摘要:

REVIEWS OF BOOKS 3 649 producing the book is said by the authors to be " the fceling that our good fortune in acquiring a large mass of previously inaccessible data leaves u s with an obligation to collect this into one place for ease of access ". Certainly. to have so many spectra brought together in one volume is most valuable, the more so since many of them have not previously been published. The molecules whose spectra are presented range from triatomic to naphthalene and even bigger molecules. There are short introductory accounts of the underlying theory and of the experimental methods, but the bulk of the book is devoted to showing and interpreting the spectra, molecule by molecule. For each molecule, the full photoelectron spectrum is shown first; and then, under higher resolution, each " band " in the full spectrum.The book is intended to be a reference work for research workers. As such it will be invaluable to anyone interested in the electronic spectra of molecules and ions; and, indeed, to anyone interested in molecular orbitals, for whatever purpose. With its hundreds of excellent line drawings, the book as a whole can be said to be well produced. There are, however, signs of too hurried preparation. Thus on page 6, figs. 6.23, 6.26 and 6.27 are stated to refer to the spectra of diacetylene, cyanoacetylene and cyanogen; but in fact the figure captions make it clear that the figures refer to acetylene-d2, diacetylene and cyanoacetylene respec- tively. The text appears not to have been checked quite as carefully as it should have been.Othei errors, not entirely trivial, lead to the same conclusion. Thus (lb2)2 is written in error for (lb# (p. 78, line 7); lB1 is written in error for 2B1 (p. 77, table 4.4; p. 79, table 4.6; p. 81, table4.7); (1b)2 is in error for (lb1)2 (p. 81, line -2); v1 is in error for v2 (the bending vibration of SO,; see p. 85); and lxU is in error for lxu (p. 170). On p. 87 (line 18), nitrous oxide is writtenin error for nitrogen dioxide; NO+ is in error for NO: (line 2); and 124" is written by mistake for 134". A little more time spent on proof reading would have eliminated these and other blemishes. A. D. WALSH Received 25th June, 1971 Chemistry of Complex Equilibria. By M. T. BECK. (Van Nostrand Reinhold Co., London, 1970.) This book, one of an analytical chemistry series, has the admirable aim of giving a broad and realistic account of complex equilibria in solution in which the chemistry is not hidden behind algebraic equations.Anyone who has but glanced at the Chemical Society publication StabiZity Constants will appreciate that this is a formidable task, especially when topics such as mixed ligand, protonated and polynuclear complexes are rightly treated in some detail. Even neglecting problems concerned with the rates of attainment of equilibria, the complexity of the composition of many common and important solutions such as those of aluminium salts or of silicates in water is depressing. There are no entirely satisfactory methods of species identification, and the physical significance of the numerous equilibria which have been postulated for such systems is highly suspect.The Hungarian author has a readable style with some entertaining asides, e.g., " Rediscovery is a fairly frequent phenomenon now ", " Sometimes a linear relationship is assumed between the price of the instrument and the value of the information obtained by its means "; he has obviously actually read many of the historically important papers which he cites, and the literature references are less exclusively Anglo-Saxon than is often the case. In some places, however, references are catalogued with little evaluation. There is a curious and basically unhealthy dichotomy in the subject between those who label themselves " inorganic " or " co-ordination " chemists, who are primarily interested in speci identification and the equilibria between them, and '' physical " or " electrolyte solution " chemists who lay emphasis on the quantitative description of physicochemical properties in general.This book is of the co-ordination chemistry variety. For example, conductivity measurements are rele- gated to a reference to C. W. Davies under " miscellaneous methods", the information obtainable from osmotic coefficient measurements is only briefly mentioned in the context of some eutectic systems, and the problems which arise from lack of knowledge of ionic activity coefficients or their variations with solution composition are largely avoided. Although in the reviewer's opinion an outstanding book which treats both the methods and the results of stability constant determinations in a readable and compact manner is still to be written this is a useful attempt.Life and earth scientists who refer to it will readily appreciate the reasons for the stark contrast between the elegant simplicity of the standard text-book treatment of simple acid- base and complex-ion equilibria, and the remarkably unhelpful replies they are likely to get from chemists to questions about the chemical equilibria in physiological fluids and natural waters! Pp. 285. Price g4.50. J. E. PRUE Received 5th May, 1971REVIEWS OF BOOKS 3 649 producing the book is said by the authors to be " the fceling that our good fortune in acquiring a large mass of previously inaccessible data leaves u s with an obligation to collect this into one place for ease of access ".Certainly. to have so many spectra brought together in one volume is most valuable, the more so since many of them have not previously been published. The molecules whose spectra are presented range from triatomic to naphthalene and even bigger molecules. There are short introductory accounts of the underlying theory and of the experimental methods, but the bulk of the book is devoted to showing and interpreting the spectra, molecule by molecule. For each molecule, the full photoelectron spectrum is shown first; and then, under higher resolution, each " band " in the full spectrum. The book is intended to be a reference work for research workers. As such it will be invaluable to anyone interested in the electronic spectra of molecules and ions; and, indeed, to anyone interested in molecular orbitals, for whatever purpose.With its hundreds of excellent line drawings, the book as a whole can be said to be well produced. There are, however, signs of too hurried preparation. Thus on page 6, figs. 6.23, 6.26 and 6.27 are stated to refer to the spectra of diacetylene, cyanoacetylene and cyanogen; but in fact the figure captions make it clear that the figures refer to acetylene-d2, diacetylene and cyanoacetylene respec- tively. The text appears not to have been checked quite as carefully as it should have been. Othei errors, not entirely trivial, lead to the same conclusion. Thus (lb2)2 is written in error for (lb# (p. 78, line 7); lB1 is written in error for 2B1 (p. 77, table 4.4; p. 79, table 4.6; p. 81, table4.7); (1b)2 is in error for (lb1)2 (p.81, line -2); v1 is in error for v2 (the bending vibration of SO,; see p. 85); and lxU is in error for lxu (p. 170). On p. 87 (line 18), nitrous oxide is writtenin error for nitrogen dioxide; NO+ is in error for NO: (line 2); and 124" is written by mistake for 134". A little more time spent on proof reading would have eliminated these and other blemishes. A. D. WALSH Received 25th June, 1971 Chemistry of Complex Equilibria. By M. T. BECK. (Van Nostrand Reinhold Co., London, 1970.) This book, one of an analytical chemistry series, has the admirable aim of giving a broad and realistic account of complex equilibria in solution in which the chemistry is not hidden behind algebraic equations. Anyone who has but glanced at the Chemical Society publication StabiZity Constants will appreciate that this is a formidable task, especially when topics such as mixed ligand, protonated and polynuclear complexes are rightly treated in some detail. Even neglecting problems concerned with the rates of attainment of equilibria, the complexity of the composition of many common and important solutions such as those of aluminium salts or of silicates in water is depressing.There are no entirely satisfactory methods of species identification, and the physical significance of the numerous equilibria which have been postulated for such systems is highly suspect. The Hungarian author has a readable style with some entertaining asides, e.g., " Rediscovery is a fairly frequent phenomenon now ", " Sometimes a linear relationship is assumed between the price of the instrument and the value of the information obtained by its means "; he has obviously actually read many of the historically important papers which he cites, and the literature references are less exclusively Anglo-Saxon than is often the case.In some places, however, references are catalogued with little evaluation. There is a curious and basically unhealthy dichotomy in the subject between those who label themselves " inorganic " or " co-ordination " chemists, who are primarily interested in speci identification and the equilibria between them, and '' physical " or " electrolyte solution " chemists who lay emphasis on the quantitative description of physicochemical properties in general. This book is of the co-ordination chemistry variety.For example, conductivity measurements are rele- gated to a reference to C. W. Davies under " miscellaneous methods", the information obtainable from osmotic coefficient measurements is only briefly mentioned in the context of some eutectic systems, and the problems which arise from lack of knowledge of ionic activity coefficients or their variations with solution composition are largely avoided. Although in the reviewer's opinion an outstanding book which treats both the methods and the results of stability constant determinations in a readable and compact manner is still to be written this is a useful attempt. Life and earth scientists who refer to it will readily appreciate the reasons for the stark contrast between the elegant simplicity of the standard text-book treatment of simple acid- base and complex-ion equilibria, and the remarkably unhelpful replies they are likely to get from chemists to questions about the chemical equilibria in physiological fluids and natural waters! Pp.285. Price g4.50. J. E. PRUE Received 5th May, 1971REVIEWS OF BOOKS 3 649 producing the book is said by the authors to be " the fceling that our good fortune in acquiring a large mass of previously inaccessible data leaves u s with an obligation to collect this into one place for ease of access ". Certainly. to have so many spectra brought together in one volume is most valuable, the more so since many of them have not previously been published. The molecules whose spectra are presented range from triatomic to naphthalene and even bigger molecules.There are short introductory accounts of the underlying theory and of the experimental methods, but the bulk of the book is devoted to showing and interpreting the spectra, molecule by molecule. For each molecule, the full photoelectron spectrum is shown first; and then, under higher resolution, each " band " in the full spectrum. The book is intended to be a reference work for research workers. As such it will be invaluable to anyone interested in the electronic spectra of molecules and ions; and, indeed, to anyone interested in molecular orbitals, for whatever purpose. With its hundreds of excellent line drawings, the book as a whole can be said to be well produced. There are, however, signs of too hurried preparation. Thus on page 6, figs.6.23, 6.26 and 6.27 are stated to refer to the spectra of diacetylene, cyanoacetylene and cyanogen; but in fact the figure captions make it clear that the figures refer to acetylene-d2, diacetylene and cyanoacetylene respec- tively. The text appears not to have been checked quite as carefully as it should have been. Othei errors, not entirely trivial, lead to the same conclusion. Thus (lb2)2 is written in error for (lb# (p. 78, line 7); lB1 is written in error for 2B1 (p. 77, table 4.4; p. 79, table 4.6; p. 81, table4.7); (1b)2 is in error for (lb1)2 (p. 81, line -2); v1 is in error for v2 (the bending vibration of SO,; see p. 85); and lxU is in error for lxu (p. 170). On p. 87 (line 18), nitrous oxide is writtenin error for nitrogen dioxide; NO+ is in error for NO: (line 2); and 124" is written by mistake for 134".A little more time spent on proof reading would have eliminated these and other blemishes. A. D. WALSH Received 25th June, 1971 Chemistry of Complex Equilibria. By M. T. BECK. (Van Nostrand Reinhold Co., London, 1970.) This book, one of an analytical chemistry series, has the admirable aim of giving a broad and realistic account of complex equilibria in solution in which the chemistry is not hidden behind algebraic equations. Anyone who has but glanced at the Chemical Society publication StabiZity Constants will appreciate that this is a formidable task, especially when topics such as mixed ligand, protonated and polynuclear complexes are rightly treated in some detail.Even neglecting problems concerned with the rates of attainment of equilibria, the complexity of the composition of many common and important solutions such as those of aluminium salts or of silicates in water is depressing. There are no entirely satisfactory methods of species identification, and the physical significance of the numerous equilibria which have been postulated for such systems is highly suspect. The Hungarian author has a readable style with some entertaining asides, e.g., " Rediscovery is a fairly frequent phenomenon now ", " Sometimes a linear relationship is assumed between the price of the instrument and the value of the information obtained by its means "; he has obviously actually read many of the historically important papers which he cites, and the literature references are less exclusively Anglo-Saxon than is often the case.In some places, however, references are catalogued with little evaluation. There is a curious and basically unhealthy dichotomy in the subject between those who label themselves " inorganic " or " co-ordination " chemists, who are primarily interested in speci identification and the equilibria between them, and '' physical " or " electrolyte solution " chemists who lay emphasis on the quantitative description of physicochemical properties in general. This book is of the co-ordination chemistry variety. For example, conductivity measurements are rele- gated to a reference to C. W. Davies under " miscellaneous methods", the information obtainable from osmotic coefficient measurements is only briefly mentioned in the context of some eutectic systems, and the problems which arise from lack of knowledge of ionic activity coefficients or their variations with solution composition are largely avoided.Although in the reviewer's opinion an outstanding book which treats both the methods and the results of stability constant determinations in a readable and compact manner is still to be written this is a useful attempt. Life and earth scientists who refer to it will readily appreciate the reasons for the stark contrast between the elegant simplicity of the standard text-book treatment of simple acid- base and complex-ion equilibria, and the remarkably unhelpful replies they are likely to get from chemists to questions about the chemical equilibria in physiological fluids and natural waters! Pp. 285.Price g4.50. J. E. PRUE Received 5th May, 1971CO MPE TE L Y NEW RE VIS ED AND RE-SET EDIT10N MODERN ASPECTS OF INORGANIC CHEMISTRY by H. J. Emeleus, D.Sc., A.R.C.S., F.R.S. *PROFESSOR OF INORGANIC CHEMISTRY, UNIVERSITY OF CAMBRIDGE) and J. S. Anderson, Ph.D., A.R.C.S., F.R.S. (DIRECTOR, NATl ONAL CHEMICAL LABORATORY) In preparing the third edition of this book the authors have attempted to make the subject matter reflect the present state of knowledge and the most important developments in inorganic chemistry. The choice of topics for discussion is necessarily somewhat arbitrary. Furthermore, some fields of inorganic chemical research -for example boron chemistry, the theory of co-ordination compounds, organometallic chemistry -are so productive of new knowledge that it is impossible to do full justice to recent progress in the whole subject.Nevertheless, it is hoped that this new edition will give the reader some picture of developments during recent years in our knowledge, our theoretical outlook and our understanding of the chemistry of the elements. The authors ask that the book be read critically, and that where possible the text should be supplemented by reference to the more important original papers. The book is written primarily for Honours students, research workers and teachers, but will also interest the Scholarship candidate in schools. 35s. ROUTLEDGE & KEGAN PAUL ivCO MPE TE L Y NEW RE VIS ED AND RE-SET EDIT10N MODERN ASPECTS OF INORGANIC CHEMISTRY by H.J. Emeleus, D.Sc., A.R.C.S., F.R.S. *PROFESSOR OF INORGANIC CHEMISTRY, UNIVERSITY OF CAMBRIDGE) and J. S. Anderson, Ph.D., A.R.C.S., F.R.S. (DIRECTOR, NATl ONAL CHEMICAL LABORATORY) In preparing the third edition of this book the authors have attempted to make the subject matter reflect the present state of knowledge and the most important developments in inorganic chemistry. The choice of topics for discussion is necessarily somewhat arbitrary. Furthermore, some fields of inorganic chemical research -for example boron chemistry, the theory of co-ordination compounds, organometallic chemistry -are so productive of new knowledge that it is impossible to do full justice to recent progress in the whole subject. Nevertheless, it is hoped that this new edition will give the reader some picture of developments during recent years in our knowledge, our theoretical outlook and our understanding of the chemistry of the elements.The authors ask that the book be read critically, and that where possible the text should be supplemented by reference to the more important original papers. The book is written primarily for Honours students, research workers and teachers, but will also interest the Scholarship candidate in schools. 35s. ROUTLEDGE & KEGAN PAUL ivIntroducing an important and authoritative encyclopedia THE INTERNATIONAL ENCYCLOPEDIA OF PHYSICAL CHEMISTRY AND CHEMICAL PHYSICS Editors-in-Chief E. A. GUGGENHEIM J. E. MAYER F. C. TOMPKINS The International Encyclopedia of Physical Chemistry a d Chemical Physics will be an authoritative and comprehensive presentation of the domaln of knowledge which lies between and overlaps chemistry and physics.Each volume--between 50 and 100 volumes are planned-will be written primarily for the physical chemist and chemical physicist, but many volumes will be of value to other scientists. The volumes will be grouped into topics, as follows: I. 2. 3. 4. 5. 6. 7. 8. 9. lo. I I. MATHEMATICAL TECH NlQUES Editor: H. JONES CLASSICAL AND QUANTUM MECHANICS Editor: PER-OLOF LOWDIN ELECTRONIC STRUCTURE OF Editor: CLYDE HUTCHISON, Jr. MOLECULAR BINDING Editor being appointed MOLECULAR PROPERTIES ATOMS (a) Electronic ( b ) Non-electronic Editors being appointed KINETIC THEORY OF GASES Editor: E. A. GUGGENHEIM CLASSICAL THERMODYNAMICS Editor: D.H. EVERETT STATISTICAL MECHANICS Editor: J. E. MAYER TRANSPORT PHENOMENA Editor: J. E. MAYER THE FLUID STATE Editor: J. S. ROWLINSON THE IDEAL CRYSTALLINE STATE Editor: M. BLACKMAN 12. IMPERFECTIONS IN SOLIDS Editor: A. B. LlDlARD 13. MIXTURES, SOLUTIONS, CHEMI- CAL AND PHASE EQUILIBRIA Editor: M. L. MeGLASHAN 14. PROPERTIES OF INTERFACES 15. EQUILIBRIUM PROPERTIES OF Editor: D. H. EVERETT ELECTROLYTE SOLUTIONS 16. TRANSPORT PROPERTIES OF Editor: R. A. ROBINSON ELECTROLYTES Editor: R. H. STOKES 17. MACROMOLECULES 18. 19. 20. 21. 22. Editor: C. E. H. BAWN DIELECTRIC AND MAGNETIC PRO PE RTI ES Editor: WILLARD STO UT GAS KINETICS Editor: A. TROTMA N-DICKE NSO N SO LUTl ON KI NET1 CS Editor: R. M. NOYES SOLID AND SURFACE KINETICS Editor: F. C. TOMPKINS RADIATION CHEMISTRY Editor: ROBERT LIVINGSTON lust published in Topic 6 Volume I ELEMENTS OF THE KINETIC THEORY OF GASES by E.A. GUGGENHEIM, M.A., Sc.D., F.R.S. This volume describes in an elementary way the most important features of the kinetic theory ofgases. and as such will prove most useful to physical chemists and chemical physicists who would not norm- ally have a standard of mathematics necessary for the more advanced treatments. 17s 6d net ($3.00) Write now for details of this outstanding encyclopedia Headington Hill Hall, Oxford 4 & 5 fitzroy Square, London W. I 122 East 55th Street, New York 22, M Y .Introducing an important and authoritative encyclopedia THE INTERNATIONAL ENCYCLOPEDIA OF PHYSICAL CHEMISTRY AND CHEMICAL PHYSICS Editors-in-Chief E.A. GUGGENHEIM J. E. MAYER F. C. TOMPKINS The International Encyclopedia of Physical Chemistry a d Chemical Physics will be an authoritative and comprehensive presentation of the domaln of knowledge which lies between and overlaps chemistry and physics. Each volume--between 50 and 100 volumes are planned-will be written primarily for the physical chemist and chemical physicist, but many volumes will be of value to other scientists. The volumes will be grouped into topics, as follows: I. 2. 3. 4. 5. 6. 7. 8. 9. lo. I I. MATHEMATICAL TECH NlQUES Editor: H. JONES CLASSICAL AND QUANTUM MECHANICS Editor: PER-OLOF LOWDIN ELECTRONIC STRUCTURE OF Editor: CLYDE HUTCHISON, Jr. MOLECULAR BINDING Editor being appointed MOLECULAR PROPERTIES ATOMS (a) Electronic ( b ) Non-electronic Editors being appointed KINETIC THEORY OF GASES Editor: E.A. GUGGENHEIM CLASSICAL THERMODYNAMICS Editor: D. H. EVERETT STATISTICAL MECHANICS Editor: J. E. MAYER TRANSPORT PHENOMENA Editor: J. E. MAYER THE FLUID STATE Editor: J. S. ROWLINSON THE IDEAL CRYSTALLINE STATE Editor: M. BLACKMAN 12. IMPERFECTIONS IN SOLIDS Editor: A. B. LlDlARD 13. MIXTURES, SOLUTIONS, CHEMI- CAL AND PHASE EQUILIBRIA Editor: M. L. MeGLASHAN 14. PROPERTIES OF INTERFACES 15. EQUILIBRIUM PROPERTIES OF Editor: D. H. EVERETT ELECTROLYTE SOLUTIONS 16. TRANSPORT PROPERTIES OF Editor: R. A. ROBINSON ELECTROLYTES Editor: R. H. STOKES 17. MACROMOLECULES 18. 19. 20. 21. 22. Editor: C. E. H. BAWN DIELECTRIC AND MAGNETIC PRO PE RTI ES Editor: WILLARD STO UT GAS KINETICS Editor: A. TROTMA N-DICKE NSO N SO LUTl ON KI NET1 CS Editor: R.M. NOYES SOLID AND SURFACE KINETICS Editor: F. C. TOMPKINS RADIATION CHEMISTRY Editor: ROBERT LIVINGSTON lust published in Topic 6 Volume I ELEMENTS OF THE KINETIC THEORY OF GASES by E. A. GUGGENHEIM, M.A., Sc.D., F.R.S. This volume describes in an elementary way the most important features of the kinetic theory ofgases. and as such will prove most useful to physical chemists and chemical physicists who would not norm- ally have a standard of mathematics necessary for the more advanced treatments. 17s 6d net ($3.00) Write now for details of this outstanding encyclopedia Headington Hill Hall, Oxford 4 & 5 fitzroy Square, London W. I 122 East 55th Street, New York 22, M Y .: a mama a a am a a a chemical nomenclature *arn: i Introduction to Chemical Nomenclature i a a a a a : By R.S. CAHN, M.A., Dr.PhiI.Nat., F.R.I.C., Editor to the Chemical : : Society, London. Price 10s. 6d. : a : A description of the principles of chemical nomenclature, particularly of modern systematic nomenclature as accepted by The Chemical Society of London. Con- : : tents include: The Use and Misuse of Nomenclature. Inorganic Nomenclature. : Organic Nomenclature: General; The Principal Functional Group; Numbering; a : Building a Name; Skeletal Types; Some Special Cases. Physico-Chemical Symbols. : : ‘ I Remarkably clear and concise . . . provides some very helpful guiding rules. So : : much information is packed into its 90-odd pages . . . all chemists can aflord to pur- : : chase (the book); they cannot aflord to do otherwise.” a -Journal of the Royal Institute of Chemistry : a a a a a a a a Nomenclature of j Nomenclature of a i Organic Chemistry Inorganic Chemistry i : IUPAC 1957 RULES. Issued by the International Union of Pure and : : Applied Chemistry.Price 15s. each. i : One of the outstanding problems in chemistry is the naming of chemical com- : pounds. At last some order has been introduced by IUPAC, whose Committees a have formulated rules acceptable as a basis to chemists throughout the world. : a m “A real contribution towards technical progress . . . unhesitatingly recommended. . . a : should be read and kept as a reference andguide for all (Chemistry) workers.” a m a a m i am a a am a a a BUTTERWORTHS a ma a a a a am a a a a a i -Transactions of the Plastics Institute ~ F o DARTON & Coo LTDo WATFORD HERTS a ENGLAND ESTABLISHED 1834 THERMOGRAPHS HYGROGRAPHS BAROGRAPHS Makers of KEW PAlTERN BAROMETERS FORTI N BAROMETERS HY GROM ETE RS MAN OM ETE RS / REGISTERED \ I R A Q I MARK ALTl METER CALI BRATORS viiiTHE CHEMICAL SUPPLY CO LTD for details of the many new products they are manufacturing Ester Solvents Alkyl & Aryl Ester PIasticisers Formaldehyde & Hexamine Special Plastic Grades Cadmium Colours Aromatic Chemicals Molybdic Products Copper Fungicides Full technical details and samples will be sent on request THE CHEMICAL SUPPLY CO LTD 7 IDOL LANE, EASTCHEAP, LONDON EC3 Tel: Mansion House 6854 Gram: Kemsupply, Phone, London ixTHE CHEMICAL SUPPLY CO LTD for details of the many new products they are manufacturing Ester Solvents Alkyl & Aryl Ester PIasticisers Formaldehyde & Hexamine Special Plastic Grades Cadmium Colours Aromatic Chemicals Molybdic Products Copper Fungicides Full technical details and samples will be sent on request THE CHEMICAL SUPPLY CO LTD 7 IDOL LANE, EASTCHEAP, LONDON EC3 Tel: Mansion House 6854 Gram: Kemsupply, Phone, London ixTHE CHEMICAL SUPPLY CO LTD for details of the many new products they are manufacturing Ester Solvents Alkyl & Aryl Ester PIasticisers Formaldehyde & Hexamine Special Plastic Grades Cadmium Colours Aromatic Chemicals Molybdic Products Copper Fungicides Full technical details and samples will be sent on request THE CHEMICAL SUPPLY CO LTD 7 IDOL LANE, EASTCHEAP, LONDON EC3 Tel: Mansion House 6854 Gram: Kemsupply, Phone, London ixL. LIGHT & CO.LTD. COLNBROOKm BUCKS ENGLAND I I I/ 999 Annual Reports on the Progress of Chemistry Back Numbers (less certain volumes now out of.print) 999 I ELEMENTS + COMPOUNDS 99-99 % to 99.9999 yo SPECTROSCOPIC CERTIFICATE SUPPLIED Collective Index of Volumes I to XLVI Inquiries are invited by: TEE CHEMICAL SOCIETY Burbgton House . London, W.lElectrons and Phonons The Theory of Transport Phenomena in Solids J. M. ZIMAN This treatise on the theory of eIectrica1 and thermal conduction in metals, semi-conductors, and insulators is written for graduate students and research workers. It gives an account of the experi- mental facts and their theoretical explanation, and the basic ideas of lattice dynamics, electron zone structure, and transport theory are developed from first principles (International Series of Mono- graphs on Physics). Text-figures 84s net Data for Biochemical Research Edited by R.M. C. DAWSON, DAPHNE C.ELLIOTT, W. H. ELLIO.TT, and K. M. JONES ‘. . . has more importance than the intrinsic value of the informa- tion it carries. Its very existence illustrates in a lively fashion the evolution from qualitative to quantitative science that is rapidly taking place in the still young but vigorously developing subject of biochemistry.’ NEW SCIENTIST Text-figures 63s net Experimental Techniques in Low- Temperature Physics GUY KENDALL WHITE ‘. . . the first of its kind in being wholly given over to the tech- niques of low temperature work, and it will meet a long-felt need.Research students just starting such work and those people wishing to extend investigations over a wider temperature range will find this publication timely and of great help. . . . The established worker in the field will also find much of value in this book.’ BRITISH JOURNAL OF APPLIED PHYSICS (Monographs on the Physics and Chemistry of Materials). Plates and text-figures 45s net Determination of Molecular Structure P. J. WHEATLEY This book discusses the main physicochemical methods used to determine molecular structure. The scope and limitations of each pethod are emphasized and examples drawn from original papers. . . . will undoubtedly be of great value to first-year university students and should stimulate them to read more advanced texts to which many references are given.’ JOURNAL OF THE ROYAL INSTITUTE OF CHEMISTRY Text-figures 35s net OXFORD UNIVERSITY PRESS - xiiiApplied Pe tr o le urn Reservoir Engineering B.C. CRAFT & M. F. HAWKINS, JR. The growth of the petroleum industry demands improved scientific methods for the analysis and prediction of oil reservoir and well performance. This book is a significant contribution to this subject, which now constitutes a well- defined, highly technical branch of petroleum engineering. Med. 8vo. 437 pages. Illustrated. 62s. 6d. Fundamentals of Chemical Engineering Operations M. G. LARIAN A textbook which covers the most important elements of a wide subject concisely and on a level suitable for under- graduate instruction.Med. 8vo. 644 pages. Illustrated. 62s. 6d. Soil Chemical Analysis M. L. JACKSON This book gives the most frequently used soil chemical analysis procedures, useful in instruction and research in soil chemistry, soil fertility and soil genesis. Because plant growth is essentially related to these fields, procedures are given for plant inorganic constituents. Med. 8vo. 498 pages. Illustrated. 57s. 6d. Electrochemical Processes in Chemical Industries A. REGNER The theoretical part of this book deals with basic laws; goes on to discuss electrolytic conductance and various types of galvanic cells and concludes with a section on electrolysis and polarization. The second part deals with industrial applications. Ex. Cr. 8vo. 464pages. 149 figures. 1957. 30s. Chemical Engineering Operations: An Intro- duction to the Study of Chemical Plant F.RUMFORD Second edition. Demy 8vo. 387 pages. Illustrated. 1957. 32s. 68. Chemical Engineering Materials F. RUMFORD A major change in this second edition is the complete re- writing of the chapter on plastics as a material for use in Second edition. Demy 8vo. 400 pages. Illustrated. 32s. 6d. ' chemical plant. CONSTABLE 8~ CO. LTD 10 ORANGE STREET, LONDON, W.C.2 xivCO MPE TE L Y NEW RE VIS EDAND RE-SET EDIT10NMODERN ASPECTS OFINORGANIC CHEMISTRYby H. J. Emeleus, D.Sc., A.R.C.S., F.R.S.*PROFESSOR OF INORGANIC CHEMISTRY, UNIVERSITY OF CAMBRIDGE)and J. S. Anderson, Ph.D., A.R.C.S., F.R.S.(DIRECTOR, NATl ONAL CHEMICAL LABORATORY)In preparing the third edition of this bookthe authors have attempted to make the subject matterreflect the present state of knowledge andthe most important developments in inorganic chemistry.The choice of topics for discussionis necessarily somewhat arbitrary.Furthermore, some fields of inorganic chemical research-for example boron chemistry, the theoryof co-ordination compounds, organometallic chemistry-are so productive of new knowledgethat it is impossible to do full justiceto recent progress in the whole subject.Nevertheless, it is hoped that this new editionwill give the reader some picture of developmentsduring recent years in our knowledge,our theoretical outlook and our understandingof the chemistry of the elements.The authors ask that the book be read critically,and that where possible the text should be supplementedby reference to the more important original papers.The book is written primarily for Honours students,research workers and teachers,but will also interest the Scholarship candidate in schools.35s.ROUTLEDGE & KEGAN PAULiIntroducing an important and authoritative encyclopediaTHE INTERNATIONAL ENCYCLOPEDIA OFPHYSICAL CHEMISTRY AND CHEMICAL PHYSICSEditors-in-ChiefE. A.GUGGENHEIM J. E. MAYER F. C. TOMPKINSThe International Encyclopedia of Physical Chemistry a d Chemical Physicswill be an authoritative and comprehensive presentation of thedomaln of knowledge which lies between and overlaps chemistry andphysics.Each volume--between 50 and 100 volumes are planned-will bewritten primarily for the physical chemist and chemical physicist, butmany volumes will be of value to other scientists.The volumes will be grouped into topics, as follows:I.2.3.4.5.6.7.8.9.lo.I I.MATHEMATICAL TECH NlQUESEditor: H.JONESCLASSICAL AND QUANTUMMECHANICSEditor: PER-OLOF LOWDINELECTRONIC STRUCTURE OFEditor: CLYDE HUTCHISON, Jr.MOLECULAR BINDINGEditor being appointedMOLECULAR PROPERTIESATOMS(a) Electronic( b ) Non-electronicEditors being appointedKINETIC THEORY OF GASESEditor: E. A. GUGGENHEIMCLASSICAL THERMODYNAMICSEditor: D. H. EVERETTSTATISTICAL MECHANICSEditor: J. E. MAYERTRANSPORT PHENOMENAEditor: J. E. MAYERTHE FLUID STATEEditor: J. S. ROWLINSONTHE IDEAL CRYSTALLINE STATEEditor: M.BLACKMAN12. IMPERFECTIONS IN SOLIDSEditor: A. B. LlDlARD13. MIXTURES, SOLUTIONS, CHEMI-CAL AND PHASE EQUILIBRIAEditor: M. L. MeGLASHAN14. PROPERTIES OF INTERFACES15. EQUILIBRIUM PROPERTIES OFEditor: D. H. EVERETTELECTROLYTE SOLUTIONS16. TRANSPORT PROPERTIES OFEditor: R. A. ROBINSONELECTROLYTESEditor: R. H. STOKES17. MACROMOLECULES18.19.20.21.22.Editor: C. E. H. BAWNDIELECTRIC AND MAGNETICPRO PE RTI ESEditor: WILLARD STO UTGAS KINETICSEditor: A. TROTMA N-DICKE NSO NSO LUTl ON KI NET1 CSEditor: R. M. NOYESSOLID AND SURFACE KINETICSEditor: F. C. TOMPKINSRADIATION CHEMISTRYEditor: ROBERT LIVINGSTONlust published in Topic 6Volume IELEMENTS OF THE KINETIC THEORY OF GASESby E. A. GUGGENHEIM, M.A., Sc.D., F.R.S.This volume describes in an elementary way the most important features of the kinetic theory ofgases.and as such will prove most useful to physical chemists and chemical physicists who would not norm-ally have a standard of mathematics necessary for the more advanced treatments.17s 6d net ($3.00)Write now for details of this outstanding encyclopediaHeadington Hill Hall, Oxford 4 & 5 fitzroy Square, London W.I122 East 55th Street, New York 22, M Y : a mama a a am a a a chemical nomenclature *arn:i Introduction to Chemical Nomenclature iaa aaa : By R. S. CAHN, M.A., Dr.PhiI.Nat., F.R.I.C., Editor to the Chemical : : Society, London. Price 10s. 6d. : a : A description of the principles of chemical nomenclature, particularly of modernsystematic nomenclature as accepted by The Chemical Society of London.Con- : : tents include: The Use and Misuse of Nomenclature. Inorganic Nomenclature. :Organic Nomenclature: General; The Principal Functional Group; Numbering; a : Building a Name; Skeletal Types; Some Special Cases. Physico-Chemical Symbols. :: ‘ I Remarkably clear and concise . . . provides some very helpful guiding rules. So : : much information is packed into its 90-odd pages . . . all chemists can aflord to pur- :: chase (the book); they cannot aflord to do otherwise.” a-Journal of the Royal Institute of Chemistry : aaa aa aaa Nomenclature of j Nomenclature of a i Organic Chemistry Inorganic Chemistry i: IUPAC 1957 RULES. Issued by the International Union of Pure and :: Applied Chemistry.Price 15s. each. i: One of the outstanding problems in chemistry is the naming of chemical com- : pounds. At last some order has been introduced by IUPAC, whose Committeesa have formulated rules acceptable as a basis to chemists throughout the world. : am “A real contribution towards technical progress . . . unhesitatingly recommended. . . a : should be read and kept as a reference andguide for all (Chemistry) workers.” am a am i am a a am a a a BUTTERWORTHS a ma a a a a am a a a a a i-Transactions of the Plastics Institute~F o DARTON & Coo LTDoWATFORD HERTS a ENGLANDESTABLISHED 1834THERMOGRAPHSHYGROGRAPHSBAROGRAPHSMakers ofKEW PAlTERN BAROMETERSFORTI N BAROMETERSHY GROM ETE RSMAN OM ETE RS/ REGISTERED \I R A Q I MARKALTl METER CALI BRATORSviiTHE CHEMICAL SUPPLY CO LTDfor details of the many new productsthey are manufacturingEster SolventsAlkyl & Aryl Ester PIasticisersFormaldehyde & HexamineSpecial Plastic GradesCadmium ColoursAromatic ChemicalsMolybdic ProductsCopper FungicidesFull technical details and sampleswill be sent on requestTHE CHEMICAL SUPPLY CO LTD7 IDOL LANE, EASTCHEAP, LONDON EC3Tel: Mansion House 6854Gram: Kemsupply, Phone, LondoniL.LIGHT & CO. LTD.COLNBROOKm BUCKS ENGLANDII I/999Annual Reports on theProgress of ChemistryBack Numbers (less certain volumes now out of.print)999IELEMENTS + COMPOUNDS99-99 % to 99.9999 yoSPECTROSCOPIC CERTIFICATE SUPPLIEDCollective Index of Volumes I to XLVIInquiries are invited by:TEECHEMICALSOCIETYBurbgton House .London, W.Electrons and PhononsThe Theory of Transport Phenomena in SolidsJ. M. ZIMANThis treatise on the theory of eIectrica1 and thermal conduction inmetals, semi-conductors, and insulators is written for graduatestudents and research workers. It gives an account of the experi-mental facts and their theoretical explanation, and the basic ideasof lattice dynamics, electron zone structure, and transport theoryare developed from first principles (International Series of Mono-graphs on Physics). Text-figures 84s netData for Biochemical ResearchEdited by R. M. C. DAWSON, DAPHNEC.ELLIOTT, W. H. ELLIO.TT, and K. M. JONES‘.. . has more importance than the intrinsic value of the informa-tion it carries. Its very existence illustrates in a lively fashion theevolution from qualitative to quantitative science that is rapidlytaking place in the still young but vigorously developing subject ofbiochemistry.’ NEW SCIENTIST Text-figures 63s netExperimental Techniques in Low-Temperature PhysicsGUY KENDALL WHITE‘. . . the first of its kind in being wholly given over to the tech-niques of low temperature work, and it will meet a long-felt need.Research students just starting such work and those peoplewishing to extend investigations over a wider temperature rangewill find this publication timely and of great help. . . . Theestablished worker in the field will also find much of value in thisbook.’ BRITISH JOURNAL OF APPLIED PHYSICS (Monographs on thePhysics and Chemistry of Materials).Plates and text-figures 45s netDetermination of Molecular StructureP. J. WHEATLEYThis book discusses the main physicochemical methods used todetermine molecular structure. The scope and limitations of eachpethod are emphasized and examples drawn from original papers. . . . will undoubtedly be of great value to first-year universitystudents and should stimulate them to read more advanced textsto which many references are given.’ JOURNAL OF THE ROYALINSTITUTE OF CHEMISTRY Text-figures 35s netOXFORD UNIVERSITY PRESS-xiiApplied Pe tr o le urn Reservoir EngineeringB. C. CRAFT & M. F. HAWKINS, JR.The growth of the petroleum industry demands improvedscientific methods for the analysis and prediction of oilreservoir and well performance.This book is a significantcontribution to this subject, which now constitutes a well-defined, highly technical branch of petroleum engineering.Med. 8vo. 437 pages. Illustrated. 62s. 6d.Fundamentals of Chemical EngineeringOperationsM. G. LARIANA textbook which covers the most important elements of awide subject concisely and on a level suitable for under-graduate instruction.Med. 8vo. 644 pages. Illustrated. 62s. 6d.Soil Chemical AnalysisM. L. JACKSONThis book gives the most frequently used soil chemicalanalysis procedures, useful in instruction and research in soilchemistry, soil fertility and soil genesis.Because plantgrowth is essentially related to these fields, procedures aregiven for plant inorganic constituents.Med. 8vo. 498 pages. Illustrated. 57s. 6d.Electrochemical Processes in ChemicalIndustriesA. REGNERThe theoretical part of this book deals with basic laws; goeson to discuss electrolytic conductance and various types ofgalvanic cells and concludes with a section on electrolysisand polarization. The second part deals with industrialapplications.Ex. Cr. 8vo. 464pages. 149 figures. 1957. 30s.Chemical Engineering Operations: An Intro-duction to the Study of Chemical PlantF. RUMFORDSecond edition. Demy 8vo. 387 pages. Illustrated. 1957.32s. 68.Chemical Engineering MaterialsF. RUMFORDA major change in this second edition is the complete re-writing of the chapter on plastics as a material for use inSecond edition.Demy 8vo. 400 pages. Illustrated. 32s. 6d.' chemical plant.CONSTABLE 8~ CO. LTD10 ORANGE STREET, LONDON, W.C.2xiCO MPE TE L Y NEW RE VIS EDAND RE-SET EDIT10NMODERN ASPECTS OFINORGANIC CHEMISTRYby H. J. Emeleus, D.Sc., A.R.C.S., F.R.S.*PROFESSOR OF INORGANIC CHEMISTRY, UNIVERSITY OF CAMBRIDGE)and J. S. Anderson, Ph.D., A.R.C.S., F.R.S.(DIRECTOR, NATl ONAL CHEMICAL LABORATORY)In preparing the third edition of this bookthe authors have attempted to make the subject matterreflect the present state of knowledge andthe most important developments in inorganic chemistry.The choice of topics for discussionis necessarily somewhat arbitrary.Furthermore, some fields of inorganic chemical research-for example boron chemistry, the theoryof co-ordination compounds, organometallic chemistry-are so productive of new knowledgethat it is impossible to do full justiceto recent progress in the whole subject.Nevertheless, it is hoped that this new editionwill give the reader some picture of developmentsduring recent years in our knowledge,our theoretical outlook and our understandingof the chemistry of the elements.The authors ask that the book be read critically,and that where possible the text should be supplementedby reference to the more important original papers.The book is written primarily for Honours students,research workers and teachers,but will also interest the Scholarship candidate in schools.35s.ROUTLEDGE & KEGAN PAULiIntroducing an important and authoritative encyclopediaTHE INTERNATIONAL ENCYCLOPEDIA OFPHYSICAL CHEMISTRY AND CHEMICAL PHYSICSEditors-in-ChiefE. A.GUGGENHEIM J. E. MAYER F. C. TOMPKINSThe International Encyclopedia of Physical Chemistry a d Chemical Physicswill be an authoritative and comprehensive presentation of thedomaln of knowledge which lies between and overlaps chemistry andphysics.Each volume--between 50 and 100 volumes are planned-will bewritten primarily for the physical chemist and chemical physicist, butmany volumes will be of value to other scientists.The volumes will be grouped into topics, as follows:I.2.3.4.5.6.7.8.9.lo.I I.MATHEMATICAL TECH NlQUESEditor: H.JONESCLASSICAL AND QUANTUMMECHANICSEditor: PER-OLOF LOWDINELECTRONIC STRUCTURE OFEditor: CLYDE HUTCHISON, Jr.MOLECULAR BINDINGEditor being appointedMOLECULAR PROPERTIESATOMS(a) Electronic( b ) Non-electronicEditors being appointedKINETIC THEORY OF GASESEditor: E. A. GUGGENHEIMCLASSICAL THERMODYNAMICSEditor: D. H. EVERETTSTATISTICAL MECHANICSEditor: J. E. MAYERTRANSPORT PHENOMENAEditor: J. E. MAYERTHE FLUID STATEEditor: J. S. ROWLINSONTHE IDEAL CRYSTALLINE STATEEditor: M. BLACKMAN12. IMPERFECTIONS IN SOLIDSEditor: A. B. LlDlARD13. MIXTURES, SOLUTIONS, CHEMI-CAL AND PHASE EQUILIBRIAEditor: M. L. MeGLASHAN14. PROPERTIES OF INTERFACES15. EQUILIBRIUM PROPERTIES OFEditor: D.H. EVERETTELECTROLYTE SOLUTIONS16. TRANSPORT PROPERTIES OFEditor: R. A. ROBINSONELECTROLYTESEditor: R. H. STOKES17. MACROMOLECULES18.19.20.21.22.Editor: C. E. H. BAWNDIELECTRIC AND MAGNETICPRO PE RTI ESEditor: WILLARD STO UTGAS KINETICSEditor: A. TROTMA N-DICKE NSO NSO LUTl ON KI NET1 CSEditor: R. M. NOYESSOLID AND SURFACE KINETICSEditor: F. C. TOMPKINSRADIATION CHEMISTRYEditor: ROBERT LIVINGSTONlust published in Topic 6Volume IELEMENTS OF THE KINETIC THEORY OF GASESby E. A. GUGGENHEIM, M.A., Sc.D., F.R.S.This volume describes in an elementary way the most important features of the kinetic theory ofgases.and as such will prove most useful to physical chemists and chemical physicists who would not norm-ally have a standard of mathematics necessary for the more advanced treatments.17s 6d net ($3.00)Write now for details of this outstanding encyclopediaHeadington Hill Hall, Oxford 4 & 5 fitzroy Square, London W.I122 East 55th Street, New York 22, M Y : a mama a a am a a a chemical nomenclature *arn:i Introduction to Chemical Nomenclature iaa aaa : By R. S. CAHN, M.A., Dr.PhiI.Nat., F.R.I.C., Editor to the Chemical : : Society, London. Price 10s. 6d. : a : A description of the principles of chemical nomenclature, particularly of modernsystematic nomenclature as accepted by The Chemical Society of London. Con- : : tents include: The Use and Misuse of Nomenclature. Inorganic Nomenclature. :Organic Nomenclature: General; The Principal Functional Group; Numbering; a : Building a Name; Skeletal Types; Some Special Cases.Physico-Chemical Symbols. :: ‘ I Remarkably clear and concise . . . provides some very helpful guiding rules. So : : much information is packed into its 90-odd pages . . . all chemists can aflord to pur- :: chase (the book); they cannot aflord to do otherwise.” a-Journal of the Royal Institute of Chemistry : aaa aa aaa Nomenclature of j Nomenclature of a i Organic Chemistry Inorganic Chemistry i: IUPAC 1957 RULES. Issued by the International Union of Pure and :: Applied Chemistry. Price 15s. each. i: One of the outstanding problems in chemistry is the naming of chemical com- : pounds. At last some order has been introduced by IUPAC, whose Committeesa have formulated rules acceptable as a basis to chemists throughout the world.: am “A real contribution towards technical progress . . . unhesitatingly recommended. . . a : should be read and kept as a reference andguide for all (Chemistry) workers.” am a am i am a a am a a a BUTTERWORTHS a ma a a a a am a a a a a i-Transactions of the Plastics Institute~F o DARTON & Coo LTDoWATFORD HERTS a ENGLANDESTABLISHED 1834THERMOGRAPHSHYGROGRAPHSBAROGRAPHSMakers ofKEW PAlTERN BAROMETERSFORTI N BAROMETERSHY GROM ETE RSMAN OM ETE RS/ REGISTERED \I R A Q I MARKALTl METER CALI BRATORSviiTHE CHEMICAL SUPPLY CO LTDfor details of the many new productsthey are manufacturingEster SolventsAlkyl & Aryl Ester PIasticisersFormaldehyde & HexamineSpecial Plastic GradesCadmium ColoursAromatic ChemicalsMolybdic ProductsCopper FungicidesFull technical details and sampleswill be sent on requestTHE CHEMICAL SUPPLY CO LTD7 IDOL LANE, EASTCHEAP, LONDON EC3Tel: Mansion House 6854Gram: Kemsupply, Phone, LondoniL.LIGHT & CO. LTD.COLNBROOKm BUCKS ENGLANDII I/999Annual Reports on theProgress of ChemistryBack Numbers (less certain volumes now out of.print)999IELEMENTS + COMPOUNDS99-99 % to 99.9999 yoSPECTROSCOPIC CERTIFICATE SUPPLIEDCollective Index of Volumes I to XLVIInquiries are invited by:TEECHEMICALSOCIETYBurbgton House . London, W.Electrons and PhononsThe Theory of Transport Phenomena in SolidsJ. M. ZIMANThis treatise on the theory of eIectrica1 and thermal conduction inmetals, semi-conductors, and insulators is written for graduatestudents and research workers.It gives an account of the experi-mental facts and their theoretical explanation, and the basic ideasof lattice dynamics, electron zone structure, and transport theoryare developed from first principles (International Series of Mono-graphs on Physics). Text-figures 84s netData for Biochemical ResearchEdited by R. M. C. DAWSON, DAPHNEC.ELLIOTT, W. H. ELLIO.TT, and K. M. JONES‘. . . has more importance than the intrinsic value of the informa-tion it carries. Its very existence illustrates in a lively fashion theevolution from qualitative to quantitative science that is rapidlytaking place in the still young but vigorously developing subject ofbiochemistry.’ NEW SCIENTIST Text-figures 63s netExperimental Techniques in Low-Temperature PhysicsGUY KENDALL WHITE‘. .. the first of its kind in being wholly given over to the tech-niques of low temperature work, and it will meet a long-felt need.Research students just starting such work and those peoplewishing to extend investigations over a wider temperature rangewill find this publication timely and of great help. . . . Theestablished worker in the field will also find much of value in thisbook.’ BRITISH JOURNAL OF APPLIED PHYSICS (Monographs on thePhysics and Chemistry of Materials). Plates and text-figures 45s netDetermination of Molecular StructureP. J. WHEATLEYThis book discusses the main physicochemical methods used todetermine molecular structure. The scope and limitations of eachpethod are emphasized and examples drawn from original papers. . . . will undoubtedly be of great value to first-year universitystudents and should stimulate them to read more advanced textsto which many references are given.’ JOURNAL OF THE ROYALINSTITUTE OF CHEMISTRY Text-figures 35s netOXFORD UNIVERSITY PRESS-xiiApplied Pe tr o le urn Reservoir EngineeringB. C. CRAFT & M. F. HAWKINS, JR.The growth of the petroleum industry demands improvedscientific methods for the analysis and prediction of oilreservoir and well performance. This book is a significantcontribution to this subject, which now constitutes a well-defined, highly technical branch of petroleum engineering.Med. 8vo. 437 pages. Illustrated. 62s. 6d.Fundamentals of Chemical EngineeringOperationsM. G. LARIANA textbook which covers the most important elements of awide subject concisely and on a level suitable for under-graduate instruction.Med. 8vo. 644 pages. Illustrated. 62s. 6d.Soil Chemical AnalysisM. L. JACKSONThis book gives the most frequently used soil chemicalanalysis procedures, useful in instruction and research in soilchemistry, soil fertility and soil genesis. Because plantgrowth is essentially related to these fields, procedures aregiven for plant inorganic constituents.Med. 8vo. 498 pages. Illustrated. 57s. 6d.Electrochemical Processes in ChemicalIndustriesA. REGNERThe theoretical part of this book deals with basic laws; goeson to discuss electrolytic conductance and various types ofgalvanic cells and concludes with a section on electrolysisand polarization. The second part deals with industrialapplications.Ex. Cr. 8vo. 464pages. 149 figures. 1957. 30s.Chemical Engineering Operations: An Intro-duction to the Study of Chemical PlantF. RUMFORDSecond edition. Demy 8vo. 387 pages. Illustrated. 1957.32s. 68.Chemical Engineering MaterialsF. RUMFORDA major change in this second edition is the complete re-writing of the chapter on plastics as a material for use inSecond edition. Demy 8vo. 400 pages. Illustrated. 32s. 6d.' chemical plant.CONSTABLE 8~ CO. LTD10 ORANGE STREET, LONDON, W.C.2xi

