ordinary co-26 Annalen, 1923, 435, 1 ; A., 1924, i, 142 ; see also K. Hem, ‘‘ Die Chemieder Cellulose,” Leipzig (1928).27 Anrullen, 1925, 445, 1; A., 1925, i, 1384.See P. Karrer, “ Die Polymere Kohlenhydrate,” Leipzig (1925)ORGAJ!lIC CHEMISTRY.-PART I. 107valent linkings are involved in the process of polymerisation and thatthe polymeride possesses a dehite molecular structure containingordinary co-valent bonds in exactly the same way as the simpleorganic compounds.The fact that the unit involved in crystalformation is very small offers no particular difE~ulty,~~ since theresults obtained by X-ray analysis can be adequately explained byassuming a regular arrangement of the units linked by co-valentbonds. The views of H. Staudinger, referred to below, and thestructures for cellulose suggested by W. N. Hawortha and by K.Freudenberg 31 may be cited as representative examples of this pointof view.Certain aspects of the micellar theory of colloids applied tonaturally occurring, highly polymerised compounds 32 may beregarded as having points in common with both the above-men-tioned hypotheses. A micellar structure has been advanced forcellulose according to which long chains of anhydro-glucose unitsare joined by covalent links in such a way that cellobiose is formedon hydrolysis.Owing to their moleculaz size these long chains aresaid to possess auxiliary valency forces comparable in magnitudewith those present in ordinary bonds, and by virtue of these inter-molecular forces the chains are held together, giving a three-dimensional array of glucose units which satisfies the conditionsdemanded by the X-ray observations. The chains of units are notnecessarily all of the same length and a bundle of such chains .heldtogether by inter-molecular forces forms a micelle. Many of thechemical and physical properties of the substances in questionreceive a ready interpretation on this basis and, in particular, thebaffling problems presented by the viscosity relations of the dis-solved substances find a qualitative explanation, arising out of thepossible variation in micellar size with change of external conditions.In certain cases it has been possible to calculate the approximatesize of the micelle, the dimensions for that present in cellulose beingsaid to be about 20 x 4 x 4pp.Ideas similar in their generalaspects have been advanced also for certain proteins and forcao~tchouc.~~The views hitherto referred to have been arrived at principallyfrom a study of natural substances and it has already been pointed29 R. 0. Herzog, Naturwi88., 1929,17,271; A., 724; compare 0. L. Sponslerand W. H. Dore, “ Colloid Symposium Monograph,” California, (1926).30 Helv.Chim. Acta, 1928,11, 534.31 Annalen, 1928, 461, 130; -4., 1928, 743.32 K. H. Meyer and H. Mark, Ber., 1928,61, [B], 593, 1936; A., 1928, 621,33 K. H. Meyer and H. Mark, Ber., 1928, 61, [B], 1932, 1939; A., 1229,1228; K. H. Meyer, 2. amgew. Chem., 1928,41,935.1252108 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.out that in many cases, notably with the proteins and caoutchouc,difficulties of isolation and purification form an almost insuperablebarrier to progress. This was realised by Staudinger, who hasadopted a different procedure in attempting to elucidate the struc-ture of highly polymerised substances. He and his collaboratorshave prepared and studied a large number of comparatively simplepolymeric substances and have sought to find models which wouldserve to explain the structure and behaviour of the more complexnatural products.For example, the insoluble polymeride poly-osymethylene acts in this way as a model for cellulose, and in asimilar manner polystyrene serves for caoutchouc, polyvinyl acetatefor certain polysaccharides and their derivatives, and the poly-merised sodium salt of acrylic acid for colloids of heteropolarcharacter such as the proteins.= The experimental results aredescribed in a long series of publications which have appeared duringthe course of the past ten years, and the knowledge thus gained hasshed an altogether new light on the nature of polymerised substances.It is obviously impossible to summarise within a few paragraphsthe range of investigations conducted by Staudinger and his colla-borators, and the polyoxymethylenes will be selected as an exampleof their general procedure.Solid polymerised formaldehyde wasrecognised many years ago35 as existing in four modifications,differing in physical and chemical properties and designated respec-tively a-, p-, y-, and 6-polyoxymethylene. In 1920 it was sug-qested 36 that the general principle involved in the structure of thesepolymerides was the formation of long chains of single formaldehydemolecules in accordance with the schemeO-CH2-O-CH2-[O-CH2],-O-CH2Finally 37 it was recognised that characteristic groups are unitedt o the ends of the chain and that the differences between the variouspolyoxymethylenes are attributable in large measure to this fact.The a-polyoxymethylenes are polyoxymethylene hydrates withmore than 100 formaldehyde molecules in the chain :HO-CH2-O-[CH2-O],-CH2-OH.In the y-polyoxymethylenes the chain is terminated by methyl ethergroups, MeO--CH2-0-[CH2-O],-CH2-OMe, which render themolecules much less reactive and less soluble.The 6-compounds 38are dimethyl ethers in which a rearrangement of a certain proportion34 H. Staudinger, Ber., 1929, 62, [B], 2893.35 F. Auerbach and H. Barschall, *4rb. Rnis. Qesund?t.-Amt., 1907, 27, 183;36 H. Staudinger, Ber., 1920, 53, 1073; A., 1920, i, 517.37 H. Staudinger, H. Johner, M. Liithy, and R. Signer, Annulen, 1929, 474,38 H. Staudinger and R. Signer, &id., p. 232.A., 1908, i, 131.155ORGANIC CHEMISTRY .-PART I.109of the formaldehyde molecules has t,aken place, in accordance withthe following scheme : -nf MeOL/H,-O. . . . . . . . CH,-0-CH,-0-CH,-OMeIOH/I.I.Me()--. . . . . . . . . . . CB2-0-CH,-CH-OMeI n each series substances corresponding to all grades of polymeris-ation from x = 1 up to x >lo0 have been prepared and in additiondiethyl and dipropyl ethers analogous to the dimethyl derivativesare known, as are also polyoxymethylene diacetates ,CH,*CO*O-CH,-O--[CH,-O],-CH,-O*CO*CH3,(X = 1 - 50).Within any given group the difference in chemical reactivitybetween closely related “ homologues ” is generally negligible, andthe physical properties change slowly with increase of x, moreespecially when x is large.A peculiar advantage attends the use offhese substances in the study of polymerisation in that the nature ofthe end group enables a trustworthy estimate of average molecularweight to be made by purely chemical methods, thus avoiding theuncertainties attached to the use of the usual physical methods whenhigh molecular weights are concerned. For example, the methoxylgroup in the y-series may be utilised for this purpose and the lengthof the chain can be determined by chemical analysis.It is worthy of remark thak y-polymerides in which the methoxylcontent is less than 1% of the molecule differ greatly from thecorresponding a-derivatives (dihydrates) in reactivity towardsalkali, and Staudinger suggests that here some indication mayperhaps be afforded of the way in which minute traces of hormonesreact in promoting the decomposition of a disproportionately largequantity of a highly polymerised product.The chemical evidence in the case of the y-polyoxymethylenespoints to a chain containing about 100 formaldehyde residues andhaving therefore a molecular weight of m.6000. It is evident, also,that the chains are composed of atoms joined by co-valent linksand that auxiliary valencies are not involved in the polymerisation.These highly polymerised substances are not homogeneous in thesense that all the molecules are equal in length and molecular weight.The molecules are, indeed, all built up on the same structural plan,but in any sample of y-polyoxymethylene some of the componentmolecules have less and some more than the average number offormaldehyde groups.For such substances the special term‘‘ polymereinheitlich ” is used.In the polyoxymethylene series, substances which are homo110 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.geneous only in this restricted sense are found by X-ray analysis tobe crystalline, and interesting questions arise as to the nature of thecrystal lattice. The arrangement of the molecules is such that thelong chains are arranged parallel to one another. This necessarilymeans that the chemically important end-groups occur at irregularintervals on account of the inequalities in the sizes of the molecules,and these end-groups are therefore notdetectable by x-ray method^.^^The forces by which the lattice is maintained must be distinguishedfrom those present, for example, in the diamond where all theatoms are bound by principal valencies in every direction.I n thepolyoxymethylenes, only in the direction of the length of the chain( L e . , in the molecule itself) are principal valencies involved. I nother directions the forces concerned are inter-molecular and of theorder of magnitude of the Van der Waals forces. The special name,crystallite,m is used to describe crystalline materials of this typewhich consist of unequal large " macro-molecules." A rough modelof the macro-molecule is to be found in a long thin rod. A bundleof these of different lengths would then form a crystallite, whilstmuch shorter rods of equal length provide a picture of the polyoxy-methylenes of low molecular weight, which consist of moleculescontaining each the same number of formaldehyde units.A further question concerns the mechanism by which the crystalsof the polyoxymethylenes are built up.In the lower members ofthe series, which exist in solution as well as in the solid state, crystalformation follows the normal course, but a different state of affairsis found in the'highly polymerised members. Here the extremelylong molecules which make up the crystals cannot exist in solution,but break up into smaller fragments as the result of Brownian move-ment. The macro-molecules therefore owe their existence entirelyto the fact that when bound together in the crystal their range ofmovement is restricted by the binding forces.The formation ofcrystals containing molecules of very high molecular weight cannot ,therefore, take place in the ordinary way by deposition from solution,but must involve the addition of formaldehyde molecules, directlyfrom the gaseous phase or from solution, to polyoxymethylenecrystals containing short chains. This addition is followed by atopochemical reaction which involves the rearrangement of normalvalencies and leads to the formation of a substance with a longerchain. It is important to note that the actual polymerisation takesplace in the solid state.It will be apparent from the above that the arguments previously39 H. Staudinger, H. Johner, R. Signer, G. Mie, and J. Hengstenberg, 2.4O H. Staudinger and R.Signer, 2. Krkt., 1929, 70, 193.physikal. Chem., 1927, 126, 425; A . , 1927, 647ORGANIC CHEMISTRY.-PART I. 111advanced in support of the “association” of C, or C1, units incellulose now lose much of their significance and in many ways a satis-factory explanation of the properties of cellulose can be obtained bytaking polyoxymethylene as a model.41 Even the characteristic pro-perty of fibre formation is imitated by polyoxymethylene. Cellulose,like polyoxymethylene, is crystalline, and possesses a smallelementary cell. The low molecular weights observed with someof its derivatives cannot be regarded as valid evidence for the‘ ‘ association ” hypothesis, in that the experimental methodsinvolved have not been proved to apply rigidly in the case ofcolloids, and also because depolymerisation may possibly take placein certain solvents, as actually happens with some polyoxymethylenederivatives.The solubilities of cellulose derivatives favour theview that a macro-molecular structure is present. For example, theacetates tend to be soluble in chloroform and insoluble in water andpetroleum, and thus resemble the acetates of the structural unitglucose. This is in agreement with the general rule that thosesolvents which are good solvating agents for the monomeric substanceare capable also of overcoming the inter-molecular forces of thepolymeride and producing solvates. Similarly the trimethyl etherof cellulose resembles methylated glucose in being soluble in water.On this view the derivatives of cellulose are to be regarded as lesshighly polymerised than cellulose itself, which may be cdmparedwith the solid polyoxymethylenes of very long chain.There is ageneral tendency for solubility to decrease with an increase in thegrade of polymerisation and it is for this reason that the extremelylong cellulose molecules are insoluble in water and cannot exist assuch in solution. In cellulose, as in polyoxymethylene, it is not tobe supposed that all the molecules are of equal length, but thesubstance is one of those to which the term “ polymereinheitlich ”is applicable. When dissolution takes place and a derivative isformed of lower molecular weight, the extent to which depolymeris-ation has occurred governs the viscosity of the derivative, gentlereaction conditions giving, for example, highly viscous celluloseacetates.A direct relationship between viscosity and molecularsize is obscured by complications arising from a tendency towardsthe formation of co-ordinate linkings (see below) and it is pointedout in a recent paper 42 that such a relationship certainly cannothold for aqueous starch solutions.Some concern may be felt for the nature of the end-groups on thisscheme. It is true that in starch and cellulose these groups canrepresent only a minute fraction of the molecule, owing to the length4 1 H. Staudinger, K. Frey, and R. Signer, Annalen, 1929, 474, 259.42 I?. Karrer and E. v. Krauss, Helv. Chim. Actz, 1929, 12, 1144112 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of the chain.In starch they may perhaps be accounted for asphosphate ester groupings, but no such masking of the reducingend-groupings can take place in cellulose. A possible solution ofthe difficulty is to consider that the lengthy cellulose moleculesfinally turn round on themselves and become endless chains.43It is interesting, therefore, to find a structure of this type suggestedin a recent paper on the polyethylene oxides, which are obtained bypolymerising ethylene oxide.44 The solid polymeride has a ringstructure corresponding to the formulaThese views may be contrasted with the micellar theory of thecolloidal nature of cellulose. According to Staudinger it is correctto speak of a micelle only if one refers to the whole crystallite ofcellulose, which can exist only in the solid state. The colloidal pro-perties of cellulose derivatives are held to be due not to the fact thatthe molecules are associated together in micelles, as in certain soapsolutions, but to the special properties possessed by very long chainswhich are equal in size to colloidal particles.In one direction thechains are colloidal in nature, while being of ordinary molecularmagnitude in the other two.Such conceptions obviously involve new ideas on the structureof organic colloids, and as a model whereby the behaviour of thesesubstances might be further elucidated the polystyrenes wereselected.45 Here again it has been found that polymerisation ofstyrene proceeds with the formation of macro-molecules built u paccording to the following general plan :By employing a variety of experimental conditions, polymeridesof all grades have been obtained and it has been shown that thesepolymerides are not micellar in structure, but resemble the polyoxy-methylenes in consisting of “ polymer-homologues.” Here it ispossible, by the use of suitable solvents, to fractionate the productsinto groups in which the individual molecules differ only slightly insize, and knowledge is thus gained of the variation of physicalproperties with increasing length of chain.In particular it appeared43 Compare W. N. Haworth, “ The Constitution of Sugars,” London (1929).44 R. Staudinger and 0. Schweitzer, Ber., 1929, 02, [B], 2395; A . , 1268.4 5 H. Staudinger, M.Brunner, K. Frey, P. Garbsch, R. Signer, and S. Wehrli,ibid., p. 241; A., 305; H. Staudinger, M. Asano, H. F. Bondy, and R. Signer,Ber., 1928,01, [B], 2575; A., 321 ; H. Staudinger and H. F. Bondy, Annulen1929,408, 1 ; A., 321ORGANIC CHEMISTRY.-PART I. 113that the viscosity of solutions of polystyrenes of equal concentrationincreased as the grade of polymerisation increased, and by makinguse of these observations it is estimated that some of the productsexamined had an average molecular weight of more than 100,000.The latter substances must therefore be " macro-molecules " in thesense referred to above and it follows that in certain cases macro-molecular substances are capable of entering into solution. Thegoverning condition is to be found in the nature of the inter-mo€ecularforce, which is stronger in the more symmetrical molecules such asthe polyoxymethylenes.Hence paraffins of molecular weight of1000 are insoluble, whereas polystyrenes of molecular weight100,000 are still readily soluble.The polystyrenes are therefore similar in structure to the polyoxy-methylenes and consist of long chains some 1000 times longer thanbroad. They are colloidal in one dimension only, and their stabilitydecreases as the length becomes extreme. They are then thermo-labile and on heating undergo a '' cracking " process with formationof lower homologues. The nature of the end groups present in thehigher homologues has not been determined directly, but those oflow molecular weight possess ring structures. This fact, consideredin conjunction with the work of J.R. Katz 46 on the nature of largerings, renders it very probable that the higher members are alsoarranged as narrow rings whose sides are close together and parallel.C6H5-TH-CH2-[CH( C6H5)-CH2]z-CH( C6H,)-~H2CH2-CH( C,H,)-[CH,-CH( C6H5)]z-CH2-CH-C,H,(x = 1-500.)This polymerised hydrocarbon provides a model for caoutchoucand guttapercha, which are constructed on similar lines to the aboveand whose colloidal properties are dependent not on a micellarstructure but on the presence of very long chains, forming macro-molecules. It is suggested that the difference between caoutchoucand guttapercha is one of cis-trans-isomerism rendered possible bythe presence of the double bond.*'Colloids of the types referred to above are designated molecularcolloids,4s since in them the colloidal particle is at the same time themolecule.They are to be distinguished from the micellar colloids,such as the soaps, which are formed by the association of particlesof lower molecular weight. Amongst the molecular colloids twodivisions may be recognised, it being always remembered that the46 Z. angew. Chern., 1929,42, 828.47 H. Staudinger, Helv. Chim. Acta, 1929,12, 1183.For a general account of organic colloids, see H. Staudinger, Ber., 1929,82, [B], 2893114 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.dividing line between the sections must be indefinite, since themolecular colloids form a continuous series of gradually increasingmolecular weight. When the molecular weight is relatively small(1000--10,000 for polystyrenes), the molecular colloids dissolvewithout swelling, giving solutions of low viscosity which obey thelaw of Poiseuille.Such substances do not possess in full the typicalcolloidal properties and are called " hemi-colloids." On the otherhand, substances of greater molecular weight (the labile macro-molecules) show marked swelling with solvents, and give highlyviscous solutions, the relative viscosities of which are dependent onpressure and show, therefore, departures from the law of Poiseuille.These are the true colloids, in the sense in which the word was usedby Graham, and to distinguish them from the hemi-colloids they aregiven the name eu-colloids (or macro-molecular colloids).The homopolar polymerides exemplified by the polystyrenesare comparatively simple cases of natural colloids.Much greatercomplexity of behaviour is shown by polymerides containingcarboxyl, hydroxyl, or other reactive groups (cellulose, starch, etc.).Here the strong dipolar character of the substituent groups mayresult in the formation of co-ordinate linkings between the molecularchains. The structure is therefore three-dimensional and, when amolecule of this nature is found in solution, still further complicationsmay occur by the formation of co-ordinate linkings between themolecule and the solvent. The most complex of all substances are,however, the heteropolar molecular colloids which are ionised andmay at the same time display both marked solvation phenomenaand a tendency towards co-ordination.As the model substance forthis class, which includes viscose and the protein substances, thepolymerides of the sodium salt of acrylic acid 49 have been studied.It must be emphasised that these organic molecular colloids haveno relationship whatever with the so-called colloidal particles ofinorganic chemistry (colloidal metals, etc.). The latter are, properlyspeaking, suspensoids or emulsoids formed by the splitting up of agiven substance into small particles. It is possible to obtain asuspensoid by dispersing an organic substance in a solvent in whichit is insoluble, but such a suspensoid sol with its roughly sphericalparticles visible in the ultra-microscope, differs fundamentally fromthe organic colloids now under consideration.Solutions of thelatter are optically empty and the colloidal particles in them areidentical with the molecules of the dissolved substance. There is,however, one important inorganic molecular colloid, namely, silicicacid, which is similar in structure to polyacrylic acid.Both the homopolar and the heteropolar molecular colloids differ49 H. Stctudinger and E. Urech, Hdv. Chim. Acta, 1929,12, 1107ORGANIC CHEMISTRY .-PART I. 115from the micellar colloids, the formation of which is due to theinter-molecular forces between comparatively small molecules, andmore particularly to the electrical forces situated on ions. Animportant criterion for distinguishing between miceller colloids andmolecular colloids is found in the observation that the former canusually be transformed into derivatives with normal solubilities,whereas the latter invariably give derivatives which dissolve ascolloids.E’urther differences between the two classes are thatsoluble molecular colloids invariably yield colloidal solutions,whereas association colloids give colloidal solutions in some solventsbut not in others, and molecular colloids, apart from ‘‘ cracking ”phenomena, do not alter in size with temperature as does themicelle in an association-colloid.It is apparent from the foregoing review that Staudinger tends toregard the micellar colloids as of comparatively rare occurrence ascompared with molecular colloids. These views, however, are notshared by K.H. Meyer’m who maintains that proteins, polysacch-arides, and caoutchouc are all built up as micelles formed by theassociation of long chains of atoms which in turn are linked byco-valent bonds. Even apart from these natural products, he holdsthat micelle formation is by no means exceptional and cites thebehaviour of tannin in water, higher hydrocarbons, substantive dyes,and the lower fatty acids in water.W. N. HAWORTH.E. L. HIRST.PART II.-HOMOCYCLIC DIVISION.THE fist discoveries of closed carbon ring-compounds with three-,four-, and five-membered rings were described in the First PedlerLecture1 by (the late) W. H. Perkin. This account of his earlywork reveals the originality and chemical insight displayed by himduring those years when he laid the foundation on which Baeyer’s“ Spannungstheorie ” was built.In accordance with recent practice in these Reports, certainsubjects in which considerable progress has been made are neverthe-less held over so that they may be more adequately dealt with on afuture occasion.This applies particularly to the subject of aro-matic substitution, in which important work has been published,especially concerning diphenyl and other dicyclic compounds.50 2. angew. Chem., 1929,42, 76; A., 542. J., 1929, 1347; A., 904116 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Attention may be directed here to a valuable summary of the workof C. K. Ingold and his collaborators in this field 2 and to an interest-ing theoretical paper by A.Lapworth and R. R~binson.~Dynamic Isomerism and Molecular Change.(Continued from Ann. Reports, 1928, 25, 118-136.)The fundamental division of this subject may be made by con-sidering (a) whether an atom or group found to migrate moveswithin or without the molecule, and (b) if a separation of parts doesoccur, whether either of these undergoes an internal rearrangement(of atoms or electrons). For instance, the N-chloroacetanilidechange is only apparently an isomeric change, there being actuallyno internal rearrangement of the whole or part of the molecule ; inprototropy (tautomerism), there is true isomeric change in theorganic electromeric ion ; in the imino-ether change, the migrationis entirely intramolecular.* Proved cases of the last type being few,the investigation of a new instance in the triarylbenzenylamidinesby A.W. Chapman is of exceptional interest, and not only for thisreason but also in that the change involves the novel feature of areversibly migrating hydrocarbon radical.The subjects of prototropy, anionotropy, addition t o conjugatedsystems, and migrations of groups will be dealt with in succession.I. Prototropy.-A valuable summary of the theory of prototropicchange and its catalysis has appeared from the Leeds laboratory.6In the same paper a new case of simple triad tautomerism is describedbased on the methyleneazomethine system >CH=N:C< $=>C:N*CH<, the full number of possible triad types constitutedfrom carbon, nitrogen and oxygen atoms being thus realised.Benzylidene-p-methoxybenzylamine and p-methoxybenzylidene-benzylamine reach the following equilibrium in alcoholic sodiumethoxide solution at 85" : (21.1 yo) ~-MeO*C,H,*CW,.N:CH*c6H~ =+=~-MeO*C6H4*CH:N*CH2*c~H~ (78.9%).The proportions of theisomerides are similar to those in the corresponding three-carbonsystem.'of the tautomerism of the three a-diketones benzyl- In a studyRec. trav. chim., 1929, 48, 797.Mem. Munchester Phil. SOC., 1927-1928,72,43; A., 546.J. W. Baker and C. K. Ingold, J., 1929,423; A., 546.Ibid., p. 2133 ; A., 1294.C. K. Ingold and C. W. Shoppee, ibid., p. 1199; A., 027.Idem, ibid., p. 447; A., 556; compare Ann. Reports, 1928, 25, 122.* C. Dufraisse and H. Moureu, Bull. SOC. ckim., 1927, [iv], 41, 1607; A.,1928, 180; H.Moureu, Compt. rend., 1928, 186, 380, 503; 1929, 188, 504,1413, 1557; A,, 1928,419; 1929,449,883,929ORG,4Pr’IC CHEMISTRY .-PART II. 117methyl-, phenylbenz yl-, and phenyl-p-methoxybenzyl- * glyoxalsthe pure diketone and keto-enol forms have been isolated and inthe last two instances the enol was also obtained in cis- and trans-isomerides, the three forms beingAr*CO*CO*CH,Ar’ Ar*COf*OH and Ar*CO*G*OHHCAr’ Ar’CHThe same equilibrium mixture results from either form of phenyl-benzyl- and benzylmethyl-glyoxals above their melting points andin each case contains 70% of the diketonic form.The interconversion of the tautomeric forms of ethyl acetoacetateis a unimolecular reversible reaction catalysed by traces of piperidine,ammonia, bromine, pyridine and quinoline, of which the first isabout 670 times as effective as the last.sThree-carbon systems.Anions of the type R6 are arranged inorder of diminishing efficiency as catalysts of prototropic change asfollows : isopropoxide > propoxide > ethoxide > methoxide >hydroxide.10 A consideration of the inductive effects of the methylgroups at once shows that this is also the order of their diminishingproton-affinity, and is therefore in complete accord with theoreticalrequirements. The proof of these inequalities comes from afurther study of the cyclohexylideneacetone-cyclohesenylacetonesystem and of the interconversion of the closely related esters ethylcyclohexylidene- and cyclohexenyl-acetate.11 There is 57 yo of thelatter (Py-)ester present at equilibrium, and under similar conditionsat 25” the relative speeds of isomeric change in the two systems areindicated by the half-change periods of 9.9 minutes for the ketonesand 14.1 hours for the esters.Analogous ketones of the cyclopentane and cycloheptane serieshave been synthesised and examined : l 2( CH,),-C:CH*COR =+= ( CH,)n-C*CH,*CORj\i v CH,(with n = 3 and 5, and R = Me and Et).The more important data with respect to the equilibration of such* Ph*CO*CO-CH,*C,H,*OMe, misnamed phenylanisylglyoxal in both original* F.0. Rice end J. J. Sullivan, Trans. Farday SOC., 1928,24, 678; A., 36.lo G. A. R. Kon and R. P. Linstead, J., 1929,1269; A., 927.l1 Ann. Reports, 1927,24, 110; 1928, 25, 76.la A.H. Dickins, W. E. Hugh, and G. A. R. Kon, J., 1929, 572; W. E.paper and abstract.Hugh, G. A. R. Kon, and T. Mitchell, ibid., p. 1435; A., 560, 1071118 AXNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.=ids and ketones with five-, six-, and seven-carbon rings arecollected in the table be10w.l~Acids (R = OH). Ketones (R = Me)./ \ / -,Mobility with %a/3 .at Mobility with ?$Et lOKOH at 100'. equi- NaOEt at 25".Ring. librium. 1 O( k, + k, )hr .-l. librium. 1 04( Ic, + Ic, ) min.-l.cycloPentane . . . 14 22 84 much> 700cycloHexane . . . 12 1.0 43 700cycZoHeptane . . . 26 0.66 65 > 3500The high mobility of cyclopentylideneacetic acid as compared withthe cyclohexylidene- and cycloheptylidene-acetic acids is noteworthy,as is also the high mobility and proportion of +ketone a t equili-brium in the five-carbon ketone.The authors l 2 regard thesecharacteristics as surprising, but an explanation of them and of thehigh mobility of the corresponding cyclopentylideneacetonitrile(below) may perhaps be found in the strain caused by the presenceof the ethylenic linkage in the cyclopentene ring : on the simpletetrahedral theory this will tend to alter the inclination of thesingle bonds on either side of it t o an extent of approximately 31" ascompared with the single bond, the angle\C=C being 125" in placeof 109ij0 for \C-C.It was to be expected from analogy that the type of tautomerisrnrepresented by > C=&CH2*CN > CH-&CH*CN wouldoccur, and a few indications of this have been recorded in recentyears. For instance, the ready conversion of ally1 cyanide intocrotononitrile was observed by P.Bruylants in 1922 l4 and byK. von Auwers in 1923,15 and S. F. Birch and G. A. R. Kon l6 at the8ame time made a general examination of the reactions of cyclo-pentenyl- and cyclohexenyl-acetonitriles from this point of view.These and several other nitriles and their ap-isomerides have now l7been found to yield equilibrium mixtures under the influence ofsodium ethoxide at 25" according to fhe equation :A. A. Goldberg and R. P. Linstead, J., 1928, 2343; A., 1928, 1214;l4 Bull. SOC. chirn. Belg., 1922, 31, 175; 1924, 33, 331; A., 1922, i, 817;l5 Ber., 1923, 56, 1172; A., 1923, i, 661.l6 J . , 1923, 123, 2440.1 7 A.KandiahandR. P. Linstead, J., 1929,2139; A., 1294.G. A. R. Kon and R. P. Linstead, Zoc. cit.1924, i, 1053ORGBNIC CBEMISTRY .-PART II. 119The proportions of the isomerides were determined iodometricallyand the more important results are given below :%US at Mobility.fly-Nitrile. equilibrium (k,+k,) . lo4 rnin.-l.a-d -cycZoHexenylacetonitrile ............ 95 920a-cycZoHexenylpropionitrile ............... 94 360a-cycZoHexenylbutyronitrile ............... 90 74cycZoPentenylacetonitrile .................. 93.5 > 1000/3-Methyl-da-pentenonitrile 99 > 1000The cyano-group has thus a powerful activating effect: theposition of equilibrium is altered slightly in the direction to beexpected by the introduction of alkyl groups in the a- position.Onthe other hand, the mobility falls with increased size of these groups.A number of anomalies in the chemistry of unsaturated nitriles arecleared up in this paper, but it may be remarked that in formulatingcondensation reactions involving substances of this type it shouldnot be forgotten that this is a pentad cyano-imino system, not 5tsimple three-carbon one, and that the nitrogen atom may be directlyinvolved when a sodium salt is produced.l*Indirect evidence of an interesting prototropic change has beenobtained from the reactions of y-chloroallyl quaternary ammoniumsalts discussed below.11. Anionot~opy.-Our knowledge of anionotropy continues todevelop rapidly, and one important outcome of this is the elucidationof certain problems involved in the addition of halogens to con-jugated systems of double bonds,lg to which reference will presentlybe made.An interesting new type of anionotropy has been realised2*which arises from the influence of an adjacent positive pole asshown in the scheme :CH, [ X]*CH:CH*NR, CH,:CH*CH[ X]*NR,.Alcoholic sodium ethoxide readily converts a trialkyl-y-chloroallyl-ammonium salt into the trialkyl-a-ethoxyallylammonium salt, theconstitutions of the initial and the final product being clear from theresults of their ozonolysis.This surprising result is satisfactorilyinterpreted in the following scheme, in which a prototropic changeinduced by the ethoxide ions is followed by a reaction involving ananionotropic rearrangement :l8 Compare A.Lapworth and J. A. McRae, J., 1922,321, 2741.(R = H, n = 4)(R = CH,, n = 4)(R = C,H,, n = 4)(R = H, n = 3) ...............+ +Ann. Repon%, 1928,25, 127.C. I<. Ingold and E. Rothstein, J., 1929, 8; A., 300120 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.CHCl:CH-CH,*$R,)X .1 OEt'CHC~:CH-~H&R, T-- CHCl*CH:CH*GR,/ prototropic change- CH,Cl*CH:CH*SR,)X/ .H *4 - y - -...+----A bH2*CH:CH*NR3}X ---- CH, :CH*&H*&R)XCH2:CH*CH( OEt)*hR,}XThe final product is an ethoxy- and not a chloro-ally1 salt becausethe ethoxide ion has a greater co-ordinating power than the chlorion,and is moreover present in excess. The ethoxyl group of the finalquaternary salt is stable to alkalis, but is hydrolysed by acids.A comparison 21 of the effects on simple three-carbon anionotropys.1 OEt'snionotropic change !of adjacent methyl or phenyl groups, cr Me-CH-CH-CH, andconfirms the conclusion reported last year c'i f iPh-CH-CH-CH,,that the phenyl group causes the greater activation of the system.The interconversion of the corresponding ethylpropenyl alcoholsand chlorides has been examined by C.Prkost.22Further examples of anionotropic changes in meso-substitutedanthracene derivatives are recorded by E. de B. Barnett and hiscollaborators.=111. Addition to Conjugated Systems.-A theory of the mechanismof the reduction of unsaturated systems has been put forward byH. Burton and C. K. Ingold 2% which satisfactorily correlates a largenumber of facts. It is held that the units added in reduction bymetals in aqueous media are not atomic hydrogen but protons andelectrons, taken up in successive steps :n f >C=y--+X s >&yH-X -+ >C--QH-XH'(Stage 1.) (Stage 2.)A proton is first added to the molecule which has become polarised21 H.Burton, J., 1929, 455; A., 564; Ann. Reports, 1928, 25, 121, 128.22 Compt. rend., 1928,187, 1052; A., 170.23 J., 1929,1754; A., 1171; Ber., 1929,62, [B], 423,1969; A , , 448, 1289.24 J . , 1929, 2022; A., 1270ORGANIC CHEMISTRY .-PART IT. 121at the surface of the metal (stage 1) : the resulting kation nexttakes up two electrons from the metal (stage 2) : the anion soproduced finally combines with a second proton : > C-QH-X 9>CH-TH-X (stage 3) and the reduction is complete.If the group X attracts electrons, it will clearly facilitate stage 1and both inductive and tautomeric effects may assist.Inunsaturatedacids or ketones the keto-group may perhaps provide an indirectroute for the addition of the first proton, in the way suggested byThiele. At the conclusion of stage 2 the net effect is that negativehydrogen (H- or Hf, 2 0 ) has been added. The whole process ofreduction is therefore the successive addition of H- and H+, whereasaddition of bromine is in the order Brf, Br.25 Consequently theaddition of hydrogen to unsaturated systems is related to prototropyin the same way as the addition of bromine is related to anionotropy.The contrast in result is well seen in the fact that as-diphenyl-butadiene yields a 1 : 2-dibromide but a 1 : 4-reduction product.The observations of R.Kuhn and A. Winterstein z6 that terminallysubstituted diphenyl-hexatriene, -octatetraene, and -decapentaeneall take up hydrogen at the two ends of the long chain are equally inaccord with the theory, and much other evidence is presented inBurton and Ingold's paper.With reference to the addition of bromine to conjugated systemsit will be well not to take the partial view that 1 : 2-addition isinherently more direct or probable than 1 : 4-addition. Thealternative products are found experimentally to be interconvertibleand the theory of anionotropy requires them to be so. It is more-over generally characteristic of the reactivity of tautomeric systemsthat a reaction which should rationally yield one substance producesits isomeride.To regard this as a two-stage process is an unneces-sary assumption. The immediate product in such reactions isfrequently found to be " indirect."The following slight modification of the scheme given in the lastReport 2' is free from the particular bias referred to :-lions of 1 : 2-bromide e 1 : 2-bromide[ions of 1 : 4-bromide e 1 : 4-bromideReagents -+-Various circumstances (structural, steric and catalytic) may beexpected to share in determining the proportions of the isomeridesinitially formed.In a re-examination of the addition of bromine to A1:3-cyclo-Helv. Chim. Acta, 1928, 11, 123; A., 1938, 281.45 Ann. Repwt8, 1928, 25, 131.21 Ann. Reports, 1928, 25, 132122 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.hexadiene and cycZopentadiene28 the results of J.Thiele are sub-stantiated in the latter case, but some 1 : 2-dibromo-A3-cydopenteneis also produced. The proportion of the 1 : 2- and 1 : 4-productscould not be determined quantitatively, but the proof of theirstructures by oxidation was confirmed.From cyczohexadiene a new crystalline dibromide is obtained whenthe bromine is added in chloroform or hexane solution below -15"and the solvent rapidly evaporated at a low temperature. Thissubstance and a liquid of the same composition which accompaniesit are regarded as stereoisomeric 1 : 2-dibromo-A3-cyclohexenes (I).Both are rapidly converted on keeping into the well-known solid1 : 4-dibromo-A2-cycZohexene (11), which is the chief or sole productCH I CHBr/ >< /\(1.) 9% p P2--g?!- (I1.)\/ \/CH, CHBr CH, CHCHBr CHBrif the bromination is carried out without special precautions. Theauthors assert that exclusive 1 : 2-addition has been effected atlow temperatures, oxidative degradation of the new substancesyielding only succinic acid and no ma'-dibromoadipic acid.Buti t is also true that no a@-dibromoadipic acid was found and thatthe solid 1 : 4-dibromide gave only succinic acid (and no ax'-di-bromoadipic acid), while analogy with the products from cyclo-pentadiene (where structures were proved) would suggest that thenew liquid isolated is probably a mixture and is likely to containsome of one or both of the possible stereoisomeric 1 : 4-bromides.The addition of chlorine to a-phenylbutadiene has been found 29to yield under a variety of conditions only the 78-dichloride.IV.Migrations of Groups.-In the Report for 1925 3O an accountwas given of the conversion of N-phenylbenziminophenyl ether intobenzoyldiphenylamine by intramolecular change involving themigration of a phenyl group. A detailed study has since been madeof the relative speeds of the change in substituted ar~limino-ethers.~lIn the transformationArO-CPhXPh -+ 0:CPh-NPhArthe various groups Ar are arranged in the following order of descend-28 E. H. Farmer and W. D. Scott, J., 1929, 172; A., 304.29 I. E. Muskat and K. A. Huggins, J. Amer. Chem Soc., 1929, 51, 2496;A., 1170.Ann. Reports, 1925,22, 114.31 A.W. Chapman, J., 1927,1743; A., 1927,874ORGANIC CHEMISTRY .-PART II. 123ing ease of migration : o-nitrophenyl>2 : 4 : 6-frichlorophenyl>p-acetylphenyl > 2 : 4-dichlorophenyl> o-chlorophenyl > m-chloro-phenyl>p-chlorophenyl and a- and p-naphthyb phenyl ando-anisyl>m-anisyl>p-anisyl( > methyl), this order being that ofthe strengths of the corresponding acids or phenols (Ar*CO,H and&*OH) and therefore of the affinities of these groups for electrons.On the other hand, with various groups attached (a) t o thenitrogen or (b) to the carbon atom of the imino-ether, a phenylgroup migrates with a velocity which diminishes in the oppositedirection in the above series, for instance, p-anisyl> phenybchlorophenyls.On these grounds the change may be formulatedelectronically and the author's view in brief is as follows :The moving group R carries its binding pair of electrons with it.An intermediate stage is assumed in which R is attached to boththe oxygen and the nitrogen atom by singlet linkages. An altern-ative possibility, which accounts better for the influence of variationsin R', is that the initial step is the direct attraction by R of one orboth of the lone electrons of the nitrogen atom.This transformation has found practical use as a method for thesynthesis of otherwise inaccessible diphenylamines of determinedconstitution.32The imino-ether change is quantitative and no reversal can bedetected. The corresponding imino-thioether, Ph*S*CPh:NPh,decomposes at the temperatures necessary for such changes, butcircumstantial evidence was obtained that a reversible conversionto thiobenzoyldiphenylamine, Ph*CS*NPh,, was also occurring.33It has now been found that the diphenyl-p-tolylbenzenyl-amidines are reversibly interconvertible above 300" :The equilibrium mixture is found by proximate analysis to containabout 65% of (11).The change is seen to be analogous to thetautomerism of the amidines discovered by H. von Pechmann in1895,34 and it constitutes the first case of the definitely reversiblemigration of a hydrocarbon radical.32 A. W. Chapman, J., 1929, 569; A., 550; C. S. Gibson and J. D. A.Johnson, ibid., p. 1473 ; A., 1090.83 Idem, ibi&., 1926,2296; A., 1926, 1138.34 Ber., 1895, 28, 869; A., 1895, i, 347124 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.A new molecular transformation involving the movement of itbenzyl group from nitrogen to carbon has been dis~overed,~~ whichwould appear to be intramolecular (although i t is not, strictlyspeaking, an isomeric change).Phenacylbenzyldimethylammoniuinbromide is converted readily by aqueous alkali into pure o-dimethyl-amino-o - benz ylace t op henoiie :[Ph*CO*CH,-&Me,*CH,Ph]OH +Ph*CO*CH( CH,Ph)*NMe, +H,O.The further investigation of this reaction will be awaited withinterest.The ni t r oamine-ni t r oaniline change in 3 - b r om o -p - t olylni t r oaminehas been followed quantitatively by a colorimetric method, andearlier results in general ~onfirrned.~~ The reaction is of the firstorder and is catalysed by various strong acids.Although hydro-chloric and nitric acids are equally effective in 50% acetic acidsolution, in 98% acetic acid nitric acid has a feeble catalytic effectcompared with hydrochloric and other acids. The authors holdthat this excludes the possibility of a two-stage process involvinghydrolytic liberation of nitric acid which might then nitrate theamine, and conclude that an intramolecular process must play theimportant part. However, the reaction is not quantitative (as atruly intramolecular change should be), nor is it free from sidereactions. The occurrence of extra-nuclear migration of the nitro-group to a foreign aniline nucleus has, moreover, been detected.It is possible that some other explanation may be found for thecurious catalytic effects mentioned.If the actual reagent innitration were nitrous acid or nitroxyl chloride, some such effectsmight occur.The claim of B. Flurscheim and E. L. Holmes3' to have founda case of intramolecular meta-migration from the side chain into thenucleus during the nitration of phenylbromocyanonitromethanehas been very completely disproved by J. W. Baker and C . I<.I n g ~ l d . ~ * On the other hand, the latter authors regard the pro-duction of p-nitrobenzoyl cyanide in the same reaction as due to thepara-migration of a nitro-group in the decomposition of the originalnitromethane, and reactions are discussed which may account forthe products observed.In this instance, once again, the fact thatno simple quantitative change can be followed makes it wiser toremain sceptical as to whether any intramolecular change is involved.The movement of various acyl groups from one oxygen atom to35 T. S. Stevens, E. M. Creighton, -4. B. Gordon, and M. MacNicol, J., 1928,36 A. E. Bradfield and K. J. P. Orton, J., 1929, 915; A., 804.3 7 J., 1928, 483; A., 403.3193; A., 180.38 J., 1929, 423; A., 546ORGANIC CHEMISTRY .-PART II. 125another of polyhydroxyanthraquinones is found to occur onlybetween adjacent hydroxyl groups39 and may be regarded asinvolving a cyclic intermediate :\/O ,0.C10*CH3xzZo*C& -+ - >\OHThe conversion of phenyl benzyl ether 40 into 4-benzyl- and2 : 4-dibenzyl-phenols by zinc chloride is largely or entirely anintermolecular process.The same is presumably true of the changeof p-naphthyl methyl ketone into its a-i~omeride,~~ catalysedparticularly by hydrochloric acid.A definite disproof of the independent existence of an inter-mediate of the type Ph*CO*N< sometimes postulated to account for&he Curtius and Hofmann reactions appears to be provided by theobservation 42 that benzoylazide decomposes in presence of tri-phenylmethyl, yielding only the usual products : Ph*CO*N, __pN2 + PhNCO. Any such reactive nitrogen compound would beexpected to combine to some extent with the triphenylmethyl.Physical Properties of Benzene Derivatives.(Continued from Ann. Reports, 1926, 23, 143-149.)Recent work on X-ray crystal analysis, on direct and indirectexamination of spectra in the infra-red region, and on the electricaland magnetic properties of organic substances has provided adefinite answer to one of the most important questions of organicchemistry, namely, that of the structure of benzene.The resultsobtained by each of these three physical methods of investigationsupport the conclusion that the benzene ring is normally of flathexagonal shape with the atoms all lying in a single plane.I. X-Ray Investigation.-It should be pointed out in the firstplace that Sir William Bragg’s formulae for the carbon skeletons ofaromatic hydrocarbons,43 in which the atoms are represented as notall lying in a single plane, were not completely proved, but wereadopted as being consistent with the X-ray observations thenobtained and with the preservation of the tetrahedral disposition ofvalencies as in diamond.A complete solution of the structural problem for hexamethyl-benzene has now been obtained by (Mrs.) K.Lonsdale 44 without3o A. G. Perkin and C. W. H. Story, J., 1929, 1399; A., 1074.40 W. F. Short and 31. L. Stewart, ibid., p. 553; A., 552.4l L. Chopin, BUZZ. Soc. chim., 1929, [iv], 45, 167; A., 661.42 G. Powell, J . Arner. Chern. Soc., 1929, 51, 2436; A., 1176.4s J., 1922, 121, 2783.I4 Trans. Fara&y SOC., 1929, 25, 356; A., 750126 AKNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.making any arbitrary assumptions. All twelve carbon atoms ofthe substance lie in one plane, deviations from it not exceeding0.1 8.The ring is a hexagon identical in size with those to be foundin graphite. The nuclear carbon atoms are thus of diameter1.42 & 0.03 8., whereas the side-chain carbon atoms are different,being in fact of the size found in diamond and aliphatic substances(diameter 1.54 A.). Other dimensions of benzene are : distance fromcentre to centre of meta carbon atoms, 2.46 8. ; breadth in this samedirection, including the two hydrogen atoms, 6-23 A. ; diameterinclusive of hydrogen atoms in para-direction, about 7 8.There can be little distortion of the hexagon, yet, as the symmetryis not completely hexagonal, the view is adopted that some distortionmust occur. It would appear possible, however, that the dis-position of the hydrogen atoms of the methyl groups might providea sufficient explanation without any distortion of the ring.The result is of the greatest importance for aromatic chemistry.The unsymmetrical introduction of polar substituents into the ringmight conceivably slightly alter the shape of the ring, but it will bewell to assume that the flat hexagonal structure with valencies all inone plane is the rule among all aromatic nuclei until evidence isfound of deviation from a single plane.The fate of the fourth valency of the nuclear carbon atoms is leftundecided by these results.A formula for naphthalene has alsobeen discussed,45 which accounts for the X-ray results with thissubstance, and in which an " anisotropic carbon atom " is presenthaving two pairs of valencies of differentLess definite but interesting results are obtained from the difiac-tion of X-rays by liquids.The haloes produced are regarded 47as due to structure. It is possible by this means to distinguishbetween is~merides,~~ to detect the presence of long, flat, or doubledmolecules, and to calculate approximate molecular dimensions.49The mean distance between molecules of paraffins with five to eightcarbon atoms and also of very long-chain compounds is about4-9 8. perpendicular to their length. The dimensions found intwo perpendicular directions are 6.2 and 3.2 8. for benzene and 6.4and 4.6 8. for cyclohexane. The diameter of menthone is found as4 5 (Mrs.) K. Lonsdale, Proc. Leeds Phil. SOC., 1929, 1, 346; A., 307.46 See ref.56.4 7 K. S. Krishnan and S. R. Rao, Indian J . Physics, 1929, 4, 39; A.,4 8 C. M. Sogani, ibid., 1927,1, 357; 2, 97; -4., 1927, 924, 1129.49 V. I. Vaidyanathan, ibid., 1929, 3, 371, 391; A., 746, 751; P. Krish-namurti, ibid., pp. 331, 507; A., 751, 989; G. W. Stewart, Physical Rev., 1929,[ii], 33, 889; A., 985; J. R. Katz and J. Selman, 2. Ph.y8ik, 1928, 46, 393;A., 1928, 222.1129ORGANIC CHEMISTRY .-PART II. 1275.35 A,, that of cadinene about 7 A. Somewhat similar informationis obtainable by measurements of viscosity in vapours."11. Infra-red Absorption and Raman Spectra.-A valuable generalreview of the significance of molecular spectra has appeared.51 Theinvestigation of structure by means of the infra-red absorption isbecoming of increasing importance and the recent discovery of the" Raman effect " has provided a new and rapid method of attackin the same direction.5,When a substance is illuminated with monochromatic light, thespectrum of the scattered light contains lines or bands which areevidence of characteristic frequencies of the molecule and correspondwith infra-red lines.The infra-red band found at a wave-length ofabout 3.4 p in the spectra of organic substances and regarded at firstas due to CH, and CH, groups is now attributed to the C=H linkage.53This band, as confirmed by the Raman method, is a t 3.4 p in paraffinhydrocarbons and at 3.25 p in benzene,54 values nearer the latterfigure being found for ethylene and tetrachloroethane. The Ramanspectrum of toluene reveals the two lines side by side with wave-lengths of 3.43 and 3.28 p respectively.A detailed study of theRaman spectra of hydrocarbons by A. S. Ganesan and S. Venkate-swaran 55 confirms the difference in frequency of the OH bonds inbenzene and cyclohexane.The values undoubtedly indicate that the C-H bond in benzeneand in compounds such as chloroform is stronger than that inparaffins or in cyclohexane. The conclusion is also reached thatthere may be two different kinds of C*H bond originating at onecarbon atom, which conception is in agreement with a similar onederived from X-ray data for hexachl~roethane.~~111. Electrical and Magnetic Properties.-(a) Optical, electricatand lnagnetic anisotropy. In an analysis of the physical peculiaritiesof aromatic compounds, (Sir) C.V. Raman and S. Bhagavantam 57emphasise the fact that these substances are characterised by a high50 T. M. Lowry and A. G. Nasini, Proc. Roy. SOC., 1929, [A], 123, 686, 692,704; A., 637.51 W. E. Garner and J. E. Lennard-Jones, Trans. Faraday Soc., 1929, 25,61 1 ; and succeeding papers.s2 (Sir) C. V. Raman and K. S . Krishnan, Indian J. Physics, 1928,2,399;A., 1928, 1075.s3 G. B. Bonino, Gazzetta, 1923, 53, 555; A., 1923, ii, 711; J. W . Ellis,Physical Rev., 1924, 23, 48 ; A., 1924, ii, 219.54 P. Pringsheim and B. Rosen, 2. Physik, 1928, 50, 741 ; A., 1928, 1307;G. B. Bonino, ibid., 1929,54,803 ; A., 740.5 5 Indian J . Physics, 1929, 4, 195; A., 1215.56 (Mrs.) K. Lonsdale, Phil. Mug., 1928, [vii], 6,433 ; A., 1928, 1079.5 7 Indian J .Physica, 1929,4,67; A., 1126128 BNNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.optical, electrical, and magnetic anisotropy both in the crystallineand in the fluid state.Experiments on the molecular scattering of light in liquids 58 andthe double refraction of crystals show the optical anisotropy ofaromatic compounds to be generally large as compared with that ofaliphatic compounds. The difference is very inadequately revealedby the values of molecular refractivity, because this propertyrepresents an average in all directions in space. An even greaterdifference is shown in electrical and magnetic anisotropy by aromaticand aliphatic compounds, as indicated in the liquid state by theKerr and the Cotton-Mouton constants, and also in the crystallinestate.59 cycZoHexane behaves as an aliphatic substance in theserespects.These physical differences are closely paralleled in theproperties of graphite and diamond, which may be regarded as ofthe aromatic and the aliphatic type respectively.This paper 57 also contains a discussion of the molecular mechan-ism responsible for these properties and for light absorption, atten-tion being directed to the conceptions of S. Dutt.60(b) Dipole moments of organic substances (continued from Ann.Reports, 1926, 23, 147-149). The publication of an authoritativework by P. Debye on the subject of molecul&r polarisation will begenerally welcomed.61 Research in this field is proceeding sorapidly that the literature dealing with this property of organicsubstances is already voluminous.Values of the dipole moments of organic substances are tabulatedbelow, including some aliphatic compounds, as these are necessaryfor the discussion of the additive nature of the moment.All availabledata have been considered in compiling this table, and in somecases the mean of more than one independent datum is given, butall important references are added. Most of the values have anuncertainty of about 0.1, although some are certainly more precise.Dipole Moments. Unit = 10-l8 E.X.U.(1) Hydrocarbons and Monosubstituted Compounds.Hydrocarbons :Olefins 8 2 ~ 63Toluene 64P' P aAlkyl halides : 63, 660-5 Chlorides 2.10.5 Bromides 1.95 8 K. S. Krishnan, Phil.Mag., 1925, [vi], 50, 697; A., 1925, ii, 1030.5D M. Ramanadham, Indian J. Physics, 1929, 4, 109; A., 122; S. Bhaga-vantam, Proc. Roy. Soc., 1929, [A], 124,545; A., 982.60 J., 1926, 1171 ; A., 1926, 830.6 1 " Polar Molecules " (Chemical Catalog Co., 1929).62 C. P. Smyth and C. T. Zahn, J . Amer. Chem. SOC., 1925, 47, 2501.a3 K. HGjendahl, Physikal. Z., 1929,30, 391 ; A., 980.64 J. W. Williams, ibid., 1028,29, 174, 683; A., 1928, 578, 1180ORGANIC CHEMISTRY .-PART II. 129Alcohols 64* 65* 66Phenol 64Ethers : 63, 64, 67, 68AliphaticAnisoleDiphenyl ether 6 7Ethylene oxide 6 8Aliphatic ; cyclohexanoneAcetaldehydeKetones : 6% 64, 6sAldehydes :P1.681-701.21.21.01.882.732-7PAryl halides : 63, 64, 66, 67, 70, 7 1Iodides 1.85Fluorobenzene 1.38Chlorobenzene 1.55Bromobenzene 1-5Iodobenzene 1.2Nitriles : 63m 72Aliphatic 3.4Benzonitrile 3.8h i n e s : 63, 67, 73Alipha.tic R*NH, 1.3; R,NH 1.0;R,N 0.76Benzaldehyde 64 2-75 AroGatic Ph-NH, 1-5; Ph2NH 1.3;Ph-NMe, 1.4Benzoic acid 134 1.0 Nitro-comnoun'ds : 630 643 6 7Esters : Nitromithane 3.05Aliphatic 1-7 Nitrobenzene 3.90Methyl benzoate 67 1.8(2) Disubstituted Benzenes.63, 649 66* 67, 703 71, 74I p - 1.60- 1.0OMe : Melrn- 1.2( p - 1.20- 1.4p - 1.7( p - 0-51.3P.0- 4.1 1 p - 2.55C1 :NO, m- 3-4Br : NO, p- 2-53NO, : OMe{ ;I 2:;0- 4-45NO, : NH, m- 4-72 -I p - 7.1NO, : CHO p - 2.4NO2 :CO2H p -NO, :NO, {;*{ :- NO, : MeC0,Me : C0,Me {;:NH, : C0,Me jz-IP-P*3.56.03.83.74.34.52.82.21.02-43.3Substances found to have negligible moments are : paraffins,benzene, diphenyl, p-xylene, s-trialkylbenzenes, p-dichloro- anddibromo-benzenes, s-tribromobenzene. In homologous series thevalues are generally remarkably constant, with some exceptions inthe case of the first member.The effects of temperature are fullydiscussed by Debye 75 and others.65, 679 70, 7665 (Miss) L. Lange, 2. Phyaik, 1925, 33, 169; C. P. Smyth and W. N.Stoops, J . Amer. Chem. Soc., 1929,5l, 3312, 3330; S. Mizushima, Proc. Imp.Am&. Tokyo, 1929,5, 15; A., 380.6 6 P . Gross, Phyaikd. Z., 1929,30,604; A., 1128.6 7 G. Hedestrand, 2. physikal. Chem., 1929, B, 2, 428.6 8 H. A. Stuart, 2. Phy&k, 1928, Sl, 490.6s K.L. Wolf,Z. physikal. Chem., 1929, B, 2,39; 3, 128; A., 743.70 C . P. Smyth, S. 0. Morgan, and J. C. Boyce, J. Amer. Chem. Soc., 1928,71 P. Walden and 0. Werner, 2. phydkd. Chem., 1929, B, 2, 10.72 J. W. Williams, ibid., 1928,138, V5; A., 121 ; 0. Werner, ibad., 1929, B,7s A. Weissberger and R. Siingewald, ibid., 5, 237; A., 1217; A. Weiss-7' C. P. Smyth and S. 0. Morgan, J. Amer. Chem. SOC., 1927,49, 1030; A.,76 0. Werner, 2. physikal. Chem., 1929, B, 4, 393; A., 1317.SO, 1536 ; A., 1928,815.4,371 ; A., 1217.berger and J. W. Williams, ibid., 3, 367; A,, 866.1927, 611. 7 5 Op. cit., pp. 19, 55.REP.-VOL. XXVI. 130 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The approximately additive nature of dipole moments in thebenzene series is now generally admitted, but some divergence ofopinion has arisen as to their detailed interpretation.Two classesof compound may be distinguished, (a) those with groups suchas OR, OAc, NR, absent from the molecule, and (b) those in whichone or more of these groups are present.In the former class, with other polar groups such as CH,, NO,, andhalogens, vector addition of their moments seems to hold withoutany large deviation.63+ 64 The compounds of zero moment men-tioned above are of this type and these results are evidence that thegroups and the ring lie in a single plane. I n this connexion, how-ever, the case of s-trinitrobenzene is of interest,64, 67 as this substancehas a real moment of 1-08 units.77 But it is not necessary to regardthis as indicating that the molecule is non-planar : a compound ofthis substance with benzene (used as solvent) is known, which hasrecently been given an unsymmetrical formula.7s Some of thiscomplex is presumably present in solution and may account for theobserved moment.The simple vector addition of dipole moments has been discussedby J.W. Williams,64 who gives the following series of group values :NO,. CHO. OH. C1. Br. OMe. C0,H. CH,. NH,.-3.8 - 2 . 8 - 1.7 - 1.5 - 1.5 - 1.2 -0.9 +0*4 + 186The position of the groups OH and NH, is criticised by P. Waldenand 0. Werner,71 and these are referred to again below. Theseauthors analyse the slight deviations from the additive law forcompounds of class (a) and conclude that there is a regular tendencyfor the moment of an o-disubstituted benzene to be low (actually,to have a smaller negative value than that calculated), which theyattribute to the mutual influence of the groups.Reference should also be made to diphenyl derivatives. Evidenceconcerning these was mentioned in the last Report,79 and otherresults have appearedso which give no support to the Kauflerformula.With the second class of substances (b), having one or more of thegroups OH, OR, NH,, NR, and OAc present in thtj molecule, animportant new factor becomes evident.63, 64, 71 Compounds ofapparently symmetrical formulae give real moments as follows :quinol diethyl ether, 1.7 ; quinol diacetate, 2.2 ; tetramethyl-p-phenylenediamine, 1.23 ; tetramethylbenzidine, 1-25 ; phloro-7 7 P.Dabye, op. cit., p. 52.7e Ann. Reports, 1928, 25, 116.a0 E. Bretscher, Helv. Phys. Acta, 1928, 1, 355; A., 980.G. M. Bennett and G. H. Willis, J., 1929, 259; A., 436ORGANIC CHEMISTRY .-PART lI. 131glucinol trimethyl ether, 1.8 ; dimethyl terephthalate, 2.2 (unit,10-ls E.S.U.). The group of compounds C(CH,X), may also bementioned : where X = C1, Br or I, the expected zero moment wasrealised,sl but when X = OR or OAc this is not the case, penta-erythritol tetra-acetate giving the value 1.9 x 10-ls unit.64 Theexplanation of these anomalies lies in the fact that the moments ofthese groups do not operate along the line of their attachment toother atoms. That this must be so follows from the formulae for thewater and ammonia molecules which have been discussed byDebye.*, An explanation of this kind, which has been used byseveral workers,m, 643 69 immediately accounts for the existence of areal moment in all molecules of class (b) and renders superfluoussuch conceptions as that of a carbonatom of pyramidal configuration.The bond from oxygen or nitrogen to the nucleus is presumablyfixed in direction, but rotation of the whole group on this line ispossible and introduces an uncertainty in calculation. The bestplan appears to be to calculate the upper and lower limits to thevalue of the moment.Thus a calculation on assumptions to bediscussed below indicates that in the extreme positions (I) and (11)of rotation in quinol diethyl ether the moment should beO.O"and 1-9 units respectively, the observed value being 1.7, but aslight rise of this value with increase of temperature which has beendetected 76 was scarcely to be expected.It is shown by A.Eucken and L. Meyer 83 that it is not justifiablet o take the resultant moment of a group OEt as operating along theline O*Et as some authors have done. The molecular moment isregarded as the vector-sum of a number of single moments each inthe direction of a separate interatomic bond. For the purpose ofsummation, however, these may be compounded for any rigidsystem such as CCH,. In these calculations the bonds attachedto oxygen in an ether are assumed to be inclined at an angle ofl10°,s4 and for amines the same angle between valencies seems tobe a reasonable supposition.Component moments deduced by these authors are :C-C H-0 C=O CHS-C H-C G O G-CI0 1-6 2.3 0.4 u.4 0-7 1-581 L.Ebert, R. Eisenschitz, and H. von Hartel, 2. physikal. Chem., 1928,82 o p . cit., pp. 63, 73.84 Compare the second configuration of H,O ; P. Debye, op. cit., p. 73.By 1, 94; A., 1928, 1308.a3 Physikal. Z., 1929, 30, 397; A., 980132 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Fair agreement is found with t,he observed values; for instance,the calculated values for phenol, p-chlorophenol and alkyl chloridesare 1.5, 2.3 and 1.9 respectively (Found : 1.6, 2-4, 2.1). The threecresols present a case where rotation will cause variation : valuescalculated are o- 1.2-1.9, m- 1.2-1-9, p - 1.5 (Found : 1.4, 1.6, 1.6).The experimental figures for p-nitroanisole and p-nitroaniline areby any method of calculation abnormally large (nitroanisole : calc.,3.3; found, 4.36) and the conclusion is inevitable that there is herea considerable mutual influence of the groups.63 There appears infact to be a permanent conjugative displacement of electrons(T effect), causing an enhanced moment, and its magnitude is in theorder N>O>Cl.This explains the large separation of OH and NH,in the group series of Williams.The physical evidence reported in this and the preceding sectionsis consistent in indicating a flat hexagonal ring structure for thebenzene molecule and in excluding several of the older f ormulze,such as those of Baeyer, Korner, Ladenburg, and Sachse. Themodel due to L.Pauling 85 is most in accordance with the facts underconsideration 57, 74 and appears to resemble closely the formula ofClaus. Such a formula justifies the scheme given by Ingold2 toaccount for the transmission of electrical effects in the nucleusdnring aromatic substitution, and should remove any objectionswhich may be held to the para-bond. Such a bond cannot admittedlybe the ordinary chemical bond between carbon atoms, for thedistance is here about twice the normal, but it may safely be assumedthat there is an intimate electrical connexion between the p-atoms.Replacement of Halogens by other Groups.This subject may be divided into two parts dealing with thereactivity of (a) nuclear and (b) side-chain halogens.I. A7uclear Halogen.-It is one of the most important advantagesof the theory of aromatic reactivity originated by Lapmorth andRobinson that it supplies a satisfactory explanation of the reactivityof halogen in such substances as p-chloronitrobenzene.This typeof reaction, which essentially involves attack by a negative ion, hasnot been discussed recently in these Reports.The fact that other meta-directing groups such as S03H, C02H,CHO and CN are also able to activate nuclear halogens in the o- orp-positions to them was shown by M. Schopff as far back as 1891,*6and known instances of such effects are numerous. Polynitro-chloronaphthalenes have equally displaceable halogen. 87 The8 5 J . Amer. Chem. SOC., 1926,48, 1132; A., 1926, 662.8 6 Ber., 1891, 24, 3771; A., 1892, 336.8 7 F.Ullmann and W. Bruck, Ber., 1908, 41, 3932; A., 1909, i, 21; 11.Rindl, J., 1913,103, 1911ORGANIC CHEMISTRY .-PART IT. 133displacement of activated halogens by a variety of reagents wasstudied particularly by W. Borsche 88 and by Kenner 89 and thereaction with piperidine has proved valuable in the hands of Turnerand his collaborators for deciding questions of orientation, parti-cularly in the diphenyl series : a rapid substitution of the piperidylradical for halogen is proof that the latter stood in either an o- ora p-position to one of the nitro-groups present in the molecule.Recent qualitative observations of interest show the remarkablyhigh reactivity of o-bromobenzoic acid in a number of reacti~ns,~land the removal of the nuclear chlorine in chlorobenzenetrisulphon-anilide by anili11e.~2 Mention may also be made of a valuablereview of the literature concerning all kinds of reaction involvingdisplacement of a group from the benzene ring.Q3The underlying principles of these processes from the point ofview of the electronic theory have been briefly discussed by Ing01d.~~The effective reagents are not the positive ions of ordinary substitu-tion which seek negative centres, but groups such M NR,, OH, OR,SR, SCN which me posit~pte-centre-seeking. The normal orientationlaws are therefore reversed.A group such as Me which repelselectrons (+I and +D effects) will have a deactivating influenceand one such as NO, which attracts electrons will activate (-1,-D effects).Moreover the nitro-group will have a powerfulconjugative or tautomeric (-F) effect which will operate by causinga local positive charge increasing at the demand of the reagent.The distribution of these charges in the ring will be the same as inordinary orientation, that is to say, the effects will appear in the o-and ppositions but not in the m-position. The direct effect ( D ) ,however, represents the influence of a diminishing field in space andwill vary in the order o>m>p.At the moment of reaction a halogen atom may be regarded asassisting in the capture of the attacking negative ion by the influenceof its own attraction for the electrons of o=h%-cl the carbon atom to which it is attached,Ju ‘L\\KA+ the process culminating in the transfer ofBer., 1909,42, 601; A., 1909, i, 232; Annalen, 1911,379, 152; A., 1911,i, 329.as J.Kenner and collaborators, J . , 1914,105, 2717; 1920,117, 852; 1921,119, 1047, 1063; 1922, 121, 489, 675; 1923, 125, 1260, 2296; 1925, 12’7,2343; 1927,680; A., 1927,456.Ann. Reports, 1926, 23, 137; 1928, 25, 115; also R. J. W. Le Fhvre,S. L. M. Saunders, and E. E. Turner, J., 1927,1168; A., 1927, 660.0-Dl W. R. H. Hurtley, J., 1929,1870; A., 1294.92 W. Davies and (Miss) E. S. Wood, J., 1928, 1122; A., 1928,746.sa M. P. de Lange, Rec. trav. chim., 1926, 45, 19; A., 1926, 278; compareJ. J. Sudborough and J. V. Lakhumalani, J . Indian Inst. Xci., 1916,1, 133.Rec. trav. chim., 1929, 48, 808134 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.the negative charge of the reagent ion across the atom in questionto the chlorine which is being ejected as an ion.A negative substituent may, however, sometimes enter the nucleusin the absence of halogen, hydrogen being replaced in a positionconforming to the same inverted law of orientation.The followingmay be regarded as cases of this kind : the conversion of nitrobenzeneby potassiocarbazole into p-nitrophenylcarbazole ; 95 the readyoxidation of resorcinol to phloroglucinol and of s-trinitrobenzene topicric acid ; the introduction of either one or two amino-groups intothe molecules of m-dinitrobenzene and s-trinitrobenzene by theaction of hydroxylamine in the presence of sodium ethoxide .96Positive poles, being highly efficient as m-directive groups innormal substit~tion,~~ should also activate halogens in the o- andp-positions, and there is considerable evidence in the literaturewhich is satisfactorily explained in this manner.For instance, thepartial (and reversible) conversion of tribromoaniline into trichloro-aniline by concentrated hydrochloric acid at 200" 98 is no doubt dueto a halogen atom becoming activated by the free pole&€€,}el in the resulting salt, assisted in each case by theinductive and direct effects of the other halogenatoms. Another set of cases of the same kind ispresented by the so-called isomeric change of halogen- .VBr ated diazonium salts discovered by H a n t z s ~ h . ~ ~ Thediazonium ion is a very powerful activator and nuclearhalogen is rapidly displaced from it by the negative ion of the saltor any other negative ion provided.Thus diazotised tribromoanilineis easily converted into a trichlorobenzenediazonium salt reducible tos-trichlorobenzene , and p-chloroaniline furnishes p - thiocyano-benzenediazonium thiocyanate. It will be noticed that the rapidityof these reactions is once again contrasted with the slowness ofordinary aromatic substitution controlled by a free positive pole.The general effect now hastens the reaction instead of retarding it.A reaction of the same kind which may be attributed to activationby a positively ionised carbon atom is that described by M. Gombergand others 99a in which tri-p-bromophenylmethyl chloride is partlytransformed into di-p-chloro-p-bromotriphenylmethyl bromide insolution in liquid sulphur dioxide.It is a property of halogen activated by electron-attracting groupsto suffer ready removal by reduction, and it was recognised by H.g6 R.Robinson, Chem. and Ind., 1925,44,117.g 6 J. Meisenheher and E. Patzig, Ber., 1906, 39, 2533; A., 1906, i, 652.g 7 Ann. Reports, 1926, 23, 130.08 R. Wegscheider, Monatsh., 1897,18, 329; A., 1897, i, 557.99 J. C. Cain, " Diazo-Compounds," 2nd Ed., 1920, pp. 75-81.DBa Ber., 1909, 42, 412; A., 1909, i, 144.BORGANIC CHEMISTRY.-PART II. 135Burton and J. Kenner that the ready elimination of halogen fromsuch substances as 4-bromo-m-phenylenediamine occurs in the saltof the base, in which it is clear that two positive poles may jointlyactivate the halogen.Comparative reactivities of nuclear halogen.A reaction velocitycoefficient represents a fact concerning one reaction under certainexperimental conditions : for different reactions or divergentconditions, the same two substances may possess widely differingcomparative reactivities. Nevertheless, when two reactions are ofsimilar polar type, the results will tend to be similar, and this is trueon the whole for the reactions of activated nuclear halogens withsodium alkyloxides and organic amines studied by A. F. Hollemanin a series of papers.2 The more important general conclusionsdrawn with reference to the polychlorobenzenes and polychloro-mono- and -di-nitrobenzenes are that chlorine atoms exert anactivating influence and that this is most effective from the m-posi-tion, but that it is slight compared with the strong effect of everynitro-group on chlorine atoms in oppositions.Thus m-dichloro-benzene is the most reactive of the three dichlorobenzenes, ands-trichlorobenzene of the isomeric trichlorobenzenes. p-Chloronitro-benzene is more reactive than its ortho-isomeride (p-, 7.2; o-, 1.9)and the introduction of each of two successive extra chlorine atomsinto the nucleus raises the yelocity 13-14 times. This preferen-tial m-activation by chlorine was to be expected : the chlorine atomdiffers from the nitro-group in having a conjugative effect ( +T)which must hinder the reaction under discussion and so leave theeffect in the m-position greatest.In such reactions it is usual for an iodine atom to react less readilythan similarly situated bromine or chlorine 3, and the same seems tobe the case in a comparison of the speeds of dissolution of magnesiumby aryl bromides and iodides under Grignard conditions.5 Thelower inductive effect and smaller tendency to pass into the anionicform characteristic of iodine as compared with bromine are con-sistent with this difference, but the comparison of chlorine andbromine is a more complicated point.The same comparison w&smade by A. H. Rheinlander in a careful study of the reactionvelocities of halogenonitrobenzenes with sodium ethoxide and bases.The bimolecular velocity coefficients at 50" for the reactions ofJ., 1922,121, 679.Rec. trav. chim., 1915,35;, 1; 1918,37, 195; 1920,39, 435, 736; 1921, 40,H.Franzen and E. Bockhacker, Ber., 1920,53, B, 1174; A., 1920, i, 604.H. W. Rudd and E. E. Turner, ibid., p. 686; A., 1928, 504.Ibid., 1923, 123, 3099.67; A., 1916, i, 22; 1918, i, 216; 1920, i, 538; 1921, i, 102, 167.4 A. Brewin and E. E. Turner, J., 1928,332 ; A., 1928,402136 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.sodium ethoxide with the three bromonitrobenzenes were k .lo5 =6.3, 0.0, and 12.2 for o-, m-, and p - : for the chloro-, bromo-, andiodo-2 : 4-dinitrobenzenes with aniline, E . lo3 = 2-75,4.21, and 1.23respectively.In connexion with the comparison in reactivity of iodine witJhchlorine or bromine it is of interest that the group OR of polynitro-aryl ethers is also displaced by amines,' and it may be concludedthat in the series C1, I, OPh, OMe, NR, a group may be used to dis-place any one which precedes it, the ease oE reaction increasing withthe distance apart in the series.It is clear that the tendency of thelast four groups to form the undissociated hydrogen compoundsHI, HOPh, HOMe and HNR, increases in that order, the seriesbeing one of increasing proton-affinity.An estimate of the comparative activating effects of the groupsNO, > SO,H > C0,H has been made by W. Davies and (Miss)E. S. Wood,s who find the ratios 70,000 : 1 : Q for these groups inreactions between mono-, di-, and tri-substituted chlorobenzeneswith aqueous-alcoholic potassium hydroxide. The nitro-group isalso stated to have the property of making other groups moreeffective activators.For instance, the introduction of the groupC0,H or SO,H into o-chloronitrobenzene in the p-position to thehalogen raises the reactivity 4.4 or 16 times respectively, althoughthe reactivity of p-chlorobenzoic and p-chlorosulphonic acids cannotbe detected. It is probable, however, that the latter reactivities,if they could be measured, would show a similar increase as comparedwith that of chlorobenzene.The remarkable influence of the nitro-group is no doubt connectedwith its capacity to form addition compounds, a point of viewparticularly stressed by Kenner, who has established the fact that&reaction is often inhibited by steric hindrance, not at the atom orgroup displaced, but at the nitro-group which activates it.A clearcase of this kind is presented by H. Lindemann and A. P a b ~ t , ~ whohave examined the effect on the speed of reaction with aniline ofintroducing a methyl group in various positions into chloro-2 : 4-di-nitrobenzene. The following are the values of relative reactivity :Parent compound. 5 Me- 6 Me- 3 Me-0.18 0.05 0.01 0.00The general depression of reactivity by the introduction of themethyl group is in accordance with its electron-repelling properties.The authors are at a loss to account for the complete inertness of the3-methyl derivative, but it may be regarded as due to st'eric hindranceto the formation of any addition compound.7 W. Borsche, Ber., 1923,56, By 1488 ; A., 1923, i, 780.8 Loc. cit. (ref. 92). Annalen, 1928,462, 24; A., 1928, 877ORGANIC CHEMISTRY.-PART II.137The exact nature and function of such an addition compound is aproblem of importance and has been discussed recently by A. Brewinand E. E. Turner.lo The following statement is based on their views.The facts may be explained by the conception that a reagent suchas sodium ethoxide or an amine first forms an addition l1 compoundat the nitro-group having the structure (I) or (11), in which the0 OH 0 0 v v tN-NR, e +$--(11.)altered nitro-group may be assumed to have enhanced activatingpower. A second molecule of amine or an ethoxide ion then attacksthis complex at the carbon atom carrying the chlorine, and thereaction proceeds to completion : or, as an alternative possibility,the radical OEt or NR, may migrate to the o-carbon atom by apurely intramolecular change.11.Side-chain Reactivity .-This subject has been discussed in thelast two Reports.12 The following account is supplementary, withspecial reference to the question of displacement of chlorine byiodine or hydroxyl.A very elegant method of measurement has been devised andapplied by .J. B. Conant, W. R. Kirner, and their colleagues todetermine the velocity of the reaction RC1 + I' ---+ R I + C1' fora variety of substances at two temperatures.13 There; is conse-quently available an exceptionally large set of accurate data. Someof these results are in the table below, the figures being reactivitiesof various substances R(CH,),Cl for this reaction in acetone at 50"referred to that of rt-butyl chloride as unity.R.n = O I 2 3 4 5 6 7H - -- 2.52 1.08 1.00 1-35 1.30 1-25Ph - 197 1-12 1.72 1.49 1.42 1-46 1-40PhOCO ca.2200 ca. lo5 86.7 372 - - - -C0,Et 42 1720 1.61 1.65 1.35 - - -- - 0.56 2.74 - - - - Ph*SM e 4 - -- 1-52 2.52 - - - -10 J., 1928,334; A., 1928,402.l1 Compare G. M. Bennett and G. H. Willis, J., 1929, 259; A., 436.12 Ann. Reports, 1927,24, 165; 1928,25, 146.l3 J. Amer. Chem. SOC., 1924, 48, 233; A., 1924, i, 273; J. B. Conant aidIt. E. Hussey, ibid., 1925, 47, 476, 488; A., 1925, i, 493, 494; W. R. Kirner,ibid., 1926, 48, 2745; 1928, 50, 2446; A., 1926, 1224; 1928, 1214; W. R.Kirner and G. H. Richter, ibid., 1929, 51, 3409.E 138 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.The general tendency of the variation of reactivity with structureis indicated by the statement (which also involves data not givenin the table) that R*CH,Cl has a velocity of reaction with iodideswhich diminishes in the following order with variation of R :Ph*CO>MeCO > CN> C0,Et >MeO>AcO> Ph*CO.CH,*CH,> Ph>CH,:CH>C,H,.For comparison with the figures for n-alkylchlorides the relative values of isopropyl chloride, tert.-butyl chloride,and cyclohexyl chloride, 0.015, 0.018, and <0.0001 respectively, areof interest. The order of the above series is identical with thatfound by A. Slator l4 for the reaction of a few of the correspondingiodides with sodium thiosulphate, but not with that found byH. T. Clarke for reactions of bromides with pyridine.15 It is im-mediately noticeable that the order in the series is one of diminishingelectron-affinity, as indicated by strengths of acids or m-directionin aromatic substitution, and this is so much the reverse of whatmight be expected in view of the elimination of chlorine as a negativeion that Conant concluded that the results could not be reconciledwith the electronic theory.It is equally true, however, that the reaction involves the intro-duction of a negative iodine ion into the molecule, and it has beenpointed out, with particular reference to aryl p- and y-chloroalkylsulphides, that the explanation may lie in the formation of a com-plex between the chloride and an iodine ion.l* This will be hastenedby any recession of electrons from the carbon atom carrying thechlorine, and, if the subsequent liberation of the chlorine ion is veryrapid, the observations are explained.This view is supported bythe fact that structural changes which increase the speed of thisreaction diminish that of hydrolysis. For instance, the y-chloro-sulphide reacts faster with iodide but more slowly in hydrolysis thanthe corresponding (3-chloro-sulphide, and the introduction of anitro-group accelerates the former but retards the latter reaction.The following comparison of the values of relative reactivity foundby Conant and by Olivier for the two reactions further illustrates thepoint. In each series the values refer to that for benzyl chloridetaken as unity.o-NO,.m-NO,. p-NO,. o-C1. p-C1. o-Br. p-Br.Iodide (Conant) l7 9.2 4.0 7.0 3.64 2.80 392 244Hydrolysis (Olivier)la 0.084 0.090 0.074 0.355 0-62 0.286 0-50An interpretation of the whole of these data from this point ofI5 J . , 1910,97,416; 1911,QQ, 1927; 1912,101,1788; 1913,103,1689.16 G. M. Bennett and W. A. Berry, J., 1927, 1676; A., 1927, 871.17 Calculated from Conant’s data, Zoc. cit.18 Ann. Reports, 1927, 24, 156.J., 1904, 85, 1286; 1905, 87, 481; 1909, 95, 93ORGANIC CHEMISTRY .-PUT II. 139view is possible. There is an observed alternation in the reactivityof successive homologues in several cases, which Conant and Kirnerattribute to an effect transmitted from the group R along thesaturated chain. This will be regarded by many as improbablewherever the chain in question exceeds three carbon atoms at themost in length, as is clear from the results of nitration of the sub-stances Ph(CH2),*NMe,X,19 from the values 20 of the second dis-sociation constants of dibasic acids, and from the study of dipolemoments.21 There are other possible factors such as a direct effectof R upon the group CH2C1 through space 22The following additional data relating to the speeds of hydrolysishave been reported by Olivier z3 for the 2 : 6-, 3 : 4-, and 3 : 5-di-bromobenzyl chlorides : 0-120, 0.207, and 0.070 respectively,referred to benzyl chloride as unity.A closely related set ofmeasurements is that of J. P. Norris and his assistants 24 for thereversible first-order reaction of substituted benzhydryl chlorides(a-phenylbenzyl chlorides) wi+h ethyl alcohol at 25".Relativevalues, referred to benzhydryl chloride as unity, are :Substituent. Velocity. Substituent. Velocity. Substituent. Velocity.041 0.01 o-Me 2.9 p-Ph 12-87% Y Y 0.045 m- 9 , 2.1 p-PhO 31.6P - 9 , 0.42 P - P, 16.2 o-Me0 93P P ' - c1, 0.15 pp'-&fez 413 p-Me0 ca. 1200p-Br 0.33 p-Et 20.9Values for ct-naphthylphenylmethyl chloride and benzylphenyl-methyl chloride are 7.2 and 0.0004 respectively.A comparison of these figures with those of Olivier for the benzylchlorides shows that the effects of substituents are parallel in thetwo series, except that the values for o-substituted benzhydrylchlorides show a special depression which may fairly be regarded asdue to steric hindrance.In an interesting study of the action of aqueous sodium hydroxideupon benzhydryl chloride 25 it is shown that the reaction is of thefirst order and practically independent of the added alkali.AlthoughAnn. Reports, 1926,23, 131.2o R. Gene and C. K. Ingold, J., 1929,1691 ; A., 1144; compare H. J. Lucas21 C. P. Smyth, ibid., 1929, 51, 2380; A., 1128.22 G. 31. Bennett and A. L. Hock, J., 1927, 477; A., 1927, 355; G. M.Bennett, F. Heathcoat, and A. N. Mosses, J., 1929,2567.S. C. J. Olivier, Rec. trav. chim., 1929, 48, 227; A,, 405; compare Ann.Reports, 1927, 24, 156.and H. W. Moyse, J . Amer. Chem. SOC., 1925, 47, 1459; A., 1925, i, 770.24 J . Amer. Chem. SOC., 1928,50, 1795, 1804, 1808, 1813; A., 1928, 1000.s5 A. M. Ward, J., 1927,445,2288; 1929, 1541 ; A., 1927, 453, 1061 ; 1929,1072140 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.this is consistent with Nef’s suggestionbivalent carbon radical thus,of the formation of a freeslow fast CHPh2C1 rH% CPh2< +R~% CHPh,*OR,the author points out that the following scheme fits the facts equallywell :C€€Ph,Cl ?$ CHPh,+ + Cl- and CHPh,’ + OR- :$ CHPh,-OR.The ready reaction of triphenylmethyl chloride in a similarmanner makes the latter explanation the more acceptable.Similarbivalent carbon radicals have also been postulated as intermediatesin some reactions of p-nitrobenzyl chloride and related substances.The former is converted by alcoholic alkali into pp’-dinitrostilbeneand by aldehydes ArCHO into substituted ethylene oxides of theA type C6H,(N02)*CH-CHAr.27 A simpler explanation may befound, however, in the enhanced reactivity of the hydrogen atomsof the methylene group of the benzyl chloride owing to the electronattraction of the halogen atom,28 the stilbene being formed throughthe intermediate C6H,(~O,)~CH2~CHC1~C~H~*NO2. The knownformation of bromodiphenacyl from phenacyl bromide and alcoholicsodium ethoxide illustrates the type of reaction :XaOEt 2Ph*CO*CH2Br --+ Ph*CO*CHBr*CH,*COPh.In conclusion, attention may be directed to two recent examplesof “ positive ” reactivity of halogen, namely, of the chlorine atomin the S02C1 groups of trichloromethanesulphonyl chloride 29 and ofdinitrobenzenesulphonyl chloride.30Stereoisomerism of Polycyclic Aromatic Cmpounds.(Continued from Ann.Reports, 1928, 25, 114-118.)The results recorded in this field during the year provide furtherconfirmation of current theories of the structure of diphenyl, andthe disproof of a number of cases of stereoisomerism among otherpolycyclic substances is also in gratifying agreement with theindications which physical measurements have given concerningthe structure of the benzene nucleus.Diphenyl Ismerim.-The view expressed by Mills 31 that the26 J. U. Nef, Annalen, 1897,298, 234; A., 1898, i, 102.27 E. Berpann and J. Hervey, Ber., 1929,62, B, 893; A., 695.28 E. Kleucher, {bid., p. 2687.29 J. F. Durand and R. Naves, Bull. Soc. chim., 1927, [iv], 41, 632; A.,30 A. T. Dam and W. Davies, J., 1929, 1050; A., 931.31 Ann. Repor&, 1926, 23, 124.1927, 645ORGANIC CHEMISTRY .-PART II.141occurrence of enantiomorphism in substituted diphenyls arises fromthe purely mechanical obstruction of rotation by (not less thanthree) ortho-situated groups has been shown to be correct by theisolation of optically active 3 : 3’-diaminodimesityl (I} by W. W.Moyer and R. Adams,32 the blocking groups being identical and ofthe least polar type possible. The following have also been resolvedinto optically active forms : 6 : 6’-dimethoxydiphenic2 : 2’-diamino-1 : l‘-dina~hthyl,~~ 2 : Z‘-dihydroxy-l : 1’-dinaphthyl-3 : 3’-dicarboxylic and 1 : 1’-dianthraquinonoyl-2 : 2’-di-carboxylic acid (II).36MeIM@H2MeQ-0 ‘S-S’(1.1 (11.) (111.)A number of other substances 37 have resisted resolution in con-formity with theoretical expectation, of which 5 : 5’-dinitro- and5 : 5’-dibenzamido-diphenic acids may be noted.38On the other hand, a few more recorded observations whichseemed to provide evidence in favour of the Kaufler formula fordiphenyl have received satisf actory alternative explanation^.^^An interesting piece of direct evidence against the formula isfurnished by H.J. Barber and S. Smiles,4O who have oxidised2 : 2’-dithioldiphenyl to a crystalline diphenylene 2 : 2’-disulphide(111) but find that the 3 : 3’- and 4 : 4’-dithioldiphenyls yield nocyclic disulphide.A stereochemical explanation has been suggested 41 of the existenceof an unexpected isomeride formed from 5’-chloro-Z’-hydroxy-2-benzoyl-m-toluic acid by the action of sulphuric acid, but it maybe asserted with confidence that the difference between the two32 J .Arner. Chem. SOC., 1929, 51, 630; A., 437.33 J. Kenner and H. A. Turner, J., 1928,2340; A., 1928,1244.34 R. Kuhn and P. Goldfhger, Annalen, 1929, 470, 183; A., 804; L.35 W. M. Stanley and R. Adams, Rec. trav. chim., 1929,48, 1035; A., 1298.3ti R. Kuhn and 0. Albrecht, Annalen, 1928, 464, 91 ; A., 1928, 1015.37 J. F. Hyde and R. Adams, J. Amer. Chem. SOC., 1928,50,2499; A., 1928,38 F. Pufahl, Ber., 1929, 62, [B], 2817.38 R. J. W. Le FBvre, J., 1929,733; A., 705.40 J., 1928, 1141; A., 1928, 769.4 1 M. Hayashi, J., 1927,2616; A., 1927, 1187.Mascarelli, Uazzetta, 1928,58,627; A., 181.1234142 ANNUAL REPORTS ON THE PROURESS OF CHEMISTRY.substances must be of another kind.The author regards themalternatively as structural isomerides and writes the conversionthus :OHChlorohydroxymethylanthraquinone is also formed from the acidunder the influence of sulphuric acid. A more probable explanationof the facts would therefore seem to be given by the followingscheme, in which it is assumed that the anthraquinone formationis reversible in two ways :C,H,Cl( OH)<go>C,H3Me =+ C,H2Cl( OH)<gg>C,H,Me sQHH co70OHC6H2c1(0H)<CO>C6H3MeThis implies a constitution for the second acid different from thatsuggested by the author.Isomeric Dimethyl-2-phenylnuphthylenediamines.-The intriguingproblem of the existence of two isomeric forms of NN'-dimethyl-2-phenylnaphthylene-1 : 3-diamine has been re-examined 42 and theearlier work of N.Lees and J. F. Thorpe 43 confirmed and amplified.The substance (IV) occurs in a- and p-forms, of which the a-baseyields only monoacyl, the p-base diacyl derivatives. The dinitroso-derivatives of the two have now been found to be one and the samesubstance, from which the p-base can be recovered. Both a- andp-bases resisted attempts to resolve them into optically active forms.The authors state that if all the nuclei and substituents lie in oneplane the phenyl group is prevented from rotating, but it should benoticed that even if this were the case no enantiomorphism wouldbe expected. They conclude that the a- and p-forms are bestrepresented as cis- and trans-isomerides, the whole being supposedto lie in one plane (V, VI).a F M e ~c 9 z e z v/ dHN/MeH/ (vI.)I d HNHMe(IV-) Me/ (v.)43 C.S. Gibson, W. S. Kentish, and J. L. Simonsen, J., 1928, 2131; A . ,1928, 1128. 43 J., 1907, 91, 12960RC;ANIC CHEMISTRY .-PUT II. 143A more satisfactory suggestion, put forward simultaneously byW. S. Kentish 44 and (Miss) M. S. Lesslie and E. E. is thatthe a-dimethyl base is a structurally isomeric methylimino-com-pound derived from a tautomeric form of the parent diamine : a-base(*NHMe, XMe), @-base (*NHMe, ONHMe). This at once accountsfor the formation of the monoacyl derivativesof the former and diacylderivatives of the latter. The supposition that the phenyl groupin these compounds cannot rotate is a misapprehension : this wouldonly be the case if the methylamino-groups were fixed in definitepositions, a supposition for which there is no justification.In pointof fact, if either the phenyl or the NHMe groups are free to rotate a tall, there can be no effective inhibition.No question arises as to the structure of the @-base, which is(IV). There is some difference of opinion, however, regarding thea-isomeride. Kentish writes it as (VII) ; but in view of the failureto resolve it into enantiomorphs Lesslie and Turner prefer theformula (VIII). These authors show that the known reactions ofthe parent base indicate at least three tautomeric forms (IX, X, XI) ;but the formula (IX) is clearly demonstrated as the normal one bytheir resolution of the base into optically active forms.CH(VIT.) (yjky (VIII.)Y NHMe li' NMeCH CH,Isomerism attributed to Inclined or Non-phmr Nuclei.-In thecourse of their extensive researches into the action of alkali metalsupon organic substances46 Schlenk and Bergmann isolated a,number of substances which were unexpected according to classicalstereochemical ideas.On the hypothesis that in polynuclearsystems the planes of adjacent rings are inclined to one another atan angle, they regarded the existence of these substances as due toa kind of cis-trans isomerism. For instance, there were describedtwo each of 1 : 2 : 3-triphenyl- and 1 : 1 : 3-triphenyl-hydrindenes,1 : 2 : 3-triphenylnaphthalenes, 9 : 10-diphenylanthracenes, 9 : 10-di-44 J., 1929, 1169; A., 923.46 Ann.Reports, 1928, 25, 152; W. Schlenk and E. Bergmann, Ber., 1929,45 Ibid., p. 1512; A., 1061.62, [B], 746 ; E. Bergmann and H. Mark, {bid., p. 750; A., 688, 689144 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.phenyldihydroanthracenes, 9-benzhydrylfluorenes, and 9-phenyl-9-benzylfluorenes; three isomeric forms were found of 9 : 10-di-hydroanthracenedicarboxylic acid and of diphenyldihydroanthra-cenedicarboxylic acid.The interpretation given of the existence of these substances isillustrated by the annexed formula for a substituted 9 : 10-dihydro-anthracene. The outer rings are supposed to beA\ lB inclined at an angle to the central nucleus, each beingbent to the same side of the plane of the latter. Thiswill clearly have the effect of differentiating betweenthe two directions perpendicular to that plane and 0 the formula should represent three stereoisomerides.To account for the existence of two diphenyl-anthracenes (unreduced) on this view, it would be necessary tomake the improbable assumption that in them the phenyl nucleiare not co-axial with the central nucleus. In further support ofthese ideas, 2 : 3-diphenylindone was stated to be resolved int,ooptically active forms by means of bornylamine.These announcements have been followed by similar ones fromother quarters involving phenylindene derivative^,^' and pairs ofdianthranyls and phenylbenzhydryldichlorodihydroanthranols.48S. Haeckel and H.Mark 49 explain the new isomerism by assuminga multiplanar formula for the benzene ring similar to that of Bragg.Recent physical work on benzene derivatives discussed above(p.126) makes both Schlenk’s and Haeckel’s explanations improbable.It is consequently reassuring to find that a number of theunexpected isomerides have already been explained away. Anattempt to repeat the resolution of diphenylindone was unsuccess-ful : 50 the second forms of 9 : 10-dihydroanthroic benz-hydrylfluorene and diphenyldiphenylene-ethylene have been foundto be mixtures, 52 and the isolation of the second fluorene-9-carboxylicacid and 9-phenyl-9-benzylfluorene could not be repeated.53 Thesubstance described as a stereoisomeric 1 : 1 : 3-triphenylhydrindeneis a structural i~omeride.~~ In addition it may also be pointed out,with reference to the two cases of isomerism discussed by Barnettand Goodway, (a) that it is difficult to believe that the isodianthranylhas been given the correct formula, since in its preparation by47 C.Moureu, C. Dnfraisse, and M. Badoche, BUZZ. SOC. chim., 1928, [iv], 43,48 E. de B. Barnett and N. F. Goodway, J . , 1929,20,813; A., 312, 700.49 J . pr. Chem., 1929, [ii], 122, 182, 349; A., 1050.50 J. Meisenheimer and W. Theilacker, Annalen, 1929,469, 26 ; A . , 448.51 H. Meerwein and A. Migge, Ber.,1929,62, [B], 1046; A., 696.52 A. Kliegl,ibid.,p. 1327; A., 812.53 R. E. Schmidt, B. Stein, and C. Bamberger, ibid., p. 1890; A., 105-1.54 K. Z2egler and F. Grossmann, ibid., p. 1768; E. Haack, ibid., p. 1771;A1381 ; A., 318.A., 1054ORGANIC CHEMISTRY .-PART II.145reduction of benzhydrylanthrone an extra carbon atom would seemto have been inexplicably introduced into the molecule, and (b) thatthe analytical figure for the second phenylbenzhydryldichloro-dihydroanthranol would agree equally well with the very probablesupposition that the substance is not an isomeride but results fromthe loss of one molecule of water.It therefore seems likely that all these cases of unexpected isomer-ism were imaginary, and it might at first sight appear that muchlabour had been wasted. When thedisproof of the supposed isomerism is complete in all instances,there will be a mass of evidence which will support the conceptionthat the rings of polynuclear hydrocarbons are in a single plane.But this is not entirely true.Natural Products.(Continued from A m .Reports, 1927, 24, 119-128.)The syn-thesis of norpinic acid, recently announced, completes at last thelogical proof of the structure of pinene. Norpinic acid was obtainedas the ultimate product of degradation of the terpene in 1896 byA. von B a e ~ e r , ~ ~ who gave it the cyclobutane formulaI. The Terpene Group.-(1) Monoterpene compounds.CH*CO,HCH*CO,HMe,@, 9but many attempts to synthesise it have been unsu~cessful.5~The difficulty has now been surmounted by C. A. K ~ I T , ~ ~ who con-densed the sodium derivative of the Guareschi imide (I) withmethylene iodide. The resulting bridged-ring imide (11) wasconverted by alkaline hydrolysis into 2 : 2-dimethylcyclobutane-1 : 1 : 3 : 3-tetracarboxylic acid, which was decarboxylated to givetrans-norpinic acid.The oxidation of terpenes with Beckmann’s chromic acid mixturehas yielded interesting results, and the method may find applicationfor identifying the constituents of terpene mixtures.ct-Terpinenegives mainly dimethylacetonylacetone.58 From Z-limonene there isobtained the keto-lactone CloH1603 prepared by Wallach fromterpineol; and among the products from ct-phellandrene are two55 K. Ziegler and F. Grossman, Ber., 1896,29,19071; A., 1896, i, 620.56 G. R. Clem0 and K. N. Welch, J . , 1928,2621 ; A., 1928, 1252.57 J . Arner. Chem. Soc., 1929, 51, 614; A., 445.68 T. A. Henry and H. Paget, J., 1928, 70; A., 1928, 295146 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.keto-lactones (111; IV), each of which is further degraded toZ- cc- isopropylsuccinic acid.COMe COMe(111.) (IV.)By the same method, both d-A3- and d-A4-carene give Z-trans-caronic acid in good yield.59 The production of this acid from anatural mixture would therefore be proof of the presence of carene.Another point of considerable interest concerns the configuration ofthe caronic acid isolated : the carene must have the &structurewith respect to the cydopropane ring, and therefore it is clear thatmolecular rearrangement occurs at some point in the course of thedegradation.(2) Xesquiterpene compounds.Work in this field during thepast two years has continued to be fruitful: the structures ofbisabolene and zingiberene have been elucidated and the chemistryof cedrene has been largely accounted for.60The formation of bisabolene by the action of acids on nerolidolindicated, by analogy with the case of linalool, the formuls (I, 11,and 111) as possible for the terpene, the point of uncertainty beingthe position of one ethylenic linkage.All three formuls areconsistent with (IV) as the trihydrochloride. 7%ARH2&CH3 Q 3 H 3 ( ( & I 3ItCH, CH,(111.)CH, A CH3 &CH3(1.1 (11.)CLCH,C l A r n T F H 3 I pCH3CH3 CH3 H3 CH3(IV.1 (V.16s C. S . Gibson and J. L. Simonsen, J., 1929,305, 909; A., 449, 819.6o L. Ruzicka and A. G. van Veen, AnnaZen, 1929, 468, 133, 143; A., 571,5 72ORGANIC CHEMISTRY .-PART II. 147The hydrocarbon from opopanax oil is identical with that regeneratedfrom the trihydrochloride and constitution (111) is assigned to it forthe following reasons.Depadation by means of ozone producesacetone and laevulic and succinic acids, but this is consistent withany of the formulae above. Decisive evidence was, however,obtained by examination of tetrahydrobisabolene (V) formed bycatalytic reduction of the terpene. The slowness of addition of twomore hydrogen atoms to yield a hexahydro-derivative is bestaccounted for by the formulze (111) and (V) for bisabolene and itstetrahydro-derivative. This is proved by ozonolysis of the latter top-methylheptan-&one and 4-methylcyclohexanone. No diacetyl-valeric acid, formic acid or formaldehyde was detected such as wouldarise if any bisabolene of the structure (I) or (11) were present.Bisabolene yields on dehydrogenation a benzene derivative oxidis-able to terephthalic acid, formation of the naphthalene nucleusbeing hindered by the hemicyclic double bond.Zingiberene has not the wide distribution in nature of bisabolene,having been obtained until recently only from ginger oil.Itsdiscovery in the oil from the rhizomes of Curcuma zedoaria, Roscoe,61is therefore of considerable interest.The crude terpene from ginger oil is shown to contain 20-30~0of bisabolene by the isolation of its trihydrochloride and by theoccurrence of acetone, lmulic and succinic acids among the productsof ozonolysis.Hexahydrozingiberene 62 is dehydrogenated over palladisedcharcoal to <-p-tolyl-p-methylheptane, which is oxidised by chromicacid to acetic, oxalic and terephthalic acids, the last in too large anamount to have arisen from the bisabolene present.As no tri- ortetra-carboxylic acid of benzene is produced, the carbon skeletonP 3A CH3 CH,ICH, \ \/A CH3 CH,QH3 PoQHZf- CHzof zingiberene is proved to be the same as that of bisabolene, con-trary to earlier conception^.^^ The dehydrogenation product(VII) was also synthesised by successive dehydration and catalyticG1 B. S . Rao, V. P. Shintre, and J. L. Simonsen, J . SOC. Chem. Ind., 1928,62 F. W. Semmler and A. Becker, Ber., 1913,48, 1814; A,, 1913, i, 743.47, 171 ; B., 1928, 799.Ann. Reports, 1927,24, 123148 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.reduction of the product from magnesium p-tolyl bromide andmet h ylheptenone.The complication due to the presence of bisabolene was avoidedby condensing crude zingiberene with ethyl diazoacetate, thezingiberene (having conjugated double bonds) alone reacting toform the acid (VIII).6* After successive hydrogenation anddehydrogenation of the ester, the product was oxidised to tere-phthalic acid.This provides a more conclusive proof of the carbonskeleton of the terpene.The dihydrozingiberene obtained by reduction with sodium andalcohol yields some cadalene when heated with sulphur. Decom-position of its ozonide with permanganate gave an acid, Cl2H2,O,,isolated as its methyl ester. By the action of sodium hypobromitethere resulted, after re-esterification, it trimethyl ester of the acidCllH1806. This completes the proof of structure, the acids havingthe constitutions (IX) and (X), and zingiberene (VI).P 3(VIII.) c02H*cH'c~/-cH3 @CO.CH, @C02HH0,C C0,H HO, CO,HThe investigationof cedrene is well advanced, although not yet com-~ l e t e .~ 5 The terpene is found in cedar-wood oil and is also producedartificially from the related alcohols cedrenol, cedrol, and #-cedrol.The molecular refraction of cedrene and the saturated characterof its tetrahydro-derivative show that it is tricyclic.66 A ketone,cedrone, C,,H,,O, together with cedreneketonic acid,C1,Hl 8(COMe)*CH,°C0,H,is afforded by the action of chromic anhydride in acetic acid. Theproduction of the former may be regarded as analogous to theconversion of limonene into carvone and involves oxidation of-CH:CH*CH- to -CH:CH=CO-.Further oxidation of cedrene-ketonic acid yields cedrenedicarboxylic acid, whereas ozonolysis ofcedrone leads to norcedreneketonic acid, convertible by hypo-bromite into norcedrenedicarboxylic acid. The last acid must beformulated asC H <?Me*CozH (or possibly C8H14<(?H'co2H ' l2 CH*CH,*CO,H CH*CH,*CO,H)'64 H. Staudinger, 0. Xluntwyler, L. Ruzicke, and 5. Seibt, Helv. Chint.b5 L. Ruzicka, and J. A. van Melsen, Annulen, 1929, 471, 40; A., 932.66 F. W. Semmler and E. W. Meyer, Ber., 1912,45, 1387; A., 1912, i, 479.Acta, 1924,7,390; A., 1924, i, 730ORGlLNIC CHEMISTRY.-PART II. 149for it differs from cedrenedicarboxylic acid in that the two carboxylgroups show unequal reactivity with respect to esterification andhydrolysis.One carbomethoxy-group of the methyl ester of this acid reactswith magnesium methyl bromide, and the resulting carbinol,?Me*CO,Me , is oxidised to cedrocamphoric acid,c7H12%H*CH,*CMe2*OHC 6 H l o < ~ ~ ~ * c o 2 H .These resu1t.s cannot be reconciled withformulae for-cedrene put forward by E. Deussen 67 and by Semmler,and they show that cedrene must be of the type (XI), or (XII) onthe basis of the alternative formula of norcedrenedicarboxylic acid.The third ring of cedrene is present in the portion C&O and canonly be three- or four-membered. A formula such as (XIII) istherefore probable for cedrene.(XII.) (XIII.)11.Constituents of Kawa Root.-The principal substances isolatedfrom kawa root (Piper methysticum) are methysticin, 4-methysticin,and yangonin and are found in the residues from the preparation ofkawa-resin. The chemical nature of these and of the resin hasbeen demonstrated in recent years by W. Borsche and his fellow-workers.Yangonin was shown by E. Winzheimer 68 to be a dimethoxy-compound, C15H140,. It behaved as a lactone, and yangonic acid,which resulted from it by the action of alkali, lost carbon dioxideabove its melting point to yield a neutral substance, yangonole.A detailed study of yangonin 69 revealed properties characteristicof pyrones, such as the formation of oxonium salts with complexacids and of a pyridone by the action of ammonia.Hydrolysisafforded first yangonic acid, C,,Hl,OB, and then either p-methoxy-cinnamic and acetoacetic acids or anisylideneacetone and malonicacid. Dihydroyanganole, the product of catalytic reduction, washydrolysed to anisylethyl methyl ketone and p-anisylpropionic acid.Consequently the structure MeO°C6H4~CH:CHoC~CH__C~~CH O*C( OMe)8 7 J . pr. Chem., 1927, [iil, 117, 273; A., 1928, 70.8 8 Arch. Pharm., 1908,246,338; A., 1908, i, 804.69 W. Borsche and (Frl.) M. Gerhardt, Ber., 1914, 47, 2902; A., 1915, i,438150 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.mas assigned to yangonin, that is, 2-p-methoxystyryl-6-methoxy-y-pyrone. Yangonic acid should beMeO*C6H,*CH:CH*CO~CH2*CO~CH2*CO2H,and yanganole the diketone MeO~C6H,*CH:CH~CO~CH2~~O~CH3.The structure of yanganole has been confirmed by synthesis.'OpMethoxycinnamoy1 chloride with the sodium derivative of methylacetoacetate furnished the diketonic ester,MeO*C,H,*CH :CH-CO*CH (CO*CH,)*CO,Me,from which yanganole was obtained by hydrolysis.An early investigation by C.Pomeranz 71 showed that methysticinwas a neutral substance, C15H1405, which yielded protocatechuicacid on fusion with potassium hydroxide. Aqueous alkali yieldedmethysticic acid, regarded as having the formula C14H1205. Thisacid was oxidised to piperonylic acid. It lost carbon dioxide aboveits melting point and was converted by boiling dilute acid or alkaliinto a ketone, methysticole, C13Hl2O3. Pomeranz concluded thatmethysticin was methyl methysticate with the structureCH2<~>C6H3~CH:CH~CH:CH~CO~CH2*C02Me.opticallyformula,appearedIt wasThis formula was supported by E.Winzheimer,72 who identifiedmethysticole with piperonyleneacetone,CH2O2:C6H3*CH:CH0CH:CH*CO*CH3,prepared some years earlier from piperonylacraldehyde and acetone.This ketone is clearly to be expected on the above view of thestructure of me thys ticin.Nevertheless the observations that methysticin took up only twohydrogen atoms on catalytic hydrogenation 73 and that it wasactive 74 made it necessary to abandon Pomeranz'sand the presence of a 7-pyrone ring as inC H 2 0 2 : C 6 H 3 * c H : C H * C H < ~ ~ ~ ~ ~ ~ c Hlikely.found that the immediate product of theaction of alka,liupon methysticin mas an isomeride, isomethysticin, which furnishedmethysticic acid on total hydrolysis.Both isomethysticin andmethysticic acid took up four atoms of hydrogen per molecule whensubjected to catalytic hydrogenation, the latter being at the sametime decarboxylated to tetrahydromethy~ticole.7~A substance, aZZo-methysticin, having the structure suggested by70 W. Borsche and C. Walter, Ber., 1927, 60, [ B ] , 2112; A., 1927, 1192.7 1 Monatsh., 1888,9,863; 1889,10, 783; A,, 1889,278; 1890, 257.7 3 L O G . cit.r3 H. Goebel, Eer. deut. Pharm. Ges., 1922, 32, 115; A., 1922, i, 657.74 Y. Murayama and Shinozaki, Chem. Zentr., 1925, ii, 2062.'i5 W. Borsche, Ber., 1927, 60, [B], 982; A., 1927, 563ORGANIC CHEMISTRY .-PART II. 151Pomeranz was synthesised from piperic acid by condensing itschloride with methyl sodioacetoacetate and removing the acetylgroup of the resulting ester,CH,02:CsH3*CH:CH*CH:CH*CO*CH( CO*CH,)*CO,Me,by means of ammonia.allo-Methysticin was of course not identicalwith methysticin, but neither was it identical with isomethysticin.76isoMethysticin was found not to have the characteristic propertiesof a p-ketonic ester of reacting with ferric chloride and forming acopper derivative. As it dissolved in sodium carbonate, the factswere explained by the structureCH20,:C6H30CH:CH*CH:CH*C (OMe) :CHCO,Hfor isomethysticin. This was now confirmed by esterifying it bymeans of diazomethane and cautiously hydrolysing the productwith acid, in such a manner that the enolic methoxyl group alonewas affected.The product of this process was found, as expected,to have the properties of a p-ketonic ester and to be identical withthe synthetic allo-methysticin.All the facts are now accounted for by the a-pyrone structurefirst action of alkali being to convert this lactone into the corre-sponding trebly unsaturated acid (isomethysticin) .77The substance #-methysticin occurring in kawa root has beenfound to be a partly hydrogenated methysticin, the latter beingdifiicult to separate from its dihydro-derivative.Kawa resin itself is composed largely of kawaic acid in the formof esters or ~yrones.~* The acid (C1,H1,03) easily loses carbondioxide and distillation of the residue yields cinnamylideneacetone,whereas its tetrahydro-derivative passes smoothly on distillationinto 8-phenylbutyl methyl ketone. The conclusion follows thatkawaic acid is the analogue of isomethysticin, being hydrolysed byacids to methyl alcohol and y-cinnamylideneacetoacetic acid orcinnamylideneacetone and carbon dioxide, but stable to alkalis.The formula, CHPh:CH*CH:CH*C( OMe):CH*CO,H is confirmed, aswas that for isomethysticin, by partial demethylation of its methylester, the product being, as expected, methyl y-cinnamylidene-acetoacetate.It is probable that kawaic acid exists in the resin in the form of'' kawain," an a-pyrone analogous to methysticin.G. M.BENNETT.78 W. Borsche, W. Rosentha1,antiC. H. Meyer, Ber., 1927, 60, [ B ] , 1135; A,,77 W. Borsche, C. H. Meyer, and W. Peitzsch, ibid., p.2113; A., 1927, 1192.78 W. Borsche and W. Peitzsch, Ber., 1929, 62, [B], 368; A., 442; also W.1927,664.Borsche and A. Roth, BeT., 1921,54, [B], 2229; A., 1921, i, 862152 ANPU’UAL REPORTS ON THE PROGRESS OF CHEMISTRY.PART III.-HETEROCYCLIC DIVISION.Oxygen Ring Compounds.SOME time ago it was observed that resacetophenone (2 : 4-dihydr-oxyacetophenone), on being heated with acetic anhydride andsodium acetate, was converted into 7-acetoxy-3-acetyl-2-methyl-chromone (I).l This reaction has been extended by R. Robinsonand his collaborators during the past few years for the preparationof many naturally occurring products containing an oxygen ring.For the synthesis of flavones (2-phenylchroruones) the generalmethod of procedure has been to heat resacetophenone or phlor-acetophenone (2 : 4 : 6-trihydroxyacetophenone) with the anhydrideand sodium salt of the appropriate substituted benzoic acid, andthen to hydrolyse the acyloxy-compound which is first formed(acylation in the 3-position does not occur as a general rule).Inthis way, from resacetophenone, anisic anhydride and sodiumanisate, there resulted 7-hydroxy-4’-methoxyflavone (11), which isprobably identical with pratol from Trifolium prateme, and fromphloracetophenone, with the requisite reagents, chrysin (I11 ;R = H) and acacetin (111; R = OMe) have been prepared.25 : 7-Dihydroxy-2’ : 4’-dimethoxyflavone also has been synthesisedby this method and subsequently converted, on demethylation, into5 : 7 : 2’ : 4’-tetrahydroxyflavone (IV), a compound which wasthought by W.R. Dunstan and T. A. Henry3 to be lotoflavin,obtained by the hydrolysis of lotusin from Lotus arabicus, butapparently the natural product is not identical with the syntheticalfla~one.~ It is interesting to note, however, that N. M. Cullinane,Me0 GO (171.)Y. Tahara, Ber., 1892, 25, 1302; W. N. Nagai, ibid., p. 1287; S. vonKostanecki and A. Rozycki, Ber., 1901, 34, 107.2 R. Robinson and K. Venkataraman, J., 1926, 2344.4 R. Robinson and K. Venkataraman, J., 1929, 61.Phil. Trans., 1901, 194, [B], 515ORGANIC CHEMISTRY .-PART m. 153J. Algar, and H. Ryan 5 have obtained 2-hydroxy-4 : 6 : 2’ : 4’-tetra-methoxybenzoylacetophenone by condensing phloracetophenone4 : 6-dimethyl ether with methyl 2 : 4-dimethoxybenzoate in thepresence of sodium at 150-160”, and have converted it by means ofhydriodic acid into 5 : 7 : 2’ : 4’-tetrahydroxyflavone, which wasthought to resemble natural lotoflavin, although complete identitywas not established. Flavones can sometimes be obtained by theaction of alkalis on the dibromides of o-hydroxyphenyl styrylketones, and, with the structure of lotoflavin in mind, N.31.Cullinane and D. Philpott have studied the possibility of pre-paring 5 : 7 : 2’ : 4’-tetrahydroxyflavone by this route from 2-hydr-oxy-4 : 6-dimethoxyphenyl2 : 4-dimethoxystyryl ketone (V). Rrom-ination, however, led to simultaneous nuclear substitution, andsubsequent treatment with alkali gave a product which was probably4-bromo-3 : 5 : 2’ : 4’-tetramethoxybenzylidenecoumaran-2-one (VI).This acylation process has also been applied to gallacetophenone(2 : 3 : 4-trihydroxyacetophenone) for the preparation of 7 : 8-di-hydroxy-2-methylchromone and 7 : 8-dihydroxyflavone, both ofwhich have been prepared previously by another method.8 Byextending the reaction to o-methoxyresacetophenone and w-meth-oxyphloracetophenone, derivatives of 3-methoxflavone have beenobtained ; in this way galangin monomethyl ether (VII ; R = Me),occurring in galanga root, has been synthesised.1° By first pre-0 0 RH O p g P h H O ~ - - - ~ O H(VII.) \/CooR (/VCOH R’ (VIII.)HO CO HO COparing the appropriate derivatives of 3-methoxyflavone and subse-quently demethylating the products, the following naturally occur-ring flavonols (3-hydroxyflavones) have been synthesised : myri-cetin l1 (VIII; R = R’ = OH), datiscetin l 2 (IX; R = H),kaempferol l3 (VIII ; R = R’ = H), fisetin l4 (X), quercetin 15(VIII; R = OH; R’ = H), and morin l6 (IX; R = OH).TheProc. Roy. Dublin SOC., 1928,19, 77; A., 703. J., 1929, 1761.7 K. Venkataraman, ibid., p. 2219.8 S. von Kostanecki and collaborators, Ber., 1903, 36, 2192, 4242.9 J. Allan and R. Robinson, J., 1924,125, 2192.10 J. Kalff andR. Robinson, J., 1925,127, 181.11 Idem, loc. cit.13 R. Robinson and J. Shinoda, ibid., p. 1973.14 J. Allan and R. Robinson, J., 1926, 2334.16 R. Robinson and K. Venkataraman, J., 1929, 61.la Idem, ibid., p. 1968.l5 Idem, Zoc. c i f 1% ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.demethylation process has been avoided in the preparation ofcertain members of this class by employing o-benzoyloxyphlor-acetophenone in the place of the o-methoxy-derivative. Hydrolysisof the primary products then led directly to the flavanol, and themethod has been used in the synthesis of galangin (VII; R = H),kaempferide (XI), and isorhamnetin 1’ (VIII ; R = OMe ; R’ = H).H O ( J $ C - - - - ~ O M e €10’“ - - - O O HHO OHHO CO C*OH (XI.) HO &*OH (XI1 .)From w-benzoyloxyphloracetophenone, O-benzylsyringic anhydrideand sodium O-benzylsyringate, with subsequent hydrolysis of theproduct, 3 : 5 : 7 : 4’-tetrahydroxy-3’ : 5’-dimethoxyflavone (VIII;R = R’ = OMe) has been prepared.18 This flavanol, which hasbeen called syringetin, corresponds to the anthocyanidin, syringidin(malvidin), but it has not yet been obtained from natural sources.By a further application of these methods the structures of the twoisomeric flavonols, gossypetin (XII) and quercetagetin (XIII) , havebeen e~tab1ished.l~ Both of these interesting products are hydroxy-quercetins and contain a tetrahydroxybenzene nucleus.Theformer has been prepared by the interaction of 2 : 4-dihydroxy-o : 3 : 6-trimethoxyacetophenone (XIV), veratric anhydride andOH Me0Ho()g&2H2*OMeHO CO (XIII.) Med (XIV.)potassium veratrate, followed by hydrolysis and subsequentdemethylation ; the synthesis of quercetagetin was effected in asimilar way from 2 : 6-dihydroxy-o : 3 : 4-trimethoxyacetophenone(XV), a series of reactions which theoretically might also yieldgossypetin.Some of the naturally occurring derivatives mentionedE$$!?CH2*OMe @8:bXXJ?hHO (XV. ) (XVI.)above have previously been prepared in other ways, but in manycases the structures assigned to the products have now for thefirst time received confirmation by synthesis.l8 Idem, ibid., 1929, 67. 17 T. Heap and R. Robinson, J., 1926, 2336.19 W. Baker, R. Nodzu, and R. Robinson, ibid., p. 74ORGANIC CHEMZSTRY .-PART III. 155By using o -met hoxyresacetophenone and o -met hoxyphlorace t o -phenone, and extending this reaction with the aid of the anhydrideand sodium salt of cinnamic acid, or a substituted cinnamic acid,it has been found possible to prepare derivatives of 2-styrylchromo-no1 2o (XVI), and a further development of the reaction has led to thepreparation of isoflavones (3-phenylchromones).Although flavonesare widespread in nature, so far only four members of the isoflavonegroup-prunetin, genistein (prunetol), irigenin, and 4-baptigenin-have been recognised, and genistein has now been synthesisedby W. Baker and R. Robinson.21 2 : 4 : 6-Trihydroxyphenylp-methoxybenzyl ketone (XVII), on cinnamoylation and subsequenthydrolysis, gave 5 : 7-dihydroxy-4‘-methoxy-2-styrylisoflavone 22(XVIII; R = H), which was converted, on complete methylation,H O O H COGH, OMe R O @ C H s C- OMe(XVII.) HO RO 0 (xvIrr.)into 5 : 7 : 4’-trimethoxy-2-styrylisoflavone (XVIII; R = Me). Thisproduct was then oxidised by potassium permanganate in aqueouspyridine to 5 : 7 : 4’-trimethoxyisoflavone-2-carboxylic acid, whichlost carbon dioxide above its melting point to give 5 : 7 : 4’-tri-methoxyisoflavone.The corresponding 5 : 7 : 4’-trihydroxyisoflav-one (XIX), obtained by demethylation, proved to be identical withgenistein from Genista tinctoria.An examination of the reactions of irigenin (XX ; R = Me) hasindicated that it is an isoflavone derivative,Z3 which, on demethyl-ation, yields irigenol (XX; R = H). In order to confirm thisstructural formula, W. Baker .and R. Robinson Z4 heated 2 : 6-di-hydroxy-3 : 4-dimethoxyphenyl 3 : 4 : 5-trimethoxybenzyl ketone(XXI) with acetic anhydride and sodium acetate, and, after hydro-lysing the acetoxy-group in the product, obtained 5-hydroxy-6 : 7 : 3’ : 4‘ : 5’-pentamethoxy-2-methylisoflavone (XXII; R =Me).*O R.Robinson and J. Shinoda, loc. cit.21 J., 1928, 3115.22 W. Baker and R. Robinson, J., 1926, 2713.23 W. Baker, J., 1928, 1022; Ann. Reports, 1928, 25, 171.24 J., 1929, 152156 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.HO CO(XXII.)&hg&CJCH:CH€’h <>OMe oMeHO CO OMe(XXIII.)Theoretically, ring closure can take place here in two directions, butthe course of the reaction is established by the fact that the product,when methylated and subsequently decomposed with alkali, yields3 : 4 : 5-trimethoxyphenol 3 : 4 : 5-trimethoxyphenylaceticacid. This pentamethoxy-derivative, on demethylation, gave5 : 6 : 7 : 3’ : 4’ : 5’-hexahydroxy-2-methylisoflavone (Z-methyliri-genol) (XXII ; R = H), the reactions and dyeing properties of whichare so similar to those of irigenol as to leave no doubt concerningthe structure of the latter substance.In an attempt to synthesiseirigenin trimethyl ether, 5-hydroxy-6 : 7 : 3’ : 4’ : 5’-pentamethoxy-2-styrylisoflavone (XXIII) was prepared by the cinnamoylation ofthe ketone (XXI), but attempts to proceed along lines similar t othose employed in the synthesis of genistein have not so far beensuccessful.It has now been shown2*“ that +baptigeniii, the glucoside ofwhich is +-baptisin from the roots of Baptisia tinctoria, is a memberof the isoflavone group with the structure (XXIV). On treatmentwith aqueous potassium hydroxide, it yielded formic acid and +baptigenetin (XXV), which was found to be identical with the 2 : 4-dihydroxyphenyl3 : 4-methylenedioxybenzyl ketone obtained by anapplication of the Hoesch reaction to resorcinol and 3 : 4-methylene-dioxyphenylacetonitrile.andO--CH,(XXIV.) (XXV.)A new route for the synthesis of derivatives of 7-hydroxyiso-flavone has been introduced 25 by the preparation of 7-methoxy-2h E.Spiith and 0. Schmidt, Afonatsh., 1929, 53 and 54, 454; A . , 1458.25 W. Baker, A. Pollard, and R. Robinson, J., 1929, 1468ORGAPJIC CHEMISTRY .-PART 111. 157isoflavone (111) from the cyanohydrin of o-m-methoxyphenoxy-acetophenone (I). The latter compound yielded, on cyclisation0 0 0(1.1 (11.) (111.)with zinc chloride and hydrogen chloride in ether, a ketiminehydrochloride, which, when hydrolysed , gave 3-hydroxy-7 -met hoxy-isoflavanone (11).7-Methoxyisoflavone resulted readily on dehydr-ation with cold concentrated sulphuric acid.It is known that dehydration of catechin tetramethyl ether (IV)is accompanied by migration of the 3 : 4-dimethoxyphenyl group,Z6so that anhydrocatechin tetramethyl ether (V) contains the carbonskeleton of the isoflavone group of natural products. The geneticOMe~~CHOH Meo@, C+e OMeMe0 CH, Me0 CH,( P a ) (V-)relationships existing between the several classes of natural pro-ducts containing an oxygen ring constitute an interesting problem,and, with this in mind, W. Baker 27 has investigated the possibilityof oxidising (V) to 5 : 7 : 3’ : 4’-tetramethoxyisoflavone (VI; R =Ale), but this particular operation has not been successfully accom-plished.This author has expressed the view, therefore, that thenaturally occurring isoflavones are not derived from substances ofthe catechin type. Furthermore, it is significant that the isoflavone(VI; R = H), corresponding to the catechins, is unknown, as alsoare the catechins corresponding to the known isoflavones.Investigations which have been carried out in Japan on thestructures of two natural products, matteucinol and carthamin, areof considerable interest. S. Fujise z8 has shown that matteucinol,a product obtained from Matteucia orientalis, is a flavanone of theconstitution (VII; R = OMe). Thus it was found to give thecolour reaction of this class with magnesium and hydrochloric acid,to be phenolic in character, and to yield a monomethyl ether withdiazomethane. On fusion with potash, p-methoxycinnamic acid26 K.Freudenberg and collaborators, Annalen, 1925, 441, 157; 1925, 446,S7; A., 1925, i, 419; 1926, 73.J., 1929, 1593.2* Sci. Papem Inst. Phy8. Chern. Rea. Tokyo, 1929, 111158 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and 2 : 4-dimethylphloroglucinol (VIII) were obtained. Matteu-cinol was synthesised by condensing (VIII) with p-methoxycinnam-oyl chloride in nitrobenzene in the presence of aluminium chloride,0 Me 0 Me(VI-)a reaction already used forduct, which appears to be(VII.) (VIII. )preparing flavanones.29 A second pro-(VII; R = H), has also been isolatedfrom the same source.These substances are of especial interestsince they contain a methylated benzene nucleus, which is veryrare among natural products. The investigation into the structureof carthamin, a red dye from safflower, has been carried out by MissC. K~rods.~O Cold dilute hydrochloric acid converts it into theRO Me0KO/\OH $ H e M e O R GH-MePH Me0 CO (XII.)I N C HHO CO (XI-)isomeric isocarthamin. Hydrolysis with dilute mineral acids givesa molecule of glucose, and, if dilute phosphoric acid is used, theglucose-free carthamidin, C,,H,,O,, together with isocarthamidin,can be isolated. As a result of a comparison of the reactions ofderivatives of these substances with those of known chalkones andflavanones it is suggested that carthamidin is 5 : 7 : 8 : 4'-tetra-hydroxyflavanone (IX) and isocarthamidin the 5 : 6 : 7 : 4'-tetra-hydroxy analogue, whilst carthamin is believed to be the chalkone(X; R = glucose residue) and isocarthamin the isomeric compound(XI).These views are confirmed by the preparation from cartham-idin of 2 : 3 : 4 : 6-tetramethoxyphenyl p-methoxystyryl ketone(XII), which was identified by synthesis.During the course of other work with oxygen ring compounds,but not directly connected with natural products, it has been29 Compere Ann. Reports, 1928, 25, 169.30 Proc. Imp. A c d . Tokyo, 1929,5, 32, 82, 86; A., 430, 703ORGANIC CHEMISTRY .-PART III. 159observed that the isomeric benzopyrylium salts (I and 11) condensewith 2-naphthol-1-aldehyde in the presence of hydrogen chlorideand that, when the resulting salts are hydrolysed, the correspondingisomeric 3- and 3‘-substituted benzo- fLnaphthaspiropyrans (111)are respectively formed.These differ from one another in the factthat the 3-substituted products give coloured solutions in hot inertsolvents, but the 3’-substituted compounds do not show thisphen~rnenon.~~ This reaction has accordingly been used by I. M.Heilbron and F. Irving32 to determine the reactive group undervarious conditions in ketones of the type CH,oCO-CH,R. Thus bycondensation with salicylaldehyde, the isomeric products (IV) and(V) can result, and these, on further treatment with hydrogenchloride and 2-naphthol-l-aldehydeY yield, on subsequent hydro-lysis, spiropyrans which can be readily distinguished.The reaction between resacetophenone and ethyl ethoxymethyl-eneacetoacetate in alcoholic sodium ethoxide has been found toyield 7-hydroxy-3 : 6-diacetyl~oumarin,~ and the process constitutesa new method for the preparation of a number of coumarins, sinceit can be extended to derivatives of resorcinol in conjunction withthe above ester or ethyl etho~ymethylenemalonate.~~ It has alsobeen observed 35 that ethyl phenylcyanopyruvate and resorcinolreact together in glacial acetic acid, in the presence of hydrogenchloride and zinc chloride, not in accordance with the normalHoesch reaction, but to give ethyl 7-hydroxy-3-phenylcoumarin-4-carboxylate. A similar reaction takes place with orcinol andp hlor oglucinol . 3631 R.Dickinson and I.11. Heilbron, J., 1927, 1699.32 J., 1929, 936.33 R. Weiss and E. Merksammer, Mimat&., 1928,50, 115; A., 73.34 R. Weiss and A. Kratz, a’bid., 1929,51, 386; A . , 821.86 Compare also A. Sonn, ibid., 1918, 51, 821, 1829; A., 1918, i, 401; 1919,W. Borsche and J. Niemann, Ber., 1929,62, [B], 2043; A., 1309.i, 192160 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Selenium Ring Compounds.Following upon the preparation of cyclotelluropentane 37 and~elenophen,~~ it is interesting to note the synthesis of cycloseleno-butane (tetrahydroselenophen) ( I ; n = 2) by G. T. Morgan andF. H. Burstall 39 from the interaction of tetramethylene dibromidewith sodium selenide. An alternative method is to act upon tetra-methylene dibromide with potassium selenocyanate with the form-ation of tetramethylene diselenocyanate (11), hydrolysis of which byalcoholic alkali, together with aerial oxidation, gives cyclotetra-methylene diselenide (111).The latter loses selenium, on heating,and yields cycloselenobutane. cycloSelenobutane, containing bi-valent selenium, combines additively with a variety of substances.QH,*CH,*Se*CN QH2*CH,*qe(cH2)%<:2>se GH,*CH,*Se.CN CH,*CH,* Se(1.1 (11.) (111.)The same authors *O have also prepared cycloselonopentane (I ;n = 3) by an application of both these methods to pentamethylenedibromide. cycloSelenopentane also readily forms addition pro-ducts, but these are, in general, rather less stable than the corre-sponding derivatives of cycloselenobutane.Indole Derivatives.Further investigations have been made during the past yearinto the various types of addition reaction into which indoles andindolenines can enter.It has been observed by S. G. P. Plant 4 1that the 8-acyldihydropentindoles (I; n = 1 ; R = Ac, Bz, orCO,Et), under certain conditions of nitration, not only give mono-nitro-substitution products but also take up the elements of nitricscid, presumably at the double linkage in the indole skeleton, withthe formation of compounds of the type (11). Of the analogous9-acyltetrahydrocarbazoles (I ; n = 2 ; R = Ac, Bz, CO,Et, orPh*CH,*CO), only the benzoyl compound gives a substance of thisCH2CI----BH2 ( J 1 2 2 ( ) 7 Z t H 2 1 ” w/NR CH, NR H, NR CH,(1.) (11.) (111.)nature, the remaining acyl derivatives, under similar conditions,37 G.T. Morgan and H. Burgess, J., 1928,321 ; Ann. Reports, 1928,25, 196.98 H. V. A. Briscoe and J. B. Peel, J., 1928, 1741; Ann. Reports, 1928,ss J., 1929, 1096. 41 Ibid., p. 2493.25, 174.40 Ibid., p. 2197ORGANIC CHEMISTRY .-PART m. 161yielding products (111; R = Ac, CO,Et, or Ph*CH,CO) whichhave resulted from oxidation at the double linkage and the conse-quent addition of two hydroxyl gr0ups.~2 These several additionproducts undergo many interesting reactions under various con-ditions. In some instances, the action of alkali on the compound(11) leads to the rupture of the indole system and the formation ofbenzene derivatives of the type (IV). H. Leuchs, A. Heller, andA. Hoffmann43 have found that, with certain limitations, theaddition reactions observed between acid anhydrides and indeno-+-indolines4* can be applied to the simpler indolenines. Thus3 : 3-dimethylindolenine (V) gives 2-acetoxy- 1 -acetyl-3 : 3-dimethyl-2 : 3-dihydroindole (VI) on treatment with acetic anhydride and~ ~ ~ ~ H 2 l n * C 0 " QT? N QJFL NAc(IV.1 (V.1 w.1sodium acetate at looo, and the analogous 2-benzoyloxy-1-benzoylderivative can be similarly prepared, but it was not possible to addphthalic anhydride. In the case of 3 : 3-dibenzyl-2-methylindolenine(VII), similar experimental conditions resulted, not in the additionof acetic anhydride or benzoic anhydride, but in the acylation ofthe tautomeric form of (VII) with the formation of 1-acetyl- or-y (CH,Ph), o-$M (+-gy)2v C : C H 2 C( OH)*Ph 0 NR NBz(IX.)N(VII.) (VIII.)1-benzoyl-3 : 3-dibenzyl-2-methylene-2 : 3-dihydroindole (VIII ; R=Ac or Bz). 2-Phenyl-3 : 3-dimethylindolenine does not combineadditively with acetic anhydride, but, on treatment with benzoylchloride and sodium carbonate, it gives 2-hydroxy-l-benzoyl-2-phenyl-3 : 3-dimethyl-2 : 3-dihydroindole (IX).Some time ago R.Pummerer 45 claimed to have prepared isatin-2-anil in two tautomeric modscations (X and XI; R = H), butthis was disputed by H. Rupe and K. Ap~theker.~~ It has nowbeen shown, however, by R. K. Callow and E. Hope4' that thearguments of the latter authors are unsound, and Pummerer's viewshave been confirmed by the preparation of both isomeric benzoylderivatives (X and XI; R = Bz) from isatin-2-anil by benzoylation44 See Ann.Reports, 1928, 26,176.42 W. H. Perkin and S. G. P. Plant, J., 1923,123, 676.43 Ber., 1929,62, [B], 871; A., 704.45 Ber., 1911,44, 338, 810; A., 1911,i, 231, 399.Hdv. Chint. Acta, 1926,9,1049; A . , 1927,61.REP.-VOL. XXVI. B*' J., 1929, 1191162 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.under the appropriate conditions. It has been recorded by J.Martinet and A. Dansette 48 that ethyl l-phenyl-4 : 5-benzodiox-v\/ NPhindole-3-carboxylate (XII), obtained from the interaction of N -phenyl-P-naphthylamine and ethyl mesoxalate, can be converted byalkalis under various conditions into 1 -phenyl-4 : 5-benzodioxindole(XIII), l-phenyl-4 : 5-benzoisatin (XIV), or the naphthacridine-(XIII.) (XIV.) (XV.)carboxylic acid (XV). The conversion of derivatives of 1 -phenyl-isrttin into the corresponding acridinecarboxylic acids has previouslybeen observed.49A series of reactions, analogous to some already used in thepreparation of carboline derivatives,5o has been employed as anadditional method for fhe synthesis of 3-keto-3 : 4 : 5 : 6-tetrahydro-4-carboline 51 (XVII). The phenylhydrazone of ethyl 8-phthalimido-a-ketovalerate, obtained by the action of benzenediazonium chlorideon et hy 1 8-phthalimido- CL - acet ylvaler ate in alkaline-alc oholic solu -tion, gave, by the usual Fischer reaction, ethyl 3-p-phthalimido-ethylindole-2-carboxylate (XVI), from which the final product wassecured by heating first with hydrazine hydrate in alcohol and thenwith hydrochloric acid.The preparation of tetrahydroharman(XVIII) by the action of paraldehyde on 3-p-aminoethylindole has -also been described.52(XVI.)coNH48 Bull. SOC. chim., 1929, [ivl, 45. 101; A., 452.(XVII. )49 P. Friedlander and K. K d z , Ber., 1922, 55, [B], 1597; A., 1922, i, 765;so R. H. F. Manske, W. H. Perkin, and R. Robinson, J., 1927, 1.61 S. Keimatsu, S. Sugasawa, and G. Kasuya, J . Pharm. SOC. Japan, 1928,62 G. Tatsui, ibid., No. 555, 453; A , , 74.R. StollB, J . pr. Chem., 1922, [ii], 105, 137; A., 1923, i, 1125.NO. 558, 762; A., 195ORUANIU CHEMIS!t'RY.-PART IU. 163E. W. McClelland 53 has prepared thionaphthindole (XIX) bythe interaction of o-thiolacetophenone with phenylhydrazine inglacial acetic acid, a reaction which proceeds readily and undoubtedlyinvolves first an ordinary Fischer synthesis to give (XX), followed*H2 0"" "GOH HMe NH NH(XVIII.) (XIX.) (XX.)Sby oxidation.The constitution assigned to the product was con-firmed by synthesising it from o-thiolbenzoic acid, which was con-verted first into the ester (=I; R = o-NO,*C,H,*CH,), then, byalcoholic potassium ethoxide, into (XXII), and hally, by reductionwith zinc dust and acetic acid, into thionaphthindole. The productshowed the general reactions of indole derivatives.Quinoline Derivatives.Although the amount of published work dealing with the cyaninedyes has been considerably less this year than during the previousyear,54 some observations of considerable interest have been made.It is well known that l-methylbenzthiazole (I) can be used for theproduction of several different types of cyanine dye, and MissE'.M. Hamer 55 has now extended our knowledge of some of theseclasses by preparing the corresponding dyes from the two methyl-naphthathiazoles (I1 and 111) and comparing them with their simpleranalogues.(1.1 (11.) (111.)All the various classes of carbocyanine dyes contain two hetero-cyclic nuclei united by the carbon chain :CH*CH:CH*, but verylittle is known of derivatives in which one or more of the hydrogenatoms attached to this chain are replaced by other groups. Theneocyanines probably provide examples of this type,s6 and Miss6a J., 1929, 1688.66 J., 1929, 2698.s4 See Ann.Reprte, 1928,26, 179.56 Miss F. 116. Hamer, J., 1928, 1472164 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.F. M. Hamer 57 has now succeeded in preparing three methylthio-carbocyanines of the structure (IV) by the action of ethyl ortho-acetate in the presence of pyridine on the corresponding l-methyl-benzthiazole alkylhalides. This is an application of Miss Hamer’swell-known method of preparing the carbocyanines with the aidof ethyl orthoformate and pyridine, but it has been found that thecarbocyanine syntheses in general cannot be satisfactorily extendedin this way. The substituted thiocarbocyanines, like the parentcompounds, are photographic sensitisers.S Me SMe ‘IAlthough many classes of cyanine and carbocyanine dyes derivedfrom quinoline and other binuclear heterocyclic compounds havebeen described, very little is known concerning the simpler, analogousderivatives of pyridine and other monocyclic systems.E. Rosen-hauer and F. BarletY58 however, have now prepared the 2 : 2/-carbo-pyridinecyanines (V) from a-picoline alkyliodide by the action ofchloroform and potash in alcoholic solution under the correct con-ditions, and a similar procedure with y-picoline methiodide yieldedthe 4 : 4’-carbopyridinecyanine (VI). These dyes, like the corre-sponding quinoline derivatives, are photographic sensitisers.Further studies 59 into the formation of stereoisomerides whichowe their existence to the cis- and trans-unions of two ring systemshave led to an investigation of the action of sodium amalgam upon5-keto-2 : 3 : 5 : 6-tetrahydro-a-quinindene (VII) in boiling alcohol.The reaction resulted only in the addition of two atoms of hydrogen,and, although two stereoisomeric forms (called A and B) of 5-keto-2 : 3 : 4 : 5 : 6 : 13-hexahydro-c+quidene (VIII) were obtained,(VII.) (VIII.) PX.167 J., 1988, 3160.O9 B. K. Blount, W. H. Perkin, and S. G. P. Plant, J., 1929, 1975.68 Ber., 1929, 62, [ B ] , 2724.See Ann. Reports, 1928,26, 183ORGANIC CHEMISTRY.-PART IlI. 165the (B) modification greatly preponderated. The interestingobservation was made that further reduction of the mixture ofthese two stereoisomerides with sodium and boiling alcohol yieldeda single modification only of 2 : 3 : 4 : 5 : 6 : 13-hexahydro-a-quin-indene (IX), a fact which can be explained if the reaction is assumedto take the following course :Furthermore it has been found that 12-keto-2 : 3 : 5 : 12-tetrahydro-p-quinindene (X) is fully reduced by sodium amalgam in boilingalcoholic solution to give both stereoisomeric forms (A and B) of2 : 3 : 4 : 5 : 12 : 13-hexahydro-p-quidene (XI), but the (B) formconstitutes by far the main part of the product, whereas, during thereduction of 2 : 3-dihydro- p-quinindene (XII) with tin and alcaholichydrochloric acid, the amounts of (A) and (B) produced are approxi-mately in the ratio of 1 : 3.It has become apparent that theamounts of the two stereoisomerides formed in these and theanalogous reactions previously investigated do not depend mainlyupon the relative strains in the two configurations, but are deter-mined by the collective effect of several factors.It has also been observed 61 that 2 : 3-dimethyl- and 2 : 3 4 -phenyl-1 : 2 : 3 : 4-tetrahydroquinoline (XIII; R = Me or Ph) areeach produced in two stereoisomeric forms during the reduction ofthe corresponding disubstituted quinolines, the relative amounts ofthe different modifications varying considerably with the nature ofthe reducing agent used.61 S.G. P. Plant and R. J. Roaser, J., 1929, 1861166 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Systems with Two (or More) Hetero-atoms.Once again many papers have appeared during the year dealingwith compounds belonging to the large number of different classeswhich contain more than one hetero-atom in the cyclic nucleus.It is impossible in this Report to deal with more than a few interest-ing points, and these involve, as a general rule, applications ofreactions which are already well known in the simpler series.Several instances of tautomerism have been recorded. Forexample, it has been observed 62 that the 2-amino-oxazolines andthe 2-aminothiazolines exist in the two modifications (I and 11;R = H), and, on interaction with phenylthiocarbimide, for example,p2-yRRCH C:NHQH2-RRCH C*NHR(S) (S)they give rise to two different products (I and 11; R = *CS-NHPh)according to the temperature.In the isooxazole series, the tauto-meric change (111) zz (IV) has been studied by the preparationof a number of derivatives of both forms.63 There is also evidencethat the fully substituted triphenylisooxazolium hydroxides (V)tautomerise to the corresponding $-bases (VI). The latter undergoloss of water to give anhydro-bases which apparently have thePhR-%Ph PhQ==QPhPhC N<OH2 CHR PhOOH NCH,R \ / 0 ph>:CPh.N:CHR Bz(VI.1 (VII.) (V.)structure (VII) .64 Some interesting observations of an analogouscharacter have been made 65 during a study of certain well-knownmethods for the preparation of pyrazolines. The action of aliphaticdiazo-compounds on ethylenic substances gives first a derivative,containing -N-N- in the ring, which then isomerises to the pyr-62 E. Fromm, Annalen, 1926, 447, 259; A., 1926, 716; E. F r o m andR. Kapeller-Adler, ibid., 1928, 467, 240; A ., 199.68 G. Ponzio and M. Torres, Gazzettcs, 1929,59,461; A., 1316.44 E. P. Kohler and A. H. Blatt, J. Amer. Chem. SOC., 1928, 50, 1217;A., 1928,652; E. P. Kohler and N. K. Richtmyer, ibid., p. 3092; A., 77.6s K. von Auwers and E. Cauer, Annalen, 1929,470,284; A., 1080.\ORGANIC CHEMISTRY .-PART M. 167azoline. If 'the ethylenic compound is an @-unsaturated ester, theintermediate substance (VIII) (the nitrogen uniting with the a-carbonatom) might undergo isomeric change in two different directionsto give (IX) or (X). The application of this reaction to a numberRyH-qH*CO,R RyH-$XI*CO,R' RQH-$j*CO,R'XCH N XC NH XCH N\/N\/N v NH(VIII. ) PX.1 (X.1of esters, with diazomethane and diazoethane, yielded exclusivelyproducts of the type (X), but the isomeric pyrazolines of type (IX)can be obtained by the action of hydrazine on p-acylacrylic esters.It seems, therefore, that the isomerisation of (VIII) proceeds in thatdirection which leads to a conjugated system of double linkages.When the unsaturated compound is an unsymmetrical dicarboxylicester, the number of possibilities is increased, and the action ofdiazomethane on methyl citraconate has yielded, together withother substances, a product (XI) in which the type (VIII) appearsto have been realised, since it does not contain a secondary nitrogenatom, and can be converted by hydrogen chloride into the normaltype through the migration of a hydrogen atom.The type (VIII)seems also to find a stable existence in the product of the inter-action of diazomethane and methyl dimethylmaleate.Me O2C*(iH-YMe C0,Me W-R(XI.) CH, N CH CeNHaNHPh (XII.1 Y \/NAmongst other types of migration reactions some examples ofthe benzidine rearrangement have been described.For instance,2-phenylhydrazino-4-phenylthiazole (XII), when treated with boil-ing dilute hydrochloric acid, gives 2 -amino -4-phenyl-5-p -amino-phenylthiazole (XIII),66 and the reaction has been extended to aconsiderable number of closely related compounds substituted inPhC N WV.) (XIII.) NH,C)-C C*.NH,the phenyl groups. Furthermore, it has been observed that 4-phenyl-hy drazino - 5 -p henyl- 3 -met h ylisooxazole ( XIV) is conver fed by heat -ing with N-hydrochloric acid into a mixture of 5-anilino-5-phenyl-6 6 P.K. Bose, J. In&an Chem. SOC., 1927, 4, 331; A., 1928, 188; P. K.Bose and B. K. Sen, aid., 1928, 5, 643; A., 79; B. C. Das-Gupta and P. I(.Born, ibid., 1929,6,495; A., 1317.NHPh*NH$-RMe PhG-Rv v. 0 168 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.3 -met hylisooxazol-4-one (XV ) and 4-imino - 5 - phenyl-5 -0-amino -phenyl-3-methylisooxazoline (XVI). The formation of the latterproduct is due to an o-benzidine rea~~angement.~~QO-gMe oNH:y;-flMe (XV-) NHPhCPh N --CPh N (XVI.1v 0 NH2 0Two interesting ring transformations are involved in the reactionsof certain benzisooxazole derivatives.68 5-Nitro-2-acetamidobenz-isooxazole (XVII), on warming with 2N-sodium hydroxide, gives3-4’-nitro-2’ - hydroxyphenyl- 5 - methyl - 1 : 2 : 4 - oxdiazole (XVIII),NO2 OH N\/CMewhich involves fission of the isooxazole ring and subsequent inter-action of the oximino- and the acetamido-group.When 5-nitro-2-hydroxybenzisooxazole is treated with acetic acid, it undergoesfission to 4-nitro-2-hydroxybenacetylhydroxamic acid (XIX),which, with methyl-alcoholic potash, is converted into 5-nitrobenz-oxazol-l-one (XX), a change which involves first hydrolysis to thefree hydroxamic acid and then a Beckmann rearrangement.g*NHCO* CH, N 0 2 0 R - f j Cr,. 0 (XVII.) (XVIII.) 0The thermal decomposition of a large number of alkylhalides ofheterocyclic nitrogen compounds which also contain other alkylgroups attached to the hetero-nucleus has been studied in order todetermine the relative tenacities of the various hydrocarbon radicals,not only when two are both attached to nitrogen atoms, but alsowhen they are bound to differing atoms, e.g., carbon and nitrogen.69The systems investigated include, amongst others, the quaternaryindazolium salts (XXI), the iodides of NN’-dialkylbenziminazolesNPh(XXIII.)I67 G.Wittig, H. Kleiner, and J. Conrad, Annalen, 1929, 469, 1; A., 466.6 8 H. Lindemann and H. CissCe, ibid,, p. 44; A., 456.69 K. von Aumers and his collaborators, Ber., 1926,58, [B], 1360; A., 1926,i, 1100; Bw., 1928, 61, [B], 100, 2411; A., 1928, 306; 1929, 76; AnrmJen,1929,469, 82; 472, 287; A., 454, 1081ORGANIC CHEMISTRY .-PART m. 169(XXII), substituted pyrazole alkyliodides (XXIII), and thiopyrine+alkyliodides (XXIV), and the results show that, as a general rule,the tenacity with which the simple alkyl groups are attached to twonitrogen atoms increases with the size of the group, and the benzyland ally1 radicals are less firmly bound than methyl, but the problemis much more complex when the various groups are attached toatoms which differ from one another.Alkloids.Pyridine Group-Hitherto very little has been known concern-ing the alkaloids from Lobelia inflata, although H.Wieland, C.Schopf, and W. Hermsen, a few years suggested formulaefor lobelanine, lobelanidine, and lobeline. As a result of morerecent workY7l however, much of the confusion which formerlyexisted has been removed and the inter-relationships of these pro-ducts have been made clear : the earlier formula have been aban-doned, and the accompanying structures, which represent com-paratively simple pyridine derivatives, are now assigned to lobel-anine (I; R = Me), lobeline (11), lobelanidine (111; R = Me),norlobelanine (I; R = H ; formerly called " isolobelanine "), andnorlobelanidine (111; R = H).The alkaloid previously isolatedand called " lobelidine," 72 is now shown to be dl-lobeline. The/ \"QH2 QH2OH*CHPh*CH,*CH CH*CH2*CHPh*OH\ /following are some of the outstanding facts in support of theseformuls : (a) Lobelanidine and lobeline can be oxidised to lobelanine,(b) further oxidation of lobelanine yields benzoic acid and l-methyl-piperidine-2 : 6-dicarboxylic acid, (c) lobelanine gives a dioximewhich, after a Beckmann rearrangement, yields the dianilide ofl-methylpiperidine-2 : 6-diacetic acid, (d) the Hofmann degradation7° Annden, 1925, 444, 40; A., 1925, i, 1087.7l H.Wieland and 0. Dragendorff, ibid., 1929, 473, 83; A., 1085; H. Wie.7a H. Wieland, Ber., 1921, 54, [B], 1784; A., 1921, i, 802.land, W. Koschma, and E. Dane, ibid., p. 118 ; A., 1086.F 170 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of lobelanine yields a neutral product, which, on subsequent reduc-tion, gives 1 : 7-dibenzoyl-n-heptane or 1 : 9-dihydroxy-1 : 9-di-phenyl-n-nonane according to the conditions, ( e ) reduction of nor-lobelanine with 1% sodium amalgam in dilute acetic acid givesnorlobelanidine, which can be methylat,ed to lobelanidine, and(f) acetophenone can be obtained from these alkaloids under avariety of conditions.The structures now assigned to these variousalkaloids have been confirmed by synthetical means. For instance,1 : 7-dibenzoyl-n-heptane-2 : 6-dione (IV), from the condensation(IV.) y? CPhiCOCiCPh (v')NYH2 C'H2COPh*CH,*CO CO*CH,*COPhof ethyl glutarate and acetophenone, gave 2 : 6-di(benzoylmethylene) -piperidine on treatment with dry ammonia at loo", and thenvarious processes of reduction led to norlobelanidine and, aftersubsequent oxidation, to n~rlobelanine.~~ Again, 2 : B-diphenyl-acetylenylpyridine (V), from the action of alcoholic potassiumhydroxide on 2 : 6-distyrylpyridine tetrabromide, gave, with 50%(by vol.) sulphuric acid, 2 : 6-diphenacylpyridine, from which nor-lobelanidine was obtained by reduction.'4F.D. Chattaway and G. D. Parkes 75 have observed that nicotinetetrachloroiodide, C1,Hl4N2,2HICl4, separates when a solution ofthe base in hydrochloric acid is added to a similar solution of iodinetrichloride. This is a particularly well-crystallised derivative andaffords an excellent method for isolating the alkaloid in a purecondition from tobacco, since the salt can be readily purified byrecrystallisation from glacial acetic acid. The free base can thenbe obtained by decomposing this salt with sodium sulphite, andsubsequently making the mixture alkaline. T. M. Lowry andW. V. Lloyd 76 have utilised the zinc chloride salt,C,,H,4N,,2HC1,ZnC12,H20,for the purification of this alkaloid.It can be prepared from zincchloride and the base in alcoholic hydrochloric acid, recrystallisedfrom 60% alcohol, and finally decomposed with potassium hydroxide.Quinoline Group-Investigations into the nature of the productsobtained from angostura bark have made considerable progressduring the year. E. Spath and G. Bapaioanou7' have isolated anew phenolic alkaloid, galipoline, from this source. It was found73 H. Wieland and I. Drishaus, Annalen, 1929,473, 102; A., 1086.'4 G. Scheuing and L. Winterhalder, ibid., p. .126 ; A., 1086.76 J., 1929, 1314.7 7 Monahh., 1929,52, 129; A . , 1087.Ibid., p. 1376ORGANIO CHEMIS!CRY.-PBT LU. 171to contain one hydroxyl and two methoxyl groups, and, on methyl-ation, yielded the related alkaloid, galipine, the structure of whichwas elucidated some time ago.'* The relative positions of thehydroxyl and methoxyl groups were not at &st apparent, but thefact that galipoline is 4-hydroxy-2-p-3' : 4'-dimethoxyphenylethyl-quinoline (I) was finally established synthetically : 4-chloro-2-3' : 4'-dimethoxystyrylquinoline, from the condensation of 4-chloro - 2 -met hylquinoline and veratraldehyde, reacted with sodiumbenzyloxide to give the corresponding 4-benzyloxy-derivative,which, on reduction and subsequent hydrolysis, yielded galipoline.OH OMeIn addition, E.Spiith and J. Pik179 have isolated a new basefrom the non-phenolic products of angostura bark, and have shownthat it is 4-methoxy-2-n-amylquinoline (11). The main observationswhich indicated its structure were : (a) it was hydrolysed withdiEculty to the corresponding phenolic base, which, after treatmentwith a mixture of phosphorus pentachloride and oxychloride, andreduction of the resulting chloro-compound, yielded 2-n-amylquinol-ine, the identity of which was established by synthesis; (b) bydistillation of the methiodide of the new base in a vacuum l-methyl-2-).~-amyl-4-quinolone (111) wits obtained, and this, on oxidation,yielded n-hexoic acid.The structure assigned to this new basewas h a l l y confirmed synthetically by condensing aniline withm-hexoylacetic ester at room temperature and heating the product(IV) for a short time at 256255". This process yielded the phenolicbase corresponding to the alkaloid, which was itself then obtainedby methylation with diazomethane.isoQuinoZine CTrwp-The isolation of an alkaloid, carnegine,Cl3Hl,0,N, from Carnegiea gigantea has been described by G.Heyl,80who found that it contains two methoxyl groups. E. Spiith8178 Compare Ann. Reports, 1924, 21, 131.'@ Ber., 1929, 62, [B], 2244.Arch. Pharm., 1928, 266, 668; A., 201.Ber., 1929,62, [B], 1021172 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.suggested that carnegine is 6 : 7-dimethoxy-1 : 2-dimethyl-1 : 2 : 3 : 4-tetrahydroisoquinoline (IIL), and proved this view to be correct by~fp~ MeO, \ / N M eCHZ M e O p T b H 2 ~ ~ e o , CHMeMeo/\//NCOlSle CMe(1.1 (11.) (111.)synthesising the alkaloid. Aceto-p-3 : 4-dimethoxyphenylethyl-amide (I), when acted upon by phosphoric oxide in boiling toluene,gave 6 : 7-dimethoxy-l-methyl-3 : 4-dihydroisoquinoline 82 (11), themethiodide of which was reduced to carnegine.The fact that the6 : 7- and not the 7 : 8-dimethoxy-derivative resulted from thisapplication of the Bischler-Napieralski reaction followed from theoxidation of (11) t o m-hemipinic acid. It has also been showna3that pectenine, an alkaloid isolated from Cereus pecten aboriginumby G. H e ~ l , ~ 4 is in reality identical with carnegine.Prompted by the fact that emetine appears to contain two6 : 7-dimethoxytetrahydroisoquinoline residues joined through the1-positions by a carbon chainja5 R. Child and F. L. Pyman 86 haveinvestigated the possibility of applying the Bischler-Napieralskireaction to the p-phenylethylamides and p-veratrylethylamides ofthe dibasic acids for the preparation of bisdihydroisoquinolines.Although the formation of even one of the two isoquinoline ringscould not be brought about by applying the usual methods to theunsubstituted p-phenylethylamides (IV ; R = H ; n = 1 to 8 ) )nevertheless the p-veratrylethylamides (IV; R = MeO; n = 4 to10) underwent intramolecular dehydration with the formation ofthe desired bisdihydroisoquinolines.An examination of some ofthese products and the corresponding bistetrahydroisoquinolinesformed by reduction indicated, however, that they did not possessthe physiological properties of emetine.It has been found that the condensation products of benzoyl-hydrazine and aromatic aldehydes undergo an intramolecular82 E.Spath and N. Polgar, Monotsh., 1029, 51, 190.84 Arch. Pharrn., 1901, 239, 459.85 Compare Ann. Reports, 1927,24, 174.86 J., 1929, 2010.E. Spiith and F. Kuffner, Ber., 1929,82, [B], 2242ORGANIC CHEMISTRY .-PART III. 173CH dehydration, which is reminiscent of the Bischler-Napieralski reaction, on treatment preferably with p amyl-alcoholic hydrogen chloride, and yield phthal-HN azines (V). These phthalazines, on hydrolysis, c yield hydrazine and o-aldehydo-ketones, and the pro-( v . ) Ph cess affords a valuable synthetical method for pre-paring substances of the latter type.E. Spath and N. Polgar 88 have observed that the 3 : 4-dihydro-isoquinolines obtained by the dehydration of substituted acyl-P-phenylethylamides can be dehydrogenated with palladium-blackat 150-180" to the corresponding isoquinoline bases, several ofwhich they have prepared in this way.Hitherto little has been known regarding the constitution ofoxyacanthine, one of the alkaloids isolated from Berberis spp., andeven its molecular formula has been in More recent work,however, has enabled E.Bpath and J. Pik190 to advance theformula (VI) for this alkaloid, although much yet remains to bedone before its constitution is definitely settled. Three oxygenatoms are accounted for as methoxyl groups, one as a phenolichydroxyl group, and the remaining two as ether linkages. An applic-ation of the Emde degradation process gave results which suggestedthe presence of two isoquinoline nuclei. The attachment of thediphenyl ether residue to each isoquinoline nucleus through methyl-ene groups was indicated by the isolation of 3-phenoxy-4-methoxy-(VII.)H 2 e e M e o m CH2MeN -0 NMeQH OMe P(VIII.)8 7 J.S. Aggarwal, N. L. Darbari, and J. N. RAY, J., 1929, 1941.88 Mo&h., 1929, 51, 190; A., 578.E. Splith and A. Kolbe, Ber., 1926,58, [B], 2280; A., 1926, 82; J. Gada-mer and W. von Bruchhausen, Arch,. Phccrrn., 1926, 264, 193; A., 1926, 627.9O Ber., 1929,62, [B], 2261174 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.benzene-1 : 4’-dicarboxylic acid (VII) by the oxidation of theproduct obtained from oxyacanthine methyl ether by the Hofmanndegradation process. A similar procedure applied to oxyacanthiiieethyl ether yielded 3-phenoxy-4-ethoxybenzene-1 : 4‘-dicarboxylicacid, which fixed the position of the phenolic hydroxyl group.Thepublication of this work on oxyacanthine by Spath and Pikl broughtforth a paper by F. von Bruchhausen and H. Sch~ltze,~l who hadarrived independently at a very similar formula (VIII) for thisalkaloid, as a result of closely related oxidation experiments, sothat agreement seems to have been reached upon the main features.There are, in consequence, several points of resemblance betweenoxyacanthine and the alkaloids curine and isochondodendrine .92Von Bruchhausen and Schultze also mention a new non-phenolicalkaloid, C1gH220N2, which they have isolated in small quantitiesfrom Berberis vulgaris.Aporphine Group.-A series of reactions, which involves theBischler-Napieralski synthesis and has previously been utilisedfor the preparation of a number of aporphine derivativesYg3 hasnow been applied by R. K.Callow, J. M. Gulland, and R. D.Haworth 94 to the preparation of 2 : 3 : 6 : 7- and 3 : 4 : 6 : 7-tetra-methoxyaporphine (IV and V). For instance, 6’-nitro-3’ : 4’-di-methosyphenylaceto- p-2 : 3-dimethoxyphenylethylamide (I) hasbeen converted by the action of phosphorus pentachloride in coldchloroform into 6’-nitro-3’ : 4’ : 5 : 6-tetramethoxy-l-benzyl-3 : 4-dihydroisoquinoline (11), the methiodide of which, on reductionwith zinc dust and hydrochloric acid, gave the amine (111).dl-2 : 3 : 6 : 7-Tetramethoxyaporphine (IV) was subsequently ob-tained by diazotisation in methyl-alcoholic sulphuric acid. Aparallel series of reactions led to dl-3 : 4 : 6 : 7-tetramethoxyapor-phine (V).The synthesis of the former of these two aporphines isMe0 Me0 Me091 Arch. Pharrn., 1929, 267, 617.O 2 See Ann. RepoTts, 1928,25, 190.93 Compare Ann. Reporb, 1928,25, 186. J., 1929, 658ORGANIC CHEMISTRY .-PART III. 175interesting in view of its bearing on the constitution of lauro-tetanine. K. Gorter assigned the structure (IV) to " isoglaucine,"Me0MeOQ \QH, MgQ,I CH 1 CHM e 0 0 y H 2 I CHMeo$@z Meo%:Tg "o&*g;Me0 CH, Me0 CH, CHZ(IV.1 (V.) (VI.1the methylation product of laurotetanine, but it has recently beenshown 95 that " isoglaucine " was impure glaucine, and conErmationof this is now derived from the fact that the reactions of the syn-thetical product (IV) do not resemble those of " isoglaucine."The formula (VI; R = H) has been allotted to isothebaine,96isolated from Papaver orientale, and, with a view to testing this,attempts have been made 97 to apply analogous synthetical methodsto the preparation of isothebaine methyl ether (VI; R = Me).It was not possible, however, in the case of 2'-nitro-3' : 4'-dimethoxy-phenylaceto-~-4-methoxyphenylethylamide (VII ; R = MeO), toconvert the amide into an isoquinoline derivative, probably onaccount of the absence from the 3-position of a strongly p-directinggroup.General experience has certainly indicated that it may bevery diflicult to carry out a Bischler-Napieralski reaction, exceptwith compounds containing an activating group, and the sameexplanation may be given of the failure to obtain a dihydroiso-quinoline derivative from 2'-nitro-3' : 4'-dimethoxyphenylaceto-P-phenylethylamide (VII; R = H) by the action of phosphoruspentachloride in an attempt to synthesise apomorphine dimethylO 6 See Ann.Reports, 1928,25, 188.90 W. Klee, Arch. Phann., 1914, 252, 211; A., 1914, i, 1086.97 R. K. Callow, J. M. Gulland, and R. D, Haworth, J., 1929, 1444176 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.ether 98 (VIII). The position in regard to the latter instance is,however, somewhat uncertain, since E. Spath and 0. Hromatkag9appear to have succeeded in obtaining the dihydroisoquinoline (IX)from this amide by the use of phosphoric oxide in boiling xylene,and to have proceeded subsequently to the synthesis of apomorphinedimethyl ether.Although the condensation of an o-nitrotoluene derivative withthe appropriate 1 -hydroxy-2-methyl- 1 : 2-dihydroisoquinoline hasprovided the first step in the synthesis of several aporphine bases,J.M. Gulland and C. J. Virdenl have found that this reactionfails when applied to 2-nitrohomoveratrole (X), but, by utilising2-nitro-3 : 4-dimethoxyphenylacetonitrile, in which the hydrogenatoms of the methylene group have received additional activation,i t has been possible to prepare the bases (XI), (XII; R = R' =MeO), and (XII; R = MeO; R' = H). Further progress towardsM e 0 , 3 \ Me0 M . o ' 3 \ Me0NO, TH*CN NO2 FHGNMe0 CH CH(X.) (XI.) (XII.)the corresponding 3 : 4-dimethoxyaporphine derivatives, whichinvolves reduction of the nitro-group, was found to be impossible,however, on account of the readiness with which these bases werehydrolysed into the original reagents by dilute acids or alkalis.Inopposition to the experience of these authors is the synthesis ofapomorphine dimethyl ether described by H. Avenarius and R.Pschorr,2 who claim to have condensed together 2-nitro-3 : 4-di-methoxyphenylacetonitrile (XIII) and l-hydroxy-2-methyl-l : 2 : 3 : 4-tetrahydroisoquinoline (XIV) with the formation of the nitrile(XII; R = R' = H), which, after hydrolysis, removal of carbonM e O A98 J. M. Gulland, R. D.. Haworth, C. J. Virden, and R. K. Callow, J., 1929,99 Rer., 1929, 62, [BJ, 325. 8 Ber., 1929, 62, [BJ, 321,1666.J., 1929, 1791ORGANIC CHEMISTRY .-PART III.177dioxide and subsequent reduction, gave the base (XV). Diazotis-ation, followed by the addition of copper powder, is said to yieldupomorphine dimethyl ether (VIII). These reactions, however,may need further investigation, since Gulland and Virden failed inseveral attempts to prepare upomorphine dimethyl ether by thismethod, and, as these authors point out, Avenarius and Pschorrclaim to have established the identity of their synthetical dl-upo-morphine dimethyl ether methiodide with the laevorotatory meth-iodide from natural sources.Diisoquinoline Group-The condensation of methoxy- or methyl-enedioxy-bases of the type ( I ; X or Y = OMe, or XX or YY =O,CH,) with formaldehyde has always given derivatives of thetype (11), by ring closure in the 2-position, and these reactions havenot provided a route for the synthesis of alkaloids of the tetra-hydroberberine class (111), which would require ring closure in the6-position.E. Spath and E. Kruta3 have now found, however,X X Xthat tetrahydropapaveroline (I ; X = Y = OH), in which thereare four free hydroxyl groups, condenses with formaldehyde to givea product which, on methylation with diazomethane, yields equalamounts of both the corresponding bases, norcoralydine (11; X =Y = OMe) and tetrahydropalmatine (111; X = Y = OMe). Theview is expressed, therefore, that in the plant the alkaloids of thisclass are produced from hydroxy-derivatives of the type (I) bycondensation with formaldehyde, followed by alkylation and subse-quent oxidation to the quaternary base.By taking advantage ofthese observations, the same authors have developed a synthesisof w o - and r-corydaline, the two stereoisomerides of the formula(IV). Papaverine was condensed with formaldehyde to yieldOMe OMeC H M e pMe0Me0 CH( * y e 0 P J H 2 vNMe0 CH, CH,J Moncctsh., 1928, 50, 341; A., 201. Ber., 1929, 62, [B], 1024178 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.methylenepapaverine (V), which was reduced catalytically tomethylpapaverine (VI). This, on electrolytic reduction, gave amixture of the two racemic methyltetrahydropapaverines (VII),which was demethylated, condensed with formaldehyde, and subse-OMe OMequently re-methylated with diazomethane to give a basic mixture,from which mesocorydaline was isolated by crystallisation fromether at 0".The bases of the tetrahydropalmatine type present inthe mother-liquor were then separated from the other basic productsby dehydrogenating them with hot alcoholic iodine, removing thequaternary salts, thus formed, in aqueous solution, and reducingthem back to the tetrahydro-bases with zinc and acetic acid. Bydissolution of these bases in dilute hydrochloric acid and fractionalprecipitation with potassium bromide, a hydrobromide was obtainedwhich yielded a small quantity of r-corydaline.The structure of coptisine (VIII), an alkaloid from Coptis j q o n i c u ,and its relationship to palmatine (IX), of which it is the di-methylene-dioxy-analogue, were made clear as a result of the work of Z . Kita-sato,5 who transformed it into the latter alkaloid.E. Spath andR. Posega 6 have now explored the possibilities of synthesisingcoptisine from substances related to it. Attempts to preparetetrahydrocoptisine (111; XX = YY = O,CH,) from palmatinechloride by demethylation, followed by methylenation and subse-quent reduction, failed, but, by demethylating tetrahydropalmatineand methylenating the product under the appropriate conditions,the authors obtained a small amount of tetrahydrocoptisine.Another route was to proceed from protopine (X) by reductionwith sodium amalgam to the corresponding secondary alcohol,Proc. Imp. Acad. Tokyo, 1926,2, 124; A., 1926, 1160,6 Ber., 1929, 62, [B], 1029; A., 707ORGANIC] CHEMISTRY.-PART III.179which was converted into the salt (XI) by evaporating its solutionin hydrochloric acid and then, on subsequent distillation of thecorresponding iodide in a vacuum, into tetrahydrocoptisine. Thelatter base can readily be converted into coptisine iodide by heatingit with iodine in alcoholic solution. R. D. Haworth and W. H.Perkin,' before the isolation of coptisine had been described, pre-pared its tetrahydro-derivative (111; XX = YY = 02CH,) duringtheir synthesis of protopine.Continuing the investigation of the preparation and propertiesof the simpler substances of the palmatine-berberine type,* S. N.Chakravarti and W. H. Perkin have applied the reactions used inthe synthesis of oxyberberine lo to the production of 3 : 10-dimeth-oxytetrahydroprotoberberine (XV). 4-Methoxyphthalidecarboxy-p-m-methoxyphenylethylamide (XIII), obtained by acting uponthe acid chloride of 4-methoxyphthalidecarboxyIic acid (XII) withp-m-mefhoxyphenylethylamine, was converted by heating with(XIII.)CH*C02HMe0(XII.)cophosphorus oxychloride into a basic substance, which yielded3 : 10-dimethoxyoxyprotoberberine (XIV) on reduction with zinc7 J., 1926, 1769; Ann. Reports, 1926, 23, 167.* S. N. Chakravarti, R. D. Haworth, and W. H. Perkin, J . , 1927, 2266,0 J., 1929, 196.lo W. H. Perkin, J. N. Ray, and R. Robinson, J., 1926, 127, 740; Ann.2275; Ann. R e p o d , 1927,24, 171.Reporb, 1926,22, 146180 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.dust and acetic acid. Further reduction by electrolytic means gave3 : 10-dimethoxytetrahydroprotoberberine (XV), which has thecharacteristic features of its 3 : ll-isomeride.Morphine Croup.-A short time ago the formula (I) was assignedby K. Goto l1 to the alkaloid sinomenine, isolated from Xinomeniumacutum, but this has now been abandoned in favour of (11) or (III).12Sinomenol, obtained from the alkaloid by potash fusion, wasoriginally thought to be 3 : 4-dihydroxy-5 : 6-dimethoxyphenanthr-ene, but it has now been shown synthetically by Pschorr's methodthat its dimethyl ether is 3 : 4 : 6 : 7-tetramethoxyphenanthrene.Furthermore i t is concluded from the reactions of sinomenine thatit must be closely related to thebainone, and sinomenol is nowregarded as 4 : 6-dihydroxy-3 : 7-dimethoxyphenanthrene (IV). Thepoint of attachment of the methylaminoethyl chain in sinomenineseems to be uncertain, both C5 and C13 being admitted as possi-bilities, and agreement does not seem to have been reached con-cerning the exact location of the double linkage, which may be inthe 7 : 8- or 8 : 14-positions. The action of mild oxidising agents on(IV.HO)Me01 211 Proc. I m p . Acad. Tokyo, 1926, 2, 7, 167; A., 1926, 1160; compare Ann.Reports, 1926,23, 171.12 H. Kondo and E. Ochiai, J . Phrm. SOC. Japan, No. 538, 1015; No. 539,20; K. Goto, Bull. Chem. Xoc. Japan, 1929,4, 103; K. Goto and H. Sudzuki,ibid., pp. 107, 163, 244; A., 830, 944; H. Kondo and E. Ochirti, Annalen,1929, 470, 224; -4,, 1088OR(xBM0 CHEMISTRY .-PART III. 181sinomenine gives a mixture of disinomenine and 4-disinomenine,to which formule of the type (V) are assigned and which maydiffer in the point of attachment of the methylaminoethyl chain.The former is said to accompany sinomenine in nature. K. Gotoand H. Sudzuki 13 have described the isolation of two new alkaloids,acutumine and sinactine, from Siwmenium acutum, although thequantities obtained have as yet been insufficient for any definiteviews to be advanced concerning their structure. The alkaloidsso far described from this source number five : sinomenine, diversine,disinomenine, acutumine, and sinactine.H. Wieland and L. F. Small 14 have pointed out that a-thebaizone,obtained by the action of ozone on thebaine, must have the con-stitution (VI), if the Gulland and Robinson formula (VII) forMeO-C CH\/CHthebaine is accepted. The results obtained in an extensive inves-tigation of the reactions of a-thebaizone and related substanceshave been found to be in agreement with these structural views,and confirm the thebaine formula.Strychnine.-In a further communication dealing with the com-plex chemistry of the derivatives of strychnine, W. H. Perkin andR. Robinson15 have pointed out that the new formula recentlyadvanced for this alkaloid l6 needsslight modification. In its revisedform (I) the heterocyclic systemN CH containing the ether oxygen isattached to C17, and not to C18.B. I<. Blount, W. H. Perkin, andS. G. P. Plant:’ from a study ofa large number of partly reducedpolycyclic compounds, have ob-served that l-acyl-1 : 2 : 3 : 4-tetra-hydroquinoline derivatives and l-acyl-2 : 3-dihydroindole derivatives(1.1l3 Bull. Chem. SOC. Japan, 1929,4,220.l4 Annalerz, 1928, 467, 17; A., 81.16 R. C. Fawcett, W. H. Perkin, and R. Robinson, J., 1928, 3089; compareAnn. Reports, 1928, 25, 193.l6 J., 1929, 964.l7 J . , 1929, 1976182 ANNUAL REPORTS ON THE PROGRESS OF UHEMISTRY.are characterised and distinguished from one another by colourreactions with potassium dichromate in 65% sulphuric acid.Members of the former class give an intense crimson colour whichpersists for some time, and those of the latter type give an intense,but rather transient, blue or violet-blue colour. The correspondingde-acylated bases give no such intense colour under these con-ditions. Strychnine gives the colour reaction of the l-acyl-2 : 3-dihydroindoles, and it is interesting to note that this skeleton ispresent in the new formula for this alkaloid, but it was absent fromthe original formula of Perkin and Robinson.A new alkaloid, vomicine, obtained as a by-product in theisolation of strychnine, has been described by H. Wieland andG. Oertel.l* It has the molecular formula C22H2,0,N2 and appearsto contain an oxide ring, as in strychnine.Lupin AZkaZoids.-The chemistry of these substances has beenthe subject of further interesting developments, the chief of whichhas been the assignment of a structural formula to lupinine. Froman examination of the products derived from lupinine by exhaustivemethylation and subsequent reduction, P. Karrer, F. Canal, K.Zohner, and R. Widmer l9 consider that this alkaloid may be repre-sented by the formula (I). The action of phosphorus penta-bromide on the fully reduced, nitrogen-free product has given whatis apparently 8-bromomethylnonane, since the unsaturated hydro-carbon obtained by adding trimethylamine and subsequently dis-tilling the corresponding hydroxide, yielded, on treatment withCH2 N CH2CH, CH,\/ vA H2(111.) PV.1Annalen, 1929,469, 193; A., 708.l9 Hdu. Chim. Acta, 1928,11,1062; A., 200ORQA?SIIC UHE1CIISTRY .-PART Kt. 183ozone, n-propyl n-amyl ketone. Although this formula is by nomeans established, the known reactions of lupinine can be explainedwith its aid. These authors have expressed the view that sparteinemay possibly be represented as a condensation product of lupinineand piperidine, for which the alternative structures (11, 111, IVYand V) can be evolved.G. R. Clemo and R. Raper 20 have found, however, that a struc-tural change in the lupinine molecule is possible during the Hofmanndegradation process, and, furthermore, they show that it is difXcultto reconcile some of the known facts in the chemistry of sparteineand the closely related lupanine with any of these alternativeformula advanced by Karrer and his co-workers for sparteine.K. Winterfeld 21 also re-afims the belief that sparteine must berepresented as a quinuclidine derivative, in which case these formuhcannot serve for this alkaloid.Tropane &mp.-The observation that the hydrolysis of bella-donnine with concentrated hydrochloric acidat 140" leads to " bellatropine," C,H,,ON, aNMe THC1 new isomeride of tropine,22 has now been shownto be inc0rrect.~3 The product of the reactionH2-yH-(?H2 H H2-'H-cH2 I T \( 1 . 1 is apparently 3-chlorotropane (I), the analogous3-bromotropane being obtained if hydrobromic acid is used in thehydrolysis.3- Membered Rings.During the past twenty years there has been a gradually increas-ing tendency to disbelieve in the existence of 3-membered ringsunless they contain at least two carbon atoms. This movementoriginated in the work of Angeli, as a result of which open-chainconfigurations for the azoxy-compounds and the N-ethers of theoximes replaced the older ring structures. Receiving considerableimpetus from the investigations of Thiele and Staudinger, similarviews, involving the formulae (I and 11), have in recent years become(1.1 R2CI=N=N R*N=NzN (11.)widely accepted for the aliphatic diazo-compounds and the azides.These two classes have some points in common and it is probablethat, in any case, they have analogous formulE. In spite of veryextensive investigations into the chemistry of the aliphatic diazo-compounds there is no really conclusive evidence for the open-chain formula, and an examination of the physical properties of2o J., 1929, 1927.2a 0. Hesse, Anwlen, 1893,277, 296.21 Arch. Pham., 1929,267, 433; A., 1186.M. Polonovski and M. Polonovski, C m p t . rend., 1928, 188, 179; A.,336; BUZZ. Soc. chirn., 1929, [iv], 45,304; A., 830184 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.these substances has now indicated that a return to the originalring structures (I11 and IV) may have to be made. H. Lindemannand H. Thiele24 determined the parachors of certain azides and(111.) R&<# RN<M N (IV.)found support for the ring structure. N. V. Sidgwick z5 has pointedout, however, that these results are not really conclusive, althoughfor other reasom he supports the older formulations. Thus, sincethe presence of a co-ordinate link causes a rise in the boiling point,if the aliphatic diazo-compounds and the azides have the cyclicconfigurations, they should boil a t approximately the same tem-peratures as the corresponding halides, but an open-chain structurewould demand boiling points close to those of the nitro-compounds.With these considerations in mind, an examination of the boilingpoints of a large number of aliphatic diazo-compounds and azideshas pointed quite definitely to the older formula.S. G. P. PLANT.24 Ber., 1928, 61, [ B ] , 1629; A . , 1928, 937. 25 J., 1929, 1108