ISSN:0365-6217    

DOI:10.1039/AR95956FP001

出版商:RSC    

年代:1959

数据来源: RSC

摘要:

ANNUAL REPORTSON THEPROGRESS OF CHEMISTRYGENERAL AND PHYSICAL CHEMISTRY1. INTRODUCTIONTHIS year’s General and Physical Chemistry Section follows the pattern oflast year’s Report. The coverage is still specialised, but the topics thathave been chosen fill in some of the gaps that were left last year. Forexample, last year there was an article on infrared intensities. This yearthere is no report covering an infrared topic, but there is one on Ramanspectroscopy. Also last year there were sections on radical polymerisation,ion-molecule reactions, and on reactions of organic substances and radicals.This year there is a section devoted to reactions in solution and another tothe reactions of atoms, small radicals, such as hydroxyl, and simple molecules.There is also a section on radiation chemistry which was not covered directlylast year.In the field of molecular structure, besides the section on Ramanspectroscopy, there is one on nuclear magnetic resonance and also anotheron the absorption spectra and stability of complex ions. The latter dealsalso with the thermodynamics of these systems. There is also a sectiondealing with the physical properties of some simple fluids, which describesthe recent developments in the thermodynamics and statistical mechanicsof these systems. Lastly there is a section on electrochemistry whichcontinues that included in last year’s report.This pattern of the General and Physical Chemistry Section will becontinued in next year’s report. It is intended that several of the subjectsnot covered in this report or the last will be dealt with next year.J.W. L.2. RADIATION CHEMISTRYTHIS report has been restricted to some aspects of the radiation chemistryof gases and liquids. Useful reviews have been published dealing withgases,l aqueous solutions,2 hydrocarbon^,^ oxidation of organic liquids,4similarities with phot~chemistry,~ evidence of radical species,6 and witha F. S. Dainton, Radiatiofi Res., 1959, Suppl. 1, 2; E. J. Hart, J . Chem. Educ.,1959, 36, 266; idem, Geneva Conf., 29, 5 (P951); G. Scholes and J . Weiss, RadiationRes., 1959, Suppl. 1, 177; M. Haissinsky, Inds. Atomiques. 1959, 3, No. 314, 37.A. Henglein, Angew. Chem., 1959, 71, 15.A. Henglein, Angew. Chem., 1959, ‘41, 393.N. A. Bach, Radiation Res., 1959, Suppl.1, 190.ti M. S. Matheson, Geneva Conf., 29, 385 (P949).R. Livingston, J. Chem. Educ., 1969, 36, 349; P. A. Giguh-e and J . A. Herman,Radiation Res., 1969, Suppl. 1, 1498 GENERAL AND PHYSICAL CHEMISTRY.general aspects.7* The proceedings of the second International Con-ference on the Peaceful Uses of Atomic Energy, held in Geneva in 1958,have been published.* The year 1959 marks the eightieth birthday ofDr. S. C. Lind, and a meeting on the radiolysis of gases was held as a tributeto his early work. The first Miller conference on Radiation Chemistry wasalso held (in Britain), and is so named in honour of the late Dr. N. Miller.Gases.-The tendency of neutral molecules to associate into clustersaround ions has been reconsidered.s At pressures approaching saturationvery large clusters may form and could react in the manner originallysuggested by Lind, but no experimental studies have been made underthese conditions.Lower pressures favour the formation of clusters con-taining 0, 1, or a characteristic small number of molecules as the pressure israised, and some data on lithium ions in krypton and xenon conform withthese predictions. Calculations of the average excitation energy with whichmolecular ions are formed have been made by applying equilibrium-rate theoryto observations of appearance potentials of parent and fragment ions, and byanother method, with reasonable agreement.g It is concluded that the ionsof simple hydrocarbons and of phosphine will persist for at least sec.without spontaneous decomposition, while those of higher and more complexhydrocarbons will not.The former ions are therefore likely to participate inion-molecule reactions when the parent species is at atmospheric pressure.The excitation of gaseous molecules by electron impact lo appears toobey the same dipole selection rules as apply to absorption of ultravioletradiation. Excitation by 500 ev electrons in oxygen and water causesimmediate disruption to radicals in some cases. Evidence of the increasingimportance of excitation rather than ionisation at low electron energies hasbeen obtained by a novel technique,ll applied to some simple alkanes.Ion-molecule reactions. This topic has been recently reviewed.12 Theuse of the mass spectrometer in electron-bombardment experiments con-tinues to provide information on appearance potentials of molecular ionsand derived thermochemical data, and also on cross sections of ion-moleculereactions.Recent studies by refined methods have dealt with alkyl iodides l3and other halides,l4 various saturated l5 and unsaturated l6 hydrocarbons,'I A. Kuppermann, J . Chem. Educ., 1959, 36, 279; A. Charlesby and A. J. Swallow,Ann. Rev. Phys. Chem., 1959, 10, 289; L. S. Polak and A. Ia. Temkin, Dokludy Akad.Nauk S.S.S.R., 1959, 125, 584.M. Burton, J . Chem. Educ., 1959, 36, 273; idem, Geneva Conf., 29, 391 (P916).J. L. Magee and K. Fnnabashi, Radiation Bes., 1959, 10, 622.D. P. Stevenson, Radiation Res., 1959, 10, 610.lo E. N. Lassettre, Radiation Res., 1959, Suppl.1, 530.l1 R. R. Williams, J . Phys. Chem., 1959, 63, 776.l2 A. F. Trotman-Dickenson, Ann. Reports, 1958, 55, 36; W. H. Hamill, J . Chem.Educ., 1959, 36, 346.13 R. F. Pottie, R. Barker, and W. H. Hamill, Radiation Xes., 1959, 10, 664; R. F.Pottie and W. H. Hamill, J. Phys. Chem., 1959, a, 887.l4 R. I. Reed and W. Sneddon, Trans. Furuday Soc., 1959, 55, 876.l5 L. Friedman, F. A. Long, and M. Wolfsberg, J. Chem. Phys., 1959, 30, 1605;1959, 31, 755; F. W. Lampe and F. H. Field, J . Amer. Chem. Soc., 1959,81, 3242, 3238.l6 R. Barker, W. H. Hamill, and R. R. Williams, J . Phys. Chem., 1959, 63, 825;P. S . Rudolph and C. E. Melton, ibid., p. 916.* References to these proceedings will be made in the form Geneva Conf., A, x (Py)where A and x denote the volume and page numbers of the English version of theseproceedings, and y denotes the paper numberSUTTON : RADIATION CHEMISTRY.9and nitric oxide,l7 reactions of 02+,1* and the formation of NH4+ fromNH3+ + NH,.19The prevalence of ion-molecule reactions in acetylene is noteworthy,both during electron and a-ray bombardment.16 Most of these reactionsproduce neutral fragments a t low pressures, but addition reactions of thetype C,H,+ + C2H2 _t Cn+2Hn+2+ are possible at higher pressures andmay account for the high yields observed in the radiation-induced poly-merisation of acetylene, though the remarkable constancy of these yieldsremains unexplained. The cyclisation to benzene which normally accom-panies this polymerisation is suppressed at low pressures and also when thereaction is sensitised by rare gases; 20 possibly this process involves excit-ation to a triplet state.An ion addition reaction of the above type wasobserved in alkyl halides; l3 the species (EtI),+ exists for a t least 1 psec.Use of rare-gas ions to induce known ion-molecule reactions has beensuccessfully applied in the radiolysis of hydrogen-deuterium mixtures,21and of ethylene.22 The former exchange reaction proceeds by a chainmechanism carried by the H3+ ion; it is suppressed by adding krypton andxenon, because of the reaction H3+ + Xe + XeH+ + H,, but not by otherinert gases since they do not react in this way. Ar+ ions react rapidly withhydrogen to form ArH+ + H ; in consequence argon has a slightly inhibitingaction on the hydrogen-deuterium exchange, but accelerates the formationof gases in the radiolysis of ethylene-hydrogen mixtures.Evidently thelatter reaction proceeds via hydrogen atoms. In some cases the additionof inert gases of ionization potential lower than that of the reactants in-creases the yield. This was observed in the radiolysis of nitrogen-hydrogenmixtures 23 and was therefore attributed to excitation rather than to chargetransfer from the rare gas to nitrogen. However charge transfer may stillbe possible in such cases if the inert-gas ion has excess of energy, and theoccurrence of such excited ions has recently been demonstrated24 by ob-servations of reactions such as Xe+ + CH,+ Xe + CHp+ which would beendothermic with ground-state ions.High energy CH,+ ions have also beenobserved during electron bombardment of propane.25The direct radiolysis of ethylene by 3 Mev electrons 22 and byy-rays 26 produces a non-volatile polymer possibly by an ionic mechanism,as well as a minor yield of gases; of these ethane is probably formed viaalkyl radicals since the addition of nitric oxide completely suppressesformation of this product.26 This use of nitric oxide as a radical scavengerhas also been applied to the radiolysis of methane, ethane, and propane; 27l7 P. S. Rudolph, C. E. Melton, and G. M. Begun, J. Chem. Phys., 1959, 30, 588;G. G. Cloutier and H. I. Schiff, ibid., 1959, 31, 793.F. M. Rourke, J. C. Sheffield, W. D. Davis, and F. A.White, J. Chem. Phys., 1959,81. 193.L. M. Dorfman and P. C. Noble, J. Phys. Chem., 1959, 63, 980.2o L. M. Dorfman and A. C. Wahl, Radiation Res., 1959, 10, 680.21 A. 0. Schaeffer and S. 0. Thompson, Radiation Res., 1959, 10, 671.22 F. W. Lampe, Radiatiolz Res., 1959, 10, 691.28 C. H. Cheek and V. J. Linnenbom, J. Phys. Chem., 1958, 62, 1475.24 G. G. Meisels, J. Chem. Phys., 1959, 31, 284.25 H. E. Stanton, J. Chem. Phys., 1959, 30, 1116.z6 K. Yang and P. J. Manno, J. Phys. Chem., 1959, 63, 752.27 K. Yang and P. J. Manno, J. Amer. Chem. SOL, 1959, 81, 3507.General10 GENERAL AND PHYSICAL CHEMISTRY.at least 40% of the hydrogen and all of the heavy hydrocarbon products areformed by radical reactions (probably hydrogen atom abstraction), and someof the remaining hydrogen is attributable to reactions of the typeCH3+ + CH,+ C,H,+ + H,.It is surprising that iodine does not sup-press the formation of hydrogen in these systems. Formation of most ofthe labelled products from the tritium-ethane reaction is also suppressedby nitric oxide; 28 the amount of tritium required for this labelling may begreatly decreased if a glow discharge is used to hasten the exchange process.29The use of microanalytical techniques has shown that the a-radiolysisof pentane produces hydrogen, methane, and unsaturated products in quitelarge initial yields.30 After only 1% reaction these yields decrease owing tosecondary reactions of hydrogen atoms with unsaturated products. Thedecomposition of butane in an electric discharge involves the excitation ofalkyl (probably butyl) radicals.31 An interesting chain reaction at highpressure in mixtures of propene and isobutane has been rep0rted.~2 This isinduced by y-rays and produces a range of useful alkylated hydrocarbonproducts.The formation of hydrogen cyanide from methane and ammoniaon a platinum catalyst is accelerated by radiation, possibly owing to theformation of radicals in the gas phase.33 The effects of nuclear-reactorradiations on several hydrocarbons and other gases have been studied; 34also the a-radiolysis of liquid and gaseous ben~ene,~5 and of uranium hexa-fluoride.36 The last substance is only slightly decomposed owing to recom-bination of primary products. The addition of hydrogen bromide toethylene induced by y-rays has been rep~rted.~' This proceeds by a chainmechanism with yields of up to lo5 molecules/100 ev in the gaseous, liquid,and solid phases, and is in many respects similar to photobromination.From further studies on the radiolysis of mixtures of nitrogen andoxygen both the initial yield of nitrogen dioxide and nitrous oxide, and theequilibria set up on prolonged irradiations can be explained by reactions ofnitrogen and oxygen atoms, but there is disagreement regarding the possibleprimary role 38 of N,+.The presence of water vapour changes the course ofthe reaction so that nitric acid is produced initially and subsequentlydecomposes when the water is consumed.39The ions, electrons,and possibly excited molecules which are formed during irradiation rapidlygive rise to hydroxyl radicals and another radical species, usually consideredto be the hydrogen atom.The molecular products hydrogen and hydrogenWater and Aqueous Solutions.--Primnry species.28 P. L. Gant and K. Yang, J . Chem. Phys., 1959, 30, 1108.29 L. M. Dorfman and K. E. Wilzbach, J . Phys. Chem., 1959, 63, 799.30 R. A. Back and N. Miller, Trans. Faraday Soc., 1959, 55, 911.31 A. Kuppermann and M. Burton, Radiation Res., 1959, 10, 636.32 P. J . Lucchesi and C. E. Heath, J . Amel.. Chem. Soc., 1950, 81, 4770.33 R. Mihail and J. Herscovici, Geneva Conf., 29, 317 (P1422).34 L. Dolle, Geneva Conf., 29, 367 (P1214).35 P. Huyskens, P. Claes, and F. Cracco, Bull. SOC. chim. belges, 1959, 68, 89.36 H.A. Bernhardt, W. Davis, jun., and C. H. Schiflett, Geneva Colzf., 29, 62 (P522).37 D. A. Armstrong and J. W. T. Spinks, Canad. J . Chem., 1959, 37, 1002, 1210.38 S. Ya. Pshzhetskii and M. T. Dmitriev, Intevnat. J . Appl. Radiation Isotopes,1959, 5, 67; idem, Zhur. fiz. Khim., 1959, 33, 463; P. Harteck and S. Dondes, J . Phys.Chem., 1959, 63, 956; idem, Geneva Conf., 29, 415 (P1769).39 A. Russell Jones, Radiation Res., 1959, 10, 655SUTTON : RADIATION CHEMISTRY. 11peroxide are also observed in yields so nearly constant for a given type ofradiation that these, also, are commonly regarded as primary products.Their origin is now generally attributed to diff usion-controlled recombin-ations between primary radicals, which are formed initially in localisedregions of high concentration. It is supposed that a fraction of the radicalsescape recombination, and these are detected by reaction with addedsolutes.The identity of the second radical species has been questioned in recentstudies, which show (a) that the product of the reaction of hydroxyl radicalswith hydrogen (presumably a true hydrogen atom) reacts much morerapidly with oxygen than with hydrogen peroxide, while the radical pro-duced by radiation reacts equally rapidly with both,m and (b) that certainradical scavengers, notably ferric ions, cupric ions,41 and a~rylarnide,~,depress the yield of molecular hydrogen in a manner bearing no relation totheir reactivity towards hydrogen atoms.Ferric ions depress the yield ofhydrogen and of so-called hydrogen atoms simultane~usly.~~ Evidently twospecies exist in these systems, and the influence of pH on reaction yields insolutions of chloroacetic acid 43 and of methanol in deuterium oxide *1suggests that gain or loss of a proton may transform one to the other.Theprimary radiation product may be a solvated electron which reacts rapidlywith oxygen, hydrogen peroxide, ferric ion, and with itself to form hydrogen;while the product of the OH + H, reaction is the hydrogen atom, reactingrapidly with oxygen and methanol, A possible equilibrium between the twoforms has been written as 4os 419 *H,O- H + OH-but there seems to be little evidence for the back reaction, i.e. the conversionof hydrogen atoms into H,O- in neutral or alkaline solution.Much of thepresent evidence suggests that a reaction such asH,O+ + H,O- H + 2H,Oexpresses the relation between the two species, so that added solutes competewith H30+ for H,O-.An alternative view is that the hydrogen atom is the primary radiationproduct, while the acid form, and the product of the OH + H, reaction, isthe species H2+.40 However, recent comparisons of the rates of reaction ofhydroxyl radicals with deuterium and with hydrogen have revealed onlysmall differences in frequency factors and activation energies.44 Thesedifferences are almost identical with those observed in gas-phase reactionsof methyl radicals with deuterium and with hydrogen, which must proceedby a bond-breaking rather than electron-transfer mechanism.Thus, itseems fairly certain that the OH + H, reaction produces a true hydrogen40 N. F. Barr and A. 0. Allen, J. Phys. Chem., 1959, 63, 928.41 J. H. Baxendale and G. Hughes, 2. phys. Chem. (Frankfurt), 1958,14, 306, 323.42 D. A. Armstrong, E. Collinson, and F. S. Dainton, Trans. Faraday Soc., 1959, 55,4a D. A. Armstrong, E. Collinson, F. S. Dainton, D. M. Donaldson, E. Hayon,44 D. Bum, F. S. Dainton, G. A. Salmon, and T. J. Hardwick, Trans. Faraday SOL,1375.N. Miller, and J. Weiss, Geneva Conf., 29, 80 (P1517).1959, 55, 176112 GENERAL AND PHYSICAL CHEMISTRY.atom. The ion H2+ was invoked originally to explain the oxidation offerrous sulphate in acid solution by hydrogen atoms. Recent studies showthat hydrogen atoms produced by the OH + H, reaction,& by electricaland thermal dissociation of hydrogen ,46 and by electrodeless discharge inhydrogen 47 also oxidise ferrous ions, to an extent which increases withacidity in the latter case.There is thus good evidence of the oxidisingproperties of hydrogen atoms in this system, but it is possible that theycould react as such, rather than as H2+ ions. The pH effect may be attri-butable to the back reaction in which ferric ions are reduced by hydrogenatoms, and the slow exchange observed during radiolysis of hydrogen-deuterium solutions & cannot be reconciled with a rapidly attained equili-brium between hydrogen atoms and H2+. Again, the hydrogen atom actssolely as a reducing agent on solutions of quadrivalent tin,49*60 though onemight have expected H,+ to oxidise this species.However, it has now beenshown that hydrogen atoms can oxidise iodide ionsJ51 and the kinetics ofthis process strongly suggest that it is due to H2+, which is formed ratherslowly from the hydrogen atom and H+. We are therefore led to thetentative conclusion that the primary species H20- may be successivelytransformed into hydrogen atoms and to H,+ under certain conditions.Further evidence of the influence of pH on the oxidising power of irradi-ated water has come from a study of the equilibria attained after prolongedirradiation in air-free solutions of simple solutes such as potassium iodide.62If this equilibrium is measured as an electrode potential, relative to that ofthe normal hydrogen electrode, then it is found to obey the relation: electrodepotential = -0.85 + 0*05910g[H+] V.Dainton and Collinson’s earliertreatments3 of this subject is thus confirmed, but interpretation of theabsolute value of the electrode potential in terms of primary radical speciesstill poses some difficult problems.The yields of primary species in deuterium oxide have now been com-pared with those in water by several methods 42~63*54 with good agreement.The fraction of initial radicals which escape recombination and are scavengedby solutes is considerably greater in deuterium oxide than in water. If oneassumes that the hydrogen (or deuterium) atoms are formed at some distancefrom hydroxyl radicals owing to migration of the electron before solvation,then the larger relaxation time in deuterium oxide would allow more timefor this migration, and this may explain the observations.& The smalleryield of radicals relative to molecular products which is observed in theradiolysis of liquid ammonia lends weight to this argument, since the relax-ation time in ammonia is very small.& Studies at high L.E.T.should be45 V. N. Shubin and P. I. Dolin, Doklady Akad. Nauk S.S.S.R., 1959, 125, 1298.46 T. W. Davis, S. Gordon, and E. J. Hart, J. Amer. Chem. Soc., 1958, 80, 4487.47 G. Czapski and G. Stein, J. Phys. Chem., 1959, 63, 850.48 H. L. Friedman and A. H. Zeltman, J. Chem. Phys., 1958, 28, 878.48 J. W. Boyle, S. Weiner, and C. J . Hochanadel, J. Phys. Chem., 1959, 63, 892.50 M. A. Proskurnin and Y.M. Kolotyrkin, Geneva Conf., 29, 62 (P2022).51 G. Czapski, J . Jortner, and G. Stein, J. Phys. Chem., 1959, 63, 1769.52 I. H. S. Henderson, E. G. Lovering, R. L. Haines, and E. J . Casey, Canad. J.53 F. S. Dainton and E. Collinson, Ann. Rev. Phys. Chem., 1951, 2, 99.54 T. J. Hardwick, J. Chem. Phys., 1959, 31, 226.Chem., 1959, 37, 164SUTTON : RADIATION CHEMISTRY. 13enlightening, since the enhanced coulombic attraction of a dense column ofpositive ions should suppress electron migration.55Yields * of the primaryproducts obtained with a wide range of radiations have now been deter-mined by the following methods: ( a ) Mechanisms established in the caseof y-radiolysis have been applied to the estimation of radical and molecularyields in the ferrous and ceric sulphate systems in O-8~-sulphunc acid.56(b) Studies on the yield of ferrous ion in aerated solutions of formic acid atpH 2 containing cupric and ferric ions have provided a measure ofG(H+OH).~’,~ (c) Measurements of GRI, GHpOat and GH in several solutionsat neutral pH have been correlated with the aid of known data on scavengerefficiency to obtain the yields of all species relevant to a common solute.59@) Measurements of G(H202) in halide solutions have been combined withother data to determine the yields of molecular products and of totaldecomposition of watermaThe results of these measurements are not strictly comparable with oneanother owing to differing conditions, but they all show a consistent trend,and lead to the following conclusions :(1) GH decreases to nearly zero with increasing L.E.T.as the radical-diffusion model would require, while GOH apparently falls to a low butpositive value. This is an illusory effect, attributed to the occurrence ofthe secondary reactionin particle tracks, so that some hydroxyl radicals which would otherwisehave formed molecular products now appear as “primary” HO, andthereby influence the above measurements. Other recent evidence forthis “ track ’’ reaction includes evolution of oxygen in air-free systems oftype (b),57 the influence of [O,] on G(Fe3+) in or-irradiated solutions,61 and theinfluence of thallous ions on radiolysis of ceric ~ u l p h a t e . ~ ~ ’ ~ ~ A value ofGo* of approximately 0.25 in the case of polonium a-rays is consistent withall the data.Since the precursors of this HO, are slightly more dispersedthan those of hydrogen peroxide, GHOp is more sensitive to scavengers.10-3~-Thallous ion reduces G=OI almost to zero, while higher concentrationsreduce GH,o,.62sBThe low value of G(Fe3+) in a-irradiated ferrous sulphate has been attri-buted to a second track reaction 62and indications of the third likely track reactionInflueme of L.E.T. (linear energy transfer).OH + HZO, ___t HO2 + H2O ( I )H + H202 + OH + H*O (2)OH + H, HSO + H (3)66 J. Read, Brit. J . Radiology, 1949, 28, 366.66 N. F. Barr and R. H. Schuler, J . Phys. Chem., 1959, 83, 808.67 D. M. Donaldson and N. Miller, Radiation Res., 1958, 9, 487.68 N. Miller, Radiation Res., 1958, 9, 633.59 H.A. Schwarz, J. M. Cafrey, and G. Scholes, J . Amer. Chem. SOC., 1959, 81, 1801.60 M. Burton and K. C. Kurien, J . Phys. Chem., 1959, 83, 899.81 C. N. Trurnbore and E. J . Hart, J . Phys. Chem., 1959, 63, 867.82 M. Lefort and X. Tarrago, J . Phys. Chem., 1959, 63, 833.6s J. Weiss and N . Miller, J . Phys. Chem., 1959, 65, 888.* The symbol G denotes the yield in molecules per 100 ev14 GENERAL AND PHYSICAL CHEMISTRY.in addition to (1) and (2) have been obtained by combining data from manysystems including solutions of vanadium salts.65 It is suggested that the Gvalues of these reactions may be as high as 0-25,0-25, and 0.35, respectively,in certain conditions. However, other studies on production of hydrogenperoxide in aerated water indicate the occurrence of reaction (2) in neutralbut not in acid solution, and this is borne out by the decrease of G(FeS+) withincreasing pH.(2) GH increases with acidity at all L.E.T.values probably owing to theinfluence of pH on the behaviour of H,O- as discussed above,5g though otherinterpretations have been offered.=(3) Though the netG-H*O(= GH,, + &I, or GOH + ~GH,oJdecreases with increasing L.E.T. rapidly up to 1 ev/A and thereafterrather slowly, estimates of the gross yield of decomposed water show verylittle variation, except perhaps at very high L.E.T. The latter estimatesmake an allowance for the hydrogen and hydroxyl radicals which recombineto water, and this allowance is generally based on statistical considerationsof the yields of hydrogen and hydrogen peroxide.A novel approach to thisproblem involves comparison of yields in deuterium oxide and in water. Onthe assumption that the gross decomposition yield is the same in bothspecies, it is concluded that the recombination yield in y-irradiated systemsis 0.8 in 0.8~-sulphuric acid, and practically zero in neutral solution," Thelatter conclusion is opposed to all previous estimates.(4) Comparisons with the predictions of the radical-diffusion model ofSamuel and Magee66 have been made along two lines. First, the fraction(l-S) of the total primary radicals which recombine to form hydrogenmolecules, hydrogen peroxide, and water is found to vary with L.E.T. in amanner quite well predicted by the theory.Difficulties appear a t veryhigh L.E.T. where an apparent and unpredicted rise in the gross GHs0 isn0ted,5~*~~ but the situation here depends critically on uncertain estimates ofthe water recombination yield. Consideration of the y-ray spurs of onlyone radical pair, which merge in cc-ray tracks, may resolve this difficulty.59Secondly, the hydrogen yields from 6oCo y-rays, 18 Mev deuterons, and32 Mev helium ions are found to vary with scavenger (NO,-) concentrationalmost exactly as required by the theory.59 This is not true of yields ofhydrogen peroxide at high L.E.T.,59 but since the theory is based on a one-radical model with parameters fitted to the hydrogen data, and since trackreactions are ignored, some disagreement is to be expected.Neverthelessthe cc-ray yields of hydrogen peroxide are reported to agree with the theoryin the case of bromide and chloride scavengingm and agreement withFlanders and Fricke's 67 theory is found in the case of iodide scavenging.68This theory employs machine calculations relating to a more realistic diffusionmodel. A rigorous treatment should take account of the two independent84 J. Pucheault and C. Ferradini, Geneva Conf., 29, 24 (P1232).66 C. Ferradini and J. Pucheault, J . Chinz. phys., 1958, 55, 772.66 A. H. Samuel and J. L. Magee, J . Chem. Phys., 1953, 21, 1080.87 D. A. Flanders and H. Fricke, J . Chem. Phys., 1958, 28, 1126.68 C. B. Senvar and E. J. Hart, Geneva Conf., 29, 13 (P1128)SUTTON : RADIATION CHEMISTRY. 15radicals, and an approach along these lines has been made by Dyne andKennedy 69 by using machine calculations, and also by Burch 70 who em-phasises the local rather than the average L.E.T.of the radiation. In itspresent form the latter theory includes the track reaction (2) and it predictsa maximum in the yield of ceric-ion reduction for radiations of intermediateL.E.T. These later treatments will be of more value when independentestimates of their many parameters are available; in the meantime thesimpler one-radical treatments are being used to determine approximatevalues of rate constants from scavenging data. Thus the rate constants forreactions of hydroxyl radical with chloride, bromide,60 and iodide ion 68 arereported as 4 x l o 9 , 1-6 x l o l o , and 1-2 x 1O1O 1.mole-l sec.-l, respectively.A very satisfactory correlation of &verse observ-ations on the radiolysis of solutions of hydrogen , oxygen, and hydrogenperoxide has been achieved on the basis of six commonly accepted radicalreactions, after allowance for the differing properties of the two reducingspecies.71 Differences in the radiolysis of static and bubbling water havealso been explained; 72 the usual rapid recombination of hydrogen andhydrogen peroxide is suppressed in bubbling water owing to removal ofhydrogen. Several studies on radiation-induced peroxide formation 73374and decomposition 75 have been reported. The use of [lSO]water enablesone to distinguish the hydrogen peroxide derived from water (presumablyby dimerisation of hydroxyl radicals) from that resulting from consumptionof oxygen; the yield of the former increases with increasing L.E.T.even inthe X- and the y-ray region.73An ingenious comparison of the rate of reaction of hydrogen atoms withdeuterium and with ferric ions has been reported,76 based on measurementsof yields of hydrogen deuteride in this system. If this ratio is combinedwith the known rate of the H + D, reaction in the gas phase, one obtainsthe value k(H+Fe~~) = 48 & 12 x lo5 1. mole-l sec.-l at 25" in 0 . 0 1 ~ -sulphuric acid. This is the first determination of the rate of reaction of ahydrogen atom in aqueous solution, and several other rate constants can bederived from it with existing data. Thus K(H+o,) = 10 & 3 x 108 1.mole-1 sec.-lIn recent Russian studies,50* 77 excited water molecules have been invokedto explain the high yields of oxidation of ferrous sulphate observed in air-free solutions, and also the increasing yield of nitrate reduction which isobserved a t very high concentrations of nitrate.Several other phenomenaSecondary reactions.*S P. J. Dyne and J . M. Kennedy, Canad. J. Chem., 1958, 36, 1518.70 P. R. J . Burch, Radiation Res., 1959, 11, 481.7 1 A. 0. Allen and H. A. Schwarz, Geneva Conf., 29, 30 (P1403).73 S. Gordon and E. J. Hart, Geneva Conf., 29, 13 (P952).75 J . D. Blackhurst, G. R. A. Johnson, G. Scholes, and J. Weiss, Nature, 1959, 189,176.74 J. Bednar and J. Teply, CoZZ. Czech. Chem. Comm., 1959,24, 127; A. I. Chernova,V.D. Orekov, and M. A. Proskurnin, Zhur. $2. Khim., 1958, 32, 2843; H. Izadian andP. Mergault, Compt. rend., 1959, 248, 2483.75 B. V. Ershler, M. A. Nezhevenko, and G. G. Miasishcheva, DokZady Akad. NaukS.S.S.R., 1959, 126, 126.76 P. Riesz and E. J. Hart, J. Phys. Chem., 1959, 63, 858.77 V. A. Sharpatyi, V. D. Orekhov, and M. A. Proskurnin, Doklady Akad. NaukS.S.S.R., 1958, 122, 852; 1959, 124, 127916 GENERAL AND PHYSICAL CHEMISTRY.also appear in concentrated solutions, such as an apparent discrepancy in4~-sulphuric acid solutions between the decrease of [Fe2+] and the ’increaseof pe3+] observed during radiolysis of iron solutions.78 Possibly directabsorption of the radiation may contribute to these effects.The ionic strength of the irradiated solution influences the yield offerrous sulphate oxidation,79 and also the yield of hydrogen in nitratesolutions.80 The activity rather than the concentration of the soluteappears to be the determining factor.The concentration of sulphate ionsinfluences the yield of radiation-induced reduction of plutonium solutions,but this appears to be due to complex formation rather than to variationsof ionic strength.81The properties of TI2+ ions formed by the action of hydroxyl radicalson Tl+ have been further studied. These ions are able to reduce di-chromate 82 and also ferric ions complexed with l,l’-bipyridyl,83 but uncom-plexed ferrous ions are oxidi~ed.~~ Further studies on the oxidation offerrous sulphate induced by a glow dischargea have shown that this ismainly due to the formation of positive ions.Aqueous solutions of organic solutes.The organic radicals formed in thesesystems by hydrogen abstraction reactions of hydrogen radicals and hydroxylradicals lead to a great diversity of products. The emphasis in recent workis on the use of refined analytical techniques to determine the initial as wellas secondary products of the radiolysis. Fatty acids%-88 and carbo-hydrates have been extensively studied; the latter produce radical dimersand subsequently polymeric material in air-free solution,8g while aeratedsolutions of mono- and poly-saccharides are either selectively oxidised a tcertain points or degraded.90 The simple course of the y-radiolysis of air-free formic acid is considerably altered at high L.E.T.85 Oxalic acid andhigher species then appear owing to reactions of carboxyl radicals in particletracks.Oxalic acid 88 forms COOH (or HCOO) radicals which then behaveas in the formic acid system, yielding carbon dioxide, hydrogen, and hydro-gen peroxide in aerated solutions. In air-free solutions the product yieldsdiminish at pH > 11; s8 this cannot be due to acid dissociation and isascribed to the equilibrium OH # H+ + 0- which has been inferred inother systems at the same pH.78 2. Spurny, Coll. Czech. Chem. Comm., 1959, 24, 1010.7s Y. Gilat and G. Stein, Geneva Conf., 29, 43 (P1617).80 H. A. Mahlman, J . Chem. Phys., 1959, 31, 993.81 M. Pages and M. Haissinsky, Geneva Conf., 29, 44 (P1156).82 T.J. Sworski, J . Phys. Chem., 1959, 63, 823.83 J. Bednar, Coll. Czech. Chem. Comm., 1959, 24, 1006, 1240.84 H. A. Dewhurst, J. F. Flagg, and P. K. Watson, J . Electrochem. Soc., 1959, 106,85 W. M. Garrison, W. Bennett, and S. Cole, Radiation Res., 1958, 9, 647.86 W, M, Garrison, H. R. Haymond, W. Bennett, and S. Cole, Radiation Res., 1959,87 P. Y. Feng and S. W. Tobey, J . Phys. Ckewt., 1959, 63, 759.88 I. Draganic, J . Chim. phys., 1959. 56, 9. 16, 18.89 S. A. Barker, P. M. Grant, M. Stacey, and R. B. Ward, Nutwe, 1959, 183, 376.90 G. 0. Phillips, G. L. Mattock, and G. J. Moody, Geneva Conf., 29, 92 (P47);M. L. Wolfrom, W. W. Binkley, and L. J. McCabe, J . Amer. Chem. SOC., 1959, 81, 1442;M. L. Wolfrom, W. W. Binkley, L. J. McCabe, T. M. Shen Han, and A.M. Michelakis,Radiation Res., 1959, 10. 37; E. A, Balazs, T. C. Laurent, A. F. Howe, and L. Varga,ibid., 1959, 11, 149.366.10, 273SUTTON : RADIATION CHEMISTRY. 17Research has continued on the radiolysis of organic dyes,g1~92 andof amino-acid~,~~,M protein^,^^,^^ and other biologically important sub-stances.97*98 Although some u-ray yields are surprisingly large 93 the resultscan generally be ascribed to reactions of hydrogen and hydroxyl radicals,and the kinetics observed in some complex cases, such as the inactivationof macromolecules, have been considered in some detail on this basisw Ithas been suggested that a solution of the dye Erioglaucine might serve as amodel system to test the efficiency of additives as biological protectingagents.92 However, biological protection against radiation is not necessarilyrelated to affinity for radicals, as some recent examples An im-portant reaction in the radiolysis of proteins is the following: 95-CO*NHCHR + 0 2 + H 2 0 -CO*NH, + RCO + H2O2Unsaturated hydrocarbons have also been studied ; loo hydroperoxidesare formed from aerated solutions possibly by direct addition of the HO,radical on to the double bond.Further studies on benzene solutions showthat Fe3+ and Cu2+ ions increase the radiation yield of phenol by a reactionsimilar to the photochemical oxidation by Fe3+0H.lo1 Although plausiblereactions of hydrogen and hydroxyl radicals can account for the radiolysisproducts neither benzene nor phenol has any scavenging action on theprecursors of molecular hydrogen or hydrogen peroxide.lo2Organic Liquids.--Parafiuts.Considerable theoretical and industrialinterest has been shown in the radiolysis of saturated hydrocarbon^.^^-^^^The products include hydrogen and a range of lower and higher hydro-carbons, together with some unsaturated members which may arise bydecomposition of excited molecules or by disproportionation of radicals.Paramagnetic-resonance techniques have helped to identify some of theradicals formed at low temperatures.l" Variation of the L.E.T. of the9l M. C. Anta and M. L. R. Santos, Internat. J . ApgZ. Radiation Isotopes, 1959, 4,261 ; A. A. Zansokhova, V. D. Orekhov, and M. A. Proskurnin, Doklady Ahad. NaukS.S.S.R., 1959, 125, 577; A. A. Zansokhova and V.D. Orekhov, ibid., p. 838.92 D. R. Kalkwarf, Geneva Conf., 29, 379 (P915).ga C . R. Maxwell and D. C. Peterson, J . Phys. Chem., 1959, 65, 935.sp W. M. Dale and J. V. Davies, Internat. J . Rudiation Biology, 1959, 1, 189; G.Peter, 2. Naturforsch., 1959, 14b, 135; D. Cavallini, B. Mondovi, B. Giovanella, andC. de Marco, Nature, 1959, 184, ~ . ~ . 