ISSN:0365-6217    

DOI:10.1039/AR9292600074

出版商:RSC    

年代:1929

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY.THE output of investigations in analytical chemistry increases involume, but there is no outstanding discovery to be reported.Progress continues to be made in the utilisation of specific reactionsfor various kations and anions, and micro-chemical methods ofdetection and estimation are being extended and developed, as isshown by the publication of a volume of “ Mikrochemie ” dedicatedto Pregl (1929). The object of much of the qualitative investig-ations is the formulation of such specific tests or reactions for eachelement or group. As examples of these tests we have Feigl’s forsilver by means of p-dimethylaminobenzylidenerhodanine, whichdepends on the formation of a red precipitate even in dilutions wherethe silver chloride precipitation cannot be observed ; this reagentalso reacts with mercury, but becomes specific for silver when potass-ium cyanide is present.l Again, the detection of aluminium by meansof the violet colour given by “ eriochromcyanin R.conc.” or thegreen fluorescence with morin in methyl-alcoholic solution is extra-ordinarily delicate, and is not interfered with by a large excess ofcobalt, nickel, or similar metals. The delicacy of these tests is suchthat it becomes difficult to be certain that the water and reagentsthemselves do not give positive reactions for aluminium. In thisconnexion there are now available specific reactions or colour testsfor silver, lead, mercury, bismuth, copper, cadmium, arsenic, anti-mony, tin, iron, aluminium, chromium, manganese, nickel, cobalt,zinc, barium, strontium, calcium, magnesium, potassium, sodium,fluoride, chloride, bromide, iodide, sulphide, thiosulphate, sulphite,sulphate, nitrite, nitrate, phosphate, borate, carbonate, cyanidc,ferrocyanide, ferricyanide, thiocyanate, and oxalate.This compre-hensive list of kations and anions has been set out in a systematicway for rapid examination by a spot test method.2Increasing use is likewise being made of the formation of complexcompounds for both the detection and the estimation of metals andcertain groups, frequently by micro-chemical examination. Cup-ferron (nitrosophenylhydroxylamine) thus finds extended use forbarium and uranyl kations because of the characteristic crystals1 K. Heller and P. Krumholz, Mikrochem., 1929, 7, 213; A., 900.2 G.Gutzeit, Helv. Chim. d c t a , 1929,12, 713, 829; A , , 898, 1254186 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.f ~ r r n e d . ~ Characteristic crystalline compounds are also formed bymeans of ammonium thiocyanate and aniline from ammoniacalsolutions of copper, cadmium, and nickel, of the general type2(C,Hs*NH*HSCN),M(NH,),(SCN),.4 These compounds recall thepyridine-thiocyanates of Spacu and his co-workers, which havefound application in the detection and estimation of a number ofmetals. It is specially important to note that copper pyridinethiocyanate, [Ch(C,H,N),](SCN),, dissolves in chloroform, giving agreen solution, so that this metal may by this means be determinedin the presence of all those metals which give white compound^.^Neutral solutions of mercury and cadmium when treated withpotassium iodide give precipitates with solutions of ethylenediaminccopper nitrate, (Cu en2)(NO,),,2H2O, of the type (XI,)(Cu en2), andthese are used to determine mercury or cadmium by macro- ormicro-methods.6 Other organic bases are available for the form-ation of these complex metallic compounds, e.g., aminopyrine,8-hydroxyquinoline, cinchonine, and quinoline, and their use may beexpected to extend.The determination of mercury as (HgI,)(Cu en2) is rapid,' but themethod of precipitation as HgCr20,,2C5H,N has the advantage ofemploying only common laboratory reagents, and it is rapid andaccurate as well, yielding a precipitate readily collected andhandled.* This method is suitable for comparatively large quan-tities of mercury, but a more frequent problem is the accurate deter-mination of small amounts in organic and inorganic materials.Ithas been found that hypophosphorous acid will reduce mercury saltsin the cold and the metal may be readily determined with 0.01N-iodine solution, provided that a slight excess of 0-O1N-thiosulphatesolution is used and the excess determined. The value of themethod is increased by the fact that it is applicable to solutionscontaining copper and iron salts and to the liquid obtained byoxidation of organic matter as in the ordinary Carius method forhalogens.9 The estimation of minute quantities of mercury may beas accurately made by the use of diphenylcarbazone, which gives thecharacteristic blue liquid, as by the formation of mercuric iodide;but the difficulty in the f i s t place is to collect the trace of mercuryfrom a liquid which contains substances capable of vitiating thedetermination.This may conveniently be accomplished byelectrolysis with small gold cathodes, which can then be introducedii A. Martini, Mikrochem., 1928, 6, 152; A., 164.Idem, ibid., 1929, 7, 30.G. Spacu and J. Dick, 2. anal. Clzem., 1929,78,241; A., 1259.G. Spacu and G. Suciu, ibid., 77,334,340 ; 78,244 ; A., 901,1259.Idem, ibid. G. Spacu and J. Dick, ibid., 1929, 76, 273; A., 416.R. Robinson, AnaZyst, 1929,54, 145; A., 631ANALYTICAL CHEMISTRY. 187into glass tubes and heated with chlorine, furnishing mercuricchloride ; or the mercury may be volatilised by heating and detectedas iodide.Perhaps the most delicate test for the volatilised mercuryis Nordlander's selenium sulphide method, for the diphenylcarbazonemethod in our experience requires very careful adjustment of theacidity of the test solutions (see also p. 193).In mineral analysis the determination of silica is always liable togive low results because of the diiZculty of deciding when the lastportions of silica, have been rendered insoluble in the reagents used.It is therefore of some value to have the molybdenum-stannitereaction which is capable of detecting traces of silica. The neutralsolution is treated with an excess of neutral ammonium molybdate,the mixture rendered faintly alkaline, and sodium stannite added.This has the effect of reducing polysilico-molybdic acid to a bluelower oxide of molybdenum, and the test can be used in the presenceof not too great an amount of phosphate.1°For some time past a great deal of attention has been devoted tothe separation of calcium and magnesium.When the metal ionsare present in substantial quantities the oxalate method of separ-ation seems to be the best, both for convenience and accuracy. Thiscannot, however, be secured unless certain conditions are strictlyadhered to. It is certain that if too much ammonium oxalate is usedsome magnesium will be precipitated with the calcium, and it willalso be impossible to precipitate all the magnesium in the filtrateunless the troublesome procedure of expelling the ammoniacal saltsis adopted.As a rule, two precipitations of the calcium are desirableto effect the separation, but it is stated that one will suffice if thesolution of the two metals is precipitated a t 70" with only a smallexcess of ammonium oxalate.ll A study of the supersaturation ofsolutions of magnesium oxalate, however, indicates that co-precipit -ation of magnesium oxalate with calcium oxalate is likely to resultif the concentration of magnesium ions or the temperature is toohigh.12 Nevertheless, it has again been shown that excess ofammonium oxalate is wanted when magnesium preponderates andhas to be retained in solution while the calcium is being precipitated.13On the other hand, for the micro-separation of calcium, an aceticacid solution is preferable for precipitating the calcium as oxalate inthe first place, the magnesium being recovered by precipitation with8-hydroxyquinoline.Much controversy has resulted from the10 F. Oberhauser and J. Schormiiller, 2. anorg. Chern., 1929, 178, 381 ; A . ,11 0. Ram, Tid88kr. Kjemi Berg., 1929,9, 2 7 ; A,, 530.1% Z. Herrmann, 2. anorg. Chem., 1929,182,395; A., 1159.1s W. T. Hall, J . Amer. Chem. SOC., 1928,50, 2704; A., 1928,1347.414188 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.discussion of the best method of conversion of magnesium ammoniumphosphate into magnesium pyrophosphate in the determination ofmagnesium. It has been shown that the refinements, such asevaporation with nitric acid to oxidise " carbon " in the precipitateand similar devices, are unnecessary,14 and we agree with thisconclusion.It is not usual t o consider a volumetric method of analysis asentitled to the description " beautiful," but this designation mayfairly be applied to the adsorption indicators developed by Fajansand his co-workers.As a lecture experiment, the reversible colourchanges of eosin, when colloidal silver bromide is present, on additionof silver or bromine ions are striking. The competition of the indi-cator anion and of the halogen ion for adsorption on the silver halideleads to nice discrimination in the choice of adsorption indicators,as, for example, fluorescein for titration of chlorides, and eosin forbromides and iodides. Thus Victoria-violet , chrome-green G, bromo-phenol-blue, and bromocresol-purple can be used to determineeither the separate halogens or chloride and iodide when together.l5A subject of much interest in the practical use of indicators for thecolorimetric determination of p H values is the magnitude of the salterror and the effect of the dissociation of the indicator itself whenattempts are made to determine the p H of an unbuffered liquid.Theerror becomes greater as the dissociation constant of the indicatoris decreased, so that those indicators become most serviceable whichcan be used in very low concentrations.16 The complexity of thissalt error and its dependence on the nature of the buffer solution mayfurther be seen from a consideration of the corrections which haveto be applied for indicators in citrate solutions.It is fortunate thatboth methyl-orange and methyl-red give quite small salt errors invarious conditions of the solutions. This circumstance permits oftheir use in colorimetric p H determinations within their range.17The salt error arises in practice in various ways ; for example, whenequal colours are given with an indicator by a solution of sodiumhydroxide and some buffer, say a borate, it does not necessarilyfollow that the pH is the same when determined electrometrically.Neutralisation of the indicator itself cannot be responsible for thiseffect except to a small extent, for errors as high as 2 units of p Hmay be obtained with phenol-red and borate mixtures. This isattributed to the salt error arising from the indicators themselves14 (Miss) A.W. Epperson, J . Amer. Chem. SOC., 1928, 50, 321; A.,l5 H. A. J . Pioters, Chem. Weekblad, 1929, 26, 6 ; A . , 161.l6 J. Eisenbrand, Pharrn.-Ztg., 1929,74, 989, 1287; A., 1157, 1266.1' I. M. Kolthoff, J . Physical Chem., 1928,32, 1820; A., 161.1928, 386ANALYTICAL CHEMISTRY. 189and is inappreciable in certain cases, e.g., with thymol-violet andalizarin- yellow G. l 8Of special interest and practical importance in acidimetric deter-minations is the fact that certain substances show a definite alterationin their ultra-violet fluorescence under the influence of a variation ofthe hydrogen-ion concentration. Quinine, for example, shows twosharp colour changes at p H 6 and 9.5, and is therefore available foruse in the titration of bases, both strong and weak; a- and p-naphtholshave been similarly used.lg As it is easy to construct a suitablecabinet fitted with so-called ultra-violet glkss for use with a mercuryarc lamp, the method becomes one of some delicacy and ease ofmanipulation.Inorganic Analysis..Qualitative.-Specific and special reactions, mainly colour reactionswith organic reagents, are described for the commoner anions andbations.20 Some new metallic complexes of cupferron,21 of thio-cyanic acid,22 and of hexamethylenetetramine z3 have been examined.Micro-reactions Inay often be carried out with advantage using a gelas mediumn2* The tests for ferrous and ferric iron with ferri- andferro-cyanide respectively are influenced by the presence of fluoridesowing to the depression of hydrogen-ion concentration,25 and thishas been utilised to prevent the interference of ferric iron with theferrocyanide test for copper;26 similarly the delicacy of the thio-cyanate test for iron is affected by the presence of other salts.27Conversely, the thiocyanate test may be applied for the detection ofsulphur, free or in the form of sulphide.28 Morin and " eriochroin-cyanin R. conc." are almost as sensitive reagents for aluminiumas sodium alizarinsulphonatle,29 the reaction of which with manyla J.W. McBain, (Miss) M. E. Laing, and 0. E. Clark, J. Gen. Physiol., 1929,la J . Eiaenbrand, Pharm.-Ztg., 1929,74, 249; A., 628.G. Gutzeit, Helv. Chim.Acta, 1929, 12, 713, 829; A., 898, 1254; P.Agostini, Ann. Chim. AppZ., 1929,19, 164; .4., 785; K. Heller and P. Krum-holz, Milcrochem., 1929, 7, 213; A., 900.A. Martini, Anal. Asoc. Qudm. Argentina, 1928,16,117 ; Mikrochem., 1928,8, 152 ; A., 164.12, 695 ; A., 899.22 Idem, ibid., 1929, 7, 30; A., 287.23 I. M. Korenman, Phamn. Zentr., 1929,70, 1 ; A., 286.A. Martini, Mikrochem., 1929,7, 236; A., 898; S. Amberg, J. Landsbury,L. SzebelMdy, 2. anal. Chem., 1928,75,166; A., 1928,1347; H. W. vanand F. Sawyer, J . Arner. Chem. SOC., 1928,50, 2630; A., 1928, 1347.Urk, ibid., 1929, 77, 39; A., 670.l6 L. Szebellbdy, ibid., 1928,75, 167 ; A., 1928,1347.27 H. W. van Urk, Chem. Weekblad, 1928,26, 703; A., 164.2a E. Griinsteidl, 2. anal. Chem., 1929,77,283; A., 899.l8 E.Eegriwe, ibid., 1929,78,438; A., 631190 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.metals has been investigated.30 The microchemical detection oflead 3 l and of zinc, molybdenum, vanadium, and silver is described.32Polysulphide may be used to replace thiocyanate in Spacu's reactionfor copper ; 33 dimethylaminobenzylidenerhodanine in alcoholicsolution forms a sensitive reagent for cuprous i0n.34Oxamide is less sensitive than dimethylglyoxime as a reagent fornickel; 35 the influence of various metals in the detection of cobaltwith cyanate has been in~estigated.3~The diphenylcarbazide test for magnesium has been applied tosilicates ; 37 the reaction; of magnesium salts with op-dihydroxy-azo-p-nitrobenzene 38 and various bisazo-dyes have been noted.39Moderate amounts of lithium, rubidium, cesium, and magnesiumdo not interfere with the detection of potassium by means of zircon-ium sulphate.*O Sodium may be detected by precipitation as thetriple acetate with uranium and cobalt 4 1 and microscopically byreaction with potassium antimonate.42 A solution of sodiumchromate and uranyl nitrate forms a sensitive reagent for potassium,rubidium, and chromium.& A scheme for the detection of alkalimetals in mixtures with most of the commoner metals is described.44Tables are given of the reactions of molybdates, nitrophospho-molybdates, tungstates, and phosphotungstates with many metalsalts.45 The identification of vanadium and cerium by means ofhydrogen peroxide have been investigated, the interfering effect ofmolybdenum being suppressed by addition of boric Photo-30 F.G. Germuth and C. Mitchell, Arner. J . Pharm., 1929,101, 46; A . , 286.31 G. DenigBs, Bull. SOC. chim., 1929, [iv], 45, 678; A., 1268.32 A. Martini, Milcrochem., 1929, 7, 231 ; A., 900.33 A. J. Folcini, Rev. Centr. Est. Farm. Bioquim., 1928,17, 306; A . , 1031.34 0. Funakdi, Mem. Coll. Sci. Kyoto, 1929, 12, 166; A., 901; referF. Feigl, 2. anal. Chem., 1928, 74, 380; A., 1928, 1108; K. Heller and P.ICrumholz, see ref. (20).35 J. LirSka, Chem. Listy, 1929, 23, 402; A., 1260.36 13. J. F. Dorrington and A. M. Ward, Analyst, 1929, 54, 327; A., 901.37 H. Leitmeier and F. Feigl, Tech. Min. Petr. Mitt., 1928, 29, 323; A . ,38 W. L. Ruigh, J.Amer. Chem. SOC., 1929,51, 1466; A., 783; refer Suitsu39 E. Eegriwe, 2. anal. Chem., 1929,76, 364; A., 630.40 R. D. Reed and J. R. Withrow, J . Amer. Chem. SOC., 1929,51, 1062; A.,41 E. R. Caley, ibid., 1929, 61, 1966; A., 1031.42 W. Bottger, Mikrochem., 1929, Pregl F'est., 14; A., 1267.43 T. Gaspar y Arnal, Anal. Fie. Quim., 1928,26, 184; A., 1928, 1347.44 N. A. Tananaev, J . Rues. Phys. Chenz. SOC., 1929, 61, 816; A,, 1267;45 T. Gaspar y Arnal, Anal. Pis. QuCm., 1928, 26, 436; A., 417.4 6 J. Lukas and A. Jilek, Chem. Listy, 1929, 23, 417; A., 1260; 2. anal.669; refer F. Feigl, 2. anal. Chem., 1927, 72, 113; A,, 1927, 1161.and Okuma, J . SOC. Chern. Ind. Japan, 1926,29,132.668 ; refer idem,ibid., 1928,50,1616,2986 ; A., 1928,868 ; 1929,166.2.anorg. Chem., 1929,180, 76; A., 668.Chent., 1929, 76, 348 ; A., 632ANALYTICAL CHEMISTRY. 191micrographs are produced for a number of crystalline derivatives ofthallium 47 and a drop test for thallium is described.48Microchemical tests for thiocyanate, fluoride, borate, chromate,and silica are described.@ Improvements have been made in themolybdate-benzidine test for for which a solution ofantimony trichloride and sodium molybdate also furnishes st sensitivereagent.51 The reaction with mannitol has been applied t o thedetection of boric acid in the presence of most of the commoner anionsand kations.52The solution of zinc ethyl in pyridine forms a delicate reagent forthe presence of active hydrogen in organic compounds.63 Threetests for nitrites depend on coupling with aromatic a m i n e ~ .~ ~ Tri-,tetra-, and penta-thionates, but not dithionates or sulphites, catalysethe reaction between iodine and sodium a ~ i d e . ~ ~ Cerous and nickelnitrates are applied to a scheme for the qualitative analysis of mix-tures of ferro- and ferri-cyanide and fhiocyanate.66 A molybdate-stannite reagent is used for the detection of traces of soluble ~ilicate.6~Tests for the differentiation of chloroamine from hypochlorite 58 andfrom free chlorine 59 are described, as also sensitive reactions forfluoride,60 bromide, and iodide.61Quantitative.-A universal indicator giving the spectrum colourshas been developed.62 The colorimetric determination of p H bymeans of indicators and associated topics have been extensively4 7 A.J. Steenhauer, Mikrochem., 1929, Pregl Fest., 315 ; A., 1269.48 N. A. Tananaev and G. A. Pantschenko, Ukraine Chem. J . , 1929,4, 121 ;A., 1032. '@ F. FeigI, Mikrochem., 1929, 7, 10; A., 284; F. Feigl and P. Krumholz,ibid., 1929,PreglFest., 77; A , , 1266; idem, Ber., 1929, 62, [B], 1138; A., 783.6o F. Feigl, 2. anal. Chem., 1929, m, 299; A., 900; H. Leitmeier, Mikro-chern., 1928,6, 144; A., 162; refer F. Feigl, 2. aml. Chem., 1928,74,386; A.,1928, 1107.61 T. Gaspar y Amal, Anal. F b . Quim., 1928,26, 181 ; A., 1928, 1346.m A. S. Dodd, Analyst, 1929, 54, 282; A., 668.58 F. Haurowitz, Mikrochem., 1929,7, 88; A., 283.54 C. Goroncy, Deut. 2. gea. gerichtl. Med., 1928, 11, 482; A., 667; W.Vaubel, (?hem.-Ztg., 1928,52, 842; A., 1928, 1346; N.M. Ronshina, J . RU88.Phys. Chem. SOC., 1929,61, 897; A., 1266.66 L. Metz, 2. anal. Chem., 1929,76,347; A., 629; refer F. Feigl,ibid., 1928,74,369; A., 1928,1106.66 P. C. Banerjee, J . Indian Chem. SOC., 1929, 6, 259; A., 786.67 F. Oberhaueer and J. Schormtiller, 2. anorg. Chem., 1929,178, 381 ; A.,414.H. W. van Urk, Chem. Weekblad, 1929,26,9 ; A., 162.Besemann, Chem.-Ztg., 1928,52, 826; A., 1928, 1345.E. Murmann, OesterT. Chem-Ztq., 1929, 32, 36; A., 413.*O F. Pavelka, Mikrochem., 1928, 6, 149; A., 162.61 H. W. van Urk, Pharm. Weekblad, 1928, 65, 1246; 1929, 66, 157; A ,162, 413192 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.in~estigated.~~ The uses have been investigated of ~ a t r e n , ~ ~ juiceof the black 4-mefhylumbellifer0ne,~~ and a number ofazo-compounds 67 as indicators, and of dimethylaminoazobenzenefor the determination of the acidity of undissociated acids.6sCopper and copper sulphste,69 potassium ~ermanganate,~~ andcupric oxide 71 have been examined as standards in iodometry, andalso the conditions favouring the stability of ferrous sulphate 72and ceric sulphate 73 solutions.The latter substance has been appliedto a number of different deterrninati~ns,~~ as also have acid iodatesolutions, of which the excess, together with the liberated iodine, istitrated with a stabilised potassium hydrogen sulphite solution.75Permanganate titrations have been made on the micro-~cale,~~ andseveral analytical applications of sodium hyposulphite 7 and ofmercuric nitrate 78 have been developed.The temperature range between which a number of metallicsulphates are stable has been examined from an analytical stand-point, with the result that temperatures applicable to the satisfactoryweighing of the sulphates are now made a~ailable.'~ The rapid63 E.Oeman, Papier-Fabr., 1929, 27, 27; A., 162; F. C . Thompson and w. R. Atkin, J. SOC. Leather-Trades Chem., 1929,13, 297; A . , 1158; J. Eisen-brand, Pharm-Ztg., 1929, 74, 989, 1009, 1287; A., 1157, 1255; A. Thiel andW. Springemann, 2. anorg. Chern., 1928,176,64,112 ; A., 41 ; F. R. McCrumband W. R. Kenny, J. Amer. Chem. SOC., 1929, 51, 1458; A . , 782; H. RUOSS,2. anal. Chem., 1929, 77, 175; A., 782; A. Thiel, 2. Elektrochem., 1929, 35,266; A., 782; J.W. MeBain, (Miss) M. E. Laing, and 0. E. Clark, J. Gen.Physiol., 1929, 12, 695; A., 899; I. M. Kolthoff, J. Physical Chem., 1928, 32,1820; A., 161; E. H. Fawcett and S. F. Acree, J. Bact., 1929, 17, 163; rl.,1255; C. E. Davis and H. M. Salisbury, Ind. Eng. Chem. [Anal.], 1929, 1,92; A., 666; F. R. McCrumb and W. R. Kenny, ibid., p. 44; A . , 413; D. H.Cameron, J. Amer. Leather Chem. Assoc., 1929, 24, 7 6 ; A., 413.H. W. van Urk, 2. anal. Chem., 1929,77, 12; A., 666.65 L. Mosendz, ibid., p. 37; A., 666.66 C . Bulow and W. Dick, ibid., 1928, 75, 81; A., 1928, 1345.6 7 N. A. Zaitzev, J. Chem. Ind. Moscow, 1928, 5, 722; A., 1029.6* A. Hantzsch and W. Voigt, Ber., 1929, 62, [B], 976; A., 666.68 S. Popov, (Miss) M. Jones, C.Tucker, and W. W. Becker, J. Amer. Clzm.70 S. Popov and A. H. Kunz, ibid., p. 1307; A., 784.71 T . F. Buehrer and C. M. Mason, Ind. Eng. Chem. [Anal.], 1929, 1, 68;72 J. A. N. Friend and E. G. K. Pritchett, J., 1928, 3227; A., 165.73 H. H. Willard and P. Young, J. Amer. Chem. Soc. 1929, 51, 149; A.,7& A. J. Berry, Analyst, 1929, 54, 461; A., 1159.75 A. Schwicker, 2. anal. Chem., 1929,77, 161; A., 782.76 J. Mika, ibid., 78, 268; A., 1260.77 B. S . Evans, Analyet, 1929, 54, 396; A., 1030.70 A. A. Guntz and J. Barbier, Chim. et Ind., 1929,21, 711 ; A., 668.Soc., 1929,51, 1299; A., 784.A., 669.287.E. VotoEek and J. Kotrba, J . Czech. Chem. Comm., 1929,1, 166; A., 620ANALYTICAL CHEMISTRY. 193methods of preparing precipitates for weighing developed inconnexionwith, for example, copper pyridine thiocyanate, can be successfullyapplied to those obtained by the classical methods with considerablesaving 01 time, e.g., silver halides, barium sulphate, calcium oxalate,nickel dimethylglyoxime.80Indirect methods for the analysis of elements difficult to separateare discu,ssed,8l and also the influence of time of outflow and drainageon burette measurements.82 For accurate micro-volumetric work,the weight burette is recomxnended,a and a description is givenof the application of micro-analytical methods to technicalproblems. aThe apparatus for the determination of water by distillation withimmiscible liquids has been modified in various ways in order toobviate the inaccuracies due to water sticking to the sides of theglass.85The determination of small quantities of mercury has attractedmuch attention, several methods g6 having been investigated inaddition to that described on p.186 ; volumetric methods for largerquantities have also been investigated.8' The hydrogenationprocess has been applied to the determination of cadmium as such inboth organic and inorganic compounds.88The presence of various enolic compounds and organic acids(excepting sulphinic acids) does not interfere with the iodometricdetermination of c0pper.8~ Small amounts of this element may bedetermined by a colorimetric process with dimethylglyoxime WJor gravimetrically, not only as the pyridine thiocyanate alreadymentioned (p. 186), but also with dibromo-S-hydroxyquinoline,9lJ.Dick, 2. anal. Chem., 1929,77,352 ; A., 901.0. Liesche, 2. angew. Chem., 1928,41, 1166; A., 1928,1346.82 J. Lindner and F. Haslwanter, ibid., 1929,42,821; A . , 1033.83 B. Ormont, 2. anal. Chern., 1928,75,209; A., 41. *' R. Lucae and F. Grassner, Mikrochem., 1928, 6, 116; A., 161.85 W. Boller, Chem.-Ztg., 1928, 52, 721; 1929, 53, 70; A., 628; F. Fried-richa, ibid., p. 287; A., 667; J. Pritzker and R. Jungkunz, ibid., p. 603; A,,1029.R. Thileniua and R. Winzer, 2. angew. Chem., 1929, 42, 284; A., 631;A. Stock and W. Zimmermann, ibid., p. 429; A., 784; J. Bodnhr, ibid., p. 826;A., 1032 ; Friederich and Buhr, Siiddeut. Apoth.-Ztg., 1928, 68, 702 ; A., 784 ;E. H. Vogelenzang, Phamn. Weekblad, 1929,66, 66 ; A., 416.M.L. Colombier, J . Pham. Ch$m., 1929, [viii], 10, 15; A., 1032; H. B.Dunnicliff and H. D. Suri, Analyst, 1929,54,405; A., 1031.H. ter Meulen and (111116.) H. J. Ravenswaay, Rec. trav. chim., 1929, 48,198 ; A., 286.8a M. I. Uschakov, J . Rum. Phys. Chem. SOC., 1928,60,1161; 2. anal. Chern.,1928,75, 228; A., 1928, 1347.S. a. Clarke and B. Jones, A d g a t , 1929, 54, 333; A., 900.REP.-VOL. XXVI. a Dl L. W. Hatlse, 2. anal. Chem., 1929,78, 113; A., 1169194 ANNU& REPORTS ON THE PROGRESS OF CHEMISTRY.whilst ‘‘ ovine ” itself may be used for lead provided the quantitypresent is not too sma.11.92Bismuth is separated from lead by precipitation as basic nitratewith freshly prepared mercuric oxide 93 or by precipitation withcinch~nine.~~ Modifications and developments of the iodidemethod for the determination of small quantities of bismuth aredescribed.95A volumetric process for determining arsenic in organic andinorganic compounds in the presence of halogens and certain heavymetals is described 96 as well as the determination of arsine by twotitrimetric methods.97 Finely divided antimony is found to besoluble in distilled water in the presence of 0xygen.~8 An improvedform of the electrolytic Marsh apparatus has been applied to anti-m ~ n y . ~ ~ Small amounts of antimony are retained by the leadsulphate obtained by diluting the solution of lead-antimony alloysin sulphuric acid.l A procedure for the preparation of antimony-free arsenious oxide is applied to the approximate determination ofminute amounts of antimony in arsenious oxide.2 Reduction ofstannic to stannous salts in acid media prior to titration withchloroamine or iodine is effected by electrolytic iron foil3 or ironnails.4Potassium cyanate is used for separations of metals of the thirdanalytical group5 8-Hydroxyquinoline has been applied t o themicro-determination of aluminium,6 and this reagent also serves toseparate this metal from phosphate and various other elements whichare normally coprecipitated by ammonia ; the conditions necessary92 V.Marsson and L. W. Haase, Chem.-Ztg., 1928,52, 993; A., 164.93 H. Rlumenthal, Z . anal. Chem., 1929, 78, 206; A . , 1258.g4 Frick and Engemann, Chem.-Ztg., 1929, 53, 601 ; A., 1033.95 Idern, ibid., p.505; A . , 1033; P. Dumont and M. Bouillenne, Compt.rend. SOC. biol., 1925, 99, 1247; A., 1033; J. Straub, 2. anal. Chem., 1920, 76,108 ; A., 287.g6 E. Schulek and P. von Villocz, ibid., p. 81 ; Ber. Ungar. pharm. Ges., 1928,4, 313; A., 285, 668.9 7 H. Kubina, Z . anal. Chem., 1929,7’6, 39; A . , 163.S. G. Clarke, Analyst, 1929, 54, 99; A., 417; J. Grant, ibid., p. 227;A., 639.u9 Idem, ibid., 1928, 53, 626; A., 165.A. Vasiliev and H. Stutzer, Z . anal. Chem., 1929,78, 97; A., 1169.C. W. Foulk and P. G. Horton, J . Amer. Chem. SOC., 1929, 51, 2416;E. Rupp and F. Lewy, Z . anal. Chem., 1929,77, 1 ; A., 671.R. Wolf and R. Heilingiitter, Chem.-Ztg., 1929, 53, 683; A., 1160.R. Ripan, Bul. SOC. Stiinte Cluj, 1928, 4, 57, 104; A., 43.A. Benedetti-Pichler, Mikrochem., 1929, Pregl Fest., 6 ; A., 1259.A., 1160.7 G.E. F. Lundell and H. B. Knowles, Bur. Stand. J . Res., 1929,3, 91 ; A .,1260A?XALYTICIAL OHEMISTRY. 195for precipitation of iron, manganese, nickel, and cobalt by thisreagent have also been investigated. 8 The complete simultaneousprecipitation of iron and phosphoric acid is possible only when theratio of iron to phosphorus is greater than two? Errors in the iodo-metric titration of iron have been traced to the presence of copper orof iron as oxide or colloidal hydroxide.1° The mechanism andlimitations of the " molybdomanganimetry " of iron salts have beeninvestigated.ll Ferric iron is quantitatively reduced by metalliccopper in boiling sulphuric acid solution; uranyl salts are similarlyreduced.12 The triphenylmethane dyes erioglaucin A or erio-greenB can be used as indicators in the permanganate titration of iron orf err0~yanide.l~Sodium chloride interferes very seriously with the precipitation ofzinc as sulphide l4 and as ammonium phosphate; l5 zinc may becompletely separated from iron, aluminium, chromium, nickel,cobalt, and manganese by precipitation from faintly acid solutionsin prescribed conditions.16 The colorimetric determination ofmanganese in the presence of silica has been examined and theprecautions necessary for accurate determination described ; l7other volumetric methods for manganese have been investigated,18and also those for c0ba1t.l~A separation of strontium from barium depends on the differentsolubilities of the bromides in isobutyl alcohol,20 and the micro-chemical separation of barium from calcium as chromate has beeninvestigated.21 Small amounts of magnesium may be determinedR.Berg, 2. anal. Chem., 1029,76,191; A., 286.E. Angelescu and C. Biliinescu, Kol1oid.-Z., 1929, 47, 207 ; A ., 632.lo E. C. Grey, J., 1929, 35; A., 286; 8ee also E. H. Swift, J . Amer. Chem.l1 P. Fleury and J. Marque, J . Pharm. Chim., 1929, [viii], 9, 479; A., 784.l2 G. Scagliarini and P. Pratesi, Ann. Chim. Appl., 1929,19, 86 ; A . , 632.l3 J. Knop and 0. Kubelkova, Chem. Listy, 1929, 23, 366, 399; J. Knop,l4 L. Dede, Ber., 1928, 61, [B], 2248; A., 43.l8 J. Majdel, 2. anal. Chem., 1929, 76, 204; A , , 285; refer Arhiv Hemiju,l7 C. Newcomb, Analyst, 1928, 53, 644; A., 164.l8 R.Lang and F. Kurtz, 2. anorg. Chem., 1929, 181, 111; A., 1032; B.Reinitzer and F. Hoffmann, 2. anal. Chem., 1929, 77, 407; A., 1032; J.Teletov and (Mme.) N. Andronikov, Bull. SOC. chim., 1929, [iv], 45, 674; A.,1260.l9 V. Cuvelier, Natuurwetensch. Tijds., 1929,11,123 ; A., 1032 ; J. Gillis andV. Cuvelier, ibid., p. 20; A., 416; G. A. Barbieri, Atti R. Accad. Lincei, 1928,[vi], 8, 406 ; A., 416.Soe., 1929, 51, 2682; A., 1260.2. anal. Chem., 1929,77, 111, 125; A., 670.Idem, {bid., p. 2463; A., 164.1928,2, 127; A., 1928, 869.2o L. Szebellddy, 2. anal. Chem., 1929, '78, 198; A., 1268.21 R. Strebinger, Mihochem., 1929,7, 100; A., 286196 A."UdL REPORTS ON THE PROGRESS OF CHEMISTRY.gravimetrically with " oxine " 22 or colorimetrically with 1 : 2 : 5 : 8-tetrah ydroxyanthraquinone .23Given certain precautions, neglected by previous workers, sodiumcan be quantitatively determined as the triple magnesium uranylacetate.24 Bromides may advantageously replace chlorides in theLawrence Smith and Berzelius alkali determinations.25 Otherinvestigations on the alkali metals have also been made.2sA simple volumetric determination of silver in the presence ofhalides and cyanides has been described,27 and also a process,gravimetric or volumetric, involving the use of mercuric cyanide.28The analytical chemistry of gallium has been investigated ; 29" cupferron " is a useful reagent in this field.Iron, aluminium, and copper can be removed from beryllium bymeans of " oxine " 30 and titanium from beryllium by p-~hloroaniline.~~Other analytical investigations of this element have been made.32Tungsten can be separated from vanadium by precipitation asquinine arsenotungstate ; 33 the precipitation of tungsten byBerzelius's method 34 and various quantitative dry methods ofexamining tungsten compounds have been in~estigated.~5 Methodsfor the gravimetric determination of vanadium are reviewed andexpanded ; 36 and a volumetric process employing iodate is de~cribed.~'Molybdenum is determined by means of permanganate following22 R.Strebinger and W. Reif, Mikrochem., 1929, Pregl Fest., 319; A., 1258.23 F. L. Hahn, ibid., p. 127; A., 1258.z4 E. R. Caley with C. W. Foulk, J. Amer. Chem. Soc., 1929, 51, 1664;25 E.Spencer and K. B. Sen, Analyst, 1929,54, 224; A , , 630.26 F. Diaz de Rada, Anal. Pis. QuCm., 1929,27, 390; A., 900; A. Thurmer,Chem.-Ztg., 1928,52, 974 ; A., 163 ; G . Jander and H. Faber, 2. anorg. Chern.,1929, 181, 189; A., 1030; refer idem, ibid., 1928, 173, 226; A., 1928, 980.A., 900.27 H. Baines, J., 1929, 2037; A., 1257.28 F. Feigl and J. Tamchyna, Ber., 1929, 62, [B], 1897; A., 1267.z9 L. Moser and A. Brukl, Monatsh., 1928, 50, 181; 1929, 51, 326; 52,263; A., 1928, 1347; 1929, 670, 1260; R. Fricke and K. Meyring, 2. anorg.Chem., 1928,176,325; A., 43.30 M. Niessner, 2. anal. Chem., 1929, 76, 135; A., 285.31 B. E. Dixon, Analyst, 1929,54, 268; A., 668.32 V. h p r , 2. anal. Chem., 1929,76, 173; A., 286; H. Fischer, Wiss.Verofl.Siemens-Konz., 1929,8, ( l ) , 9; A., 1031 ; L. Moser and F. List, Monatsh., 1929,51,181 ; A., 416.33 A. Jilekand J. Lukas, J . Czech. Chem. Comrn., 1929,1,263; A., 785.84 V. Spitzin, J . Russ. Phys. Chem. SOC., 1928, 60, 1229; 2. anal. Chem.,as V. Spit& and L. Kaschtanov, J. Ru88. Phys. Chem. soc., 1928, 60,s6 L. Moser and 0. Brandl, Monatsh., 1929,51, 169 ; A., 416.57 E. H. Smith and R. W. Hoeppel, J. Amer. Chem. SOC., 1929, 51, 1366;1928,75, 433; A., 166.1333; 2. anal. Chem., 1928, 75, 440; A,, 166.A,, 786ANALYTICAL UHEMISTRY. 197reduction with zinc ; 38 thallous salts may also be titrated in hydro-chloric acid solution with this reagent if potassium chloride beadded.39The separation of osmium and ruthenium under various conditionsis described ; 40 6-nitroquinoline is a precipitant for palladi~rn.~~A detailed investigation has been made of the methods for theseparation of lithium from sodium, potassium, and magnesium.42Further work is reported on the analytical chemistry of tantalum andniobium .43The methods for determining ferrocyanide have been reviewedand preference is given to the permanganate titration.44 In thetitration with zinc,45 diphenylamine can be used as internal indi-cator.46 Modifications of the direct gravimetric method for carbondioxide 47 have been made to eliminate interference by chloride and~ulphide.~~ Thymolphthalein is recommended for titration ofcarbon dioxide with b a r ~ t a .~ ~Volumetric processes for determination of sulphate have beeninvestigated depending upon the use of benzidine acetate, theformation of yellow lead iodide and determining excess of barium bymeans of dichromate; methods applicable in the presence offluorides are given.51 Iodometric methods for various sulphur acidsare described.52 A rapid volumetric process for selenium, afterprecipitation in the usual way, has been devi~ed.5~3* J.Kassler, 2. anal. Chem., 1928, 75, 457; A., 165.3o A. Jilek and J. Lukaa, Chem. Listy, 1929, 23, 124, 155; J . Czech.40 S. Sait6, Bull. Imt. P h p . Chem. Res. Tokyo, 1929, 8, 164; A,, 671.4 1 S. C. Ogburn, jun., and A. H. Riesmeyer, J. Amer. Chem. SOC., 1928,50,42 L. Moser and K. Schutt, Monatsh., 1929,51, 23; A., 414.43 W. R. Schoeller and C. Jahn, Analy,?t, 1929, 54, 320; A., 902; W.It.Schoeller, ibid., p. 453; A., 1160; G. W. Sears, J. Amer. Chem. Soc., 1929, 51,122 ; A., 287.44 P. P. Budnikov, J.Russ. Phys. Chem. SOC., 1928,60,1159; A., 1928,1348.45 Azot Chemical Factory, Jaworzno, Przemylsd Chem., 1929, 13, 65; A.,46 I. M. Kolthoff, ibid., 1929,26, 298; A., 785.4 7 R. C. Wiley, J . Arne?. Chem. Soc., 1929,51, 222; A., 285.4s W. H. J. Vernon and L. Whitby, J . SOC. Chem. Ind., 1928, 47, 2 5 5 ~ ;B., 1928, 866; R. Chandelle, Bull. SOC. chim. Belg., 1929,38, 248; A . , 1257.40 C. J. Schollenberger, I n d . Eng. Chem., 1928, 20, 1101; A., 1928, 1346.so G. Testoni, Ann. Chim. Appl., 1928,18, 408; A., 1928, 1345; Z. Minda-lev, 2. anal. Chem., 1928, 75, 392; A., 162; D. Kiiszegi, $bid., 1929, 77, 203;A., 782.51 H .Ginsberg with G. Holder, 2. angew. Chem., 1929,42, 314; A., 528.52 A. Schwicker, 2. anal. Chem., 1929, 77, 278; A., 899; R. Wollak, ibid.,Chem. Comm., 1929,1,82; A., 669, 783, 416.3018; A., 166.416; H. Moll, Chern. Weekbhd, 1928,25, 657; A., 165.p. 401; A., 1030; P. Szebednyi, ibid., 78,36; A., 1030.63 E. BWWch, Chen~.-Ztg., 1928.62, 878; A., 42198 ANNUAL REPORTS ON TEE PROGRESS OF CHEMISTRY.The presence of ashless filter paper hastens the volatilisation ofsilica when treated with hydrofluoric and sulphuricSeveral investigators deal with colorlmetric 55 and with gravi-metric and volumetric 56 processes for phosphoric acid, and with theacidimetric 57 and iodometric 58 determination of phosphorousacid.The volumetric methods for fluorides involving the formation offluosilicate are described.59 The determination of halogens inorganic substances by electrolytic oxidation by the use of Gasparini’sapparatus has been investigated.60 Other papers deal with thedetermination of chloride, bromide in sea water,62 hyp~chlorite,~~per~hlorate,~~ and iodide.65Dimethyl-a-naphthylamine gives a more permanent colorationthan a-naphthylamine in nitrite determinations ; 66 this anion maybe separated by esterification.67 Reduction methods for large 68and small 69 quantities of nitrate are examined, and also gasometricmethods for nitrous 0xide.~054 T.Heczko, 2. anal. Chem., 1929, 77, 327; A., 900.5 5 B. V&sbrhelyi, Mikrochem., 1929, Pregl Fest., 329; A., 1256; E.Truogand A. H. Meyer, Ind. Eng. Chem. [Anal.], 1929, 1, 136; A., 1158; S. N.Rozanov, Trans. Sci. Inst. Fertilisers, Moscow, 1928, No. 55, 139; A., 1158;C. Bordeianu, Ann. sci. Univ. Jassy, 1929, 15, 372 ; A., 782 ; A. Y. Levitzki,Nauch. Agron. Zhur., 1927, 4, 783; A., 899.56 M. Ishibashi, Mem. Coll. Sci. Kyoto, 1929, 12, 23, 39, 49, 135; A., 529,783; N. Krilenko, Arhiv Herniju, 1928, 2, 197; A., 1928, 1346; W. Smith,Quart. J . Pharm., 1929, 2, 238; A., 1159; M. Hegediis, 2. anal. Chem., 1928,75, 111; A., 1928, 1346; K. Somoya, Sci. Rep. Tdhoku Imp. Univ., 1928,17,1289; A., 667; R. Dworzak and W. Reich-Rohrwig, 2. anal. Chem., 1929,77,14 ; A ., 667 ; W. Stollenwerk and A. Baurle, ibid., p. 81 ; A ., 667 ; Drachoussofand Douchy, Chirn. et Ind., 1928, 20, 823; A ., 42.5 7 T. Milobqdzki and K. Boratyfiski, Rocz. Chem., 1928, 8, 554; A., 414.58 A. Schwicker, 2. anal. Chem., 1929,78, 103; A., 1158.69 E. Bayle and L. Amy, Compt. rend., 1929,188, 792; A., 529; W. Siegel,2. angew. Chem., 1929, 42, 856; A,, 1158.K. Heller, 2. anal. Chem., 1929, 76, 408; A., 528; idem, with F. Horaand K. Willingshoffer, ibid., 78, 127; A., 1168.61 R. K. McAlpine, J . Amer. Chem. SOC., 1929,51, 1065 ; A., 782 ; A. Frost,Trans. Inst. Pure Chem. Reagents, MOSCOW, 1927, No. 6, 35; A., 1029; L.Moser with R. Miksch, Mikrochem., 1929, Pregl Fest., 293; A., 1255.6a A. I. Kogan, Ukraine Chem. J., 1928,3,131; A., 1029.63 J . R. Lewis and R. F. Klockow, J . Amer. Chesn. SOC., 1928,50,3243; A.,64 0. S. Federova, 2.anal. Chem., 1929, 78, 749; A., 1255.6 5 J . F. Reith, Rec. trav. chim., 1929, 48, 386; A., 667.6 6 F. G. Germuth, Ind. Eng. Chem. [Anal.], 1929,1, 28; A., 414.6 7 W. M. Fischer and A. Schmidt, 2. anorg. Chem., 1929,179,332; A , , 667.68 A. Seyewetz, Bull. SOC. chim., 1929, [iv], 45, 463; A., 1030.6s B. G. Simek, Chem. Listy, 1928,22,363, 473; A., 42.50 H. Menzel and W. Kretzschrnar, 2. angao Chem., 1929,42, 148 ; A., 414.162ANALYTICAL CHEMISTRY. 199Hydrogen peroxide, and indirectly lead dioxide, can be titratedwith ceric sulphate.71Organic Analysis.&uaZitative.-M. Wagenaar 72 describes microchemical reactionsof (a) homatropine, ( b ) caffeine, (c) theobromine, (d) quinine, (e)quinidine, (f) cinchonine, (9) cinchonidine, (h) physostigmine, (2)piperine, and (j) sparteine ; similar tests are described for morphineand allied substances 73 and for yohimbine 74 ; also colour reactionsare given for hydrastine and pa~averine,?~ p ant ha rid in,^^ bile acids,"gallic acid and tannin, '8 col~hicine,~~ salvarsan and neosalvarsan,80adrenaline, ergot alkaloids, 82 allant0in,8~ lzevulose,s4 and isobutylalcohol.855 : 5-Dimethyldihydroresorcinol (" methone " or " dimedon ")yields characteristic condensation products with aldehydes ; 862 : 4-dinitrobemaldehyde is a valuable reagent for the characteris-ation of amines and reactive methylene gr0ups.8~ Thiolacetamideis useful for identifying arsinic acids 88 whilst methanesulphonylchloride 89 and phenyl- and o-tolyl-thiocarbamides are applied tothe identification of amines.The p-nitrobenzyl ether esters of o-,m-, and p-hydroxybenzoic acids are de~cribed,~~ and some reactions71 N. H. Furman and J. H. Wallace, jun., J. Amer. Chem. Soc., 1929, 61,1449 ; A , , 783.72 Phamn. Weekblad, 1928,65-(a) p. 1213, ( b ) p. 1334; 1929,66--(c) pp. 1,131, (d) p. 177, ( e ) p. 197, (j) p. 253, (9) p. 261, (h) p. 381, (i) p. 405, (j) p. 809;A., 79, 200, 460, 584, 584, 584, 584, 707, 829, 1319, respectively.73 L. Ekkert, Pharm. Zentr., 1029, 70, 165; A . , 584.74 G. DenigAs, Mikrochem., 1928, 6, 113; A., 201.75 C . A. Rojahn and F. Stdmann, Pharm. Zentr., 1929, 70, 277; A.,76 H. W. van Urk, Pharm. Weekblad, 1929,66,313; A., 702.7 7 L. Cuny, J . Pharm. Chim., 1928, [viii], 8, 358; A., 1928, 1389; Compt.78 S.A. Celsi, Rev. Centr. Est. Farm. Bioquim., 1928, 16, 642; A., 86.79 L. Ekkert, Pharm. Zentr., 1928, 69, 662; A , , 86.80 H. W. van Urk, Phaww. Weekblad, 1929, 66, 297; A., 585.81 A. Orrix, Ann. Chim. Appl., 1929,19, 239; A., 1093.82 H. W. van Urk, Pharm. Weelcblad, 1929, 66, 473; A., 832.83 R. Fosse and (Mlle.) V. Bossuyt, Compt. rend., 1929,188, 106; A . , 196.~44 L. Ekkert, Pharm. Zentr., 1928, 69, 805 ; A., 174.86 A. Kutzlnigg, Z . anal. Chem., 1929, 77, 349; A., 948.86 D. Vorliinder, ibid., p. 241 ; A., 924 ; G. Klein and H. Linser, Mikrochem.,87 G. M. Bennett and W. L. C. Pratt, J., 1929, 1465; A., 1070.88 H. J. Barber, ibid., p. 1024; A., 833.89 C. S. Marvel and J. P. Belsley, J. Amer. Chem. SOC., 1929, 51, 1272; A.,90 T.Otterbacher and F. C. Whitmore, ibid., p. 1909; A., 922.91 F. F. Blicke and F. D. Smith, ibid., p. 1947; A., 926.829.rend. SOC. Biol. 1928, 99, 613 ; A., 699.1929, Pregl Fest., 204; A., 1292.684200 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.of primary arsines,92 and condensation products of p-aminoazo-benzene with higher fatty acids.93&mntatitive.-Investigations on the elementary analysis of organiccompounds may be reviewed under the following heads : carbon andhydrogen,g4 nitrogen,95 halogens generally,96 and iodine in particular,especially when present in small amount,9' sulphur,9* phosphorusand arsenic,99 antimony,l tin,2 mercury: selenium, and tell~rium.~Directions are given for the micro-determination of the acetylvalue 5 and of the methylimino-,6 methoxyl, and ethoxyl groups.'A method for determining formaldehyde is based upon condens-ation with potassium cyanide to form the potassium compoundof hydroxyacetonitrile ; 13 " methone " (5 : 5-dimethyldihydro-92 S.S. Nametkin and V. Nekrassov, 2. anal. Chem., 1929, 77, 285; A.,949.93 H. H. Escher, Helv. Chim. Acta, 1929, 12, 27; A., 293.94 S. Avery, Ind. Eng. Chem., 1928, 20, 1232; A., 86; A. Boivin, Compt.rend., SOC. Biol., 1929, 100, 502 ; A., 1323 ; Compt. rend., 1928, 187, 1076 ; A.,204; F. Hernler, Mikrochem., 1929, Pregl Fest., 140; A., 1323; W. M. Lauerand F. J. Dobrovolny, ibid., p. 243; A., 1323; F. Bock and K. Beaucourt,ibid., 1928, 6, 133; A., 204; M. Nicloux, Bull. SOC. Chirn. biol., 1928,10, 1271 ;A., 204 ; R.Goubau, Bull. SOC. chim. Belg., 1928,37, 335 ; A., 42 ; D. B a k u ,Ber., 1928, 61, [ B ] , 2336; A., 42.g5 F. Halla, Mikrochem., 1929, 7, 202; A., 899; W. M. Lauer and C. J.Sunde, ibid., Pregl Fest., p. 235 ; A., 1323 ; F. Hernler, ibid., p. 154 ; A., 1323 ;I. Marek with M. KrajEinoviE and G. Zaljesov, Bull. S_oc. chim., 1929, [iv], 46,555; Arhiv Hemiju, 1928, 2, 169; A., 1928, 1346; S. Okido, Bull. Inst. Phys.Chem. Res. Tokyo, 1929, 8, 2 ; A., 337 ; G. Wallerius, Tekn. Tihskr., 1928, 58,Kemi, 33 ; A., 85.98 W. Roman, Biochem. Z., 1929,207,416; A., 713; F. Hein, K. Hoyer, andK. Klar, 2. anal. Chem., 1928,75,161; A . , 1928, 1389.8 7 J. Schwaibold, ibid., 1929, 78, 161; A., 1256; Chem-Ztg., 1929, 53, 22;A., 337 ; J.F. Reith, Chem. Weekblad, 1929,26, 26 ; A., 337 ; Rec. tTUV. chim.,1929,48,264; A . , 414; J. F. McClendon and R. E. Remington, J. Amer. Chem.SOC., 1929, 51, 394; A., 413; G. Lunde, K. Closs, and J. BOB, Mikrochem.,1929, Pregl Fest., 272; A., 1323; T. Leipert, ibid., p. 266; A., 1323; E. I. vanItallie, Pharm. Weekblad, 1929, 66, 629; A., 1093.Q8 I. Marek, Bull. SOC. chim., 1928, [iv], 43, 1405; A., 337; F. Hein, K.Hoyer, and K. Klar, 2. anal. Chem., 1928, '75, 161; A., 1928, 1389; E. A.Smith and J. W. Bain, Canadian Chem. Met., 1928,12, 287; A., 1928, 1389;K. Heller, Mikrochem., 1929,7, 208; A., 948; A. Friedrich, ibid., Pregl Feet.,91 ; A., 1323.SQ K. Heller, Mikrochem., 1929, 7, 208; A., 948.1 S. Ghosh, Indian J. Med. Rm., 1929,16, 467; A., 1188.2 H. Gilman and W.B. King, J. Amer. Chem. SOC., 1929,51, 1213; A., 713.3 F. Hernler, Mikrochem., 1929, Pregl Fest., 154; A., 1323.4 H. D. K. Drew and C. R. Porter, J., 1929,2091 ; A., 1323.5 F. Pregl and A. Soltys, Mikrochem., 1929, 7, 1 ; A., 337.8 A. Friedrich, ibid., p. 196; A., 949; P. Haa8, ibid., p. 69; A., 337.7 A. Friedrich, ibid., p. 186; A., 948.8 F. Lippich, 2. anal. Chem., 1929,76,241,255; A., 460ANALYTICAL CHEMISTRY. 201resorcinol) is applied quantitatively t o formaldehyde andlor acet -aldeh~de.~ Silver nitrate is used as an absorbent for ethylene whichis recovered by diminishing the pressure.10 Quantitative methodsfor the following acids are described : hydrocyanic,ll formic andacetic,12 butyric,13 pyruvic,l4 citric and tartaric,15 lactic,ls andamino -acids.17The reaction between thiosemicarbazide and iodine has beeninvestigated in acid and in alkaline solution,l* while determination ofthe ammonia which is obtained together with hydrazine by hydro-lysis of semicarbazide is applied to the micro-analysis of ketones.lBThe solubility of the picrate interferes with the accuracy of themethod of determining hexamethylenetetramine by means of thissalt .20Sugars and allied compounds continue to attract much attention.21Methylene-blue is completely precipitated by picric acid.22 Likethe strychnine salt, brucine silicotungstate is of variable com-position.23A., 949.@ D. Vorlgnder with C. Ihle and H. Volkholz, Z . anal. Chem., 1929,77, 321 ;lo V. N . Morris, J .Amer. Chem. SOC., 1929,61,1460; A., 948.l1 W. P. Malitzky and M. T. Koalovaky, Milrochem., 1929, 7, 94; A., 337.lP P. Fuchs, 2. anal. Chem., 1929,78, 126; A., 1323.la R. J. Allgeier, W. H. Peterson, and E. B. Fred, J . Bact., 1929, 17, 79;lP B. H. R. Krishna and M. Sreenivaeaya, J. Indian Inst. Sci., 1929,12A,A., 1093.41 ; A., 677. '' F. Phone, R ~ v . Itccl. E88. Prof., 1928,1O, 101 ; A,, 836.l6 E. Lehnartz, Z . phY8iOl. Chem., 1928,179, 1 ; A., 48 ; T. E. Friedemannl7 L. Rosenthaler, Biochm. Z., 1929, 207, 298; A., 713; W. Grassmannl8 A. Gaffre, J . Phurm. Chirn., 1929, [viii], 9, 19; A., 302.lo R. P. Hobson, J., 1929, 1384; A., 949; S. Veibel, ibid., p. 2423; referao C. V. Bordeianu, Ann. 8ci. Univ. Ja88y, 1929, 15, 380 ; A., 836.21 F.Gonz&lez and A. Gimeno, Anal. Pis. QuCm., 1929,27,39; A., 798; T.F d i , Bul. Perm. Tokyo, 1928, No. 100, 106; A., 836; C. Kullgren and H.Tydh, Handl. Ing. Veten8-8-Akad. Stockholm, 1929, No. 94; A., 1278;P. Fleury and J. Marque, Compt. rend., 1929,188, 1686; A., 948; H. Elmer,Ber., 1928,61, [B], 2364; A., 60; J. Voicu and (Mlle.) V. Dumitreacu, Bul. SOC.Chim. R o d n b , 1929, 11, 15; A., 1189; A. A. Gabreels and A. L. vanScherpenberg, Chem. Weekblad, 1929, 26, 394; A., 1045; W. Braun and B.Bleyer with W. Elhardt, 2. a d . Chem., 1929,76, 1 ; A., 206 ; A. B. Schach-keldian, J. Ruse. Phya. Chem. Soc., 1928,60, 1617; A., 298; R. Biazzo, Ann.C h h . Appl., 1928,18,447 ; A., 85.2a M. Fraqoie and (Mlle.) L. Seguin, J. Pham. Chim., 1929, [viii], 10,6 ; A.,1084.B.Kljatschkina and M. Strugadski, Arch. Pharm., 1929, 267, 177; A.,708.and A. I. Kendall, J. Biol. Chem., 1929, 82, 23; A., 677.and W. Heyde, 2. phY8iOl. Chem., 1929,183,32 ; A., 949.Bull. SOC. chim., 1927,41, 1410; A,, 1927, 1172.a202 ANNUAL REPORTS ON THE PROGRESS OB CHEMISTRY.Pyrazolones and aromatic sulphonarylamides can be titratedalkalimetrically.24 The blue coloration formed by diphenylamineand ferric sulphate is applied to the determination of the former.25A process applicable to mixturcs of anthraquinone with benzanthroneis described, the latter being first oxidised to mthraquinonecarboxylicacid.26Physical Hethods.A number of examples of the use of radio-elements as indicatorsis de~cribed.~' The theory of physical titration (e.g., turbidimetricanalysis) is discussed ; 2* many ordinary titrations can, when carriedout in Dewar flasks, be followcd therm~metrically.~g The additionof glycerol greatly augments the stability of the suspensions ofbarium sulphate obtained for nephelometric purposes.30Much work has been carried out on spectrographic methods ofanalysis.31 These have been applied in particular to the detectionof lead in gold-copper-silver to the determination of iridium,rhodium, and palladium in platinum,33 detection of beryllium,3*determination of strontium, barium, and cmium in rocks andmineral watersY35 of zinc in solution, and of molybdenum in stee136The spectrophotometer is preferred to the colorimeter for the deter-mination of aluminium by means of al~minon.~'Electrochemical Nethods.Electrolytic.-The separation of niobium and tantalum in tantaliteby electrolytic hydrolysis is described,3s and also the reduction of24 K.Heller and Z. Fleischhans, J. pr. Chem., 1929, [ii], 123, 146; A., 1324.26 A. Thiel, 2. Elektrochem., 1929, 35, 274; A . , 836.26 P. I. Sokolov and L. Gurevich, J. Chem. Ind. MOSCOW, 1928, 5, 308; A.,2 7 F. Paneth, 2. angew. Chem., 1929, 42, 189; A., 528; R. Ehrenberg,28 E. N. Gapon, Ukraine Chem. J., 1929, 4, 149; A., 1254.29 C. Mayr and J. Fisch, 2. anal. Chem., 1929,76,418; A., 528.30 J. Kzepelka and A. Kalina, Chem. Listy, 1928,22,545 ; A., 163.s1 T. Negresco, J. Chim. physique, 1928, 25, 343, 363; A,, 161; C. C.Nitckie, Ind. Eng. Chem.[Anal.], 1929,1,1; A., 412 ; H. Thurnweld and G. F.Huttig, 2. anal. Chem., 1929,76,260; A., 413; F. Gromann, 2. anorg. Chem.,1929,180,267 ; A., 784.82 W. Gerlach and E. Schweitzer, 2. anorg. Chem., 1929, 181, 101 ; A., 1031.sa Idem, ibid., p. 103; A . , 1033.34 H. Fesefeldt, 2. physikal. Chem., 1929, 140, 254; A., 530.s 5 F. Zambonini and V. Caglioti, Atti R. Accad. Lincei, 1928, [vi], 8, 268;86 H. Thurnwald, 2. anal. Chem., 1929, 76, 336; A., 530; W. Gerlach and37 E. W. Schwartze and R. M. Hann, Science, 1929, 69, 167; A., 901.38 L. F. Yntema, Amer. Electrochem. Xoc., 1929, May; A., 671.205.Mikrochem., 1929, Pregl Fest., 61 ; A., 1258.A , , 415.E. Schweitzer, ibid., 77, 213; A., 782ANALYTICAL CHEMISTRY. 203nitrates to ammonia by sodium amalgam produced by electroly~is.~~A polarographic investigation with the dropping-mercury cathode ofsolutions of arsenious oxide in hydrochloric acid has been carried out .40A modified electrolytic apparatus is described which permitsof reducing the weight of platinum required,41 as well as the use ofmercury 42 and of Wood's metal as cathodes.43 Results of numerousexperiments on the separation of metals by Sand's method are given.44Electrolytic methods are described for the rapid determination oftin,45 thallium,46 bismuth,47 cadmium and zinc,4* and lead.49Potentimetric.-Quinhydrone for analytical work should be freefrom iron ~ a l t s .5 ~ Several modifications of apparatus have beendescribed, mainly in the direction of simplification.51Ceric sulphate has been used as a volumetric oxidising agent forchromium in the presence of certain other metals 52 and for ferro-cyanide.% Reaction of this anion with gallium has been examined,=whilst ferricyanide in alkaline solution has been used for vanadiumand hypo~ulphite,~~ arsenic, antimony, tin, and thallium.66315; 2.Elektrochem., 1929, 35, 18; A., 284.3g M. Rabinovitsch and A. S. Fokin, J . Rztss. Phys. Chem. SOC., 1929, 61,40 K. KaEirkov&, J . Czech. Chem. Cornm., 1929, 1, 477; A., 1266.41 H. J. S. Sand, Analyst, 1929, 54, 275; A., 672.42 W. Moldenhauer with K. F. A. Ewald and 0. Roth, 2. angew. Chem.,1929,42,331; A., 631.43 H. A. J. Pieters, Chem. Weekblad, 1928, 25, 706; A., 161; compare H.Paweck and R. Weiner, 2. anal. Chem., 1927,72,225; A., 1928, 143.44 N.Vensovitch, Bull. SOC. chim. Belg., 1928, 37, 353; A., 286.45 J. h6da and R. Uzel, J . Czech. Chem. Comrn., 1929,1, 203; A , , 671.46 A. Jdek and J. Lulras, ibid., p. 417; A., 1159.*' Idem, ibid., p. 369 ; A., 1033.48 E. Brennecke, 2. anal. Chem., 1928,75, 321 ; A., 164.4g H. Topelmann, J . pr. Chem., 1929, [ii], 121, 289; A., 669; A. Seiser, A.Necke, and H. Miiller, 2. angew. C'hem., 1929,42,96; A., 286.50 M. Tr6nel and C. Bischoff, 2. angew. Chem., 1929,42, 288; A., 528.51 D. A. MacInnes and M. Dole, J . kmer. Chem. SOC., 1929, 51, 1119; A.,666; A. Uhl, 2. anal. Chem., 1929,77, 280; A., 899; I. I. Shukov and G. P.Avsejevitsch, 2. Elektrochem., 1929, 35, 349 ; A., 899 ; T. Heczko, 2. anal.Chem., 1928, 75, 183; A., 1928, 1345; B .Kamieriski, Bull. Acad. Polonaise,1928, A, 33; A., 1928, 1345; L. Kohler, Chem.-Ztg., 1929, 53, 69; A., 528;E. Miiller and H. Kogert, 2. anal. Chem., 1928,75,235 ; A . , 42 ; H. H. Willardand A. W. Boldyreff, J . Amer. Chem. SOC., 1929, 51, 471; A., 413; F. L.Hahn, 2. anal. Chem., 1929, 76, 146; A., 283; L. Kahlenberg and A. C.Krueger, Amer. Electrochem. SOC., Sept. 1929; A., 1255; T. Callan and S .Horrobin, J . SOC. Chem. Ind., 1928, 4 7 , 3 2 9 ~ ; B., 154.52 H. H. Willard and P. Young, J . Amer. Chem. SOC., 1929,51,139; A., 287.s8 N. H. Furman and 0. M. Evans, ibid., p. 1128; A., 670; K. Someya,64 S. Ato, Sci. Papers Inst. Phys. Chem. Res. Tokyo, 1929, 10, 1 ; A., 416.5~5 C . del Fresno and L. ValdBs, Anal. Pis. Qukm., 1929, 27, 368; A., 901 ;56 Idem, {bid., p. 268; A., 1257.2. anorg. Chern., 1929, 181, 183; A., 1032.8. anorg. Chem., 1929,183, 261 ; A., 1267204 ANNVAL REPORTS ON THE PROGRESS OB CHEMLSTRP.Silver and cadmium may be consecutively determined withbromide and ferrocyanide re~pectively.5~ Methods have beendescribed for the determination of coppery5* of small quantities oflead,59 of chromic acid in presence of vanadicy600f ironY6l manganese,62gold and platinum,64 osmiumy65 boric acid,66 iodides,67iodomercurates,6* and thence indirectly of morphine.69Conductmetric.-A visual method for carrying out conducto-metric titrations has been described 70 and applied to the rapiddetermination of sulphate in drinking water.71 The neutralisationof phosphoric acid by sodium hydroxide has been investigatedc onduc tometrically. 72.B. A. ELLIS.J. J. Fox.5 7 E. Muller and H. Hentschel, 2. anal. Chenz., 1928, 75, 240; A., 42.58 (Miss) M. E. Pring and J. F. Spencer, Analyst, 1929, 54, 609, 676; A.,59 H. Millet, Trans. Faraday SOC., 1929,25, 147 ; A., 531.6o E . Zintl and P. Zaimis, 2. Elektrochem., 1928,34, 714; A., 1928, 1348.61 T. Heczko, 2. anal. Chem., 1929,78,247; A., 1260; H. Brintzinger andW . Schieferdecker, ibid., p. 110; A., 1159; B. A. Soule, J . Amer. Chem. Xoc.,1929,51,2117; A., 1032.1259.62 B. F. Brann and M. H. Clapp, ibid., p. 39; A., 286.63 H. Brintzinger and W. Schieferdecker, 2. anal. Chem., 1929,76, 277 ; A . ,64 E. Miiller and R. Bennewitz, 2. anorg. Chem., 1929,179, 113; A., 532.c 5 W. R. Crowell and H. D. Kkschman, J . Amer. Chem. SOC., 1929, 51,6 6 I. V. Grebenschtschikov and T. A. Favorskaia, J . Ruse. Phys. Chem. Soc.,6 7 0. TomiEek, J . Czech. Chem. Comm., 1929, 1, 443; A., 1168.6 8 L. Maricq, Bull. SOC. chirn. Belg., 1929, 38, 259; A., 1259.6g Idem, ibi&., p. 265; A., 1320.70 G. Jander and 0. Pfundt, 2. Elektrochem., 1929,35,206; A., 662.7 1 H. Fehn, G. Jander, and 0. Pfundt, 2. angew. Chem., 1929,42, 158; B.,72 (Miss) J. C. Lanzing and L. J. van der Wolk, Rec. trav. chim., 1929, 48,417.175,1695; A., 287, 1029.1929, 61, 561 ; A., 1030.342.83; A . , 284

ISSN:0365-6217    

DOI:10.1039/AR9292600185

出版商:RSC    

年代:1929

数据来源: RSC

摘要:

BIOCHEMISTRY.The Intake and Accumulation of Electrolytes by Plant Cells.D. R. HOAGLAND and his co-workers in the laboratory of PlantNutrition in California, whose researches on the fresh-water algaNitella were discussed in earlier reports,l have published an interest-ing review which embodies a great deal of more recent work.a Nostriking advance is recorded, but they have obtained many furtherdata to support their view that the intake of substances into livingcells can be interpreted only in terms of ions, and not, as W. J. V.Osterhout and others suggest, in terms of undissociated molecules.They also insist that the accumulation of solutes in the vacuolarsap of plant cells, often to a concentration many times that of thesurrounding medium, is dependent on energy exchanges, and cannotbe explained by adsorption phenomena on the sap colloid^,^ which,in the case of Nitella sap, are more or less non-existent. Thechemical or electrical reactions responsible for this output of energymust, it is admitted, take place in exceedingly thin layers of proto-plasm, which must necessarily imply a high degree of heterogeneityin the protoplasmic system.The experimental evidence in supportof this assumption was discussed in last year’s R e p ~ r t . ~ In viewof the large number of papers published in recent years on thepermeability of artificial membranes it is interesting to note that,if Hoagland’s views be correct, no artificial cell can imitate com-pletely a living cell unless arrangements be made to supply energyin suitable form to the artificial system.Fat MetuboEism in the Pbnt.During the past few years there has been a great increase in theinterest displayed in the field of plant fats.Although much funda-mental work remains to be done and is being done in the field ofseed fats and oils, it is pleasing to note that the fatty substances ofgreen plants, yeasts and bacteria representing more physiologicallyactive tissues are beginning to receive attention.Phosphtides.-The work of Schulze and his school on the seedphosphatides was inconclusive, in that preparations free from sugarwere seldom obtained, and only through the similarity of the de-l Ann. Repmi%, 1926,22, 313; 1926, 23, 223.Protoplama, 1929, 6, 610.W. Stiles, &id., 1927,6, 677. Ann.Reports, 1928, 25, 227206 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.composition products could the presence of true animal lecithin orkephalin be inferred. P. A. Levene 5 has recently been able toobtain in bulk some commercial preparations of crude phosphatidefrom the soya bean. By intensive fractionation he has obtained apure preparation of lecithin which is free from sugar, a kephalincontaining only 10% of its nitrogen in the non-amino- form, andproducts resembling animal cuorins (i.e.’ with an N : P ratio of 1 : 2 ;which are now considered to be mixtures of decomposition products).Most of Levene’s work has been recently substantiated by B.Rewald.6 This clear demonstration that the phosphatides of theseed do not differ from the well-known phosphatides found in thcanimal body makes their absence in the cabbage leaf, wherein theirplace is taken by calcium phosphatidate, the more remarkable,and raises the question of the physiological relationship existingbetween the phosphatides of the seed and of the leaf.Will a plantsuch as the soya bean, having lecithin and kephalin in its seed, havecalcium phosphatidate in its leaves ‘1 Such an occurrence would betotally unexpected if we regarded the phosphatides in the usualway as essential constituents of the cell. A. C. Chibnall and €1. J.Channon suggest that the difference might be understood if the r61eof the two types of phosphatides were different either in their effectson permeability or as agent.s in the transport of fat, but obviouslymuch further research into the distribution cf the various phospha-tides in seeds and green plants will be necessary before any suchgeneralisation can be made.Turning to the lower organisms, we find the same conflictingevidence. G.G. Daubney and I. S. Macleans show that the phospha-tides of yeast consist of the usual mixture of lecithin and kephalin,which on hydrolysis gives rise to a larger proportion of unsaturatedthan saturated acids. This low proportion of saturated acid is alsofound in the soya-bean phosphatides, and cabbage calcium phos-phatidate, but the reverse is the case in the phosphatides of tuberclebacilli. These have recently been examined in some detail by R. J.Anderson and exhibit such unusual characters that they warrantmore than a passing reference.The acetone-ether insoluble fractionwas found to consist of a wax (referred to later, p. 212) and a phos-phatide. The latter contained 0.40y0 of nitrogen, all of which canP. A. Levene and Ida P. Rolf, J . Biol. Chern., 1925, 62, 759; 1926, 68,285; A., 1925, i, 487; 1926, 982.Biochem. Z., 1929, 211, 199; A . , 1347. ’ Ann. Reports, 1927, 24, 230; A. C. Chibnall and H. J. Channon, Biochem.J . , 1929, 23, 176; A . , 729.Biochem. J., 1927, 21, 373.J . Biol. Chern., 1927,74, 637; 1929,83, 169, 505; A,, 1927, 1114; 1929,1108, 1342BIOCHEMISTRY. 207be distilled off as ammonia with alkali, and 2.14% of phosphorusand showed no reducing properties when an aqueous suspensionwas boiled with Fehling's solution.An investigation of the products given by acid hydrolysis yielded5.4% of glycerophosphoric acid, 13.8% of an unidentified sugaracid, 13.9% of glucose, 30.50/, of palmitic acid, W8Y0 of oleic acid,and 20.9% of a new liquid saturated fatty acid.The substance,if it is a chemical entity, which Anderson is not yet prepared tocertify, is obviously more complex than any of the well-recognisedphosphatides, and is especially interesting in that over 50% of it ismade up of saturated fatty acids. The separation of the individualacids presented considerable difficulties, and the new liquid saturatedacid, which Anderson calls phthioic acid, was obtained free fromoleic acid only by hydrogenating the latter and removing the re-sulting stearic acid as ether-insoluble lead soap.Phthioic acid is acolourless liquid which sets to a white solid when cooled in ice-waterand liquefies on warming to 10". Its constitution is not yet deter-mined, but it exhibits a specific rotation in alcoholic solution of + 1.5" (see p. 209).This tubercle phosphatide has been found to have powerfulpathogenetic properties. F. R. Sabin and C. A. Doan* observedthat intraperitoneal injections of an aqueous suspension of thesubstance into normal rabbits caused a large increase in monocytes,epithelioid and giant cells and that the injections were followed bythe development of massive typical tubercular tissue in the peritonealcavity. Phthioic acid gives practically identical reactions, so thatit is obvious that the active principle of the phosphatide is associatedwith this new interesting acid.The above account of recent work shows that the concept of onlythree well-defined phosphatides, viz., lecithin, kephalin, and sphingo-myelin, which appeared sufficient to explain data derived fromanimal sources, may need modification when we come to considerthe plant and micro-organisms.The lessons to be learnt from the'( jecorin " and (' cuorin " stories, however, can still be taught withadvantage, for the phosphatide field is one which occasionallyattracts biologists, and in no other is experience more essential. Inthe work lo of V. Grafe, H. Cranner and their schools on the so-calleddiffusible water-soluble phosphatides of vegetable tissues, no attempthas been made to isolate these phosphatides in any state of purity;indeed, their very existence has not yet been satisfaetorily demon-strated : the work calls for no further comment.Plant Glycerides.-Mention was made in another section of last* Quoted by R.J. Anderson (ref. 9).lo S e e F. C. Steward, Biochem. J., 1928, 22, 268; A., 1928, 334208 ~ C B L REPORTS ON THE PROGRESS OF CHEMISTRY.year’s Report l1 of the new methods employed by Hilditch and hisco-workers to determine the structural composition of glycerides.Further work la has confirmed their earlier conclusion that there isa pronounced tendency to even distribution of the fatty acidsthroughout the glycerides of seed (kernel) fats as a class. If themolecular proportion of unsaturated to saturated acids in the wholefat exceeds about 1.6 to 1, the saturated acids are almost whollypresent in the form of mixed glycerides : if the aforesaid molecularproportion is reversed, increasing amounts of fully saturated glycer-ides are found to be present, but in every case except one so f a r ex-amined the mixed saturated-unsaturated glycerides present containsaturated and unsaturated acids in molecular ratios lying withinthe comparatively narrow limits of 1.3-1-6 to 1 : finally, whenfully saturated glycerides are present in quantity, no simple tri-glyceride has been detected (even when one acid forms 30--50%of the whole of the saturated acids, e.g., lauric acid in coconut andpalm-kernel fats or palmitic and stearic acids in cacao butter orillip6 tallow) unless the composition of the saturated fatty acid is sosimple that one acid is present in overwhelming excess (e.g., myristicacid in nutmeg butter, which contains a considerable proportionof trimyristin).In the case of non-seed plant fats, such as laurelfat, the glyceride structure is much more heterogeneous. Althoughthe molecular proportions of saturated and unsaturated acids inthe whole fat are approximately equal, the fat contains 26% offully saturated triglycerides (mostly trilaurin) and the molecularratio of the saturated to unsaturated acids in the mixed glyceridesshows further that tri-unsaturated glycerides must be present inquantity. This work on the glycerides is enabling Hilditch slowlyto accumulate data with respect to the distribution of fatty acids inthe seed fats, but the evidence is still somewhat scanty and diffuse.Certain acids, such as oleic and linoleic, occur in fair to considerableproportions in most fats, but the four acids, lauric, myristic, erucic,and pitroselinic (A6 :7-octadecenoic), stand out quite definitelyin their nature and proportion in the respective cases of the fourorders, Palm@, Myristicem, Cruciferce, and Urnbelliferc~.~~Turning to the fats of green parts of the plant and of micro-organ-isms, we h d the problem rendered far more difficult by the presenceof considerable proportions of phosphatides and unsaponifiablematerial.Investigation of the fatty acids obtained after saponi-fication of the acetone-ether soluble material from cabbage l4l1 Ann.Reports, 1928, 25, 85.l2 G. Collin and T. P. Hilditch, Biochem. J., 1929 (in the press).l3 T. P. Hilditch, Proc. Roy. Soc., 1928, B, 103, 111; A., 1928, 1059; B. C.l4 A. C. Chibnrtll and H. J. Channon, Biochm. J., 1927, 21, 479; L929, 23,Christian and T. P. Hilditch, Biochem. J., 1929,23,327 ; A ., 855.176; A., 1927, 799; 1929, 724BIOCHEMISTRY. 209showed that the fatty acids were very highly unsaturated (iodinevalue, over 200). The greater part consists of linoleic and linolenicacids (acids of higher degree of unsaturation were not found), withonly small amounts of palmitic and stearic acids. Analysis of asimilar fraction from yeast l6 showed an iodine value of 77, and thepresence of oleic and linoleic acids.In both these cases the fattyacids from the glyceride fractions are more unsaturated than thosefrom the corresponding phosphatide fractions, which is the reverseof that usually found in the animal body. Examination of the fattyacids from dried spinach leaves, without previous removal of phos-phatides,ls showed a mixture similar to that from cabbage, i.e.,small amounts only of saturated acids and much oleic, linoleic, andlinolenic acids. Especially interesting is Anderson's analysis of theaceton-ther soluble fraction of tubercle fat.17 Palmitic, stearic,and cerotic acids were obtained from the solid fatty acid fraction.The liquid fatty acid (iodine value, 53.8) was hydrogenated, andstearic acid removed, leaving liquid unsaturated acids, which werefractionated as methyl esters in a very high vacuum.Two newacids were obtained after saponification of the two chief fractions :(1) Tuberculostearic acid, C18H3602, m. p. 14-15", which is isomericwith stearic acid and shows no biological activity; (2) phthioicacid, identical with the slightly crude acid prepared from the phos-phatide (see p. 207). The latter is isomeric with cerotic acid,C,,H,,O,, and is optically active ([.ID = 7.98"). The biologicalactivity is comparable with that of the acid isolated from thephosphatide.The very high degree of unsaturation of the glyceride fatty acidsof cabbage leaves raises interesting points in connexion with thesuggestion of J. B. Leathes and H. S. Raper l8 that the temperatureat which fats are formed determines the degree of unsaturation.Terroine and others,l9 working with AspergiZZus niger, and L.K.Pearson and H. S. RaperY2O working with A . niger and Rhixopusnigricans grown a t temperatures varying from 17" to 35", haveshown that the degree of unsaturation of the fatty acids falls withrise of temperature. A. C. Chibnall and H. J. Channon l4 found nosignificant change for winter- and summer-grown cabbage. Butthe very low proportion of saturated acids in the fat, together withthe presence of large amounts of saturated hydrocarbon and ketone,l5 C. G. Daubney and (Mrs.) I. S. Maclean, Biochem. J., 1927,21,373; A.,1928,203.A., 1928, 855.J. H. Speer, E. C. Wise, and M. C. Hart, J . BkZ. Chem., 1928, 82, 105;1 7 R.J. Anderson and E. Chargaff, ibid., 1929, 84, 703.18 " The Fats," 2nd ed., London, 1926.1s BuU. SOC. C h h . Bbl., 1927, 9, 604.2o Bbchem. J., 1927, W, 876; A., 1927,906which can be considered as similar to them in physical properties(see p. 211), suggested that these should be included when thequestion of “ liquidity ” of the protoplasmic fats was under dis-cussion. If this be done, the iodine value in the case of the winter-grown leaves is 137, 136 and of the summer-grown 91, 99.These investigations of non-seed fats disclose an entirely differentcomposition and distribution from those usually met with in seedfats, and the field promises to be a fruitful one for future research.Aliphatic Ketones.-The presence of aliphatic methyl ketones invegetable oils, especially essential oils, has long been known, and in1910, H.D. Dakin 21 suggested that they are formed from the cor-responding fatty acids by p-oxidation in a way analogous to hissynthesis of these ketones from fatty acids by hydrogen peroxide.More detailed information concerning the production of these ketonesby moulds has been obtained during the past two years. W. N.Stokoe 22 grew Penicillium palitans on a gelatin medium containingdeodorised coconut oil, and was able to isolate methyl amyl, methylheptyl, and methyl nonyl ketones, showing that oxidation of thecorresponding fatty acids had taken place at the @-carbon atom,with the intermediary production of the P-ketonic acid. Smallamounts of the corresponding secondary alcohols also were formed.The selective action of P .palitans and Oidinum lactis on fatty acids,keto-esters, methyl ketones, and carbinols was then studied. Thehigher fatty acids (above lauric) were not absorbed, consequentlyhigher methyl ketones were not produced. The keto-esters werenormally oxidised without the production of methyl ketones :only in the presence of fatty acids or fat, which hindered the respir-ation of the organism, were these substances formed. Stokoe there-fore considers that the normal course of decomposition of the p-keto-acid is the formation of the fatty acid containing two carbon atomsless and acetic acid-the production of the methyl ketones is ab-normal, and is due to adsorption of poisonous fatty acids in themycelium impeding respiration.Very similar results have beenobtained by 0. A ~ k l i n , ~ ~ who has studied the production of methylketones from fatty acids and triglycerides by P . glaucum : likeStokoe, he failed to obtaip any evidence for the suggestion thatP-hydroxy-acids are precursors of the @-keto-acids. The results,which bear out Dakin’s original suggestion very completely, enableus to assume the origin of such methyl ketones as are met with inplant products.Less clear is the metabolism of the higher aliphatic ketone and21 J . BioZ. Chem., 1908, 4, 221; A., 1908, i, 134.22 Biochern. J., 1928, 22, 80; A., 1928, 335.33 Biochem. Z., 1929, 204, 253; A,, 473BIOCHEMISTRY. 21 1corresponding paraffin isolated by H. J. Channon and A. C.Chib-nall 24 from cabbage leaves. Higher paraffins, generally consideredto be C2,H56, C29H60, C,,H,,, or C35H,2 from their melting points,are, in small amount, very widely distributed in the plant kingdom.The crude product isolated from the cabbage melted at 63-67"and was shown by combustion to contain about 1% of oxygen.From it, a paraffin, m. p. 62.8", and a ketone, m. p. 80-5--81", wereobtained. S. H. Piper 25 showed by X-ray analysis that the paraffinwas nonacosane, C29H60, and that the ketone also contained 29carbon atoms. The carbonyl group was in the middle of the chain,but this was so long that he could not be certain whether the ketonewas di-n-tetradecyl ketone or pentadecyl tridecyl ketone. Nowthe presence of a ketone so closely allied to the paraffins suggestedat once the metabolism of the latter from fatty acids :One molecule of myristic acid and one of palmitic might condenseto form pentadecyl tridecyl ketone, which would yield nonacosaneon reduction. Synthesis of the two ketones suggested by Pipershowed, however, that the cabbage product was di-n-tetradecylketone, and not the unsymmetrical pentadecyl tridecyl ketone ;consequently, if the above scheme of metabolism holds, the pre-cursor of the ketone is pent,adecoic acid.In view of the strongevidence now available against the occurrence in natural fats ofhepta- and penta-decoic acids Channon and Chibnall prefer to leaveopen the question of the immediate precursor of the ketone untilfurther experimental data are available.Plant Sterols.-Recent advances in the chemistry of vitamin-Dhave rather detracted from any interest that can be gleaned fromrecent work on sterols in relation to the plant and plant metabolism.Recent work has, in fact, only intensified the complexity of theproblem, for it has increased the number of possible phytosterolswithout suggesting in any way a possible mode of metabolism inthe plant.Anderson and his colleagues 26 have shown that wheatgerm oil, corn oil, and wheat bran fat contain no homogeneoussitosterol as had been usually found in plant products. The sterolsconstitute a mixture containing dihydrositosterol, and a t leastthree isomeric forms of sitosterol, which can be separated by frac-24 Biochem. J., 1929, 23, 168; A., 729.25 See previous reference.26 R.J. Anderson, R. L. Schriner, and G. 0. Burr, J . Amer. Chem. SOC., 1926,48, 2987; B., 1927, 49; R. J. Anderson and R. L. Schriner, ibid., 1926, 48,2976; A., 1927, 49; R. J. Anderson and F. P. Nabenhauer, ibid., 1926, 48,2997212 PLNNUBL REPORTS ON THE PROURESS OF CHEMISTRY.tioilation of the acetyl derivatives and are designated a-, p-, andy-sitosterol respectively. These differ in melting point and opticalrotation. y-Sitosterol, which is the most readily obtained by frac-tional crystallisation, melts at 147-148" and yields y-sitostanol,m. p. 143-144", on reduction. p-Sitosterol, which correspondsclosely to the sitosterol of the literature, could not be obtained pure,but gave on reduction p-sitostenol, m.p. 139-140", which cor-responds closely to natural dihydrositosterol. ct-Sitosterol differsfrom the other two isomerides in that its bromo-derivative, throughwhich it is purified, cannot be debrominated. The presence ofdihydrositosterol and y-sitosterol in soya bean has been shown byK. BronstedtY2' but the latter sterol appears to be absent from rapcoil. The chief sterol of yeast was shown many years ago to beidentical with the ergosterol of Tanret. Mrs. I. S. Maclean 28 hassince shown the presence of a second sterol, zymosterol, m. p.108-log", which was separated fairly readily by crystallisation.H. Wieland and M. as an^,^^ who benzoylatc the yeast sterols beforefractionation, claim to have isolated three further sterols. One ofthem gives colour reactions similar to those of ergosterol, but theother two differ from both ergosterol and zymosterol in this property.The unsaponifiable wax obtained by R.J. Anderson30 fromtubercle bacilli (see p. 206) has not yet been completely investigated.It appears to possess both acidic and alcoholic properties.Nitrogenous Netabolism in the Plant.Methods of Analysis of Nitrogenous Products in Plant Material.-In recent methods for estimating the various forms of nitrogen inplant extracts there is evidence of a more critical outlook which isvery welcome. The Van Slyke method for estimating amino-nitrogen, introduced in 1912 and followed by his now well-knownmethod of determining nitrogen distribution in proteins, naturallyappealed to plant chemists and was applied somewhat indiscrimin-ately to plant extracts.It was tacitly assumed that these extractswould have a composition similar to that of a protein digest-anassumption which seemed well founded in light of the older workof E. Schulze and his school at Ziirich. Most of this work, however,was fragmentary and a complete investigation of the aqueous extractof lucerne enabled H. B. Vickery 31 to show quite definitely that it'scomposition was more complex than had hitherto been supposed.The " basic " nitrogen precipitated by phosphotungstic acid was a2' 2. physiol. Chern., 1928,176, 269.2 8 Biochem. J., 1928, 22, 22; A., 1928, 329.f 9 Anmlen, 1929,473, 300; A., 1200.31 Plant Physwl., 1927, 2, 303; A., 1928, 107.30 J . Biol.Chem., 1929, 85, 339BIOUHEMISTRY. 213very complex mixture containing only small amounts of the hexonebases. Many non-basic nitrogenous substances, as well as peptidesyielding large amounts of monoamino-acids on hydrolysis, werepresent. Vickery therefore considers that the determination of“ basic ” nitrogen in plant extracts may be very misleading, anddoes not recommend it. His summary of the lucerne investigation,which has unfortunately been published in a report 32 difficult ofaccess to European investigators, should be read by all interestedin plant nitrogen. Only 22% of the soluble nitrogen was accountedfor in crystalline form; yet the Van Slyke method is assumed toaccount for 3 - 4 times this amount in most plant extracts. Modific-ations of this method are also required if the extract or plantmaterial contains volatile bases such as nicotine, cyanogeneticglucosides, or much nitrate.H. B. Vickery and G. W. Pucher33determine the preformed ammonia and “ amide ” nitrogen in tobaccoextracts by the method of 0. Folin and L. E. Wright,= using per-mutite to separate the ammonia from free nicotine in the distillate.Foreman’s methodY35 referred to in last year’s Report, should beapplicable here. For the determination of nicotine itself, attentionmay be directed to papers by J. Bodnhr and V. L. Nagy 36 and byF. D. Chattaway and G. D. Parke~.~’The latter workers make use of the fact that the base forms acrystalline, stable, and sparingly soluble tetrachloroiodide. Bymeans of it nicotine can be easily and accurately estimated, sincein the presence of a large excess of hydrogen chloride it separatespractically quantitatively, even from dilute solutions, as a heavyprecipitate which can be collected on a Gooch crucible and driedwithout loss.Alternatively, the precipitate collected on the cruciblemay be added to an excess of a warm concentrated solution ofpotassium iodide acidified with acetic acid, and the iodine liberatedestimated by sodium thiosulphate. H. B. Vickery and G. W.Pucher 38 have determined the apparent dissociation constants ofnicotine, and make use of these to determine the proportion of free(volatile) nicotine and nicotine present as salts in tobacco, whichis of industrial importance.That the usual method of determining nitrate nitrogen by De-varda’s alloy may give misleading results in the presence of certainplant constituents, such as asparagine, was first pointed out byQuoted in T.B. Osborne and L. B. Mendel, “Year Book,” CmegieImtitutwn of Wa8hingtolz,” 1925, 24, 354.s3 J. BWZ. Chem., 1929, 83, 3.34 Ibid., 1919, 88, 461; A,, 1919, ii, 371.36 Ann. Reports, 1928,2!5, 236.38 Biochem. Z., 1929,208, 410; A,, 729.37 J., 1929, 1314, 2817; A., 729. 38 J . Bwl. Chem., 1929, 84, 233214 ANNUAL REPORTS ON THE PROURESS OF UHEMSTRY.R. C. Burrell and T. G. Phillips,39 who recommended a modification ofthe phenoldisulphonic acid method. The errors due to the presenceof cyanamide or urea (in the case of fertilisers) were overcomeby C. H. Jones, who carried out the reduction of the nitrate in acidsolution by means of reduced iron powder.40 This method hasrecently been modified and applied to plant extracts by H.B. Vickeryand G. W. Pucher 41 so as to permit the determination of nitratenitrogen in the presence of volatile bases such as nicotine. Otherpapers dealing with the determination of nitrate nitrogen in planttissues should be noted.42The presence of cyanide nitrogen in plants, due either to freehydrocyanic acid or to cyanogenetic glucosides, is generally ignoredby workers in this field. That the glucosidic cyanogen was verylabile was pointed out by M. Traube 43 and later workers; a IOSS,for instance, of as much as 6% of the hydrogen cyanide may beincurred by plunging the leaves into boiling alcohol.L. R. Bishop 44has recently devised a method whereby most of the cyanogeneticglucoside is decomposed by heating with water, and the remainderby emulsin. The operation is performed in a closed apparatusthrough which air is drawn, and the liberated hydrogen cyanide isestimated by absorption with potash. Methods of determiningthe nitrogen partition in cyanophoric plants, based on the above,have been worked out by Miss M. E. Robinson45 and applied toPrunus laurocerasus. A committee of the American Society ofPlant Physiology have issued recommended methods for the chemicalanalysis of plant tissues, dealing with such factors as sampling,drying o€ tissues and the determination therein of carbohydrates,fats and various forms of nitrogen, e t ~ .* ~ These recommendationsare based on the personal experience of workers in the respectivefields, and should prove a useful guide to those whose training andinterest are in the biological side of plant problems.In 1927, R. Fosse 47 announced the identification of a new nitro-genous substance, allantoic aeid, in Phaseolus vulgaris, which isprecipitated from the expressed juice as dixanthylallantoic acid39 J . Biol. Chem., 1925, 65, 229; A., 1925, i, 1367.I n d . E n g . Chem., 1927,19, 267; B., 1927, 262.*l Ibid., AnalyticalEd., 1929, 1, 121.4z E. M. Emmert, Science, 1928, 68, 457; A., 1928, 762; Sessions andShim, P l a n t Physiol., 1928, 3, 499; H. F. Holtz and C. Lsrson, ibid., 1929, 4,285.43 Ann. J a r d .Bot. Buitenzorg., 1907, 21, 101.44 Biochem. J., 1927, 21, 1162; A., 1927, 1228.4 5 Ibid., 1929, 23, 1099; A., 1346.4 6 Plant Physiol., 1926, 1, 397; 1927, 2, 196, 206, 497.47 Camp. rend., 1926,183, 1114; A., 1927,284BIOCHEMXSTRY. 21548803.495061525364556667by means of xanthhydrol and purified through the mercuryIt can be determined quantitatively by acid hydrolysis to urea,which is then estimated as xanthylurea in the usual way withxanthhydrol. Applied to the extract from Acer pseudoplatanus,the method gave yields of allantoic acid as high as 0.68 g. per kilo.of fresh leaf material. Investigation of several seeds, especiallySoya hispanida, shows that they contain an enzyme, allantoinase,which will hydrolyse allantoin to allantoic a~id.4~ Making use ofthe fact that the seed also contains uresse, Fosse has devised amethod for determining allantoin in the presence of urea.Hestates, that some seeds contain a third enzyme, an oxidase,capable of transforming uric acid into allantoin. A modified methodof determining urea as dixanthyl urea has been devised by F. W.Allen and J. M. Lu~k.5~Methods of estimating the relative amounts of various proteinsin seeds, so that changes during ripening and germination may befollowed, have received but little attention. P. F. Sharp andB. L. Herrington 53 have investigated the proteins of wheat, andL. R. Bishop 54 those of barley, from this point of view.The Transport of Nitrogenous Xubstances in Plants.In last year’s Report the contributions of T.G. Mason and E. J.Maskell 55 to the problem of the transport of carbohydrates werebriefly mentioned. This year there falls to be recorded a continu-ation of their researches on the cotton plant, in which the variationsin gross amount and the flow of nitrogen between the leaves andbark have been investigated. Their results on the diurnal variationsin leaf nitrogen come a t an opportune time, as certain of the earlierresults recorded in the literature 56 have recently been called intoquestion. A. C. Chibnall57 concluded from a review of previouswork, and from his own experiments with Phaseolus multi$orus,that if the quantity of nitrogen in the leaf was expressed in termsof the fresh weight of the leaf there was undoubtedly a fall in totalnitrogen in the leaf during the night, which was shown to be due tothe decomposition of protein and the translocation of the resultingR.Fosse and A. Hieulle, Bull. SOC. C h h . Bkl., 1928,10, 310; A., 1928,R. Fosse and A. Brunel, C!omp. rend., 1929,188,426 ; A., 353.R. Fosse, A. Brunel, and P. de Graeve, ibid., p. 1418; A., 847.Ibid., 1929, 189, 213; A., 1107.J. Biol. Chem., 1929, 82, 693; A,, 962.Cereal Chemistry, 1927, 4, 249; B., 1927, 761.J. Imt. Brewing, 1928, 34, 101; 1929, 35, 316.Ann. Reports, 1928,25, 229.Reviewed by Miss M. E. Robinson, New Phyt., 1929,28, 117.Ann. Reporb, 1923, 20, 223; 1924, 21, 192216 ANNUAL REPORTS ON THE PROGRESS OB CHEMISTRY.products probably in the form of asparagine. Miss C.A. Gouwen-tak 68 has queried the validity of these results, on the ground thatthe percentage fall in total nitrogen observed (2-5 & 0.2) was small,and that the fresh-weight basis for nitrogen comparison is notphysiologically sound. She cites experiments of her own on Helian-thus annuus, showing no significant variation during the night whenthe leaf nitrogen is expressed as mg./dm.2 of leaf surface. P. K.M ~ t t e s , ~ ~ who worked with Vicia faba, Lupinus lutens, and Phase-olus multijbrus, obtained results of the same order as Chibnall’s :there was a fall in total nitrogen and protein nitrogen during thenight on both a fresh-weight and a leaf-area basis of comparison.As the three main variables in the leaf-water, carbohydrates,and nitrogenous products-can all vary independently, it will berealised that any basis of comparison must rest on assumptions thevalidity of which may be doubtful, or at any rate, open to discussion.As the carbohydrate fluctuation is the greatest, E.J. Maskell andT. G. Mason60 express their results on the basis of residual dryweight (dry weight less total carbohydrates) as well as on the basisof fresh weight.The earlier workers mentioned above made their diurnal com-parison between samples collected in the evening and on the follow-ing morning. With far more experimental material available,Maskell and Mason have been able to make collections a t intervalsof 3 hours over a period of 36 hours. Each collection consisted oftwo samples, each of which consisted of three mature leaves takenfrom each of twenty plants.By both their methods of comparisonthere was a fall, allowing for sampling error, of about 4% in totalnitrogen during the night. That this can be ascribed to the trans-port of organic nitrogenous substances synthesised in the leaf followsfrom further observations. By regional analysis of the plant tissuethe authors show that there is a gradient of organic non-proteinnitrogen outwards from the leaf, i.e., the concentration is greatestin the leaf parenchyma and shows a progressive fall on passage, viathe main veins and petiole, downward through the bark. Further,the gradient in nitrate nitrogen-which ringing experiments showis translocated upwards through the wood, and not through thebark as suggested by 0.F. Curtis 6oa-is in the opposite direction.That protein synthesis from nitrate therefore takes place in theleaves, and that these organs supply nitrogen in organic form toother parts of the plant during the night would seem now to be5 8 Rec. trav. bot. rderlandais, 1929, 26, 19.5Q 2. w h . BWL, Abt. E., 1926, 1, 472.Ann. Bot., 1929, 34, 206, 616; A., 864.6~ AWT. J . Bot., 1923, 10, 361BIOUHEMISTRY. 217fairly well established. The gradient of organic non-proteinnitrogen, as mentioned above, is downwards from the leaf to thebark, and analysis shows that this is due mainly to what the authorsrefer to as the residual nitrogen and to amino-nitrogen. Theasparagine nitrogen shows a progressively higher concentrationon passage from the leaf parenchyma down to the sieve tubes, andlaterally from the sieve tubes to the rays.Maskell and Masontherefore suggest that the residual and the amino-nitrogen may beconcerned mainly with transport and that asparagine is connectedmainly with storage. This conclusion is interesting in that itsupports the general hypothesis of Prianischnikoff , who opposesthe view, originally propounded by Pfeffer and supported by Schulzeand Chibnall, that asparagine, besides serving as a storage ofammonia, is also one of the substances in which organic nitrogenin a form suitable for easy resynthesis of protein is conveyed fromone part of the plant to another.61The interpretation of all their experimental data by Matjkelland Mason on a gradient basis is naturally open to argument, butthere can be no doubt as to the interest of their results, and as tothe advance that they have made in methods of experimentation.It would seem that the problem of translocation of nitrogen in theplant will be solved only when the sieve-tube sap can be collectedin quantity sclfficient for chemical analysis, and this, unfortunately,presents experimental difficulties that cannot be overcome at thepresent time.The above-mentioned workers discuss briefly thefactors responsible for the movement of organic nitrogen in the sievetubes and find that the problem is here even more complex. Theeffect of constricting the channel of transport (by partial ringingof the bark) suggests that diffusion is a factor in the process oftransport, but that the rate of movement is greatly in excess of thatdue to diffusion alone.It appears probable that, as in the case ofsugar transport, there is some agency at work accelerating difhsionin the sieve tubes.The Development of Proteins in the Seed.-The form in whichnitrogen is translocated in the plant again becomes a crucial questionwhen some recent work on the synthesis of protein in the ripeningseed is considered. E. Schulze 62 showed that the husks of severalleguminaceae contain considerable quantities of asparagine, withsmall amounts of the usual protein amino-acids, choline, trigonelline,etc. The developing embryo, unlike the husk, contains little or noasparagine, and consequently Schulze assumed that the asparaginetranslocated from the leaves passed &st of all into the husk and61 See footnote, ref.66.62 2. phyeiol. Ohena., 1911,7l, 31; A., 1911, ii, 322218 m m REPORTS ON THE PROGRESS OF CHEMISTRY.thence into the embryo. A. Kiesel G3 has carried out similar ex-periments with ripening rye ears, and has noted, together with theother substances mentioned above, the presence of relatively largeamounts of aspartic acid and the complete absence of asparagine.This observation led him to discuss as one alternative the possibilitythat amino-acids, etc. (Bausteine), were translocated to the activecentres of the developing grain in excess of requirements, and thatthe excess was stored as aspartic acid instead of the more usualasparagine.The evidence for this point of view, however, is notvery convincing. All investigators seem to agree that no accumula-tion of simple nitrogenous products occurs at any stage during theripening of the grain, showing that as fast as these substances enterthe immature grain they are used for the synthesis of protein. Itis to be expected, then, that under these conditions of intensesynthetic activity asparagine would undergo almost immediatedeamidation (for enzymes capable of doing this are known to occurin the plant) 64 to provide ammonia for amino-acid and proteinsynthesis. The presence of much aspartic acid in the ripening ryeears, therefore, is not incompatible with the theory of the trans-location of asparagine from the leaves to the active centres in thedeveloping grain, as Kiesel admitted as a second alternative.With regard to the development of the individual proteins in thegrain, H.E. Woodman and F. L. Engledow 65 have shown that inwheat the two main proteins, gliadin and glutenin, appear in thequite immature grain (33 days from ear emergence), and that theincrease in the amount of gliadin is more rapid than that of glutenin.At the end of 50 days the first signs of coherent gluten formationwere observed, denoting a critical stage in the development of thegrain marking the beginning of the desiccation period. Thereafterthe amount of glutenin remained roughly constant, but the gliadincontent continued to increase until complete maturity of the grain.L. R. Bishop,66 using somewhat more elaborate methods ofanalysis, has traced the development of the proteins in the barleygrain.Sampling was commenced at a correspondingly earlierperiod than that observed by Woodman and Engledow (6 daysafter anther emergence), and it was found that albumin and globulinwere the chief proteins then being formed. The quantity of glutelinwas at first greater than that of hordein, but the rate of synthesisof the latter was more rapid and in the final stages the amount of it63 2. physiol. Chem., 1924, 135, 61; A., 1924, i, 689; see also Ann. Reports,64 See footnote, ref. 56.6 5 J . Agric. Res., 1924, 14, 563; A., 1925, i, 217.6 6 Ph.D. Thesis, Cambridge, not yet published.1925, 22, 212BIOCHEMISTRY. 219exceeded that of the glutelin.The developmental curves obtainedby Bishop show that there is a regular relationship between theamounts of the individual proteins and the total nitrogen of theindividual grain, suggesting that the nitrogen entering the grain ispartitioned out regularly to the various centres synthesising theproteins on some mass-action or related basis. In other words,the relative amounts of hordein and glutelin in the mature grainare determined solely by the total nitrogen of the grain, and areunaffected by conditions such as soil or season except in so far asthese affect the supply of nitrogen to the plant. This relationshipappears to hold within a variety or strain, as has been shown bymany analyses of mature grains of Plumage Archer of total nitrogenvarying between 1-2yo and 2.4% of the dry weight.Differencesin protein distribution occur between varieties.Xeed Proteins.The application of existing methods is slowly adding to ourknowledge of the proteins of seeds. The chief interest perhaps isto be found in the extension of work on cereal proteins. W. IF.Hoffman and R. A. Gortner 67 have prepared several new alcohol-soluble proteins of the gliadin class, all of which have been analysedby the Van Slyke method.D. B. Jones 68 and his co-workers have investigated many newglutelins, which they prepare by extracting the cereal meal with60% alcoholic potash and acidifying the extract to throw down thecrude glutelin-the gliadin remaining in solution. The glutelin ispurified by re-solution in alkali and reprecipitation.On treatmentof an aqueous sodium hydroxide solution with ammonium sulphate,an a-glutelin separates at about 3% saturation and a p-glutelin atabout 16% saturation.These methods of preparing glutelins have been called intoquestion by M. J. Blish and R. AX. Sand~tedt.6~ Reviewing thepublished data for the amide- and the arginine-nitrogen for wheatglutenin, they find variations from 12.4% to 18.8% and from 8.18%to 12-94y0, respectively. They first showed that both these valuesvaried with the strength of the alkali used during the initial ex-traction, and have in consequence evolved a method whereby theglutenin can be prepared without coming into contact with alkali6 7 Colloid Symposium Monograph, 1925, 2, 209.6 8 F.A. Csonka and D. B. Jones, J . Biol. Chern., 1927, 73, 321 ; A., 1927,799; D. B. Jones and F. A. Csonka, ibid., 1927, 74, 427; A., 1927, 1227;F. A. Csonka and D. B. Jones, ibid., 1927,745,189 ; A., 1927,1227 ; D. B. Jones,ibid., 1928,78,289; A., 1928, 1063; F. A. Csonka and D. B. Jones, ibid., 1929,82, 17; A., 857.a@ Ibicl., 1929, 85, 196220 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.at all. Acetic acid diluted with methyl alcohol to an alcoholicconcentration of 70% is used as solvent. Starch, etc., are removedby centrifuging, and the glutenin is precipitated at pH 7.0 withoutexcess of allCali being present at any time. The treatment is re-peated many times and the glutenin is finally extracted with 70%alcohol to remove traces of gliadin.Thus prepared, it has physicalproperties quite distinct from those of ordinary glutenin and contains22% of amide-nitrogen and only 9% of arginine-nitrogen. Treat-ment with aqueous alkali in the way customary for the preparationof glutelins leads to products similar to those obtained by previousworkers. Part of the nitrogen, however, remains in solution, andon hydrolysis this material gives 25% of amide-nitrogen and 7-8%of arginine-nitrogen-values similar to those given by gliadin. Blishand Sandstedt consider that these results show clearly that true“glutenin” is more complex than either gliadin or what hasgenerally been regarded as glutenin, that it undergoes an irreversiblealteration in chemical structure when dispersed in an alkalinemedium, and that this factor has influenced the composition andproperties of all the so-called glutelins that have been so far preparedfrom other cereals.Synthesis of Phytol.P.G. Fischer and K. Lowenberg have now brought t o a successfulconclusion their research into the constitution of phytol, the alcoholcomponent of chlorophyll. R. Willstiitter and his co-workers in1911 70 obtained by oxidation of phytol a ketone which they con-sidered to be Cl,H340. Fischer and Lowenberg 71 reduced theozonide of phytol-a C,, compound-with hydrogen in presence ofpalladised calcium carbonate and obtained glycollaldehyde and thissame ketone, which must therefore be C18H,,0. They next assumedthat phytol was built up of reduced isoprene units, and that itsconstitution might be 3 : 7 : 11 : 15-tetramethyl-A2-hexadecen-1-01(IV). This would give on hydrolysis of the ozonide a ketone,6 : 10 : 14-trimethylpentadecan-2-one (I).The latter substancewas accordingly synthesised from farnesol, and was found to beidentical with the ketone derived from phytol. The constitution ofphytol thus established has now been confirmed by synthesis.72The ketone (I) was synthesised this time from #-ionone,73 and oncondensation with acetylene it yielded 3 : 7 : 11 : 15-tetramethyl-Al-hexadecinen-3-01 (11). On reduction with hydrogen and70 Anden, 1910,378, 73; 1919, 418, 121; A., 1911, i, 144; 1919, i, 448.7 1 Ibid., 1928, 464, 69; A , , 1928, 989.73 Ibid., 1929,475, 183; A., 1421.73 I. M. Heilbron and A. Thompson, J., 1929, 883; A., 790, had meanwhilereported the synthesis of the ketone from farnesolBIOCHEMISTRY.221palladised calcium carbonate, this gave 3 : 7 : 11 : 15-tetramethyl-A'-hexadecen-3-01 (111). Warmed with acetic anhydride for somehours at loo", (111) gave the acetate, which underwent aniono-tropic change with the formation, together with other products,of 3 : 7 : 11 : 15-tetramethyl-A2-hexadecen-1-01 (IV), identical inall respects with natural phytol.(1.1 CHMe2*[CH2]3*CRMe*[CH2]3*CHMe*[CH2],*COMe(11.) CHMe,*[CH2]3.CHMe*[CH21,.CHMe*[CH2]3*CMe(OH)*CiCH Pic*Pa(111.) CHMe2*[CH2]3*CHMe*[CH2]3~CHMefCH2]3*CMe(OH)*CH:CH2(IV.) CHMe2fCH2],-CHMe*[CH2]3*CHMe*[CH2]3*CMe:CH*CH2*OHt7lutathione.Interesting developments in the chemistry of glutathione havetaken place during the course of the year.(Sir) F. G. hop kin^,^^ whofirst isolated this substance in 1921, produced evidence, which atthe time seemed quite satisfactory, that it was a, dipeptide, diglut-amylcystine. The analytical data for sulphur and total nitrogenwere in fair agreement with this structure, though the amino-nitrogen, as determined by Van Slyke's method, was somewhathigh. Hopkins's structure seemed to be confirmed by the synthesisof diglutamylcystine by C. P. Stewart and H. E. T~nnicliffe.~~The first suggestion that the dipeptide structure was not in com-plete accordance with analytical data came from G. Hunter andB. A. who obtained fairly clear evidence that the materialhitherto called glutathione, and considered a chemical entity,contained another amino-acid.Hopkins at first doubted this newevidence,77 but a long reinvestigation in his laboratory, undertakento co&m or refute it, has shown definitely that a third amino-acid, glycine, is undoubtedly present in all preparations of gluta-thi0ne.7~ The new evidence shows that the substance is a tripep-tide, and it has now been obtained in crystalline form not only byHopkins, but also by E. C. Kendall and his co-workers, whoseresearches are discussed a little later. Hopkins has revised histechnique for the preparation of glutathione, and now obtains ayield of the order of 1 g. per kilo. of fresh yeast by precipitatingthe tripeptide as a cuprous salt in the presence of 0-5N-sulphuricl4 Biochem.J., 1921,15,286; A., 1921,636.Ibid., 1926,19, 207; A., 1926, i, 796.78 J. Bwl. Chem., 1927,72, 147; A., 1927, 477.7 7 Ibid., p. 186; A., 1927, 478.78 Ibid., 1929,84,*269; A., 1491; Ncctzcre, 1929,124, 446; A., 1322222 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.acid. It is undoubtedly a tripeptide of glutamic acid, glycine andcysteine, but the analysis for amino-nitrogen by Van Slyke’s methodgives a value nearly 50% in excess of that which would be givenby a single free amino-group, an observation which, as Hopkinspoints out, helps to explain his bias towards the dipeptide structureassigned to the original crude glutathione. That the Van Slykefigure is actually in excess of the true free amino-nitrogen wouldappear to follow from the observation of L.J. Harris reported inHopkins’s paper, and from the electrometric titrations of N. W.Pkie and K. G. Pinhey made in his l a b ~ r a t o r y . ~ ~ Hopkins is notyet prepared to assign a definite structure to the tripeptide, butrecords many observations which show that under certain con-ditions the molecule displays a degree of instability which is unusual,even when compared with the somewhat unstable cyst,ine-containingpeptides synthesised by M. Bergmann.*O It is impossible here torecount them in full, but briefly stated they are : (1) sulphur isreadily removed by alkali in the presence of lead acetate, (2) aerationat room temperature at prr 7.6 brings about the conversion of onlySO% of the thiol into the disulphide form, the remainder of thesubstance losing both sulphur and nitrogen, (3) when the tripeptideis boiled in pure aqueous solution, much decomposition occurs,and, together with other unidentified products, the diketopiperazineof glycine and cysteine (or, in the case of the disulphide form, di-glycylcystine dianhydride) and glutamic acid have been isolated.Decomposition extends to the carbon atoms, and nearly 14% of thecarbon is lost as carbon dioxide after 50 hours’ boiling.Almost simultaneously with the publication of Hopkins’s newresults appeared those of E.C. Kendall 81 and his associates. Theoriginal method of isolating glutathione has been improved and thecompound obtained crystalline. Analysis of the product againleaves no doubt that it is a tripeptide of glutamic acid, cysteine andglycine, to which they give the tentative formulaHO,C*CH,*NH*CO*CH(NH,). CH,* CH,.CO*NH* CH( C0,H) *CH,* SHon the following evidence : (1) After treatment with nitrous acidand long hydrolysis with concentrated hydrochloric acid, they wereable to isolate glycine as hippuric acid, but no glutamic acid. Thisshows that the glycine is attached through its amino-group, andthat the amino-group of the glutamic acid is not substituted. (2)The action of hydrogen peroxide in the presence of ammonia gives79 J . BioZ. Chem., 1929, 84, 321; A., 1492.80 M. Bergmann and F. Stather, 2. phyeiol. Chem., 1926,162, 189; A., 1926,81 E. C. Kendall, B. F. McKenzie, and H. L. Mason, J . Biol. Chem., 1929,631.84, 666BIOOHEMISTRY.223carbon dioxide, and after hydrolysis no glycine or glutamic acidcould be separated, but only succinic acid. This shows that prob-ably the amino-group of the glycine is attached to the a-carboxylgroup of the glutamic acid.It does not appear to the Reporter that the last conclusion isvalid.82a Moreover, the formula proposed is in direct conflictwith some of Hopkins's results : it does not explain, for instance,the formation of the diketopiperazine of glycine and cysteine onboiling in aqueous solution. Further results will be awaited withgreat interest. In the meanwhile, M. Dixou and N. U. Meldrum 82have stated that the tripeptide is physiologically inert ; the un-doubted activity of the older impure glutathione preparations inthis respect, thereleore, still remains an unsolved mystery.C'erebrosides .During the past few years E.Klenk has published a series ofpapers on brain cerebrosides, and some of his recent conclusionshave an interesting bearing on the structure of sphingosine andcerebronic acid.Sphingosine has been considered to be a dehydroheptadecyl-amine, CH3*[CH,],1*CH:CH*C3€€4( OH) 2*NH,, chiefly from the workof P. A. Levene and C. J. West. On oxidation with chromic acidthey obtained an acid, m. p. 4 8 4 9 " , which was considered tobe pure n-tridecoic acid, because its mixed m. p. with a sample ofsynthetic acid was unchanged and its amide melted at 98-99".Oxidation of dihydrosphingosine gave an acid (mol. wt. 250) meltingat 53", which they considered to be n-pentadecoic acid (mol.wt.242). In an earlier paper,@ products melting at 60-61" (mol.wt. 243) were described. At that time Levene 85 accepted 51 O asthe m. p. of his purest synthetic tridecoic acid, although he with-drew it the following year 86 and substituted 45.5", which is still 2"higher than the m. p, recorded by any other observer. E. Klenk 87has repeated this work, and finds that the acid obtained by oxidationof sphingosine melts after intensive purification at 52.5-53" andgives analytical figures for myristic acid. The acid obtained byoxidation of dihydrosphingosine melts at 62" and is shown to be82 Nature, 1929, 124, 512 ; A., 1334.82a. A paper by Kendall and his associates (Proc. Mayo Clinic, 1929, 4, 359)appeared after this Report had been sent to the printer.New evidence showsthat the formula in the text is untenable, and that the tripeptide is probably y-glutamylcysteinylglycine. This was thought to be the most probable formulaby Pirie and Pinhey, and is not in conflict with Hopkins's results.J . Biol. Chem., 1914, 18, 482.2. physiol. Chern., 1929, 185, 169.s4 Ibid., 1913-4,16, 553.85 Ibid., 1914, 18, 467. P. A. Levene et aE., itrid., 1915, 23, 71224 AXNUAL REPORTS ON THE PROGRESS OF OHEMISTRY.palmitic acid. Klenk therefore considers that sphingosine contains18 carbon atoms and is CH3*[CH,],,*CH:CH*C,H4(OH)2*NH2. Hisanalytical data seem convincing, and there would appear to be butlittle doubt that Levene was misled by the high m. p. of his initialsynthetic tridecoic acid.Klenk 88 has also attacked Levene'sstructure for cerebronic acid (a-hydroxypentacosoic acid of thelignoceric acid series), alleging that on oxidation with permanganateit gave a tricosoic acid and not lignoceric acid. Levene and F. A.Taylor 89 repeated their previous work and refused to accept thisconclusion. Klenk 90 then treated cerebronic acid with hydriodicacid and obtained lignoceric acid : accordingly he re-stated his viewthat cerebronic acid was a-hydroxylignoceric acid. Taylor andLevene 91 have now given a more lengthy reply. In the first placethey emphasise the fact that in their original paper of 1922 92 theypointed out the possibility of the occurrence of other acids inaddition to cerebronic in the fraction composed principally of thatacid.They have oxidised a large quantity of cerebronic acid andhave fractionated the esters of the resulting crude acids. A 'frac-tion yielding a tetracosoic acid, mol. wt. 367, m. p. 78.5-79-5",similar to the one previously prepared, was readily obtained. Fromthe lower-boiling esters, an acid of mol. wt. 356 and m. p. 77.8-78*6", corresponding to Klenk's tricosoic acid, was also obtained,but on further fractionation it was shown to be impure-togetherwith acids of higher molecular weight, it yielded an acid whichgave the analytical figures of docosoic acid (m. p. 74.2-75.2"),but which was shown on more exhaustive fractionation to containmaterial of still lower molecular weight. Taylor and Levene areconvinced that the present results show that the cerebronic acidfraction was originally a mixture of acids, some of which may notbelong to the lignoceric series, and therefore that the question ofthe number of cerebrosides occurring in tissues, as well as the problemof the structure of the fatty acids entering into their structure, isin need of re-investigation.Crystalline Insulin.During the past year the elucidation of the problem of thehomogeneity or otherwise of the crystalline insulin fmt isolatedfrom the commercial product by Abel has been materially furthered .9388 Z.phyt?iol.Chem., 1928, 174, 214; A., 1928, 868.a9 J . Biol. Chem., 1928, 80, 227; A., 321.O0 8. physiol. Chem., 1928, 179, 312; A., 321.J . Biol. Chern., 1929, 84, 23; A., 1479.e2 Ibid., 1922, 62, 227; A., 1922, i, 714.OS Ann.Reports, 1926,533, 238; 1927,24, 261; 1928,25, 261BIOCHEMISTRY. 225One of the most important contributions in this field is that ofC. R. Harington and D. A. These workers have obtainedfrom the crude material, by the use of a simpler modification ofAbel’s method and also by a method of their own, active crystallinepreparations of which the uniform activity indicates “ that theirsubstance has a closer relation t o the specific insulin activity thanthat of an inert adsorbent of an intensely active contaminant.”In Harington and Scott’s own method of inducing crystallisationthe solution of insulin is treated with saponin and ammonia, centri-fuged, and adjusted to pH 5.6, and from this solution the micro-crystalline product separates on keeping in rhombohedra approxim-ating to cubes which are standing on one corner and thus appearunder the microscope in hexagonal outline.They are weaklydoubly refracting with a refractive index of approximately 1.58.Digitonin may be used in place of saponin.Batches of the crystalline material prepared by different methodswere assayed by four independent workers (K. Culhane, H. P. Marks,D. A. Scott, and J. W. Trevan 95), the average result being 23.3international insulin units per mg., with a standard deviation fromthe mean of 0-6. K. Freudenberg and W. Dirscherl 96 recordthe value of 26 international units per mg. for a preparation ofcrystalline insulin obtained from Professor Abel. H. Jensen,0.Wintersteiner, and E. M. K. Geiling 97 have prepared crystallineinsulin from the islet tissue of the cod and pollock and find that itis identical in crystalline form, physiological activity, and in itssulphur and nitrogen contents with that prepared from bovineinsulin. These workers find that the activity of both fish andbovine insulin is about 24 international units per mg., which is inclose accord with the figure obtained by Harington and Scott.The latter workers 98 point out that there exist amorphous prepar-ations available commercially with an activity in the neighbourhoodof 20, and sometimes as high as 22, units per mg., and infer that theproduction of crystals from such material would accordingly notentail the preparation of a highly active principle from a crudemixture, but rather the creation of conditions allowing the crystal-lisation of a substance already almost pure.The analogy is thereforewith the crystallisation of serum-albumin rather than with theisolation of a hormone such as adrenaline, a conclusion which issupported by the observations of K. Freudenberg, W. Dirscherl,and H. Eyer,Q9 who find that by the Debye-Scherer method theD4 Bkhem. J., 1929,23, 384; A., 861.96 2. phymhl. Chem., 1929,180, 212; A., 367.Oli Ibid., p. 397; A., 861.97 J . Phzm. Exp. Ther., 1929, 36, 116; A., 861. LOC. C i t .Natumk., 1929,17, 603; A., 1110.REP.-VOL. XXVI. 226 BNNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.crystals do not behave differently from amorphous insulin andtherefore resemble protein crystals.Crystalline insulin is thereforeregarded as being the true active principle of the gland in so far asthe function of the latter in relation to carbohydrate metabolismis concerned. It is suggested that, as in the case of iodothyreo-globulin, the physiological activity is a property, not of the proteinas a whole, but of a specific constituent or grouping contained withinits molecule. The comparison of the thyroid protein and insulin isof great interest, and Harington a,nd Scott conclude their remarksas follows :" The thyroid protein is differentiated from other proteins in anobvious manner by its iodine content, and the specific constituent,being a simple amino-acid, can be readily separated from the rest ofthe molecule ; the insulin protein bears no such chemical earmark,unless it be the high content of sulphur.The analogy which we havedrawn between the thyroid protein and the insulin protein must notbe taken to indicate that we believe such a separation of the specificgroup to be necessarily practicable in the latter case. As a theoreticalpossibility, however, it seems worth bearing in mind."Moreover it suggests a possible explanation for some remarkablyhigh unitage values already recorded in the 1iterature.lW. Dirscherl 2 has published interesting observations on theaction of pepsin on insulin, on acetyl insulin, and on the materialregenerated from acetyl i n s ~ l i n . ~ He finds that the inactivation ofinsulin by pepsin is comparable with the digestion of a protein bythat enzyme, the process having an optimum of pH 1-8 at 45".Acetyl insulin is only slightly affected after three hours of suchtreatment.In accord with these results it is found that formoltitration of a pepsin-insulin digest shows an increase in arnino-nitrogen (from 10 to 18% of the total nitrogen), whilst acetyl insulinshows only a slight increase after 24 hours. I?. Bischoff andM. Sahyun4 have studied the denaturation of insulin by concen-trated ice-cold sulphuric acid, and find that the product, which isacid-insoluble at pH more acid than 4.5, retains half its potency :addition of formaldehyde t o the sulphuric acid completely destroysthe potency of the final product. The denaturation by sulphuricacid is irreversible.Further data on this subject have beenrecorded by K. Freudenberg, W. Dirscherl, and H. Eyer,5 who findH. Jensen and E. M. K. Ceiling, Ann. Reports, 1928, 25, 262; V. duVigneaud, E. M. K. Geiling, and C. A. Eddy, J. Phrm. Exp. Ther., 1928, 33,497; A,, 1928, 1160; F. Bischoff and M. Sahyun, J. Biol. Chem., 1929, 81,167 ; A., 358.2. phyeiol. Chem., 1929,180, 217; A., 357.3 Ann. Reports, 1928, 25, 262.J . Biol. Glum., 1929, 81, 167; A., 358. LOG. citBIOCHEMISTRY. 227that the slow inactivation of insulin by meam of formaldehyde ispartly reversible under the a'ction of very dilute hydrochloric acid,and suggest that the inactivation is not due to the action of form-aldehyde on amino-groups. B. Stuber and K. Lang state that inweakly alkaline solutions condensation compounds of insulin andcholic or deoxycholic acid are formed.Cholylinsulin and deoxy-cholylinsulin are physiologically active when administered eithersubcutaneously or orally. The two methods of administration arestated to be equally effective, but the dose must be large, some200-300 units.The Chemistry of Muscle Processes.Adenylic Acid and the Formation of Ammonia in Muscle.-Tn theReport of last year reference was made to a series of papers fromEmbden's laboratory dealing with the subject of the functionalformation of ammonia in muscle and the relationship of adenylicacid t o this process. In the first of these communications G.Embden, C. Riebeling, and G. E. Salter give results which demon-strate that the formation of ammollia in freshly minced frog- andrabbit-muscle pulp is considerably increased by the addition ofadenylic acid but is not influenced by added urea.The ammoniaformation from the added nucleotide may reach 80-85% of thetheoretical value. Even after brief electrical stimulation of theintact frog's muscle an increase in the ammonia value results, andafter prolonged stimulation the ammonia may reach nine times itsinitial value.A seasonal variation in the amount of the ammonia precursor inRam esculenta has been demonstrated by G. Embden and H. Wasser-meyerYg who h d that a maximum is reached in May. Afterprolonged exercise by jumping, the ammonia content of thegastrocnemius removed from the intact frog is increased, whilst ifa period of rest follows the exercise the ammonia decreases.Theincrease in ammonia following work is more easily demonstrated inR. esculenta than in R. temporaria, but if the latter animal is kept a tan artificially increased temperature (26-27") during the autumn,effects are obtained similar to those recorded in the case of theformer animal in May. The reversibility of the formation of freeammonia in the isolated gastrocnemius of the frog has been inves-tigated by G. Embden, M. Carstensen, and H. Schumacher.lo Therecombination process is most easily demonstrated in spring andsummer frogs, whilst in winter the reversibility is greater, so thatNaturwiss., 1929, 17, 646; A., 1110.Ibid., 1928,179, 161; A., 346.' Ann. Reports, 1928, 25, 266.8 2. phymhl.Chem., 1928,179, 149; A., 346.lo Ibid., p. 186 ; A., 346228 m u RXPORTS ON THB: P B O G ~ S S OF ~ ~ M I S T R Y .it is diflicult to show the initial increase under direct electricalstimulation unless this is so prolonged as to damage the muscletissue and so interfere with the resynthesis. Nevertheless, byincreasing the rate of stimulation it is possible to demonstrate theinitial increase, the intervals between stimuli becoming too short topermit of recombination of the ammonia. That adenylic acid, andpossibly adenosine, are the sole sources of the ammonia formed inthose muscle processes is the conclusion of G. Embden andH. Wassermeyer,ll who have investigated the composition ofextracts from the hind limb muscles of the frog and from the bicepsfemoris of the rabbit.A relationship is found between the nitrogenof the copper-lime precipitates from such extracts and the freeammonia, originally present in the extract. The sum of these twovalues is more or less constantly five times that of the ammonianitrogen obtained after complete deaminisation by 2% sodiumbicarbonate solution. The validity of the inference is considerablystrengthened by further results from Embden’s laboratory, publishedby G. Schmidt,l2 which demonstrate that adenylic acid from muscleand adenosine (which has not yet been shown to occur free inmuscle) are easily deaminised by rabbit-muscle juice, whereasadenine, guanine, guanosine, and guanylic acid are unaffected.The ammonia production is due to two deaminases, one specific foradenylic acid, the other for adenosine.A highly active preparationof the former deaminase, with an optimum a t pH 5-9, was obtainedby adsorption on aluminium hydroxide, from which the enzymecould be eluted by sodium phosphate solution. The adenosinedeaminase remains in solution during the adsorption process.Inosinic acid, the deaminisation product of the adenylic acid ofmuscle, was isolated in the course of these investigations.Schmidt makes the rather remarkable observation that theadenylic acid of muscle differs from that of yeast, since the latter,unlike the former, is not attacked by the muscle deaminase. Thisobservation is the subject of a further communication by G. Embdenand G. Schmidt l3 in which it is stated that the physical constantsof the two acids, as determined by observation of the specificrotations, melting points and mixed melting points, reveal definitedifferences. I n addition to the difference in the behaviour of thetwo acids towards the muscle enzyme it is also found that theyeast acid is much more susceptible to acid hydrolysis than is themuscle acid.K. Pohle l4 records the isolation from ox-heart muscleof adenylic acid identical with that isolated from skeletal muscle.It remains, in concluding our survey of this important series ofl1 2. phyeiol. Chem., 1928,170,226; A., 346. I%?., p. 243; A., 346.Ibid., 1929,l84, 261; A., 1329. IW., 1929,181, 130; A., 691BIOCHEMISTRY. 