6 1 ; J. Kopoldova, J. Kolousek, A. Babicky,and J . Liebster, Geneva Conf., (P2117) ; R. S. Yalow, Radiation Res., 1959,11, 30.g5 W. Bennett and W. M. Garrison, Nature, 1959,183, 889.96 H. Fricke, W. Landmann, C. Leone, and J. Vincent, J . Phys. Chem., 1959,65, 932.s7 D. R. Anderson and B. J. Joseph, Radiation Res., 1959, 10, 507; G. Fletcherand S. Okada, ibid., 1959, 11, 291.O8 See, for example: W.F. Serat and J. F. Mead, Radiation Res., 1959, 11, 370;S. Munk and G. Stein, Geneva Conf., (P1618); F. M. Defilippes and W. R. Guild, Radi-ation Res., 1959, 11, 38; S. Okada and G. Fletcher, ibid., p. 177.Og L. Augenstine, Radiation Res., 1959,10, 89; F. Hutchinson and D. A. Ross, ibid.,loo P. G. Clay, G. R. A. Johnson, and J. Weiss J . Phys. Chem., 1959, 65, 862;lol J. H. Baxendale and D. Smithies, J., 1959, 779.lo2 K. C. Kurien, P. V. Phung, and M. Burton, Radiation Res., 1959, 11, 283.lo$ R. M. Lincoln, R. L. Rogers, H. Burswasser, and V. J. Keenan, Ind. Eng. Chem.,1959, 51, 547; H. N. Dunning and J. W. Moore, ibid., p. 161; A. M. Brodsky, Yu..A.Kolbanovsky, E. D. Filatova, and A. S. Tchernysheva, Internat. J . AppZ. RadiatzonIsotopes, 1959, 5, 57.lo* L.S. Polak, A. V. Topchiev, and N. Y . Chernyak, Geneva Conf., 29, 162 (P797);M. S. Matheson, ibid., 29, 217 (P948).p. 477.P. G. Clay, J. Weiss, and J. Whiston, Proc. Chem. SOC., 1959, 12518 GENERAL AND PHYSICAL CHEMISTRY.radiation has no influence on yields of hydrocarbons observed a t high doserates from hexane and cyclohexane,lo5 or on the distribution of productsfrom n-pentane.lo6 Random recombination of primary alkyl radicalsaccounts very well for the heavy hydrocarbon products observed in thelatter case, and it is suggested that the lack of dependence on L.E.T. is dueto the preponderance of such reactions over first-order radical reactions,such as hydrogen abstraction from the parent hydrocarbon. On this viewone would expect the recombination yield to decrease at low dose rates, andthis has been observed during radiolysis of cyclohexane105 and of cyclo-hexane-cyclopentane mixtures.lo7 In the latter case the yields of bicyclo-hexyl and bicyclopentyl formed at high dose rates correspond with the yieldsof cyclohexyl and cyclopentyl radicals, as determined by the addition ofiodine.Studies on the radical-scavenging action of dilute solutions ofanthracene in hexane Io8 and cyclohexane,lm but not in polysiloxanes,l0glead to a similar conclusion. The observed relation between the anthraceneconsumption and the ratio [anthracene]/(dose rate)+ conforms with a mech-anism based upon radical recombination in which anthracene captures onlya small fraction of the radicals.Thus we have the interesting situation that the initial effects of radiolysisof hydrocarbons are largely dependent on dose rate but not on L.E.T.,while the exact reverse applies to water.On present evidence this appearsto be due to differences in radical diffusion and reaction rates, rather thanto a basic difference in mechanism. Thus the yield of radicals scavenged byiodine decreases slightly with increasing L.E.T. in the case of hexane andcyclohexane and of 2 ,2,4-trimethylpentane,l1° which conforms with a radical-diffusion mechanism in which a large fraction of the primary radicals escapefrom the track. Detailed studies on the hydrocarbon yields from irradiatedcyclohexane 111 show that about 15% of the primary decomposition leadsdirectly to the formation of cyclohexene, possibly by diffusion-controlledreactions in particle tracks.Reactions of hydrogen and of cyclohexylradicals (initial G = 4-0) can account for the other major hydrocarbonproducts, namely bicyclohexyl and cyclohexene, and these are suppressedby the addition of iodine, oxygen, or benzene. The origin of the hydrogenformed in this system is more complicated. Thus G(H,) is lowered from 6.5to 3.8 by iodine,l12 to 2.1 by benzoquinone,lls and to approximately 0.5 bymixtures of iodine and benzene.1l2 Possibly the benzene effect involves transferof excitation knergy, while the iodine quenching is accompanied by formationof hydrogen iodide,l14 and is presumably due to simple hydrogen-atom scaveng-ing. A curious decrease of G(H,) during radiolysis has been 0b~erved.l~~106 H.A. Dewhurst and R. H. Schuler, J . Amer. Chem. SOC., 1959, 81, 3210.106 A, E. de Vries and A. 0. Allen, J . Phys. Chem., 1959, 63, 879.107 R. H. Schuler and G. A. Muccini, J . Amer. Chem. SOC., 1959, 81, 4115.108 A. Charlesby and D. G. Lloyd, Proc. Roy. Soc., 1959, A , 249, 51.109 A. Charlesby, W. H. T. Davison, and D. G. Lloyd, J . Phys. Chem., 1959, 63, 970.110 R. H. Schuler, J . Phys. Chem., 1959, 63, 925.111 H. A. Dewhurst, J . Phys. Chem., 1959, 63, 813.112 M. Burton, J. Chang, S. Lipsky, and M. P. Reddy, Radiation lies., 1959, 8, 203.113 G. E. Adams, J. H. Baxendale, and R. D. Sedgwick, J . Phys. Chem., 1959, 63,114 G. Meshitsuka and M. Burton, Radiation Res., 1959, 10, 499.116 W.S. Guentner, T. J. Hardwick, and R. P. Nejak, J . Chem. Phys., 1959, 30, 601.854SUTTON : RADIATION CHEMISTRY. 19Paraffins are oxidised when irradiated in presence of oxygen to alcohols,aldehydes, and fatty acids. This reaction has possible industrial signi-ficance and has attracted much interest.116 As in the peroxidation ofcumene,l17 the formation of peroxy-radicals appears to be the primaryprocess. The oxidation of cyclohexene proceeds by a chain mechanismsimilar to that observed with photochemical initiation.lls The sulphoxid-ation of hydrocarbons containing oxygen and sulphur dioxide is also a chainprocess with possible industrial use.119The radiolysis of cyclohexane illustrates the diffi-culty of determining yields of radicals from scavenger effects unless themechanism is well established.Thus the total yield of radicals deducedfrom iodine consumption is 5.6,120 from formation of cyclohexyl iodide iniodine is 8,ll1 from oxidation yields in oxygen is 7-2,ll1 and from consumptionof anthracene is 6-5.l0S The rapid decomposition of hydrogen iodide inirradiated systems leads to difficulties in the use of iodine as a scavenger forhydrogen at0ms.1~~ Attention has been drawn to the possible role of iodineas an acceptor for slow electrons rather than as a radical ~cavenger,~~ andan outstanding example of this behaviour is found in the radiation-inducedpolymerisation of isobutene.121 In addition to iodine, both oxygen andbenzoquinone 121,122 suppress this reaction, but this action is due to captureof secondary electrons, thereby forming negative ions which neutralise theiortic-initiating species.Among the reagents recently suggested as radical scavengers in organicsystems are the following: ( a ) ferric chloride, which is reduced by manyorganic radicals,l= (b) tetranitromethane, which forms the coloured trinitro-methane with H, HO,, or alkyl radicals,12* (c) acetone, which appears toreact specifically with hydrogen atoms in irradiated propyl alcohol, butdoes not form a readily andysable (a) benzophenone, whichreacts with both hydrogen and methyl radicals in irradiated isopropylalcohol,lZ6 (e) ally1 alcohol, which is converted into tetrahydroxyhexaneduring photolysis of acetone and of aqueous hydrogen peroxide,127 (f) butane-thio1,12s and (g) sulphur dioxide129 which are both consumed during theradiolysis of some hydrocarbons with typical radical yields.KineticRadical scavengers.116 J. L. Liebenthal, L. F. Albright, and A. Sesonske, Geneva Conf., 29, 107 (P794);I. Drimus, G. Ionad, A. Dragut, P. Vasilesco, and V. Dumitresco, ibid., 29, 152 (P1316).117 M. Durup, J. Durup, F. Kuffer, and M. Magat, Geneva Conf., 29, 143 (P1215).118 M. Brun and R. Montarnal, Compt. rend., 1958, 24'7, 2361.1ls J. F. Black and E. F. Baxter, Geneva Conf., 29, 162 (P797).120 R. W. Fessenden and R. H. Schuler, J . Amer. Chem. SOC., 1957, 79, 273.121 E. Collinson, F. S. Dainton, and H. A. Gillis, J . Phys. Chem., 1959, 63, 909.122 W. H. T. Davison, S. H. Pinner, and R.Worrall, Proc. Roy. Soc., 1959, A , 252,las E. A. Cherniak, E. Collinson, F. S. Dainton, and G. M. Meaburn, Proc. Chem.1*4 A. Henglein, J. Langhoff, and G. Schmidt, J . Phys. Chem., 1959 63, 980.125 J. D. Strong and J. G. Burr, J . Amer. Chem. SOC., 1959, 81, 775.126 J. G. Burr and 3. D. Strong, J . Phys. Chem., 1959, 63, 876.lB7 D. H. Volman, J. C . Chen, and L. W. Swanson, J . Amer. Chem. SOC., 1959, 81,128 T. D. Nevitt, W. A. Wilson, and H. S. Seelig, Ind. Eng. Chem., 1959, 51, 311.I*@ A. Henglein, K. Heine, W. Hoffmeister, W. Schnabel, Ch. Schneider, and H. Uri,187; R. Worrall and S. H. Pinner, J . Polymer Sci., 1959, 34, 229.SOC., 1958, 54756.Geneva Con., 29, 206 (P962)20 GENERAL AND PHYSICAL CHEMISTRY.studies on the influence of benzoquinone and of ferric chloride on the radio-lysis of several alcohols and other simple organic liquids have providedestimates of the radical and molecular yields in these systems.l13 Some“ molecular ” hydrogen and methane are formed by reactions independentof the presence of these scavengers; the remainder is attributed to hydrogenabstraction reactions of hydrogen and of methyl radicals.The markedeffect of these two scavengers on the radiolysis of methanol has been con-firmed,130 though quantitative agreement on this point and on the directradiolysis is lacking. An interesting investigation of the radiolysis ofmethyl trideuteroacetate has been reported.131 In the gas phase, methaneis formed by reactions of methyl radicals which are suppressed by iodine ordiphenylpicrylhydrazyl, but most of the products in the liquid phase areformed in liquid “ cage ’’ reactions which are unaffected by added scavengers.General. The decomposition of benzoyl peroxide in several organicsolvents can be induced by y - r a y ~ .~ ~ ~ The reaction rate is not simplyrelated to the yield of radicals, but rather to the rate of thermal decom-position of peroxide in these solvents.Studies on the radiation-induced polymerisation of vinyl monomers inorganic 133 and aqueous media have been continued in order to deter-mine the yields of initiating radicals. The kinetics of this process are oftenmodified by energy transfer,l= and an interesting case has been reported inwhich reaction rate constants apparently vary with the composition of thesolution.135 The probability of ion-molecule reactions in unsaturatedsubstances should not be forgotten, and evidence of ionic rather than radicalpolymerisation has been found with isobutene,121J22 2,4,4-trimethylpent-l-ene,lS various substances at low temperatures,137 and the dimerisation ofterminal olefins.l=The radiolysis of chloro- and bromo-hydrocarbons 139 generally leads tothe breakage of the carbon-halogen bond.The chlorine atoms producedfrom chloro-hydrocarbons react rapidly with added hydrocarbon, forminghydrogen chloride,140 and also to exchange with the chlorine atoms in alkylchlorides,”l though the latter reaction is not always quantitative. Some130 N. N. Lichtin, J. Phys. Chem., 1959, 83, 1449.131 P.Ausloos and C. N. Trumbore, J. Amer. Chem. SOC., 1959, 81, 3866.132 S. Okamura and S. Futami, Doitai to Hoshashen, 1959, 2, 95.183 A. Chapiro, J. Phys. Chem., 1969, 88, 801; V. A. Krongauz and K. H. S. Bag-dasar’yan, Zhur.fiz. Khim., 1958,32, 1863; E. J. Henley and C. Chong Ng, J. Polymer.Sci., 1959, 36, 511; K. Makino, G. Meshitsuka, K. Kuwata, and K. Hirota, Doztaz toHoshashen, 1959, 2, 322; S. Okamura, T. Manabe, S. Futami, T. Iwasaki, A. Nakajima,K. Odan, H. Inagaki, and I. Sakurada, Geneva Con,., 26, 176 (P1350).134 A. Chapiro and N. Maeda, J . Chim. phys., 1959, 56, 230; J . C. Arthur, R. J.Demint, and R. A. Pittman, J . Phys. Chem., 1959, 63, 1366.135 A. Chapiro, P. Cordier, V. K. Hayashi, I. Mita, and J. Sebban-Danon, J. Chim.phys,, 1959, 56, 447.136 Eve de Gorski and G.de Gaudemaris, Compt. rend., 1959, 248, 969.137 A. P. Sheinker, M. K. Yakovleva, E. V. Kristal’nii, and A. D. Abkin, DokladyAkad. Nauk S.S.S.R., 1959,124, 632.138 P. C. Chang, N. C. Yang, and C. D. Wagner, J. Amer. Chem. SOC., 1959,81, 2060.13s W. S. Wilcox, Radiation Res., 1959, 10, 89.140 R. A. Back, E. A. Cherniak, E. Collinson, W. Cooper, F. S. Dainton, G. M.Meaburn, N. Miller, W. H. Stafford, G. A. Swan, P. S. Timmons, D. C. Walker, andD. Wright, Geneva Cunf., 29, 115 (P1516).141 R. E. Johnson and C. E. Miller, J . Phys. Chem., 1959, 83, 641SUTTON : RADIATION CHEMISTRY. 21interesting reactions induced by radicals derived from carbon tetrachloride 142and chloroform 143 have been reported.Radiation induces rapid decom-position of tetrachloroethylene,lu chloral hydrate,145 and bromal hydrate,l&that have been saturated with air and water, owing to chain reactions, butaqueous solutions of chloroform are decomposed to hydrogen chloride,carbon dioxide, and hydrogen peroxide in relatively low yields which areindependent of dose rate.147The possible use of polyphenyl compounds as coolants in nuclear reactorshas been investigated.l& Although fairly stable to y-radiation, these com-pounds are appreciably decomposed by reactor radiation at high temper-atures. Other compounds studied from this view-point include saturatedfluorocarbons 149 and bromine t15fluoride.l~~ Decomposition yields of theorganic substances may attain 2 or 3 molecules per 100 ev, owing mainly tocarbon-carbon bond breaks.Sometimes radiation forms radicals which are not readily produced byother methods; in this way unusual reactions are initiated and new com-pounds may be synthesised.Some interesting examples include solutionsof bromobenzene in which the carbon-bromine bond is broken,151 the syn-thesis of new bases from triethylamine,162 of acyl chlorides from alcohols andcarbon tetrachloride,lB of porphin-like substances from simple pre-cursors,1w the isomerisation of N-alkyl-N-vinylsulphonamides,ls and asynthesis of Lauth's Vi01et.l~~Dosimetry.-Calibrations of the ferrous sulphate chemical dosimeter havenow been made over a wide range of radiations and are summarised byMiller.58 The value of G(Fe3+) relating to polonium a-rays was recently re-ported as 5.2 & 0.1; 157 it has since been reported *l as 5.1 &- 0-1 and, inanother laboratory 62 as 5.5 & 0.1.High concentrations of oxygen stronglyinfluence this yield.61 A method of employing curie amounts of poloniumas an external radiation source has been described,158 the value of G(Fe3+) re-lating to this filtered radiation is somewhat lower. Determinations ofG(Fe3+) for X-rays of 14 and 35 kev have been reported as 14.4 0.7 arid14a R. L. Webb, Geneva Conf., 29, 331 (P824).14s I. Eliezer, H. J. G. Hayman, and G. Stein, Geneva Conf., 29, 113 (P1619).144 J . W. Sutherland and J. W. T. Spinks, Canad. J . Chem., 1959, 37, 79.R. F. Platford and J. W. T. Spinks, Canad. J . Chem., 1959, 37, 1022.146 H.Heusinger, R. J. Woods, and J. W. T. Spinks, Canad. J . Chem., 1959,37, 1127.147 J. Teply and J. Bednar, Geneva Conf., 29, 71 (P2114); J. Teply, CoZZ. Czech.Chem. Comm., 1959, S4, 1933.148 W. G. Burns, W. Wild, and T. F. Williams, Geneva Conf., 29, 266 (P51); D. R.de Halas, ibid., 29, 287 (P611); C. A. Trilling, D. W. Bareis, J. G. Burr, and R. H. J.Gercke, ibid., 29, 292 (P1779).Ids J. H. Simons and E. H. Taylor, J . Phys. Chem., 1959, 63, 636; P. Y. Feng,Geneva Conf., 29, 166 (P922).150 S. J. Yosim, J . Phys. Chem., 1958, 62, 1596.161 G. A. Swan and P. S. Timmons, J.. 1958, 4669.15% G. A. Swan, P. S. Timmons, and D. Wright, J., 1959, 9.15s E. I. Heiba and L. C. Anderson, J . Amer. Chem. SOC., 1959, 81, 1117.u4 A.Szutka, J. F. Hazel, and W. M. McNabb, Radiation Res., 1959, 10, 597.156 F. W. Stacey, J. C. Sauer, and B. C. McKusick, J . Amer. Chem. SOC., 1959, 81,156 P. Balestic and M. Magat, J . Phys. Chem., 1959, 63, 976.15' C. N. Trumbore, J . Amer. Chem. Soc., 1958, 80, 1772.1b8 E. J. Hart and J. Terandy, Rev. Sci. Instr., 1958, 29, 962.98722 GENERAL AND PHYSICAL. CHEMISTRY.72 GENERAL AND PHYSICAL CHEMISTRY.normal intensities are produced. With NN-dimethyl+nitroaniline inmethyl alcohol, for example, the NO, Raman line near 1300 cm.-1, asexcited by Hg 4358A, could be photoelectrically recorded49 with asolute : solvent molar ratio as low as The analytical advantages areobvious; and the effect may well mitigate the difficulties of working withcoloured samples, yellow or red excitation being used.Raman scattering inthe resonance region has recently been studied for p-nitroaniline and sodiumnitrite 50 and also for various aromatic nitro-compounds in different solventswhich cause displacements of the absorption bands.51Not all the Raman lines of a given species are equally affected; for theycan be influenced by different electronic absorption regions. Moreover theintensities of the absorption bands play an important part, as well as theirpositions. Fluorescence should be absent, otherwise it may mask theresonance Raman effect. The theory of the phenomenon has recentlybeen considered anew by Behringer,!j2 who concludes (as indeed has beenobserved by Shorygin and Kruschinski 53) that the intensity should riseless steeply than Shorygin's theory predicts, as vo approaches closely to vabs..Inorganic Species.-For vibrational assignments and structural deter-minations it is of advantage to use, not only Raman data (including polaris-ation), but also infrared absorption data (including band contours).(a) Neutral molecules.Woodward, Hall, Dixon, and Sheppard 54 haveobtained the Raman spectrum of liquid trimethylboron at -100" c andmade an assignment. From a comparison of calculated and observedentropies they conclude that the methyl groups rotate freely. Overend andEvans 55 have studied carbonyl dibromide and carbonyl bromide chlorideand compared their vibrational spectra with those of other carbonyl halides.Liquid dinitrogen tetroxide has recently been twice reinvestigated and somenew assignments suggested.%$ 57 The labelled molecule 15N,0, was alsostudied,57 and product rules discussed. Excitation with helium 58 andpotassium lamps7 has made it possible to obtain the complete Ramanspectrum of the highly coloured chromyl chloride, and a force field has been~alculated.~* The mercuric cyanide molecule has been studied in aqueoussolution by Woodward and Owen 59 and by Poulet and Mathieu.60 Funda-mental assignments basedupon infraredcombination frequencies are confirmed.The vibrational spectra of trisilylamine and tristrideuterosilylaminehave been obtained by Ebsworth et aL61 and by Robinson62 (see also49 J.Behringer, 2. Elektrochem., 1958, 62, 544.50 I. I. Kondilenko and P.A. Korotov, Ukruin. $2. Zhur., 1958, 5, 765.51 V. M. Pivovarov and N. D. Ordyntseva, Optics and Spectroscopy, 1959, 0, 403.52 J. Behringer, 2. Elektrochem., 1958, 62, 906.53 P. P. Shorygin and L. Kruschinski, 2. Physik, 1958, 150, 332.54 L. A. Woodward, J, R. Hall, R. N. Dixon, and N. Sheppard, Spectrochim. Acta,55 J. Overend and J. C. Evans, Trans. Faraduy Soc., 1959, 55, 1817.56 I. C. Hisatune and R. V. Fitzsimmons, Spectrochim. Acta, 1959, 206.57 G. M. Begun and W. H. Fletcher, Spechochim. Acta, 1959, p. 764.58 H. Stammreich, K. Kawai, and Y . Tavares, Spectrochim. Ada, 1959, 438.60 L. A. Woodward and H. F. Owen, J., 1959. 1055.80 H. PouIet and J.-P. Mathieu, Compt. rend., 1959, 248, 2079.61 E. A. V. Ebsworth, J. R. Hall, M. J. Mackillop, D.C. McKean, N. Sheppard, and6% D. W. Robinson, J . Amer. Cham. SOC., 1958, 80, 5924.195.9, p. 249.I,. A. Woodward, Sfiectrochim. Actu, 1958, 13, 202WOODWARD : RAMAN SPECTROSCOPY. 73Kriegsmann and Forster 63). From selection-rule considerations it is concludedthat, doubtless owing to d+ x-bonding, the NSi3 skeleton is planar. TheN-Si stretching force constant is about 4 x 105 dynes/cm.Similar considerations applied to the observed skeletal frequencies ofdisilyl sulphide and bistrideuterosilyl sulphide show that here ther-bonding is insufficient to straighten the Si-S-Si skeleton, and the bondangle is about 100". The same bent structure is found for disilyl selenideand the corresponding de~tero-cornpound.~~ It is therefore very interestingthat, Lord, Robinson, and Schumb 67 had interpreted the spectra of disilylether as indicating a Ziaear Si-0-Si skeleton, whereas force-field calculationssuggest a bond angle less than 180" both for this molecule,68 and also forbistrimethylsilyl ether.6g Very recently McKean, Taylor, and Woodward 70have elucidated the skeletal shape by a study of the Raman spectrum ofdisilyl [lBO]ether.For a linear skeleton the symmetrical skeletal stretchingfrequency would be unaffected by substitution of oxygen-18 for oxygen-16;but if the skeleton is bent, there must be an isotopic displacement. Infact a small displacement was observed. We are thus dealing for thefirst time with what may be called a quasi-linear case, i.e., one in whichthe bond angle, though definitely less than 180°, is so large (probably about150") that the vibrational selection rules for a linear skeleton appear to beobeyed.Many other silicon compounds have been studied by the Raman method,principally by Russians workers and by Kriegsmann and his collaborators.They include SiD,I; Me,SiX, (X = H, F, or Br); 71 X(SiMe,), (X =NHor CH,); 69 O(SiMe,X), (X = H, OH, c1, or C6H5); 72 phenyl- and halogeno-silanes and -siloxanes; 73 alkyl-, alkenyl-, and aryl-silanes; '4 Et,SiX (X =halogen, OH, OD, or NH,) ; 75 hexa-alkyldisiloxanes; 76 polyalkoxysiloxanes; 77silicon-oxygen chain molecules of type 0,Sin+l(OMe),,+4; 7* hexamethylderivatives of cyclotrisiloxane and cyclotrisilazane ; 79 (Me,SiO), with n = 4,63 H.Kriegsmann and W.Forster, 2. anorg. Chem., 1959,298,212: sample probably134 E. A. V. Ebsworth, R. Taylor, and L. A. Woodward, Trans. Faraday SOC., 1959,65 H. R. Linton and E. R. Nixon, J . Chem. Phys., 1958, 29, 921.66 H. R. Linton, Diss. Abs., 1958, 19, 687.137 R. C. Lord, D. W. Robinson, and W. C. Schumb, J . Amer. Chem. SOC., 1956, 78,D. C. McKean, Spectvochim. Ada, 1958, 13, 38.$9 H. Kriegsmann, 2. Elektrochem., 1957, 61, 1088.70 D. C. McKean, R. Taylor, and L. A. Woodward, Proc. Chem. SOC., 1959, 321.71 H. Kriegsmann, 2. Elektrochem., 1958, 62, 1033.78 H. Kriegsmann, 2. anorg. Chem., 1959, 299, 78.73 H. Kriegsmann and K. H. Schowtka, 2. phys. Chem. (Leipzig), 1958,209, 261.74 Y . P. Egerov, Khim. i Prakt. Primenenie Kremneorg. Soedinenii, Trudy Konf.Leningrad, 1958, No.3, 37.75 Y. I. Ryskin and M. G. Voronkov, Khim. i Pvakt. Primenenie Kremneorg. Soedi-nenii, Trudy Konf. Leningrad, 1958, No. 3, 42.76 V. V. Bazilevich, A. A. Grundyrev, N. S. Nametkin, G. M. Panchenkov, and A. V.Topchiev, Khim. i Prakt. Primenenie Kremneorg. Soedinenii, Trudy Konf. Leningrad,1958, No. 3, 103.77 A. N. Lazarev and M. G. Voronkov, Khim. i Prakt. Primenenie Kremneorg.Soedinenii, Trudy Konf. Leningrad, 1958, No. 3, 52.7@ H. Kriegsmann and W. Forster, 2. anorg. Chem., 1959, 298, 223.impure and therefore results uncertain (personal communication).55, 211.1327.A. N. Lazarev, Optika i Sfiektroskofiiya, 1958, 4, 80574 GENERAL AND PHYSICAL CHEMISTRY.5, and 6; 8o tetramethylcyclodisilthian and hexamethylcyclotrisilthian.~~The approximate force constants of Si-X bonds (X = halogen, 0, S, N, C,H) in a large number of compounds have been reviewed by Kreigsmann: B2when X is strongly electronegative considerable double-bond character isindicated.Various silicon isocyanate derivatives have been studied 83 andthe nature of the bonding discussed. The vibrational spectra of disilyl-acetylene 84 are in harmony with the expected linear skeletal structure andfreely rotating silyl groups.Helium excitation has given 85 the complete Raman spectrum of ironpentacarbonyl, which provides strong support for the trigonal bipyramidalmodel. The same technique has produced some results for di-(x-cyclo-pentadienyliron) tetracarbonyl in solution,86 but these are not consistentwith the structure having a centre of symmetry, as determined by X-raydiffraction of the solid.Some change appears to occur on solution, and theauthors remark on the " puzzling situation."Raman evidence for the aqueous silicate ion has been brieflystated to favour the modified tetrahedral structure Si02(OH),2-. Re-examination of the chromate ion with helium excitation@ has yieldedimproved values for the fundamental frequencies, and force constants havebeen calculated (e.g., Kcr-o = 5.48 x lo5 dynes/cm.). Results for thedichromate ion (helium excitation) 89 were incomplete.The vibrational spectra of co-ordination compounds, including complexions, have been reviewed by Mathieu with extensive literature references.The same author and Poulet 91 have given a general discussion of data onthe CN frequencies in complex cyanides.Values are listed for tetrahedral,plane square, and octahedral ions, and trends for isoelectronic sets and fordifferent oxidation states of the central metal atom are discussed. TheRaman spectrum of Hg(CN),2- in solution has been studied by Woodwardand Owen59 and by Poulet and Mathieu.GO The latter suggest thatHg2(CN)62- may also be present. Italian workers have been speciallyactive in the field of complex cyanides. The spectrum of Pd(CN),2- hasbeen obtained,92 and force constants have been calculated for this ion(kr,l-c approx. 2.9) 93 and for CI-(CN),~- (kcr-c = 1.93).94 Cyanide fre-(b) Ions.H. Kriegsmann, 2. anorg. Chem., 1959, 298, 232.81 H. Kriegsmann and H.Clauss, 2. anorg. Chem., 1969, 300, 210.82 H. Kriegsmann, 2. anorg. Chem., 1959, 299, 138.83 J . Goubeau, E. Heubach, D. Paulin, and I. Widmaier, 2. anorg. Chem., 1959, 300,84 R. C. Lord, D. W. Mayo, H. E. Opitz, and J. S. Peake, Spectrochim. Acia, 1958,83 H. Stammreich, 0. Sala, and Y . Tavares, J. C'hem. Phys., 1959, 30, 856.86 F. A. Cotton, H. Stammreich, and G. Wilkinson, J . Inorg. Nuclear Chem., 1959,13' D. H, Fortnum, Diss. Abs., 1959, 19, 2240.88 H. Stammreich, D. Bassi, and 0. Sala, Spectrochim. A d a , 1958, 12, 403.89 H. Stammreich, D. Bassi, 0. Sala, and H. Siebert, Spectrochim. Acta, 1958,13, 192.91 J.-P. Mathieu and H. Poulet, Compt. rend., 1959, 248, 2315.92 G. B. Bonino, P. Chiorboli, and G. Fabbri, Atti Accad.naz. L i ~ c e i , Rend. Ckasse93 0. Salvetti, Atti Accad. naz. Lincei, Rend. Classe S c i . 3 ~ . mat. nat., 1959, 26, 226.94 V. Caglioti, G. Sartori, and C. Furlani, Atti Arcad. naz. Linrei, Rend. Clasqe Sci.194.12, !47.9, 3.J.-P. Mathieu, J . Inorg. Nuclear Chem., 1958, 8, 33.Sci.fis. mat. nat., 1959, 26, 137.$s. mat. nut., 1958, 25, 260WOODWARD : RAMAN SPECTROSCOPY. 75quencies, which are by far the most intense in the Raman spectra, havebeen reporteds5 for Ru(CN),~- and alsog6 for OS(CN),~-. A study ofCU(CN),~- has been published.s7A prominent feature of the Rainanspectrum of vitreous silica (excited by Hg 2537 A) is an intense con-tinuum, of unexplained origin, extending from below S cm.-l to a fairlysharp cut-off at about 560 cm.-l.Crystals show Raman lines due to external lattice modes as well as theinternal vibrations of the groups present.Papers have recently appearedon crystalline sodium nitrite (5 out of 6 expected external frequenciesobserved 99) and the sulphates of nickel and manganese.lm An extensivestudy of the hydrated sulphates of magnesium and zinc has been publishedby Lafont.lol In this work the Raman spectrum of saturated aqueousmother-liquor was also examined and interpreted as indicating the presenceof numerous very small and randomly oriented " crystallites." The in-fluence of optical activity on the Raman spectra of crystals has been treatedt heore tically.lo2May, Stryland, and Welsh l4 havemeasured the shifts of vibrational frequencies as a function of gaseousdensity over the pressure range from 100 to 2300 atm.At the change toliquid state there is an abrupt frequency change, which therefore cannot beexplained as a simple density effect. The same authors have also reportedperturbations of frequencies in the rotational bands of hydrogen at highpressures; and Mikhailov,16 working at normal temperature and at 200" c,and with pressures up to 450 atm., has observed broadening and mergingof the rotational Raman lines of nitrogen.The symmetrical stretching frequency of mercuric chloridein solutions has been found by Allen and Warhurst to show a roughlylinear correlation with the logarithm of solvent dielectric constant, whencethey deduce that the Hg-Cl bond has about 2Sy0 of ionic character.Inter-action between nitrate ions and uranyl ions in aqueous solution causeschanges in the intensity of a Raman line characteristic of the latter.lo5 Theeffect of zinc chloride as solute upon the intensity and polarisation of aRaman line of methyl alcohol (as solvent) has been investigated 105,106 for arange of concentrations.The spectra of the mixtures AsC1, -+ POCI, and SbCl, + POCI, consist lo7(c) Vitreous solids and crystals.Molecular 1nteraction.s.-(a) Gases.(b) Liquids.95 G. B. Bonino and P. Chiorboli, Ann. Chim. (Italy), 1959, 49, 1.96 G. B. Bonino, P. Chiorboli, and G. Fabbri, Atti Accad. naz. Lincei, Rend. Classes7 P. Chiorboli, J . Inorg. Nuclear Chem., 1958, 8, 133.913 B. P. Stoicheff, P. Flubacher, A. J. Leadbetter, and J.A. Morrison, S+ectrochinz.9Q A. Tramer, Compt. rend., 1959, 248, 3546.loo D. Krishnamurti, Proc. Indian Acad. Sci., 1958, 48, A , 355.101 R. Lafont, Ann. Phys., 1959, 4, 905.10% V. Chandrasekharan, 2. Physik, 1959, 154, 43.103 A. D. May, J. C. Stryland, and H. L. Welsh, Spectrochim. Acta, 1959, p . 765.lo* G. Allen and E. Warhurst, Trans. Faraday SOC., 1958, 54, 1786.lo5 S. Minc and 2. Kecki, Rev. universelle des Mines, 1959, 15, 491.106 S. Minc and S. Osiecki, Roczniki Chem., 1958, 32, 1416.107 P.-0. Kinell, I. Lindqvist, and M. Zackrisson, A d a Chem. Scand., 1959, 13, 1159.S c i . 3 ~ . mat. nut., 1958, 25, 401.Ada, 1959, p . 76476 GENERAL AND PHYSICAL CHEMISTRY.of the superposed spectra of the pure components with small frequencychanges which vary continuously with composition and are ascribed todipolar interactions.In contrast, a system such as SbC15 + POCl, showsnew lines which are evidently due to covalently linked molecular complexes.Comparison of the Raman spectrum of an equimolar mixture SbCI, +POCl, + POMe, with the spectra of the binary mixtures SbCl, + POCl,and SbCl, + POMe, clearly demonstrateslo8 that POMe, is a strongerdonor than POCl,. The presence of 1 : 1 complexes in mixtures of borontrichloride and boron trifluoride with dimethyl ether has been detected.logFrom the changes in the N-H and C=O frequencies of formamide in thepure liquid and in solutions, the presence of both monomer and trimer isinferred.l1° Changes of association are suggested as the cause of the ob-served effect of melting upon the spectra of halogen derivatives of aceticacid.lll Differences in the spectra of quinoline 112 and pyridine 1-oxide 113in various solvents have been ascribed to hydrogen bonding.The intensityof a line of salicylaldehyde is found to remain unaffected in solutions towhich pyridine has been added in sufficient quantity to open the chelatering; and it is hence concluded that this frequency is not to be assigned toa vibration of this part of the molecule.Organic Compounds.-The size and lack of symmetry of many organicmolecules preclude complete assignments and reliable structure determin-ations from vibrational data, and often the most that can be done is torecord characteristic features that may be of use for identification.Thestructural analysis of hydrocarbons by means of their Raman spectra is thesubject of a review by Sushchinskii,l15 who points out that differences ofcharacteristic line parameters (including width and intensity as well asfrequency) can indicate the numbers and positions of groupings in a moleculeand in favourable cases permit a more or less complete empirical determin-ation of the structure.Continuing work on fluorinated ethylenes, Theimer and Nielsen 116 havegiven an assignment for the l-bromo-l-chloro-2,2-difluoro-derivative.Studies of the structure of some derivatives of ethylene and styrene havebeen reported.117 Costoulas has made an assignment for methyl iso-thiocyanate, and organic isothiocyanates have also been studied by Ham andWillis.119 Assignments have been proposed for bromopentafluoroethanelw andvinylidene chloride.121 The observed Raman spectrum of octa-1,3,5,7-tetraene108 P.-0.Kinell, I. Lindqvist, and M. Zackrisson, Acta Chem. Scund., 1959, 13, 190.109 J, R. Moyer, Diss. Abs., 1959, 19, 3149.110 P. G. Puranik and K. V. Ramiah, J . Mol. Spectroscopy, 1959, 3, 486.111 I. D. Poliakova and S. S . Raskin, Optics und Spectroscopy, 1959, 6, 220.112 P. Chiorboli and A. Bertoluzza, Ann. Chim. (Italy), 1959, 49, 245.113 K. Ramaiah and V. R. Srinivasan, Proc. Indian Acad. Sci., 1959, 50, A , 213.114 P. Chiorboli, Ann. Chim. (Ituly), 1959, 49, 27.115 M. M. Sushchinskii, Spectrochim. Actu, 1959, 14, 271.116 R. Theimer and J. R. Nielsen, J.Chem. Phys., 1959, SO, 98.117 Ya. S. Bobovich and V. V. Perekalin, Dokludy Akad. Nuuk S.S.S.R., 1959, 127,118 A. Costoulas, Spectrochim. Actu, 1959, p. 781.119 N. S. Ham and J. B. Willis, Spectrochim. Actu, 1959, 781.120 P. Klaboe and J. R. Nielsen, J. Chem. Phys,, 1959, 30, 1375.121 J. C. Evans, J . Chem. Phys., 1959, 80, 934.1239WOODWARD: RAMAN SPECTROSCOPY. 77in solution (Hg 5641 excitation) favours an all-trans structure.122 Astudy of the spectra of deuterated chloroacetic acids confirms previousassignments. Trifluoroacetic acid, its anion, and some of its derivativeshave been investigated by Robinson and Taylor,l% who point out thesimilarity between CF3*C0,- and the isoelectronic CF3*N02 molecule.The molecules of urea, thiourea, and acetamide all possess two basic sites:the vibrational spectra of their hydrochlorides 125 support the view that thecations normally formed are of the ammonium (rather than the oxoniumor sulphonium) type.The Raman spectrum of pentyloxyacetates havebeen investigated 126 in an unsuccessful attempt to discover a correlationbetween vibrational frequencies and odour.Diffuseness of the Raman lines of 1,3-dioxalan is takenlZ7 to indicatethat the ring is slightly puckered. Daly12* has obtained the Raman andinfrared spectra of cyclopropyl cyanide and has suggested a complete assign-ment. Methylenecyclopropane has been studied 129 and its unusuallyhigh C=C stretching frequency explained as due to mechanical coupling withring-stretching modes. The observed frequencies of 4,Pdimethylcyclopentenehave been interpreted 13* in terms of a planar-ring model.The Raman andinfrared spectraof chlorocyclohexane in the liquid and the vapour statetwo characteristic C-C1 stretching frequencies, whereas in the solid only onepersists. Hence it is concluded that there are two isomers in equilibriumin the liquid and vapour, but only one of them in the solid. The Ramanspectra of bicyclopentyl and dicyclopentylalkanes have been r e ~ 0 r t e d . l ~ ~The vibrational frequencies of hexafluorobenzene have been determinedfrom the Raman and infrared spectra by Steel and Whiffen 1% and also byDebouille.lX The assignments given in the two papers are not, however,completely in agreement. Vibrational spectra of [ 1,4,5,8-2H&naphthalenehave been obtained by Mitra and Bernstein1= and, together with theknown spectra of the normal and completely deuterated molecules, used asthe basis for a complete assignment.The frequencies of isoxazole have been observed 136 and plausibly assignedby analogy with furan and pyrrole.Selenophen and its methyl hornologueshave also been investigated.13'122 E. R. Lippincott, W. R. Feairheller, jun., and C. E. White, J . Amer. Chern. Soc.,1959, 81, 1316.153 C. Otero, J. R. Barcelb, and F. GomCz Herrera, Anales veal Soc. espafi. Fis.Qdm., 1959, 55, B, 205.134 R. E. Robinson and R. C . Taylor, Spectrochim. Actu, 1959, p. 764.126 E. Spinner, Spectrochim. Acta, 1959, p. 95.lZ7 S. A. Barker, E. J. Bourne, R. M. Pinkard, and D.€2. Whiffen, J., 1959, 802.128 L. H. Daly, Diss. Abs., 1959, 19, 3145.12n E. J. Blau and W. J. Taylor, Spectrochim. Ada, 1959, p. 763.lSo J. L. Lauer, W. H. Jones, and H. C . Beacheil, J. Ckem. Phys., 1959,30, 1489.lal K. Kojima and K. Sakashita, Bull. Chem. SOC. Japan, 1958, 31, 7%.132 S. V. Markova, P. A. Bazhulin, V. I. Stanko, and A. F. Plate, Izvest. Akad. Nauk133 D. Steele and D. H. Whiffen, Trans. Faraday Soc., 1959, 55, 369.ls4 L. Debouille, Bull. Classe Sci., Acad. roy. Belg., 1958, 44, 971.135 S. S. Mitra and H. J. Bernstein, Canad. J. Chem., 1959, 57, 553.136 S. Califano, F. Piacenti, and G. Speroni, Spectvochim. Ada, 1959, 86.13' N. A. Chumaevskii, V. M. Tatevskii, and Y . K. Yurev, Optics and Spectvoscopy,F. Nerdel, G. Heck, and G.Potzscher, J. pya&. Chem., 1959, 8, 171.S.S.S.R., Otdel khim. Nuuk, 1959, 1280.1959, 6, 2578 GENERAL AND PHYSICAL CHEMISTRY.Rotational isomerism. Rotational isomers have distinct Raman linesand the Raman method is of considerable value for the determination of thestructures of the different forms and the study of the effects of changes oftemperature, etc., upon the equilibria between them. During the periodwith which this Report is mainly concerned several examples of this kindof work have been published.From the number of fundamentals observed for dichloroacetyl chloride 1%it has been concluded that in the liquid and the vapour state two formsexist, of which only the more polar persists in the solid. In the less polarform the oxygen atom is probably cis with respect to the hydrogen, the morepolar form being obtained from this by rotation through 90" about the C-Caxis, For 2,3-dimethylbutane comparison of observed frequencies with theresults of calculations for different models gives evidence139 for tworotational isomers in the liquid.The temperature dependence of Ramanintensities for ethylene dichloride and dibromide have been usedl*O as anindication of the amounts of trans and gauche forms present. Solvationeffects are invoked to explain the observation that in alcohol solution thenumber of gauche molecules appears to diminish as the temperature islowered, whereas in the pure liquids the reverse occurs.L. A. W.8. NUCLEAR MAGNETIC RESONANCETHE volume of work published on the application of high-resolutionnuclear magnetic resonance spectroscopy to problems in chemistry hasincreased remarkably during the past few years.Improvements in appar-atus and techniques, such as the attainment of high homogeneity andstability for large magnetic fields, have uncovered much new informationabout nuclear spin energy levels which has in turn increased our knowledgeof electronic structure and assisted the study of many structural and kineticproblems in physical chemistry. In this report some of this material pub-lished during the past two years will be described.General and Theoretical Work.-The nuclear magnetic resonance spectrumof a molecule in the liquid or gaseous state is determined by the combinationof two separate effects.In the first place the magnetic field experiencedby any nucleus is screened by surrounding electrons to an extent whichdepends on its chemical environment. This leads to the " chemical shift "phenomenon which distinguishes chemically non-equivalent nuclei in thesame molecule. The second effect is an indirect coupling between nuclearspins through the polarisation of electron spins. This coupling leads to atendency for neighbouring nuclear spins to be parallel (or sometimes anti-parallel).is frequently the disentanglement of these two contributions, Le., theproblem of spectral analysis. When the chemical shifts and spin-couplingA. Miyake, I. Nakagawa, T. Miyazawa, I. Ichishima, T. Shimanouchi, and189 R. I, Podlovchenko, L. M.Sverdlov, and M. M. Sushchinskii, Optics and Spectro-140 M. Mazumdar, Indian J . Phys., 1959, 33, 92.In the interpretation of any particular spectrum, the first problem .S. Mizushima, Speclrochzna. Acta, 1958, 13, 161.scopy, 1959, 6, 96POPLE: NUCLEAR MAGNETIC RESONANCE. 79constants are separated, they can be interpreted in terms of electronic wavefunctions and very often used for applications to structural problems, suchas conformation and tautomerism.Spectral analysis is always simplified if chemical shifts are large com-pared with spin-coupling constants, when the spectra often consist of simplemultiplets depending on the number of neighbouring nuclei. If the twOeffects are of the same order of magnitude, however, the spectrum is nolonger simple and has to be calculated by detailed quantum-mechanicalmethods. The various types of spectra can be classified according to ascheme in which neighbouring letters in the alphabet are used for nucleiwhere the spin-coupling constant is comparable with the chemical shift .IThus ABX indicates a system of three non-equivalent nuclei, one of whichis well removed from the other two in the spectrum.Similarly, AB, is usedfor a system in which two of the nuclei are equivalent, but the AB chemicalshift is not large compared with the AB coupling constant. Simplest classesof spectra (AB, ABX, AB,, etc.) were dealt with some time ago, and recentpapers have studied some more complex systems, laying particular emphasison the determination of relative signs of the coupling constants.(It is notpossible to determine absolute signs experimentally.) The complete solu-tion for an AB, spectrum has been given and applied to methanethiol andmethan01.~ With the latter, it is possible to vary the chemical shift throughthe whole range by altering the concentration of alcohol in solution. Mc-Garvey and Slomp have given a full treatment of the ethyl group (A2B3)and applied it to a number of examples. ABX, spectra have been studiedby Mortimer5 and by Cohen and Sheppard6 with applications to somesubstituted propenes. The ABX, system has been examined by Fessendenand Waugh and applied to trans-propenylbenzene. The same authors haveexamined some three-spin spectra * (ABC) and shown how it is sometimesessential to carry out experiments at different magnetic field strengths tosolve the problem unambiguously.The general system AB,, for all valuesof q, has now been solved explicitly and applied to isobutane (AB,). Cohen,Sheppard, and Turner lo have shown how the proton spectra of compoundswith naturally occurring carbon-13 can be used to obtain additional couplingconst ants.There have been a number of contributions to the theory of the chemicalshift, largely directed towards breaking down the total shift into local contri-butions and contributions from more distant parts or substituents in themolecule. Chemical shifts are closely related to diamagnetic susceptibilities,as both arise from the electronic currents induced by a magnetic field.J. A.Pople, W. G. Schneider, and H. J. Bernstein, " High Resolution Nuclear2 R. J. Abraham, J. A. Pople, and H. J. Bernstein, Canad. J . Chem., 1958, 36, 1302.D. Kivelson and M. G. Kivelson, J . Mol. Spectroscopy, 1958, 2, 518.B. R. McGarvey and G. Slomp, J . Chem. Phys., 1959, 30, 1586.F. S. Mortimer, J . Mol. Spectroscopy, 1959, 3, 335.A. D. Cohen and N. Sheppard, Proc. Roy. SOL., 1959, A , 252, 488.R. W. Fessenden and J. S. Waugh, J . Chem. Phys., 1959, 30, 944.R. W. Fessenden and J. S. Waugh, J . Chem. Phys., 1959, 31, 996.J. S. Waugh and F. W. Dobbs, J . Chew. Phys., 1959, 31, 1235.Magnetic Resonance," McGraw-Hill, New York, 1959.1" :\. D. Cohen, N. Sheppard, and J. J. Turner, Proc. Chem. Soc., 1058, 11880 GENERAL AND PHYSICAL CHEMISTRY.Glick and Ehrenson l1 have expressed Pascal’s magnetic susceptibility rulesin a form separating atomic and hybridisation effects and then find in X-Hbonds that the proton screening correlates well with the hybridisationsusceptibility parameter.Theoretical work suggests that the principalfeatures determining proton-screening constants are the local electrondensity (determined by electronegativity considerations) and the diamagneticanisotropy of neighbouring groups. Narasimhan and Rogers 12 haveexamined this in detail for propane, where there is a chemical shift betweenthe methyl and methylene groups. They find that this shift is too large tobe explained entirely by the anisotropy of C-C and C-H bonds, but are ableto get a consistent picture by allowing for the difference in local electrondensity which fits in with electronegativity differences determined by othermethods.The same authors have also considered the effect of the aniso-tropy of carbonyl groups on the proton shielding in amides,l3 There hasbeen some further work on the effect of aromatic ring currents, which leadto a reduction in screening.l* The quantum-mechanical theory of dia-magnetic susceptibility of such molecules has been extended to the calcul-ation of currents in separate rings and the consequent changes in screeningin various parts of the m01ecule.~~J~At a higher level of precision there have been some calculations of screen-ing in simple atomic systems. Ormand and Matsen l7 have found screeningconstants for 2-, 3-, and 4-electron atoms and ions.Marshall and Pople 18have calculated the reduction in the screening of a hydrogen atom when it isplaced in an electric field, a simplified model for the changes observed inh ydrogen-bonded systems.Considerable progress has been made recently in the theoretical inter-pretation of the magnitudes and signs of spin-coupling constants. It hasbeen known for some time that these constants obey certain empiricalrules 1 such as being greater for the trans-position in substituted ethylenesthan for the cis-position. Similarly in substituted ethanes, the trans-valueis substantially greater than the gauche. The consistency of rules such asthese has been well established by studies such as those of Cohen and Shep-pard 6 and of Sheppard and T~rner.1~ On the theoretical interpretation,much of the most important work is due to Karplus.Karplus and Ander-son 20 developed a general valency-bond theory for proton-proton constants,using Rumer-Pauling diagrams. The theory indicates that, for non-bondedprotons, the coupling constant is a sensitive measure of deviations fromperfect pairing. For methane they obtain good agreement with experimentwithout including non-perfect pairing structures. Karplus 21 made a further11 R. E. Glick and S. J . Ehrenson, J. Chem. Phys., 1958, 29, 459.12 P. T. Narasimhan and M. T. Rogers, J. Chem. Phys., 1959, 31, 1302.13 P. T. Narasimhan and M. T. Rogers, J. Phys. Chem., 1959, 63, 1388.14 C . E. Johnson and F. A. Bovey, J . Chem.Phys., 1958, 29, 1012.15 J . A. Pople, Mol. Phys., 1958, 1, 175.16 R. McWeeny, Mol. Phys., 1958, 1, 311.17 F. T. Ormand and F. A. Matsen, J. Chem. Phys., 1959, 30, 368.18 T. W. Marshall and J . A. Pople, Mo2. Phys., 1958, 1, 199.1s N. Sheppard and J. J. Turner, Proc. Roy. Soc., 1959, A , 252, 506.20 M. Karplus and D. H. Anderson, J. Chem. Phys., 1959, 30, 6.21 M. Karplus, J. Chem. Phys., 1959, 30, 11POPLE : NUCLEAR MAGNETIC RESONANCE. 81study of the " contact " contribution (k, depending on the value of thewave function at the nucleus) to the coupling constant for protons andfluorine nuclei in alkanes and alkenes. His calculations gave an excellentinterpretation of the relative cis-trans-values in ethylene and gauche-trans-values in ethane.Contributions to proton-proton constants other thanthe contact type are small. The coupling constants for protons in gem-positions are much smaller, and can be of either sign. A full theory of thishas recently been published by Gutowsky, Karplus, and Grant.22 Theyfind that the calculated coupling constant decreases from 32 clsec. to zero asthe valency angle increases from 100" to 125", after which it becomes nega-tive. There is considerable experimental evidence supporting this rule andit may be that measurement of the coupling constants is a useful way ofestimating the angle.There has been some theoretical work on coupling constants in aromaticsystems. McConnell 23 has investigated the contribution of electron polaris-ation via the x electrons, which can have considerable range.These contri-butions are rather small however, although they may dominate for sufficientlylarge separations. Williams and Gutowsky made a study of hydrogenand fluorine coupling constants in fluorobenzene and found that the largestcontribution is generally that carried by s electrons through the contactinteraction. However, for fluorine atoms, there are significant one-electroncontributions. Muller and Pritchard 25 have measured coupling constantsbetween protons and carbon-13 nuclei and correlated them with the amountof s character of the carbon atomic orbitals in the bonds. There is littleevidence for dependence on ionic character.The shape of nuclear resonance signals in systems where some form ofexchange is taking place can be used to measure the rates of such processes,given an adequate theory.For example, slow exchange between twopositions with different screening constants gives two signals, whereas forrapid exchange only one averaged signal is found. Earlier theories of theintermediate line shape have been simplified by McConnell26 who hasintroduced a modified form of the Bloch phenomenological equations. Thetheory of the collapse of multiplet signals by exchange processes is consider-ably more complicated, but the lines along which it should develop havebeen indicated by Ka~lan.~'Applications of Proton Resonance.-Several authors have worked onschemes for cataloguing proton resonance data, appropriate reference com-pounds being used.Tiers 28 has suggested tetramethylsilane as an internalreference and has published a considerable amount of data. Becker29has examined the effect of molecular interactions on some of the compoundsfrequently used as internal references (cyclohexane and tetramethylsilane).22 H. S. Gutowsky, M. Karplus, and D. M. Grant, J . Chem. Phys., 1959, 31, 1278.23 H. M. McConnell, J . Chem. Phys., 1959, 30, 126.24 G. A. Williams and H. S. Gutowsky, J . Chem. Phys., 1959, 30, 717.25 N. Muller and D. E. Pritchard, J . Chem. Phys., 1959, 31, 768.26 H. M. McConnell, J . Chem. Phys., 1958, 28, 430.27 J. I. Kaplan, J . Chem. Phys., 1958, 28, 278.28 G. V. D. Tiers, J . Phys. Chem., 1958, 62, 1151.28 E. D. Becker, J . Phys. Chern., 1959, 63, 137982 GENERAL AND PHYSICAL CHEMISTRY.Most cases showed shifts of 1-4 clsec.(at 40 Mc/sec.) depending on concen-trations, but benzene as a solvent led to rather larger shifts because of thespecial effects of aromatic ring currents.There has been further work on the proton resonance spectra of a numberof hydrocarbons and derivatives. Narasimhan, Laine, and Rogers 30have measured and analysed the spectrum of liquid propane (ansystem). Analyses have also been carried out for azulene anda~epleiadylene.~~ These non-alternant aromatic compounds show featureswhich cannot be explained by the ring-current model used for alternantcompounds and it seems that the non-uniform distribution of charge in themolecule has to be taken into account. Two papers have been published onaromatic carbonium ions.Maclean, van der Waals, and Mackor32 havedetected the additional proton in the carbonium ions of highly basic com-pounds such as 9,10-dimethyl-l,2-benzanthracene, although the spectra areblurred by exchange phenomena. Spectra of some triarylcarbonium ionshave been examined 33 and show shifts to low field values compared with thecorresponding neutral compounds.The proton magnetic resonances of allene and propyne and some deriv-atives have been measured and analy~ed.=-~~ The long range couplingbetween protons at opposite ends of allene-type molecules is 6-7 c/sec.,exceptionally large for such a separation. Nordlander and Roberts 37 havefound the spectrum of allylmagnesium bromide to be of the AX, type,suggesting a rapid exchange between two configurations :BrMg-CH,-CH=CH, CH,=CH-CH,MgBrOther hydrocarbons and derivatives which have been studied includebicycloheptadiene and a number of cis- and trans-decalins.39 Thesecondensed ring systems show much sharper spectra in the cis-form, presum-ably owing to greater flexibility.Brownstein40 has studied shifts due tosteric effects in substituted cyclohexanes and found a shift to low field forring protons near bulky substituents.There have been several papers on substituted aromatic hydrocarbonsand related compounds. Richards and his co-workers 4l942 have studied anumber of para-disubstituted and trisubstituted benzenes. Chemical shiftsare found to vary widely but the ortho-, rneta-, and $am-coupling constants30 P.T. Narasimhan, N. Laine, and M. T. Rogers, J. Chem. Phys., 1958, 28, 1257.31 W. G. Schneider, H. J. Bernstein, and J . A. Pople, J. Amer. Chem. SOC., 1958, 80,32 C. Maclean, J . H. van der Waals, and E. L. Mackor, MoZ. Phys., 1958, 1, 247.33 R. B. Moodie, T. M. Connor, and R. Stewart, Canad. J . Chem., 1959, 37, 1408.34 E. B. Whipple, J . H. Goldstein, and W. E. Stewart, J . Amer. Chem. SOC., 1959,35 E. B. Whipple, J. H. Goldstein, and L. Mandell, J. Chem. Phys.,l 959, 30, 1109.36 E. B. Whipple, J. H. Goldstein, L. Mandell, G. S. Reddy, and G. R. McClure,37 J . E. Xordlander and J. D. Roberts, J. Amer. Chem. SOC., 1969, 81, 1769.38 F. S. Mortimer, J . Mol. Spectroscopy, 1959, 3, 528.39 J . Musher and R. E. Richards, Proc. Chem.SOC., 1958, 230.40 S. Brownstein, J. Amer. Chem. SOC., 1959, 81, 1606.41 R. E. Richards and T. Schaefer, Trans. Faraday SOC., 1958, 54, 1280; Proc. Roy.42 J . B. Lcaiic and R. E. Richards, l m r t s . Faraday SOC., 196'3, 55, 707.3497.81, 4761.J . Amer. Chem. Soc., 1959, 81, 1321.Soc., 1958, -4, 246, 429; Mol. Phys., 1958, 1, 331POPLE : NUCLEAR MAGNETIC RESONANCE. 83are relatively constant from one molecule to another. Several authors 43-45have worked on the rather complex proton and fluorine spectra of fluoro-benzene, deriving most of the spin-coupling constants.Several papers have been published on high-resolution proton spectra ofaromatic five-membered rings. In furans, thiophens, and pyrroles, theproton spin-coupling constants are usually all of the same order of magnitude.This was found by Richards and Leane 46 for substituted furans and thiophensand by Abraham and Bernstein47 for furan and pyrrole.In pyrrole,quadrupole effects of l4N broaden the proton NH signal but do not interferewith spin-coupling with other protons. The couplings between the NHproton and the protons on the a- and P-carbons of the ring are nearly equalin magnitude. Several studies have been made of thiophen derivative^.^*-^In 3-methylthiophen Corio and Weinberg 51 found that there is a detectablecoupling between protons separated by as many as five bonds.An interesting suggestion about the proton resonance of porphyrins hasrecently been made by Becker and Bradley.52 In coproporphyrin-I, methylester, the signal assigned to the two N-H protons is at higher field than anyknown protons in organic compounds. This is attributed to a ring currentshift to high field (opposite to the usual shift since the protons are inside theconjugated ring).The structure of some organosilicon compounds has been studied bynuclear magnetic resonance methods by Ebsworth and Sheppard 53 and bySeyferth, Castellano, and Waugh.54 Huggins and Carpenter 55 have com-pared the nuclear resonance of chloroform and trichlorosilane in variousbasic solvents.These measurements indicated that trichlorosilane is aweaker base and a slightly weaker acid than chloroform.Several authors have applied nuclear resonance to structural problems inalkaloid ~ h e m i s t r y . ~ ~ ~ ~ ~ Goodwin, Shoolery, and Johnson 57 have found thatthe hydrogen nuclei of the methylenedioxy-group in aporphine alkaloids arenon-equivalent.This implies that the other aromatic ring is not co-planarwith the ring containing the methylenedioxy-group and opens up the possi-bility of new stereochemical features. In the field of steroids, Shoolery andRogers have examined the spectra of a wide range of molecules and have43 B. Bak, J , N. Shoolery, and G. A. Williams, J . Mol. Spectroscopy, 1958, 2, 525.44 S. Fujiwara, M. Katayama, and H. Shimizu, Bull. Chem. SOC. Japan, 1959, 32,4.i M. Kimura, S. Matsuoka, S. Hattori, and I<. Senda, J . Phys. SOC. Japan, 1959,46 R. E. Richards and J. B. Leane, Trans. Faraday Soc., 1959, 55, 618.47 R. J. Abraham and H.J. Bernstein, Canad. J . Chem., 1959, 37, 1056.48 S. Gronowitz and R. A. Hoffman, Arkiv Kemi, 1958, 13, 279.49 S. Fujiwara, M. Katayama, S. Hayashi, H. Shimizu, and S. Nishimura, Bull.50 K. Takahashi, Y. Matsuki, T. Mashiko, and G. Hazato, Bull. Chew SOC. Japan,s1 P. L. Corio and I. Weinberg, J . Chem. Phys., 1959, 31, 569.52 E. D. Becker and R. B. Bradley, J . Chem. Phys., 1959, 31, 1413.53 E. A. V. Ebsworth and N. Sheppard, J . Inorg. Nuclear Chem., 1959, 9, 95.54 D. Seyferth, S. Castellano, and J. S. Waugh, Gazzetta, 1958, 88, 1267.55 C. &I. Huggins and D. R. Carpenter, J . Phys. Chem., 1959, 63, 238.56 H. Conroy and J. K. Chakrabarti, Tetrahedron Letters, 1959, No. 4, 6.57 S. Goodwin, J. N. Shoolery, and L. F. Johnson, Proc.Chem. SOC., 1958, 306;102.14, 684.Chem. SOC. Japan, 1959, 32, 201.1959. 32, 156.J . ,-3?rzeu. Client. SOC., 1959, 81, 300884 GENERAL AND PHYSICAL CHEMISTRY.shown that the technique is valuable in structure determinationem Slompand McGarvey 59 have examined 6-methyl-steroids and shown how 6a- and6p-methyl groups can be differentiated.The proton resonance spectra of a number of amino-acids have beenmeasured.60j61 Bovey and Tiers have examined many acids and otherglycyl peptides in trifluoroacetic acid. They are able to draw a numberof conclusions about charge distribution, inductive effects, rates of protonexchange, and base strengths.Bovey, Tiers, and Filipovitch 62 have recently published an interestingpaper on high resolution spectroscopy of polymer solutions.In appropriatecases, the motion of the chain is rapid enough for spectra to be obtained withmoderate resolution. Comparison of the polystyrene spectrum with that ofcumene shows significant differences attributed to clustering effects of phenylgroups in the polymer.Proton magnetic resonance is frequently a valuable aid in solving cis-trans-isomerism problemsYB3 particularly if use can be made of the empiricalrule that trans-coupling constants are the greater. The technique hasrecently been used by Elvidge to confirm the cis-trans-form of p-methyl-muconic acid. Jackman and Wiley have studied p-methylglutaconic acid.In the field of rotational isomerism in substituted ethanes, nuclear resonancespectra can be used to determine relative populations of the various formsand sometimes their rate of interconversion.The types of spectra forvarious kinds of molecule with slow and rapid rotation about the singlebond have been classified 66 and a number of new examples studied experi-mentally?'Other applications have been made to conformational problems associatedwith six-membered saturated ring compounds. Here again it is oftenpossible to make use of the empirical rule that trans-coupling constants be-tween bonds attached to neighbouring carbon atoms are greatest. Lemieux,Kullnig, Bernstein, and Schneider 68 have given a number of examples andEliel G9 has recently made a study of conformational equilibria in substitutedcyclohexyl bromides.Applications involving Nuclei other than Protons.-Boron hydrides givedetailed magnetic resonance spectra, from both boron nuclei and protons.However, owing to the rather complicated structures of these compoundsthe interpretation is often difficult and a number of reassignments haverecently been published.Williams and Shapiro '0 have re-interpreted the58 J. N. Shoolery and M. T. Rogers, J . Amer. Chem. SOL, 1958, 80, 5121.59 G. Slomp and B. R. McGarvey, J . Amer. Chem. Soc., 1959, 81, 2200.60 0. Jardetzky and C. D. Jardetzky, J . Bid. Chem., 1958, 233, 383.61 F. A. Bovey and G. V. D. Tiers, J. Amer. Chem. SOC., 1959, 81, 2870.62 F. A. Bovey. G. V. D. Tiers, and G. Filipovich, J . Polymer Sci., 1959, 38, 73.6s D. Y. Curtin, H. Gruen, and B. A. Shoulders, Chem. and Ind., 1958, 1205.64 J.A. Elvidge, J . , 1959, 474.65 L. M. Jackman and R. H. Wiley, Proc. Chem. Soc., 1958, 196.66 J. A. Pople, MoE. Phys., 1958, 1, 3.67 J. Lee and L. H. Sutcliffe, Trans. Faruday SOL, 1959, 55, 880.68 R. U. Lemieux, R. K. Kullnig, H. J. Bernstein, and W. G. Schneider, J . Amer.6B E. L. Eliel, Chem. and Ind., 1959, 568.70 R. E. Williams and I. Shapiro, J . Chem. Phys., 1958, 29, 677.Chem. SOL, 1958, 80, 6098POPLE NUCLEAR MAGNETIC RESONANCE. 85spectrum of decaborane due to Schaeffer, Shoolery, and Jones.71 Williams,Gibbins, and Shapiro 72 have also re-interpreted the B,H,, spectrum assome of the lines in the previously published spectrum have now been shownto be due to B,H, as an impurity. The same authors have examined hexa-borane 73 (B,H,,) and find that the spectra of both nuclei can be interpretedin terms of two types of BH group in the ratio 5 : 1, consistent with theproposed pentagonal pyramid structure.Boron chemical shifts for a rangeof typical boron-containing compounds have been given by Phillips, Miller,and Muetterties74 and other authors.75 Values of the B-H coupling con-stant are also given.Nitrogen chemical shifts have been studied in three papers by Schmidt,Brown, and Williams.7, The first paper deals with ammonia and relatedcompounds including various ammonium salts and ammonia in inorganiccomplexes. In the second paper they examine nitrates, nitrites, and nitro-compounds. Considerable variations in chemical shifts and line widths arefound.For example, organic compounds containing nitro-groups showpositive chemical shifts and large line widths relative to normal nitrates.The third paper deals with nitrogen in compounds containing amino- andcyano-groups, including acetonitrile, urea, and glycine.Fluorine nuclear resonance spectra are frequently studied, as thefluorine-19 nucleus has spin and there are no complications due to quadru-pole broadening. Filipovich and Tiers 77 have given shielding values for arange of fluorine compounds, using trichlorofluoromethane as solvent andinternal reference. Other measurements on a range of chlorofluorocarbonshave been published by Smith and Smith.78 An interesting problem thathas recently been studied is the structure of sulphur tetrafluoride (SF4).79The fluorine spectrum corresponds to two pairs of non-equivalent nuclei,suggesting that the structure as CzV symmetry (non-planar).The sameapplies to SeF,.8* In sulphur tetrafluoride, intermolecular fluorine exchangealso occurs and its rate, as a function of temperature, has been studied byMuetterties and Phillips.80 They suggest fluorine-bridged structures asexchange intermediates ,The mercury-199 and proton nuclear resonance spectra of some dialkyl-mercury compounds have been obtained.8l The results indicate an increaseof mercury shielding along the series Me < Prn < Et < Pri. The chemicalshifts of lead in a few compounds have been given by Piette and Weaver.8271 R. Schaeffer, J. N. Shoolery, and R. Jones, J . Amer.Chem. SOC., 1957, 79, 4606.72 R. E. Williams, S. G. Gibbins, and I. Shapiro, J . Chem. Phys., 1959, 30, 320.75 R. E. Williams, S. G. Gibbins, and I. Shapiro, J . Chem. Phys., 1959, 30, 333.74 W. D. Phillips, H. C. Miller, and E. L. Muetterties, J . Amer. Chem. SOL, 1959,81,75 T. P. Onak, H. Landesman, R. E. Williams, and I. Shapiro, J . Phys, Chem,, 1959,76 B. H. Schmidt, L. C. Brown, and D. Williams, J . Mol. Spectroscopy, 1958, 2, 539;77 G. Filipovich and G. V. D. Tiers, J . Phys. Chem., 1959, 63, 761.78 T. S. Smith and E. A. Smith, J . Phys. Chem., 1959, 83, 1701.79 F. A. Cotton, J. W. George, and J. S. Waugh, J . Chem. Phys., 1958, 28, 994.80 E. L. Muetterties and W. D. Phillips, J . Amer. Chem. SOC., 1959, 81, 1084.81 R. E. Dessy, T. J.Flautt, H. H. Jaffd, and G. R. Reynolds, J . Chem. Phys., 1959,Be L. H. Piette and H. E. Weaver, J . Ckm. Phys-, 1958, 28, 735.4496.63, 1533.1958, 2, 551; 1959, 3, 30.30, 142286 GENERAL AND PHYSICAL CHEMISTRY.Orgel 83 has given a theory of shifts of ions with the d10s2 configuration, show-ing how they depend on interconfigurational mixing brought about byenvironments of less than cubic symmetry. Order of magnitude calculationsare made for Pb2+ and agree reasonably with experiment.Intermolecular and Solvent Effects.-Nuclear resonance spectra, particu-larly proton spectra, are very sensitive to intermolecular action, and anincreasing number of studies of solution changes are being made. Basiccomparisons should of course be made with isolated molecules in the gasphase (as has been done for simple hydrides 84) but the more common prac-tice is to compare spectra with those of the same species in dilute solution insome inert solvent such as cyclohexane.Hydrogen bonding leads to shifts to low field which become very largein strong symmetrical hydrogen bonds as in potassium hydrogen maleate andpotassium hydrogen phthalate (measured in dimethyl sulphoxide by For-sen 85), The hydrogen-bond shift has been used to investigate associationin dilute solutions of alcohols.By a careful study of the variation of thehydroxyl chemical shift with alcohol concentration in carbon tetrachloride,Saunders and Hynes6 deduced that a t low concentrations there existedmainly a monomer-trimer equilibrium.This view is contested by Becker,87however, who considers that the data are also consistent with the presenceof dimers. Drinkard and Kivelsons8 have studied water and methylalcohol in acetone and dimethyl sulphoxide to find relative hydrogen-bondstrengths.The hydroxyl resonances of spectra of carboxylic acids behave ratherdifferently with dilution. Reeves and Schneider 89 found that acetic acidshowed shifts to low field with dilution but that the curve finally turned upat low concentrations and moved sharply to high field. This they inter-preted in terms of polymer-dimer equilibria in concentrated solution chang-ing to dimer-monomer equilibria with dilution. The influence of thedielectric constant of the solvent on the monomer-dimer equilibrium isclearly shown by the data.In a later paper, Reevesg0 has extended thiswork to other carboxylic acids.Electrolytes.-In aqueous solutions of strong acids, the acid proton signalis coalesced with the water signal because of rapid exchange. However,there is an associated shift in this mean position with acid concentration andthis can be used to study dissociation. Hood et ~ 2 1 . ~ ~ 9 ~ ~ have continued aseries of papers on this topic and have examined heptafluorobutyric acid andiodic acid. Happe and Whittakerg3 have measured proton shifts in thenitric acid-water and nitric acid-potassium nitrate systems. They find83 L. E. Orgel, MoZ. Phys., 1958, 1, 322.84 W. G. Schneider, H. J . Bernstein, and J. A. Pople, J . Chem. Phys., 1958, 28, 601,85 S.Forsen, J. Chem. Phys., 1959, 31, 852.86 M. Saunders and J . B. Hyne, J. Chem. Phys., 1958, 29, 253.E. D. Becker, J. Chem. Phys., 1959, 31, 269.W. Drinkard and D. Kivelson, J. Phys. Chem., 1958, 62, 1494.L. W. Reeves and W. G. Schneider, Trans. Faraday SOL, 1958, 54, 314.L. W. Reeves, Trans. Faraday SOC., 1959, 55, 1684.91 G. C. Hood and C. A. Reilly, -1, Chem. Phys., 1958, 28, 329.92 G. C. Hood, A. C. Jones, and C. A. Reilly, J. Phys. Chem., 1959, 63, 101.93 J . A. Happe and A. G. Whittaker, J. Chem. Phys., 1959, 30, 417WILLIAMS: ABSORPTION SPECTRA4 AND STABILITY OF COMPLEX IONS. 87that nitrate ion is effective in unshielding the protons of nitric acid. Infact the chemical shift can be used for accurate analysis of nitric acid-watermixtures in the region of concentrated acid.Cations other than protons also produce a shift in the water resonanceline which can be measured as a shift per mole.Axtmanng4 measured aseries of such molar shifts and found that they varied linearly with corre-sponding pKa. The Pb2+ and UOZ2+ ions were exceptions, and this wasattributed to some covalent binding with water. Connick and Poulson 95studied the fluorine resonance spectrum of a number of metal fluoride com-plexes in aqueous solution. Unlike simple fluorine compounds, no simplecorrelation was found with the electronegativity of the metal ion or thestability of the complex. Itoh and Yamagata 96 have examined the iodineresonance of iodide ions in solutions of alkali iodide.Paramagnetic ions have considerable effect on the nuclear resonance ofwater, broadening the signals by rapid spin-lattice relaxation and causing ashift through the " contact " effect, the unpaired electron density extendingoutwards from the ion on to the water molecules.Morgan and Nolle97have measured proton-spin relaxation times in solutions of chromic, man-ganous, nickel, cupric, and gadolinium ions. They found that in largemagnetic fields, relaxation times were shorter than expected on the basis oflow-field values, suggesting that some of the processes are field dependent.The manganous ion, in particular, leads to a large difference between thelongitudinal and transverse relaxation times TI and T2, a fact attributed tothe contact interaction with unpaired electrons.King and Davidson 98provided evidence in support of this by showing that the difference dis-appears if the Mn2+ ion forms a complex in a way which shields it fromwater.Connick and Poulson 99 have studied the relaxation of oxygen-17 nucleiof water by various paramagnetic ions. The chromic ion is the least effective,presumably because the first co-ordination sphere does not exchange rapidlywith other water molecules. If relaxation can only occur in the first co-ordination shell, it is possible to place lower limits on the exchange rate ofother ions. Shulman and WyludalW also found an oxygen-17 shift in thediamagnetic direction for Gd3+ ions. The interpretation of this effect hasbeen discussed by Orgel.lolJ. A. P.9. THE ABSORPTION SPECTRA AND STABILITY OF COMPLEX IONSTHE last ten years have brought considerable advances in our informationabout and understanding of the thermodynamic and spectroscopic properties94 R.C. Axtmann, J . Chem. Phys., 1959, 30, 340.9-5 R. E. Connick and R. E. Poulson, J . Phys. Chem., 1959, 83, 568.96 J. Itoh and Y . Yamagata, J . Phys. SOC. Japan, 1958, 13, 1182.97 L. 0. Morgan and A. W. Nolle, J . Chem. Phys., 1959, 81, 365.98 J. King and N. Davidson, J . Chem. Phys., 1958, 29, 787.99 R. E. Connick and R. E. Poulson, J . Cheiiz. Phys., 1959, 30, 759.*OO R. G. Shulman and B. J. Wyluda, J . Chem. Ph~ps., 1959, 30, 335.lo' L. E. Orgel, J . Chew. Phys., 1959, 30, 161788 GENERAL AND PHYSICAL CHEMISTRY.of complex ions.1-6 This report will indicate the general nature of theseadvances concentrating upon the work of the last two years.Occasionalreference will be made to lattice energies and solubilities where these help inthe understanding of complex-ion stabilities.The formation of a complex ion is an interchange reaction of the generalkind AB + CD + AC + BD but where A and C are ions and B and Dare water molecules. In interchange reactions the free-energy change isusually so small that although it is often possible to calculate rather accur-ately the free energies of formation of the individual species, e.g., the latticeenergy of AC from the properties of the gas ions A and C, the interchangefree-energy difference remains difficult to understand. For this reason thestudy of complex ions has developed by obtaining a number of empiricalcorrelations, about spectra and stabilities, and then relating these to par-ticular theories, already well known to the physicist, The very rapidaccumulation of information in the last ten years has necessitated rapidchanges of outlook, even in the writings of individual authors, on the differenttheoretical models.This report will stress the nature of the observationsrather than the measure of agreement with different theories.Section (a) introduces the primaryquantities used in making correlations between the properties of complexesand the properties of the components of the complexes. Section (b) reportsbriefly on theoretical advances. Section (c) details new knowledge aboutcomplexes of inorganic ligands. Section (d) does the same for arganicligands.The report is divided into sections.(a) The primary reference quantitiesCation Properties-Ionisation potentials and electronegativity.The com-pilation 7 of spectroscopic data for atoms and ions has been extended virtuallyto the end of the Periodic Table. This enables earlier work * on the com-parison of the properties of atoms and ions to be improved and extended.As ionisation potentials are frequently used in the assessment of electro-negativity the special character of the ionisation of transition-metal cationsshould be n~ted.