229papers, to mention one further study from Embden’s laboratory.In this, H.Wassermeyer 15 deduces from the electrometric titrationcurves of adenylic acid and of inosinic acid that the two acids areof comparable strength, since, although the latter acid is strongerthan the former within the range of the first dissociation constant,this difference disappears in the range of the second dissociationconstant. From this it is concluded that the ammonia, formedduring the contraction of the muscle tends to push the reactiontowards the alkaline range. It is therefore clear that the processof ammonia formation may be an important part of the buffermechanisms of the muscle.The view that adenylic acid is the precursor of the ammonia ofmuscle is supported by J. K. Parnas,l6 who previously had stressedcertain difficulties in the way of accepting it.17 Parnas finds thatin fresh muscle the purine bases are present chiefly as free nucleo-tides.In winter frogs the fresh muscle contains 82% of the purinenitrogen in the form of the adenine nucleus and 18% in the hypo-xanthine nucleus, whilst in summer frogs the corresponding figuresare respectively 89% and 11%. Mechanical injury transforms thegreater part of the adenylic acid into inosinic acid. When groundfor a few minutes, the muscle pulp gives 23% and 77% of purinenitrogen for the adenine and hypoxanthine nuclei respectively. Inwinter the deaminisation of the adenylic acid corresponds quanti-tatively to the traumatic formation of ammonia. Muscle stimul-ation under anaerobic conditions produces a conversion of adeninenuclei into hypoxanthine nuclei, equivalent to the ammonia pro-duction, but under aerobic conditions the ammonia production isgreatly in excess.It is suggested that this may be due to thedeaminisation of other substances leading to a resynthesis of adenylicacid from inosinic acid.W. Mozolowski l 8 still finds certain difficulties in acceptingadenylic acid as the sole source of the ammonia, which is formedin sterile blood on keeping. In part such ammonia arises fromadenylic acid, but the deaminisation of this acid cannot account forthe whole of it. None the less the purine content of the blood ofvarious animals bears a close relationship to the extent of theammonia formation; for instance, the blood of man, the pig andthe rabbit contains greater quantities of purine bases than doesthe blood of the ox and horse, and greater quantities of ammoniaare forrned in the former than in the latter.In fresh blood thepurine bases are present practically exclusively as nucleotides,l7 A m . Report%, 1927,84, 238.l5 Z.phy&ol. Chem., 1928,178, 238; A., 397.lo Bioehm. Z., 1929,206, 16; A., 698.Bhchtn. Z., 1929, $208, 160; A., 688230 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.particularly adenylic acid. Free adenine is not found in the blood.During the formation of ammonia in the blood the adenylic acid issplit with the formation of inosinic acid, and the latter is stated tobe further broken down with the formation of free phosphoric acid.Previous reference has been made to the failure to correlate theprocesses of traumatic formation of lactic acid and ammonia inmuscle; l9 M.Lehnartz 2o has studied the process in the frog’sgastrocnemius in isotonic and isometric contractions. It is foundthat the ammonia formation depends on the interval betweensuccessive stimuli. For instance, with 100 stimuli at 4-secondintervals no formation of ammonia is detected, whereas with intervalsof 1 second the ammonia formed is considerable.21 The lactic acid/ammonia ratio varies from 9-22 with l-second intervals to infinitywith longer intervals.Pyrophosphate in Muscle.-In the Report of last year 22 referencewas made to the demonstration by K. Lohmann of the presence ofpyrophosphate in muscle. During the past year further observ-ations on the occurrence and behaviour of pyrophosphate have beenmade by the same worker.The first 23 of this important series ofpapers gives in greater detail the results which were briefly describedlast year. In addition to the methods of identification to whichreference was then made, the method of electrometric titration hasbeen used and the resultant titration curves compared with thoseof authentic pyrophosphate. Quantitatively the biological pyro-phosphate is determined as the difference between the “ true ”inorganic phosphate plus phosphagen phosphate, and the valueobtained after seven minutes’ further hydrolysis by means ofN-hydrochloric acid at 100”.Further investigation 24 has shown that pyrophosphate is widelydistributed in Nature, being found in bacteria, yeast, pea seedlings,in the striated muscle of invertebrates and vertebrates, and in mostof the organs of vertebrates.All cells which can utilise carbo-hydrates appear to contain this readily hydrolysable pyrophosphate.I n a, further paper 25 the physiological behaviour of the pyro-phosphate fraction is described. The pyrophosphate level of theintact frog’s muscle in oxygen remains steady while resting forperiods up to 20 hours and also during moderate stimulation.More severe stimulation produces some hydrolysis of the pyro-phosphate to orthophosphate, whilst in heat and chloroform rigoralmost all the pyrophosphate is hydrolysed. In a pulp of frog’sIs Ann. Reports, 1928, 25, 258.2o 2. physiol.Chem., 1929,184, 183; A., 1332.a1 See also Embden, Carstensen, and Schumacher, p. 227.Ann. Reports, 1928, 25, 260.Ibid., 1928,203, 164; A,, 347.Biochm. Z., 1928,202, 466; A., 208.26 Ibid., p. 172; A., 347BIOCHEMISTRY. 231muscle or in a sodium bicarbonate-potassium chloride extract ofthe muscle the pyrophosphate is completely hydrolysed duringautolysis at No, and 75% of the orthophosphate formed during thisprocess arises from the pyrophosphate.As has already been stated, all cells which utilise carbohydrateappear to contain pyrophosphate, yet the respiration and thedegradation of the carbohydrate by the cell are not dependent onthe pyrophosphate fraction. Pyrophosphate administered orally isexcreted in the urine as orthophosphate within 24 hours.Two further communications deal with the possible associationsof pyrophosphate with other muscle-cell constituents.0. Meyerhofand K. Lohmann26 find that some of the loosely combined iron ofthe muscle cell may be removed with the pyrophosphate, but itcould not be decided whether the iron was combined with thepyrophosphate in the cell. More recently, K. Lohmann2' hasdescribed the isolation of the pyrophosphate fraction through thebarium salt. Neutral hydrolysis of the complex salt thus obtainedresults in the formation of pyrophosphoric acid and adenylic acid,whilst after brief treatment with hot dilute acid there are obtainedtwo molecules of orthophosphoric acid, one molecule of adenine,and one of pentosephosphoric acid.In view of the importancenow attached to adenylic acid in relation to muscle function, thissuggested association of the nucleotide with the newly discoveredpyrophosphoric acid gains added interest. Bearing in mind thewide natural distribution of pyrophosphate which the foregoingobservations reveal, it is not surprising to find that H. D. Kay28records the widespread presence of pyrophosphatase in mammaliantissues, the distribution being similar to that of the orthophosphorices terase.Phosphagen.-Data continue to accumulate rapidly regarding thephysiological behaviour of the creatinephosphoric acid constituentof muscle. Early in the year under review there appeared a lengthypaper by C. H. Fiske and Y. Subbarow 29 giving in detail resultseagerly awaited since the original announcement by these workersof the discovery of the chemical nature of ph0sphagen.m Variousmethods are described for the isolation of creatinephosphoric acidfrom deproteinised muscle filtrates.In one of these the creatinephosphoric acid is obtained as the crystalline barium hydrogen salt,but the yield is only some 5% of the total labile (phosphagen)phosphorus of the original extract. Another method, in which the28 Biochem. Z., 1928, 203, 208; A., 347.27 Naturwiss., 1929, 17, 624; A., 1098.28 Biochern. J., 1928, 22, 1446; A., 99.2s J. Biol. Chem., 1929, 81, 629; A., 590.30 Ann. Report8, 1927, 24, 266232 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.final product was isolated as the crystalline calcium hydrogen salt,C,H,0,N3PCa,4H,0, gave a 70% yield, and this is interpreted asindicating strongly that the whole of the labile phosphorus is presentas creatinephosphoric acid.The structure proposed for thecompound is that already suggested by Meyerhof and L0hmann.3~Fiske and Subbarow find that the creatinephosphoric acid ofmuscle is hydrolysed when the muscle is stimulated, when theblood supply is cut off, and when lactic acid or potassium chlorideis injected intravenously. The injection of creatine does notincrease the concentration of the phosphagen in the muscle. Thetitration curve of the calcium hydrogen salt indicates a second aciddissociation comtant, pk,, 4.58, and since by the method of intravitalstaining the interior of the muscle cell is shown to be distinctlyacid (Rous), it is concluded that the hydrolysis of creatinephosphoricacid during the muscular contraction is accompanied by theliberation of a large amount of base and consequently functions asa mechanism for neutralising acid.Another important contribution to the study of creatinephosphoricacid has been made by D.Na~hmansohn.~~ In this investigationthe isometric coefficient, Km, and the isometric-time coefficient, K,,of the isolated muscle have been measured. The former coefficientis the tension developed in kilograms x muscle length in cm./phosphagen phosphoric acid split off in mg., whilst the lattercoefficient has as an additional factor in the numerator theduration of the tetanus in seconds. Kt is about 15 for two-seconds tetanus, 32 for five-seconds, and 50 for ten-seconds.Theanaerobic resynthesis for periods of tetanus of varying length isabout 30% of the amount hydrolysed. In curarised muscle, evenfor tetanus of two seconds' duration, the Kt value is relatively highand changes little with length of period or number of stimuli. Itfalls with submaximal and increases with excessive stimulation.When the muscle is immersed in phosphate-Ringer solution, asynthesis of creatinephosphoric acid occurs in excess of the restinglevel and up to 95% of the creatine present. In single isometriccontractions less phosphagen is decomposed at lower temperaturesthan at higher temperatures even though the tension developed andthe lactic acid formed may be the same.The K , value for 30 to50 stimuli is 70-100 a t 4" and 40-60 at 24". Nachmansohnconcludes that the extent of decomposition of phosphagen is closelyrelated to the speed of excitation and carries his observations a stagefurther in a later communication 33 in which the relationship of thea1 Ann. Reports, 1928, 25, 263.a2 Biocltem. Z., 1929, 208, 237; A., 843.aa IbicE., 1929, 213, 262BIOCHEMISTRY. 233process to the chronaxie of the muscle in the normal state and undervarious abnormal conditions is considered. The present positionhas also been summarised by 0. Meyerhof in similar terms.In studying the effect of " training " on the muscle, i.e., repeatedfaradisation in the intact animal, D. Ferdmann and 0. Feinschmidt 35find that there results a marked increase in the creatinephosphoricacid. On discontinuing the " training," the normal level is reachedafter 4 to 6 days.On the other hand, no change is noted in thepyrophosphoric acid or in the hexosephosphoric acid during the" training " period.E. Lehnartz 3t3 has published an important paper which attemptsto correlate the various synthetic and breakdown processes in whichthe active substances of the muscle participate. It is found thatthere is a considerable enzymic synthesis of creatinephosphoric acidin muscle press juice at a suitable slightly alkaline reaction. Parallelwith this there is a breakdown of lactacidogen and pyrophosphoricacid. The adenylic acid ion is found to have a high degree ofspecificity for furthering the synthesis of pyrophosphoric acid, andunder its influence the synthesis takes place more rapidly than inany other ionically stimulated chemical process in the muscle.Inosinic acid and adenosine are without influence on the syntheticprocess.This result is of interest in view of the suggested correl-ation (Lohmann) between adenylic acid and pyrophosphoric acid towhich reference has already been made in the present Report.Methylgwnidine in Muscle.-The presence of methylguanidine inextracts from ox flesh was recorded nearly 25 years ago, and itsisolation from muscle tissues generally and other tissues has beenfrequently accomplished since. The methods chiefly employed haveinvolved the use of silver nitrate and barium hydroxide or othersimilar reagents, and the possibility of the base arising by secondarychanges from creatine was therefore not excluded.The isolation ofmethylguanidine from muscle extracts by methods free from suchobjections is the subject of three papers by A. Smorodincev andA. N. Adova3' and one by S. A. K0marov.~8 Sinco the formerworkers have isolated the base by direct precipitation with picricacid and, in somewhat poor yield, as the benzenesulphonate, andsince the latter investigator records its isolation as the picrolonatefrom the phosphotungstate fraction of the muscle extract, it isconsidered to exist preformed in the muscle. Moreover, 0. Flossner34 Natumuiss., 1929, 17, 283; A., 844.36 Z. physiol. Chem., 1929,183, 261 ; A., 1193.36 Iba., 1929,184, 1 ; A., 1337.87 IW., 1929,180,192; 181,77; 182,269; A., 342,589,839.88 Biochem.Z., 1929, 211, 326; A., 1329.H 234 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and F. Kutscher 39 record its presence along with adenine in theurine of athletes. The best yield of the base obtained by Komarovwas 0.06 g. per kilogram of fresh ox muscle, which is not regardedas comprising the total amount present, whilst Smorodincev andAdova obtained 0.0134% from dog muscle.The Phosphatase of Bone.The description by M. Martland and R. Robison 4o of the prepar-ation and use of the phosphatase of ossifying bone, the existence ofwhich was first revealed a few years ag0,~1 will be welcomed in viewof the usefulness of this powerful enzymic weapon. The enzyme isbest prepared from the bones of young growing rachitic rats byextraction with chloroform water during 7-10 days, the boneshaving first been split longitudinally and the marrow removed.Evaporation of the filtered extracts over sulphuric acid in evacuateddesiccators yields a dry residue weighing 5-8 mg.per c.c., no lossof activity occurring during the drying process. PurXcation canbe effected by various methods ; for instance, an inactive proteinpresent in the dried residue may be precipitated at its isoelectricpoint ( p , 54), the enzyme may be precipitated with a mixture ofalcohol and ether, or resort may be had to dialysis or ultrafiltration.No evidence of the existence of a co-enzyme for the bone phosphatasecould be obtained.The Hydrolysis of Hexosediphosphoric Acid by Bone Phosphatase.-The phosphatase preparation described in the foregoing has beenused by Martland and Robison 42 to free the sugar component of thehexosediphosphoric acid of yeast from its phosphate groups. It willbe recalled that the yeast diphosphoric acid has been identified byMorgan and Robison 43 as y-fructose-I : 6-diphosphoric acid, andon the removal of the phosphate groups the sugar should change tothe equilibrium mixture of the c(- and p-stereoisomerides of fructosehaving [a]5461 -111".The free sugar obtained by Martland andRobison, even when the hydrolysis was conducted at p , 7, showeda specific rotation of -76", and under other conditions of reactionvariable but likewise low results were obtained.In view of thenow recognised rble of phosphoric acid in achieving transformationsof carbohydrates during the hydrolysis and synthesis of the estersformed by these two compounds, this result, in the opinion of theReporter, in no way invalidates the earlier conclusions of Morganand Robison regarding the structure of hexosediphosphoric acid.3D 2. BioZ., 1928, 88, 382; A., 466.*O Biochem. J., 1929, 23, 237; A., 603.*l Ibid., 1923, 17, 286; A., 1923, i, 730.42 LOC. cit. 43 Ann. Reports, 1927, 24, 262BIOCHEMISTRY. 235The structure originally suggested is supported by further evidencebrought forward by Morgan.44 It is shown that when the methylhexosidediphosphoric acid is formed under conditions which favourthe formation of the amylene-oxidic or stable configuration, none theless the product obtained is found to be the butylene-oxidic orreactive modification, and from this it is inferred that the 6-positionis esterified with phosphoric acid, thus preventing any possibilityof the production of the amylene-oxide ring even under conditionsfavourable to its formation.The Hexosemonophosphoric Acid of Yeast.The nature of the hexosemonophosphoric acid f i s t isolated fromyeast fermentations by Robison has not yet been fully elucidated.Apart altogether from the possible presence in the monophosphoricacid of the interesting trehalosemonophosphoric acid obtained byRobison and Morgan and described in the Report of last year,45it seems highly probable that the residual monophosphoric acid isnot homogeneous.This view is strongly supported by certainresults, as yet incomplete, of R. Robison and E. J. King,46 fromwhich it may be deduced that the main component is an aldose,almost certainly glucosemonophosphoric acid. This component isregarded by P. A. Levene and A. L. Raymond4' as y-gIucose-5-phosphoric acid :CH(OH)*CH(OH)*CH(OH)*CH-CH(O*P03H2)*CH2*OH.This conclusion is reached on the basis of the rate of hydrolysis ofthe methylglucosidic compound formed from the free acid in acidmethyl alcohol at room temperature. The observed rate is that ofa substance possessing the y-lactal or butylene-oxidic structure.The phosphoric acid group cannot therefore be regarded as beingattached to position 4. It is considered that position 6 is excluded,since the osazone of the Robison ester differs from that of theNeuberg ester (which is fructose-6-monophosphate). It is to benoted, however, that the method of glucoside formation employedby Levene and Raymond would lead to the production of they-lactal product should the hydroxyl group of position 4 be free tocondense. Moreover, E.J. King and W. T. J. Morgan48 have44 Report of the Meeting of the Biochemical Society (Feb. 4th), J . SOC.46 Report of the Meeting of the Biochemical Society (Feb. 4th), J . SOC.47 J . Biol. Chem., 1929, 81, 279; A., 423.48 Report of the Meeting of the Biochemical Society (Feb. 4th), J . SOC.Chem. Ind., 1929, 48, 144.Chem. Ind., 1929, 48, 143.4 6 Ann. Repo~ta, 1928, 25, 247.Chem.Id., 1929, 48, 143236 ANNUAL REPORTS ON r n ~ PROGRESS OF CHEMISTRY.shown that by suitably varying the conditions of the condensationit is possible to obtain both y- and 8-lactal products, i.e., both thebutylene- and the amylene-oxidic glucosides. In this case bothpositions 4 and 5 must be free. In a later communication King andMorgan49 review all the available evidence and conclude that themost probable structure of the aldose ester constituent of thehexosemonophosphoric acid is that of glucose-3-monophosphoricacid :CH( OH)*CH( OH) *CH( O*PO,H,)*CH( OH)*CH*CH,*OHThe essential evidence upon which this conclusion is based is asfollows : positions 1 and 2 are excluded, since an osazone is formedwithout loss of the phosphate group; positions 4 and 5, on thegrounds mentioned above; position 6, on the same grounds asthose brought forward by Levene and Raymond.% Position 3therefore alone remains for the attachment of the phosphoric acidgroup.This argument is of course based upon the acceptance ofthe y-fructose-1 : 6-diphosphoric acid structure for the yeastdiphosphate, and the assumption, for which good evidence exists,61that the yeast monophosphate is essentially a glucose derivative.Should either of these views be modified as a result of future inves-tigations, the arguments considered above will require to be recast.L- -O---IThe Processes of Bone Formation.Bone and ossifying cartilage have been shown to contain aphosphata~e~5~ and this enzyme is regarded as playing an activepart in the processes of ossification by effecting the hydrolysis ofcertain phosphoric esters which H.D. Kay and R. Robison 53 andM. Martland and R. RobisonS4 have shown to be present in theblood. The concentration of inorganic phosphate in the tissuefluid is thereby raised so that calcium phosphate is deposited. Insupport of this hypothesis evidence was furnished that the phos-phatase is secreted in the region of the osteoblasts and hypertrophiccartilage cells. When severely rachitic bones were immersed insolutions of calcium hexosemonophosphate or calcium glycero-phosphate, deposition of calcium phosphate took place in theperiosteum and in the matrix of the proliferating and hypertrophiccartilage, but, on the other hand, no deposit was observed in the49 Report of the Meeting of the Biochemical Sooiety (Mar. 16th), 1929, 48,5O LOC.cit.61 See J. Pryde and E. T. Waters, Bbchem. J., 1929,23, 673; A., 962.62 Ann. Rep&, 1923,20, 189.64 Biochm. J., 1926, a0, 841; A., 1926, 968.296.sa Ibid., 1924, 21, 197BIOCHEMISTRY. 237small-celled cartilage of the epiphysis (R. Robison and K. M.S o a m e ~ ) . ~ ~ Similarly it w&s shown, by examining the cartilagesand bones of human embryos and young infants that, although theossified portions of young normal bones contained phosphatase inhigh degree, the non-ossifying cartilage was in all cases devoid ofthe enzyme (M. Martland and R. Robison).56 H. B. Fell andR. Robison 57 have published an important paper which continuesthe investigations briefly outlined in the foregoing.The interestof this study, both from the point of view of technique and of results,is such that a detailed review is justified. The object has been tocorrelate the growth, development and phosphatase activity ofisolated early embryonic femora and of undifferentiated limb-budscultivated in vitro, and t o compare these processes in the explantswith the corresponding processes in the normal embryonic limb.When explanted in vitro by a technique which is carefullydescribed, the femur of the embryo chick at an early stage indevelopment is completely deprived of a vascular system, nervousconnexions, adjacent skeletal structures and of association withthe limb musculature. Nevertheless, it is shown that the explantduring cultivation in vitro is able to continue its anatomical develop-ment on the same general lines as in the normal limb, and at thesame time undergoes a histological differentiation which is correlatedwith at least one of the chemical activities of the normal ossifyingcartilage.The femora cultivated i n vitro differed from the normalembryonic femora of the same age mainly in their much smallersize, in having relatively larger epiphyses, in the absence of amarrow cavity, and in being encased by a considerably thinner andmore compact sheath of periosteal bone. All these differences maybe attributed, in part at least, to the absence of certain mechanicaland nutritional factors normally supplied by the blood. Aninteresting contrast was observed between the histological develop-ment in vitro of the 6-day femora and the 3-day limb-buds.Nodifferentiation into structures corresponding to the epiphysis anddiaphysis took place in the cartilage formed from originally undif-ferentiated 3-day mesenchyme. On the other hand, the explanted6-day femora which, at the time of explantation were composed ofvery simple early cartilage, developed epiphyses and diaphysesduring the same period of cultivation. Thus under the conditionsof the experiments, the self-differentiating capacity of the 6-dayfemur was considerably greater than that of the 3-day limb-bud.It is shown that t,he femora, entirely devoid of phosphatase when5 5 Biochem. J . , 1924, 18, 740; A., 1924, i, 904.56 Ibid., p.1354; A., 1926, i, 201.57 Ibid., 1929, 23, 767; A., 1197238 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.removed from the 6-day embryo, synthesise the enzyme duringcultivation in vitro and that the production of the phosphatasefollows very closely the progress of histological differentiation inthe cartilage. For instance, the first appearance of phosphatase inthe explanted 6-day femora, after 3 days’ cultivation, coincidedwith the first appearance in the cartilage of a zone of enlarged cells.The extension of this zone and increased enlargement of the cellsin the later cultures were accompanied by a corresponding increasein the amount of phosphatase. The parallelism between enzymesynthesis and histological differentiation is most clearly shown byconsidering the ratio of phosphatase to the dry weight of the femur( A / W ) .With the increasing proportion of hypertrophic cells andthe gradual development of periosteal bone observed up to thetwenty-first day of cultivation, there was found an increase in thevalue of A/W from zero to a maximum of 0.35. The degenerationwhich was observed in the 24-day, and still more extensively in the27-day cultures, was accompanied by a halt in the increase of thisratio, followed by a fall to the value 0.26 a t 27 days. Furtherevidence of this parallelism was provided by the chance inclusionin the series of one culture (15-day) in which, for some reason, thehistological differentiation was very backward and for which thevalue A/W proved to be correspondingly low.On the other hand,it was shown that the cartilage formed during cultivation of 3-dayembryonic limb- buds is entirely of the small-celled (undifferentiated)type and that even after 21 days’ cultivation this cartilage synthesisesno phosphatase. From the results of these remarkably interestinginvestigations Fell and Robison conclude that in the developmentof skeletal tissue in vitro phosphatase is synthesised by cartilageonly if hypertrophic cells are present.During the year under review, cert’ain other interesting observ-ations on the chemistry of calcification have appeared. N. W.Taylor and C. Sheard 58 have investigated by X-ray diffractionpatterns and by optical methods several types of calcified tissues,including normal bone, dental enamel, rachitic bone, bone low inphosphorus, and salivary and tubercular calculi, and find that thesolid inorganic phase consists essentially of very small crystals ofapatite minerals of the general formula 3Ca,(PO,),,CaX,, where X,ordinarily represents CO,, F,, (OH),, 0, SO,, and Ca which mayto some extent be replaced by Mg.The typical minerals of thisformula are podolite, dahllite and fluorapatite. No evidence of thepresence of brushite, CaHP0,,2H20, was obtained either in normalor in pathological deposits. On the other hand, M. J. Shear,&I. Washburn, and B. Kramer 59 still regard the composition of bone5 8 J . Bwl. Chem., 1929, 81, 479; A., 463. Ibid., 1929,83, 697; A., 1326BIOCHEMISTRY. 239as an open question and state that the presence of CaHPO, in bonegenerally, and in primary calcification especially, should not beoverlooked. R.Klement 60 has published data which lead him tothe conclusion that the inorganic portion of bone consists principallyof a basic calcium phosphate of the composition 3Ca3(P04)2,Ca(OH)2,with inclusions of alkaline-earth carbonates and alkali bicarbonates.B. Kramer, M. J. Shear, and M. R. McKenzie find no deviationfrom the normal in the ratio of the residual calcium to phosphorusof the bones of growing rats as a result of the administration ofmassive doses of irradiated ergosterol (see also p. 251). On theother hand, C. G. Lambie, W. 0. Kermack, and W. F. Harvey 62state that the administration of parathyroid hormone to ratsappears to cause a change in the form in which calcium exists inthe bones.Speciific Carbohydrates and Immunology.In the Report for 1926 there was summarised the progress achievedin elucidating the r6le of specific carbohydrates in immunologicalreactions.Further reference to this interesting field is necessitatedby recent publications from the American school which is particularlyassociated with its development. W. F. Goebel and 0. T. Avery,63with the view of coupling known sugar residues with proteins ofascertainable antigenic properties, have synthesised p-a.minopheno1-p-glucoside and p-aminophenol- p-galactoside and have coupledthese, after diazotisation, with globulins and albumins. They haveobtained the following four protein-sugar complexes : phenol-p-glucosideazoglobulin, phenol- p-galactosideazoglobulin, phenol- p-glucosideazoalbumin, and phenol- p-galact osideazoalbumin. Theseare referred to as gluco- or galacto-globulins and -albumins respec-tively.The steps employed in the synthesis were as follows.Acetobromohexose, prepared from the penta-acetyl compound, wascondensed with silver p-nitrophenoxide and after de-acetylation ofthe condensation product there was obtained p-nitrophenol- p-hexose; this was reduced to the p-aminophenol compound byhydrogenation in the presence of a platinum catalyst : couplingwith the protein was achieved in the usual way by means of sodiumnitrite and hydrochloric acid at 0". I n the case of the globulincompounds the glucose-protein contained 17 y/o of reducing sugarand the galactose-protein 10%.The immunological reactions of these sugar-protein compoundshave been investigated by 0.T. Avery and W. F. Goebel 64 and it60 2. phy8iOl. Chem., 1929, 184, 132; A., 1328.6 1 J . Biol. Chem., 1929, 82, 655; A., 960.e2 Nature, 1929, 123, 348; A., 475.63 6. Exp. Ned., 1929,50, 821. 64 Ibid., p. 533240 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.is found that, when two chemically different carbohydrate deriv-atives are bound to the same protein, the resulting antigens exhibitdistinct immunological specificity. On the other hand, when thesame carbohydrate radical is conjugated with two chemically differentand serologically distinct proteins, both of the sugar proteins formedacquire a common serological specificity.Thus the newly acquiredspecificity of the artificially prepared sugar-proteins is determinedby the chemical nature of the carbohydrate radical. The simplecliff erences in the molecular codguration which distinguish the twoisomerides glucose and galactose suffice to orient protein Specificitywhen the two sugars are coupled to the same protein. The uncon-jugated glucosides, although they are not themselves precipitablein the serum from animals immunised with the homologous sugar-protein, nevertheless inhibit in a specific manner the reaction betweenthe homologous sugar-protein and its specific anti-body. The sugmcompounds unattached to proteins are non-antigenic but specific-ally reactive, as is shown by these inhibition tests.These simpleartificially prepared glucosidic compounds are therefore placed inthe class of carbohydrate haptenes, the most conspicuous examplesof which are the specific polysaccharides naturally found in certainmicro-organisms.I n another communication W. S. Tillett, 0. T. Avery, and W. F.Goebel give the results of a study of the active and passiveanaphylaxis induced by the sugar-proteins in guinea-pigs. Whenthese animals are passively sensitised with the serum of rabbitsimmunised with the gluco-globulin, they exhibit typical anaphylacticshock when subsequently inoculated with gluco-albumin, whilst theserum of rabbits immunised with galacto-globulin similarly sensitisesguinea-pigs to galacto-albumin. Guinea-pigs actively sensitisedwith the sugar-proteins are also subject to anaphylactic shock wheninjected after 2 days with sugar-proteins containing the samecarbohydrate radical as that present in the sensitising antigen,regardless of the kind of protein with which it is combined.Theunconjugated glucosides, although themselves not capable ofinducing shock, will inhibit the anaphylaxis if injected prior to theintroduction of the toxigenic sugar-protein, and if the carbohydrateis the same as that combined in the sugar-protein molecule. Theseresults appear to the Reporter to be extremely suggestive and far-reaching in their implications and the success of this direct attackon the a,pparently complicated problems of immunology is indeedvery gratifying.A further highly interesting observation in this field has beenmade by M.Heidelberger, 0. T. Avery, and W. F. Goebel,G6 whoJ . Exp. Med., 1929, 50, 551. 66 Ibid., 1929, 49, 847; A., 1201BIOUHE~TRY. 241find that by partial acid hydrolysis of gum-arabic in the cold thereis obtained an immunologically specific carbohydrate Comparablein its precipitating activity for Types I1 and I11 antipneumococcussera with the bacterial soluble specific substances themselves. Onfurther hydrolysis the carbohydrate yielded galactose and two ormore complex sugar acids, one of which appeared to be an aldobionicacid similar to those isolated from the specific polysaccharides ofthe Type I11 pneumococcus and the Type A Friedliinder bacillus.Thk acid was subsequently obtained in a crystalline condition byM.Heidelberger and F. E. Kcndall,67 who provisionally ascribe toit the structure of a- or P-glucurono-3- or -6-a-galactose.A. Stull6* finds that the speck& soluble carbohydrate of Type I11pneumococcus described by Heidelberger, Goebel, and Avery 69can be isolated from an unbuffered culture medium after 18 hoursof growth. The whole of the specific carbohydrate, which was theonly specific precipitating material found, was contained in thedistilled water extract of the fat-free material. J. Furth andK. Landsteiner 70 find that from the main serological types of thetyphoid-paratyphoid groups of organisms specific precipitable sub-stances can be obtained. Pronounced chemical differences were notobserved, but the substances are rich in carbohydrates and containvery little protein.Small quantities of a material apparently of afatty nature were detected.The Molecular Weight of Ncemoglobin.An interesting application of the diffusion coefficient of a sub-stance in solution to the calculation of the radius and weight of theparticle has bien made by J. H. Northrop and M. L. A n s ~ n , ~ l whohave calculated, with the help of the Einstein equation, themolecular weight of carbon monoxide-haemoglobin. It has beenfound that the difEculties inherent in determining the diffusioncoefficient of a slow-moving substance of large molecular dimensionscould be overcome if the rate of diffusion was accelerated by allowingthe process t o occur through a thin porous plate between two solu-tions of different concentrations.Suitable plates were preparedfrom sintered porous Jena glass or from alundum. The constantof the apparatus is found by standardising it with a substance ofknown diffusion coefficient, after which the required diffusioncoefficient, D, can be obtained. The Einstein equation, D =RT/6xNrq , in which N is Avogadro's number, q t'he viscosity of the6 7 J . Biol. Chem., 1929, 84, 639.Ann. Reports, 1926, 23, 248.70 J . Exp. Ned., 1929, 49, 727; A , , 1200.71 J . Gen. Phyeiol., 1929, 12, 643; A., 687.Ibid., 1929, 82, 641; A., 968242 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.liquid, and Y the radius of the molecule, then permits of the calcu-lation of the molecular weight.The specific gravity was assumedto be the same as that of solid haemoglobin, and from the observeddiffusion coefficient, 0.0420 4 0-0005 cm.2 per day at 5", themolecular weight of carbon monoxide-haemoglobin is calculated tobe 68,500 & 1,000. This figure agrees within the experimentalerror with that of 67,000 found by Adair 72 by osmotic pressuremeasurements, and of 68,000 found by Svedberg 73 from experimentson the rate of sedimentation produced by very rapid centrihging.Hcemochromogens.Several important publications dealing with hzmochromogenand related compounds have appeared during the past year.M. L. Anson and A. E. Mirsky 74 have made a study of the com-pounds formed by reduced haematin and cyanide. One of theseis found to be a typical haemochromogen and to it the name cyano-haemochromogen has been given.It probably contains one cyano-group to each molecule of haematin. The haemochromogen formedfrom hemoglobin is a compound of denatured globin and reducedhaematin, one molecule of the former being able to convert tenmolecules of reduced haematin into haemochromogen. It is foundthat edestin and zein are less efficient as bases in the formation ofhzmochromogens than is denatured globin. R. Hill 75 finds thathaemochromogens generally are formed by the union of the reducedhamatin molecule with two molecules of the nitrogenous substance.This is supported by data derived from a study of the pyridine,nicotine, and cyanide compounds of reduced haematin. The newcyanohaemochromogen described by Anson and Mirsky,76 whichthese workers found to contain one molecule of alkali cyanide to eachmolecule of reduced haematin, is shown to be analogous to thecarbon monoxide compound of reduced hzematin.It combines with asecond molecule of cyanide to form a true hzemochromogen, or withone molecule of nicotine to form a mixed nicotine-cyanohamo-chromogen. The name " cyano-reduced haematin '' is proposed forit and the previously suggested name of cyanohzemochromogen istransferred t o the hzemochromogen containing two molecules ofcyanide described by Hill himself.The Linking between the protein and the prosthetic group inhzemoglobin has been studied by F. Haurowitz and H. W a e l ~ c h , ~ ~72 Ann. Reports, 1926, 23, 251.7 3 Ibid., 1924,21, 263; 2.physikal. Chern., 1927,127, 51; A., 1927, 716.7 4 J . Gen. Physiol., 1928, 12, 273; A., 87.75 Proc. Roy. Soc., 1929, B, 105, 112; A., 1004.5 6 L O C . cit.7 7 2. phy8iOz. Chem., 1929, 182, 82; A., 713BIOCHEMISTRY. 243who confirm the findings of Hill and Holden ‘8 concerning theformation of a true hemoglobin, capable of absorbing molecularoxygen, from native globin and haemin. I n similar manner,coupling was observed between native globin and dimethyl meso-haemin and with reduced haemin. It is therefore considered that theunsaturated side chains and carboxyl groups of hzemin do notparticipate in the linkage with globin. Haurowitz and Waelschcould not, from their spectroscopic observations, find any evidencefor coupling between globin and haematoporphyrin (Nencki) (compareHill and Holden, Zoc.cit.).Cytochrome and Respiratory Enzymes.--In previous Reports 79attention has been directed to the fundamental work of D. Keilinon cytochrome. A further publication by the same author 80 dealswith the close association which exists between this respiratorypigment and the oxidase systems of the cell. Earlier work hasestablished the presence in all zrobic organisms of cytochrome withits three haematin compounds a’, b’, and c’, and of an unboundhaematin compound similar to the protoporphyrin of hzemoglobin.Of these four haematin compounds, the components a’ and c’ ofcytochrome are not autoxidisable, whilst b’ of cytochrome (in washedmuscle and dried yeast cells) and the unbound haematin are aut-oxidisable, and the last in the reduced state combines with carbonmonoxide.The haemochromogen precursor of cytochrome is alsoautoxidisable, but does not combine with carbon monoxide. Thesehaematin compounds are responsible for the thermostable peroxidasereaction of the cell, a reaction which is revealed by the oxidation ofvarious chromogens such as bemidine, guaiacum and p-phenylene-diamine in the presence of hydrogen peroxide. The cells of yeast,muscle, and other tissues also contain an insoluble thermolabileindophenol oxidase which is responsible for the oxidation of cyto-chrome, especially of its non-autoxidisable a’ and c‘ components, asthe oxidation of cytochrome is inhibited or abolished by the samefactors which inhibit or abolish the activity of the indophenoloxidase.Cytochrome in the living cell is reduced by variousorganic molecules (metabolites) which, being activated by dehydrases,become hydrogen donators. All factors which inhibit the activityof the dehydrase system of the cell, such as narcotics, warming to52”, and very low temperatures also delay the reduction of oxidisedcytochrome. It is therefore concluded that cytochrome acts as acarrier between two types of activating mechanisms in the cell:(a) the dehydrases activating the hydrogen of organic molecules ,78 Ann. Reports, 1927, 24, 265.Ibid., 1926, 22, 238; 1926, 23, 251; 1927, 24, 268.Proc. Roy. Soc., 1929, B, 104, 206; A,, 470244 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.and (b) the indophenol oxidam activating oxygen.Cytochrome thusacts as a hydrogen acceptor which is specifically oxidised by theindophenol oxidase. It is thought that the autoxidisable hamatincompounds, b' of cytochrome, unbound hamatin, and the haemo-chromogen precursor of cytochrome may also act as carriers betweenthe hydrogen donators and molecular oxygen, and also as directcatalysts promoting the oxidation of substances which are notactivated by specific dehydrases.Xynthetic Porphyrins.-No attempt can be made here to reviewadequately the considerable volume of work on synthetic porphyrinsand related compounds which continues to appear from the Germanlaboratories, but it is felt that some reference to the synthesis ofhaematoporphyrin, protoporphyrin, and haemin by H.Fischer andK. Zeile 81 will be welcomed by the biochemist. When an absolutealcoholic solution of diacetyldeuteroporphyrin 82 and potassiumhydroxide is boiled, haematoporphyrin is obtained. Its hydro-chloride is crystallographically and spectroscopically identical withnatural haematoporphyrin hydrochloride. At 105" in a highvacuum the free haematoporphyrin passes almost quantitativelyinto protoporphyrin identical with that derived from blood. Thesynthetic haematoporphyrin hydrochloride is converted by hydrogeniodide in glacial acetic acid into mesoporphyrin. From the syntheticprotoporphyrin, hamin, C34H,,04N4ClFe, has been prepared. It isidentical with natural haemin. At the present stage of these inves-tigations H.Fischer regards the following as the most satisfactoryformula for haemin :CH,= CH:CH2 I 1 CH -CH:CH, 3/-iThe formation of porphyrins in living organisms is the subject oftwo papers to which reference will be made in concluding this sectionof the Report. H. Fink 83 in a lengthy communication deals withthe accumulation of coproporphyrin in yeasts cultured over a longperiod. In all the yeast,s the spectrum of cytochrome was recog-nisable, and the accumulation of the porphyrin did not kill the83 Bwchem. Z., 1929, 211, 66; A., 1340.61 Annalen, 1929, 468, 98; A., 333. a2 Ann. Reportrr, 1927, 24, 270BIOCHEMISTRY. 246yeasts, nor did it alter the type of their metabolism. A. A. H. vanden Bergh 84 records the excretion by a patient suffering fromcongenital porphyrinuria of coproporphyrin identical with thatsynthesised by H.Fischer from aetioporphyrin IILS5The Chemistry of the Fat-soluble Vitamins.In the field of the fat-soluble vitamins many interesting resultshave accumulated during the past year. The main interest ofworkers in this field has been directed towards the following fourproblems : (a) the possible identity of vitamin-A with the hydro-carbon carotin, (b) the speciiicity of the arsenic and antimony tri-chloride tests for vitamin-A, (c) the chemical relationship of vitamin-D with ergosterol and its derivatives, and (d) the question of" hypervitaminosis " as a result of the excessive administration ofvitamin-D preparations. These questions will be consideredseriatim.Vitamin-A and Carotin.-Carotin is a coloured hydrocarbon ofplant origin having the formula C,,H5,. Its constitution is not yetfully elucidated, but it appears to possess 11 double bonds, ofwhich 8 are probably conjugated.86 The question of the possibleidentity of this interesting hydrocarbon with the vitamin hasreceived previous consideration mainly by Steenbock and hiscollaborators in America and by Drummond in this countryYs7 andfrom the evidence then accumulated it seems not unnatural thatthe question of possible identity should have been dismissed. Thediscussion has been reopened by B.von Euler, H. von Euler, andH. Hellstrom,88 who point out that in previous biological tests ofthe vitamin-A activity of the carotinoid pigments, no provision wasmade for the presence of vitamin-D in the diet and the resultsobtained by the earlier investigators are not regarded as trustworthy.It is true that in the earlier work growth-promoting activity wasoccasionally detected, but this was then ascribed to the presence ofthe vitamin as a contaminant of the carotin.Before the resultspublished during the past year by other workers are considered,those of von Euler and his associates will first be reviewed. B. vonEuler, H. von Euler, and P. Karrer s9 find that the addition of dailydoses of purified carotin to the basic diet of rats in amounts of0.10 to 0.03 mg. produces an increase in growth comparable with that** PTOC. K . Akad. Wetenach. Ameterdam, 1929, 32, 16 ; A., 696.86 L.Zechmeister, L. von Cholnoky, and (Frl.) V. Vrabhly, Ber., 1928, 61,Ann. Rep&, 1927,24, 270.[B], 666; A., 1928, 624.J . BWZ. Chern., 1921, 46, PTOC. xxxii; Biochem. J., 1919, 13, 81.He&. O h h . A&, 1929,12, 278; A., 610.08 Biochm. Z., 1928,203, 370; A., 368246 ANNUAL REPORTS ON THE PROURESS OF CHEMISTRY.obtained with vitamin-A. Pure carotin and the isomeric carotinoidlycopin (found in tomatoes) give the Rosenheim-Drummond anti-mony trichloride colour reaction, and when the liver extracts ofthe carotin-fed rats were tested colour intensities were obtainedsimilar to those given by the livers of normally fed rats. Thegrowth-promoting effect is not general to all carotinoids, sincenegative growth results were obtained with lycopin and its carb-oxylic acid, and with xanthophyll, a-crocetin, bixin, and capsanthin.These pigments, it is to be noted, give the antimony trichloridereaction.Positive growth effects were obtained with dihydro-a-crocetin if vitamin-D in the form of irradiated arachis oil was feda t the same time. Further results of a similar nature are publishedin a later paper by H. von Euler, P. Karrer, and M. Rydb0m.w Inaddition to the compounds already mentioned, growth tests werecarried out on the following carotinoid derivatives with negativeresults : norbixin, dehydronorbixin, fucoxanthin, and dihydro-a-crocetin methyl ester. Carotin with a melting point of 182-183"fed to rats in daily doses of 0.03 mg. produced continuous growth.It is admitted that the nature of the preparation does not excludethe possibility of the presence in the carotin of a very active sub-stance, but on the other hand the purest carotin preparations are themost active vitamin-A preparations yet obtained.Carotin fromstinging nettles is found to be slightly less active than that fromcarrots and it is argued that if accompanying impurities are respon-sible for the biological activity they do not occur solely in the carrot.Di-iodocarotin was found to be active and it is thought that it isnot the carotin derivative itself but a product derived from it afterresorption which is the growth-promoting substance. Resultsobtained with lutein appear to be variable, but a recent paper byH. von Euler and H. Hellstrijm91 states that it exhibits specificgrowth-promoting properties.B. von Euler, H. von Euler, andp. Karrer g2 have made a histological examination of the epiphysesof rats kept on a diet containing both carotinoid material andsufficient amounts of vitamin-D. Growth continues but boneformation is deficient. In rats which have received more than theminimum necessary amount of carotin the excess accumulates inthe liver.D. L. Collison, E. M. Hume, I. Smedley-Maclean, and H. H.Smith g3 have examined the vitamin-A substance of green spinach,cabbage leaves, and of carrots, and find that it is contained in theBer., 1929, 62, [ B ] , 2445 ; A., 1343.O 1 Biochem. Z., 1929, 211, 252; A., 1334.O2 Ibid., 1929, 209, 240; A., 1112.93 Biochem. J., 1929, 23, 634; A., 1202BIOCHEMISTRY.247most highly unsaturated fraction of the unsaponifiable matter. Asfar as the process of purification employed by them extended, itremained associated with the carotin crystals. Carotin was separ-ated in a crystalline condition from all three sources and while noclaim is made that the specimens obtained were of a high degree ofpurity, none the less the vitamin-A activity of the specimens ofhighest melting point (176178' ; from the cabbage material)was not less than that shown by specimens of lower melting point(163-164" ; from spinach). It is suggested that the presence of fatin the diet or of something in the unsaponifiable fraction of the fatis possibly necessary for the utilisation of carotin. The associationof vitamin-A activity with carotin in the carrot has been investigatedby T.Moore,w who, using a basal diet containing vitamin-l) in theform of irradiated ergosterol in arachis oil, finds that a daily dosageof 100 mg. of fresh carrot sufficed to cure xerophthalmia and torestore good growth in rats deprived of vitamin-A. Carrot fat fromwhich much of the carotin ha,d been removed was active in dosesof 0-4 mg. daily, whilst carotin itself (m. p. 174O), recrystallisedmany times, was found to be active in doses of 0.01 mg. daily.The foregoing data certainly strongly suggest that chemicallypure carotin can restore growth in rats suffering from deficiency ofvitamin-A. None the less, the Swedish workers appear to considerthat it is improbable that the vitamin-A of cod-liver oil is carotinitself and the suggestion has been put forward that several sub-stances possessing the physiological activity of the vitamin mightexist.The vitamin-A of cod-liver oil, for example, might be derivedfrom the carotinoids of marine algae. Von Euler and his associateshave indeed suggested that the vitamin-A activity is not theproperty of any single substance but is due to the presence in variousmolecules of the ( ( polyene " grouping, a system of double bondswhich gives rise to colour reactions and which is held to possesscatalytic powers in uiuo. It has been stated in the foregoing thatvon Euler, von Euler, and Karrer find that excess carotin accumu-lates in the liver, but on the other hand a recent note by T.Moore 95suggests that carotin does not accumulate as such in the liver,although there is a marked increase in the vitamin-A content asmeasured by the antimony trichloride reaction. A somewhat similarresult has been recorded by L. S. PalmerP6 who states that pig'sliver contains a minute quantity of an unsaponifiable pigment,soluble in light petroleum, which strongly resembles carotin in solu-bility and in adsorption properties and gives some of the colourQ4 Biochem. J., 1929, 23,803; A., 1202.s6 Lamet, 1929, ii, 380; A., 1343.O 6 Amer. J . PhYSiOz., 1929, 87, 663; A., 463248 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.reactions, but not others, given by carotinoids. Prom a qualitativeand a quantitative study of its spectroscopic properties it is con-cluded that the liver pigment cannot be carotin.It will be obviousfrom the following section of this Report that arguments based oncolour tests must be employed with discretion, but it is by no meansinconsistent with the present trend of work on vitamin-A that carotinand closely related substances are capable of forming the vitaminwhich subsequently may accumulate in the liver.The Colour Reaction for Vitumin-A.-A considerable amount ofwork has recently appeared relating to the applicability of theRosenheim-Drummond colour reaction for vitamin-A. J. C.Drummond and R. A. Mortong7 have subjected it to a criticalexamination in parallel with biological and spectrographic tests oncod-liver oil. They rightly stress the considerable variations in thebiological method in view of the individual nature of the responsesof many animals, and state that quantitative differences of less than100% in vitamin-A potency cannot be detected with certainty bythe biological method.On the other hand, the relative valuesobtained by all three methods were in agreement, and in particularthe agreement between the colorimetric and the spectrographicmethod was very close. As far as cod-liver oil is concerned, theseworkers unhesitatingly recommend the colorimetric method of assay,and Professor Drummond states that in what is admittedly a verywide range of experience no single case has been encountered inwhich there has been disagreement between the animal tests andthe intensity of the blue colour showing maximum absorption near608 pp.In regard to the spectrographic test (intensity of the ultra-violet absorption band of cod-liver oil at 328 pp; Morton andHeilbron 98) 0. Rosenheim and T. A. Webster 99 state that dehydro-ergosterol shows selective absorption in the ultra-violet region at320-328 pp. It is inactive in promoting growth and gives noantimony trichloride reaction, from which it is concluded that thespectrographic test, at any rate by itself, cannot be taken as acriterion of vitamin-A .Amongst those workers who have used the colour test and obtainedconsistent results are E. R. Norris and I. S. Danielson,l E. M. Bailey,H. C. Cannon, and )I. K. Fishery2 and N. ever^.^ The first-men-tioned and last-mentioned workers stress the importance of theconcentration of the oil used in the tesf.Only at low concentrationsQ7 Bwchem. J., 1929, 23, 786; A., 1202.QQ Biochem. J., 1929, 23, 633; A., 1202.Ann. Reports, 1928, 25, 268.1 J. Bwl. Chem., 1929,83, 469; A., 1202.a Quart. J. Phamn., 1929,2, 227; A., 1203.Cmn. A&. Exp. Sta. Bull., 1928, No. 296, 334; A., 103BIOUHEMISTRY. 249is the colour developed proportional to the amount of oil used, andby working at such low concentrations Norris and Danielson obtainedresults in good agreement with those of the biological method.Bailey, Cannon, and Fisher find a good agreement between thecolour test and the standard U.S. Pharmacopoeia feeding tests. Onthe other hand, certain difficulties and inconsistencies in the testwere encountered by G.M~nasterio,~ W. S. Jones, A. E. Briod,S. Arzoomanian, and W. G. Christian~en,~ H. Steudel,6 H. vonEuler, M. Rydbom, and H. Hellstrom,7 and by P. B. Hawk.* Ofthese, perhaps the most striking result is that of Euler, Rydbom,and Hellstrom, who found that the product from an alcoholicextract of a sample of cod-liver oil gave a reaction with about fourtimes the intensity of that of the original oil. Von Euler, Karrer,and Rydbom 9 fmd that antimony trichloride colour reactions aregiven by lycopin, b i d , capsanthin, a-crocetin, dihydro- a-crocetin,xanthophyll, di-iodocarotin, dihydroisonorbixin, dihydro-a-crocetinmethyl ester, fucoxanthin, zeaxanthin, lutein, and tri-iodocarotin.These workers therefore conclude that the test is given by manycarotinoids which do not promote growth and hence that thereaction is not generally applicable to the investigation of vitamin-A.The depth of colour is very greatly influenced by oxidation of thec arot inoid .Ergosterol and the Formation of Vitamin-D.-Despite manyingenious attacks on the problem, it cannot yet be said that themechanism of the formation of vitamin-D from ergosterol has beenelucidated.The course of the various changes which occur whenergosterol is irradiated has been the subject of a, spectrographicinvestigation by R. B. Bourdillon, C. Fischmann, R. G. C. Jenkins,and T. A. Webster.1° The antirachitic activity of irradiatedergosterol solutions has been compared with their absorption spectra,both before and after removal of unchanged ergosterol, and evidencehas been obtained which points to the successive formation of threesubstances or groups of substances.The first of these shows anabsorption band similar to that of ergosterol with a maximum at280 pp but more than twice as intense. This substance is believedto be vitamin-D. The second product which is formed by furtherirradiation of the first has a maximum absorption at 240 pp and hasno antirachitic activity. The third substance formed in turn fromthe second possesses neither antirachitic activity nor specific absorp-Biochem. Z . , 1929, 212, 66; A., 1343.J . Arner. P?mrrn. ASSOC., 1929, 18, 263; A., 610.Bwchem. Z., 1929, 207, 437; A., 726.IW., 1929, 208, 73; A., 861.Science, 1929,89, 200; A., 1111.a LOC. C i t .lo Proc. Roy. SOC., 1929, B, 104, 661; A., 727250 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.tive capacity. The fist substance, which is presumed to be thevitamin, is obtained in the form of colourless glassy masses whichhave failed to crystallise. Reasons are given for supposing thatergosterol when irradiated changes directly into the vitamin withoutthe loss of any large part of its molecule. Careful measurements ofthe extinction coefficients during irradiation point to the presencein the purest preparations of the first substance of some 55% ofthe vitamin. The smallest daily dose of such a preparation whichcould be detected in the course of a 14-day feeding experimentby radiographic measurements of calcification would be about1/400,000 mg., i.e., a total in 14 days of 3-5 x g.Multipliedby the above figure of 55%, the result, 1.9 x g., representsthe amount of the smallest dose of the pure vitamin detectable bythese workers’ methods. In their own words : “ This is in almostludicrously close agreement with the value (2 x g.) found byFosbinder, Daniells, and Steenbock and by Coward. . . .” 11 Aninvestigation somewhat similar to the foregoing has been carriedout by C. E. Bills, E. M. Honeywell, and W. M. Cox,12 and wasreferred to in the Report of last year. The results agree with thoseof Bourdillon and his associates, and also with those of G. Tixier,13in not associating the maximum antirachitic activity developedduring irradiation with the substance responsible for the absorptionband of shorter wave-length (240-253 pp).There is some evidencefhat a certain degree of antirachitic potency can be developed inergosterol by irradiation with soft X-rays.14 The activation is notascribed to the production of ultra-violet radiations by the X-rays.The change in the absorption spectra of the irradiated product isthe same as that produced by ultra-violet irradiation.Another mode of attack on the problem of the nature of vitamin-Dis that of 0. Rosenheim and N. K. Adam,15 who have investigatedthe unimolecular films formed on water by the irradiation productsof ergosterol, and find them to resemble those of certain ketoniccholesterol derivatives, The results are expressed by plottinghorizontally the areas per molecule in square hgstrom units againstthe lateral compression of the films in dynes per cm., plottedvertically. Ergosterol itself gives the steepest curve, followed bySubstance A (vitamin-D), Substance B, Substance C, and oxy-cholestenone with curves of decreasing steepness in the order given.Oxycholesterylene (A4: 6-cholestadiene-%one) gives a curve veryAnn. Reports, 1928, 25, 274. 12 Ibid., p. 273.l3 Compt. rend., 1929, 188, 206; A., 359.14 A. Knudson and C. N. Moore, J . Biol. Chem., 1929, 81, 49; A . , 359;l6 Proc. Roy. SOC., 1929, B, 105, 422.I%. Delaplace and G. Rebidre, Compt. rend., 1929, 188, 1169; A., 727BIOCHEMISTRY. 251closely approximating to that of the vitamin and the ultra-violetabsorption spectra of the two substances are very closely similar,and of intensity about twice that of ergosterol. Oxycholesteryleneis, however, devoid of antirachitic properties both before and afterirradiation. The lability of the hydrogen of the secondary alcoholgroup is considered to be the controlling factor of the changes inducedby ultra-violet irradiation of ergosterol, and it is suggested that thevitamin may have to be looked for amongst the ergosterol deriv-atives formed as by-products in the production of the ketone.Despite its failure to solve the problem of the nature of vitamin-D,the method used by Rosenheim and Adam is one of fascinatingingenuity.Hypervitaminosis.-It is now recognised that very excessive dosesof irradiated ergosterol or other preparations rich in vitamin-D mayexercise it very damaging influence on the growing animal. Theproblem arises purely from the fact that very potent preparationsof vitamin-D are available, and is not likely to be encountered in awell-balanced normal diet. Attention was first directed to thisproblem by Pfannensteil16 and by H. Kreitmair.17 L. J. Harrisand T. Moore18 find that young rats lose weight and die ona synthetic diet containing 0.1% of irradiated ergosterol. Someindication was obtained that a considerable increase in the allowanceof vitamins-B and -C served to alleviate the condition. It wasfurther shown that the lethal dose of irradiated ergosterol becomesnon-toxic concurrently with the destruction of vitamin-D by over-irradiation. In a later paper Harris and Moore l9 show that themanner of irradiation does not influence the severity of the effectsand find that excessive doses of ergosterol irradiated in alcohol, inoil, or in the absence of any solvent produce specific ill-effects.L. J. Harris and C. P. Stewart 2O find that a synthetic diet containing0.1 yo of irradiated ergosterol produces a marked rise in the inorganicphosphate of the blood and a considerable rise in the serum calcium.The former effect is eventually obtained even in adult animals,although in these the serum calcium does not increase. A generalpost-mortem finding as a result of " hypervitaminosis " is the wide-spread occurrence of abnormal deposits of calcium throughout thebody, particularly in the vascular system, spleen, kidney, liver, andlungs. J. A. Collazo, P. Rubino, and B. Varela 21 and F. Holtz andT. von Brand22 have obtained somewhat similar results on admin-16 Klin. Woch., 1927, 6, 2310.1 7 Munch. med. Woch., 1928, 75, 637; A., 1928, 1406.18 Bwchem. J., 1928, 22, 1461; A., 105.21 Biochem. Z . , 1929, 204, 347; A., 476.28 2. physiol. Chem., 1929, 181, 227; A., 611.Ibid., 1929, 23, 261; A., 610. 2o Ibid., p. 206; A,, 610252 ANNUAL REPORTS ON THE PROGRESS OF OHEMISTRY.istering excessive doses of “ vigantol,” a potent preparation ofvitamin-D. The last -mentioned investigators, however, appear t ohave some doubt concerning the origin of the effect and consider thatit may not be due to “ hypervitaminosis ” but to a toxic impurity inthe “ vigantol.” J. C. Hoyle and H. B~ckland,~~ giving 1% ergo-sterol, irradiated in oil, found no lethal effect for a period of morethan 50 days. No persistent or marked loss of weight occurred,but urinary calculi were found post-mortem. It seems probable tothe Reporter that considerable variations in the final effect of exces-sive doses of irradiated ergosterol may be related to the balance ofother dietetic factors. Indeed, J. B. Duguid, M. M. Duggan, andJ. GoughZ4 find that the calcification effects in the muscular andvascular systems described by Kreitmair and Moll are most readilyobtained when the irradiated ergosterol is administered along withan otherwise vitamin-free diet although it is possible that factorsother than the absence of the other vitamins, e.g., the calciumcontent of the diet, may be in part responsible for the observedeffects.A. C. CHIBNALL.J. PRYDE.23. Biochem. J . , 1929, 23, 558; A., 853. 24 Private communication