~*l* These ionisations often occur with a change in con-figuration. Orgel has therefore suggested that the ionisation energies(dn-2s2) -+ (dfi-2> should be used to assess electronegativities of the1 Symposium on Co-ordination Chemistry, Danish Chemical Society, Copenhagen,* Symposium on Co-ordination Chemistry, Rec.Truer. chim., 1955, 75, 1.3 I ‘ Chemistry of the Co-ordination Compounds,” Pergamon Press, London, 1958.4 International Conference on Co-ordination Chemistry, Chem. SOC. Spec. Publ. No-13, 1959.I ‘ Quelques Problkmes de Chimie Mindrale,” The Tenth Solvay Conference onChemistry, ed. R. Stoops, Brussels, 1956.Discuss. Furuduy Soc., 1958, 26; see also P. George and D. S. McClure, Progr.Inorg. Chem., 1959, 1, 381; G. Schwarzenbach, Angew. Chemie, 1958, 70, 4.51; F. J. C.Rossotti, “ Modern Co-ordination Chemistry,” Interscience, New York, 1959, p. 1.C . E. Moore, “ Atomic Energy Levels,” Nat.Bur. Stand. Circ,, No. 467, Vol.L. H. Ahrens, J . Inorg. Nucl. Chem., 1956,2, 290.L. E. Orgel, ref. 5, p. 289.1954.1-111, 1959.lo R. J. P. Williams, J., 1956, 8WILLIAMS : ABSORPTION SPECTRA AND STABILITY OF COMPLEX IONS. 89transition-metal bivalent ions, Irving and Williams l1,l2 prefer the observedionisation potentials which involve d-state energies. The difference iscritical at copper(I1) and chromium(rI), for high-valency cations, and in thesecond and third transition series. The validity of either scale depends uponthe degree to which the d states are involved in bonding. In either case theassessment is crude for there will be a considerable drop in electronegativitybetween chromium(I1) and manganese(11) and between copper(I1) andzinc(I1) as here the filling of the core reduces the number of available emptystates in a specific manner. Orgel’s definition has obvious theoreticaladvantages in that it separates effects due to d and to s-p states althoughthis in itself may be misleading. The electronegativity of an ion withseveral spin states changes with spin state, being higher the lower the spin.Ionisation potentials have also been used in an effort to assess the donorpower of cations.11 Other electronegativity scales than those based onionisation potentials are used but are much less readily understandable.They are not discussed further here as they cannot be related to primaryquantities.12Internal electron repulsion.The effect of a core of electrons of highangular quantum number is twofold.First, because of inefficient screeningthe field produced by the atom or ion is larger than expected. Secondly,the core repels negative charge. The sum of these two spherically sym-metrical effects is that the atom or ion has a higher electron affinity thanwould be expected from a hydrogen-atom model. This is measured by theionisation potential. Polarisation of the core by an external field intro-duces two additional features. The change in radial polarisation (i.e. ,expansion of the core) further alters the effective electronegativity of thecation without regard to the symmetry of the field.13 Fields of particularsymmetry introduce angular polarisation which again stabilises the centralatom in the field-ligand field t h e ~ r y .l - ~ > l ~ The general idea that the coreexpands and contracts in the presence of different ligand fields has beendiscussed qualitatively for many years * but recently Schaffer and Jorgen-sen l5 have suggested a semiquantitative way of estimating this effect. Theelectron-electron repulsion terms for an atom can be expressed in terms ofthe Racah parameters B and C. B changes with the magnetic quantumstates and C with the spin states. When an atom or ion is placed in a field,B and C change with the nature of the ligands producing the field. Byl1 H. Irving and R. J. P. Williams, J., 1953, 3192; ref. 6, p. 123.l2 Electronegativity scales are discussed by Rossotti, ref. 6; K. Ito, Nuturwiss.,1959, 46, 445.13 C.K. Jrargensen, “ Absorption Spectra of Complexes of Heavy Metals,” EuropeanRes. Off ., U.S. Army (Frankfurt), Contract DA-91-508-EUC-247.l4 L. E. Orgel, J . Chem. Phys., 1955, 23, 1004, 1819, 1824.l5 C. E. Schaffer and C. K. Jrargensen, ref. 3, p. 143; C. K. Jerrgensen, ref. 6, p. 110.* Ligand field theory often introduces an effective radial polarisation by discussingboth d , ~ and d,a bonds. In early discussions of these effects the concomitant change ininternal electron-electron repulsion was disregarded. As this term can be discussedapart from angular polarisation and as the initial stress of ligand field theory is on thelatter polarisation alone i t seems appropriate to restrict the title ligand field theory tothe discussion of angular polarisation.Radial polarisation occurs in elements outsidethe transition series and the transition elements are those to which ligand field theory isusually confined90 GHNERA4L AND PHYSICAL CHEhIISTRY.considering transitions between states which do not differ in stability throughdifferences in angular polarisation, B can be connected to the radialpart of the wave functions. Thus by measuring B or C it is in principlepossible to assess the spread of the core electrons over the ligands. In anactual measurement B can only be determined by assuming constant radialparts of the wave function during the excitation from one magnetic quantumstate to another, i.e., during a spectroscopically observable d-d. transition.If the character of the field changes on excitation from the ground to theexcited state, together with the radial part of the wave function, then theobserved value of B from spectra, which we will call B', will not be simplyrelated to the B defined on the above theory.This distinction between themeasured and the theoretical quantity should be remembered in discussionof Racah parameters although its importance is unknown. Anotherestimate of the spread of core electrons over the ligands can be obtainedfrom paramagnetic resonance experiments.16 Much theoretical work isbeing done on this problem and also on the general nature of the orbitals ofhigher quantum number in non-hydrogen-like atoms and the effect ofexternal and internal charge upon these orbitals.17-19The size of a free gas ion must be arbitrarily defined.The problem of defining size for assumed non-polarisable ions was tackledbetween 1920 and 1940 by Goldschmidt and Pauling amongst others.20Transition-metal ions are polarisable so that size is dependent upon fieldstrength as well as upon field symmetry.Thus, ionic size is not a para-meter which can be introduced prior to knowledge of the nature of thefield around an ion but is only one more reflection of the character, strength,and symmetry of that field.21 The effect of centrosymmetric changes offield can be seen by a consideration of the effect of covalency on the size ofthe core. Covalency which employs high principal quantum number s states,e.g., 4s or 6s, is equivalent to a change in total charge on the nucleus as feltby the core electron of lower principal quantum number, e.g., 3d or 4j.Thus the core will expand as this charge is reduced and the ion or atomwill effectively expand.The effect of angular polarisation has been dis-cussed several times.21 Change of spin state greatly affects the size of anion. This is well brought out by comparison of the second and the thirdtransition series with the first. The radii in the first row fall generally butgo through two shallow minima while only one deeper minimum is shownin the second and the third row.Ligand Properties.-It is more difficult to give numerical definition toproperties of ligands than to properties of central ions and atoms in com-plexes. The electronegativity can be assessed by reference to the ionisationpotential of molecules or donor character of ligand, but its acceptor power16 J.Owen, ref. 3, p. 430; K. Kido and T. Watanabe, J . Phys. SOC. Japan, 195917 L. E. Sutton and I;. E. Orgel, ref. 1, p. 17; D. P. Craig, A. Rlaccoll, R. S. Nyholm,18 D. p. Craig and E. A. Magnusson, ref. 6, p. 116.19 R. G. Breene, Phys. Rev,, 1959, 113, 809.20 See K. H. Stern and E. S. Amis, Chem. Rev., 1959, 59, 1.21 N. S. Hush and M. H. L. Pryce, J . Chem. Phys., 1057, 26, 143; 1958, 28, 244;The sizes ofions.14, 1217.L. E. Orgel, and L. E. Sutton, J., 1954, 332.N. S. Hush, ref. 6, p. 145WILLIAMS : A4BSORPTION SPECTRA AND STABILITY OF COMPLEX IONS. 91although frequently invoked is largely without definition. Usually, acceptorcharacter is assumed from the availability of empty antibonding x-orbitalsor of empty d-orbitals of the ligand.22 Until recently no attempt was madeto do other than discuss the symmetry of these wave sfunctions relative tothe wave functions of the central atom. In the last 4 - 5 years, however,the radial distribution of the ligand orbitals has been tentativelyanalysed.17*18 Another quantity which is much used in discussing ligandproperties is the dipole moment but here again there is the difficulty ofassessing the dipole in the presence of the cation.This involves the resolu-tion of the polarity in a ligand relative to its polarisability. Even withsimple ligands such as the halide ions, polarity, now referring to the ionicfunction x/r, changes down the series in the order F- > C1- > Br- > I-,in the opposite sense to polarisability.The still greater difficulty of givingprecise definition to the properties of larger ligand molecules has forcedthe use of such little-understood quantities as the acid dissociation con-stants of ligands as guides to donor p o ~ e r . ~ ~ - ~ ~ There has been considerablediscussion as to the value of this procedure. A more fundamental butmuch more approximate approach is the molecular-orbital treatment ofthe complete complex, metal and ligands, which has now been attemptedin several case~.~0~31(b) The ligand-cation fields *The simplest field is that supplied by ligands which can be representedby point charges. Such a field is used in the Born-Mayer calculation oflattice energies.This model has been carried over into the discussion ofcomplex ions. The next stage of increasing complexity is a field of negativepoint charges which polarise a cation. Crystal field theory is basically ofthis kind. The discussion of lattice energies and heats of hydration oftransition-metal salts including both these terms on a purely electrostaticmodel is not very successful, and Orgel 32 pointed out that a better under-standing could be reached if the s-$-state electronegativity of the cationwas taken into account. The electronegativity he uses has been men-tioned earlier (p. 88). His model contains a necessary inconsistency if hisg2 J. Chatt, ref. 3, p. 515.2s J. Blerrum, Chem. Rev., 1950, 46, 381.24 A.E. Martell and M. Calvin, " Chemistry of the Metal Chelates," Prentice-Hall,25 3. F. Duncan, Austral. J . Chem., 1959, 12, 356; Discuss. Faraday SOC., 1957,28 H. Irving and H. S. Rossotti, Acta Chem. Scancl., 1956, 10, 72.27 J. G. Jones, J. B. Poole, J. C. Tomkinson, and R. J. P. Williams, J . , 1958, 2001.28 G. Schwarzenbach, G. Anderegg, W. Schneider, and H. Senn, Helv. Chim. Acta,2e D. E. Goldberg and W. C. Fernelius, J . Phys. Chem., 1959, 63, 1246.30 R. L. Belford, M. Calvin, and G. Belford, J . Chem. Phys., 1957, 26, 1165.31 H. L. Schlafer, 2. phys. Chem. (Frankjurt), 1956, 8, 373.32 L. E. Orgel, J., 1952, 4756, and ref. 9.* It may appear that the part played by d electrons and states and their propertieshas been over-stressed in this report when ligand fields are being considered.The stressis on these properties because they supply readily measurable quantities (magneticand spectrophotometric) which can be related to field strengths. On the whole, littlecan be discovered about s and p states or electrons and their properties in compounds.The interaction between d electrons and states and the field rarely, if ever, suppliesmore than 20% of the total interaction energy.New York, 1953, p. 76.24, 129.1955, 38, 114792 GENERAL AND PHYSICAL CHEMISTRY.calculations are to be quantitative. The field for the d electrons is differentfrom that used in assessing the overall field for the cation. This incon-sistency is most easily recognised by considering what is implied by usinga varying electronegativity for each cation.% The effect of change ofelectronegativity is a change in polarisation of the anion or ligand. Changeof polarisation implies a change of the equivalent-charge cloud of the ligand(or a change of the position of its equivalent point charge relative to thecation), and this polarisation is different for each cation.But in calculatingthe polarisation of the (d-electron) core it is necessary to keep the ligand-charge cloud constant, independently of cations. Many authors have beeninclined to accept this approach as the best that can be done.6~~4-40 Itshould be noted that the relative polarising power of a cation increases withthe same increments as the theoretical angular polarisation energy of delectrons, ie., as 0 : 1 : 2 : 3 for manganese(II), iron(n), cobalt(rI), andnickel(@, the increments in polarising power being measured by the incre-ments in ionisation potentials.Ligand field theory has received muchsupport from absorption-spectra measurements. It undoubtedly permitsthe correct assignment of transitions, demonstrating that the treatment ofsymmetry-dependent properties is satisfactory.1-6 This Report will notreview such aspects of the theory. The discussion of energies of excitationis made by reference to the spectrochemical series. This is the series ofligands which produce increasing spectroscopic splitting energies, A,between states of different magnetic quantum number. This seriesis I- < Br-< C1- < OH- < RC0,- < F-5 H,O < NCS- < NH, < en 5NO,- < o-phenan < CN-.It has been found to be largely independent ofcation although the increments between members of the series are not.On any theory which assumes that there is no change in electron distributionon change from the ground state to the excited state A becomes a measureof the field strength of the ligand. Some confusion has arisen on thispoint. In the literature two definitions of A are used. The first, by thetheoretician, is that A is the splitting between two sets of d states in anoctahedral field in ,the ground state of the complex. The second is that A isthe observed splitting energy calculated from the spectrum of a complex.It is probably better to call the former lODp until the identity between thetwo definitions of A, often implied by the theoretician,6 has been established.This procedure will be used here.In theory the stabilisation of the groundstate due to angular polarisation is calculable from the product of the ground-state splitting energy, lODq, and a stabilisation factor S which depends onlyupon the number of d electrons in the central atom and the field symmetry,i.e., 1ODq.S (rt.b., not A.S). As A but not lODq is experimentally measurablethe only available comparison is between thermodynamic data and A.S. (The33 C. K. Jerrgensen, L. E. Orgel, and R. J. P. Williams, ref. 6, p. 180.34 J. W. Linnett, ref. 6, p. 7.35 L. E. Sutton, ref. 4, p. 23.8’ J. S. Gri%ith, J. Inorg. NucEear Chzsrn., 1956, 2, 229.98 J.Bjerrum and C. K. Jlzrrgensen, liec. Trav. chirn., 1956, 75, 116.s9 W. G. Penney, Trans. Faraday SOC., 1940, 36, 627.40 H. Freiser, Q. Fernando, and G. E. Cheney, J. Phys. Chew., 1959, 68, 250.P. George, Rec. Trav. chim., 1956, 75, 671WILLIAMS: ABSORPTION SPECTRA AND STABILITY OF COMPLEX IONS. 93calculation will not apply if 6- and x-bonding, radial polarisation, occurs.)It is salutory to remember that this quantity is always less than ZOyo of,for example, the hydration heat of a metal ion. The main energy contri-bution on formation of a complex does not come from angular polarisationof the d electrons.A second, more empirical, approach to ligand-cation interaction wasbased on electronegativity a 1 0 n e . l ~ ~ ~ ~ This suggested that the ligand wouldbe polarised by the cation in proportion to the ionisation potential of thecation. This treatment has some advantages in discussion of energyquantities but is unable to describe properties dependent on symmetry asit implies a centrosymmetric covalency only.It is particularly applicableto the comparison between cations of subgroups A and B. An objection tothis approach is that it suggests that the stability of metal complexes shouldalways follow the same sequence, that of the electronegativity, indepen-dently of ligand. This is not the case.*2 The nature of the problem canbe seen from a consideration of the major contributions to the free energyof a complex ML in aqueous solution. There is an ionic term which isuniversally treated as a function of charge, x, and an inverse function ofinteratomic distance, Y.This term controls the magnitude of the entropyof formation of the complex and contributes to its enthalpy. There is alsoa covalent, polarisation, term which is dependent upon cation electro-negativity and ligand polarisability. For cations of subgroup A it has beenobserved that the free energy of complex formation for the same series ofcomplexes is proportional to ionic functions, e.g., z2/r, ionisation potentials,aelectr~negativities,~~ and entropies of hydration.42 The confusion in inter-pretation which results will be removed when the mutual interdependenceof these quantities is r e ~ o g n i s e d . ~ ~ , ~ ~ Progress in the understanding of thefree energies of complex formation in these cases can only be made by thestudy of heat and entropy data.When comparing cations of subgroup Bwith those of subgroup A the character of an interchange becomes important.In these reactions it is possible for the ionic component of the free energy todiminish while the covalent component increases. In such a case the cationsof subgroup A will form either no complexes or distinctly weaker complexesthan the cations of subgroup B. An example of this behaviour is found inchloride complexes. It is the heat term which causes the enhanced stabil-isation of the ions of subgroup B elements.42 Electronegativity parametersor ionisation potentials do not correlate with the free energy of complexformation in such cases.Stability orders are not independent of ligand butelectronegativities and ionisation potentials are. The required parametermust contain ionic and covalent components for both the initial and finalcomplexes in the interchange reaction. No satisfactory treatment alongthese lines has yet been d e ~ e l o p e d . ~ ~ , ~ ~ - * ~41 M. Calvin and N. C. Melchior, J. Amer. Chem. SOC., 1948, 70, 3270.42 R. J . P. Williams, J . Phys. Chem., 1954, 58, 121.43 D. P. Mellor and L. Maley, Nature, 1947, 159, 370.44 W. C. Fernelius and L. Van Uitert, Acta Chem. Scund., 1954, 8, 1726.45 C. L. van Panthaleon van Eck, ref. 4, p. 170.46 R. G. Charles, J. Amer. Chem. SOC., 1954, 76, 6854.47 E. Uutsilia, Finska Kemistsamfwzdets Medd., 1958, 67, 10194 GENERAL AND PHYSICAL CHEMISTRY.The discussion of the stability of complexes-of transition-metal ions byreference to electronegativity can be linked to the crystal-field approachthrough the use of molecular-orbital theory.l-s Symmetry propertiesdevelop in crystal-field and molecular-orbital theories in an identical manner.Energy quantities are differently treated as the electronegativity ofthe cations, including differences in this quantity due to differences inenergies of d states, is included in the molecular-orbital description but notin the crystal-field theory.The field experienced by the d electrons is nowcation-ligand dependent instead of just ligand dependent. The molecular-orbital approach has led to an examination of spectra for terms whichmight be sensitive to covalency, involving d orbitals.Independently, twoauthors have used the intensities of the d-d transition~.l~*~~ The intensitiesfall in the ligand sequence, H,O < NH, < en < C1- < NO,- < Br-,which closely parallels ligand polarisability. This series has been knownfor some while as the hyperchromic series. Paramagnetic resonanceabsorption spectroscopy has also been used with much success.16 A morefundamental attack on the problem of covalency has been made by Schafferand J@rgensen15 and others.46 They have examined the changes in theRacah parameters, B’, from one complex to another. Their discussion runsas follows.If the formation of a metal-ligand bond involves transfer of electronsto the s and p states of the metal, then, owing to the penetration of thesestates inside the core of the d states, the s-9 covalency alters the energy ofthe d states independently of the symmetry of the field of ligands.The dstates spread out and the electron repulsion energies change. Changes inthe d states are also brought about by covalency involving a change in theoccupation of these orbitals themselves. Once again the d orbitals willspread out as covalency increases. Overall knowledge about the reductionin core-electron repulsion energy and therefore indirectly of the increase incovalency can now be obtained by determining the value of the parameterB’. This is found from the examination of the spectra of a complex. Ifthere are two or more transitions involving the same change in A .S butdifferent changes in the value of total magnetic quantum number, then thetransitions will differ in energy and there will be different internal electronrepulsions, and B’ can be calculated by solving simultaneous equations for B’and A. From the decrease in the values of B’ a ligand series has been builtup called the nephelauxetic series which, it is suggested, represents theincrease in covalent character in the binding of a given cation. The seriesis F- < H,O < NH, < en < SCN- < Cl- < CN- < Br-. This is a totallydifferent series from the spectrochemical one. It appears to reflect thepolarisation of the ligand (covalency) much more than does the spectro-chemical series which appears relatively oversensitive to x-bonding, themetal acting as donor.Clearly both these series assess properties of thefield but it is not clear exactly which properties they do assess. There isno general correlation between either series and complex stability. Asthere are large numbers of transitions involving changes in A, B’, and C’ incertain cations, e.g., manganese(n), the internal consistency of their para-meters can be checked. The values of A and B’ should be independent oWILLIAMS : ABSORPTION SPECTIi.4 AND STABILITY OF COMPLEX IONS. 95the exact transition. In some examples very good consistency is obtained 48but in others the position is not so satisfa~tory.~~ A greater wealth ofexperimental material is required in order to appreciate the factors affectingA, B’, and C’.An attempt has also been made to set up a nephelauxetic series ofcation^.^^^^^ The order, increasing covalency, amongst tervalent elements, isMoIII < CrIII < FeIII < RhIII < Corn.Down a group in the PeriodicTable the order would appear to be CrIII > Monl > WIIl, CoIII 5 RhIII 21 Ir1IXbut NiII < PdII < PtII. These are exactly the orders expected from theionisation potentials of the cations. To this extent the nephelauxetic seriesfor cations would appear to have the same basis as that originally given forIrving and Williams’s stability order for complexes. The crystal fieldparameter, A, does not parallel the nephelauxetic series of cations in allcases, e.g., in the tervalent ions it is FeIE1 < CrxI1 < CoIII < MoIII < RhIII,and amongst the bivalent ions MnlI to ZnII it is ligand dependent.A third assessment of ligand field strength can be made from the effectof ligands upon the magnetic moments of cations.has used thisapproach in the.discussion of the fields due to ligands in iron complexes.The series is similar to but not the same as the spectrochemical series. Such aseries is likely to differ from the two spectrochemical series as it involves theeffect of ligands upon B’ and C’ as well as the splitting energy betweendifferent states.Finally field strengths can be estimated from thermodynamic data.f-6The assessment is best made by comparing a series of cations with one ligand.The effect of size of a ligand is illustrated by comparing the complexes ofgroup IIA cations.The additional effect of polarisation can be examinedby comparing the ions across a transition series, say from calcium(z1) tozinc(I1). It is convenient, in order to relate this polarisation to theoreticalquantities, to divide the absolute free energy of formation of a complex orthe lattice energy of a compound into two parts.51 The plots are somewhatdifferent for dfferent ligands as is illustrated in the Figure. Curve A isfound with a very slightly polarisable and curve B a strongly polarisableligand. The slope of a line joining two elements, whose angztZar polarisationin a field must be zero (crystal field theory), e.g., manganese(n), calcium(rI),and zinc(II), is labelled R. R is assumed to be related to spherically sym-metrical polarisation.I t is clearly not an electrostatic parameter arisingfrom the calcide contraction for R has the smallest value with the smallestanion, F-. It has not the same value in the two halves of the transitionseries (cf. rare-earth series). The vertical difference between the broken linesand a given point is labelled Q; this is thought of as the angular polarisationenergy in crystal field theory and is dependent on field symmetry. In thistheory Q is related to 10Dq.S and can be compared with the measurable A.SWilliams48 L. R. Pallalardo, J . Chem. Phys., 1959, 31, 1050; L. J. Heidt, G. F. Koster, andA. M. Johnson, J . Anzer. Chem. SOC., 1958, 80, 64i1, and references therein; C. K.Jmgensen, Acta Chem. Scand., 1958, 12, 903.4s C.E. Schaffer, ref. 3, p. 149.60 R. J . P. Williams, “ Symposium on Hzematin Enzymes,” Canberra, 1959, Perga-61 This procedure has been used by a great number of authors, see refs. 5 and G.mon Press, t o be published; see also L. E. Orgel, ibid96 GENERAL AND PHYSICAL CHEMISTRY.in order to establish the validity of this theory in treating both thermo-chemical and spectroscopic informatiom61 1 1 1 1 1 1 1 l 1 1Ca Sc T i V Cr Mn Fe Co Ni CP ZnAtomic numberA plot of lattice energy or absolute heat of complex formation against atomic number for thebivalent ions of thejirst transition series. The full lines aredrawn between points f o r adjacent elements while the broken lines are drawn betweenions with empty, half-filled, or completely filled d shells.( A ) represents results ob-tained with ligands of low polarisability whilst (B) represents data with ligands ofhigh polarisability.The Plot as schematic.The slope of the dotted lines is referred to as R in the text.On molecular orbital theory there is no reason to suppose that thechange in total core polarisation will be continuous with atomic numberespecially between d4 and d5 and d9 and dl0 configurations, and the separ-ation of Q from the other energy terms becomes artificial. The questionthen is not whether the separation of Q from the rest of the energy is strictlyvalid but whether it is a good approximation permitting an estimate of theimportance of angular and spherically symmetrical polarisations separately.The point is brought home in the discussions of the stability of the d4 and d9states about which there has been prolonged argument.6 If Q is to repre-sent an angular polarisation in cases where curve B is obtained, a verylarge Jahn-Teller stabilisation in crystal field theory must be assumedfor copper(I1) and chromium(I1) ligands and a very small effect for iron(11)and cobalt(I1).On the other hand, as the d4 and d9 configurations areassociated with high electron affinities, the large value of Q can be explainedas due to the exceptionally strong polarising power of these cations. In thiscase the separation of Q from the rest of the energy term is artificial. Experi-ment shows too that Q for copper(I1) (a9) does not increase from ligand tligand in the same way as Q does for other ions such as nickel(n) (ds).1x1cases where Q for d9 and d4 is relatively small (curve A ) , then the importantcontribution to Q could well be the angular polarisation. It is easy to seethat there must be some stabilisation energy contribution from both polar-isations but it is very difficult to analyse theoretically the total energy intothe two components.% The slope Rcan be greater or smaller in the first half of the transition series than in thesecond. Possible reasons forall these effects have been discussed but the discussions are somewhattentative because of the absence of sufficient data. These discussionsinvolve a further analysis of polarisation in terms of a- and n-bonding. Thegeneral idea is that x-donor ligands (halides, oxyanions, water, and sul-phide) stabilise the earlier elements in the series through the emptyacceptor d, metal orbitals and that n-acceptor ligands stabilise the laterelements through the d, donor character of these cations.Much of thisdiscussion cuts across the original distinction of angular and radial polaris-ation implied in the discussion of the Figure. It does bring out the generalpoint that the nephelauxetic series is related to R but leaves Q and A ill-defined. Similar discussions of the compounds of higher valency cations andof the cations of the later transition series are not possible because there istoo little information.Much confusion has also been caused through a lack of appreciation of thenature of interchange reactions, The measurement of the stability ofcomplex ions is that of the free energy of interchange reactions such asM(aq.) + 2L Both M(aq.) and ML, give rise to plots such asare given in the Figure.The experimental heat change or free-energychange is the small difference between two such plots. It may be thatchanges in R or changes in Q from water to the ligand, L, largely dominatethe overall interchange free energies in certain cases but the dominant factorappears to vary with cation even for one ligand. The hydrates give a plotlike curve A . If the new ligand gives a plot like curve B then part of thestability sequence of ML, will be ZnrI < CUE > NiIr > C d I > FeII > MnII,with zinc in an indeterminate position.If the new ligand gives a plot likecurve A , in which the stability of nickel is even more accentuated relative tocopper than in the hydrates, then the stability sequence will be ZnII <NiII > Cur1 > CoII > FeIl > MnII. There are several changes of ligand-field character relative to water possible on making such an interchange.For example, (i) increases in both B and x donor character, (ii) increasesin a donor and decrease in x donor character, (iii) decrease in B donor andincrease in x donor character, (iv) decrease in both B and x donor character.In the discussion of complex formation even by such a ligand as ammoniamany of these factors have been invoked. Thus, it is implied that ammoniais a weaker x donor than water,33 is a stronger o d~nor,~-ll and is morep01arisable.l~ It does not seem to the Reporter that progress in these dis-cussions can be made without more experimental information covering awider variety of ligands and cations, and advances will depend on accurateheat data rather than on further correlations of free energies.At themoment it appears that all the different factors contribute to stahilisations,REP.-VOL. LVI 1 )There are other complications too.The values of Q can be greater or smaller too.ML,98 GENERAL ANT) I’HYSICAL CHEMISTRY.and that the generalisations based on either electronegativity or crystalfield theory above are over-simplifications.In the following sections on thermodynamic data little attention will bepaid to entropy changes as it appears that these are reasonably well under-stood52 and little new information has been obtained about them.Heatdata will be mentioned whenever they are available. Author references willonly be made to new data on complex stabilities, free energies, publishedsince the compilations of Sillh, Bjerrum, and Schwar~enbach.~~(c) Complexes of inorganic ligandsHydration Energies.-Heats of hydration of cations have been discussedby several authors. Early work used a simple electrostatic model in calcul-ations involving few empirical quantities. More recently the polarisation ofthe cation by the water molecule9~39 has been discussed as well as thepolarisation of the water molecule by the c a t i ~ n . ~ ~ ~ ~ ~ In calculations aboutthe former the water molecule is treated as possessing a fixed polarity,although this may not be the polarity of the isolated water molecule, whereasfor the latter the polarity of the water molecule is assumed to vary with theionisation potential of the cation.There can be little doubt that both thesepoints of view contain useful but rough approximations.54 No full under-standing of the stability of a complex ion can be obtained without a betterappreciation of the hydration free energies, for water is more often than nota ligand in the interchange reaction which produces a complex. Spectro-chemical data indicate that water induces a rather small splitting energy, A,it is early in the spectrochemical series, and does not alter the values of B’very greatly from those of the gas ion.Together with the thermodynamicobservation that the slope, R, of the Figure is smaller than that for any otherligand except fluoride (fluoride and water both give graphs of type A ratherthan of type B), these facts suggest that water is relatively slightly polaris-able. The small value of A may depend upon the inability of water to actas a x-electron acceptor. Its x-donor character could explain why A and Qare relatively large for the early elements in the transition series.55Fluorides.-The fluoride ion occurs earlier (i.e., smaller A) than water inthe spectrochemical series and earlier (i.e. , larger B’) in the nephelauxeticseries. It is the least effective of all ligands in bringing about a change ofspin state of a central cation. Plots of lattice energies of fluorides of thebivalent ions of the first row of transition metal ions (curve A ) show thatthe slope, R, is less than that for water, in keeping with the lower polaris-ability of the fluoride ion, but that Q increases slightly from water tofluoride.The fluoride ion is increasingly polarised along the series man-ganese(11) to copper(r1) as shown by the stretching frequencies of the M-F52 E. L. King, J . Phys. Chem., 1959, 63, 1070; J. H. B. George, /. Ainev. Chew.53 J. BjErrum, L. G. SillCn, G. Schwarzenbach, ‘‘ Stability Constants of Metal Tont4 A. D. Buckingham, Discuss. Furuduy SOC., 1957, 24, 151.55 R. J. P. Williams, Discuss. Faraday SOC., 1958, 26, 123.SOC., 1959, 81, 5530.Complexes, Parts I and 11, The Chemical Society, LondonW IILTAMS : ARSOKPTION SPECTRA ANI) ST:lBJLT'I'Y 01; COMPLEX IONS.09bond.56 There are great differences between fluoride cheniistry and that ofthe other halides. Sidgwick 57 reports that whereas group IIA fluorides areanhydrous later transition-metal fluorides are hydrated. The solubility ofsalts increases in the unparalleled sequenceMgII < CaII < Mnn < CoJl < Ni*I < Cuu > ZnIIConnick 58 has discussed the stability of the fluoride complexes from thepoint of view of the heat and entropy results he and his co-workers haveobtained during a number of years. The entropy data fall into a patternwhich is readily interpreted on an ionic model for aqueous entropies.52 Theheat data and therefore the overall free energies are more difficult to under-stand.They have been discussed also by B a b k ~ . ~ ~ The most polarisingcations, such as mercuric,57 form only weak fluoride complexes, and the heatterm amongst tervalent ions falls in the order ScrII > A P > FeIII > In111while the entropy follows z ~ / Y , i.e., A1111 > FeIII > ScTIr > InIrI. The datasuggest that the heat term for complex formation with highly polarisingcations is dominated by the higher polarisability of water relative to thefluoride ion, and that therefore in an interchange reaction between waterand fluoride ions the free energy of the change M(H,O) M F is lessfavourable the more polarising the cation becomes. This also explains therelative hydration and solubility of fluorides.Chlorides, Bromides, and Iodides.-The spectrochemical series is H,O >F- > C1- > Br- > I-.The nephelauxetic series is F- < H,O < C1- <Br- < I-. The relative ability of the anions to stabilise a promoted electronconfiguration of a cation is unknown except that fluoride is less able thanany of the other anions to induce such a change. The stability of metalcomplexes is either F- > C1- > Br- > I- or I- > Br- > C1- > F-,42360,61The latter order is found only with the cations CuI, AgI, AuI, AuIII, PdII,PtIV, PtII H g J I1 CdII , , TP TPII, PbII, SnII, BPI, Sbl*I, and TerV. Thevalues of R (curve B) increase in the sequence I- > Br- > C1- > H,O > F-,but the values of Q do not show any very systematic variation, or evenappreciable change.62 Within this series of ligands and also amongst theseries oxide, hydroxide, water, acetate, ~ x a l a t e , ~ ~ there is insufficient changein Q greatly to influence an interchange free energy. Several attemptshave been made to understand these confusing and apparently contradictorythermodynamic data.One explanation 63 is that the metals, known asclass (b) metals, with which iodide forms the most stable complex, are themost polarising. The stability order depends on the heat terms in all the66 D. W. A. Sharpe, Discuss. Faraday SOC., 1958, 26, 186.67 N. V. Sidgwick, " The Chemical Elements and their Compounds," Oxford Univ.Press, 1950.5* R. E. Connick and R.E. Poulson, J . Phys. Chem., 1959, 63. 568; R. E. Connickand A. D. Paul, J . Amer. Chem. SOC., 1958, 80, 2069; J. W. Kury, A. D. Paul, I.. G.Hepler, and R. E. Connick, J . Amer. Chem. SOC., 1959, 81, 4185.69 A. I<. Babko and L. G. Shimadina, Rziss. J . Inorg. Chem., 1959, 1, 183; -A. K.Babko, Rzassian J . Inorg. Chem., 1959, 1, 485.6o S. Ahrland, J. Chatt, and N. R. Davies, Quart. Rev., 1958,12, 266.6l R. G. Carleson and H. Irving, J., 1954, 4390; see ref. 4, p. 13.62 The data are given by P. George and D. S. McClure, ref. 6, and are discussed in133 R. Abegg and G. Bodlander, Z. amrg. Chem., 1889, 20, 453.refs. 5 and 61 0 0 GENERAT, AND PWYSTCXT, CHEMISTRY.cases wliicli have been investigated so far.G4 This approach has been de-veloped recently by including in class (b) the cations which are highlypolarising relative to their ionic function z2/r.This explains why the stabil-ity order for the different halides with these cations follows the nephelauxeticseries, and increasing values of R. The orders of the values of A and Q,which are not simply related to one another or to R, can be understood ifhere as elsewhere they are assumed to be rather sensitive to changes inx-bonding, the ligand acting as the donor. An alternative explanation isthat the order I- > Br- > C1- > F- represents the decreasing strength ofa,-acceptor bonding by the ligand.60j This explanation is generally usedhowever in the discussion of the stability of unsaturated ligands, e.g.,cyanide ~omp1exes.l~ Cyanides differ markedly from halides in the relativevalues of A and of Q.The order F- > C1- > Br- > I- in the other series of cations [class (a)]requires an entirely separate explanation.Here thermodynamic data areavailable in sufficient quantity to show that the formation constants of thehalide complexes for which this stability order holds are dependent onentropy changes for their stabilisation and differ entirely in this respect fromclass (b) cations. The order of the entropy term 42352 as far as it has beendetermined is in all cases F- > C1- > Br- > I-, and there are good theoreti-cal reasons for expecting this order. Another factor here is that the cationsin this group are mainly small so that steric factors too will militate againstthe formation of complexes with the very large halide anions.Hydroxides, Acetates, and 0xalates.-These three anions are groupedtogether as they co-ordinate through oxygen carrying a negative charge.They occur in the spectrochemical series close to fluoride, i.e., have weakereffective fields than water, and in the nephelauxetic series between waterand chloride, i.e., they form more covalent complexes.The value of R in bothparts of the transition series (see Figure) increases in the order: water,acetate, and oxalate, hydroxide, oxide. In their combination with the cationsof the later transition elements the value of Q changes slightly if at all in thisseries of anions.55 From the limited data available Q appears to in-crease in the same way as R in the early part of a transition series, both Qand R being greater than for the later elements.The study of thermo-dynamic properties of the complexes G6, 67 shows that although the acetates,malonates, and oxalates are often formed endothermically, hydroxide com-plexes of the transition metals are formed exothermically. As the complexesof all these ligands are most stable with the most polarising cations, evenwhen these are large and the entropy terms small, it must be presumed thatthe heat terms are less endothermic, or more exothermic, with these heaviercations of the later groups. All the complexes are stabilised by favourableentropy changes. An explanation involving x-bonding has been offered ofthe anomalous position of these ligands in the spectrochemical series and of64 J.M. Austin, R. A. Matheson, and H. N. Parton, “ The Structure of ElectrolyticSolutions,” ed. W. J. Hamer, Wiley, New York, p. 365; E. L. King, J . Chem. Educ.,1953, 30, 71; M. G. Evans and G. H. Nancollas, Trans. Faraday SOC., 1953, 49, 363.66 R. J. P. Williams, Proc. Chcm. SOC., 1960, 20.66 G. H. Nancollas, Discz~ss. Faraday Soc., 1957, 24, 108.67 G. H. Nancollas, j . , 1956, 744; and see ref. 6WILLIAMS : ABSORPTION SPECTRA AND STABILITY OF COMPLEX IONS. 101the variation of the apparent field strength with co-ordination partner in thetransition series,& The stability sequence of Irving and Williams is obeyedwith these ligands, but this could not have been predicted from a know-ledge of A.Outside this series chromium(I1) acetate is more stable 68 thanmanganese(@ acetate, and its hydroxide is more insoluble. Such resultsconfirm the stability order predicted from the electronegativity of the twoions but could not be deduced from considerations of A. In the study ofhydroxides and acetates the interpretation is greatly hindered by the form-ation of polynuclear complexes. Much work has been done recently in thisfield. It has been well surveyed this year 69 and no report on this materialis made here.Su1phates.-These complexes were discussed by Prue in last year’s Report.Now heat and entropy data have become available7O on the cations frommanganese(@ to copper(I1). These show, much in keeping with expect-ation,ll that the heat terms do not follow Irving and Williams’s stabilitysequence and that the complexes of large ions are stabilised by larger heatterms than small ions of the same group of the Periodic Table.All methodsof comparing field strengths suggest that of the oxyanions, sulphate, nitrate,and perchlorate give a weaker field than does water but the position ofcarbonate and phosphate in any series of field strengths is not clear.71 Theyappear to behave more like acetate and hydroxide than like sulphate.Thiocyanates and Thiosu1phates.-These ligands lie close to water in thespectrochemical series but are associated with lower values of B’-whichsuggests greater covalency. 159 72 Stabilities of the M-CNS complexes followIrving and Williams’s stability sequence.73 A point of great interest is thenature of the co-ordination-whether it is through sulphur or nitrogen inthe thiocyanates or through sulphur or oxygen in the thiosulphates.Thereis now considerable structural evidence 74 to show that the binding is gener-ally through sulphur in those cases where the stability sequence amongstthe halides is I- > Br- > C1- > F-, but is through nitrogen with othercations. The change in the structure corresponds with a change in stabilitysequence from M-SCN > M-NCS to M-NCS > M-SCN or from M-S,O, >M-O,S, to M-O,S, > M-S,O,. As there can be little change in entropy inthese inversions of the ligand, the changes in order must presumably repre-sent a change in the order of the heat terms.Examples illustrate this. Theformation of the argentous thiosulphate complex (Ag-S) is exothermic 75while that of the barium complex is endothermic76 (Ba-O). The heat of6R I<. 1-5. Yatsimirskii and T. I. Federova, Zlriw. neovg. KJiim., 1956, 1, 2310.69 L. G. Sillh, Quart. Rcv., 1959, 13, 146.V. S. K. Nair and G. H. Nancollas, J., 1959, 3934; A. J. Zeilen, J . Awzer. CIteiiz.SOL, 1959, 81, 5022.J. R. Van Wazer and C. F. Callis, Chem. Rev., 1958, 58, 1011; V. P. Vasil’yev,Zhztr. neorg. Khim., 1958, 3, 2060; U. P. Strauss and S. B. Ross, J . Amer. Chem. SOC.,1959, 81, 5292, 5295, 5299.72 C. E. Schaffer, ref. 4, p. 153.7s K. 13. Yatsimirskii and V. D. Korsbleva, Zhzzr. neorg. Khim., 1958, 3, 339.74 Russian literature over the last ten years is the main source; see P.C. H. Mitchell75 R. L. Seth and A. K. Dey, 2. phys. Chem. (Leipzig), 1959, 210, 108; K. B. Yatsi-76 I. J. Evans and C. B. Monk, Trans. Furuduy SOC., 1952, 48, 934.and R. J. P. Williams, J., to be published.mirskii and L. V. Gus’kova, Zhur. neorg. Khim., 1957, 2, 2039102 GENERAL AND PHYSICAL CHEMISTRY.formation of chromic thiocyanate 77 (Cr-N) is -2.0 kcal. while that ofmercuric (Hg-S) is -9 kcal. per thio~yanate.~~ The changes in order of thethermodynamic quantities are not reflected in the spectrochemical serieswhich is constant independently of metal and is given by Jargensen andSchaffer 72 as C1- SCN- > H20 NCS-. The parallel with the discus-sion of the relative stability of the different halide complexes is obviousbut it is extended by a comparison between thiocyanates and seleno-cyanates.Recent Russian work7Sp79 and that of Chatt and his co-workers reveal the order SeCN- > SCN- for the more polarising cations(e.g., argentous, lead, mercuric, and cadmium). The order of A is sulphur >selenium.81 Crystallographic studies show that in vitamin BIz the cobaltatom can bind selenocyanate (Co-Se) and thiocyanate (Co-S) .s2 Strongfield complexes may bind such ligands in different ways from weak field com-plexes. Other ligands which have two possible co-ordinating sites havebeen studied and it appears that a similar differentiation between cationscan be made on the basis of the choice of ligand partner which the cationmakes, e.g., in nitrite,83 sulphite, thiourea,s4 and urea complexes.Cyanide Comp1exes.-This ligand is as high as any in the spectrochemicalseries and is also associated with a low value of B’.Many of its complexesare of low pin.^^,^^ Their extreme stability and difficulty of reversibilitymake the study of the stability of the complexes very difficukS6 The com-plexes do not conform to Irving and JVilliams’s stability sequence.23 Thesequence is broken by the high value for the ferrous complex (cf. phen-anthroline and bipyridyl complexes). The confirmation 5 3 9 8 6 that thestability sequence of the B elements is HgIr > ZnIl CdII is interesting asthis is not the order with the larger, highly polarisable, saturated ligands,c g . , halide ions and sulphur complexes, where it is C&* > ZnIJ, but is theorder with bipyridyl and o-phenanthroline, i.e., ligands which act as x-acceptors and which have small donor atoms.Complexes of Phosphorus and Arsenic Ligands.-Study of the spectra ofcomplexes of these ligands has placeds1 the ligand-field parameter A in thefollowing order P > N > As.This is not the order of the stability of thecomplexes of these ligands with the metals under study which isP > As > N.60 Thus, if the explanation of the spectrochemical sequence isthat it strongly reflects dHp, bonding then this effect cannot explain thestability series. dnPn bonding is expected17 to increase in the sequenceN < P < As, polarity in the sequence As < P < N, and polarisability inthe sequence As > P > N.On the first and last counts arsenic and phos-77 C. Postmus and E. L. King, J . Phys. Chem., 1955, 59, 1208.T 6 V. F. Toropova, Zhur. neorg. Khim., 1956, 1, 243.7Q A. M. Golub and Yu. V. Kosmatyi, Zhur. neorg. Khim., 1959, 4, 1347; A. M.Golub, L. I. Romanenko, and V. M. Samoilenko, Ulirain. khzm. Zhur., 1959, 25, 50;A. M. Golub and G. B. Pomerants, Russian J . Inorg. Chem., 1959, 4, 349.80 S. Ahrland, J. Chatt, N. R. Davies, and A. A. Williams, J., 1968, 264, 276, 1403.81 L. E. Orgel, J. Chatt, and G. A. Gamlen, J., 1959, 1047.*2 D. Hodgkin, personal communication.83 K. Nakamoto, J. Fujita, and H. Murata, J . Amer. Cltem. SOC., 1958, SO, 4817.84 T. J. Lane, A. Yamaguchi, J. V. Quagliano, J. A. Ryan, and S. Mizushima, J .R5 H.Freund and C. R. Schneider, J . Amer. Chem. SOC., 1959, 81, 4780.R6 ill. S. I3lackie arid V. Gold, J . , 1959, 3932, 4039.Amer. Chem. SOC., 1959, 81, 3824WILLIAMS : ABSORPTIUN SPECTRA AND STAEILITY OF COMPLEX IONS. 103phorus ligands should bind more firmly to heavier elements of transitionand B subgroup series, and particularly is this so as phosphorus and arsenicare large, while on the second count it might be expected that elements inthe first transition series will prefer nitrogen donors to either of these ligands.The relative position of phosphorus as a donor, as compared with arsenic,is that phosphorus complexes are always stronger. Here then dmfin bondingis more important than polarisability.60 The comparison of the heat offormation 87 of a phosphorus and of a nitrogen complex of nickel has ledto the unexpected order N > P for the heats of reaction.Complexes of Sulphur and Selenium.-Schwarzenbach 88 has started astudy of sulphide complexes.This has already thrown light on the solu-bility of some insoluble sulphides. Very little is known of the spectra ofM-SH Complexes, but the thermodynamic data available indicate that Ris very large and Q is small except in the case of copper(I1). Anomalouslylarge values of Q for cupric ion relative to expectation on crystal field theoryare often observed with highly polarisable anions, e.g., iodide. The atomicnumber-stability plots are of curve B type. This has been interpreted6variously as due to the high polarising power of this cation and a largeJahn-'Teller effect.In the sequence : oxide, sulphide, selenide, telluride thevalues of R increase towards the heavier anions6 The increase in Q islarge at cupric but for nickel, cobalt, and iron there appears to be littlechange. This brings about the much greater insolubility of the cupricsalts . 53(d) Complexes of organic ligandsOrganic Ligands Co-ordinating through Oxygen.-During the last two orthree years little work has been done on a broad group of metals with ligandsin this class. PerrinB9 has studied the ferric complexes of five aliphaticacids and observed that there is a rough correspondence between acid disso-ciation constants and stability. He also discusses the formation of thefamiliar basic ferric acetate polymers.Rossotti has detected polymersin solutions of cupric aliphatic-anion salts. Martell and his co-workers 91have examined the infrared vibration frequencies of some metal acetyl-acetonates and found them to fall in the sequence CuII > NiIl> ColI > CdII,i.e., parallel to the stability constants. Fernelius and his co-workers 92have further extended their detailed work on the complexes of substitutedp-diketones. The stability sequence for the bivalent chelates of Tiron" isCuJI > PbJJ > ZnII > Nil1 > CoTI > CdII.Y3 Here the stabilities of lead andzinc complexes exceed those of all first-row transitions-metal ions except*' L. Sacconi, G. Lombardo, and P. Paoletti, ref. 4, p. 141.88 G. Schwarzenbach, H. Ziist, and 0.Giibeli, ref. 4, p. 141.D. D. Perrin, J., 1959, 1710.D. L. Martin and F. J. C. Rossotti, ref. 4, p. 182; see also S. Chaberek, K. L.Gustafson, R C. Courtney, and A. E. Martell, J . Amer. Chem. Soc., 1959, 81, 515; K. C.Courtney, S. Chaberak, R. L. Gustafson, and A . E. Martell, ibid., p. 519; R. L. Gustafsonand A. E. Martell, ibid., p. 535.91 K. Nakamoto, P. J. McCarthy, and A. E. Martell, ref. 4, p. 178.92 B. B. Martin and W. C. Fernelius, J . Amer. Chern. SOC., 1959, 81, 2342.98 R. Nasanen, Acta Chem. Scund., 1959, 13, 869.* Tiron is catcchol-3,6-disul~~l~~~iic acitl J04 GENERAL AND PHYSICAL CHEMISTRY’.copper. This order is observed too with other anionic ligands and is pos-sibly general to all highly polarisable anionic ligands.Watters 94 continuedhis studies on mixed ligand complexes with an examination of the cupricoxalat e-ethylenediamine complex.Co-ordination through Nitrogen only.-Ligands co-ordinating throughnitrogen lie above oxygen and (probably) uncharged sulphur in the spectro-chemical series but the sulphur co-ordinating ligands lie highest in thenephelauxetic series while the oxygen ligands lie lowest. Most ligands co-ordinating through nitrogen are uncharged so that it is usually assumed thatthe stability of their complexes is controlled by heat terms. Recent worksupports this view.95$96 On the other hand, the binding of sulphur inRS-methyl compounds does not appear to be associated with a considerableheat term.g6 The heat terms are then neutral nitrogen > neutral sulphur.It has been supposed that values of A in ammine complexes could be used tocalculate heat terms on complex formation but this supposition has beenquestioned.There is disagreement between different authors 97 on theorigin of heat terms on the formation of chromous and cupric ammines.Complexes of substituted ethylenediamines have been studied.98 Theseligands bring about changes of spin state where the parent ion does not.99Monoethanolamine forms complexes in the expected stability sequences.looFernelius and his co-workers lol have continued stability measurements overa range of temperature. 2-Picolinylamine and 2-2’-aminoethylpyridineform more stable complexes than does ethylenediamine despite their lowerbasicity. This work adds to the considerable literature on the relationbetween pK, and log K (Le., acid dissociation constant and stability con-stant), much of which indicates that n-bonding in metal complexes27destroys the linearity which might have been expected between thesequantities ,259 26The stability of chromous complexes of ethylenediamine placeschromium(11) between iron(@ and cobalt(r1) in a stability series,lo2 but itsglycine complex is more stable than that of cobalt(I1) lo3 and its acetate is a tleast as stable as that of nicke1(11).68 The changing sequence illustrates thepreference for oxygen ligands early in the transition series and for nitrogenligands later in the series.The effects can be broken down in terms ofR and Q in the two parts of the ~ e r i e s .~ . ~ ~ The complexes of some nitrogenbinding dyes104 have also been studied but no very novel features arise.94 J. I. Watters, J . Amer. Chem. Soc., 1959, 81, 1560.95 L. Westerman, Diss. Abs., 1959, 20, 71.s6 M, Ciampolini, P. Paoletti, and L. Sacconi, ref. 4, p. 184; G. H. McIntyre, B. I’.Block, and W. C. Fernelius, J . Amer. Chem., SOC., 1959, 81, 529.97 See Discuss. Furuduy SOL, 1958, 26; papers by J. W. Linnett, L. E. Orgel, C. I<.Jarrgensen, and R. J. P. Williams.9* K. G. Poulsen and C. S. Garner, J . Amer. Chewz. SOL, 1959, 81, 2615.99 F. Basolo, Y . T. Chen, and R. K. Murman, J . Amer. Chem. Soc., 1954, 76,956.loo P. K. Migel’ and A. N. Pushnyak, Russ. J . Inorg. Chem., 1959, 4, 601.lo1 D. E. Goldberg and W.C. Fernelius, J . Phys. Chem., 1959, 63, 1246.l o 2 R. L. Pecsok and 5. Bjerrum, Acta Chem. Scand., 1957, 11, 1419.lo3 K. B. Yatsimirskii, Zhur. neorg. Khim., 1956, 1, 2451.104 F. A. Snavely, B. D. Krecker, and C. G. Clark, J . Amer. Chem. Soc., 1959, 81,2337WILLIAMS: ABSORPTION SPECTRA AND STABILITY OF COMPLEX IONS. 105Further studies of imidazole complexes have been undertaken.lo5 Thestability of the cobaltous and manganous complexes are much as expected.Interestingly, all metal imidazole complexes from calcium(I1) to zinc(1r) aremore stable than the corresponding ammonia complexes despite the order ofbasicity of these ligands. This is of great importance in biological systems.In these complexes and in histidine complexes lo6 no ionisation of imidazoleto an anion has been reported.This evidence militates against Pauling'ssuggested imidazole ionisations in haem~globin.~~ The study of substitutedimidazoles,107 histidine,lW histamine, and benzimidazoles lo8 as ligandsreveals little unexpected. The oxygen-carrying capacity of some of thesecomplexes is being studied in detail.lWThe third main group of nitrogen ligands to be studied are the deriv-atives of pyridine. Some theoretical work has been started.l1° Jonassenand Rolland ll1 found no linear relation between the stability of argentouspyridine complexes and the acid dissociation constants of the amiiiopyridines.Jillot and Williams 112 failed to observe such a relation in the study of thecyanopyridines complexing ferrous dimethylglyoxine. The absorptionspectra of cupric methylpyridine complexes has been interpreted on thebasis of ligand field theory.l13 The exact formulze of the complexes donot appear to have been established in this work.Detailed informationon the stability of o-phenanthroline and bipyridyl complexes is nowa~ailable.1~~ These ligands are the most powerful nitrogen-chelating com-pounds available. Discussion of the stabilities is confused by the differentdata on the manganous c0mp1ex.l~~ However, it is clear that steric hindranceplays a considerable part in reducing the stability of cupric complexesrelative to their hydrates. A totally different impression of the reasons forthe stability sequences is obtained if the steric problem is not considered.It is clear that the stability of bipyridyl and o-phenanthroline complexes fallsrapidly outside the transition series, i.e., Q is large.gOxidation reduction potentials both for FeII-FeIII 116 and CuI-CuI 117complexes of phenanthroline and bipyridyls have been examined and thelo5 R.B. Martin and J. T. Edsall, J . Amer. Chem. Soc., 1959, 81, 4044.lo6 R. Leberman and B. R. Rabin, Trans. Faraday SOC., 1959, 55, 1660; J. F.Drake and R. J . P. Williams, Nature, 1958, 182, 1084.lo' F. Jones and F. Holmes, ref. 4, p. 181; T. J. Lane and J . hI. Daly, J . Amer.Chem. SOL, 1959, 81, 2953.lo8 H. Irving and 0. A. Weber, J , , 1959, 2560.loo P. Silvestroni, Ricerca Sci., 1959, 29, 301; L. F. Larkworthy and R. S. Nyholm,Nature, 1969, 183, 1377; M.J. Cowan, J. M. F. Drake, and R. J. P. Williams, Discuss.Faraday SOL, 1959, 27, 217; J. A. Elvidge and A. B. P. Lever, Proc. Chem. SOC., 1959,195.110 H. L. Schlafer and E. Konig, 2. fihys. Chem. (Frankfurt), 1959, 19, 265.ll1 H. B. Jonassen and C. C. Rolland, Report to Office of Naval Research, Project112 B. R. Jillot and R. J. P. Williams, J., 1958, 462.llS D. J. Roger, J . Inorg. Nuclear Chem., 1959, 11, 151.lt4 H. Irving, ref. 4, p. 13; G. Anderegg, Helv. Chim. Acta, 1959, 42, 344; R. I.Bystroff, Diss. A h . , 1959, 20, 877.115 Cf. H. Irving, ref. 4, p. 13; R. J. P. Williams, ref. 55; R. R. Miller and m7. W.Brandt, J . Amer. Chem. SOC., 1955, 77, 1384.116 G. F. Smith and W. M. Bannick, Talanla, 1959, 2, 348; P. George, G. I. H.No. Nnr.685.Hanania, and D. H. Irvine, J., 1959, 2548; J. C. Tomkinson and R. J. P. Williams, J . ,1958, 2010.117 B. R. James and R. J. P. WiIliams, ref. 4, p. 139106 GENERAL AND YHYSlCAL CHEMIS'I'RY.results discussed, There is no simple relation between lie and pK>l values ofthe ligands.Co-ordination through both Nitrogen and Oxygen.-The heats andentropies of formation of ethylenediaminetetra-acetic acid complexes ofmany metals are now known.fl* The entropy values are relatively easilyunderstood 2s they increase with decreasing size of the cation. The heatsof formation show a confused picture. In the rare-earth series there appearto be two groups of ions, the first up to gadolinium forms complexes exo-thermically, the second after gadolinium endothermically.However,throughout the series the heat terms are of relatively little significance andthe small differences along the series could hardly be used to test any theory.The agreement between the results of different authors is not yet as goodas might be expected. In the lanthanide series of cations the formation ofmalonate complexes 113 is endothermic although the stabilities increasefrom lanthanum(rr1) to lutetium(II1). The stability sequence is entropydependent. These results imply that the stabilities of the complexes aredependent on the radii of the ions. The radii of rare-earth ions show a well-known dependence 120 on atomic number but do not appear to be dependenton the symmetry of the ligand field. It is not known if the changes of radiiowe their origin to angular polarisation or radial polarisation of the coreby the field, though the independence of symmetry argues in favour ofradial polarisation.The shift of the position of the absorption band121is very slight on change of ligand, being somewhat irregular in direction.The stability increments in the rare-earth series are often quite irregulartoo, e.g., in acetate,122 g l y ~ o l l a t e , ~ ~ ~ N-2-hydroxyethylethylenediamine-t riacet at e,124 and diet hylenetriaminepenta-acet ate .124 The limited inform-ation on the actinide series of cations suggests that here again there areregular and irregular stability sequences which are not readily correlatedwith absorption band shifts.125 Amongst cations of subgroup A of thePeriodic Table the heats of comples fortnation with ENTA are endothermicfor small ions and exothermic for larger ions.l18 For ions of equal size theformation of a complex of a subgroup B ion evolves more heat than that ofa subgroup A ion.In the transition series manganese(r1) to copper (11) it isnot possible to understand the heat terms on any existing theory. Onegreat difficulty with the study of complexes of this ligand is its unknownmode of co-ordination to the different cations. It is often forgotten thatmuch of the theory of complex stabilities applies only to the simplest sym-metry cases9 The structures of the solid complexes are very revealing.Their symmetry is complicated by the different M-0 distances and differentL. A. K.Staveley and T. Randall, ref. 6, p. 157; A. E. Martell, Rec. 'I'rav.chim., 1955, 75, 257; R. H. Betts and 0. F. Dahlinger, Cunad. J . Chem., 1059,37, 91.119 E. Gelles and' G. H. Nancollas, Trans. Faruday SOL, 1956, 62, 98, 680.120 D. H. Templeton and C . H. Dauben, J . Amer. Chem. Soc., 1954, 76,5237.I z 2 A. Sonesson, Actu Chem. Scand., 1958, 12, 165, 1937.123 A. Sonesson, Actu Chem. Scand., 1959, 13, 998.12* R. Harder and S. Chaberek, J . Inorg. Nuclear Chem., 1959, 11, 184.1 2 j \Y. T. Carnal1 and P. R. Fields, J . Amer. Chem. Soc., 1959,81, 4445, and referencesL. Holleck, osterr. Chem. Ztg., 1959, 65.thereinWILLIAMS : ABSORPTION SPECTRA AND STABILITY OF COMPLEX IONS. 107classes of N-C-C-0 ring.126 Other studies of ethylenediaminetetra-aceticacid complexes include work on the different oxidation states of plutonium 127and iron.128 In the latter work five different polyaminocarboxylic acids ofdifferent basicity have been compared and a rough relation between stabilityand basicity has been established.Complexes of NNN'N'-tetrakis(phosph0-methyl) cyclohexane- 1,2-diamine and diethylene triamine-NNiV'N"N''-pent a-acetic acid with series of transition-metal cations 129 have also been studied.The observations strictly parallel those on ENTA complexes.Another frequently studied ligand in this group is 8-hydroxypinolineand its derivatives. This ligand forms the same chelate ring as ENTA andmost amino-acids. It is, however, unsaturated and its complexes with thelater transition metals are relatively more stable than those of subgroup Ametals.8-Hydroxyquinoline stands much higher in the spectrochemicalseries than glycine or ENTA, salicyaldehyde higher than carboxylic acids,and o-phenanthroline higher than eth~lenediamine.~ The stability sequencefor the 5-sulphonic acid derivative is much as expected though there isevidence of dimerisation with higher-valent cations such as iron(II1) andthorium(1v). There is some work 479131 on heats of 8-hydroxyquinoline com-plexes but different methods yield very different results. Detailed spectro-photometric studies have been made on the nickel complexes of 8-hydroxy-7-nitroquinoline-5-sulphonic acid.132There have again been many studies of complexes of amin0-a~ids.l~~Datta, Leberman, and Rabin 13* have continued their detailed analysis ofthese complexes. Amongst a series of peptides there is quite a good relationbetween acid dissociation constant and stability of the complexes of a givenmetal.The stability sequences of metals are much as expected. In thiswork care is needed in deciphering the proton ionisations as it is known thatpeptide, imino, amino, and carboxylic acid groups, and water molecules inthe co-ordination sphere, can ionise. Bennett has studied the stabilityof complexes of optically active ligands and Pelletier 136 the effect of tem-perature on arginine complexes. The heat of reaction between silver(1) andglycine is disconcertingly temperature dependent.13'Co-ordination through aliphatic alcohols has now been studied in several126 H.A. Weakliem and J. L. Hoard, J . Amer. Chem. SOC., 1959, 81, 549; G. S.Smith and J. L. Hoard, ibid., p. 556.12' A. D. Gel'man, P. I. Artyukhin, and A. I. Moskvin, Russ. J. Inorg. Chem., 1969,4, 599.128 J. Bond and T. I. Jones, Trans. Faraday SOL, 1959, 55, 1310.120 C. V. Banks and R. E. Yerick, Analyt. Chiw. Acta, 1959, 20, 301 ; G. Anderegg,P. Nageli, F. Miiller, and G. Schwarzenbach, Helv. Chim. Acta, 1959, 42, 827.13* C. I;. Richard, R. L. Gustafson, and A. E. Martell, J . Amer. Chem. SOL, 1950,81, 1033, 6355.131 D. Fleischer and H. Freiser, J , Phys. Chem., 1959, 63, 260.132 T. Nortia, Suomen Kem., 1959, 32, B, 58.la3 N. C. Li, E. Doody, and J . M. White, J . Amer. Chem. SOC., 1957, 79, 5859;S. G. Shuttleworth and R. L.Sykes, J . Amer. Leather Chemists' Assoc., 1959, 54, 259;see ref. 4 ; R. Osterberg, Arkiv Kemi, 1959, 13, 393.134 S . P. Datta, R. Leberman, and B. R. Rabin, Nature, 1959, 183, 745; idem, Trans.Faraday SOC., 1959, 55, 1982; see N. C. Li and M. C. M. Chen, J . Amer. Chew. SOC.,1958, 80, 5678.135 W. E. Bennett, J . Amer. Chem. Soc., 1959, 81, 246.13* S. Pelletier, Comfit. rend., 1959, 248, 2567.13i S. P. Datta and A. I<. Grzybowski, J., 1069, 1001108 GENERAL AND PHYSICAL CHEMISTRY.cases.l= The lead complexes of monoethanolamine are much less stablethan those of copper and zinc. The hydroxyl groups of gluconic acid ionisein strong alkali.139 The stability sequence 14* for the complexes of o-amino-phenol is CuII > NirI > CoII > MnIl but there is some uncertainty aboutthe stability of the ferrous complex, as insufficient precautions were taken toprevent oxidation.Organic Ligands containing Sulphur.-A considerable number of sulphur-containing ligands have been studied ; these include aliphatic amines incor-porating sulphur,la ~ y s t e i n e , ~ ~ ~ mercapt~acetates,~~~ glutathiones,lUmercapt~purines,~~~ and thiophen01s.l~~ The relative stability sequences inthe transition series are invariably MnrI < FeII < CoII < NiII < CuII > ZnII.However, the increments in the sequences are unusual.Irving 114 has com-pared the results of stability measurements of complexes with the ligandMeX*CH,CH,*N(CH,-CO,H),, where X is (a) oxygen and (b) sulphur.Stronger complexes of (a) than (b) are formed by the subgroup A cations,Mn**, PbII, and ZnII. Stronger complexes of (b) than (a) are formed by Fe*I,C O ~ , NiII, and C U ~ and by Cdn and HgII. This suggests that: (i) ligand (a)is more polar than ligand (6) (this is required to explain the subgroup Aorder); (ii) ligand (b) is more polarisable than ligand (a) (this is required toexplain the results with CdIl and HgII); but (iii) this advantage is off-set byligand size (required to explain why the stability order for ZnII is theopposite of that of CdII and HgII); and (iv) ligand (b) is a better x-electronacceptor than ligand (a) (required to explain the FeII, CoII, and NiII stabilities).(i), (ii), and (iii) mean that R is nearly constant and (iv) that Q is larger inthe transition series with (b) than with (a). Modification of the ligand to (c)HS*CH,*CH,*N (CH,*CO,H), increases the stability of the complexes of MnII,FelI, CoII, NiII, and ZnII, but does not change that of complexes of subgroupA elements.l*' There is no change of Q but a large change of dR. All com-plexes of the cations ZnII, Cdu, Hgl*, and PbII are similarly more stable.This increase in stability is not regular and with zinc(1r) alters the stabilityorder from NiII and CoIr > ZnII for (b) to ZnII > NiII and CoII for (c). Itwould appear that ligand (c) is much more highly polarisable than (b) but isnot as effective as a d, electron acceptor. This appears to be a generaldifference between R-S- and R-S-R. The former increases R while thelatter has its greatest effect on Q. In fact a general method of separatingpolarisation (o-bonding) from x-bonding seems to be provided by the138 R. L. Pecsok and his co-workers, J . Amer. Chem. Soc,, 1955, 77, 202, 1489;189 D. T. Sawyer, K. S. George, and J. B. Bagger, J . Amer. Chem. SOL-., 1959, 81,140 P. Sims, J., 1959, 3648.141 E. Gonick, W. C. Fernelius, and B. E. Douglas, J . Amer. Chenz. Soc., 1954, 76,142 A. Albert, Biochem. J., 1952, 50, 690.143 Q. Fernando and H. Freiser, J . Amer. Chem. Soc., 1958, 80, 4180.144 R. B. Martin and J. T. Edsall, J . Amer. Chem. SOC., 1959, 81, 4044.146 G. E. Cheney, H. Freiser, and Q. Fernando, J . Amer. Chem. Sor., 1959, 81,146 R. G. Charles and H. Freiser, J . Amer. Chem. SOC., 1952, 74. 1385.14' G. Schwarzenbach, G. Anderegg, W, Schneider, and H. Senn, Helv. Chim. Acta,1957, 79, 4069.5893.4671.2611.1955, 38, 1147WILT-TAMS : ABSORPTION SPECTRA AND STABILITY OF COMPLEX IONS. 109comparison of the stabilities of elements such as PbII, ZnII, and NiII.lMConsiderations such as these classify C1-, Br-, and I- with RS- and RO-,and SCN-, CN-, and NCS- with bipyridyl and o-phenanthroline.Change in Spin State of a Complex.-It is now recognised that a changeof spin state on change of ligand is common in the first transition series.149When such a change takes place a number of different energy terms areinvolved so that it is almost impossible to analyse the problem. Some ofthe most important factors150 on change to lower spin are (i) the increasein the number of available bonding d orbitals, (ii) the increase in the electronrepulsion terms C, in the central ion, (iii) the polarisation energy of the centralion, (iv) the change in the field, lODq, due to the ligand because of its in-creased polarisation in the field of the cation, (v) the decrease in the Racahparameter B due to the spreading of the electrons of the cation over theligand, and (vi) increase in steric hindrance due to bond shortening. Theproblem was first discussedll in terms of the balance between factors (i),(ii), and (vi). The specific example chosen was the difference between thecomplexes of ferrous iron with o-phenanthroline and with Z-methyl-o-phen-anthroline. A somewhat similar discussion 9937 can be made by consideringthe balance between (ii), (iii), and (vi) but it has the advantage that it canbe given quantitative expression. Unfortunately in the quantitative treat-ment it is necessary to assume that the field of the ligand is independent ofthe spin state of the cation and that the Racah parameters B and C are inde-pendent of the state of the atom and therefore determinable from atomicspectra. This is not ~0.14 Thus the quantitative treatment of change ofspin state is in danger of giving a false impression of the energy termswhich stabilise low spin complexes. There are now quite a few cases wherea change of spin state has been studied in s01ution.l~~ Apart from the caseof the ferrous-phenanthroline system, where it would appear that thechange of spin state occurs on the addition of the third ligand, there arestudies on nickel and ethylenediamine~,l~~-~~l on nickel and dimethyl-g l y o ~ i r n e , ~ ~ ~ and on ferric porphyrins with ba~es.~,~O In some cases therelation between the successive step equilibrium constants is abnormal inthat the free energy of one of the later steps greatly exceeds that of one ofthe earlier ones.152 If a change of magnetic state occurs without such alarge jump in step constant then we expect an equilibrium mixture ofdifferent magnetic states5* In fact many cases of such equilibria are nowknown where the cation may or may not have the same stereochemistry inthe two spin states. In some cases the stereochemistry is unlikely to bewell defined, e.g., in nickel solutions in dioxan, as solvent interactions withions have an important influence.150 A further difficulty arises if the changeof spin state introduces a change in symmetry of the field. In the case of148 J. Chatt, ref. 3, p. 515.149 J. B. Willis and D. P. Mellor, J . Amer. Chem. Soc., 1947, 69, 1237; F. Basolo,and W. R. Matousch, J . Amer. Chem. SOC., 1953, 75, 5663; R. J. P. Williams, J , , 1955,137.150 C. J. Ballhausen and A. D. Liehr, J . Amer. Chem. SOC., 1959, 81, 538.151 H. C. Clark and R. J. O’Brien, Canad. J . Chem., 1959, 37, 436; L. Sacconi,P. Paoletti, and R. Cini, J . Amer. Chem. SOC., 1958, 80, 3583; M. A. Porai-Koshits,Zhur. neorg. Khim., 1959, 4, 730.lj2 D. Dryssen, F. Krasokec, and L. G. Sill&, A d a Chem. Scand., 1959, 13, 60110 GENERAL AND PHYSICAL CHEMISTRY.ferrous iron the symmetry of the ground and promoted state complexes isoctahedral. In the case of nickel(I1) the preferred stereochemistry of thehigh spin state is of octahedral or tetrahedral symmetry, depending onligand size, while that of the promoted state is tetragonal. Now, dependingupon the strength of the tetragonal element of the field either in roughlyoctahedral or tetrahedral complexes one of the two states of differentmagnetic moment may be the more stable. The Jahn-Teller effect is anadditional factor which must be considered in the case of the tetragonalnickel complexes.The Reporter thanks Dr. C. S. G. Phillips for much help.R. J. P. W.V. GOLD.J. W. LINNETT.J. A. POPLE.J. E. B. RANDLES.J. S. ROWLINSON.T. M. SUDGEN.H. C. SUTTON.R. J. P. WILLIAMS.L. A. WOODWARD