ISSN:0365-6217    

DOI:10.1039/AR9292600205

出版商:RSC    

年代:1929

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY.THE new X-ray methods for the investigation of the structure ofcrystals have given a great and welcome impetus to the moreintensive study of minerals. The numerous workers, who are nowattacking the many problems by these methods, may be dividedinto two schools. Physicists, naturally looking a t the matter froma physical point of view, are apt to regard each mineral species as adistinct individual-they speak of " this crystal " ; and they areusually content to copy from the text-books data for the molecularweight and density on which to base their calculations, regardlessof the fact that these may have been determined by mineralogistson different types of material from separate localities, and differentagain from the material that is being examined afresh by the X-raymethods.The mineralogist, on the other hand, is apt to treat theempirical formula of the text-books with less respect, and, beingless familiar with the X-ray data, he has more faith in the resultsof the physicist. He thus attempts to manipulate the chemicalformula to fit the X-ray data, whereas the physicist adjusts theX-ray data to fit the formula. A notable exception to such pro-cedure is mentioned below for tremolite in the amphibole group.To correct the long-accepted and apparently simple formula for acommon rock-forming mineral is a great triumph for the newX-ray methods.Minerals have grown under such varied conditions that we cannotassume two crystals of the same species to be exactly alike, unlessperhaps they grew side by side in the same rock cavity.Eachcrystal has, in fact, its own individuality. It is therefore imperativethat the material should be examined not by a single method, butalso by other methods, and further, on the same sample of material.For this reason many of the isolated determinations-chemical,physical, or X-ray-now published are practically useless for thepurpose of any future correlation of data.Constitution of Silicates.The atomic structures of a considerable number of silicate mineralshave been worked out in detail by X-ray methods by W. L. Braggand his co-workers at Manchester. These include beryl, phenakite,olivine, monticellite, the humite group, zircon, topaz, staurolite,kyanite, fibrolite, andalusite, diopside, and tremolite.Generalcollected accounts of this important mass of work have been give254 A ~ K L REPORTS ON THE PROGRESS OF CHEMISTRY.by him.1 Models have been constructed to represent all thesestructures, and a series of stereoscopic photographs of these andother models has been issued in conjunction with Sir WilliamBragg.2 Two-dimensional pictures of such structures viewed in theusual way often seem to be a mere confused assemblage of balls androds, but when viewed in the simple folding stereoscope suppliedwith the photographs they stand out in the solid with remarkableclearness.A large number of silicates have also been examined by X-raymethods by B. Gossner and his co-workers in Munich. Here, inmany cases, the chemical composition and the density have alsobeen determined on the same sample of material.The object ofthis work has been, not so much to determine the minute structure,but to deduce a chemical formula corresponding with such amolecular weight that a whole number of complete molecules shallbe accommodated in the unit cell. The minerals already examinedinclude zunyite, leifite, phenakite and dioptase, nepheline, benitoite,scapolite and melilite groups, apophyllite, cordierite, kornerupine,sapphirine, nep tunite, epididymi t e and eudidymit e, t hor tveitite ,rhodonite, babingtonite, and several members of the amphibolegroup. A brief general account of a, portion of this work has beengiven by G~ssner.~With the object of testing the exactness of the stoicheiometricratios in some common silicate minerals, B.Gossner * and hispupils have made careful analyses in duplicate on specially selectedmaterial. I n four specimens of olivine from different localities theratio SiO, : RO varied from 1 : 1.93 to 1 : 1.99, showing a slight *excess of silica over that required by the orthosilicate formula; butwhen the small amount of water (expelled only at 1100") is includedwith the bases the silica shows a slight deficiency, SiO, : RO thenvarying from 1 : 2-00 to 1 : 2.05. Three analyses of almandine gavethe ratios R,O, : RO : SiO, = 1 : 2.61 : 2-66, 1 : 2-61 : 2.71, and1 : 2.54 : 2.69, showing in all cases an excess of both alumina andsilica over that required by the garnet formula R,03,3R0,3Si0, or3SiO,Fe,Al,O,.The excess of alumina is explained by the iso-morphous replacement of Al, for SiFe (or M,O, for FeSiO,) to theextent of 3 mols. %; and the excess of silica over that required forthe RSiO, portion of the formula may perhaps be explained by itsfilling in odd spaces in the crystal structure, or perhaps by an iso-morphous replacement of silica and aluminium, which differ onlyPTOC. ROY. SOC., 1927, [A], 114, 450; A., 1927, 601; Proc. Roy. Inrrt.,1927,25, 302; A., 1927, 1015; l"ran8. Faraday Soc., 1929,25,291; A., 749.First series, 1928 ; second series, 1929 (Adam Hilger, Ltd., London).Ber., 1928,61, [B], 1634; A., 1928, 1172.4 2. angew. Chem., 1929, 42, 176MTNERALOUICAL CHEMISTRY. 255slightly in their atomic radii. An analysis of water-clear sanidineshowed, on the other hand, a deficiency in silica, namely 1.077 mols.instead of 1.128 required by the felspar formula.In certain silicate minerals the small amount of water (1 or 2%),which is expelled only at high temperatures (about lOOO"), presentsa difficulty in arriving a t a satisfactory formula.Such water hasoften been ignored, being regarded as adsorbed, or present as anadventitious impurity, or due to the incipient decomposition of themineral. Cases are noted below under amphibole and beryl; andother examples are given by topaz, cordierite, kornerupine, staurolite,etc. It is noted that the X-ray analysis of tremolite now definitelyrequires the addition of this water in the structure, while apparentlyin beryl (W.L. Bragg, 1926) the structure can be explained withoutit. Olivine, always regarded as an anhydrous orthosilicate, alsoappears to contain some water. B. Gossner 5 has made specialtests for water in perfectly fresh olivines from six 1ocaJities andfound 0.78-1-07% ; later tests 4 on four more olivines showed0.79-0-83~0 of water, which is expelled only a t 1100". M. Aurous-seau and H. E. Merwin 6 find only O-lS% of water in olivine fromHawaii.A recently published book by W. Eitel, " Physikalische Chemieder Silikate " (Leipzig, 1929), deals more especially with the glassyand crystalline conditions of silicates, systems of equilibrium, andthe bearing of these on technical problems.gives a long series of sixty-onechemical analyses, together with density and optical determinationsfor various rock-forming members of the amphibole group.Thematerials were separated by heavy liquids in a centrifugal apparatusfrom the finely powdered rocks. Seven isomorphous series are dis-tinguished, and these fall into two groups, namely, those ( 1 4 )from crystalline schists and those (5-7) from igneous rocks.( 1 ) Anthophyllite, H,Mg ,Si,O,,-Griinerit e, H,Fe ,Si 8024.(2) Tremolite, H,Ca,Mg,Si,O,,-Actinolite, H2Ca,Fe,Si,024.(3) Glaucophane, HJYa,Mg&SSi,O,,-Riebeckite, H,Na,FeII,Fe~,Si(4) Glaucophane, H,Na2Mg&l,Si,0,4-Tremolite, H,Ca,Mg,Mg,Si,O,,.( 5) Cpmmon green hornblendes H,~a,Mg4~,Si,0,z-H,Ca,Fe,A1,Si,0,z.tremolite-actinolite molecules) 11 H,Ca,Mg,Si,0,,-H,Ca,Fe,Si80,4.(rmstures of syntagmatite andcluding pargasite and basaltic H,Ca,Mg,Al,Si,O ,,-H,Ca2Fe4A1,Si ,O 22.(6) Syntagmatitic hornblendes (in-hornblende)inite, hastingsite, katophorite, H,Na,Mg4Si,0,,-H,Na,Fe,Si,0,,.arfvedsonite)Amphibole Group.-W.Kunitz1I (7) Alkali-iron-amphiboles (imer-Centr. Min., 1926, [A], 307.Arner. Min., 1928, 13, 559.JahTb. Min., BeiLBd., 1929, [A], 60, 171256 AN”& REPORTS ON THE PROGRESS OF CHEMISTRY.In several of these series the density and refractive indices showa regular increase with increasing iron content. In the basaltichornblendes the refractive indices also increase with the percentageof titanium dioxide. The formulae written in the following manner :Anthophyllite.. ................................. [( SiO,) ,]H2Mg2Mg2Mg3T r e m o li te ....................................... [(SiWalH&aaMgaMg,Glaucophane .................................... [(SiO,) slH2Na2~2Mg3Syntagmatite ...................................[( Sio8) 6 (A102 )alHf,Ca2Mg&g2Arfvedsonite.. .................................. [( si08) 6(Sio!d)21H2Na2Mg2%2show more clearly the replacements of [NaAl] for [CaMg], of [NaSi]for [CaAl], etc. These isomorphous replacements are discussed inconnexion with the sizes of atoms, and whether hornblende, augite,or mica should separate from the magma under various conditions.B. Gossner 8 with F. Mussgnug and F. Spielberger have examinedvarious members of the amphibole group, chemically and by X-raymethods, with the idea of adjusting the formulae so that a wholenumber of complete molecules shall be contained in the unit cell.By the rotating-crystal method they obtain the following dimensionsfor the unit cell :a.b. c. Axial angle 8.Act inoli te ............ 9.91A 18.5A 6.36 A. 74O 24’Glaucophane ......... 9.72 17.89 6-37 74 50Basaltic hornblende 9.88 18.10 6-31 74 16Arfvedsonite ......... 9.87 18.31 5.33 9 9Barkevikite ......... 9.92 18-30 6.33 9 )Kaersutite ............ 9-86 18.17 6.39Aenigmatite ......... 10.02 14.73 8-12 101 ”68,a and yabout 90’.All these, with the exception of aenigmatite, show a close agree-ment, and they can be referred to the general formula (“ Bauplan,”or building scheme) Si,O,Mg,,Si,O,MgCa [i.e., the tremolite formulaCaMg,(SiO,),], with four molecules in the unit cell, or eight moleculesof the type R,Si,O,.Individual analyses are explained by theisomorphous mixing of a great variety of molecules derived byreplacement from these two part molecules. E”or example, Si,O,MgCamay be replaced by Si,o,Mg,, Si,O,Na,H,, %,06Na4, S i , o , ~ a ,and finally by A1,06Na&, ; whilst Si,o,Mg, changes with TiO,E‘e,,A1406, or Fe,O,. In an actual case, the arfvedsonite analysed isrepresented by the following molecules :0.190 Si20,Fe20.003 Fe40,0.007 Al,O,0.2000.066 Si,O,FeCa0.060 Si,O,Fe(NaH)0.01 1 Si20 ,Mn( NaH)0.063 Si,O,(NaH),0.020 Si,O,Na,0.200Jahvb. Min., Beit.-Bd., 1928, [A], 58, 213; Centr. Min., 1929, [A], 6; 2.K k t . , 1929, 72, 111; A., 1223MINERALOGIUAL CHEMISTRY.257Aenigmatite and cossyrite present a difficulty, and variousorientations of the crystals and alternative. formulae are tested.With the cell dimensions quoted above, the general formula thatappears the most probable is 6SiO,Fe,TiO,Fe, allowing for twomolecules in the unit cell, or seven molecules of the general typeR2Si206. Aenigmatite therefore does not strictly fall into theamphibole group. Similarly, rhodonite? babingtonite,1° and wol-lastonite do not conform with the monoclinic pyroxenes, whichcontain four molecules of R2Si206 in the unit cell, nor with the ortho-rhombic pyroxenes with eight molecules of R2si206.F. Machatschkill deduces a general formula for the monoclinicamphiboles as XY,(Si,Al),(O,OH,F),,, where X = Ca, Na, K, andY = Mg, Fen, Fern, Al, also Ti and Mn.The special cme discussedis based on the chemical analysis of a hypersthene-hornblende rockfrom Greenland, and after deducting 16% of hypersthene andneglecting small amounts of olivine and iron ores, the special formuladeduced for this hornblende isThe mutual replacement of atoms in the " X " and " Y '' groupsand of A1 for Si depends, not on their valencies, but on their sizesbeing such that they will fit into the crystal structure, with a certainaccommodation between different pairs, for example, A1 for Sitogether with OH for 0. The assumption of the replacement ofaluminium for silicon is made to account for the occasional deficiencyin silica below the metasilicate ratio; but it seems curious to thinkof aluminium taking the part of silicon in a silicate.Any variationshown by analyses from the ratio X : Y = 1 : 3 is further explainedby an interchange of atoms between these two groups. Obviouslyby shuffling atoms about in this way any analysis might be fitted inwith any formula.B. E. Warrenl2 has determined for tremolite from New Yorkthe cell dimensions a = 9.78, b = 17.8, c = 5.26 A. (a : b : c =0.550 : 1 : 0.295, p = 73" SS'), with two molecules H2Ca2Mg,(Si0,),in the unit cell. Except for the double length of the b-axis, thesedimensions are very close to those of diopside,l3 and with certainmodifications, the arrangement of the atoms is very similar in thetwo minerals. Tetrahedral groups of four oxygen atoms surroundingeach silicon atom are linked by shared oxygens to form endlesschains parallel to the vertical c-axis of the crystal. In tremolite(Ca,Na)(Mg,Ii'eLI,Fe")(AZ,Sil,)(O,,rOHI,).Q B.GossnerandK. Bruckl, Centr. Min., 1928, [A], 316; A., 495.lo B. Gossner andF. Mussgnug, ibid., 1928, [A], 274; A., 382.l1 2. Kriet., 1929, 71, 219.18 Ibid., 72, 42; Abs. Thwes Mass. Inst. Tech., 1929, No. 4, 74; A., 1130.la B. E. Wmen and W. L. Brctgg, 8. Krist., 1928,69,168; A., 1223.REP.-VOL. XXVI. 258 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.two such diopside chains are linked together and there are fourchains in the unit cell. The calcium and magnesium atoms, alllying on diad axes, are surrounded by eight and six oxygens respec-tively. Such a structure will accommodate only ten magnesiumatoms in the unit cell, and the two extra ones required by the usually-accepted formula CaMg,(SiO,), are replaced by four (OH) groups,which occupy the same space as four oxygen atoms.The newformula, requiring 2.2% of H20, agrees well with the best publishedanalyses when these are recalculated with small isomorphous replace-ments (Si,Al), (Mg'Fe), (Ca,Na,K), and (OH,F) ; but the presenceof water was not actually proved in the sample of material used forthe X-ray analysis. This crystal structure explains the fibroustexture of the mineral, which is very prominent in the amphibole-asbestos variety, and the prism-cleavage of 56".This new formula, H2Ca2Mg5(Si0,)8, for tremolite, deduced froma consideration of the crystal structure as determined by X-raymethods, is identical with that arrived at independently and byquite another method by W.Kunitz (see above), and it seems to befully established. The apparently simple formula CaMg,(SiO,), forthis common rock-forming mineral has been familiar in the text-books since the third edition (1850) of Dana's < < System of Miner-alogy." P. A. von Bonsdorff in 1821 found about 1% of fluorineand water in tremolite; Penfield and Stanley (1907) found 2.03y0;Allen and Clement (1908) 2.31-3.04%; and W. Kunitz (1929)1.97-2.28y0 in actinolite. This water is expelled only at tem-peratures up to 1000". Penfield and Stanley accounted for it,partly in a bivalent group RIIIO(F,OH),, and partly as acid hydrogenin their general formula H,Si,O,, for the " amphibole acid," whichwas supposed to have a controlling influence (<' mass effect ") onthe isomorphous replacements.Allen and Clement regarded thewater as " dissolved " in the crystal and not chemically combined.The new formula appears to have been first given by P. Niggli inthe second edition of his " Lehrbuch der Mineralogie " (1926, vol. 2,p. 468), where, after quoting the usual formula, he remarks thatpart of the magnesium is almost always replaced by hydrogen andthat many analyses agree wellwith the formula [Si04,Si02],Ca2Mg5H,.In a rather more obscured form it was earlier given by B.Gossner l4 as [2Si0,Ca,4Si0,Mg],[ZSi02,Mg02H2], which reduces toS. K8zu15 has found that when common hornblende is heated tol4 2.Krist., 1924, 60, 364.l6 S. KBzu, B. Yoshiki, and K. Kani, Sci. Rep. TGhoku Imp. Univ., 1927,* Note added in proof.-The formula 8Si0,,5Mg0,2Ca0,H20 was suggestedH2c?&5si8024.*[3], 3, 143.by W. T. Schaller, Bull. U.S. Geol. Surcey, 1916, 610, 136; A., 1916, ii, 631MINEIEBLOQIOllL OHEMISTRY. 259750" there is a marked contraction in volume and a sudden changein the optical constants, the material being then changed into thehigh-temperature modifkation corresponding with basaltic horn-blende. This change appears to be of some structural significance.ApopFyylZite.-New analyses of apophyllite from various localitiesby B. Gossner and 0. Kraus16 show that small amounts of fluorineare invariably present. A new formula is written in the form4[H,Si,05,Ca( OH),],KF, in which part of the fluorine is replaced byhydroxyl and a small amount of potassium by sodium.The watercommences to be lost only at 245' with a destruction of the crystalstructure, and it does not behave like water of crystallisation orzeolitic water. X-Ray examination gives a unit tetragonal cell ofdimensions a = 12.73, c = 15.84 8., containing four molecules.The pronounced optical anomalies are explained by the partialreplacement of fluorine by hydroxyl, the difference in volume ofthese constituents causing a strain in the crystal structure.Andalusite, Bibrolite, and Kyanite.-These trimorphous aluminiumsilicates, though very different in their physical characters, arefound by X-ray analysis to have much the same size of unit cell,containing in each case four molecules Al,Si05.In the followingtable of the cell dimensions those of topaz are added for comparison.Andalusite 1' ......... 7-76 A. 7.90 A. 5-56 A. Vk2Fibrolite la ............ 7.43 7.58 5.74 VYKyanite lo ............ 7.09 7.72 5.56 ?9 , 2o ............ 7-122 7-883 5.650 PTopaz *l ............... 4.64 8.78 8.38 V?These minerals, which with the exception of kyanite are allorthorhombic, show several curious relations that have not yetbeen elucidated. Andalusite has a certain crystallographic relationto topaz ; and the manganiferous variety " viridine " has on opticalgrounds been regarded m a distinct species. Fibrolite also has apeculiar satellite " mullite," the structure of which cannot bedistinguished from that of fibrolite.The chemical formula A16Si,0,,l6 2. Krtkt., 1928,68, 596; A., 1036.l7 W. H. Taylor, &id., 1929, rl, 205.la Idem, ibid., 1928, 68, 503.l@ W. L. Bragg and J. West, Proc. Roy. Soc., 1927, [A], 114, 450; A., 1927,601; W. H. Taylor and W. W. Jackson, ibid., 1928, [A], 119, 132; A., 1928,693; S. Nhay-Szab6, W. H. Taylor, and W. W. Jackson, 2. Kwkt., 1929,71,117.C. M. Cardoso, j'ortschr. Min. K ~ t . Petr., 1927, 12, 18; Ber. 8iiCh.a.Akad. Wise., 1928, 80, 165; E. Schiebold and C. M. Cardoso, PoTtSchr. Min.K&t. Petr., 1929, 13, 61.21 N.A. Alston and J. West, Proc. Roy. SOC., 1928, [A], 121, 358; 2. KI-ist.,1928,6S, 149; A., 16.a. b. c. Space-group260 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.assigned to " mullite " is explained as perhaps due to the partialreplacement of silicon atoms by aluminium atoms in the fibrolitestructure.18 In the triclinic kyanite the angles between the crystallo-graphic axes and the edges of the unit cell are cc = 90" 5&', p = 101" 2',y = 105" 44q' ; but other axes can be chosen, all approximately a tright angles, namely, a = 90" 54', = 90" 5', y = 90' 27', the dimen-sions of this pseudo-rhombic cell being a' = 264368, b' = 7.883,c' = 5.650 A.This corresponds with a slightly distorted close-packed cubic structure marked out by the oxygen atoms. Oxygenatoms are grouped tetrahedrally around the silicon atoms, and octa-hedrally around the aluminium atoms, as in topaz (p. 265) andstaurolite (p.265).Beryl.-A set of detailed analyses 22 made on beryls of differenttypes shows considerable deviations from the usually acceptedformula Be3Al,Si,01,. The pink tabular crystals of the " rosterite "variety from Elba contain appreciable amounts of alkalis (Li200-43, Na20 4.22, &O 2.25, Cs,O 0.91yo) together with water 0434%." Emerald " from Colombia gave less alkalis (O-SS%), but more water(1*84y0), together with Cr203 0.077y0, accounting for the colour ; andclear blue " aquamarine " from Siberia gave alkalis 1-04y0, water0-98y0. The variations in composition are explained by assumingmixtures with the main molecule Be3A1,Si,0,, of molecules R,Si03and R,Al,Si,O,, where R, is Li,, Na,, I$, Cs,, together with some Be,Cay Mg. Small amounts of alkalis and water have also been foundin beryl from Japan.23Certain transparent green beryls when heated to 400450'change in colour to blue ; 24 and this is now much used in the tradefor improving the colour of these gem stones.Epididymite and Zudidymite.-These rare dimorphous mineralswith the composition HNaBeSi308 are found by X-ray methods tohave unit cells of very nearly the same dimensions :a.b. c. Mol. vol. Space-group.Epididymite 25 ... 12.65 A 7.41 A 13.53 A. 168.5 v?Eudidymite 26 . . . 12-70 7.34 14-0 1 159-3 GhIn each case the unit cell contains eight molecules and the arrange-ment of the atoms is probably much the same. There is, however,a wide difference in the axial angle, epididymite being orthorhombic22 F. Zambonini and V.Caglioti, Cfazzetta, 1928, 58, 131 ; A., 1928, 731.23 T. Uemura, Japan. J . Chem., 1926,2,117; A., 1928, 1211; J. Yoshimura,24 J. Kurbatov and W. Kargin, Centr. Min., 1927, [A], 361 ; A., 1928,730.25 B. Gossner and F. Mussgnug, Batschr. V . BoZcEBchmidt, Heidelberg, 1928,Bull. Chem. SOC. Japan, 1926,1, 239 ; A., 1927, 129.117.B. Gossner and 0. &&us, Centr. Min., 1929, [A], 267MINERALOGI(3AL CHEMISTRY. 261(p = 90")degree ofP-quartz.Pekparand eudidymite monoclinic with p = 77" 26'. This lowpolymorphism is somewhat similar to that of a- andG%oup.--E'. Machatschki 2' points out that W. Wahl'sco-ordination formulae (Ann. Reports, 1927, 24, 294) for albite[Al,(Si0,),(Si,06)2]N~ and anorthite [Al2O2(SiO,),]Ca do not explainthe isomorphism of this pair of minerals in the series of plagioclasefelspars.As the fundamental unit of silicate structures, he takes atetrahedral group of four 0 - 2 ions around a, Si+4 ion. Aluminiumwith 0 - 2 may have a co-ordination number 4 or 6, and when 4it may take the place of silicon in the tetrahedral group of oxygens.Similarly, Be+2 and perhaps B+3 may also occupy this position.Since tetrahedra, cannot fill space, the cavities between them maybe occupied by the metal ions. In the felspar type of silicatestructure (where Si + Al : 0 == 1 : 2) every oxygen ion is commonto two adjaaent tetrahedra, and the " formulae " are writtenAlbite ... [gj$)3]-'Nat1.Formulae on similar lines are also suggested by Machatschki forthe metasilicates and the orthosilicates.In his " metatype," withSiO, or NO,, two oxygen ions are in common for adjacent tetra-hedra, and an endless chain (similar to that deduced by 13. E. Warrenand W. L. Bragg for the pyroxenes and amphiboles, p. 257) isrepresented byI 7 0 r% 00 0 I iI I " Metatype " . . . -Si-0-Si-0-Si-0-Si-0 Rn4 (or RI, RTI1,).0In his " orthotype " there is no linking of oxygen ions in adjacenttetrahedra, and here separate molecules can exist, the formulabeing then of the ordinary co-ordination kind." Orthotype " ... . . . . . . [:>EX<:] -4R112 (or RI RL1.1).In the " felspar type " and the " metatype " the structures arecontinuous and there are no separate molecules. These are the'' open structures " of W. L.Bragg and J. West,28 which includequartz, beryl, phenakite, etc. For beryl, the metatype formula iswritten as [(Si02),(Be0,),]-6 A.l+3Al+3.The unit cell dimensions of the various felspars, as determined byCentr. Min., 1928, [ A ] , 97; A., 1928, 1349.Pm. Roy. Soc., 1927, [A], ll4,469; A., 1927,601262 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.E. Schiebold,dg are tabulated below. The base-centred cell containsfour molecules KAlSi,O, (orthoclase), NaAlSi,O, (albite), orCaAl,Si,O, (anorthite). In the plagioclase felspars, the substitutionof Na-Si for CeA1 in passing from albite to anorthite is accompaniedby a small contraction of the lattice, the greatest variation being inthe c-axis. The change of the molecular volume is, however, notan exact linear function of the chemical composition, there being amaximum at the albite-anorthite mixture 1 : 1, corresponding withlabradorite. The entry of potassium causes a considerable enlarge-ment of the lattice dimensions, the a-axis showing the greatestchange whilst the c-axis is here little affected.The X-ray examina-tion emphasises the pseudo-cubic character of the felspars, and thestructure can be considered as based on a close-packed arrangementof 32 oxygen atoms.Adularia . . . . . .Sanidine . . . . . .Microcline . . . . .Hyalophane.. .Albite .... . . . . .Oligoclase . . .Labradorite.. .Anorthite ...a.8.6lA.8.428.448-608-238-168-238.185b. C.13.07A. 7.26.A.12.92 7.1413.00 7.2112.92 7.1213.00 7-2612.90 7-1312.91 7.1612.895 7-09a.90" 0'90 090 790 094 393 493 3193 13B- Y.116" 3' 90" 0'116 35 90 0115 50 89 65116 35 90 0116 29 88 9116 22 90 4116 3 89 67116 65 91 12The felspars have been studied from many points of view.Theyare important constituents of most kinds of igneous rocks, and theclassification of such rocks is in part based on the kind of felspar thatthey contain. Ready means for the determination of the felsparsare therefore needed. Graphs plotting the variation of the variousoptical data with the chemical composition are given in thetext-books on petrography and rock-forming minerals. The severalgraphs of refractive indices and chemical composition have beenexamined critically by H. L.Alling,3O and collecting together thedata on which these have been based, he finds that in many casesthey depend on old and untrustworthy chemical analyses, and thatthe optical data have not always been determined on the materialactually analysed. Much attention has been paid to the deter-mination of the felspars by the Fedorov method with the aid of theuniversal microscope stage. The felspar in a thin rock-slice iscovered with a glass hemisphere of nearly the same refractive indexas that of the mean of the mineral, and it can be brought into anydesired position by rotation about three axes a t right angles, theseaxes being provided with graduated circles. By this means thes9 Fortschr. Min. Krist. Petr., 1927, 12, 78; 1929, 14, 62; Tram. Famday30 J .cfeol., 1929, 37, 462.SOC., 1929, 25, 316; A.4749MMERA.LOB1CA.L CHEMISTRY. 263different types of twinning, the orientation of the three principaldirections of vibration, and the optic axial angle can be determinedand plotted on graphs. This method has been largely developedby L. Duparc and his pupils in Geneva, and a summary of recentwork is given in " Mineralogical Abstracts." 31m e felspar diagram orthoclase-albite-anorthite has been studiedin detail by J. H. L. V ~ g t . ~ ~ Various equilibrium diagrams are given,and he tabulates the Or : Ab : An ratios in the rock, in the separatedfelspam, and in the residual magma. Finally, the felspars have beenstudied from the point of view of their application in ceramics,enamel-ware, etc.,,Melilite &mp.-The following X-ray data have been determinedby B.Gossner and F. Mussgnug : 34Mols. in unit cell. a. C.Gehlenite . . . 4 Mols. SiO,Ca,,Al,O, 11.11 A 5.06 A.Melilite ...... 4 Mols. CaO,Si,O,CaMg 11-12 6-09Sarcolite .... . . 6 Mols. Si,08AlNa,Si,08A1,Ca,3Crt0 17.6 15-59Gehlenite and melilite, both with the space-group D t , are thusclosely related, and their composition is expressed as mixtures ofthe molecules CaO,SiO,Ca,Al,O, (velardefiite), CaO,SiO,Ca,SiO,Mg(hkermanite), and CaO,SiO,NaSiO,Al, in which there may also bereplacements Al, = SiMg, CaMg = NaAl, and SiNa = AlCa. Onthe other hand, sarcolite, with space-group ch, is more closelyrelated to the scapolite group, and the composition is expressed asan addition compound of scapolite (3Si2O,Al2Ca,CaO) with 39Ca0.From a consideration of the published analyses of the mineralsiikermanite, humboldtilite, melilite, gehlenite, and sarcolite, H.Berman36 deduces a general formula for the whole group as(Ca + Na)Bo_zMgy~zSi30_(yt.1,070, where x = 0 to 3, y = 0 to 10,and x = 0 to 20.End members of the series are : Bkermanite,Ca,MgSi,O, ; gehlenite, Ca2A12Si07 ; soda-melilite, N%Si307 ; andsub-melilite, CaSi,O,.Mim Grroup.4. Jakob 36 has continued his work of laboriouslyanalysing a large number of micas, giving also in some cases opticaldata for the material analysed, but no density determinations.Since the last Report he has made 28 new analyses of muscovites and31 Min. Mag., 1928, Abatr., 3, 515.32 Skrifter Norske V'idensk. Akad., 1926, No.4.33 B., 1928, 53, 193, 263.34 Centr. Min., 1928, [A], 129, 167.s6 2. Krist., 1928,69,217; 1929, 69, 403, 511; 1929,70, 493; 1929, 72,327;Arner. Min., 1929, 14, 389.A., 1263264 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.phlogopites.are deduced for muscovite and phlogopite respectively :For individual specimens such formule as the followingW. Kunitz 37, seeing that some of his analyses do not check withthose of Jakob made on material from the same locality, has repeatedhis work and finds that calcium enters only occasionally in verysmall amounts into the composition of muscovite and biotite.The composition of the micas has been further discussed by A. N.Winchella and A. 3’. Hallim0nd,3~ the debatable points beingwhether the ratio K20 : SiO, is constant or not at 1 : 6, and whetherA120, replaces RO or MgSiO,.X-Ray examinationsof the micas have so far led to no definiteresults. The superposed lamella show rotations and oblique trans-lations and the data obtained do not appear to give the true crystallat ti~e.~ONepheZine.-J. Morozewicz 41 reviews recent work on the com-position of nepheline and adheres to the formula he proposed in1907, namely K2A12Si,010,nNa2A12Si208, where n is usually 4 butmay vary to 6.This is regarded as a double aalt rather than anisomorphous replacement of potassium and sodium. Four newanalyses of elzolite are in agreement with this formula. The rocksfrom which the analysed mineral was separated show a range ofsilica from 54.95 to 62-86%, and the K20 : Na,O ratio ranges from1 : 2.3 to 1 : 23.6.I n spite of this variation in composition of themagma from which the minera.1 crystallised, the K20 : Na20 ratioin the mineral varies only from 1 : 4 to 1 : 4-5.X-Ray examination of water-clear nepheline from Vesuvius byB. Gossner 42 gave a unit hexagonal cell of dimensions a = 10.05,c = 8-43 A,, and containing twelve molecules Na2A12Si20,. Etch-figures suggest that nepheline belongs to the hexagonal-pyramidalclass, whilst the other physical characters suggest the dihexagonal-bipyramidal class. The X-ray data point to the latter with the3 7 2. Krist., 1929, 70, 508.58 Amer. Min., 1927, 12, 267 ; 1928,13, 52, 567.39 Ibid., 1927, 12, 413; 1928, 13, 451.40 C.Mauguin, Compt. rend., 1928, 186, 879; A., 1928, 463; C. Mauguinand L. Graber, ibid., 1928,186, 1131; A . , 1928, 611; C. Mauguin, &id., 1928,187,303; A., 1928, 1077; C. Mauguin, Bull. Soc.fmng. Min., 1928,51,285.4 1 Bull. Amd. Polonaise, 1928, [ A ] , 111; A,, 46.42 Centr. N i n . , 1927, [ A ] , 150MINERALOGICAL CHEMISTRY. 265space-group C&. C. Gottfried 43 h d s a unit hexagonal cell a =10.09, c = 8-49 A. containing twenty-four molecules NaAlSiO,, andspace-group C;.XtauroZite.-The following X-ray determinations by differentauthors show a close agreement in the dimensions of the unit cell,but there are considerable differences in the chemical formula. Nonew analyses or density determinations have been made of thematerial examined.Mols.in unit cell. a. b. c. Space-groups.v;: (2) 45 4 Mols. HFeA15Si2013 7-81 16-59 5.64 v17( I ) 44 2 Mols. HFe,AI,Si,O,, 7.84 A 16-52 A 5-61 A.I (3) 46 4 Mole. H,FeA14Si,01, 7-82 16.52 5.63 VliISelecting fresh axes and another unit cell for kyanite, Cardosod5traces a relation between kyanite and staurolite for the purpose ofexplaining the regular intergrowth of these two minerals. N&ray-Szabb 46 also suggests a relation between the structures of kyaniteand staurolite, and supposes the staurolite structure to be representedby alternate slabs of Fe(OH), and BAl,SiO, (kyanite).Topaz.-A unit cell of dimensions a = 4.64, b = 8-78, c = 8.37 A.and containing four molecules [Al(F,OH)],SiO, was deduced byJ. Leonhardt in 1923 for topaz from San Luis Potosi, Mexico.L.Pa~ling,~' using the co-ordination theory of ionic crystals, assumedthe fundamental polyhedra for topaz to be an octahedron of oxygenand fluorine anions surrounding each aluminium ion, and a tetra-hedron of oxygen ions about each silicon ion. The structure sodeduced agrees with the data of Leonhardt. This has been con-h e d by N. A. Alston and J. West,48 who h d for topaz fromNigeria the unit cell dimensions a = 4.64, b = 8.78, c = 8.38 A.The close agreement in these figures for material from differentlocalities is remarkable when we consider that topaz may range inchemical composition from fluor-topaz (AlF),SiO, to hydroxy-topaz(AlOH),SiO, and in density from 3-35 to 3-65. Colourless to faintbluish or greenish crystals are abundant in the alluvial tin depositsof Northern Nigeria; but this material has never been analysedchemically. From determinations of the refractive indices (a =1-615-1.621, p = 1.622-1.628) and optic axial angle (2V = 64" 28'-65" M'), A.Schoep 49 concludes that these crystals are fluor-topazcontaining about 20% of fluorine.2. Krist., 1927, 65, 100. 44 C. Gottfried, ibid., 66, 103.46 Refs. as (20).47 PTOC. Nat. A d . Sci., 1928, 14, 603; A., 1928, 1176.48 Pmc. Roy. Soc., 1928, [A], 121,358; A,, 15; 2. Kmkt., 1928,69, 149.49 Natuurwetmach. Tijda., 1928,10, 3; A., 1928, 503.I 246 S. NBray-Szab6, 2. Krist., 1929, 71, 103266 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Tourmaline.-W. Kunitz 5O gives twenty new chemical analyses,together with density and refractive index determinations, fortourmalines from various localities.He divides them into twoseries : the dravite series of magnesium-iron tourmalines, and therubellite series of lithium-iron tourmalines ; and the chemicalcomposition is explained by the isomorphous mixing of the followingmolecules :( 1 ) Dravite molecule .................. 8Na2Mg6A112Si12B6062(4) " Uvite ,, ..................... H8Ca2Mg8A110Si12B6062(2) Schorl ,, ..................... H,Na2Fe,A~12Si12B,0,2(3) Rubellit:, ,, ..................... H,Na2[L~1],A112Sil,B,062(5) " Tsilaisite " molecule.. ............. H,Na2Mn,A112Si12B60,2(6) (Higher alumina). .................... H,Na2Fe,A11,SillB,0,2In most cases the composition can be explained by a mixture oftwo of these molecules : (1) and (2) for the dravite series, and (2)and (3) for the rubellite series.In both these series the density andrefractive indices show a regular increase with the increase of theschorl or iron molecule. In the dravite series the vertical crystal-lographic axis c shows a slight decrease with increasing iron content.The extra molecules (4), (5), and (6) are invoked to explain thecomposition of tourmalines richer in calcium (up to 5.35y0 CaO),manganese (up to 8.21% MnO), and aluminium. The lithium in therubellite molecule is quite distinct from the other alkali metals, andit forms a group [LiAl] replacing [MgMg], similar to the replacementof [ L a ] for [CaMg] in the pyroxenes and of [Li,Si] for [FeII], inthe lithia micas.These replaceable groups have the same sum ofthe valencies and nearly the same sum of atomic volumes. Theabove formulae are intended to express the close relationship betweenthe tourmalines and the micas.51 These minerals occur in intimateassociation in rocks, and tourmaline is often found altered to mica.3'. Machatschki 52 from a collection of published analyses deduces,on the same lines as he did for the monoclinic amphibolesand pyroxenes (p. 257), a general formula for tourmaline asXY,B,Si,H,O,,, where X = Cay Na, and some &I1, and Y = Li,Mg, Mn, Fey Al. Special formulae to fit particular analyses rangefrom Ca,(MgloA11,)B,Sil,Hlo093 to Na3(LiAl,,)BsSi,8H,0,,. FromX-ray rotation photographs he gets for different tourmalinesdimensions ranging from a = 15.81, c = 7.10 A.to a = 16.02,c = 7.22 8. for the unit hexagonal cell containing three molecules~ ~ s ~ 3 ~ i 6 ~ z ~ 3 ~ , but the number of atoms is too complex for anyattempt a t their grouping.50 Chem. Erde, 1929, 4, 208; A., 905.61 W. Kunitz, Portschr. Min. Krist. Petr., 1927, 11, 313; A . , 1928, 148.s2 2. Krbt., 1929, 70, 211267Hiscellanwus Minerals.Boleite and Cumengeite.-Preliminary results 53 of an X-rayexamination of boleite gave a cubic unit cell of edge 15.6 A. con-taining thirty-two molecules PbCl,,Cu(OH),. A new analysis ofcubo-octahedral crystals has given the formula3PbC12,3Cu(OH), ,AgCl,and further X-ray examination shows a unit cube of edge 15.40 A.containing nine such molecules.54 Cumengeite 54 occws as tetra-gonal pyramids on the six faces of cubes of boleite.Analysis gavethe formula 4PbC1,,4Cu(OH),,H20, and the cell dimensions area = 15-17, c = 24.71 8. Calculation gives eleven such moleculesin the unit cell, but this number does not agree with the body-centredstructure of space-group Dii. To fit the X-ray data there must beforty-four molecules P~CI,,CU(OH)~ in the unit cell. The closenessof the a dimensions of boleite and cumengeite allows of the parallelgrowth of these two minerals. The cubo-octahedral crystals ofboleite show only slight optical anomalies, and the so-called " cubicboleite " or pseudo-boleite occurring as simple cubes is distinguishedby a higher double refraction in its outer zones.Analysis and theX-ray patterns show that these are really identical, the surfacedifferences being evidently due to an intergrowth with cumengeite.Boracite.-X-Ray examination of boracite 55 throws a doubt onthe usually accepted formula Mg,CI&,O, (of w. Heintz, 1859).The rhombic-dodecahedra1 crystals are built up of twelve ortho-rhombic hemimorphic pyramids in such a manner that the twelve(100) faces give the external faces of the composite crystal. Theoptic axial plane is parallel to the longer diagonal and the polarc-axes are parallel to the shorter diagonal of a dodecahedra1 face.The positive ends of the polar axes are directed towards alternatepseudo-triad axes, and this gives rise to the well-known pyroelectricproperties of the mineral.X-Ray measurements gave for the unitcell dimensions of colourless crystals (d 2.92-2-97) a = b = 16.97,c = 12.00 8. ; and for greenish crystals (d 2.97-3.10) containingsome ferrous iron a = b = 17.11, c = 12-10A. This would giveseven (or 7.3) molecules of Mg,C1,BI6O,, in the unit base-centredcell, which from considerations of symmetry is improbable. A newanalysis leads to a formula Mg,5Cl,B,,0,,,; or more simplyMg,C12B1,0,,, eight (7.845) molecules of which can be accommodatedin the unit cell. It would be of interest to determine by X-ray63 B. Gossner, Amer. Min., 1928, 13, 580; A., 749.64 B. Gossner and M. Arm, 2. Krist., 1929,72, 202.65 J. W. Gruner, Amer. Min., 1928, 13, 481; Amer. J . Sci., 1929, [v], 17,453 ; A., 149268 m u m REPORTS ON THE PROQRESS OF OHEMISTRY.methods whether the structure is truly cubic at a temperature above265".Domeykite &oup.-The several copper arsenide minerals fromMichigan have been examined by X-ray methods and by themetallographic method on polished surfaces under the microscope.L.S. Ramsdell56 finds that domeykite (Cu,As) is a definite compound,but it gives a different X-ray pattern from that given by artificialCu,As obtained with fused mixtures of copper and arsenic; whenheated, however, it changes into a form corresponding with theartificial product. Algodonite (Cu,As) is also found to be 8 defmitecompound, although it cannot be prepared artificially in fusions ;when heated, it breaks down into a mixture of Cu,As and Cu-Assolution.Whitneyite (Cu,As) is a mixture of algodonite and theCu-As solutions. Arsenic up to 4% can be present in solid solutionin copper. F. Machatschki 57 finds, on the other hand, that bothalgodonite and whitneyite are mixtures of : (1) a cubic substancewhich appears to be metallic copper contaminated with arsenic andhas a lattice constant u = 3.647-3.651 8.; and (2) a compoundpoorer in copper than Cu6As, possessing the hexagonal type of close-packed structure with lattice constants u = 2.598-2.599, c =4-213-4.215 8.Fuhlerx Group.-X-Ray examination of tetrahedrite " fromHungary " by J. Palacios 58 gave a unit cell of edge a = 10.39 A.and containing eight molecules Cu,SbS,. W. F. de Jong 59 obtainedfor different specimens u = 10.190-10-555 A., with eight moleculesCu,SbS, in the unit cell.F. Machatschki60 also examinedmaterial from various localities and found for Cu-Sb fahlerz (tetra-hedrite) u = 10.32 A., which increases to 10.41 when much silverreplaces copper, and decreases to 10.19 in tennantite when arsenictakes the place of antimony in the formula R1,Rn1S3. These authorsare all agreed in rejecting the old formula 4Cu2S,Sb2S3, but they takeno account of the bivalent metals, principally iron and zinc, whichare almost invariably present in fahlerz. This mineral shows, infact, a wide range in chemical composition and in density; but notin a single case were these determined for the materials used for theX-ray analysis. V. V. Nikitin 61 points out a similarity in theatomic structure suggested by Machatschki for fahlerz with those ofchalcopyrite and zinc-blende; and he also emphasises the fact thatthese minerals are often found in parallel growth on crystals of5 G Amer.Min., 1929, 14, 188; A., 1264.5 7 Jahrb. Min., BeiZ.-Bd., 1929, [A], 59, 137.5 8 Anal. Pis. Quh., 1927,25, 248; A., 1927, 1015.6 9 Proefschrift, Delft, 1928.Go Norsk Cfeol. Tidsskr., 1928, 10, 23; Z. KTist., 1928, 68, 204; A., 1928,1080. 61 Z. Kmkt., 1929,69,482; A., 1263WNERALOCICAL OHEMISTRY. 269fahlerz, due to the similarity, not only of structure, but also ofmolecular volume. He makes the interesting suggestion thatmolecules of zinc-blende, chalcopyrite (CuFeS,), and perhapsmetacinnabarite (HgS), may be present in solid solution or even veryfinely disseminated in the fahlerz substance. This seems to afforda satisfactory explanation of the departure of analyses from theideal formula Cu,SbS,.Spinel.-Certain artificial gem spinels differ from ordinary spinelin containing a large excess of alumina over that required by thespinel formula MgAl,O,.These have been studied in detail byF. Rime 62 by all the available methods. Each pear-shaped dropis a single crystal and shows rounded faces of the cube, octahedron,and rhombic-dodecahedron, and the silky upper surface shows aminute reticulated crystalline pattern. The axis of the pear, corre-sponding with the direction of growth under the oxyhydrogen blow-pipe, usually coincides with a cubic axis of the crystal. X-Rayexamination by the Laue, rotating-crystal, and powder methodsshows no essential difference between these artificial spinels ofvariable composition and natural spinel; and the powder photo-graphs are the same as those given by y-Al,O,.The following tablegives a selection of the determined data :Composition. SI'. €3. nD. Edge a of unit cube.MgO,A1203MgO, 1-7A1,o3 3.604 1.7239Mg0,3-3A.l2O3 3.620 1.7272 7-96MgO, 4A120, 3.625 1.7284 7.92Mg0,6A1203 - 1.7288 7.913.577 1.7190 8.02 A. -The conclusion reached is that the material consists of a solidsolution or mixed crystal of y-Al,O, in spinel. When spinels thatcontain an excess of alumina are tempered for some hours at 800"they become cloudy and show a moonstone schiller and asterism,due, as shown under the ultra-microscope, to the separation ofminute particles. Tempered for longer periods, the stones becomeopaque; the Lauegrams then show two series of spots, and thinsections under the microscope show a regular network intergrowthof spinel and corundum.This change is accompanied by an increasein density from 3.62 to 3.81, corresponding with the inversion ofy-A1203 to a-A1203 (corundum).Sources of Supply of the Less Common Elements.Practical uses for more and more elements are gradually becomingknown. Detailed accounts of the modes of occurrence and the62 JaM. Min., BeiLBd., 1928, [A], 58, 43; A., 1928, 730. See also P. F.Ken, Amer. Min., 1929.14, 269270 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.precise localities where the rarer minerals have been found, often bychance, have been recorded in mineralogical literature in a more orless haphazard manner.When any particular element is discoveredto have some economic application, there is an immediate call forit, and the mineralogical records, if made available by suitableindexes, should then be of some use. Even for the abundantelements, such as aluminium, a knowledge of the various modes ofoccurrence and distribution of its several minerals, such as cryoliteand bauxite, is of importance.For the elements already in practical use this aspect of the subjectis dealt with in several books on economic geology and ore deposits.A book collecting together the scattered information on the geo-chemical distribution of the chemical elements has recently beencompiled by G.Berg, “Vorkommen und Geochemie der mineral-ischen Rohstoffe ” (Leipzig, 1929) ; and another dealing more withgeneral principles by F. Behrend and G. Berg, ‘‘ Chemische Geologie ”(Stuttgart, 1927).Beryllium.-In view of the possible use of light and strong alloysof aluminium and beryllium in aeronautics, there have been manyinquiries for sources of this element. Beryl, the most abundantberyllium mineral (Be about 5%), usually occurs as isolated crystalsin certain pegmatite veins, large crystals being occasionally found inthe felspar quarries of the south of Norway, and larger crystalsweighing one or two tons have been found in New Hampshire. Arecent find of large crystals is reported from Namaqualand, SouthAfrica, and a beryl deposit is worked for emeralds of gem quality inthe Leydsdorp district, north-eastern Tran~vaal.6~ A new find ofmassive white beryl, apparently in considerable quantity, is reportedin the Masull ravine, near Merano in Trentino.64 Other mineralscontaining a higher percentage of the metal, namely, hambergite(Be 19yo), phenakite (16&y0), bertrandite (15y0), beryllonite (7%),chrysoberyl(7 yo), and euclase (Syo), are of more sparing occurrence ;while bromellite, Be0 (Ann.Reports, 1925,22,277), is known only asa few minute crystals. The old felspar quarry near Pisek in Bohemia,which has yielded a variety of beryllium minerals, has recently beenreopened.65 A list of localities where beryllium minerals have beenfound is given by M.Hosenfeld.66Bromine.-Carnallite from Solikamsk, govt. Perm, Russia, con-tains 0.17--0.30% of bromine, apparently present as a double saltJ. M. Le Grange, Truns. Beol. Xoc. S. Africa, 1930, 32 (for 1929).64 E. Dittler, Tsch. Min. Petr. Mitt., 1929, 40, 188.65 J. V. hlizko, Viistnik Stdniho Geol. 08tuvu ~eakoslovenskd Repbliky,1928,4, 23.6% Was. Ye~6.f. S~~TWPW-KOWZ., 1929,8, [l], 21 ; B., 722MINERALOGICAL CHEMISTRY. 271KCl,MgBr,,GH,O. Large amounts appear to be available.67 Apamphlet on the production and occurrence of bromine has beenissued in the series '' The Mineral Industry of the British Empire andForeign Countries " (Imperial Institute, London, 1928).Ccesium-The main source of caesium, now used in thermionicvalves, is the mineral pollucite ( C S , ~ 34%).This has been producedin some quantity from the felspar quarries in pegmatite a t Andoverand other localities in Maine, U.S.A.6* In general appearance,pollucite is very similar to quartz, and perhaps it has been over-looked in some other pegmatites. Other caesium-bearing mineralsare cEsium-beryl, rhodizite, and lepidolite ; the last, when minedfor lithium, may come to be of importance as a source of cesium.Lepidolite from South-West Africa was found to contain Cs,O 0.60y0with Rb,O 1-73y0.69Germanium-Many minerals have been examined spectro-graphically for germani~m.~o Traces were found in the tin orescassiterite and stannite, in zinc ores, native copper, and varioussilicates. Apart from the germanium mineral argyrodite, andgermanite, the largest amount (0.1%) was found in enargite fromMexico.Gallium.-Various minerals have been examined spectro-graphically for gallium. Lepidolite from California 71 yielded0-007~0 of the metal, and a green kaolin 72 from Japan had contentsof the order 0~0004-@004%.Hafnium.-A review of the mineralogy of hafnium has been givenby 0.I. Lee.73 I n zirconium minerals the ratio HfO,: ZrO,vanes from 0.007 to 0.5 with an average of O*02.74 In zircon, thecontent of hafnium appears to increase with the radioactivity (dueto traces of thorium and uranium), and altered zircons (alvite andcrytolite) are richer than unaltered.Iodine.-In small amounts iodine is of wide distribution (Ann.Reports, 1927, 24, 294).It is recorded (I 0.13y0) in the salineencrustations of V e s ~ v i u s , ~ ~ in the gases escaping from various67 N. N. Efremov and A. A. Veselovski, J . CAem. Ind. Moscow, 1928, 5,88 E. E. Fairbanks, Amer. Min., 1928,13, 21.6 0 J. Jakob, Schweiz. Min. Petr. Mitt., 1927, 7 , 139; A . , 45.' 0 J . Papish, F. M. Brewer, and D. A. Holt, J . Amer. Chem. SOC., 1927, 49,71 J. Papish and D. A. Holt, J . Physical Chcm., 1928,32, 142; A., 1928,265.72 S. Iimori, Sci. Papera Inst. Phys. Chem. Res. Tokyo (Supplement), 1929,1365 : A . , 1163.3028; A., 1928, 146; J. Papish, Econ. Geol., 1928, 23, 660; 1929, 24, 470.10, No. 8; A., 420.Chem. Reviews, 1928, 5, 17.74 G. von Hevesy and K. Wiirstlh, 2. physikal. Chem., 1928, 139, 605; A.,75 L.Coniglio, Ann. R. Oscsematorio Vesuviano, 1925, [iii], 2, 123.288272 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.mineral springs,76 and in rock phosphate^.'^ A pamphlet on theproduction and occurrence of iodine has been issued in the series" The Mineral Industryof the British Empire and Foreign Countries "(Imperial Institute, London, 1928).Lithium.--Lithium minerals, lepidolite, spodumene, and ambly-gonite, are found in considerable quantities at several places in theOiseau River district in Manitoba.'8Radium-A report dealing withthe uses of radium, more especiallyfor medical treatment, and with its production and sources of supplyhas been issued by the Radium Sub-committee of the Committee ofCivil Research (London, 1929). The production from the westernAmerican carnotite fell from 354 g.of radium element in 1921 to12 g. in 1923 and has now ceased. The present restricted supply isobtained from the richer uranium ore associated with copper oresin Katanga, Belgian Congo. A recent discovery of pitchblende inthe Gordonia district of Cape Province as isolated crystals (uraninite)in pegmatite is less promising than would be a lode deposit withlarge mammillated masses of pitchblende. The copper belt now beingexplored in Northern Rhodesia is perhaps a likely place for futuredevelopments. All igneous rocks contain minute amounts ofradium; for example, C. S. Piggot 79 finds in granites from theeastern United States from 0.378 to 4.826 x 10-l2 g. of radium pergra'm of rock.Rubidium.-A method for the extraction of rubidium saltsfrom carnallite has been given by G.Jander and H. Faber.80 J.Jakob 69 records the presence of Rb,O 1.73% in lepidolite fromSouth-West Africa, and l.16y0 has been found in lepidolite fromJapan.81Ruthenium-This is present as a minor constituent of pink kaolinfrom Tanokami, Japan, the colour of which is supposed to be dueto the presence of rhodium and ruthenium.82Selenium.-The use of photo-sensitive cells for television and thetransmission of pictures is calling for an increased supply of thiselement. A new occurrence of selenium minerals has been foundin the Roter Bar mine at Andreasberg in the Harz Mountains,' 6 T. von Fellenberg, Biochem. Z., 1928,193, 384; A., 1928, 611.7 7 E. Wilke-Dorfurt, J.Beck, and G. Plepp, 2. anorg. Chem., 1928, 172,'I3 J. S. De Lury, Industrial Development Board of Manitoba, Winnipeg,79 Amer. J . Sci., 1929, [5], 17, 13; A., 1036.2. anorg. Chern., 1929,127, 321.S. Iimori and J. Yoshimura, Bull. Chem, Soc. Japan, 1926, 1, 237; A . ,344; A., 1928, 864.1927.1927, 129.82 Idem, ibid., 1929, 4, 1 ; A., 420MINERALOGICAL OHEMISTRY. 273analyses of the picked ore showing Se 2P-27%.= The seleniumores from the earlier known occurrences in the Harz Mountains 84have been studied by the metallographic method in polished sectionsunder the microscope.85 A new selenium mineral has been detected,and named klockmannite (CuSe),86 in intimate association withthe umangite (Cu,Se,) of the Sierra de Umango in Argentina,Lehrbacb in the Harz Mountains, and a t Skrikerum in Sweden.Selenium in a form soluble in water, perhaps as selenious acid or asan alkali selenite, has been found in saline encrustations (Se 1.25%with Te o.04y0) in the crater of Vesuvius.8'New Minerals.An eleventh dictionary list of new mineral names for the period1926-1928 gives 190 names, several of which are merely synonymsor of little value.88 Some rare minerals of the platinum group, ofwhich a preliminary mention was made in the last report (1927,24,311) have now been more fully described.Potarite, PdHg, dis-covered by the late Sir John Harrison, crystallises as octahedra inthe cubic system.@ Palladium antimonide, Pd,Sb, from theTransvaal platinum fields has been named stibi~palladinite.~~Another new platinum mineral from the same district is listed belowunder the name cooperite.Several new crystallised iron sulphatesare described from a mine in Arizona, where a body of pyritic orehad been burning underground for some years ; they were probablyformed when the mine was flooded with water in the attempts toextinguish the fire.91Bismutotuntulite,g2 tantalate (and niobate) of bismuth,Bi203,(Ta,Nb)20,, as large orthorhombic crystals in a pegmatitevein on Gamba Hill, Uganda. Analyses show Bi,O, about soy0,H. Rose, 3'ortachr. Min. Krist. Petr., 1927, 12, 72; W. Geilmann m dH. Rose, Jahrb. Min., BeiLBd., 1928, [A], 57, 785.84 Sel'enium was extracted on sl moderately large scale from these ores atTilkerode in the eastern Harz a hundred years ago, and the product appearsto have been marketed in the fornr of small medallions showing in relief a bustof Berzelius.Examples of these are preserved in the apartments of theChemical Society and in the Mineral Department of the British Museum(L. J. Spencer, Min. Mag., 1928, 21, 404).85 G. Frebold, Centr. Min., [A], 1927, 16, 196.8 6 P. Ramdohr, Centr. Mini., [A], 1928, 225; A . , 289. *' F. Zambonini and L. Coniglio, Ann. R. Osservatorio Vemviano, 1925,[iii], 2, 3.L. J. Spencer, Min. Mag., 1928, 21, 556.Idem, ibid., p. 397; A., 1928, 612.P. A. Wagner, " The Platinum Deposits and Mines of South Africa,"Edinburgh and London, 1929, p. 12; H. Schneiderh6hn, Centr. Min., [A],1929, 193.g1 C . Lausen, Amer. Min., 1928, 13, 203.88 E. J.Wayland and L. J. Spencer, Min, Mag., 1929,22, 186274 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Ta,O, 31-41%, Nb20s 14-6%, and the mineral is analogous tostibiotantalite (Sb,Ta,08). If the formula is written as(BiO),Ta,O, and the axial ratios are readjusted, the mineral shows aclose relation to tantalite (Fe,Ta,O,). The black crystals are inpart altered to a pinkish-yellow hydrated material which seems toconsist of a mixture of two minerals.93 sulpharsenide of platinum, Pt(As,S),, as minutesteel-grey fragments and rectangular rods found in the con-centrates from the platiniferous norites and dunites of the Bushveld,Transvaal. Examined by reflected polarised light, it is seen to beanisotropic and probably orthorhombic.It presumably belongs tothe marcasite group and is dimorphous with sperrylite (PtAs,).Like sperrylite, it is attacked neither by aqua regia nor by nascentchlorine (when the mineral is treated with solid potassium chlorateand hydrochloric acid). After ignition the material yields to aquaregia.G~drnundite,~~ sulphantimonide of iron, FeSbS, as small silver-white to steel-grey crystals embedded in calcite. The ortho-rhombic crystals are isomorphous with mispickel (FeAsS), and thetwo minerals, very similar in appearance, are associated together inthe lead and zinc ore a t Gudmundstrop, near Sala, Sweden.Hydr~thorite,~~ hydrous thorium silicate, ThSi0,,4H20, occurring,together with thorogummite and pilbarite, as an alteration productof mackintoshite in a pegmatite vein a t Wodgina, Western Australia.It is pale pink or cream-coloured, earthy, and very friable, and isoptically isotropic.L ~ r n i t e , ~ ~ calcium orthosilicate, occurring as a constituent of ametamorphic rock at the contact of chalk and dolerite near Larnein County Antrim.The finely granular rock shows an unusualassemblage of minerals, including spurrite ( 2Ca2Si04,CaC0,),larnite (Ca,SiO,), merwinite (3Ca0,Mg0,2Si02), gehlenite, spinel,and calcite. Larnite is monoclinic with optical characters agreeingwith those of the artificial a-Ca,SiO,. When the larnite rock isheated to dull redness and allowed to cool, it falls to powder, due tothe inversion to y-Ca,Si04.Larsenite and Calciurn-lar~enite.~~ These two minerals occur inveinlets in the massive zinc ore a t Franklin Furnace, New Jersey.Larsenite is an orthosilicate of lead and zinc, PbZnSiO,, and formsO3 R. A. Cooper, J . Chem. Met. Min. SOC. S. AfTica, 1928, 28, 281; A.,94 K. Johansson, 2. IL&t., 1928, 68, 87; A., 788.95 E. S. Simpson, J . Roy. SOC. W. Australia, 1928, 13 (for 1927), 37.O6 C. E. Tilley, Min. Mag., 1929,22, 77; A., 787.O 7 C. Palache, L. H. Bauer, and H. Beman, Amer. Min., 1928, 13, 142,Cooperite,1928, 1111.334; A., 787MINERALOGICAL CHEMISTRY. 275colourless orthorhombic prisms isomorphous with olivine. Incalcium-larsenite about half of the lead is replaced by calcium, theformula being (Pb,Ca)ZnSiO,. This massive white mineral isremarkable in showing a brilliant lemon-yellow fluorescence whenexposed to ultra-violet rays. It is intimately associated withwillemite, hardystonite, and clinohedrite, and in the mass theseminerals are scarcely distinguishable, but in the ultra-violet raysthey show fluorescent glows respectively brilliant green, violet, and~range-red.~* This property enabled pure material to be selectedfor analysis.Mits~herlichite,~~ hydrous double chloride of potassium andcopper, K2CuC14,2H20, as minute greenish-blue crystals on thesurface of a saline stalactite from the floor of the crater of Vesuvius.The crystals are tetragonal like those of the artificial salt preparedby E. Mitscherlich in 1840.NahwZite,l sodium hydrogen carbonate, not previously definitelyrecognised as a mineral, is so named from the formula NaHCO,,to distinguish it from the other sodium carbonate minerals. Itoccurs as a constituent of a white crystalline saline encrustationfound in 1888 on the walls of a Roman conduit a t the Baths of Nero,which was exposed during the construction of the railway line fromBaia to Naples. When the conduit was opened the containedatmosphere was highly charged with carbon dioxide. Analysis ofthematerial showsvarying amounts of sodiumcarbonateandsulphatewith 7.48--8.45% of H,O, and they are interpreted as mixturesof thermonatrite (Na2C03,H20), trona (Na,C03,NaHC0,,2H20),nahcolite (NaHCO,), and thenardite (Na,SO,), each of which wasalso determined by its optical characters.Larsenite displays a pale violet fluorescence.Probertite,2 hydrous borate of sodium and calcium,Na2CaB 6H,O,as rosettes of glassy columnar monoclinic crystals embeddedin kernite and secondary borax in the Kramer district, Kern Co.,California. Probertite (also known as kramerite) and kernite (orrasorite) are the primary minerals in a lode-like deposit formedby hot springs in Miocene beds. Secondary minerals derived fromthem are borax and ulexite.L. J. SPENCER.9 * C. Pelache, Amr. Min., 1928,13, 330; L. J. Spencer, ibid., 1929,14, 33.99 F. Zambonini and G. Csrobbi, Ann. R. Osservatorio Vauwiano, 1926,[iii], 2, 7.1 F. A. Bannister, Min. Ma3., 1929, 22, 53; A., 536.2 A. S. Ertkle, Amer. Min., 1929, 14, 427

ISSN:0365-6217    

DOI:10.1039/AR9292600253

出版商:RSC    

年代:1929

数据来源: RSC

摘要:

CRYSTALLOGRAPHY.THE year 1929 has been remarkable not so much for new discoveriesas for the systematic arrangement of the resuIts of previous re-searches, so that the subject of Crystallochemistry has alreadytaken very definite shape. The lead given by V. M. Goldschmidt hasbeen followed with success. One of the outstanding events of theyear was the meeting of the Faraday Society on the occasion of hislecture. The papers and discussion at this meeting, which is theGrst international meeting of X-ray crystallographers, have beencollected in “ Crystal Structure and Chemical Constitution,’’ whichgives an excellent picture of the present state of the subject.At the same time a conference was held under the auspices ofSir William Bragg at the Royal Institution, at which the question ofnotation and methods of publication of crystal structures were dis-cussed and committees set up for proposing means for standardisingand improving them.It is to be hoped that ways will be found ofmaking the results of structural analysis more intelligible and moregenerally available.New book^.-" Kristallographische und StrukturtheoretischeGrundbegriffe,” by P. Niggli, gives a very complete account of thegeometrical basis of crystal structure. The particular contributionof Niggli, which follows the tradition of Schoedies and Fedorov andbrings it up to date by the consideratlion of individual atomicdomains, has not yet found very much application in practice, butit is bound to do so when detailed experimental investigations havebeen co-ordinated into general systems.“ Rontgenspectroscopie und Kristallstrukturanalyse,” by A.Scheede and E.Schneider, is another complete text-book ofX-ray crystallography, particularly valuable for its accounts ofchemical analysis by emission and absorption spectra.“ Cristallographie GBometrique,” by H. Bouasse, gives a compre-hensive account of classical crystallography and the derivation ofspace-groups. The determination of crystal structure by means ofX-rays is treated rather superficially, but most aspects of the workare covered.1 Published by the Faraday Society.“ Handbuch der Experirnentalphysik,” Band VII, I Teil, AkademischeVerlagsgesellscha f t m . b . H . , Leipzig .3 de Gruyter, Berlin. * Paris, Librairie DelagraveCRYSTALLOGRAPHY. 277‘‘ Zur Nomenklatur der 32 Kristallklassen,” by Friedrich Rime;“ nber ein neue Herleitung und Nomenklatur der 230 Kristallograph-ischen Raumgruppen,” 5 by Ernst Schiebold, with an atlas of the230 space-groups containing 313 uncoloured and 36 coloured plates.A discussion of this latest contribution to the systematics of space-groups will have to be postponed to a later Report.The colouredplates have an undoubted advantage in enabling complicated space-groups to be easily grasped.“ A Summary of Published Information on X-Ray Investigationof Alloys ” 7 (1921-1928), by (Miss) C. F. Elam, contains all therelevant data on alloy structures except the details of complicatedstructures.The ‘‘ Strukturbericht ” of the Zeitschrift fur Krishllographie hasnow completed its account of inorganic crystals, except metals,and is already an indispensable work of reference.Less than half of the relevant papers (over 400) which haveappeared during the year can be mentioned here.Four branchesof crystal physics, vuix., magnetic properties of crystals, X-ray optics,electron diffraction in crystals, and the Raman effect in crystals,are h t dealt with; then follows a systematic account of crystalstructures determined during the last year ; and finally a discussionof X-ray dif€raction in liquids.The Magnetic Properties of Crystals.This is one of the branches of crystal physics which are developingvery rapidly. It has long been known that the diamagnetic suscepti-bility varies considerably with direction in the crystal, but it hasfallen to the Indian workers to show how this variation is relatedto the arrangement of the ionic or molecular groups in the crystallattice.In the carbonates and nitrates 8 of the alkali and alkaline-earth metals the direction of the maximum diamagnetic suscepti-bility is always perpendicular to the plane of the carbonate or nitrateradicals ; and for those aromatic compounds whose crystal structureis known, the striking fact emerges that the direction of maximumsusceptibility is perpendicular to the plane of the benzene l oHexamethylbenzene is of particular interest because its crystalstructure has been accurately determined by means of X-rays l1ti Abhandlungen der math.-phya.Klasse der Sachs. Akad. der Wiss., Band40, No. V, Schlussheft. Verlag von S. Hirzel, Leipzig, 1929.J . Inst. Met&, 1929, 41, 329.8 I(. S. Krishnran and (Sir) C. V. Raman, Proc. Roy. SOC., 1927, [ A ] , 115,a S. Bhagavantam, ibid., 1929, [ A ] , 124, 545; A., 982.10 Idem, Indian J . Physics, 1929, 4, 1; A., 1133.11 (Mrs.) K. Lonsdale, Proc. Roy. SOC., 1929, [A], 123, 494; A., 760.549 ; A., 1927, 925278 m u REPORTS ON THE PROGRESS OF CHEMISTRY.(see p. 304), so that the orientation of the flat benzene ring relativeto the crystal lattice is known with certainty. The magneticproperties of this substance have now been determined l2 and arefound to accord with the above generalisation. It is also importantthat in the plane of the ring the magnetic and optical properties agreein showing a slight anisotropy.It is clear that a knowledge of thedirections of maximum and minimum susceptibility in the case ofsuch compounds affords valuable evidence as to the truth of theircrystal structure determined by means of X-rays. The values ofthe magnetic anisotropy in some aromatic compounds are quiteremarkable ; for example, in naphthalene the susceptibility perpen-dicular to the plane of the benzene ring is four times that parallel toit, and in graphite the susceptibility perpendicular to the cleavageplane, which is parallel to the net of the benzene ring, is seven times l3that parallel to it. The aliphatic compounds have an altogethersmaller magnetic anisotropy,10 and as yet no general relation betweenthe characteristic grouping of the carbon chains and the magneticproperties has emerged.The magnetostriction of bismuth has been discovered by Kapitza,14who has shown that a rod placed parallel t o the magnetic fieldexpands when it is grown parallel to the trigonal axis but contractsif grown a t right angles to it.This is the first diamagneticsubstance in which magnetostriction has been observed, and theeffect is remarkable by reason of its large magnitude, beinggreater than that of iron. It also shows that the binding forcesbetween the atoms of crystals can be modified considerably by avery strong magnetic field. The magnetic susceptibilities of singlecrystals of bismuth and antimony parallel to and perpendicular tothe principal axis have also been measured.15Investigations on the magnetic properties of ferromagnetic sub-stances have received a great impulse from the development of thetechnique of preparing single crystals of metals : those of iron, nickel,and cobalt may be obtained of such a size that a cube of about 5 cm.side may be cut out from the matrix.16 The magnetisation bothparallel to and perpendicular to the field in various directions onplates cut parallel to the faces (loo), (110), and (111) of thesecrystals has been determined.lG9 l 7 Single crystals of zinc and12 S.Bhagavantam, Proc. Roy. SOC., 1929, [A], 126, 143.13 (Sir) C. V. Raman, Nature, 1929, 123, 945; A . , 871.l4 P. Kapitza, ibid., 124, 53; A., 989.l5 C. Nusbaum, Physical Rev., 1927, [ii], 29, 905; A., 1928, 1314.16 S.Kaya, Sci. Rep. TGhoku Imp. Univ., 1928, 17, 640; A., 1928, 1081.1 7 K. Honda and S. Kaya, ibid., 1926, 15, 721; A., 1927, 298; S. Kaya,ibid., 1928, 17, 1157; A., 633; W. L. Webster, Proc. Roy. SOC., 1926, [ A ] ,107, 496; A., 1926, ii, 369; W. Sucksmith, H. H. Potter, and L. Broadway,ibid., 1928, [ A ] , 117, 471; A., 1928, 110; K. Beck, Diss., Zurich, 1918; mealso Bull. Nat. Ree. Council, 1922, 3, 180CRYSTALLOCIWHY. 279cadmium l8 have been similarly prepared and investigated. Theresults are more complicated than those obtained with polycrystallinerods and plates, and show the intimate relation which exists betweenthe magnetic properties and the crystal structure. The variation ofthe magnetisation of iron with temperature l9 up to the Curie pointhas been studied. The magnetostriction 20 and magnetoresistance 21effects have now been investigated as comprehensively as the mag-netisation for both iron and nickel, so that full experimental dataare now available as to the magnetic properties of these two metalsand of cobalt.Theoretical research on ferromagnetism is also proceeding rapidly,but on quite different axioms from those employed formerly.Theolder theories 22 of ferromagnetism, although giving a generaldescriptive, and in some cases quantitative, account of the direc-tional properties of single ferromagnetic crystals, did not throw anylight on the origin of the phenomenon. The new theory of W.Heisenberg 23 employs only the fundamental conceptions of quantummechanics and shows that ferromagnetism arises from the exchangedegeneracy of the electrons in the different electronic systems of thelattice.The theory can only be said to have just begun, and 0. vonAuwers,24 in a critical review of the crystallographic and magneticdata of ferromagnetic elements and compounds, points out itsfailures and limitations. It is a much more fundamental theorythan its predecessors and is already being developed so as to includemore of the phenomena of ferromagnetism. R. H. Fowler andP. Kapitza 25 have successfully applied it to determine the changeof specific heat a t the Curie point and the change of size producedduring magnet ostriction.Faraday showed that when transparent substances were placedin a strong magnetic field and a beam of plane-polarised light waspassed through them, a small rotation of the plane of polarisationoccurred. The effect is generally very small, but Becquerel showedl8 J.C. McLennan, R. Ruedy, and (Miss) E. Cohen, PTOC. Roy. SOC., 1928,[A], 121, 9 ; A., 19.lo K. Honda, H. Masumoto, and S. Kaya, Sci. Rep. T6holcu I m p . Univ.,1928,17, 111; A,, 1928, 823.2o K. Honda and Y. Masiyam, ibid., 1926,15, 755; A., 1927,299; W. L.Webster, PTOC. Roy. SOC., 1925, [ A ] , 109,570; Y. Masiyama, Sci. Rep. TdhokuImp. Univ., 1928, 17, 945; A., 19.21 W. L. Webster, Proc. Roy. SOC., 1926, [ A ] , 113, 196; 1927, [ A ] , 114,611; A., 1927, 11, 605; S. Kaya, Sci. Rep. Tdhoku Imp. Univ., 1928, 17,1027 ; A., 20.22 K. Honda and Junzo Okubo, ibid., 1916, 5, 153; G.S. Mahajani, Phil.Trans., 1929, [ A ] , 228, 63; A., 495.23 2. Physik, 1928, 49, 619; A . , 1928, 1300.24 Physikal. Z., 1928, 29, 921; A., 127.25 PTOC. Roy. SOC., 1929, [ A ] , 124, 1; A., 761280 ANNUAL R,EPORTS ON THE PROGRESS OF CHEMISTRY.that in certain crystals, namely, tysonite (Ce,La,Di,)F3, parisite(Cap) (CeF)Ce( CO,), , and bastnasite (Ce,La,Di) (CO, ), (Ce,La,Di)B, ,all containing rare-earth elements, relatively enormous rotationsoccurred. J. Becquerel and W. J. de Haas 26 have continued theinvestigation, and the following is given as an example of the magni-tude of the rotation : at a temperature of 1-95" K., and for a thick-ness of 1 mm. with wave-length 3830 8., and a magnetic field of26-7 kilogauss, the rotation is 18.26 x .The saturation value of therotation is more easily obtained at low temperatures, since therotation obeys the law p/pm = tanh CmH/RT, where p, is thesaturation value of the rotation and Em is a constant. The valueof Em is found to be one Bohr magneton, showing that only oneelectron is responsible for the magnetic rotation. The active ionhas been shown27 to be Ce"', with which is associated an intenseabsorption band at 3270 A. At low temperatures the absorptionbands become extremely fine, showing a well-marked Zeemaneffect,28 and Becquerel has put forward a tentative theory toaccount for this group of interesting phenomena.X-Ray Optics.In one of the most interesting papers of the year on X-ray optics,W.L. Bragg 29 shows the close resemblance between the formationby a lens of a real image of an object and the derivation of thestructure of a crystal from the scattered beams of X-rays, and givesthe mathematics uniting all the information involved. The workis essentidy an extension of the Abbe theory of microscopic visionto the scattering of X-rays by a crystal grating. We may supposethe formation of the real image by a lens to take place in the follow-ing stages. (The object is supposed for the sake of simplicity toconsist of a simple line-grating illuminated by a parallel beam normalto the grating.) Spectra of several orders will be produced andbrought to foci in the focal plane of the lens. These spectra havingthe appropriate phase relations may be considered as light-sourceswhich suffer mutual interference with the production of the imageof the object.The greater the number of the spectra in the focalplane of the lens which contribute to the final image, the morefaithful is its representation of the object. When a parallel beamof X-rays falls upon a crystal, we obtain experimentally only thefirst stage in the formation of the image, namely, the production ofthe separate spectra. The reflexion of any plane hw two properties,26 J . Phy8. Radium, 1929, [vi], 10, 283; 2. Physilc, 1929, 57, 11; A . , 1134.27 Compt. rend., 1929, 188, 1156; A., 633.28 J . Phy8. Radium, 1929, [vi], 10,313 ; 2. Physik, 1929, 58, 206 ; A . , 1234.29 2. Krbt., 1929, 70, 476; Brit.J . Radiology, 1929, 2, 66PLATE I[To face page 281.CRYSTALLOGRAPHY. 281its deviation from the direction of the incident X-ray beam and itsintensity, but it differs from the optical spectra in that it only occursaccording to the Bragg law, i.e., when the crystal is set in anappropriate position with respect to the incident X-rays. It is thislast condition, apart from the difficulty of focusing X-rays, whichmakes it impossible to form an image of a crystal structure directly.If we consider two of the optical spectra which are symmetrical withrespect to the undeviated beam, we see that they give rise in theplane of the image t o interference bands. These are perpendicularto the line joining the spectra, spaced at intervals depending on thedistance apart of the spectra, and of intensity proportional to thatof the spectra.The X-ray spectra occur only one at a time, andhence, to obtain an image corresponding to the optical one, we mustproduce, optically or by mathematics, all the sets of interferencefringes which would be produced if the X-ray spectra occurred all atonce and could interfere with one another. Bragg carries out thisprocess by photographing on the same print forty sets of black andwhite interference fringes oriented, spaced, and of such intensitiesthat they imitate on a macroscopic scale those which would beproduced by the X-ray spectra themselves. The result is a pictureof the atoms of the crystal flattened down on to one plane-thatperpendicular to the axis about which the crystal was rotated inobtaining the spectra. An example of such a photograph is givenin Plate I, and the atomic arrangement which it represents in Fig.1.Such a visual synthesis of the crystal structure is of immense helpin understanding the Pourier method of analysis, and a useful checkon the results obtained by calculation.In another paper, Bragggives the mathematical treatment of the same problem.50 Heextends R. J. Havighurst's method,3l applicable to the distributionof atoms along a line in the structure, to their distribution over aplane. In Fig. 2, the results of such calculations for a planenormal to the c axis of diopside are plotted like a map, the contoursindicating the electron density at any point. The fourteen para-meters obtained by this method for diopside agree to within 0-5%withthose calculated by the earlier method of W.L. Bragg and J. West.32Fundamental in the study of the crystal structure is the knowledgeof the scattering power of each liind of atom for X-rays of any wave-length. A wave-mechanical theory of scattering of X-rays by atomsand molecules has been added to the important papers on thissubject .%3O Proc. Roy. SOC., 1929, [ A ] , 123, 537 ; A., 748.s1 J . Amer. Chem. SOC., 1926, 48, 2113; A., 1926, 995.32 Z . Krist., 1928, 09, 168; Chem.-Zentr., 1929, i, 2013; A . , 1223." 2. Phyeib, 1928, 61, 213282 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Warnings to those who analyse crystal structures are to be foundin two papers. C. Mauguin34 emphasises the fact that the X-rayanalysis may sometimes be misleading if the crystal has a peculiarstructure.The families of the micas have almost the same structuralunit in the plane of the cleavage independently of their composition,FIG. 1.0000000but there are two apparent exceptions in biotite and the chlorites.The exception cannot be real in the cme of the latter because thedirect interpretation of the X-ray results leads to the conclusionthat there are 8/3 hydrogen atoms per unit cell, and we are forcedto assume, in spite of X-ray data, a cell three times as large. Biotiteforms an intermediate stage in the transition between the chloritesand the other micas. The rotation photographs obtained with34 Cornpt. rend., 1928, 187, 303URYSTALLO(XWHY.283chlorite show layer lines which correspond to a unit three timessmaller than that of the other micas, i.e., of the layer lines obtainedwith the other micas only every third occurs in the case of chlorite.In biotite also only every third occurs, but, instead of completeabsence of spots in what would be the first and second layer lines, afaint continuous line is obtained. Mauguin interprets these resultsFIQ. 2.by supposing that the oxygen configuration is constant in all themicas, but that a slight rearrangement of the electropositive ions inthe chlorites and biotites gives rise to these anomalies. W. Lin-nick35 examined the photographs obtained by passing a beam ofCu-K radiation through a thin sheet of mica which had been heatedto redness.The distribution of spots led him to suppose that themica was behaving &s a two-dimensional grating, and he believedthat the heating had separated the cleavage flakes into such thinlayers that they no longer behaved as a three-dimensional lattice.8s Nature, 1929,123, 604; A., 492284 ANNUAL REPORTS ON TEE PROGRESS OF CHEMISTRY.Bragg 36 showed that this assumption was quite unnecessary, for aslight rotation of the flakes relative to one another during the processof heating was sufficient to give rise to this effect : a rotation of64’ is enough to give a pattern simulating that of the two-dimen-sional lattice because of the great length of the c-axis in mica.This is a good example of the difficulties which arise in the interpre-tation of photographs when one axis of the crystal is much greaterthan the other two.Electron Diffraction in Crystals.Perhaps the most striking discovery of recent years is the associa-tion of wave motion with moving material particles.As early as1924, L. de Broglie 37 showed on purely theoretical considerationsthat this association should occur, and that the wave-length would begiven by the relation A = h/mw, where h is Planck’s constant, andmu the momentum of the particle. If this formula is applied to thecase of electrons, we find the wave-lengths characteristic of theelectrons which have fallen through potential differences of 10, 100,1000, and 10,000 volts to be 3.86, 1-22, 0.386, and 0.120 A.U.respectively, corresponding to very soft, soft, hard, and very hardX-rays.W. Elsasser 38 showed how de Broglie’s predictions mightbe tested by allowing electrons of suitable velocity to fall on a singlecrystal of a metal and observing whether they were scattered inaccordance with Bragg’s law, just as in the cwe of X-rays. C. J.Davisson and L. H. Germer 39 had been experimenting on the reflex-ion of electrons from a plate of nickel; by accident their apparatuswas broken and air admitted, and after the damage had beenrepaired the reflexion from the nickel was found to have beenaltered. This was traced to changes in the crystalline state of themetal surface, and these authors therefore investigated the reflexionof electrons from a single crystal instead of from a polycrystallineaggregate. A beam of electrons was made to fall normally on thecrystal, and it was at once found that the deflected electrons were notdiffusely scattered, as required by classical theory, but concentratedinto a number of narrow beams whose orientation with respect tothe crystal was quite in accord with its symmetry. By assigning tothe electrons the wave-length given by de Broglie’s theory, theyfound that the reflected beams were approximately in the directionsrequired by Bragg’s law and the crystal structure.The small butconsistent deviation from Bragg’s law was subsequently shown 4036 Nature, 1929,124, 126; A., 984.38 Naturwiss., 1926, 13, 711.3D PhysiCaZ Rev., 1927, 30, 706; A . , 1928, 102.4o H. Bethe, Naturwiss., 1927, 15, 786; Ann.Phy&k, 1928, [iv], 87, 66;3 7 Compt. rend., 1924, 179, 39.A., 1928, 677, 1303CJRYSTAIJLOaRAPHY. 285to be due to an accelerating potential of about 15 volts which actedupon the electrons as they entered the crystal. As the originalvelocity of the electrons was only about 50 volts, the effect of thisboundary potential was very considerable, and when allowance hadbeen made for it, the observations agreed very closely with thetheory. Thus the association of a wave motion with movingparticles was established by both theory and experiment, and thework of G. P. Thomson,41 E. R ~ p p , 4 ~ S. Kiku~hi,4~ and others hasamply confirmed this.It will be realised that this discovery provides us with anothertechnique whereby the structure of crystals may be investigated.Kikuchi has taken excellent photographs of electrons scattered bypassing through the thinnest possible flake of mica with an exposureas short as 2 seconds.A triangular network of spots was obtained,and this pattern was interpreted as being due to the two-dimensionallattice of atoms in the net planes parallel to the cleavage. As thethickness is increased, the crystal begins to give a pattern corre-sponding to a three-dimensional lattice, some of the spots on theformer pattern disappearing and others being enhanced. Finally,with a still greater thickness, a pattern is produced which is crossedby numbers of black and white lines. The first pattern is neverobtained with X-rays, the second is the familiar Laue picture, but thethird is quite peculiar to electron scattering.When the electronsfall on a fairly thick flake they are scattered several times beforeemerging on the other side, and we should therefore obtain thesame result if we replaced the electron beam by a point source ofelectrons on the surface of the mica, radiating in all directions. Inthis case some electrons would always fall on every plane at the angIerequired for reflexion according to the Bragg law, and hence weshould obtain black lines produced by the reflexion of electrom fromthe various planes. Where the electrons were reflected out of themain beam, there would be a deficiency giving rise to the whitelines. Kikuchi has been able to show in a favourable case, such asthat of mica, how the orientation and cell size of the structure maybe determined, and the beginning of the next essential step has beenmade by G.P. Thomson in deriving the P curve for gold. There isevery reason for believing that it will soon be possible to determinestructures completely by this method.Electrons are reflected in large quantity on passing through the'l Proc. Roy. SOC., 1928, [ A ] , 117, 600; 119, 651; 1929, [A], 125, 362;42 Physikal. Z., 1928,20, 837; Ann. Physik, 1929, [v], 1, 773, 801 ; A., 619.43 Japan. J. Physics, 1928, 5, 83; Proc. Imp. Acad. Tokyo, 1928, 4, 271,A., 1928, 3, 938; A., 1209.276, 364, 471; A., 124286 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.thinnest films which can be prepared, whereas the scattered X-radi-ation from such films cannot be detected.There is thus a largespecial field open to electron analysis. Thin h s of all kinds-of oxides 44 formed by corrosion of metals, of animal and plant fibres,of adsorbed gases,3g and of fats on the surface of liquids-aresuitable subjects for examination by the method. Finally, theheating properties of electron beams make them ideal for investig-ating changes of structure at high temperatures.The Ramn Effect in Crystals.The Raman effect was discovered, like so many other newphenomena, by tracing to its origin a small and apparently insignifi-cant fact. As early as 1922, Sir C. V. Raman45 and his co-workershad found what they called a " trace of fluorescence " in a numberof liquids when strongly illuminated.It was natural to supposethat this was due to a small amount of impurity, but very carefulpurification failed to make the " fluorescence " disappear. Thephenomenon could not be a true fluorescence, however, becausenearly all of a great variety of very pure liquids showed the effect.In 1928 its true nature was revealed by spectroscopic examination.Monochromatic illumination gives rise to scattered light, and in thespectroscope there appears a strong line of unaltered frequencybordered on each side by a number of faint lines. Similar sets of linesappear whatever the wave-length of the incident light, and this, aswell as the occurrence of lines on the short wave-length side of theunmodified line, proves that this is a new phenomenon. The differ-ences in frequency between the modified and the unmodified linesof each substance were found to approximate to the frequencies ofits infra-red absorption bands.At first it was thought that theoryrequired these frequency-shifts to be exactly equal to the frequenciesof the absorption bands, but subsequent work46 has shown that itis not so. The frequency-shifts of the modified lines are equal todifferences between any two characteristic frequencies of the mole-cule, one of which must be an absorption frequency. The closecorrelation existing between the Raman effect and molecular vibr-ations makes this effect of great importance to chemistry andphysics. It can show what molecular groups exist in certain com-pounds and in what way they are modified by their environment;it is equally applicable to all states of matter.In crystals we have a good medium for investigating, by means of44 M.Ponte, Cornpt. rend., 1929, 118, 244; A., 367.46 Indian J . Physice, 1928, 2, 387, 399; A . , 1928, 686, 1075.46 R. M. Langer, Nature, 1929, 123, 346; A., 379; G. H. Dieke, ibid.,p. 664; A., 490; C. P. Snow, Phil. Mag., 1929, [vii], 8, 369; A,, 1216CRYSTALLOGRAPHY. 287the Raman effect, the characteristic modes of molecular vibration,for all similar molecules are oriented in the same direction. Muchwork hrts been done on the Raman effect in &* 51, 52and the observed frequency-shifts correspond to wave-lengths inthe infra-red of 77, 48, 37.5, 28, 24.8, 21.4, 14-3, 12.6, 9.41, and8 .6 ~ . These should be compared with the infra-red absorptionbands, uiz., 78, 38, 26.0, 20.75, 12.5, 9.02, and 8.50~. The corre-spondence between these sets of figures, although striking, is mislead-ing, because the intensities of corresponding lines are not at dl alike.Thus, in the Raman spectra the strongest lines correspond with 77,48, and 21.4y, whilst in the absorption spectra the strongest are 86,9-02, 12.5, and 20.75p, 48p being entirely absent.60 We shouldexpect the light scattered from a crystal to be polarised on accountof the regular orientation of the molecules. This has been foundby Cabannes,u who shows that the 21.4 and 48p radiations arealmost completely polarised perpendicular to the incident andscattered light, and 37.5~ parallel to the incident light.This stateof polarisation is the same whether the axis of the crystal is parallelto or perpendicular to the incident light. Complicated polarisationeffects have also been observed in calcite.=In calcite there also exists a well-defhed Raman spec-trum 47, 49* s~ having frequency-shifts corresponding with 63.8,35-3, 14.1, 11.4, 9.24, 6.99, and 5.70~. The infra-red absorptionbands occur at 94, 55, 30, 28, 14.0, 11.4, 7.0, and 6 . 7 ~ . The differ-ences in the intensities of the two sets are again remarkable : 9.24~is a strong line in the Raman spectrum and is absent in the absorptionspectra, tw it corresponds to an inactive frequency. The absorptionfrequencies of calcite have been identified with the vibrations ofthe atoms within the CO, group and of this group as a whole in thecrystal lattice.The occurrence in the Raman spectrum of thefrequency which is inactive in the absorption spectum 55 is anexample of the way in which it will be possible greatly to enlarge our47 G. Landsberg and L. Mandelstam, 2. Physilc, 1928, 50, 769; A., 9 ;R. W. Wood, PhiE. Mag., 1928, 6, 729; A., 1928, 1306; H. Nisi, Proc. Imp.Acad. Tokyo, 1929, 5, 127; A,, 742.4s P. Pringaheim and B. Rosen, 2. Physik, 1928, 50, 741 ; A., 1928, 1307.40 I. R. RBo, Indian J . Physics, 1928, 3, 123; A., 1928, 1306.6o K. S. Krishnan, Nature, 1928, 122, 606; Indian J . Physics, 1929, 4,61 M. Czerny, 2. Physik, 1929, 53, 317; A., 378.Oa J. Cabannes, Cmpt. rend., 1929,188,249 ; A., 378.63 Idem, {bid., p.1041; A., 627.64 M. Kimura and Y. Uchidrt, Japan. J . Physics, 1928, 5, 97; A., 241;b s C . Schaefer, C. Bormuth, and F. Matossi, 2. Physik, 1926, 39, 648; A.,131; A., 1216.Sci. Papers Inst. Phys. Chem. Rm. Tokyo, 1929, 11, 199; A., 1216.1927, 6288 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.knowledge of the states of excitation of ionic groups. The way inwhich chemical substitution affects the vibrations of the group isillustrated by a comparison of the Raman lines for CaCO,, zlix.,6.9, 9-18, 13.95p, with those of NaNO,, vix., 7.17, 9.30, 13-7p.56 Itappears from the two lower wave-lengths that a loosening of the bondbetween the components of the radical has occurred in the NO,group, but for the higher wave-length a tightening has taken place.Gypsum 50, 56% 57 affords an interesting example of the way in whichionic groups retain their identity in a crystalline environment.Thereare four prominent lines in the Raman spectrum, at 9.9, 8.81, 2.94,and 2 . 8 6 ~ . The first two can be shown to be due to the SO, radical,and the last two to the molecules of water of crystallisation. Inaqueous sulphate solutions a line 58 is always obtained at 1 0 . 2 ~ ~and it is thought that the two at 9.9 and 8.81 in gypsum are derivedfrom it, the change and splitting being produced by the insertion ofthe sulphate ion into the crystal lattice. The lines at about 3pcorrespond with those given by water itself and by and itseems justifiable to expect that we may always detect in this way thepresence of water of crystallisation as distinct from water ofconstitution in a crystalline substance.Crystal Chemistry.The remaining part of the report can now more properly be calledCrystal Chemistry than Crystal Structure, for increasing emphasisis being laid on the chemical significance of the structures revealedby X-rays rather than on the structures themselves.Sufficientwork has now been done to make possible a systematic classificationof solid substances, which expresses at the same time the structureand the chemical and physical properties. The classification firstoutlined by Grimm 59 and Fajans happily follows in great part thatadopted by mineralogists, with the addition of organic substances asa separate group. The four chief divisions are metallic, metalloidalor adamantine, ionic, and molecular, but these groups are not sharplydefined and pass insensibly into one another.An example of howthe compounds of the element carbon are divided into all four groupsis given by A. von Antropoff; 80 Fe,C metallic, Sic adamantine,Na,C ionic, and CH, molecular ; and this classification is used in the66 C. Schaefer, F. Matossi, and H. Aderhold, Physikal. Z., 1929, 30, 581 ;67 R. G. Dickinson and R. T. Dillon, Proc. Nut. Acad. Sci., 1929, 15, 695;6 8 S. K. Mukherjee and P. N. Sengupta, Indian J . Physics, 1929, 3, 503;6s Geiger and Scheel, " Handbuch von Theoretischer Physik," Vol. 21.6o 2. E'lektrochem., 1928, 34, 113.A., 1216.A., 1216.A., 976CRYSTALLOGRAPHY. 289following discussion.It will be seen that this arrangement differsfrom that in previous Reports only in the position of the metals andin the absence of a separate class for elements. Elements, in fact,do not either chemically or physically form a natural division : themajority are metallic and the remainder metalloidal or molecular.Metallic Crystals.-Our knowledge of the metallic state is moreunsatisfactory from the theoretical standpoint than that of any ofthe other groups. The physical meaning of the forces bindingmetallic atoms together is still obscure, and the chemical lawsregulating the formation of intermetallic compounds are still unknownin the main, although their foundations have been laid by the workof A. Westgren and G. PhragmBn, A.J. Bradley, and W. Hume-Rothery described in the last Report.61 A review of the presentstate of this subject has been made by J. D. Bernal.82 A classific-ation of the metallic elements according to their atomic volumes andtheir places in the periodic system is proposed, and upon this togetherwith considerations of crystal structure, there is based a classificationof intermetallic compounds as metallic ionic, metallic homopolar,and purely metallic, depending upon the presence or absence of ionsand covalent linkages in the structure. The relation between theseand the physical properties (particularly electrical and magnetic)of the metals is discussed. A suggested explanation of the Hume-Rothery rules 6l fixing the ratio of the number of valency electronsto atoms in a structure as 3/2, 7/4, or 21/13, is that they are due tocovalent linkages, and this is supported by the fact that most of thecompounds obeying the rules have a diamagnetism much too largeto be accounted for by single atoms.The question as to how far Vegard’s rule for the lattice dimensionsof mixed crystals holds in intermetallic systems, and how far Gold-Schmidt is justified in using it in deducing atomic radii in metals inthe way described in last year’s Report, is discussed by A.F. Westgrenand G. Phragm6n.m By measurements of series with similar crystalstructure, e.g., Cu-Al, Ag-Al, Ni-Al, they find in every case con-siderable contraction from what would be expected according toVegard’s rule ; the same is true in the system Cu-Zn, Ag-Zn, Ag-Cd,Cu-Mg, and Fe-W, where compounds exist, and hence it is concludedthat Vegard’s rule only holds where the component metals areclosely related, such as Cu-Au or Mo-W.The constancy of anatomic volume in mixtures must be considered only as a firstapproximation, there being an almost universal tendency for it tobe lower than in the pure elements.Ann. Reports, 1928, 25, 298 et seq.62 Trane. Faraday SOC., 1929, 25, 367 ; A., 987.Ibid., p. 379; A., 987; A. Westgren and A. Almin, 2. physikal. Chem.,REP.-VOL. XXVI. K1929, [B], 5, 14290 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.V. M. Goldschmidt 6* has determined the crystal structure ofrhenium; it is hexagonal close-packed, a = 2.752 & 0.001, c =4.448 0.002 A., and resembles that of osmium.The atomicradius is 1.371 8., which is nearly a mean between those of tungstenand osmium, wix., 1-41 and 1-34 A., respectively. The density is21 4. These results are an illustration of the delicacy of X-raymethods in dealing with extremely minute quantities of material.The structure of strontium as face-centred cubic is confirmed byA. J. King,65 F. Simon and V. E. Vohsen,66 and F. Ebert andH. Hartmann 67 ; a = 6.075 8. a t room temperature and 6.05 a t thetemperature of liquid air. Barium 68 has a body-centred lattice,a *= 5.01 A. The atomic radii are Sr 2,135, Ba 2.17 8.M. Wolf 69 and H. Terrey and C. M. Wright 70 have re-investigatedthe structure of solid mercury and confirmed the results of L. W.McKeehan and P.P. Ci0ffi.71 The structure is rhombohedral-pseudocubic, a = 4.60 A., a = 98" 14', being a slight distortion ofcubic close packing.The high-temperature form of manganese has been found byE. Persson and E. Ohman72 to be the so-called y- or electrolyticmanganese, first studied by Westgren and Phragmh It is tetra-gonal, a = 3-77, c = 3-52 8., with a face-centred structure. Thepure metal has not been examined in this phase, which is only stableabove 1191", but its existence is verified by extrapolation from anumber of manganese alloys in which this phase is stable at lowertemperatures. The Cu-Mn alloys form a continuous series of solidsolutions varying from the cubic Cu, a = 3.61 A., to the tetragonaly Mn. The conclusions are confirmed by thermal analysis 73 andby the study of the system Mn-N (see p.292).A. Pabst 74 has investigated the structures of the gold amalgams.Up to 15% of mercury a normal solid solution is formed. The nextphase is a hexagonal close-packed structure approximating to thecomposition Au,Hg. At higher mercury contents, two more phaseswith complicated structures were found.E. Persson 75 has made a thorough study of the system Cu-Mn-A161, Z.physika1. Chem., 1929, [ B ] , 2, 244; A., 493.6 5 Proc. Nat. Acad. Sci., 1929, 15, 337; A., 749.6 6 Ibid., p. 695; A., 1221.6 7 2. anorg. Chem., 1929, 179, 418; A., 631.6 8 A. J. King and G. L. Clark, J . Amer. Chem. Soc., 1929,51, 1709; A., 869.69 2. Physik, 1929, 53, 72; A., 382.7* Phil. Mag., 1928, [vii], 6, 1055; A., 16.71 Physical Rev., 1922, 19, 444; A., 1923, ii, 864.72 Nature, 1929, 124, 333.73 (Miss) M.Gayler, J . Iron Steel Inst., 1927, 115, 393.7 p 2. physikal. Chem., 1929, [ B ] , 3, 443; A., 987.75 2. P l y s i k , 1929, 5'7, 116; A., 1132CRYSTALLOGRAPHY. 291to find the conditions under which the ferromagnetic Heusler alloysare produced. He concludes that they are due to the definite com-pound Cu,MnAl, which exists in annealed specimens. Both themanganese and the aluminium atoms seem to be placed on a face-centred lattice, but there are two alternative positions for the copperatoms, the whole structure being a variant of the body-centred cubicstructure with a double cell side. This is in agreement with thework of H. H.Potter,76 who used single crystals.In the quenched alloys this double structure is not observed, butthe maximum of magnetism is found with alloys having the samecomposition as that of the compound Cu,MnAl. S. Valentiner andG. Becker 77 conclude from this that the magnetic properties cannotbe due to any particular armngement of the copper and manganeseatoms, but this does not necessarily follow, for it is possible thatthe arrangement is statistically similar to that of the true compound.The past year has been notable forstudies on a very important set of metallic compounds, wix., thoseof the transitional elements Cr, Mn, Fey etc., with the elements of thefirst series, B, C, N. These compounds are alike in that the lighterelement does not replace the metallic one, but enters the gaps in thelattice without altering the size to any great extent.Definite com-pounds are formed as well as solid solutions. The properties of thesealloys are of the greatest importance because essentially they are thebasis of the utility of steel. The nitrides have been most studied.The iron-nitrogen system has been examined by G. Hagg,78 R. Brill,79and A. Osawa and S. Iwaizumi,so who are all in substantial agree-ment. The compounds are prepared in all cases by passing ammoniaover heated iron, but their properties seem t o depend only on theirnitrogen content and are independent of the temperature and otherconditions of preparation. Apart from a very slight solid solutionof nitrogen in iron, two compounds, Fe,N and Fe,N, are found.The first is cubic, a = 3.86 B., each cell containing four atoms ofiron in a face-centred arrangement (compare y-iron, a = 3-63 B.)and one nitrogen atom, probably in the centre of the cell surroundedby six iron atoms.Fe,N, according to Hiigg, is orthorhombicpseudo-hexagonal, a = 2-76, b = 4.82, c = 4.42 A., the iron atomsbeing in a hexagonal close-packed arrangement, but the position ofthe nitrogen atoms is uncertain. Osawa has not found the ortho-Interstitial compounds.76 Proc. Physical Soc., 1929, 41, 135; A., 494.7 7 2. Physik, 1929, 57, 283; A . , 1220.70 Nature, 1928,121, 826; 122,314, 962; A., 1928, 605, 1081; 1929, 124;79 2. Krist., 1928, 68, 379; A., 748.a0 Ibid., 69, 26; A.; 1220; Sci. Rep. T6hoku Imp.Univ., 1929, 18, 79;Nov. Act. Reg. SOC. Upsala, [iv], 7, No. 1.A., 086292 ANNUAL REPORTS ON THE PROGRESS OF OHEMISTRY.rhombic lattice, but, as the variation from the hexagonal is very small,this is not surprising. An intermediate phase containing 8-11%of nitrogen has been found only by Hagg : it is hexagonal close-packed and differs very little from Fe,N. It has so far been foundimpossible to produce cobalt or nickel nitrides by the ammoniaprocess, but L. R. Ingersoll and J. D. Hanawalt81 have produceda tetragonal nickel nitride by sputtering the metal in nitrogen.HaggS2 has also investigated the system Mn-N. Four phases arefound: the first seems to be a solid solution of nitrogen in thetetragonal y-manganese (see p. 290) and is only stable above 500";the next, stable below 400°, is probably Mn4N and is closely similarto Fe4N, manganese atoms being on a face-centred cubic lattice,u = 3.855-3.86 8.; the third is similar to the hexagonal Fe,N witha variable composition (N = 9-12%); and the fourth, with 14%of nitrogen, is face-centred tetragonal, pseudo-cubic, u = 4.19,c = 4.03 A.The first phaseappearing is the hexagonal Cr,N, but in this case there is a secondphase, Cr-N, with the rock-salt structure, isomorphous with thenitrides of V, Ti, Sc, Zr, and Nb. Thus the whole range of elementsfrom scandium to cobalt show a gradation of behaviour towardsnitrogen. All these nitrides have the common property of metallicconductivity.The tetragonal structure in quenched steels mentioned in the lastreport has now been thoroughly studied by S.Sekito,84 G. Kurd-jumov, and E. Kaminsky 85 and N. Seljakof.86 The existence of atetragonal lattice containing interstitial carbon is confirmed, butthe most interesting result is that the axial ratio, particularly the caxial length, increases with the carbon content, the structure beingidentical with that of a-iron for zero carbon content. In a quenchedsteel the axial ratio, and consequently the carbon content, in thelattice diminishes steadily from the surface inwards, the rate depend-ing on the velocity of cooling. The hardness of the steel seems alsoto be a function of the carbon content of this tetragonal phase. Onbeing annealed, it breaks down even at such a low temperature as100".At higher temperatures the austenite (y-iron) disappears andan a-iron-cementite (Fe,C) mixture is formed.T. Bjurstrom and H. Arnfelt 87 examined the Fe-B system and*l Physical Rev., 1929, 34, 972 ; A., 1368.82 2. physikal. Chem., 1929, [ B ] , 4, 346; A., 1221.83 Ibid., 1929, [ B ] , 3, 229; A., 747.84 Xci. Rep. T6hoku Imp. Univ., 1929,18, 69 ; A , , 986.8 6 2. Physik, 1929, 53, 696; 55, 187.86 Nature, 1929, 123, 204; A., 246.R. Blix 83 has investigated the Cr-N system.2. phyeikal. Chem., 1929, [B], 4, 469; A., 1138URYSTALLOGRdpHY. 293found two phases: Fe,B with a body-centred tetragonal lattice,a = 5.10, c = 4.24 8., and FeB with an orthorhombic lattice.Some interesting consequences of the effect of small quantities ofthe light elements on the polymorphism of iron are suggested byT.D. As F. Wever 89 has pointed out, the addition ofsmall quantities of other elements tends either to make the y- (face-centred) iron disappear in the phase system or to make it the stableform at all temperatures. In particular, silicon tends to make y-irondisappear, and carbon and oxygen to make it stable. Iron is prac-tically never free from the latter elements. By extrapolation,Yensen finds that the amount of silicon required to prevent thea 4 y change in iron would be vanishingly small in the absence ofcarbon and oxygen ; consequently, absolutely pure iron would showno allotropic forms and would remain body-centred at all temper-atures. It would be very interesting to see whether such iron couldbe produced experimentally.So far the only interstitial compound of hydrogen known withcertainty is Pd,H.the existenceof such a compound seems tlo be proved, although its compositionis somewhat variable. It is face-centred cubic, a = 4.017, m against3.873 8. for pure palladium. Nickel and platinum may formsimilar compounds but the evidence so far is confLicting.91Adamantine Compounds.-There is some difficulty in finding asuitable name for this class of compound. Chemically, it consistsmostly of compounds of the transition metals with the lower elementsof Groups IV, V, and VI, so-that sulphides would seem to be toonarrow a term and metalloidal too vague. The compounds arecharacterised by a binding of a homopolar nature throughout thecrystal, but the use of the term " homopolar " might give rise toconfusion with organic crystals." Adamantine " is chosen becausethe greater number of them actually have the diamond structure or avariant of it, and the diamond is the most perfect example of thishind of binding in crystals. Of the sulphides, covelline has beenstudied by H. S. Roberts and C. J. Ksanda 92 ; the natural mineralis identical with CuS (prepared either by precipitation or by directsynthesis), it is hexagonal, a = 3-80, c = 16-43 8., in agreement withthe results of B. Gossner and F. Mu~sgnug,~~ and contains 6 copperFrom the work of J. D. Hanawalt88 Science, 1928, 68, 376; A., 1135.8@ Naturwiss., 1929, 17, 304; A . , 745.90 Physical Rev., 1929, [ii], 33, 444.91 R.Salvia, Anal. Pis. Quim., 1929, 27, 285; A., 870; S. Valentiner andG. Becker, Natumuiss., 1929, 17, 639; A., 1130; L. R. Ingersoll and J. D.Hanawalt, Phyeical Rev., 1929, 34, 972 ; A,, 1368.@a Amer. J. Sci., 1929, [v], 17, 489; A., 870.93 Centr. Min., 1927, [A], 410294 ANNUAL REPORTS ON THE PROGRESS OF UHEMISTRY.and 6 sulphur afoms. The space group is DS and a, structure isproposed, but the X-ray data are not sufficient to verify it. L.Thomassen 94 has examined the binary compounds of the platinummetals with the elements of Groups V and VI. Nine compounds,OsTe,, OsSe,, RuTe,, Ruse,, RuS,, PtP,, PtAs,, PtSb,, and PdAs,have the pyrites structure; four, PdTe,, PtTe,, PtSe,, and PtS,,have the cadmium iodide structure; and two, PdSb and PdTe,have the nickel arsenide structure.It was thought that, fromanalogy with iron compounds, some of these new compounds mightbe ferromagnetic, but this is not so. G. Hagg 95 has investigated thebinary systems of iron with P, As, Sb, and Bi, but they do not offermany analogies ; Fe,P has a tetragonal body-centred cell, space group8;; Fe,P is hexagonal; FeP may exist, but its structure is com-plicated. Fe,As is tetragonal, a = 3.63, c = 5.97 8., the cell contain-ing two molecules, and the arsenic atoms apparently being arrangedon tetragonal axes between two iron atoms; FeAs is orthorhombicwith a distorted nickel arsenide structure. FeSb has the latterstructure but is of variable composition. FeSb, has the space groupQiz and is apparently isomorphous with marcasite, FeS,, andIollingite, FeAs,, studied by Frielinghaus 96 and W.F. De J ~ n g . ~ ’A. Westgren, G. Hagg, and S. Erikssong8 have investigated t,heCu-Sb and Ag-Sb systems. In the former, there are three phases :solid solution, a hexagonal close-packed phase of composition vary-ing from 19 to 25% of Sb (roughly corresponding with the compoundCu3Sb), and a definite compound Cu,Sb with a tetragonal structureapparently isomorphous with Fe,As (see above). In the Ag-Sbsystem a hexagonal close-packed phase was also found correspondingroughly to Ag,Sb, but the remaining phase (from 20 to 25% of Sb,of variable composition) is orthorhombic pseudo-hexagonal.The phosphides and arsenides of some bivalent metals have beenstudied by L.Passerini 99 : Zn3P2, Cd,P,, Mg,P,, Zn,As,, and Cd3As2are all isomorphous and belong to a new structure type with a cubiccell a z 6 B., containing six metal atoms in the centre of the facesand of the edges of the cube and 4 arsenic or phosphorus atoms inthe centres of alternate octants (iai). The structure has a certainanalogy to that of zinc blende.The more complicated adamantine compounds have been verylittle investigated, but P. Machatschki has examined the structureof a great number of tetrahedrides which are complicated antimony94 2. physilial. Chem., 1929, [BI, 2, 349; [ B ] , 4, 277; A . , 1221.9 5 2. Krist., 1925, 68, 470; A . , 749; see also refs. (78).96 Diss., Greifswald, 1926. 9 7 Physica, 1926, 6, 325.9 8 2.physikal. Chem., 1929, [ B ] , 4, 453; A . , 1139.9s Gazzetta, 1928, 58, 655, 775; A., 125, 246.2. Krist., 1928, 68, 204; A., 747CRYSTALLOURAPHY. 295sulphidea of the general formula R3SbS3 (R = Cu, Ag, etc., or Fe,Zn, Pb, etc.). The unit cell is cubic, a = 10.3 8., and containscomponent cells very similar t o zinc blende, a = 5.42 A. The exactpositions of the atoms are somewhat uncertain owing to the variablecomposition. Another similar compound, sulvanite, Cu3VS,, hasbeen studied by de Jong 2 ; it is also cubic, a = 10-75 A.Ionic Compounds.-The moat important contribution made to thestudy of ionic crystal structures is that of L. Pauling 3 on “ ThePrinciples Determining the Structures of Complex Ionic Crystals.”Here the ideas of Goldschmidt on the importance of ionic size andthe results of W.L. Bragg’s silicate investigations are systematisedand extended into a set of rules which give the possible structures forionic compounds composed of a number of positive and negativeions of different sizes. The rules do not apply where the ions arevery large or where homopolar bonds are found, but they neverthe-less cover the greater part of inorganic crystals. The guidingprinciple is that the geometrical nature of a structure is primarilydetermined by the anions which may be considered as forming co-ordination polyhedra around the smaller kations. This idea hadalready been used extensively by Bragg and Goldschmidt, butPauling has made the important addition that, not only the arrange-ment of anions round each kation, but also that of kations roundeach anion must be considered; in general terms, the stability of astructure is assured only when the charge induced by neighbouringkations on an anion is equal and opposite to its own charge.Thefive rules are as follows :(1) “ A co-ordinated polyhedron of anions is formed about eachkation, the kation-anion distance being determined by the radiussum and the co-ordination number of the kation by the radius ratio.”As in the great majority of cases the anions are 0” or F’ ions ofradius 1.33 8., the co-ordination depends only on the kation. Thenumber is 3 (triangle) for B’II; 4 (tetrahedron) for (,Irr), Be**, Li’,SiIv, ( A P ) ; 6 (octahedron) for AlIII, Mg**, TirV, Sc’II, MoVr, NbV,Z P .Where the co-ordination is greater than 6, as with largekations, the great distortion of the polyhedron renders the ruleinapplicable.(2) “ I n a stable co-ordination structure the electric charge ofeach ion tends to compensate the strength of the electrostaticvalence bonds reaching it from the katiom a t the centres of thepolyhedra at which it forms a corner; that is, for each anion =Ci zj/vi”, where is the charge of the anion, zi the charge of thekation, and v i the number of anions surrounding each kation, the2. Krist., 1928, 68, 522; A., 988.J . Amer. Chem. SOC., 1929,51, 1010; A., 748296 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.sum being taken for all kations whose polyhedra have this anion astheir common corner. For example, in topaz each oxygen ion iscommon to one silicon tetrahedron and two aluminium octahedra.Consequently, C x / v = i- + + = 2, whereas each fluorine ion iscommon to 2 aluminium octahedra, and C x/v = $ + 8 = 1.(3) “ The presence of shared edges and particularly of shared facesin a co-ordinated structure decreases its stability.This effect is largefor kations with large valence and small co-ordination number andis especially large in case the radius ratio approaches the lower b i tof stability of the polyhedron.” The truth of this rule depends onthe Coulomb repulsion of neighbouring kations, which is naturallylarger when an edge of two polyhedra is shared than when a corneris shared, and still larger when a face is shared. Consequently,silicon tetrahedra tend to share only corners with other polyhedra.Titanium octahedra share only corners and edges, whilst aluminiumoctahedra sometimes, as in corundum, share faces.(4) “ In a crystal containing different kations, those with largevalence and large co-ordination number tend not to share polyhedronelements with each other.” Consequently, silicon tetrahedra shareno elements with each other if the oxygen-silicon ratio is equal to orgreater than 4, e.g., topaz, zircon, olivine, and orthosilicates ingeneral. This gives an important method of classification forsilicates.(5) “ The number of essentially different kinds of constituents ina crystal tends to be small.” This rule is of a much more doubtfulcharacter than the others.It is certain that in a number of purelygeometrical possibilities the actual one in nature will probably notbe the most complicated, but it would seem unsafe to go further.The rules are supplemented by consideration of how the poly-hedra built together in this fashion are liable to be distorted by theirmutual forces.To do this completely would require a solution ofthe equation of state of the crystal to find the minimum crystalenergy, but empirical rules have a wide range of validity. Poly-hedra of oxygen ions about tervalent and quadrivalent kations aredistorted in such a way as to shorten shared edges and edges bound-ing shared faces to 2.50 A. instead of 2.7 A. These rules, which areadmittedly only a rough first approximation, have neverthelessalready proved extremely valuable for the accurate prediction ofcrystal structures to be checked by X-rays, or for the selection ofstructurally plausible crystal structures when the X-ray data areambiguous or insufficient.An example of the first use is affordedby the case of brookite and topaz discussed in last year’s Report.4The second is exemplified by the cases of cyanite (see below, p. 299),Ann. Reports, 1928, 25, 285, 286CRYSTALL0~RAPH.Y. 297of the chlorides of the bivalent metals,5 and of the A class of thesesquioxides of the rare-earth metals.6 From the measurements ofG. Bruni and A. Perrari,’ Pauling has calculated the probablestructure of the chlorides of Cd, Mg, Ni, Co, Mn, Zn, Ru, Rh, Pd,Ir, and Pt. Each metal atom is surrounded by six chlorine atomsat the corners of a regular octahedron which shares six edges withneighbouring octahedra to form a double layer of chlorine atomswith the metal atoms between.Three of these layers, attachedtogether by the residual attraction of the metals, go to build up therhombohedra1 cell. This structure seems to be stable for compoundsof the type AX,, where A has a co-ordination number 6 and X is nottoo polarisable, in which case there is a transition to the cadmiumiodide class. In the case of the A type of the sesquioxides, Le.,those of La, Ce, Pr, and Nd, Pauling has proposed a similar layerstructure of shared octahedra instead of that proposed by W. H.Zachariasen.* A further example of the application of Pauling’sprinciples is shown in his theory of the silicotungstic acids (seep.301).We may divide ionic crystals into three main groups : (1) simpleoxides and halides of the type &&, (2) complex oxides, includingsilicates, of the general type &Bp . . . . . .X,, not containingseparate complex iom of the type A&, and (3) complex ionic com-pounds and co-ordination compounds.A number of new structural types have been found among simplecompounds. I. Oftedal9 has studied the trifiuorides of the rare-earth metals La, Ce, Pr, Ne, and Sa, which are isomorphous with thenatural mineral tysonite. The structure is hexagonal, a z 7.1,c N“ 7.3 8., containing 6 molecules RE”,. The space group is Q.The metal atoms form a hexagonal close-packed assembly, but theposition of the fluorine atoms, owing to their very small scatteringpower, is still doubtful.0. Hassel and S. Nilssen lo have deter-mined the structure of bismuth fluoride. It is cubic, a = 5.85 A.,with 4 molecules in the cell; the bismuth atoms form a face-centredcubic structure with the fluorine atoms probably on the cell edgesand in the centres of the octants, each bismuth atom being thussurrounded by 14 flourine atoms. The crystal structures of thefluorides of the metals of Group VIII have been studied by 0. Ruffand E. Ascher l1 : FeF,, CoF,, NiF,, and PdF, have the rutile5 PTOC. Nut. Acad. Sci., 1929, 15, 709; A., 1221.7 Atti R. Accad. Lincei, 1926, [vi], 4, 10; A., 1926, 995.* 2. physikal. Chem., 1926,123, 134; A., 1926, 1195; 8.Krist., 1929, 70,D 2. phy8ikal. Chem., 1929, [B], 5, 272; A., 1223.lo 8. amorg. Chem., 1929, 181, 172; A., 987.2. Krist., 1929, 69, 415; A., 1223.157.l1 Ibid., 1929, 183, 193.K 298 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.structure, and there are two new types-those of FeF, and COP,,which are hexagonal, and of RhF3 and PdF,, which are orthorhom-bic. The full X-ray data, however, have not yet been published.H. Brakken and L. Harang l2 have determined the structure ofPbCl,, PbBr,, and HgCl,. The first two are isomorphous, and allhave the same space group QA6. All the atoms lie in symmetryplanes and the structure is probably molecular. The existence ofsimilar molecules of PbCl has been suggested by the study of thechlorocarbonates of lead by M.Matthieu and (Mine.) N. Demas-sieux. l3Italian and other workers l 4 have made an extensive study of iso-morphism of the compounds of the bivalent metals Zn, Ni, Mg, Co,Fe, Mn, Cd, and Ca, whose atomic radii range from 0.75 to 1-08 ,&.Fluorides, chlorides, oxides, hydroxides, carbonates, and sulphideshave been studied by X-ray methods, both singly and in mixedcrystals. Except for extreme members, such its Ca and Zn, completemiscibility in the solid state is found for most compounds, and itappears from these studies that the only relevant factor for iso-morphism is ionic size. A point of some interest is the formationof mixed crystals of hydroxide by precipitation from solutions ofthe mixed chlorides .Of complex oxides, apart from silicates, the spinels have been moststudied in the past year.S. Holgersson 15 has prepared and examined17 of these, all isomorphous and with cell size varying from 8-04 A.for CuA1,04 to 8.57 ,&.for MnFe,O,. Spinels have been made withnearly every one of the bivalent metals Cu, Zn, Ni, Mg, Co, Fe, Mn,Cd, and the tervalent metals Al, Cr, Fe. Other interesting spinelsare those of cobalt, including tricobaltic tetroxide 16 and the pig-ments ZnCo,04 and SnCo,0,.17 J. Bohm l8 has made a thoroughgtudy of the natural and artificial hydrated iron oxides, which appearto be mixtures of anhydrous oxides with various proportions ofsemi-hydroxide FeO(OH), which exists in an o(- and a y-form : onlyl2 8. Rrist., 1928, 68, 123; A., 631.l3 Compt.rend., 1929, 189, 333, 536; A., 1154, 1252.l4 G. Natta, Gazzetta, 1928, 58, 344, 419 ; G. Natta and L. Passerini, ibid.,pp. 541, 597; 1929, 59, 129; L. Passerini, ibid., p. 144; A . , 639; A. Ferrari,A. Celeri, and F. Giorgi, Atti R. Accad. Lincei, 1929, [vi], 9, 782; A., 996;S. Holgersson and A. Karlsson, 8. anorg. Clzem., 1929, 182, 255; A.,1130.l5 Lunds Ulziv. irsskr., [ii], Avd. 2, 23, 9; Chem.-Zentr., 1929, i, 372; A . ,1131.l6 S. B. Hendricks and W. H. Albrecht, Ber., 1928, 61, [B], 2153; A., 15;G. Natta and L. Passerini, Gazzetta, 1929, 59, 280; A., 870; L. Passsrini,Atti R. Accad. Lincei, 1929, [vi], 9, 338; A., 673.l7 G. Natta and L. Passerini, Gazzetta, 1929, 59, 620.l8 2. Krist., 1928, 68, 567; A . , 988CRYSTALLOGRAPHY. 299the f i s t is found in natural minerals.Both structures are ortho-rhombic, and the a-form is isomorphous with diaspore, AIO(0H).8iZicates.The investigation of the main types of silicate structureis nearing completion. Their study has been much simplified bythe facts that the mineralogical classiikation of silicates has provedto be a natural one, and that X-rays have shown all members of suchfamilies as felspars, pyroxenes, micas, etc., to have nearly identicalstructures. A complete survey of the present state of knowledgeof the silicate structures, which has been so largely his own work, isgiven by W. L. Bragg.lg The great advantage of his method ofworking was that it rigorously followed the X-ray data so that thepositions assigned to the atoms are quite independent of any theoriesas to the constitution of silicates.Nevertheless, as the work con-tinued, the general plan of building of silicates became apparent,and we are now in a position to predict complicated structures andeven to reduce the method of prediction to rules as Pauling hasdone.20 Many important silicate types have been completely deter-mined in the past year. C. Menzer21 has made a very thoroughstudy of the garnet group, the general formula of which isA3B2Si3012, where A is Ca, Fe, Mn, or Mg, and B is Al, Fe, orCr. The cell is cubic, a z 12 a,, containing 4 molecules, but thecubic symmetry makes the structure a relatively simple one.Pauling’s rules are very well followed : each silicon atom is sur-rounded by 4 oxygen atoms, each aluminium by 6 oxygens, and eachcalcium by 8 oxygens. All the silicon tetrahedra are separate, andevery oxygen atom has as neighbours one aluminium, one silicon,and two calcium atoms.It is a typical ortho-structure in Machat-schki’s sense.22The structure of the three forms of aluminium silicate is now fullyknown. Andalusite has been shown by W. H. Taylor 23 to have a verysimilar structure to sillimanite, both being based on chains of alumin-ium octahedra bound together by silicon tetrahedra, but havingbesides a certain number of aluminium atoms-in sillimanite be-tween 4 oxygen and in andalusite between 5 oxygen atoms-so thatthe formula of these compounds might be written Al*AlSiO,,whereas in cyanite all the aluminium atoms are between 6 oxygenatoms.The structure of cyanite has been altered2* in regard tothe position of the silicon ions, since Pauling had pointed out thatthese lay too close together in the structure originally proposed.25lS Trans. Faraday SOC., 1929, 25, 291 ; A., 749.2o See p. 295. 21 2. Krist., 1929, 69, 300.22 See Ann. Reports, 1928, 25, 284. z3 2. Krist., 1929, 71, 205.24 S. Nriray-Szab6, W. H. Taylor, and W. W. Jackson, 2. Krist., 1929,26 W. H. Taylor and W. W. Jackson, Proc. Roy. SOL, 1928, [ A ] , 119, 132.71, 117300 ANNUAL REPORTS ON THE PROGRESS OF OHEMISTRY.The structure of staurolite has close analogy to that of cyanite,its has been pointed out by G. M. Cardoso.26 S. NAray-Szab6 26 hascompleted its analysis and shown it to be essentially composed oflayers of cyanite and ferrous hydroxide in very much the same wayas in the humite series, so that its formula should be written2A12Si0,,Fe(0H),. The structure of norbergite, the first of theolivine-clinohumite series, has been determined by W.H. Taylorand J. West 28 : it consists of alternating layers of Mg,SiO, andMg(OH),. Norbergite, chondrodite, humite, and clinohumite con-sist respectively of 1,2, 3, and 4 layers of olivine separated by onelayer of Mg(OH),.B. E. Warren29 has now analysed the structure of tremolite.His results are detailed in the Report on Mineralogical Chemistry(p. 257), but it is noteworthy that the formula now found, which isbased on X-ray data, actually agrees better with chemical analysisthan the older formula, thus showing the value of X-ray methodsfor the determination of the constitution of complex substances.E.Schiebold30 has shown that the felspars, monoclinic andtriclinic, have all very similar structures but the actual structure hasnot yet been worked out. The relationships between the felsparsundoubtedly depend on a substitution of aluminium in silicon-oxygen tetrahedra. Such structures are found in the ultramarinesNa8A16Si602,S,, on which F. M. Jaeger 31 has continued his researches.The basis of the structure, and of that of the natural mineralsnosean and hauyine, is a skeleton of 12 atoms of aluminium and 12 ofsilicon, all inside oxygen tetrahedra and linked into a cubic structure.The remaining atoms of sodium, sulphur, etc., are placed in the holesof the structure, some in fixed and others in free positions. Thisexistence of a silicon-aluminium skeleton will probably explain allthe peculiar properties of zeolitic minerals, in which replacementof atoms can take place without any alteration of structure.Complex Ionic Compounds.-Compounds of the symmetrical AX,ion form a very defhite class.The particular nature of the AX,ion seems to be almost immaterial. Beryllo-fluorides, sulphates,perchlorates, and permanganates all form isomorphous compoundsand mixed crystals.32 A particularly interesting study is the system26 Ber. Sachs. Alcad. Wiss., 1929, 80, 165; Centr. Min., 1928, [ A ] , 11, 390.27 2. Krist., 1929, 71, 103.28 Ibid., 70, 461 ; see also Ann.Reports, 1928, 25, 284. 29 Ibid., 72, 42.30 Trans. Paraday Soc., 1929, 25, 315; A., 749; Fortschr. Min. Krist.81 Trans. Paraday SOC., 1929, 25, 320; A., 749; Proc. K. Akad. Wetensch.82 P. C. Ray, Nature, 1929, 124, 480; A., 1220; W. R. C. Curjel, ibid.,Petr., 1927, 12, 78.Amsterdam, 1929, 32, 166, 167.1929,123, 206; A., 246CRYSTALLOGRAPHY. 301BaS0,-KMnO, 33 ; here a univalent kation and a univalent anion bothreplace bivalent ions without any apparent difficulty, isomorphismagain seeming to depend only on ionic size. L. Vegard and A. Maur-stad have completely determined the structure of the anhydrousalums KAl(S04)2, NaAl(SO,),, NH,Fe(SO,),, and KCr(SO,),. Theyare hexagonal, space group Di ; the sulphate ions have simple trigonalsymmetry and are rather similarly arranged to those of KLiSO,.Each aluminium atom is surrounded by 6 and each potassium atomby 12 oxygen atoms.The structure of gypsum, CaS0,,2H20, hasbeen determined by E. Onorat0.~5 It is a typical layer lattice inwhich the calcium and sulphate ions lie in the b planes separatedby the water molecules. E. Broch 36 has established the form of themonoclinic tungstates of Fe, Mn, Co, Ni, and Mg, and shown thatpotassium per-rhenate, KReO,, belongs to the scheelite type.The form of the chlorate ion has been exactly determined byW. H. Zachariasen,3’ who has studied the structure of sodium andpotassium chlorates by means of Fourier analysis. This shows with-out possibility of doubt that the chlorine and oxygen atoms do notlie in a plane, as the carbon and oxygen atoms do in the CO,” ion,but form an obtuse pyramid, the oxygen atoms being in a triangleof 2.38 A.side and the chlorine atom being 0.48 A. out of ithe plane.This arrangement is probably also found in the ions PO,”’, SO,”,As03”’, SeO,”, and SbO,”’-in fact, wherever the valency of thecentral atom is less by 2 than its full valency. The formation ofan AX, ion out of one of AX, is consequently merely the removal ofone of the anions without distortion of the rest of the structure.This is in agreement with the suggestion of A. M. Taylor,38 based onspectral data, that the bonds holding together such ions are of asemipolar and not of an ionic type.Pauling has extended his ideas on the linking of oxygen polyhedrato the explanation of complex ions of the silicotungstic acids.39 Inhis view, the essential basis of the structure is 12 tungsten atoms,each surrounded by 3 oxygen atoms and 3 hydroxyl groups andlinked together through the former into a structure resembling atruncated tetrahedron.Inside this tetrahedron is found thecharacteristic ion, SiO, for silicotungstates, BO, for borotungstates,etc., thus giving a formula for silicotungstic acid,H,[SiO,,W,,O,g(oH)3,1.33 G . Wagner, 2. physikal. Chem., 1929, [B], 2, 27; A., 247.34 2. Krist., 1929, 69, 519; A., 1221.38 2. physikal. Chem., 1928, [B], 1, 409; 1929, [B], 6, 22; A., 245.s8 Trans. Faraday Soc., 1929, 25, 314; A., 749.38 J . Amer. Chem. SOC., 1929, 51, 2868; A. G.Scroggie and G. L. CIark,35 Ibid., 71, 277.2. Krist., 1929, 71, 601, 617.Proc. Nat. A d . Sci., 1929, 15, 1 ; A., 246302 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.I n this way he is able to explain the large number of molecules ofwater of crystallisation and the basicity of the acids. Similarexplanations probably hold for all ions containing large numbers ofmetallic atoms. 0. Hassel and H. Kringstad40 have continuedtheir work on complex co-ordination compounds, in particular thecobaltammine and chromammine chloratosulphates and perchlorato-sulphates, both in hexammino- and pentammineaquo-forms. Theexistence of two kinds of complex anion makes very little differenceto the nature of the structures, which are in all cases cubic.K. Hermann and \V.Ilge 41 have studied tetramethylammoniumperchlorates and permanganates : the structure is tetragonal. Afterconsideration of possible alternatives, both ions are shown to betetrahedral. In connexion with such compounds, it should bementioned that the statements in last year's Report require cor-rection ; Vegard's original structure 42 for the iodide only differedfrom those of other workers in the position of the carbon atoms, andno mention was made of the subsequent paper43 in which hedescribed the correct structure.MoZecuZur CrystaZs.-From the strictly crystallographic point ofview, the system of classification for molecular substances should bebased on the way in which the separate molecules are bound togetherto form the crystal. This may vary froin van der Waals forces,as in permanent gases and hydrocarbons, to cases where the polarityof the molecules is so strong that the force binding the positive endof one molecule to the negative end of another is as effective as in anionic crystal such as those of ice, dibasic acids, or sugars. However,insufficient structures have been studied to make this classificationpossible, and that now to be employed is based on the inner con-stitution of the molecule, the chief divisions being ( I ) simple mole-cular structures, (2) aliphatic, and (3) aromatic compounds.(1) The structure of solid nitrogen has been studied by L.Vegard 44and by J. de Smedt and W. H. Kees0m.~5 Both find a cubic cell,a = 5.66 pi., containing four molecules.Vegard considers the struc-ture to be cubic, space group T4, the distance between two atoms in amolecule being 1.06 A., and the molecular structure resembling thatof argon (face-centred cubic, u = 5.42 A.). On the other hand, theother investigators, from identical X-ray data, conclude that thestructure is tetragonal on account of the double refraction. Solidnitrogen exists in two forms, one stable below 36" Abs., and the other40 2. anorg. Chem., 1929, 182, 281; A., 1222.41 2. Krist., 1929, 71, 47.43 Ibid., 1927, [vii], 4, 985; A . , 1928, 7.44 Nature, 1929, 124, 267, 337; Naturwiss., 1929, 17, 643, 672; A . , 987,1130; 2. Physik, 1929, 58,497.4 6 Proc. K . Akad. Wetensch. Ameterdam, 1929, 32, 746; A., 1130.42 Phil. Mag., 1917, [vi], 33, 395CRY STALLOQRAPHY. 303between 36-62' Abs.It may be, as in the case of methane, thatalthough the apparent temperature was below 36" Abs., the necessaryexposure of the substance for the X-ray examination caused theouter layers to be above the transition temperature, and the cubicstructure described really belongs to p-nitrogen, the a-form havingdouble refraction. Alternatively, the double refraction may, as inmany similar cases, be due to strain.An important controversy has been settled in a very thoroughstudy by W. H. Barnes46 of the structure of ice. Single crystalswere used and the temperature ranged from 0" to - 183".The cell is hexagonal, a =: 4.53 pi., c = 7.41 A, containing fourmolecules. The oxygen atoms can bedefinitely placed in a wurtzite arrangement, but the position of thehydrogen atoms is still indeterminate, although they are almostcertainly placed somewhere between the pairs of oxygen atoms.The structure agrees with that of (Sir) W.H. Bragg4' and D. M.Dennison.48 This still leaves open the question as to the chemicalnature of ice. Barnes inclines to the view that it is an ionic structureThe space group is D&.0 of H' and 0". A molecular structure H/ \H would seem impos-sible from the cell and the symmetry, but it must be rememberedthat, with its small scattering power, a larger cell due to hydrogenalone would probably not be detected, and evidence on othergrounds, particularly the Raman effect,49 favours the existence ofwater molecules in ice, although these ,are so strongly polar thatthe whole structure will obviously resemble an ionic crystal in itsphysical properties.(2) J.C. McLennan and W. G. Plummer 53 have determined thestructure of methane. The molecules are in a face-centred cubicarrangement, a = 6.35 8., and the space group is either T, or T:.The hydrogen atoms cannot be exactly placed but are probablytetrahedrally arranged. No different structure was found above an3below the transition temperature, 20" Abs.The structure of urea has been determined by S. B. H e n d r i ~ k s . ~ ~The cell is tetragonal, a = 5-73, c = 4-77 B., containing 2 molecules,space group Dill. The carbon, oxygen, and two nitrogen atoms lie ina plane. The polar axis of the molecule is parallel to the tetragonalaxis, and the amine end of one molecule is next to the oxygen in theneighbouring molecule, forming a typical polar molecular structure.46 Proc.Roy. Soc., 1929, [ A ] , 125, 670.47 Proc. Physical SOC., 1922, 34, 98.4 8 Physical Rev., 1921, 17, 20.49 I. R. R$o, Indian J . Physics, 1928, 3, 123; A., 1928, 1306.51 J . Amer. Chem. SOC., 1928, 50, 2466; A., 1928, 1175.Phil. Mag., 1929, [vii], 7, 761; A., 750304 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.Thiourea has a similar structure, but of lower, orthorhombicsymmetry.A.Miiller 52 explains the well-known alternation of properties betweencompounds with odd and even numbers of carbon atoms as being dueto the zigzag character of the chain. When the number of carbonatoms is even, the orientations of the end groups are parallel; whenit is odd, they make an angle with each other.This difference affectsthe placing of the molecules in the next layer, leading t o a differencein the inclination of the chain which affects the physical properties.In the dicarboxylic acids studied by W. A. C a ~ p a r i , ~ ~ this differenceresults in the c axis of the crystal being doubled in the odd-carbonacids. New measurements on fatty acids and their salts have beenmade by S. H. PiperSeveral further studies have been made on pentaerythritol 56 andits substitution products, but all now agree to a tetrahedral structureof the carbon atom. The most interesting is that of dibenzylidene-pentaerythritol by F. A. van Melle and H. B. J.S h ~ r i n k . ~ ~ Thehexagonal cell contains 3 molecules of the structureConsiderable work has been done on long-chain compounds.and by G. T. Morgan and E. H ~ l m e s . ~ ~H Heach posscssing a diagonal axis along its length. This implies thatthe substituents of the carbon atoms marked * all lie in a plane.Even if the position of the hydrogen atom is neglected, this is rathera remarkable result and invites further study. A number of measure-ments have been made by A. Reis and W. Schneider 58 on the cellsand space-groups of tartaric and fumaric acids and their salts andother similar substances. I. Nitts 59 has made a similar examinationof the rhombic formates.(3) (Mrs.) K. Lonsdale 60 has now published a full account of the52 Proc. Roy.Soc., 1939, [ A ] , 124, 317; A., 869.54 J., 1929, 234; Trans. Faraday SOC., 1929, 25, 348; A . , 751.5 5 J . Soc. Chem. I n d . , 1928, 47, 3 0 9 ~ ; A , , 245.5 6 E. Emst, 2. Krist., 1928, 68, 139; A . , 751 ; (Miss) I. E. Knaggs, Proc.Roy. SOC., 1929, [ A ] , 122, 69; A . , 246; H. Moller and A. Reis, 2. Krist.,1928, 68, 385; A., 988; H. Mark and G. von Susich, ibid., 69, 106; A . , 1223.5 7 2. Krist., 1928, 69, 1 ; A., 1223.5 8 Ibicl., 68, 543, 586; 69, 49, 62; A., 988, 1223.50 Xci. Papers I n s t . Phys. Chem. Res. Tokyo, 1928, 9, 151.6o Proc. Roy. SQC., 1929, [ A ] , 123, 494; A , , 750; Trans. Faraday SOC.,53 J., 1928, 3235.1929, 25, 352CRYSTALLOGRAPHY. 305structure of hexamethylbenzene, based on exact intensity meaaure-ments of a great number of planes, and on an exhaustive considerationof alternative structures.The cell is triclinic, a = 9.010, b = 8.926,c = 5.344 A., a = 44" 27', 8 = 116" 43', y = 119" 34', but is verypseudo-hexagonal. The benzene rings and the six methyl groupsall lie within the c plane or within 0-1 8. of it. The molecule isnearly hexagonal but actually only possesses a centre of symmetry,and the molecules in successive layers show no particular relation toeach other. The diameter of the carbon atom is 1.42 A. Thisdemonstration would seem to decide the flat character of thebenzene ring, but unfortunately it is by no means certain that thenature of the ring does not depend on its substituents. The inves-tigation of naphthalene and anthracene with the object of finding theexact position of the carbon atoms has been made by J.M. Robert-son.61 Here the evidence points equally conclusively to a puckeredring, but as the paper was published in error before completion,fuller comment is deferred.The study of a very interesting group of aromatic substances hasbeen made by J. Hengstenberg and H. Mark S Z ; the structures ofdiphenyl, phenanthrene, and fluorene are very similar (excepting thatin the last two the c axis is doubled), which suggests that the twomain benzene rings must be similarly placed in all cases. Theyhave further investigated G3 the series of " polyenes,"C H .b:fj.k:& C.C H6 5 6 5in which double- and single-bonded carbon atoms alternate, and findthat the increase in length per pair of double-bonded carbon atomsis 1.5 8., as against 2.5 8.in the p a r a h , pointing to a chain ofthe type I-I-1-1- rather than a simple zigzag, thus w.An enormous amount of work has been done in the past yearon the structure of cellulose and its derivatives, on rubber, silk, andsimilar substances, all of which have in common the existence ofvery long molecules consisting of identical groups bound together bycovalent links. It is impossible in the space of this report to com-ment on this work, and only a few of the most important referencesare given.a Further work has shown that the size of the pseudo-cell of cellulose is probably twice as large as previously believed,Proc. Roy. Soc., 1929, [ A ] , 125, 642; A., 1367.82 2. Krtkt., 1929, 70, 287.83 Trans.Faraday Soc., 1929,245, 414.64 H. Mark and K. H. Meyer, 2. phyaikal. Chem., 1929, [B], 2, 115; 4,431 ;A., 246, 1132; K. R. Andress, {bid., [B], 2, 380; I(. Weissenberg, Natuwisa.,1929, 17, 181, 624; A., 493; C. Trogus and I(. Hess, 2. phy&al. Chem.,1929, [B], 4, 321 ; [B], 5, 161 ; A., 1222; A. Burgeni and 0. Kratky, ibid.,[B], 4, 401; A., 1132; F. D. Miles and J. Craik, Nature, 1929,123, 82; A.,126306 ANNUAL REPORTS ON THE PROGRESS OF CHEMISTRY.but the matter is still under dispute. The complexity of thequestion is shown by the observations of H. Mark and G. vonSusich ,65 who examined the process of mercerisation of cellulosewith very intense X-rays, and found that two intermediate com-pounds are formed in the course of five minutes.The use of veryshort exposure times will probably prove of great value to chemistsin the examination of intermediate phases which it is impossible toisolate.X-Ray Diffraction in Liquids.I n the past year the study of X-ray diffraction in liquids has greatlyincreased. It is rapidly becoming a standard method of examin-ation. A very complete and satisfactory theory has been developedby J. A. Prins.66 Two main cases are considered : in the first, whichholds for monatomic liquids, the scattering a t any angle 6 can beexpressed by the formulasin sr J(s) = $NA2 + $NA2Lm4nr2g(r) - sr dr74x sin 46A ' where A is the amplitude of scattering per atom, s =and g(r) is the distribution function for the scattering centres.If the atoms in the liquid are assumed to be approximately in contact,g(r) can be determined and the diffraction distribution calculated.It agrees very closely with that observed for the diffraction in liquidmercury, which was examined by a very ingenious method in whichthe X-ray tube and photographic plate moved round the horizontalsurface of the liquid. I n the case of scattering from polyatomicmolecules, account has to be taken of the interference of wavesscattered by different parts of the same molecule; the formulanow becomessin srwhere 2, is a function of the molecular structure.molecule, b being the distance between the atoms,J(s) = ~ N A : + +Njz/m4hrr2g(r) - sr dr,For a diatomic-A: = 2A2[1 +'GI and 3 = 4A2Calculations on the basis of this formula agree very well with theresults obtained for carbon tetrachloride. The formula breaks downif the molecules are anisotropic, and here the question arises as tohow far such molecules in the liquid arrange themselves in an orderedway, giving rise to the so-called cybotactic state postulated by G . W.Stewart. According to6 6 2. Phgsik, 1929, 56, 617; A., 1132.This part of the subject is still in dispute.65 Natumoiss., 1929, 17, 803CRYSTALLOGRAPHY. 307Prins, long-chain molecules must be roughly parallel, but need not bestraight or arranged in layers. There are objections to the assump-tion of a cybotactic state on the grounds that the large opticalscattering which parallel arrangements of molecules would demandis not observed. This is discussed by C. V. Raman and K. S.Krishnan67 and I. R. Riio.68 Another case considered is that ofsolutions, where it is shown that the pattern of the solution does notconserve the maxima of either solute or solvent but gives rise to apattern dependent on the concentration. Particularly interestingare the results for ionic solutions. by thestudy of solutions with heavy ions such as those of bromine or iodine,that these arrange themselves in a statistical lattice, owing to theirmutual repulsion which is dependent on the concentration. Experi-mental work on liquids and amorphous solids has largely beencarried out by Indian workers, in particular by P. Kri~hnamurti.~~A great number of aromatic and aliphatic liquids has been studied.Notable differences have been observed between o-, p - , and m-com-pounds, and the existence of inner rings points in the cases of anumber of acids and alcohols to the existence of association in theliquid state.'l The work has been done entirely by photographicmethods, but it agrees with that of G. W. Stewart 72 by the ionis-ation method. J. J. Trillat 73 has devised an elegant method ofexamining surfaces or interfaces by means of X-rays at glancingangles, and shown that long-chain compounds in the solid and theliquid state are definitely oriented in the neighbourhood of thesurf ace.Here Prins hasJ. D. BERNAL.W. A. WOOSTER.G 7 Proc. Roy. SOC., 1928, [ A ] , 117, 1, 589.G 8 Indian J . Physics, 1928, 3, 1.Nature, 1929, 123, 84; A . , 125; see also H. Shiba and T. Watanabe,Sci. Paper8 Inst. Phys. Chem. Res. Tokyo, 1929, 187.'O Indian J . Physics, 1928, 3, 225, 307, 331, 507; 1929, 4, 99; A . , 246,751, 989, 1220; V. I. Vaidyanathan, ibid., 1929, 3, 371, 391; A., 751, 746;K. Banerjee, ibid., p. 399; A., 750; H. F. Hertlein, 2. Physik, 1929, 54, 341.71 J . A. Prins, Nature, 1929, 123, 908; A., 746.71 Physical Rev., 1929, [ii], 33, 889; A . , 985.73 J . Phys. Radium, 1929, [vi], 10, 32; A., 631