ISSN:0365-6217    

DOI:10.1039/AR9595600007

出版商:RSC    

年代:1959

数据来源: RSC

摘要:

INORGANIC CHEMISTRY1. INTRODUCTIONTHIS year’s Report follows closely the pattern of those of recent years,elements being classified on the basis of the long form of the Periodic Table.General coverage of work published in 1959, rather than a series of reviews,has been attempted; the first volumes of two series devoted to reviews ofrecent work augment considerably the recent review literature of inorganicchemist rj7.l’The choice of a unified scale for atomic weights was discussed at the 1959meeting of the I.U.P.A.C.,3 and, provided the International Union of Pureand -4pplied Physics agrees, it seems certain that the exact number 12 forthe atomic weight of carbon-12 will become the primary standard in 1961.The 1957 Report of the I.U.P.A.C. Commission on Inorganic Nomenclaturehas now appeared.* of Palmer’s“ Valency ” and the collected papers presented at a Symposium on HydrogenBonding.6 Contributed papers to symposia on “ Mechanisms of InorganicReactions ” and “ The Teaching of Inorganic Chemistry ” have also beenpublished.’ The English translation of the Zhurnal neorganicheskoi Khimiiis now appearing.8Reviews have been published on inorganic polymer^,^ clathrate com-pounds,1° stereochemical effects of unshared pairs of electrons,ll quantitativestudies of hydrolytic equilibria,12 perfluoroalkyl derivatives of metals andnon-metals,13 lattice energies of inorganic mechanisms ofredox reactions,15 the Szilard-Chalmers effect in solids,16 graphitic com-pound~,~’ and mixed metal oxides.l8 Many other reviews are mentionedunder individual elements or in the general account of co-ordination com-pounds at the beginning of Section 3.New books include a revised edition“ Advances in Inorganic Chemistry and Radiocheniistry,” ed. H.J. EmelCus2 “ Progress in Inorganic Chemistry,” ed. F. A. Cotton, Interscience Publishers Inc.,and A. G. Sharpe, Academic Press Inc., New York, Vol. I, 1959.New York, Vol. I, 1959.See e.g., Proc. Chem. SOC., 1959, 330.W. G. Palmer, “ T‘alency,’’ C.U.P., 2nd edn., 1959.4 “ Nomenclature of Inorganic Chemistry,” Butterworths, London, 1959.6 “ Hydrogen Bonding,” ed. D. Hadii, Pergamon Press, London, 1959.7 J. Phys. Chem., 1959, 63, 321; J . Chem. Edztc., 1959, 36, 441, 502.8 Russzan Journal of Inorganic Chemistry, The Chemical Society, Landon ; the€I.J. EmelCus, Proc. Chem. SOC., 1959, 202; V. V. Korshak and 1C. K. Mozgova,translated journal a t present begins a t Vol. 4 of the original.TTspekAi Khim., 1959, 28, 783.10 L. Mandelcorn, Chem. Rev., 1959, 59, 827.11 A. W. Searcy, J. Chem. P l y . , 1959, 31, 1 .L. G. SillCn, Quart. Rev., 1959, 13, 146.13 J. J . Lagowski, Quart. Rev., 1959, 13, 233.T. C. Waddington, Ref. 1 , p. 158.15 H. Taube, Ref. 1, p. 1.G. Harbottle and N. Sutin, Ref. I , p. 268.17 W. Rudorff, Ref. 1, p. 224; G. R. Hennig, Ref. 3, p. 125-I* R. \Yard, Ref. 2, p. 465112 INORGANIC CHEMISTRY.Many papers continue to be published on inorganic chemistry in non-aqueous solvent systems; among solvents which have been investigatedduring the past year are acetyl chloride,lg benzoyl brornide,,O molten acet-amide,21 phosphorus oxychloride,22 selenium oxychloride,23 and moltenarsenic and antimony tribromide~.~~ Much of this work is summarised in arecent review.25 The properties of solutions in two well-investigated sol-vents, sulphuric acid 26 and sulphur dioxide,27 have also been criticallyreviewed; it now seems certain that simple self-ionisation according to theequationmust be eliminated as the basis for acid-base type interaction in the lattersolvent.As in the last year’s Report, the chemistry of organic derivatives ofnon-metals and metalloids is not covered systematically; the increasinguse of vacuum technique for the manipulation of volatile alkyl and sub-stituted-alkyl derivatives has led, however, to a blurring of the traditionalboundary between inorganic and organic chemistry in this field, and becauseof the very rapid progress made during the past year accounts of somework on these compounds have been included.2s0, = so,+ + so2-2.TYPICAL ELEMENTSHydrogen.-A review of the catalytic activation of hydrogen by metalions and complexes in solution has been published, and the RhCIe3- ion hasbeen added to the list of cata1ysts.lInterest in very strong hydrogen bonds has continued. A full analysisof the structure of palladium dimethylglyoxime shows that the O-H 0distance is 2.59 A (instead of 2.40 A as reported earlier); on the basis ofthe empirical relations between the 0-H 0 distance and the 0-Hstretching frequency which have been reported, this should correspond to~(0-H) -2450 cm.-l, but the molecule shows no important absorption in thisregion., (It is very surprising to find that in the isomorphous platinumderivative, O-H - 0 is reported to be 3.03 A and, incidentally, themiddle C-C bond of the ligand to be 0.lOA longer than in the palladiumcompound.) A similar state of affairs persists for other compounds1s R.C. Paul, D. Singh, and S. S. Sandu, J., 1959, 316, 319; K. Goyal, R. C. Paul,and S. S. Sandu, J., 1959, 322; B. S. Manhas, R. C. Paul, and S. S. Sandu, J., 1959,325; J . Singh, R. C. Paul, and S. S. Sandu, J., 1959, 845.2O V. Gutmann and K. Utvary, Monatsh., 1959, 90, 751.21 G. Jander and G. Winkler, J. Inorg. Nuclear Chem., 1959, 9, 24, 32, 39.22 V.Gutmann and M. Baaz, Monatsh., 1959, 90, 239, 256, 271, 426, 729, 744; 2.anorg. Chem., 1959, 298, 121.Z3 J. Klikorka and I. Pavlik, Chem. Listy, 1958, 52, 2222.a4 G. Jander and K. Giinther, 2. anorg. Chem., 1958, 297, 81; 1959, 298, 241;G. Jander and I<.-€€. Swart, ibid., 1959, 299, 252.25 V. Gutmann and M. Baaz. Angew. Chem., 1959, 71, 57.26 R. J. Gillespie and E. A. Robinson, Ref. 1, p. 386.87 T. H. Norris, J. Phys. Chem., 1959, 63, 383; J. L. Huston, ibid., p. 389.J . Halpern, J. Phys. Chem., 1959, 63, 398; J. F. Harrod and J. Halpern, Canad.D. E. Williams, G. Wohlauer, and R. E. Rundle, J. Amer. Chem. SOL, 1959,81, 755.J . Chem., 1959, 11, 1933.a E. Frasson, C. Panattoni, and R. Zannetti, Acta Cryst., 1959, 12, 1027containing short hydrogen bonds (e.g., potassium phenylacetate), and thevalidity of these relationships now appears d ~ u b t f u l .~ A preliminaryaccount of the structure of sodium hydrogen diacetate gives 0-H - - 0as 2-42 A in this compound; the infrared absorption spectrum does notappear to have been investigated. Mention of many other structures whichcontain hydrogen bonds is made elsewhere in this report.Group 1.-The properties of solutions of aIkali (and alkaline-earth) metalsin liquid ammonia and amines have been reviewed.6 Lithium borohydridehas been shown to form compounds with one, two, three, and four moleculesof ammonia.' Ammoniates of potassium, rubidium, and czsium amideshave been described, and a survey of the crystal structures of the alkali-metal amides has been given.*Pure lithium selenide, obtained by interaction of the elements in a sealedtube at 300°, is cream in colour, but turns red and liberates hydrogen selenideon exposure to air (hence previous reports that the cornpound is red).9 Astudy of the system NaF-HF-H,O a t 0" and -15' reveals the existenceof the following compounds : NaHF,; NaF,2HF; NaF,3HF; NaF,4HF.laThin sheets of czesium chloride evaporated on to an amorphous film carrierhave the NaCl structure; the Cs-Cl distance is 3.474& compared with3-566 A in ordinary body-centred cubic czesium chloride.llGroup 11.-Pure magnesium iodide may be obtained by the action ofmagnesium powder on molten mercuric iodide.12 In the system Mg(OH),-H,O,-MgO,, Mg(OH), and MgO, are the only solid phases; the lattercompound, like zinc and cadmium peroxides, has the pyrites structure withan 0-0 distance in the peroxide ion of 140A.Strontium peroxide octa-hydrate contains chains of composition -0,2--(Hz0),-022--(H20)8- inwhich strong hydrogen bonds hold the units together. The structure of thecompound BaO,,H,O, consists of Ba2+ ions and infinite helical chains ofperoxide groups, held together by hydrogen bonds.13A neutron-diffraction study of gypsum, CaS04,2H,0, shows that thesulphate ion contains two types of S-0 bond; two S-0 distances are1.479 5 0-010 and two 1-497 0.014 A, the latter being those of the S-0bonds which are hydrogen bonded to water molecules. There is, however,no significant departure from the tetrahedral angle for the sulphur ~a1encies.l~Confirmation that calcium carbide contains an acetylide ion has a t last beenprovided by another neutron-diffraction investigation : the C-C distanceis 1-20 A, much less than those in Lac, (1.28 A) and UC, (1.34 A), both ofwhich are metallic conductors (calcium carbide is an insulator).It is* N. Albert and R. M. Badger, J . Chem. Phys,, 1958, 29, 1193.J. C. Speakman, Proc. Chem. Soc., 1959, 316.M. C. R. Symons, Quart. Rev., 1959, 13, 99; W. 1,. Jolly, " Progress in InorganicE. A. Sullivan and S. Johnson, J . Phys. Chern., 1959, 63, 233.R. Juza and A. Mehne, 2. anorg. Chem., 1959, 299, 33, 41.W. D. Johnston and R. R. Heikes, J . Amer. Chem. SOC., 1958, 80, 5904.Chemistry," 1959, 1, 235.lo J.S. Morrison and A. W. Jache, J . Amer. Chem. SOC., 1959, 81, 1821.l1 K. Meyerhoff and J. Ungelenk, Acta Cryst., 1959, 12, 32.l2 J. O'M. Bockris and E. H. Crook, Chem. and Ind., 1959, 1163.l3 N.-G. Vannerberg, Arkiv Kemi, 1959, 14, 17, 99, 115, 125, 147; C. W. W. Hoff-l4 M. Atoji and R. E. Rundle, J . Chem. Phys., 1958, 29, 1306.mann, R. C. Ropp, and R. W. Mooney, J . Amer. Chem. Soc., 1959, 81, 3830114 I NOHG ANT(' CHEMISTRY.suggested that in the lanthanum and uranium compounds one or moreelectrons from the formally dipositive cation is in an antibonding orbital ofthe C22- ion which may overlap with a conduction band in the solid state.15Group 111.-Boron.' The enrichment of boron in boron-10 by means ofthe reactionAnisole,llBF,~li,~ + 1°BF3(,, a Ani~ole,~~BF,~~~,~ + 11BF3c,,for which the enrichment factor (l0B/l1B) (liq)/(l0B/l1B) (g) is 1.029 at 25",is a useful laboratory method; l6 an alternative process makes use of thet-butyl sulphide complex of boron triflu0ride.l' In a new method for thepreparation of elemental boron, a melt of potassium fluoroborate, potassiumchloride, and potassium fluoride is electrolysed a t 800", a Monel-metalcathode and a graphite anode1* being used.A new (rhombohedral) formof boron has been obtained by pyrolysis of boron tri-iodide vapour on tanta-lum, tungsten, or boron nitride a t 800-1000". The structure consists ofnearly regular icosahedra in a slightly deformed cubic close packing; halfthe boron atoms in an icosahedron are bound by conventional single bonds toatoms of other icosahedra, and each of the remaining atoms participates ina three-centre bond with two atoms from two different neighbouring icosa-hedra.lg Bonds within the icosahedron range from 1.73 to 1.79 A, conven-tional bonds to other icosahedra are 1.71 A, and three-centre bonds are2-03 A.Two reviews20921 of the structures of the boron hydrides give accountsof attempts to place them on a systematic basis; the discovery of newhydrides and of ions derived from them will be useful in testing structuraltheories.Diborane is formed from silane and boron trichloride in the presence ofmethyl radicals generated by the photochemical decomposition of azo-methane.22 It does not react with boron trichloride in the absence ofethers; in their presence, reactions according to the schemesB2H6 -t BCI3 + 3RzO 3RZ0,BHzCIB,H, + 4BC13 4- 6R20 6R20,BHC12take place.The formation of these products accounts for the low yield ofdiborane when alkali-metal borohydrides are treated with excess of borontrichloride in ethereal so1utions.a The interaction of diborane and silyl ortrimethylsilyl cyanide results in the formation of an adduct H,SiCN,EH, orMe,SiCN,BH, ; when this is heated the corresponding silyl hydride iseliminated and a solid polymer (BH,CN),, which is only slowly hydrolysedl5 M. Atoji and R. C. Medrud, J. Chem. Phys., 1959, 31, 333.l6 A. A. Palko, Ind. Eng. Chem., 1959, 51, 121.l7 A. A. Palko, J. Chem. Phys., 1959, 30, 1187.l8 G. T. Miller, J.Electrochem. Soc., 1959, 106, 815.19 B. F. Decker and J . S. Kasper, Acta Cryst., 1959, 12, 503.2o VC'. N. I,ipscomb, " Advances in Inorganic Chemistry and Radiochemistry," 1959,21 R. W. Parry and L. J . Edwards, J. Amev. Chem. Soc., 1959, 81, 3554.2% R. Schaeffer and L. Ross, J. Amer. Chrm. SOC., 1959, 81, 3486.23 H. C. Brown and P. A. Tierney, J. Inorg. Nuclear Chem., 1959, 9, 51.1, 118SH.IHPE TYPICAL f3IXMENTS. 115by hot water, is formed.= The di-n-butyl analogue of this polymer is aviscous liquid obtained from the compounds Bun2BC1 and Me,SiCN orAgCN; this substance, on treatment with sodium in liquid ammonia, givesthe hitherto unknown monomeric compound B U ~ ~ B O N H ~ . ~ ~ The trimer(Me2N*BH2), has been obtained by heating the dimeric compound withpentaborane.26 Diborane reacts with thiophan and diethyl sulphide toyield the compounds (CH,),S,BH, and Et,S,BH,; borane forms much morestable adducts than boron trifluoride with these thio-ethers, whereas thereverse is true for ordinary ethers.Moreover, adducts like Et,S,BH, aremuch more stable than their oxygen analogue^.^'Trimethylboron can be prepared by the action of the compound Me3Al.&13on boric oxide or borax at 100-170" or on butyl borate at room temper-ature.2s Alkylated boranes may be obtained by the interaction of sodiumborohydride, hydrogen chloride, and boron trialkyls at 150-175" ; the useof lithium borohydride or lithium aluminium hydride enables lower temper-atures to be employed.29 Alkylboranes are also formed when triethylamine-borane reacts with olefins (e.g., isobutene, hex-1-ene) a t 200" in the absenceof a ~olvent.~OAn X-ray diffraction study of the compound (NH3)2BHzCl shows thatthis substance is really [(NH3)2BH2]+C1-; since it results from the interactionof ammonium chloride and the " diammoniate of diborane," further evidencefor the formulation of the latter compound as [(NH,),BHI,J+BH,- is pro-vided.,l The velocity of hydrogen production in the reaction betweensodium borohydride and water shows that one hydrogen atom of the BH,-ion reacts faster than the others; the presence of the intermediate ionBH3*OH- has been proved by the isolation of a sodium salt and the studyof its infrared spectrum.32Ammonia-triborane, H,N*B,H,, may be obtained by the action ofammonium chloride on the compound NaB,H8 in the presence of etherat 25":An alternative method utilises the reactionsNaB3H, + NH&I + H, + H,N*B,H, + NaC2 5 OEtgO-78"B,HlO + R2O 4 #32H, + R20B,H,R,OB,H, + NH, __t H,N.B,H, + R,Obest yields being obtained when R20 = tetrahydrofuran.% The compoundis dimorphic, a disordered tetragonal form being stable at 25", and an24 E.C. Even, W. 0. Freitag, J. N. Keith, W. A. Kriner, A. G. MacDiarmid, andS. Sujishi, J . Amer. Chem. SOC., 1959, $1, 4493.25 E. C. Even, W. 0. Freitag, W. A. Kriner, and A. G. MacDiarmid, J . Amer. Chem.SOC., 1959, 81, 5106.26 G. W. Campbell and J. Johnson, J . Amev. Chem. Soc., 1959, 81, 3800.27 T. D. Coyle, H. D. Kaesz, and F. G. A.Stone, J . Amer. Chem. SOC., 1959,81, 2989.26 7. Iyoda and I. Shiihara, Bull. Chem. SOC. Japan, 1959, 32, 304.29 L. H. Long and M. G. H. Wallbridge, Chem. and Ind., 1959, 295.30 E. C. Ashby, J . Amer. Chem. SOC., 1959, 81, 4791.s2 J. Goubeau and H. Kallfass. 2. anorg. Chem., 1959, 299, 160.33 G. Kodama, R. W. Parry, and J. C. Carter, J . Amer. Chem. SOC., 1959, 81, 3534.C . E. Nordman and C. R. Peters, J . Anzer. Chem. Soc., 1959, 81, 3551116 IN OKG AN TC CI1 r? &I T ST R Y .ordered nionoclinic form at lower temperatures. The molecules of bothmodifications contain a triangle of boron atoms with a non-coplanar NH,group at one corner; the arrangement of hydrogen atoms suggests that theB,H7 group is a strongly distorted fragment of the B4H10 molecule, but thealternative description of the compound H,N-B,H, as a bridge-substituteddiborane, (H,NBH,)B2H5, cannot be eliminatedxThe dipole moment of tetraborane is 0.56 4 0.1 D .~ The complexkinetics of deuterium exchange between B2D, and B4H10 have been studied;boron atoms also exchange, but detailed investigations have not yet beenreported.36 A polyhorane carbonyl B4H,C0 has been obtained by thesealed- t ube reactionBZH,, + 2CO ___) BkHaCO + BHSCOat 25", and its vapour pressures have been rec0rded.~7A compound of formula B2H203 has been identified as an intermediatein the partial oxidation of the borane B5H,, and the structure (1) is suggestedfor it on the basis of infrared and nuclear magnetic resonance studies.=Hexaborane, B,H,,, results from the complex reactions whichtake place between the pentaborane B,Hll and trimethyl-amine or ethers.= In a mass-spectrometric examination ofa sample of crude tetraborane, evidence for the existence of aheptaborane, perhaps B7H13 or B,H,,, was obtained.40Decaborane forms adducts with one, two, and three mole-compounds with four and five molecules of amine; a t 0" thesecompounds decompose, forming unidentified products.41 It also forms acomplex with three molecules of pyridine which is stable at 105" and doesnot react with trimeth~lamine.~~ Decaborane in acetonitrile can be titratedas a monobasic acid with aqueous alkali,43 but the statement that indimethylformamide it functions as a dibasic acid is incorrect.& The Grignardreagent BloH,MgBr is formed from decaborane and methylmagnesiumiodide in ether; with alkyl fluorides it yields alkyl derivatives of de~aborane.~~In the compound B,,H,,(CH,*CN), acetonitrile molecules replace hydrogenatoms on the two end boron atoms in BloH14; there is little change in theboron framework or in the acetonitrile group when the molecule is formed.46Since the replacement of a hydrogen atom by an acetonitrile group resultsH I /r\ '\y yo B( I )I cules of dimethylamine, and phase studies provide evidence for34 C .E. Nordman and C. Reimann, J . Amer. Chem. SOC., 1959, 81, 3538.35 J. R. Weaver, C. W. Heitsch, and R. W. Parry, J . Chem. Phys., 1959, 30, 1075.36 J. E. Todd and W. S. Koski, J . Amer. Chem. SOC., 1959, 81, 2319.37 A. B.Burg and J. R. Spielman, J . Amer. Chem. SOC., 1959, 81, 3479.38 J. F. Ditter and I. Shapiro, J . Amer. Chem. SOC., 1959, 81, 1022.39 J. L. Boone and A. B. Burg, J . Amer. Chem. Suc., 1959, 81, 1766.40 R. W. Schaefer, K. H. Ludlum, and S . E. Wiberley, J . Amer. Chem. SOC., 1959,41 S. J. Fitch and A. W. Laubengayer, J . Amev. Chem. SOC., 1958, 80, 5911.4a L. Burkhardt and N. R. Fetter, Chem. and I n d . , 1959, 1191.43 R. W. Atteberry, J . Phys. Chem., 1958, 62, 1458.44 J. V. Griffiths and R. L. Williams, Chem. and I n d . , 1959, 655.45 J. Gallaghan and B. SiegeI, J . Amer. Chem. SOC., 1959, 81, 504.46 J. van der M. Reddy and W. N. Lipscomb, J . Chem. Phys., 1959, 31, 610.81, 3157SHARPE: TYPICAL ELEMENTS. 117in the addition of an electron, the compound is formulated electronicallyas (2).The acetonitrile may be displaced by diethylcyanamide or triphenyl-phosphine or may add primary amines across the CZN bond to give C-sub-stituted imine derivatives of decaborane (3),1. - - +CH,~Lt:N-B,,H,,-N~C-CH, (2)+ - - +C H 3-C=N-B,,H ,,-N=C-C H , (3) / I H R I I R HTrimethylamine gives two products, one analogous to the triphenyl-phosphine complex, and the other a benzene-insoluble substance displayingan N-H stretching frequency in the infrared region; this may be a saltcontaining the B,,HIo2- ion.47 The exchange of deuterium between deca-borane and deuterium oxide in dioxan occurs most rapidly with the bridgehydrogen atoms; of the terminal hydrogen atoms, those on boron atomsnumbered 6 and 9 in the decaborane (4) exchange fastest and those onatoms 1 and 3 slowest. Under electrophilic conditions (decaborane incarbon disulphide in the presence of deuterium chloride and aluminiumchloride), exchange takes place at the terminal positions on boron atoms2, 4, 6, 7, 8, and 10, and not in the bridges.483(4)The use of a reduced cobalt oxide on pumice as a catalyst greatly im-proves yields in the synthesis of borazole from ammonium chloride andboron tri~hloride.~~ Tri-B-alkoxytri-N-methylborazoles may be preparedby the action of sodium derivatives of alcohols and phenols on tri-B-chloro-tri-N-methylb~razole.~~ Interaction of boron trichloride and primaryamines 51 yields triamino-derivatives of boron which on pyrolysis affordB-aminoborazoles and then stable polymers of formula (5).Many chemical properties of diboron tetrachloride have been described.Chlorine, bromine, and oxygen cleave the boron-boron bond even below O",with the formation of trihalides and boric oxide; cyanogen is added, formingthe compound B,C1,,1*5C,N2 (boron trichloride combines with 0.5 or 1 moleof cyanogen) ; phosphine forms the stable compound B2C1,,2PH,.Watei-47 M. F. Hawthorne and A. R. Pitochelli, J . Amer. Chem. SOC., 1958, 80, 6685;46 I. Shapiro, M. Lustig, and R. E. Williams, J . Amer. Chem. SOC., 1959, 81, 838;49 H. J. Emele'us and G. J. Videla, J., 1959, 1306.50 M. J. Bradley, G. E. Ryschkewitsch, and H. H. Sisler, J . -4mer. Chem. SOL., 19.59,61 D. W. Aubrey and M. F. Lappert, J., 1959, 2927.1959, 81, 5519.J.A. Dupont and M. F. Hawthorne, ibid., p. 4998.81, 2635118 INOKGANIC CHEMISTRY.effects hydrolysis to the lower boric acid B,(OH), and hydrogen chloride a troom temperature ; at 160", decomposition occurs according to the reactionB&I, + 6H,O + 2H3B0, + 4HCI + H,Hydrogen sulphide combines at low temperatures, giving the adductsB,Cl,,H,S and B2C1,,2H,S, but a t room temperature boron trichloride,hydrogen, and the sulphide B,S, are produced. Dimethyl sulphide, how-ever, forms stable addition compounds B,Cl,,Me,S and B,C14,2Me,S. Thecompound BCl,=SH, the oxygen analogue of which is unknown, is formed asa by-product in the reaction with hydrogen ~ulphide.~, The B-B bondenergy in diboron tetrachloride, obtained from the heat of the reaction withchlorine, the B-Cl bonds in B,Cl, and BCl, being assumed to be identical,is 79 k ~ a l .~ ,Tetrachloroborates and chlorotrifluoroborates of the NO+, PH4+, andorganic cations have been obtained by the interaction of chlorides andboron trichloride or trifluoride in anhydrous hydrogen chloride as solvent .aTri-a-naphthylboron reacts with one equivalent of sodium in tetrahydro-furan to form a paramagnetic solution of the sodium salt of the tri-a-naphthylboron anion ; in diethyl ether a diamagnetic dimeric anion isproduced. The sodium salt in the solid state is diamagnetic (and therefore,presumably, is a polymer); the disodium salt is always diamagnetic, aswould be expected.%The existence of the solvated Ph2B+ cation in ethyl methyl ketonewas reported last year; a solid 2,2'-bipyridyl complex (Ph,Bbipy)ClO, hasnow been obtained from the products of the reactionPh2BCI + AgCIO, __t AgCl+ Ph2BCIOdin nitromethane; 2,2'-bipyridyl is then added, and the complex is precipit-ated by ether.56 Contrary to earlier reports, .boron trifluoride does notform a compound with sulphuric acid; boron trichloride reacts vigorouslywith the acid to give boron tri(hydrogen sulphate), B(HSO,),, a whitedeliquescent powder which combines with sulphuric acid to form the complexacid HB(HS0,),.57Because of their importancein polymerisation catalysts, compounds of aluminium alkyls have continuedto attract attention.58 Infrared studies show that in the systemA1,Me4C1,-TiCl, the compounds Al2Me,C1, and TiMeC1, are present .59Although the Ziegler catalyst which results from the interaction of diethyl-aluminium chloride and biscyclopentadienyltitanium dichloride is the com-pound (C,HJ2TiC1,A1Et,, the presence of an unidentified titanium(1v)species is essential for the polymerisation of ethylene, and the rate of poly-52 E.F. Apple and T. I<. Wartik, J . Amer. Chem. SOC., 1958, 80, 6153, 6155, 6158.53 S. R. Gunn, L. G. Green, and A. I. Von Egidy, J . Phys. Chem., 1959, 63, 1787.54 T. C. Waddington and F. Klanberg, Naturwiss., 1959, 20, 578.55 C . W. Moeller and W. K. Wilmarth, J . Amer. Chem. SOC., 1959, 81, 2638 (cf.56 J. M. Davidson and C. M. French, Chem. and Ind., 1959, 750.57 N. N. Greenwood and A. Thompson, J., 1959, 3643.58 K.Ziegler, Chem. SOC. Special Publ., 1959, N o . 13, 1.59 M. P. Groenewege, 2. phg's. Chem. ( I ; ~ a n k f u ~ l ) , 1958, 18, 147.Aluminium, gallium, indium, and thallium.T. L. Chu and T. J. Weismann, ibid., 1956, 78, 23)SHARI'E: TYPICAL ELEMENTS. j 11)merisatiori can be controlled by regulation of the oxygen content of theet hylene.60 The system tri-isobu t ylaluminium-ti t anium tetrachloride cata-lyses the trimerisation of symmetrical acetylenic compounds to hexa-substituted benzenes .61 Titanium tetrachloride, aluminium, aluminiumchloride, and benzene interact to give the compound Al,TiCl,Ph, probably(6), which effects polymerisation of ethylene and propene.62Gallium trifluoride, obtained by heatingthe metal in hydrogen fluoride a t 500°, isisomorphous with ferric fluoride ; the com-pounds NH,GaF, and NH,AlF, are also [ c'\T,/C'\*,/Ph ] AICI,(6) isomorphous.63 A large number of co-ordination compounds of gallium dichloride(now well established to be Ga+GaCl,-) with ketones, ethers, amines, andother compounds have been described, and have been shown to have thegeneral structure [GaL4] +[GaCl,] -, where L is the monodentate ligand.64Complexes of gallium dibromide are similar.It has been shown that galliumcan take part in heteropolyanion formation, and salts containing the[GaRlo,0,J3- ion have been prepared.G5The only products of the reaction between thallic chloride and sodiumhydroxide in aqueous solution are the hydroxide Tl(OH), and sodiumchloride ; unlike aluminium, gallium , and indium, thallium does not formbasic salts under these conditions.66Group 1V.-A review of the preparation and properties of cyanogen hasbeen given.67 Cyanogen fluoride, concerning the existence of which therehas been much discussion, has been fairly conclusively identified by spectro-scopic methods among the products of the fluorination of cyanogen.68 Anew method for the preparation of cyanogen chloride is the action of chlorineon an aqueous suspension of potassium cyanozincate a t room tem~erature.,~The crystalline compound formed by the polymerisation of hydrogencyanide is a dimer of structure N-C*CH=NH.'OVery pure silicon is obtained by decomposition of silane (made fromsilicon tetrachloride and lithium aluminium hydride) on a hot silicon surfaceby means of radio-frequency heating.'l The mixture of silanes whichresults from the interaction of magnesium silicide and dilute phosphoricacid has been separated by gas-liquid chromatography; nuclear magnetic6o D.S. Breslow and N. K. Newburg, J . Amar. Chenz. Soc., 1959, 81, 81.61 B. Franzus, P. J. Canterino, and R. A. Wickliffe, J . Amer. Chcun. SOC., 1959, 81,62 G. Natta, G. Mazzanti, and G. Pregaglia, Gazzetta, 1959, 89, 2066.63 F. M. Brewer, G. Garton, and D. M. L. Goodgame, J . Inorg. Nuclear Chcm., 1959,64 S. M. Ali, F. M. Brewer, J. Cadwick, and G. Garton, J . Inorg. Nuclear Chem., 1959,65 B. N. Ivanov-Emin and Y . I. Rabovik, Zhur. neorg. Khim., 1958,3,2429; 0. W.66 M. A. Glushkova, Zhur. neorg.Khim., 1959, 4, 1657 [J. Inorg. Chenz. (U.S.S.H.),67 T . K. Brotherton and J. W. Lynn, Chem. Rev., 1959, 59, 841.68 E. E. Aynsley, R. E. Dodd, and R. Little, Proc. Chew. Soc., 1959, 265.69 H. Schroder, Z. anorg. Chem., 1958, 297, 296.i o T. Wadsten and S. Andersson, A d a Chem. Scand., 19.59, 13, 1069.71 J. M. Wilson, Resenrch, 1969, 12, 91.C I / \Cl' ' c ,1514.9, 56.9, 124.Rollins and J. E. Earley, J . Amer. Chem. Soc., 1959, 81, 5571.1959, 4, 7471120 INORGANIC CHEMISTRY.resonance studies show that, in addition to the hydrides already known,two isomers of formula Si,H,, and higher members of the series are present.