ISSN:0365-6217    

DOI:10.1039/AR9292600276

出版商:RSC    

年代:1929

数据来源: RSC

摘要:

INDEX 03’ AUTHORS’ NAMESABEL, E., 55.Acharya, D. P., 53.Acker, E., 69.Acker, (Frl.) H., 59.Acklin, O., 210.Acree, S. F., 192.Adam, N. K., 250.Adams, R., 141.Aden, T., 52, 63.Aderhold, H., 288.Adova, A. N., 233.Aggaxwal, A. L., 69.Aggarwal, J. S., 173.Alber, H., 49.Albrecht, O., 141.Albrecht, W. H., 67, 298.Algar, J., 153.Allan, J., 153.Allen, F. W., 215.Allgeier, R. J., 201.Alling, H. L., 262.Almin, A., 289.Alresch, K., 67.Alston, N. A., 259, 265.Amberg, S., 189.Ammer, G., 70.Amy, L., 198.Anderson, C. G., 95.Anderson, R. J., 206, 209,211, 312.Andress, K. R., 305.Andrew, L. W., 33.Andronikov, (Mme.) N., 195.Angelescu, E., 195.Angell, F. G., 62.Anson, M. L., 241, 242.Antropoff, A. von, 288.Apotheker, K., 161.Arm, M., 267.Arnall, F., 38.Arnfelt, F., 38.Arnfelt, H., 292.Arzoomanian, S., 249.Asmo, M., 112, 212.Ascher, E., 64, 66, 297.Ashton, F.W., 45.Aston, F. W., 35.Atkin, W. R., 192.Ato, S., 203.Aubel, E. van, 36, 37.Auerbach, F., 108.Aurousseau, M., 255.Auwers, K. von, 118,166,168.Avenarius, H., 176.3Avery, 0. T., 239, 240, 241.Avery, S., 200.Avsejevitsch, G. P., 203.Bachmann, W., 43.Badoche, M., 144.Backlin, E., 12.Biiurle, A., 198.Baeyer, A. von, 145.Bailey, E. I%., 248.Bain, J. W., 200.Bainbridge, K. T., 43.Baines, H., 196.Baker, H. B., 24, 27.Baker, J. W., 116, 124.Baker, W., 154, 155, 156, 157.Bakes, W. E., 101, 102.Bakken, H. E., 45.Blilinescu, C., 196.Bamberger, C., 144.Banerjee, K., 307.Banerjee, P.C., 191.Banerji, P., 47.Bannister, F. A., 275.Bannister, L. C., 40.Barber, H. J., 141, 199.Barbier, J., 192.Barbieri, G. A., 49, 195.Barfuss-Knochendoppel, H. R., 69.Barlet, F., 164.Barnes, W. H., 303.Barnett, E. de B., 120, 144.Barratt, S., 47, 64.Barschall, H., 108.Bastow, S. H., 39.Basu, S., 63.Bauer, L. H., 274.Baumgarten, P., 60.Bay, Z., 63.Bayle, E., 198.Beaucourt, K., 200.Beck, J., 272.Beck, K., 278.Becker, A., 147.Becker, G., 291,293.Becker, K., 69.Becker, W. W., 192.Becquerel, J., 280.Bedel, C., 50.Behr, A., 86.Behrens, H., 64.Belsley, J. P., 199.310 INDEX OF AUTHORS’ NAMES.Benedetti-Pichler, A., 194.Benesch, E., 197.Bennett, C. W., 54.Bennett, G. M., 130, 137, 138, 139,Bennewitz, R., 204.Benrath, A., 70, 71, 73.Benrath, H., 71, 73.Berg, G., 270.Berg, L., 72.Berg, R., 195.Bergh, A.A. H. van den, 245.Bergmann, E., 140, 143.Bergmann, M., 76, 105, 106, 222.Berman, H., 263, 274.Bernal, J. D., 289.Bernhauer, K., 93.Berry, A. J., 192.Berry, W. A., 138.Besemann, 19 1.Bethe, H., 284.Bhagavantam, S., 127, 128,277,278.Biazzo, R., 201.Bills, C. E., 250.Biltz, W., 46.Bincer, H., 74.Birch, S. F., 118.Birge, R. T., 12, 20, 21.Birstein, V., 23.Bischoff, C., 203.Bischoff, F., 226.Bishop, L. R., 214, 215, 218.Bjurstrom, T., 38, 292.Blatt, A. H., 166.Bleyer, B., 201.Blicke, F. F., 199.Blish, M. J., 219.Blix, R., 38, 292.Blount, B. K., 164, 181.Blumenthal, H., 194.Bockhacker, E., 135.Bodendorf, K., 56.Bodenstein, M., 54.Bodnar, J., 213.Bock, F., 200.Boe, J., 200.Boeseken, J., 74.Bohm, F., 60.Bohm, J., 298.Bottger, W., 190.Boevin, A., 200.Bogue, R.H., 45.Boldyreff, A. W., 203.Boller, W., 193.Bond, W. N., 12.Bondy, H. F., 112.Bone, W. A., 26, 27.Bonhoeffer, K. F., 20, 41, 58.Bonino, G. B., 127.Bonneau, L., 42.Boratyhki, K., 198.Bordeianu, C. V., 198,201.Bormuth, C., 287.199.Borsche, W., 133, 136, 149, 150, 151,Bose, P. K., 167.Bossuyt, (Mlle.) V., 199.Botolfsen, E., 63.Bouasse, H., 276.Bouillenne, M., 194.Bourdillon, R. B., 249.Bowen, N. L., 73.Boyce, J. C., 129.Rradbury, G. M., 60.Bradfield, A. E., 124.Bradley, A. J . , 289.Bragg, (Sir) W., 125, 254, 303.Bragg, W.L., 253, 257, 259, 260, 280,281, 284, 299.Brand, T. von, 251.Brand], O., 196.Braun, L., 35.Braun, W., 201.Brauns, D. H., 100.Brennecke, E., 203.Bretscher, E., 130.Brewer, F. M., 271.Brewin, A., 135, 137.Bridel, M., 99.Bridgman, P. W., 42.Briggs, S. H. C., 61, 68.Briggs, T. R., 72.Brigl, P., 104.Brill, R., 291.Brindley, G. W., 75.Briner, E., 55.Brinton, P. H. M. P., 48.Brintzinger, H., 203.Briod, A. E., 249.Briscoe, H. V. A., 27, 49, 59, 160.Broadway, L., 278.Broeh, E., 65.Broecker, L. E. von, 59.Bronstedt, K., 212.Brown, E. H., 47.Bruchhausen, W. von, 173, 174.Bruck, W., 132.Bruckl, K., 257.Bruin, P., 28.Brukl, A,, 196.Brunel, A., 215.Bruni, G., 297.Brunner, E., 63, 67.Brunner, M., 112.Bruylants, P., 118.Buckland, H., 252.Budnikov, P.P., 197.Buehrer, T. F., 102.Bulow, C., 192.Biihr, 193.Burgeni, A., 305.Burger, M., 54.Burgess, H., 160.Burgess, W. M., 42.Burnett, A. J., 22.Burr, G. O., 211.159INDEX OF AUTHORS’ NAMES. 31 1Burrell, R. C., 24.Burstall, F. H., 160.Burton, A. C., 16.Burton, H., 120, 135.Busch, F., 52.Busse, W. F., 58.Butescu, D., 200.Cabannes, J., 287.Cadenbach, G., 63.Caglioti, V., 64, 202, 260.Cain, J. C., 134.Caley, E. R., 190, 196.Callan, T., 203.Callow, R. K., 161, 174, 174, 176.Cambi, L., 55.Cameron, F. K., 45, 69, 71.Canal, F., 182.Canneri, G., 49.Cannon, H. C., 248.Cardoso, G. M., 259,300.Carobbi, G., 275.Carrihre, E., 61.Carstensen, M., 227.Carter, J.S., 64.Carter, N. M., 76, 77, 78, 79.Carter, S. R., 69.Carugati, M., 70.Caspari, W. A., 304.Castel, P., 61.Cauer, E., 166.Celeri, A., 72, 298.Celsi, S. A., 199.Chakravarti, S. N., 179.Chalisev, A. A., 43.Chandelle, R., 197.Channon, H. J., 206,208, 209,211.Chapin, R. M., 54.Chapman, A. W., 116, 122, 123.Chargaff, E., 209.Charlton, W., 95.Chattaway, F. D., 170, 213.Chatterji, A. C., 29.Chauvenet, E., 50.Chibnall, A. C., 206, 208, 209, 211,Child, R., 172.Chlopin, V., 46.Cholnoky, L. von, 245.Chopin, L., 125.Chretien, A., 70, 71, 73.Christian, B. C., 208.Christiansen, J. A., 60.Christiansen, W. G., 249.Cioffi, P. P., 290.CissBe, H., 168.Claasen, A., 28.Clark, G. L., 301.Clark, 0. E., 189, 192.Clarke, H.T., 138.Clarke, S. G., 193, 994.Clemo, G. R., 145, 183.215.Closs, K., 200.Clough, G. W., 85.Cobb, J. W., 49.Cohen, (Miss) E., 279.Colani, A., 72.Collazo, J. A., 251.Collin, G., 208.Collins, S. C., 69.Collison, D. L., 246.Colombier, M. L., 193.Conant, J. B., 78, 137.Coniglio, L., 271, 273.Conrad, J., 168.Constable, F. H., 40.Cooper, R. A., 274.Copisarow, M., 29.Cornec, E., 70, 71, 73.Cousen, A., 35.Cowdrey, G. W., 76, 78.Cox, W. M., 250.Craik, J., 305.Cranner, H., 207.Creighton, E. M., 124.Crockford, H. D., 71.Crossmann, F., 144.Crowell, W. R., 204.Csonka, F. A., 219.Culhane, K., 225.Cullinane, N. M., 153.Cuny, L., 199.cupr, V., 196.Curjel, W. R. C., 47, 300.Curtis, 0. F., 216.Cuvelier, V., 195.Czerny, M., 287.Dadieu, A., 19.Dahl, O., 72.Dakin, H.D., 210.Damianovich, H., 40.Damiens, A., 63.Dane, E., 169.Daniels, F., 58.Danielson, I. S., 248.Dann, A. T., 140.Dansette, A., 162.Darbari, N. L., 173.Darwin, C. G., 14.Das-Gupta, B. C., 167.Daubney, G. G., 206,209.Davidowicz, J., 50.Davidson, S., 66.Davies, E. C. H., 31.Davies, W., 133, 136, 140.Davis, C. E., 192.Davisson, C. J., 14.De Broglie, L., 11, 284.De Broglie, M., 23.Debye, P., 128, 130, 131.Dede, L., 51, 195.De Graeve, P., 216.De Haas, W. J., 36, 37,280312 INDEX OF AUTHORS’ NAMES.Deines, 0. von, 60.De Jong, W. F., 268,294,295.De Lange, M. P., 133.De Lange, W., 53.Delaplace, R., 250.DelBpine, M., 68, 69.Del Fresno, C., 203.De Liefde, W., 28.Demassieux, (Mme.) N., 52, 298.Deniges, G., 190, 199.Dennis, L.M., 61, 62.Dennison, D. M., 18, 303.Dent, F. J., 49.Desmarest, M., 99.De Smedt, J., 302.Deubel, A., 52.Dewsen, E., 66, 149.Dhar, N. R., 29.Diamond, H., 37.Diaz de Rada, F., 196.Di Capua, C., 71.Dick, J., 52, 186, 193.Dick, W., 192.Dickens, A. H., 117.Dickinson, R., 159.Dickinson, R. G., 288.Dieke, G. H., 286.Dillon, R. T., 64, 288.Dilthey, W., 50.Dirscherl, W., 225, 226.Dittler, E., 270.Dixon, B. E., 196.Dixon, M., 223.Doan, C. A., 207.Dobbins, J. T., 45.Dobrovolny, F. J., 200.Dodd, A. S., 191.Dole, M., 203.Donovan, P. P., 101.Dore, W. H., 107.Dorner, O., 43.Dorrington, B. J. F., 190.Dorsch, K. E., 41.Douchy, 198.DoyIe, R.J., 29.Drachousof, 198.Dragendorff, O., 169.Drew, H. D. K., 60, 80, 94, 102, 200.Drishaus, I., 170.Druce, J. G. F., 43.Drummond, J. C., 248.Duffek, V., 61.Dufraisse, C., 116, 144.Duggan, M. M., 252.Duguid, J. B., 252.Dumanski, H., 43.Dumitrescu, (Mlle.) V., 201.Du Mont, H., 94.Dumont, P., 194.Dunin, M. S., 30.Dunn, J. S., 62.DunniclifT, H. B., 46, 59, 69, 193.D w t a n , W. R., 162.Duparc, L., 263.Durmd, J. F., 140.Durrant, P. J., 70.Dutt, S., 128.Duval, (Mme.), 68.Duval, C., 68.Du Vigneaud, V., 226.Dworzak, R., 198.Eagles, B. A., 221.Eakle, A. S., 275.Ebert, F., 71, 290.Ebert, L., 131.Eddington, A. S., 12.Eddy, C. A., 226.Edwards, 0. K., 32.Edwards, W. A. M., 40.Eegriwe, E., 189, 190.Efremov, N.N., 271.Ehrenberg, R., 202.Eichelberger, L., 86.Eisenbrand, J., 188, 189, 102.Eisenschitz, R., 131.Eitel, W., 49, 52, 255.Ekkert, L., 199.Ekwall, P., 61.Elam, (Miss) C. F., 277.Elford, W. J., 22.Elhardt, W., 201.Ellis, J. W., 21, 127.Elrid, E., 69.Elsasser, W., 284.Elsner, H., 101, 102, 201.Embden, G., 227, 228.Emmert, E. M., 214.Engemann, 194.Engledow, F. L., 218.Enk, E., 66.Ephraim, F., 47, 57.Epperson, (Miss) A. W., 188.Eriksson, S., 38, 294.E r s t , E., 304.Escher, H. H., 200.Etridge, J. J., 31.Eucken, A., 131.Euler, B. von, 245, 246.Euler, H. von, 245, 246, 249.Evans, B. S., 192.Evans, 0. M., 203.Evans, U. R., 39, 40.Evers, N., 248.Ewald, K. F. A., 203.Eyer, H., 225.Faber, H., 196, 272.Fairbanks, E.E., 271.Fairbourne, A., 76, 78, 79.Faltis, F., 92.Farmer, E. H., 122.Favorskaia, T. A., 204.Fawcett, E. H., 192INDEX OF AUTHORS' NAMES. 313Fawcett, R. C., 181.Federova, 0. S., 198.Fehn, H., 204.Feigl, F., 190, 191, 196.Feinschmidt, O., 233.Felix, B. B. C., 74.Fell, H. B., 237.Fellenberg, T. von, 272.Ferdmann, D., 233.Fernandes, L., 58.Ferrari, A., 70, 72, 297, 298.Fesefeldt, H., 202.Fetzer, W. R., 59.Fichter, F., 63, 65.Fink, H., 244.Fisch, J., 202.Fischbeck, K., 43.Fischer, F. G., 220.Fischer, Hans, 244, 245.Fischer, Hellmut, 44, 196.Fischer, J., 64, 69.Fischer, Joseph, 58.Fischer, O., 50, 61.Fischer, W., 44.Fischer, W. M., 29, 198.Fischler, F., 93.Fischmann, C., 249.Fisher, H.K., 248.Fiske, C. H., 231.Fleischhans, Z., 202.Fleury, P., 195, 201.FlBrsheim, W., 101.Fl6mner, 234.Flugge, R., 67.Fliirecheim, B., 124.Foerster, F., 60.Fogg, H. C., 51.Fokin, A. S., 203.Folcini, A. J., 190.Folin, O., 213.Foote, H. W., 71, 73.Fome, R., 199, 214, 215.Foulk, C. W., 194, 196.Fowler, R. H., 279.Fowles, G., 43.Frangois, M., 46, 201.Frangon, M., 47.Franke, W., 39.Franzen, H., 135.Frear, G. L., 45.Frebold, G., 273.Fred, E. B., 201.Fredenhagen, K., 63.Vreiman, A,, 31.Freudenberg, IC., 86, 87, 98, 104, 107,157, 225.Frey, K., 111, 112.Frick, 194.Fricke, R., 30, 45, 196.Friedel, E., 23.Friedel, G., 22, 24.Friedeman, T. E., 201.Friederich, 193.Friedlzinder, P., 162.Friedrich, A., 200.Friend, J.A. N., 73, 192.F r o m , E., 166.Frost, A,, 198.Fuchs, P., 201.Fiirth, J., 241.FWh, R., 13.Fujioka, Y., 19.Fujise, S., 157.Fukai, T., 201.Funakoshi, O., 190.Furman, N. H., 199, 203.Gabreels, A. A,, 201.Gadamer, J., 173.Gabler, G., 58.Gaffre, A., 201.Gall, H., 66.Cane, R., 139.Ganesan, A. S., 127.Ganguly, P. B., 29.Gapon, E. N., 202.Garbsch, P., 112.Garner, W. E., 127.Gaspar y Arnal, T., 190, 191.Gaythwaite, W. R., 32.Geiling, E. M. K., 225, 226.Gereces, A., 100.Gerhardt, (Miss) M., 149.Gerlach, W., 202.Germann, F. E. E., 69.Germer, L. H., 14, 284.Germuth, F. G., 190, 198.Gfeller, H., 59.Ghosh, S., 200.Giauque, W. F., 20.Gibson, C. S., 123, 142, 146.Giese, H., 50.Gilbert, F.L., 61, 81.Gilbert, L. F., 47.Gilchrist, H. S., 78.Gillie, J., 195.Gilman, H., 200.Gimeno, A., 201.Ginsberg, H., 197.Giorgi, F., 72, 295.Gleu, K., 54.Goebel, H., 150.Goebel, W. F., 239, 240, 241.Goergen, S. M., 102.Goldberg, A. A., 118.Goldfinger, P., 141.Goldschmidt, V. M., 38, 65, 290.Gomberg, M., 134.Gonz&lez, F., 201.Goodway, N. F., 144.Gordon, A. B., 124.Goronev. C.. 191.Gortne;,'R. 'A., 2 1 8.Gossner, B., 254, 255, 256, 257, 258,259, 260, 261, 263, 264, 267, 293314 INDEX OF AUTHORS’ NAMES.Goto, K., 180, 181.Gottfried, C., 265.Goubau, R., 200.Goubeau, J., 34.Gough, J., 252.Gouwentak, (Miss) C. A., 216.Graber, L., 264.Grafe, V., 207.Graham, F. V., 60.Gramkee, B. E., 72.Grant, J., 57, 194.Grassmann, W., 201.Grassner, F., 193.Grebenschtschikov, I.V., 204.Green, B. M., 101, 102.Grey, E. C., 195.Grimm, H. G., 35.Gromann, F., 202.Gross, P., 129.Grubitsch, H., 49.Griinsteidl, E., 189.Gruner, J. W., 267.Gulland, J. M., 174, 175, 176.Guntz, A. A., 192.Gurevich, L., 202.Gutbier, A., 69.Gutzeit, G., 185, 189.Haack, E., 144.Haas, P., 200.Haase, L. W., 193, 194.Hac, R., 59.Haeckel, S., 144.Hagg, G., 38, 291, 292, 294.Hahn, F. L., 196, 203.Hall, W. T., 187.Halla, F., 50, 200.Haller, H. L., 87, 89.Hallimond, A. F., 264.Hamasumi, M., 69.Hamer, (Miss) F. M., 163, 164.Hammick, D. L., 33.Hampton, H. A., 105.Hanawalt, J. D., 292, 293.Hann, R. M., 202.Hantzsch, A., 192.HanuS, J., 43.Harington, C.R., 225.Harris, L., 56.Harris, L. J., 251.Hart, M. C., 209.Harteck, P., 20, 41.Hartel, H. von, 131.Hartmann, F., 290.Hartmann, H., 45.Harvey, W. F., 239.Hasebrink, A. M., 40.Haslwanter, F., 193.Hwel, O., 297, 302.Haufe, E., 60.Haurowitz, F., 191, 242.Havighurst, R. J., 281.Hawk, P. B., 249.Haworth, R. D., 174, 175, 176, 179.Haworth, W. N., 94, 95, 96, 97, 102,Hayashi, M., 141.Heap, T., 154.Heathcoat, F., 139.Heczko, T., 198, 203, 204.Hedestrand, G., 129.Hedges, E. S., 30, 31.Heidelberger, M., 240, 241.Heilbron, I. M., 80, 90, 159, 220, 248.Heiling6tter, R., 194.Hein, F., 200.Heisenberg, W., 279.Heitler, W., 20.Helfenstein, A., 92.Helferich, B., 76, 94.Heller, A., 161.Heller, K., 185,189,190,198,200,203.Hellriegel, W., 47.Hellstrdm, H., 245, 246, 249.Hendricks, S.B., 298, 303.Henecka, H., 66.Hengstenberg, J., 110, 305.Henley, (Miss) R. V., 30.Henley, W. J. R., 32.Henry, T. A., 145, 152.Hentschel, H., 204.HeDburn. J. R. I.. 30.103, 104, 105, 107, 112.Hehng, M., 70. ’Hermann, K., 302.Hermsen, W., 169.Hernler, F., 200.Herrington, B. L., 2Herrmann, Z., 187.Hertlein, H. F., 307Hervev, J., 140.5.Herzog; R.. O., 104, 07.Hess, K., 74, 104, 106, 305.Hesse, O., 183.Hevesy, G. von, 271.Heyde, W., 201.Heyl, G., 171, 172.Hibbert, H., 76, 77, 78, 70.Hickinbottom, W. J., 99.Hicks, J. F. G., 39.Hieulle, A., 215.Hilditch, T. P., 208.Hill, A. E., 72.Hill, D. G., 41.Hill, H. S., 78.Hill, R., 242, 243.Hincke, W.B., 48.Hinnuber, J., 40.Hinshelwood, C. N., 53.Hirst, E. L., 97, 104, 105.Hoagland, D. R., 205.Hobson, R. P., 201.Hock, A. L., 139.Hock, H., 66.Hojendahl, K., 128.HBlterhoff, E. 60INDEX OF AUTHORS’ NAMES. 315Holtje, R., 57.Honig, M., 93.Honigschmid, O., 34, 35.Hoeppel, R. W., 196.Hoermann, F., 62.Hoffman, W. F., 219.Hoffmann, A., 59.Hoffmann, Alfred, 161.Hoffmann, F., 49, 195.Hoffmann, G. F., 60.Hoffmann, J., 48.Hofmann, K. A., 44.Hofmann, U., 44.Holden, 243.Holder, G., 197.Holgersson, S., 37, 67, 298.Holleman, A. F., 135.Holmberg, B., 82, 87.Holmes, E., 304.Holmes, E. L., 124.Holt, D. A., 271.Holtz, F., 251.Holtz, H. F., 214.Honda, K., 278, 279.Honeywell, E. M., 250.Hoon, R.C., 69.Hope, E., 161.. Hopff, H., 103.Hopkins, (Sir) F. G., 221.Hora, F., 198.Hornig, A., 60.Horrobin, S., 203.Hosenfeld, M., 44, 45, 270.Hoskins, C. R., 64.Hoth, W., 54.Houssa, A. J. H., 87.Hovorka, V., 43.Howells, W. J., 71.Hoyer, K., 200.Hoyle, J. C., 252.Hudson, C. S., 94, 99.Hudson, J. C., 39.Huttig, G. F., 67, 72, 202.Huff, E. R., 60.Huggins, K. A., 121.Hugh, W. E., 117.Hughes, 0. L., 73.Hume, E. M., 246.Hume-Rothery, W., 70, 289.Humme, H., 45.Hunt, J. K., 58.Hunten, K. W., 33.Hunter, E., 105.Hunter, G., 221.Hunter, H. L., 51.Hurd, C. D., 64.Hurtley, W. R. H., 133.Hussey, R. E., 137.Hyde, J. F., 141.Ihle, c., 201.Iimori, S., 271, 272.nge, w., 302.Illig, K., 44, 45.Inganni, A., 70.Ingersoll, L.R., 292, 293.Ingold, C. K., 31, 116, 119, 120, 124,Ipatiev, V. N., 42.Ipatiev, V. N., jun., 42.Ironside, R., 13.Irvine, (Sir) J. C., 76, 100, 102.Irving, F., 159.Isbell, H. S., 94.Ishibashi, M., 198.Ishikawa, F., 70.Itallie, E. J. van, 200.Itallie, T. B. van, 92.Iwaizumi, S., 291.139.Jackson, R. F., 102.Jackson, W. W., 259, 299.Jacobsohn, K;, 24.Jaeger, F. M., 300.Jaenckner, W., 58.Jahn, C., 197.Jakob, J., 263, 271, 272.Jakubson, S. I., 56.James, C., 51.James, R. G., 62.Jander, G., 63, 196, 204.Jander, W., 50, 52.Jantsch, G., 49, 67.Jellinek, K., 43, 52.Jenkins, F. A., 35.Jenkins, R. G. C., 249.Jensen, H., 225, 226.Jessop, G., 59.Jilek, A., 190, 196, 197, 203.Johanssen, K., 274.Johner, H., 108, 110.Johnson, C.R., 35.Johnson, J. D. A., 123.Johnston, H. L., 20.Johnston, J., 45.Jones, B., 193.Jones, C. H., 214.Jones, C. W. H., 55.Jones, D. B., 219.Jones, (Miss) M., 192.Jones, N. C., 63.Jones, W. S,, 249.Jordan, K., 70.Jorissen, W. P., 56.Josephson, K., 95, 106.Judy, P. R., 52.J u g , R., 69.Jungkunz, R., 193.Kacirkova, K., 203.Kahlenberg, L., 203.Kailan, A,, 60.Kalaehne, E., 56316 INDEX OF AUTHORS’ NAMES.W, J., 163.Kalina, A., 202.Kallmann, H., 41.Kamieliski, B., 203.Kaminsky, E., 292.Kandelaky, B., 61.Kandiah, A., 118.Kangro, W., 67.Kani, K., 258.Kantera, R., 65.Kapeller-Adler, R., 166.Kapitza, P., 278, 279.Kargin, W., 260.Karlsson, A., 37, 67, 298.Karrer, P., 92, 106, 111, 182,Kaschtanov, L., 58, 196.Kassler, J., 197.Kmsler, R., 67.Kasuya, G., 162.Katz, J.R., 104, 113, 126.Kay, H. D., 231, 236.Kaya, S., 278, 279.Keesom, W. H., 302.Keilin, D., 243.Keimatsu, S., 162.Kempkens, J., 65.Kendall, A. I., 201.Kendall, E. C., 222.Kendall, F. E., 241.Kenner, J., 75, 132, 135, 141.Kenny, W. R., 192.Kentish, W. S., 142, 143.Kenyon, J., 32, 87, 90.Kermack, W. O., 239.Kerr, C. A., 145.Kerr, P. F., 269.Kichlu, P. K., 53.Kiesel, A., 218.Hikuchi, S., 285.Kiliani, H., 94.Kimura, M., 287.King, A. J., 290.King, A. S., 20.King, E. J., 235, 236.King, H. J. S., 43.King, W. B., 200.Kircheisen, E., 60.Kirner, W. R., 137.Kirschman, H. D., 204.Kisch, B., 31.Kitasato, Z., 178.Klar, K., 200.Klee, W., 174.Klein, G., 199.Kleiner, H., 168.Klemenc, A., 41.Klement, R., 239.Klemm, W., 48.Klenk, E., 223, 224.Kleucher, E., 140.Kljegl, A., 144.Khe, W.D., 46.246, 249.245,Klingler, E., 65.Klinkenburg, A., 73.Klippel, H., 59.Kljatschkina, B., 201.Klockow, R. F., 198.Knaggs, (Miss) I. E., 75, 80, 304.Kneser, H. O., 53.Knop, J., 195.Knowles, H. B., 194.Knudson, A., 250.Kohler, L., 203.Koerner, O., 50, 67.Kogan, A. I., 198.Kogert, H., 203.Kohler, E. P., 166.Kohlrausch, K. W. F., 19.Kolbe, A., 173.Kolthoff, I. M., 188, 192, 197.Komarov, S. A., 233.Kon, G. A. R., 117, 118.Kondo, H., 180.Konopicky, K., 40.Kopp, H., 31.Korenman, I. M., 189.Kornfeld, (Frl.) G., 65.Koschara, W., 169.Koslovsky, M.T., 201.Kossodo, M., 68.Kostanecki, S. von, 152, 153.Kbszegi, D., 197.Kotrba, J., 192.Kdzu, S., 258.Kraiczek, R., 73.KrajEinoviE, M., 200.Krakowiecki, S., 56.Kramer, B., 239.Kranig, J., 68.Kratky, O., 305.Kratz, A., 159.Kraus, C. A., 47.Kraus, O., 259, 260, 261.Krauss, E. von, 111.Krauss, F., 61, 68, 69.Kraut, H., 50.Kreitmair, H., 251.Kremers, K., 73.Khpelka, J., 202.Kretzschmar, W., 198.Krilenko, N., 198.Krings, W., 52, 65.Kringstad, H., 302.Krishna, B. H. R., 201.Krishnamurti, P., 307.Krishnan, K. S., 16, 126, 127, 128,Krishnaswami, K. R., 58.Krombach, H., 70, 71, 73.Krueger, A. C., 203.I(rumholz, P., 185, 189, 190, 191.Kruta, E., 177.Ksanda, C. J., 293.Kubelkova, O., 196.Kubina, H., 194.277, 287, 307INDEX OF AUTHOB8' NAMEIS.317Kuffner, F., 172.Kuhn, R., 83, 86, 92, 121, 141.Kullgren, C., 201.Kunitz, W., 255, 264, 266.Kunz, A. H., 192.Kunz, K., 162.Kurbatov, J., 260.Kurdjumov, G., 292.Kuroda, (Miss) C., 168.Kurtz, F., 196.Kutscher, F., 234.Kutzlnigg, A., 199.Kuzmenko, S. M., 31.L a m , F., 64.Lainau, A., 69.Laing, (Miss), M. E., 189, 192.Lakhumalani, J. V., 133.Lambie, C. G., 239.Lande, (Mme.), 72.Landsberg, G., 287.Landsbury, J., 189.Landsteiner, K., 241.Lang, K., 227.Lang, R., 196.Langdon, G. M., 22.Lange, B., 62.Lange, (Miss) L., 129.Lange, W., 56, 67.Langer, R. M., 286.Laming, (Miss) J. C., 204.Lapworth, A., 116, 119.Larson, C., 214.Lauer, W. M., 200.Lausen, C., 273.Lavin, G.I., 58.Leathes, J. B., 209.Lebeau, P., 63.Le Blanc, M., 67.Le Boucher, L., 68.Lee, 0. I., 271.Lees, N., 142.Le FBvre, R. J. W., 133, 141.Le Grange, J. M., 270.Lehmann, G., 66.Lehnartz, E., 201.Lehnartz, M., 230, 233.Leimbach, G., 70.Leipert, T., 200.Leisek, E., 60.Leitmeier, H., 190, 191.Lenher, S., 27.Lenher, V., 60.Lennard-Jones, J. E., 127.Lerch, W., 46.Leroux, J. A. A., 70.Lesslie, (Miss) M. S., 143.Leuchs, H., 161.Levene, P. A., 87, 89, 94, 206, 223,224, 236, 236.Levi, (Miss) M., 47.Levitzki, A. Y., 198.Lewis, B., 63, 64.Lewis, J. R., 198.L e v , F., 194.Libina, D. M., 65.Liebrich, E., 61.Liesche, O., 193.Linde, H., 69.Lindemann, H., 136, 168, 184.Lindner, J., 193.Linnik, W., 283.Linser, H., 199.Linstead, R.P., 117, 118.Lippich, F., 200.LiSka, J., 190.List, F., 196.Lloyd, W. V., 170.Lobinger, K., 60.Lawenberg, K., 220.Lowy, O., 40.Lohmann, K., 230, 231, 232.London, F., 20.Long, C. W., 97.Lonsdale, (Mrs.) K., 126, 126, 127,277, 304.Lorah, J. R., 46, 71.Lorenz, R., 42, 53, 70, 72.Lortie, L., 49.Loth, O., 69.Lowry, T. M., 59, 61, 81, 88, 93, 127,Lucas, H. J., 139.Lucas, R., 193.Luck, J. M., 215.Luhrs, A., 68.Luthy, M., 108.Luft, F., 63.Lukas, J., 190, 196, 197, 203.Lunde, G., 200.Lundell, G. E. F., 194.Lunge, G. H., 66.Lux, A., 86.Lyche, R. T., 93.170.Maass, O., 33, 58.McAlpine, R. K., 198.McAulay, A. L., 39.McBain, J. W., 22, 189, 192.McClelland, E.W., 163.McClendon, J. F., 200.McCrosky, C. R., 60.McCrumb, F. R., 192.Macdonald, J. L. A., 76.McD&e, R. O., 72.Macgillavry, D., 104.Machatschki, F., 257, 261, 266, 268,MacInnes, D. A., 203.McIntosh, D., 26.McKeehan, L. W., 290.McKenzie, B. F., 222.Mackenzie, J. E., 94.McKenzie, M. R., 230.294318 INDEX OF AUTHORS’ NAMES.Maclean, (Mrs.) I. S., 206, 209, 212,McLennan, J. C., 18, 75, 279, 303.Macmaster, J. C., 21.MacNicol, M., 124.McRae, J. A., 119.McVicker, W. H., 21.Mahajani, G. S., 279.Majdel, J., 195.Majert, D., 63.Malhotra, K. L., 46.Malitzky, W. P., 201.Malquori, G., 69, 70, 71, 73.Manchot, W., 55, 66.Mandelstam, L., 287.Manley, J. J., 26.Manske, R. H. F., 162.Marek, I., 200.Maricq, L., 204.Mark, H., 74, 103, 107, 143, 144, 304,246.MMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMM305, 306.:arkert, L., 86.larks, H.P., 225.:arque, J., 195, 201.:arsh, J. K., 21, 22.lamhall, A. L., 58.:arsson, V., 194.:artin, W. H., 22.Iartinet, J., 162..artini, A., 186, 189, 190..artland, M., 234, 236, 237.larvel, C. S., 199.:ascarelli, L., 141..asing, G., 72.:asiyama, Y., 279.:askell, E. J., 215, 216.:ason, C. M., 192.:ason, H. L., 222.:ason, T. G., 215, 216.:asumoto, H., 279.:athers, F. C., 60.:atheson, G. L., 58.latoba, S., 69.:atossi, F., 287, 288.Iatsukawa, T., 72.latthieu, M., 298.Iauguin, C., 264, 282.:aurstad, A., 301.:ay, G., 45.Iayer, E.W., 148.:ayr, C., 202.lead, T. H., 73.:ebane, W. M., 46.Ieerwein, H., 56, 144.iegson, N. J. L., 69.ieierson, G. A., 62.ieisenheimer, J., 134, 144.Leissner, W., 36.[eldrum, N. U., 223.[elle, F. A. van, 304.[eloche, V. W., 61.[elsen, J. A. van, 148.[enzel, H., 58, 198.Menzer, C., 299.Menzies, A. C., 18.Menzies, A. W. C., 28.Merksammer, E., 159.Merwin, H. E., 255.Metz, L., 191.Meulen, H. ter, 193.Meuwsen, A., 55.Meyer, A. H., 198.Meyer, C. H., 151.Meyer, F., 46.Meyer, J., 65.Meyer, K. H., 103, 107, 115, 305.Meyer, L., 131.Meyerhof, O., 231, 232, 233.Meyring, K., 196.Michalek, J. C., 53.Mie, G., 110.Migge, A., 144.Mika, J., 192.Mikeska, L. A., 87.Miksch, R., 198.Miles, F.D., 305.Miller, (Miss) C. C., 56.Miller, E. J., 97.Miller, L. B., 45.Millet, H., 204.Mills, 140.Milobedzki, T., 56, 198.Mindalev, Z., 197.Minsaas, J., 93.Mirsky, A. E., 242.Mitchell, C., 190.Mitchell, T., 117.Mizushima, S., 129.Mobius, E., 67.Moller, H., 304.Moelwyn-Hughes, A. E., 99.Mottig, H., 53.Mohammed, S., 59.Moldenhauer, W., 53, 54, 203.Moll, H., 197.Monasterio, G., 249.Monypeny, (Miss) M. W., 22.Moore, C. N., 250.Moore, T., 247, 251.Morey, G. W., 73.Morgan, G. T., 160, 304.Morgan, S. O., 129.Morgan, W, T. J., 234, 235, 236.Mori, R., 89.Morlet, E., 72.Morozewicz, J., 264.Morris, V. N., 201.Morton, R. A., 248.Mosendz, L., 192.Moser, L., 196, 198.Moskowitz, S., 72.Mottes, P. K., 216.Moureu, C., 144.Moureu, H., 116.Moyer, W.W., 141.Moyse, H. W., 139INDEX OF AUTHORS’ NAMES. 319Mozolowski, W., 229.Muller, A., 99.Miiller, Alex, 75, 304.Miiller, Erich, 61, 203, 204.Miiller, Ernst, 66.Miiller, H., 203.Miiller, R., 40.Miiller, W. J., 40.Muench, 0. B., 69.Mukherjee, S. K., 288.Mulliken, R. S., 19.Mumford, S. A., 33.Muntwyler, O., 148.Murakami, T., 69, 71, 72.Murayama, Y., 150.Mureck, H. G., 61.Munnann, E., 191.Murodka, H., 69, 70.Musket, I. E., 122.Mussgnug, F., 256,257, 260,263, 293.Mutaftschiew, Z. C., 40.Nabenhauer, F. P., 211.Nachmansohn, D., 232.Nagasalro, N., 49.Nagy, V. L., 213.Namasivayam, D., 30.Nametkin, S. S., 200.NBray-Szab6, S., 259, 265, 299.Nasini, A. G., 127.Natta, G., 37, 67, 71, 298.Naves, R., 140.Necke, A., 203.Nef, J.U., 140.Negresco, T., 202.Nekrassov, B. V., 75.Nekrassov, V., 200.Neumeister, A., 71.Neuscheller, J., 93.Newcomb, C., 195.Newton, R. F., 43.Nicholson, V. S., 95.Nicloux, M., 200.Niederer, K., 61.Niemann, J., 159.Niessner, M., 196.Nieuwenberg, C. J. van, 48, 50.Niggli, P., 276.Nilutm, V. V., 268.Nikolaiev, V. I., 72, 73.Nilssen, S., 297.Nishimura, H., 72.Nisi, H., 287.Nistler, J., 93.Nitckie, C. C., 202.Nitta, I., 304.Noddack, I., 65.Noddack, W., 65.Nodzu, R., 164.Noe, A., 87.Norris, E. R., 248.Norris, J. F., 139.Northrop, J. H., 241.Nouvel, 45.Noyes, W. A., 55.Nuka, P., 64.Nusbaum, C., 278.Oberhauser, F., 50, 191, 187.Ochiai, E., 180.ohman, E., 290.Oeman, E., 192.Oertel, G., 182.Oftedal, I., 297.Ogawa, Y., 38, 69.Ogburn, S.C., jun., 197.Oglesby, N. E., 72.Ohle, H., 90, 93, 96.Okido, S., 200.Okubo, J., 279.Oldham, J. W. H., 100.Oliverio, A., 42.Olivier, S. G. J., 139.Onorato, E., 301.Orlandi, C., 58.Ormont, B., 193.Orrh, A., 199.Orton, K. J. P., 124.asawa, A., 38, 291.Ott, E., 86.Otterbacher, T., 199.Owens, W. M., 80, 90.Oya, S., 72.Pabst, A., 38, 136, 290.Pacsu, E., 99.Pagel, H. A., 48.Paget, H., 145.Pakschwer, S., 72.Palache, C., 274, 275.Palacios, J., 268.Palmaer, W., 39.Palmer, L. S., 247.Paneth, F., 40, 202.Pantschenko, G. A., 191.Papaioanou, G., 170.Papish, J., 271.Parker, T. W., 60.Parkes, G. D., 170, 213.Parnas, J. K., 229.Partington, J.R., 59, 60.Partridge, E. P., 45.Paaserini, L., 37, 67, 71, 294, 298.Patat, F., 41.Patten, C. G., 66.Patzig, E., 134.Pauling, L., 63, 132, 265, 296.Pavelka, F., 191.Paweck, H., 203.Peacock, D. H., 77.Pearson, L. K., 209.Peat, S., 96.Pechmann, H. von, 123320 INDEX OF AUTHORS’ NAMES.Peel, J. B., 27, 49, 69, 160.Peitzsch, W., 161.Pdabon, H., 72.Percival, E. G. V., 67, 68.Perkin, A. G., 125.Perkin; W. H., 115, 161, 162, 164,Perkins, T. R., 46.179, 181.Pernot,-(Mlle.) M., 70.Persson, A,, 52.Persson, E., 290.Peters, K., 40.Peterson, W. H., 201.Petrenko, B. G., 73.Petrenko, G. J., 73.Petrikaln, A., 19, 56.Pfannensteil, 251.Pfeiffenberger, A., 70.Pfundt, O., 204.Phillips, A.W., 34.Phillips, H., 32, 87, 90.Phillips, J. W. C., 33.Phillips, T. G., 214.Philpott, D., 163.Phragmh, G., 289.Pickard, R. H., 87.Picon, 62.Pierce, J., 65.Pieters, H. A. J., 48, 188, 203.Pikl, J., 171, 173.Pineau, J., 69.Pinkey, K. G., 222.Piper, S. H., 75, 211, 304.Pirie, N. W., 222.Pirrone, F., 54, 201.Plaksin, I., 72.Plant, S. G. P., 160, 164, 165, 181.Platt, M. E., 78.Plepp, G., 272.Plotnikov, V. A., 66.Plummer, W. G., 75, 303.Pohland, E., 47.Pohle, K., 228.Polessitsky, A., 46.Polgar, N., 172, 173.Pollard, A., 156.Polonovski, Max, 183.Polonovski, Michel, 183.Pomeranz, C., 160.Ponte, M., 286.Ponzio, G., 166.Poole, J. H. J., 12.Popov, S., 192.Porter, C. R., 96, 200.Portillo, R., 46.Posega, R., 178.Posnjak, E., 72.Posternak, S., 89.Posternak, T., 89.Potter, H.H., 278, 291.Powell, G., 126.Pratesi, P., 69, 196.Pratt, W. L. C., 199.Pregl, F., 200.Prescott, C. H., jun., 48.Prdvost, C., 120.Price, W. J., 55.Pring, (Miss) M. E., 204.Pringsheim, P., 101, 127, 287.Prins, J. A., 307.Pritchett, E. G. K., 192.Pritzker, J., 193.Probst, J., 57.Prochovnick, V., 93.Proisl, J., 65.Pryde, J., 236.Pschorr, R., 176.Pucher, G. W., 213, 214.Pufahl, F., 141.Pugh, W., 51.Pummerer, R., 161.Purcell, R., 53.Purcell, R. H., 26.Purves, C. B., 78.Pyl, G., 54.Pyman, F. L., 172.Quayle, 0. R., 78.Querenghsser, H., 61.Quin, J. P., 94.Rabinovitsch, M., 203.Rhc, F., 98.Raman, (Sir) C. V., 16, 17, 127, 277,278, 286, 307.Ramanadham, M., 128.Ramdohr, P., 273.Ramsdell, L.S., 268.Rao, B. S., 147.Rbo, I. R., 287, 303, 307.Rao, S. R., 126.Raper, H. S., 209.Raper, R., 183.Rapin, G., 65.Raschig, K., 98.Rasetti, F., 20.Raub, E., 70.Ravenswaay, (Mlle.) H. J., 193.Rawlins, F. I. G., 19.Ray, J. N., 173, 179.Ray, P., 47.Ray, P. C., 300.Rayleigh, (Lord), 53.Raymond, A. L., 89, 94, 235, 236.Rebibre, G., 250.Reed, R. D., 190.Reich, W., 104.Reichardt, H., 68.Reich-Rohrwig, W., 198.Reid, A., 13.Reif, W., 196.Reilly, J., 101.Reinders, W., 73.Reiner, L., 31.Reinitzer, B., 195IXDEX OF AUTHORS' NAMES. 321Reis, A., 304.Reith, J. F., 198, 200.Remington, R. E., 200.Remy, H., 68.Restaino, S., 70.Rewald, B., 206.Rheinlander, A.H., 135.Ricca, B., 54.Rice, F. O., 117.Richards, T. W., 34, 47.Richter, G. H., 137.Richter, H., 50.Richtmyer, N. K., 166.Rick, A., 59.Riebeling, C., 227.Riesenfeld, E. H., 68.Riesmeyer, A. H., 197.Riiber, C. N., 93.Riley, H. L., 26, 43, 68.Rindl, M., 132.Rime, F., 269.Ripan, R., 49, 60, 194.Roberts, H. S., 293.Robertson, A., 99.Robertson, J. M., 305.Robinson, (Miss) M. E., 214.Robinson, P. L., 27, 49, 60.Robinson, R., 89, 116, 134, 152, 153,154, 156, 162, 179, 186.Robison, R., 234, 235, 236, 237.Rockstroh, J., 48.Rodebush, W. H., 53.Rodriquez Pire, L., 65.Ram, O., 187.Roell, E., 54.Rordam, H. N. K., 82.Rojahn, C. A., 199.Rojansky, V., 12.Rolf, (Miss) I. P., 206.Roman, W., 200.Ronshina, N.M., 191.Rose, A., 42.Rose, H., 273.Rosen, B., 127, 287.Rosenhauer, E., 164.Rosenheim, A., S7.Rosenheim, O., 248, 250.Rosenkranz, E., 72.Rosenthal, W., 151.Rosenthaler, L., 201.Rosinsky, W., 83.Rosser, R. J., 165.Rossetti, C., 57,Rostkovski, A. P., 71, 72.Roth, A., 151.Roth, O., 203.Rothachild, K., 50.Rothstein, E., 119.Roudnick, J., 65.Rounsefell, E. O., 70.ROUSS, H., 192.Rowlands, J. R., 59.Rozsnov, S. N., 198.REP.-VOL. XXVI.Rubino, P., 251.Rudat, A., 43.Rudd, H. W., 135.Rudge, E. A,, 38.Ruedy, R., 278.Rum, R., 73.Ruff, O., 64, 66, 69, 71, 297.Ruhemann, M., 40.Ruigh, W. L., 190.Rupe, H., 161.Rupp, E., 13, 14, 194, 285.RUM, W., 51.Russell, A., 21, 22.Ruzicka, L., 146, 148.Ruzicka, W., 93.Ryan, H., 29, 163.Rydbom, M., 246, 249.Sabin, F.R., 207.Sachtleben, R., 35.Slingewald, R., 129.Sahyun, M., 226.Sait6, S., 197.Salisbury, H. M., 192.Salomon, H., 92.Salter, G. E., 227.Salvia, R., 293.Samwel, P. J. P., 104.Sand, H. J. S., 203.Sandstedt, R. M., 219.Sandved, K., 70.Sanfourche, A., 50.Sauemald, F., 73.Saunders, S. L, M., 133.Sawyer, F., 189.Sayce, L. A., 67.Scagliarini, G., 59, 195.Schachheldian, A. B., 201.Schaefer, C., 18, 287, 288.Schaefer, K., 59.Schairer, J. F., 73.Schaller, W. T., 258.Scheede, A., 276.Scheffer, J., 60.Schemjakin, F. M., 30.Schenck, R., 70.Scherpenberg, A. L. van, 201.Scheuing, G., 170.Schiebold, E., 259, 262, 277, 300.Schieferdecker, W., 203.Schikorr, A., 39.Schikorr, G., 39,Schimmel, F., 66, 69.Schinle, R., 104.Schlenk, W., '143.Schlubach, H.H., 93, 101, 102.Schlundt, H., 46.Schmager, H., 56.Schmid, H., 65.Schmidt, A,, 29, 198.Schmidt, E. A. W., 972.Schmidt, G., 228.322 INDEX OB AUTHORS’ NLMES.Schmidt, O., 166.Schmidt, R. E., 144.Schmidt, T., 61.Schneider, E., 276.Schneider, W., 304.Schoeller, W. R., 197.Schon, K., 93.Schopf, C., 169.Schopff, M., 132.Schollenberger, C. J., 197.Schormiiller, J., 60, 187, 191.Schramm, W., 68.Schroder, W., 70.Schrodinger, E., 11.Schroter, R., 86.Schuth, W., 48.Schulek, E., 194.Schultze, H., 174.Schulz, G., 70.Schulze, E., 217.Schumacher, H., 227.Schumacher, H. J., 66, 68, 64.Schutt, K., 197.Schwaibold, J., 200.Schwartze, E.W., 202.Schwarz, R., 60, 61, 67.Schweitzer, E., 202.Schweitzer, O., 112.Schwicker, A., 192, 197, 198.Scott, A. F., 36.Scott, D. A., 226.Scott, W. D., 122.Scroggie, A. G., 62, 301.Sears, G. W., 197.Seguin, (Mlle.) L., 201.Seibt, S., 148.Seiser, A., 203.Sekito, S., 292.Seljekoff, N., 292.Selman, J., 126.Semenzov, A., 74.Semmler, F. W., 147, 148.Sen, B. K., 167.Sen, K. B., 196.Sengupta, P. N., 280.Seyewetz, A., 198.Sharp, P. F., 216.Shear, M. J., 239.Shiba, H., 307.Shibata, Z., 62.Shinagawa, T., 71.Shinoda, J., 163, 166.Shinozaki, 150.Shintre, V. P., 147.Shoppee, C. W., 31, 116.Short, W. F., 126.Shriner, R. L., 211.Shukov, I. I., 203.Shurink, H. B. J., 304.Sidgwick, N. V., 106, 184.Sieber, H., 76.Siegel, W., 198.Shapiro, c.v., 19.Sievertz, V., 31.Signer, R., 108, 110, 111, 112.Silberstein, J., 70.Rimek, B. G., 198.1 Simon, A., 60, 62, 61.Simon, F., 40, 290.Simonsen, J. L., 142, 146, 147.Simpson, E. S., 274.Simpson, I. A., 90.Skinner, A. F., 100.gkramovsky, S., 48.Slater, A., 138.Slavin, M., 73.Small, L. F., 181.Smallwood, H. M., 41.Smiles, S., 141.Smith, A. D., 66.Smith, E. A,, 200.Smith, E. H., 196.Smith, F. D., 199.Smith, G. F., 46, 93.Smith, H. H., 246.Smith, J. W., 27, 36.Smith, L., 62.Smith, S. B., 72.Smith, W., 198.Smithells, C. J., 61.Smita, A., 28, 41, 63.Smorodincev, A., 233.Smyth, C. P., 128, 129, 139.Snow, C. P., 286.Soames, K. M., 237.Sogani, C. M., 126.Sokolov, P.I., 202.Soltys, A., 200.Someya, K., 198, 203.Soni, C. L., 69.Sonn, A., 83, 169.Souci, S. W., 93.Soutar, C. W., 76.Spack, A., 71.Spacu, G., 62, 60, 186.Skaliks, w., 49.Spiith, E.., 156, .170, 171, 172, 173,Speer, J. H., 209.177, 178.Spender, E.,. 196.Spencer, J. F., 204.Spencer, L. J., 273.Spielberger, F., 266.Spittle, H. M., 61.Spitzh, V., 68, 196.Sponer, (Miss) H., 21.Sponsler, 0. L., 107.Springemann, W., 192.Sreenivasaya, M., 201.Sthlhane, B., 72.Stanley, W. M., 141.Stather, F., 222.Shudinger, H., 108, 110, 111, 112,113, 114, 148.Steck, L. V., 73.Steenhauer, A. J., 191MDEX OF AUTHORS’ NAMES. 323Steiger, G., 64.Stein, B., 144.Stein, C. P., 64.Shiner, W., 63.Stephan, E., 71.&Arba-Bohm, J., 48.Stern, S., 65.Steudel, H., 249.Stevens, T.S., 124.Stevenson, J. W., 102.Steward, F. C., 207.Stewart, A. W., 21.Stewart, C. P., 221, 251.Stewart, F. B., 68.Stewart, G. W., 126, 307.Stewart, M. L., 126.Stiles, W., 205.Stilwell, C. W., 67.Stock, A., 44, 47, 193.Stockdale, J., 40.Stokoe, W. N., 210.Stoll6, R., 162.Stollenwerk, W., 198.Stoops, W. N., 129.Story, C. W. H., 126.Stranski, J. N., 40.Straub, J., 194.Strebinger, R., 195, 196.Stringfellow, W. H., 63.StrufEmann, F., 199.Strugadski, M., 201.Stscherbakov, J. G., 65.Stuart, H. A., 129.Stuber, B., 227.Stuhlmann, H., 66.Stull, A., 241.Stutzer, H., 194.Subbarow, Y., 231.Suciu, G., 186.Sucksmith, W., 278.Sudborough, J. J., 133.Sudzuki, H., 180, 181.Sugaeaws, S., 162.Sugden, (Miss) R., 70.Sugden, S., 31, 32.Sullivan, J.J., 117.Sunde, C. J., 200.Sunier, A. A., 36, 72.Suri, H. D., 46, 193.Susich, G. von, 304, 306.Suwelack, O., 30.&6da, J., 203.Swart, E., 28.Swift, E. H., 195.Szebelledy, L., 189, 196.Szebednyi, P., 197.Tiiufier, K., 93.Tskei, T., 72.Tamchyna, J., 196.Tananaev, N. A., 190, 191.Tartar, H. V., 46, 71.Tasman, A., 66.Tatmi, G., 162.Taylor, A. M., 19, 301.Taylor, F. A., 224.Taylor, H. S., 41.Taylor, W. H., 259, 299, 300.Tchakirian, A., 48.Teletov, J., 195.Terres, E., 64.Terrey, H., 37, 290.Terroine, 209.Terry, E. M., 86.Testoni, G., 197.Thater, K. L., 48.Thaysen, A. C., 101, 102.Theilacker, W., 144.Thiel, A., 192, 202.Thiele, H., 184.Thiessen, P.A., 48, 60, 61, 67.Thilenius, R., 193.Thompson, A., 90, 220.Thompson, F. C., 192.Thomson, G. P., 13, 14,286.Thomson, (Sir) J. J., 13, 26.Thorpe, J. F., 142.Thiirmer, A., 196.Thurnwald, H., 202.Tillett, W. S., 240.Tilley, C. E., 274.Timmermans, J., 27.Tipler, A. F., 60.Titschack, 54.Tixier, G., 250.Todt, F., 39.Topelmann, H., 203.Tolmatmheff, P., 46.TomiEek, O., 204.Torres, M., 166.Townley, J. E., 73.Traube, M., 214.Trautz, M., 72, 69.Travers, A., 46.T&nel, M., 203.Trevan, J. W., 226.Trillat, J. J., 40, 307.Trogus, C., 306.Tronstad, L., 40.Truog, E., 198.Tscherniaev, J., 69.Tschugaev, L., 69.Tsuzuki, Y., 104.Tucker, C., 192.Tunnicliffe, H. E., 221.Turley, H.G., 90.Turner, E. E., 133, 136, 137, 143.Turner, H. A., 141.Turner, W. E. S., 36.Tuyn, W., 37.Tyden, H., 201.Uchida, Y., 287.Uemura, T., 260324 INDEX OF AUTHORS' NAMES.Uhl, A., 203.Ullmann, F., 132.Umbach, H., 68, 69.Urech, E., 114,Urk, H. W. van, 189, 191, 192, 199.Uschakov, M. I., 193.Uzel, R., 203.Vaidyanathan, V. I., 126, 307.Valdes, L., 203.Valensi, G., 71.Velentiner, S., 291, 293.Vallance, R. H., 73.Vanee, J. E., 73.Vanzetti, B. L., 42.Varela, B., 251.Vargha, L. von, 90, 96.V&sArhelyi, B., 198.Vasiliev, A., 194.Vaubel, W., 191.Veen, A. G. van, 146.Vegard, L., 301, 302.Veibel, S., 201.Venkataraman, K., 152, 153.Venkateswaran, S., 127.Vensovitch, N., 203.Vernon, R. H., 80.Vernon, W.H. J., 197.Veselovski, A. A., 271.Vickery, H. B., 212, 213, 214.Viebock, F., 92.Villecz, P. von, 194.Virden, C. J., 176.Vogel, F., 57.Vogelenzang, E. H., 193.Vogt, J. H. L., 263.Vohsen, V. E., 290.Voicu, J., 201.Voigt, W., 192.Volkholz, H., 201.Volkmer, H., 64.Voogd, J., 36, 37.Vorliinder, D., 59, 199, 201.Voskressenskaja, N. K., 71.VotoEek, E., 98, 192.Vournasos, A. C., 44.Vrabbly, (Frl.) V., 245.Waelseh, H., 242.Wagenaar, M., 199.Wagner, G., 301.Wagner, P. A., 273.Wagner-Jeuregg, T., 33, 86.Wehl, W., 46.Walden, P., 129, 130.Wallace, J. H., jun., 199.Wallerius, G., 200.Walter, C., 150.Walter, J. M., 47.Walter, Z. T., 46.Walti, A., 89.Ward, A. M., 139, 190.Wardlaw, W., 61, 62, 67, 68.Warren, B.E., 257, 300.Wartenberg, H. von, 69.Waasermeyer, H., 227, 228, 229.Wassmuth, E., 58.Watanabe, T., 307.Waters, E. T., 236.Wayland, E. J., 273.Webb, H. W., 55.Webb, J. I., 104.Webster, T. A., 248, 249.Webster, W. L., 278, 279.Wegscheider, R., 134.Wehrli, S., 112.Weichselfelder, T., 68.Weiner, R., 203.Weiss, R., 159.Weissberger, A., 129.Weissenberg, K., 74, 105, 305.Welch, K. N., 145.Wendehorst, E., 61.Werner, O., 129, 130.West, C. J., 223.West, J., 259, 260, 265, 281, 300.West, W. A., 28.Westgren, A., 38, 289, 294.Weston, F. R., 26.Wever, F., 293.Weyer, P., 61.Whelm, M. S., 78, 79.Whitby, L., 43, 197.White, A. H., 45.Whitmore, F. C., 199.Widmer, R., 182.Widmer, Rose, 92.Wieland, H., 39, 169, 170, 181, 182,Wijk, A. van der, 55.Wiley, R. C., 197.Wilke-Dorfurt, E., 61, 272.Wilkins, H., 32.Willard, H. H., 192, 203.Willey, E. J. B., 53.Williams, J. W., 128, 129.Williams, S. V., 61.Willingshoffer, K., 198.Willis, G. H., 130, 137.Willisford, L. H., 72.Willstiitter, R., 50, 104, 220.Wilson, G. L., 93.Winchell, A. N., 264.Winter, D. A., 26.Winterfeld, K., 183.Winterhalder, L., 170.Winterstein, A., 92, 121.Wintersteiner, O., 225.Winzer, R., 42, 70, 72, 193.Winzheimer, E., 149, 150.Wise, E. C., 209.Withrow, J. R., 190.Witmer, E. E., 12.Witt, J. C., 45.212INDEX OF AUTHORS’ NAMES. 325Wittig, G., 168.Woitinek, H., 71.Wolf, H., 194.Wolf, K. L., 129.Wolf, L., 56.Wolf, M., 290.Worn, P., 70.Wolfrom, M. L., 92.Wolk, L. J. van der, 204.Wollak, R., 197.Wood, (Miss) E. S., 133, 136.Wood, (Miss) L., 45.Wood, R. W., 18,287.Woodman, H. E., 218.Woodstock, W., 61.Woolcock, J., 53.Wooster, C. B., 56.Wright, C. M., 37, 290.Wright, L. E., 213.Wiinschendorff, M. H., 57.Wiirstlin, EL., 271.Yensen, T. D., 293.Yntema, L. F., 202.Yoshiki, B., 258.Yoshimura, J., 272.Young, P., 192, 203.Young, W. G., 64.Zachariasen, W. H., 297, 301.Zahn, C. T., 128.Zaimis, P., 204.Zaitzev, N. A., 192.Zaljesov, G., 200.Zambonini, F., 70,202,260,273, 275.Zechmeister, L., 104, 245.Zeile, K., 244.Zelizko, J. V., 270.Zemplh, G., 99, 100.Ziegler, K., 144.Zilg, H., 57.Zimmermann, A., 53.Zimmermann, W., 193.Zintl, E., 42, 204.Zocher, H., 23, 24.Zohner, K., 182.Zunino, 79.Zvjaginstsev, 0. E., 42

ISSN:0365-6217    

DOI:10.1039/AR9292600309

出版商:RSC    

年代:1929

数据来源: RSC