(Seven products have been shown to be formed in the analogous reactionwith magnesium germanide.72) Monosilane reacts with methanol to yielda mixture of methoxysilanes, the reaction being catalysed by metalliccopper.73 Infrared and Raman spectroscopy show that the configurationround the sulphur and selenium atoms in silyl sulphide and selenide is notlinear; 74 the planar configuration round the nitrogen atom in trisilylaminehas, however, been confirmed.75 Hexamethyldisiloxane, Me,Si*O-SiMe,, isa non-donor solvent, and iodine forms a purple solution in it; aluminiumchloride decomposes it, giving the compounds Me,SiCl and Me,Si*O.AlCl,,and aluminium bromide reacts ~imilarly.7~'' Silicon monoxide," obtained from silicon and silica by quenching thevapour, is found by X-ray investigations to be a mixture of the startingmaterials; 77 this does not, of course, preclude the existence of SiO as anunstable intermediate solid phase.Silicon imide, Si(NH),, may be pre-pared from silicon tetrachloride and liquid ammonia; it decomposes whenheated, forming ill-defined polymers of approximate composition Si,(NH),N,and Si,(NH)N2, then Si3N4.78 A phosphide Si,P is obtained from silane andphosphine a t 450"; it is a blue-black amorphous substance which a t 600"decomposes into silicon and the phosphide SiP.79 The wurtzite form ofsilicon carbide has been obtained80 by the thermal decomposition of tri-chloro(methy1)silane in hydrogen at 1500".It is not possible to review here substantial developments in the organicchemistry of silicon; attention may, however, be directed to a review 81 ofthis subject and to recent papers on polymeric silicon-methylene com-pounds s2 and on the mechanism of substitution a t a four-co-ordinatedsilicon at0rn.8~ The preparation and properties of adducts of amines andsilicon halides (and the corresponding germanium and tin compounds) havebeen described.84As was mentioned earlier, evidence for the existence of higher germaneshas been obtained,72 and a tetra- and a penta-germane have been identifiedamong the products of the action of 10% hydrochloric acid on magnesiumgermanide.= Hexachlorodigermane, Ge,Cl,, may be prepared by the72 K.Borer and C. S. G. Phillips, Proc. Chem. SOG., 1959, 189.73 B. Sternbach and A. G. MacDiarmid, J . Amer. Chem. SOC., 1959, 81, 5109.74 E. A. V. Ebsworth, R. Taylor, and L. A. Woodward, Trans.Faraday SOC., 1959,c5 H. Kriegsnian and W. Forster, Z. anorg. Chem., 1959, 298, 212.'~3 A. H. Cowley, F. Fairbrother, and N. Scott, J., 1959, 717.77 G. W. Brady, J . Phys. Chem., 1959, 63, 1119.78 0. Glemser and P. Naumann, 2. anorg. Chem., 1959, 298, 134.79 G. Fritz and H. 0. Berkenhoff, 2. anorg. Chem., 1959, 300, 205.8o K. M. Merz and R. F. Adamsky, J . Amer. Chew. Soc., 1959, 81, 250.81 D. Wittenberg and H. Gilman, Quart. Rev., 1959, 13, 116.s2 G. Fritz and B. Raabe, 2. anorg. Chew., 1959, 299, 232; G. Fritz and J. Grobe,ibid., p. 302.83 L. H. Sommer and C . L. Frye, J . Amer. Chem. Suc., 1959, 81, 1013; R. H. Prince,.I., 1959, 1783.84 J. E. Fergusson, D. K. Grant, R. H. Hickford, and C. J. Wilkins, J., 1959, 99;E. Bannister and G.W. A. Fowles, J., 1959, 310.85 E. Amberger, Angem. Chem., 1959, 71, 372.55, 211SHA4RPE : TYPICAL ELEMENTS. 121microwave discharge method from germanium tetrachloride vapour.*6Although hexachlorogermanates have been prepared, germanium tetra-chloride (unlike stannic chloride) does not function as an acid in liquidhydrogen chloride.87Conductometric titration of sodium and dimethylstannane in liquidammonia indicates the formation of the compounds SnMe,Na,, SnMe,HNa,and (SnMe,Na),; the last compound, which can be obtained pure and isstable at room temperature, reacts with ammonium bromide to give di-methylstannane and a polymer of empirical formula SnMe,, and withmethyl iodide to give hexameth yldistannane . 88 Trime t h ylplumbane,Me,PbH, is formed in the reaction between trimethylchloroplumbane andpotassium borohydride in liquid ammonia a t -33"; the compoundMe,PbBH,, from which ammonia subsequently removes a borane group, isprobably first pr0duced.8~ Trimethylplumbane decomposes above - loo",probably forming methane and the hydride Me,Pb*PbMe,H.Tetramethyl-lead reacts with pentafluoroethyl iodide under the influence of heat or ultra-violet light to give the compound Me,PbC,F,.SoA structure of outstanding interest is that of bisthiourealead(I1) chloride,in which the lead atoms are seven-~o-ordinated.~~ Each lead atom has 2sat 3-02, 2s at 2.92, and 2Cl at 3-17 A; all of these are shared with neigh-bouring lead atoms in a chain polymer, and the configuration round thelead is roughly that of a trigonal prism; in addition, each lead has onemore chlorine atom (not shared) near the centre of a lateral face of theprism, at a distance of 2.75 A.Solid ammonia has an approximately face-centredcubic structure, the lone pair of electrons apparently being involved inhydrogen bonding to three other molecules ; this precludes the possibilityof inversion of the molecule in the solid state, a conclusion also supportedby infrared spectroscopic evidence.s2 Ammonia hydrate, NH,,H,O, con-tains chains of water molecules linked by hydrogen bonds of length 2-78 A;these chains are cross-linked by ammonia molecules into a three-dimensionalnetwork by 0-H - - N and 0 .- H-N bonds of length 2-78 and 3.25 (meanvalue) , respe~tively.~~ Glow-discharge electrolysis of liquid ammonia,ammonium nitrate being used as an inert electrolyte, leads to the productionof h y d r a ~ i n e .~ ~ A phase study9* of the NH,-H,O, system shows theexistence of two compounds, NH,,H,O, (m. p. 24") and 2NH,,H,O, (whichmelts incongruently a t -133").Tetrafluorohydrazine, first made by the heterogeneous reduction ofnitrogen trifluoride with metals, is also produced, together with difluorodi-imine, N,F,, in the homogeneous reaction of the trifluoride with mercuryGroup V.-Nitrogen.R6 D. Shriver and W. L. Jolly, J . Amer. Chevn. SOC., 1958, 80, 6692.87 T. C . Waddington and F. Klanberg, Naturwiss., 1959, 20, 578.88 S. F. Kettle, J., 1959, 2936.8Q R. Duffy and A. K. Holliday, Proc. Chem. Soc., 1959, 124.no H.D. Kaesz, J. R. Phillips, and F. G. A. Stone, Chem. and Ind., 1959, 1409.91 M. Nardelli and G. Fava, Acta Cryst., 1959, 12, 727.w I. Olovsson and D. H. Templeton, Acta Cryst., 1959, 12, 827, 832.93 A. Hickling and G. R. Newns, Proc. Ghern. SOC., 1959, 272, 368.94 K. E. Mironov, Zhur. neorg. Khim., 1959, 4, 153 u. Inorg. Chem. (U.S.S.K.),1959, 4, 621122 ZNORGANIC CHEMISTRY.in an electric discharge.95 Difluorodi-imine is also obtained, with nitrogentrifluoride, by electrolysis of ammonium fluoride in anhydrous hydrogenfluoride; cis- and trans-forms can be separated by distillati~n.~~ The com-pound reacts with acidified iodide solution :NZF, + 21- N, + 12 + 2F-Difluoroamine, NHF,, has been obtained as one product of the fluorinationof urea,97 or, in small amounts, by the reaction between nitrogen trifluorideand arsenic at 250-300" (the source of the hydrogen is not menti~ned).~~It melts at -116", boils at -23.6", and is explosive; aqueous hydriodicacid decomposes it rapidly:NHF, $- 4HI 21, -t NHdF 3- HFAttempts to repeat Ruff and Staub's preparationg9 of the compound byelectrolysis of ammonium hydrogen fluoride have not been succe~sful.~~A review of the inorganic azides has been given,100 and the mechanismof the azide-nitrite reaction has been studied.lO1 In the presence of excessof perchloric acid at 0" there are two mechanisms:N,-NO,- + H,NO,+ N20, + H,O -% N,*NO +- NO2- N2 4- N20slow fast fastHN, + H,NO,+ __t N,*NO + H,Of -+ N, + N,Oslow fastIn a sodium azide-hydrazoic acid buffer the rate-determining step isN3-+ H,NO,+ __f N3*N0 -b H20slowand is followed by rapid decomposition of the nitrosyl azide.Oxygenexchange between nitrous acid and water proceeds via the formation ofdinitrogen trioxide a t high concentrations and via the formation of theH,NO,+ ion at low concentrations.lo2 The structure of dinitrogen trioxidehas been discussed, and it is concluded that it is O,N*NO with a x-onlyN-N bond.lNElectrical conductance and transport measurements show that dinitrogentetroxide in nitric acid is almost completely dissociated into NO+ and NO,-ions.lW Several new salts of the NOf ion, including those of condensedphosphoric acids lo5 and fluoro-acids of Group IV elements,lo6 have beendescribed.An outstanding contribution to the literature of phosphorus Phosphorus.95 J, W.Frazer, J. Inorg. Nuclear Chem., 1959, 11, 166.D6 M. Schmeisser and P. Sarton, Angew. Chem., 1959, 71, 623.97 E. A. Lawton and J . Q. Weber, J. Amer. Chem. SOC., 1959, 81, 4755.98 A. Kennedy and C. B. Colburn, J. Amer. Chem. SOC., 1959, 81, 2906.99 0. Ruff and L. Staub, Z. anorg. Chem., 1931, 198, 32.100 B. L. Evans, A. D. Yoffe, and P. Gray, Chem. Rev., 1959, 59, 515.lol G. Stedman, J., 1959, 2943, 2949.102 C. A. Bunton, D. R. Llewellyn, and G. Stedman, J., 1959, 568; C. A. Bunton103 J . Mason (Banus), J., 1959, 1288.l o 4 J. D. S. Goulden, W. H. Lee, and D. J . Millen, J., 1959, 734.lo5 F. Seel, R. Schmutzler, and K. Wasem, Angew. Chem., 1950, 71, 340.lo6 P.Bouy, Ann. Chim. (France), 1959, 4, 853.and G. Stedman, J., 1959, 3466SHARPE TYPICAL ELEMENTS. 123chemistry has been the publication of Volume I of Van Wazer's b00k,l07which includes a full and authoritative account of the oxyacids and theirsalts. Other reviews dealing with various aspects of the chemistry of theelement include those on condensed phosphates,loS metal complexing byphosphates ,log and the phosphonitrilic ha1ides.ll0A yellow solid hydride, (PH),, is obtained, together with some phosphinc,by the action of lithium hydride on phosphorus trichloride or tribromide inether, preferably a t -30". The compound is insoluble in all the usualsolvents; when heated ifi vaczco at 500°, it decomposes into phosphorus andphosphine.lll The chloride P,C14 has been obtained by mercury-dischargereduction of the trichloride and condensing out the white solid a t -45";it melts at -35" and decomposes a t room temperature, forming the tri-chloride and non-volatile yellow solids.Attempts to replace the chlorineby fluorine were unsuccessful.l12 The physical properties of the mixedhalide PCl,F, have been re-examined, and it has been shown 113 that itundergoes a slow transformation into the ionic form PCl,+PF,-.The cyclic polymers (CF,P), and (CF,P), (m. p. 66" and -33", b. p. 145"and 190", respectively) are made by the action of mercury on the com-pound CF,PI, at room temperature, or (together with higher polymers)by pyrolysis of P2(CF,)4 or (CF,),PH at 350"; the pentamer is largely con-verted into the more stable tetramer when it is heated.Oxygen reactswith the tetramer in a fluorocarbon solvent to form polymers of formula(CF,PO,), ; hydrolysis under suitable conditions yields the new phosphines(CF,PH), and H2(CF,P), from the tetramer and pentamer re~pective1y.l~~When heptafluoroiodopropane is heated with phosphorus at 200", the com-pounds (C,F,)PI, and (C,F,),PI, but no (C,F,),P, are formed; severalderivatives of them have been described.l15Trimeric phosphonitrilic chloride has an almost planar molecule withLClPCl= 102", LNPN = 120°, P-N = 1.57 h;, and P-C1= 1.98 A.11sMethylphosphonitriles, (Me,PN),, of which the trimer and tetramer havebeen characterised, have been made from trichlorodimethylphosphorane ,Me,PCl,, and ammonium chloride ; 117 they are remarkable among phospho-nitrile derivatives in that they dissolve in cold water without decompositionand decompose, instead of polymerising to a rubber, at 350400".Trimericand tetrameric diamidophosphonitriles, [PN(NH,)& and 4, are formed whenethereal solutions of the chlorides are slowly added to excess of liquidammonia and the resulting solution is stirred for several hours; they arewhite hygroscopic substances which decompose when heated, with liberationlo' J. K. Van Wazer, " Phosphorus and Its Compounds," Interscience Publ. Inc.,New York, 1958, Vol. I.lo8 E. Thilo, Naturwiss., 1959, 46, 367.lo9 J. R. Van Wazer and C. F. Callis, Chem. Rev., 1958, 58, 1011.110 N. L. Paddock and H. T. Searle, " Advances in Inorganic Chemistry and Radio-chemistry," 1959, 1, 348; R.A. Shaw, Chem. and Ind., 1959, 412.111 E. Wiberg and G. Muller-Schiedmayer, Ber., 1959, 92, 2372.112 A. Finch, Canad. J . Chem., 1959, 37, 1793.lls T. Kennedy and D. S. Payne, J . , 1959, 1228.114 W. Mahler and A. B. Burg, J . Arner. C h e w SOL, 1958, 80, 6161.115 H. J. Emel6us and J. D. Smith, J., 1959, 375.116 E. Cipollini, F. Pornpa, and A. Ripamonti, Ricercu sci., 1958, 28, 205.5.11' I T . T. Searle, R o c . Chcnz. SOC., 1959, 7124 INORGANIC CHEMISTRY.of ammonia. They are soluble in, but slowly decomposed by, water. Thetrimer has been identified among the products of the reaction betweenphosphorus pentachloride in chloroform and liquid ammonia at -50°, andit is likely that the amides are intermediates in the synthesis of the phospho-nitrilic ch1orides.lls Trimeric phosphonitrilic chloride reacts with tri-methylamine at room temperature, yielding tetramethylammonium chlorideand a solid of approximate composition [PNClo.,s(NMe2)l.,2]3; no similarreaction occurs with triethylamine or pyridine.Sodium acetylide replacedsome of the chloride by a~ety1ide.l~~ In a new synthesis of the trimeric andtetrameric fluorides,12* the compounds P3N5 and CF3*SF, or NF, are allowedto react a t 700”.The preparation of phosphinoborine polymers has been briefly described :thermal decomposition of the monoborane adduct of tetramethyldiphosphanegives the trimer and tetramer, and a higher chain polymer, of empiricalcomposition Me,PBH,; a similar chain polymer is obtained from the com-pound Me,PH,BH, in the presence of triethylamine at 200”.Other alkyl-phosphanes behave similarly.121A polymeric oxide (PO), may be obtained by electrolysis of triethyl-ammonium chloride in phosphorus oxychloride at 0” between platinumelectrodes (it is then deposited as a brown solid at the cathode), or by boilingphosphorus oxybromide in dry ether with magnesium. The analogoussulphide is produced similarly from phosphorus thiobromide and magnesium ;it is hydrolysed by alkali to phosphorus, hypophosphite, and sulphide.lZ2The oxidation of phosphorus vapour in the presence of moisture leads tothe formation of an orange substance of empirical formula P,OH, suggestedto consist of a polymeric network of phosphorus atoms with some hydroxylgroups attached.12,Hypophosphates are stable to aqueous alkali, but the action of moltenalkali results in the formation of orthophosphate; cupric ion-catalysedoxidation by hypobromite yields a mixture of ortho- and(7)pyro-phosphate.(8)Hyyochloritc oxidation of red phosphorus in the presence of alkali gives riseto salts of a new acid H,P,O,,, the structure of which appears to be (7).Oxidation of this with iodine in a bicarbonate buffei- results in the formationof an acid believed to be (8).12* The rate of exchange of the hydrogen atomL.F. Audrieth and D. B. Sowerby, Chew. and I n d . , 1959, 748.119 A. B. Burg and A. P. Caron, J . Amer. Chem. SOL, 1959, 81, 836.120 T. J. Mao, R. D.Dresdner, and J. A. Young, J . Amer. Chem. Soc., 1959, 81, 1020.A. B. Burg, J. Inorg. Nztclear Chew., 1959, 11, 258; R. 1. Wagner and F. F.(‘aserio, ibid., p. 259.122 W. Kuchen and H. G. Beckers, Angela. Cheni., 1959, 71, 163; H. Spantlau antiA. Beyer, Naturwiss., 1959, 46, 400.lZ3 H. Harnish, 2. aPzorg. Chem., 1959, 300, 261.12* 13. Blaser and K.-H. Worms, 2. anopg. Chem., 1959, 300, 229, 237, 260STTARPR TYPICAL ELEMENTS. 1%bonded to phosphorus in phosphorous acid with deuterium oxide has beenfollowed by Raman spectroscopy; it increases with increase in the acidityof the solution, suggesting that formation of species such as H,DPO3+ isinvolved; in solutions of salts of the acid, exchange is very slow.125The reaction between phosphoric oxide and ammonia yields mainlyderivatives of pyrophosphoric acid; the action of heat then produces anammonium polyphosphate in which phosphorus atoms are joined halfthrough oxygen atoms and half through -NH- groups.lZ Phosphorictrihydrazide, OP(N,H,),, is obtained by the action of phosphorus oxy-chloride in ether on anhydrous hydrazine in ethereal suspension.127 Theacid HP02Cl, is formed when the oxychloride P,03C14 (made by heating amixture of molar composition 4Poc1, : P,O, a t 200') is cooled to -30" andtreated with the calculated quantity of water.12sFused orthophosphoric acid absorbs 1.08 moles of boron trifluoride a troom temperature with liberation of heat; the absorption results in adecrease in both the viscosity and the electrical conductivity. This isbelieved to be due to a reduction in the extent of hydrogen bonding and tothe replacement of a proton-switch conduction mechanism by normal ionicmig1-ati0n.l~~ Paper chromatography leads to the conclusion that knowncrystalline calcium phosphates in the polyphosphate region all containunbranched-chain anions; the mixed salt of formula Na,CaP,018 is a tri-metaphosphat e Na,Ca (P,O,) ,A review of the history of '' phosphorus trisulphide, P2S3 " leads to theconclusion that there is no evidence for the existence of this substance as astable phase.131 When tetraphosphorus trisulphide addsIP+S iodine to form the compound P,S31,, the P4S3 skeleton isI s 1 partly broken and the structure of the product is (9).13, The(9) selenide P,Se3 is isomorphous with the low-temperature formof the corresponding ~u1phide.l~~Arsine reacts with sodium and lithiumamides in liquid ammonia to give derivatives of formulze NaAsH, andLiAsH,; both form di- and tetra-ammoniates.In the absence of a solventthe products are ammonia and solids of approximate compositionNa,AsH and L ~ , A s H . ~ ~ ~ The compounds (CF,),As*NH,, [(CF,),As],NH,(CF,),As*NHR (R = Me or Et), and (CF,),As*NMe, have been made by theinteraction of chlorobistrifluoromethylarsine and ammonia or amines.l%Potassium meta-arsenate, which exists in three forms stable at differenttemperatures, is formed on dehydration of potassium dihydrogen a r ~ e n a t e . l ~ ~'The y-form, stable at room temperature, contains linear chain anions ofs, ;,PIArsenic, antimony, and bismuth.125 R.B. Martin, J . Amer. Chem. SOC., 1959, 81, 1574.126 M. Becke-Goehring and J. Sambeth, 2. anorg. Chertz., 1958, 297, 287.1-27 R. Klement and K. 0. Knollmiiller, Nuturwiss., 1958, 45, 515.I z 8 H. Grunze, 2. anorg. Chem., 1959, 298, 152.129 N. N. Greenwood and A. Thompson, J., 1959, 3493.I3O S. Ohashi and J. R. Van Wazer, J . Amer. Chem. SOC., 1959, 81, 830.131 A. R. Pitochelli and L. F. Audrieth, J . Amer. Chem. SOC., 1959, 81, 4458.132 D. A. Wright and B. R. Penfold, Acta Cryst., 1959, 12, 465.133 E. Kewlen and A. Vos, Acta. Cryst., 1959, 12, 323.134 W. L. Jolly, J . Amer. Chem. SOC., 1959, 81, 1029.135 W. R. Cullen and H. J. EmeEus, J . , 1959, 372.136 E. Thilo ant1 I<. DostAl, Z.anorg. Chenz., 1959, 298, 100I26 INORGANIC CHEMISTRY.high molecular weight ; from mixtures of the dihydrogen arsenate and thedihydrogen phosphate products containing arsenic and phosphorus atomsstatistically distributed are obtained.The methylstibines MeSbH, (very unstable) and Me,SbH are obtainedby the interaction of dimethylbromostibine and sodium borohydride indiethylene glycol dimethyl ether (" Diglyme ',). Dimethylstibine reactswith hydrogen chloride, liberating hydrogen, or with the compound B,H,Br,liberating diborane. Tetramethyldistibine, Sb,Me,, reacts with diboraneat 100" to give the compound Me,Sb*BH,; this does not form a complexwith trimethylamine, but when heated with this compound it decomposes,yielding trimethylamine-borine, Me,N,BH,, as the main product. It showsno tendency to polymerise, and the general lack of reactivity has beentaken to indicate the existence of x-bonding between the antimony andboron atoms.137the molecule is atrigonal bipyramid with Sb-C1 (apical) = 2-34 and Sb-C1 (basal) = 2-29 A.In the addition compound POCl,,SbCl, the oxygen of the phosphorus com-pound occupies one of the octahedral positions round the antimony andLSbOP is 144"; this is the first determination of the structure of acomplex in which an oxychloride is the donor.139 Antimony pentachloridehas also been shown to form stable complexes with sulphoxides and sul-phones.140Melting-point depression and vapour-pressure data suggest that the ionBiz2+ is present in molten bismuth trihalide-bismuth systems.141 Measure-ment of the vapour pressure of bismuth trichloride over bismuth mono-chloride and over pure bismuth trichloride shows that the solid mono-chloride is barely stable with respect to its solid disproportion p r 0 d ~ c t s .l ~ ~The structure and semi-conducting properties of bismuth telluride have beenreviewed.laGroup VI.-The densities of solid and liquid ozone at 77.4" K are 1-728and 1.614 respectively.lU The existence of the fluoride O,F, has been con-firmed; it is obtained by the action of an electric discharge on a mixture ofoxygen and fluorine at 77" or 90" K and 12 mm. pressure as a blood-redcompound (m. p. 83" K) which decomposes a t 116" K to oxygen and di-fluorine d i 0 ~ i d e . l ~ ~ Spectrophotometric and electron-spin resonance in-vestigations support earlier evidence that the alkali-metal ozonides containthe 0,- ion, and also show that this ion is probably formed during thedecomposition of hydrogen peroxide in alkaline media.146Sulphur tetrafluoride can be made by the action of sulphur dichlorideon sodium fluoride suspended in acetonitrile at 70-80"; a large number ofAntimony pentachloride forms a molecular lattice;137 A.B. Burg and L. R. Grant, J . Amer. Chenz. SOL, 1959, 81, 1.138 S. M. Ohlberg, J . Amer. Chem. Soc.. 1959, 81, 811.139 I. Lindqvist and C.-I. Brand&, Acta Cryst., 1959, 12, 642.140 I. Lindqvist and P. Einarsson, Ada Chem. Scand., 1959, 13, 420.141 M. A. Bredig, J . Phys. Chem., 1959, 63, 978.142 A. J. Darnel1 and S.J. Yosim, J . Phys. Chem., 1959, 63, 1813.143 D. A. Wright, Research, 1959, 12, 300.144 A. G. Streng and A. V. Grosse, J . Amer. Chein. SOC., 1959, 81, 805.145 A. D. Kirshenbaum and A. V. Grosse, J . Amer. Chem. SOC., 1959, 81, 1277.146 A. D. McLachlan, M. C. R. Symons, and M. G. Townsend, J., 1959, 952SIIAKPJ? : TYP1C:UA I<LICTtIl~N'l'S. 127its reactioiis with organic compounds have been studied.147 Nuclearmagnetic resonance studies confirm that sulphur and selenium tetrafluorideshave the CzV rather than the tetrahedral structure, and show that the rateof fluorine exchange between the apical and equatorial positions increasesin the order SF, < SeF, < TeF,.la Pentafluorosulphur hypofluorite hasbeen shown 149 by electron diffraction to have the structure F,SOF withthe average S-F distance 1.53, O-F 1-43, and 0-S 1.64 A.Peroxydisulphurylfluoride, S206F2, reacts with sulphur dioxide to yield the new compoundS308F2, a liquid, for which the structure F*S02*O*S02~O*S0,F is suggested.150Microwave spectroscopy has been used 151 to show that (' sulphur mon-oxide " (formed by the action of an electric discharge on a mixture of sulphurand sulphur dioxide) is in fact disulphur monoxide having the surprisingstructure SSO with S-S = 1.88, S-0 Liquidsulphur dioxide as a solvent has been further studied: 152 the exchange of35S between the solvent and thionyl chloride is catalysed by antimonypentachloride, an intermediate compound SOC12,SbC15 being formed.Catalysis of the exchange by tetramethylammonium chloride is preventedby addition of antimony pentachloride, the compound Me,NSbC16 beingformed preferentially. Anhydrous thiosulphuric acid, which is very un-stable, has been obtained by the interaction of hydrogen sulphide and sulphurtrioxide in the absence of a solvent or in a freon at -78", or by the actionof hydrogen sulphide on chlorosulphonic acid a t the same temperature.153The action of sulphur trioxide on a solution of the compound H2S6 in amixture of ether and carbon disulphide at -78" leads to the formation of theacid H2S703, which reacts further with sulphur trioxide thusH2S,O, + so, + H,S,O,and is oxidised by chlorine or iodine to a polythionic acid of formulaH2S,,06.154 Thionyl cyanide, which is unstable, results from the action ofthionyl chloride vapour on freshly precipitated silver cyanide.l= The com-pound NH,SO,, formerly believed to be the amide of permonosulphuric acid,has been shown 156 by infrared and nuclear magnetic resonance spectroscopyto be the zwitterion H3N+*O*S0,-.The compound S7NH is well known; the di-imide S,(NH),, obtained asa by-product in the action of ammonia on disulphur dichloride, has nowbeen separated by adsorption chromatography on alumina.It is a colour-less solid, soluble in organic solvents but not in water, which melts withdecomposition a t about 140"; the relative positions of the imide groups1.46 A, and LSSO = 118".147 W. C. Smith, C. W. Tullock, E. L. Muetterties, W. R. Hasek, F. S. Fawcett,14* E. L.Muetterties and W. D. Phillips, J . Amer. Chem. Soc., 1959, 81, 1084.14* R. A. Crawford, F. B. Dudley, and K. Hedberg, J . Amer. Chem. SOL, 1959, 81,I5O J. E. Roberts and G. H. Cady, J . Amer. Chem. SOL, 1959, 81, 4166.151 D. J. Meschi and R. Y . Myers, J . Mol. Spectroscopy, 1959, 8, 405.154 D. E. Burge and T. H. Norris, J . Amer. Chem. SOC., 1959, 81, 2324, 2329.153 M. Schmidt and G. Talskp, B e y . , 1959, 92, 1526, 1539.Is4 M. Schmidt and H. Dersin, %. hratzirforsch., 1959, 14b, 735.lS6 U. Wannagat and R. Pfeiffenschneider, 2. anorg. Chem., 1958, 297, 151 ; R. E.V. A. Engelhardt, and D. D. Coffman, J . Amer. Chem. SOC., 1959, 81, 3185.5387.P. W. Schenk and H. Bloching, Ber., 1959, 92, 2333.Richards and R. W. Yorke, J . , 1959, 28211% J NO K C; AN 1C C TI E M 1 S'TRY,have not yet been e~tablis1ied.l~~ Sulphur nitride suspended in carbon-tetrachloride reacts with chlorine to give the compound S,N,Cl,, which isconverted by silver difluoride into the fluoro-compound S,N,F,.Bothcompounds are quantitatively hydrolysed by alkali to ammonia, sulphite,and halide; the structures (10; X = C1 or F) are suggested.15* Thechemistry of the sulphur nitrides and related compounds has been re-viewed.159 The interesting compound (Ag,S)NO,, best madefrom silver nitrate and carbon disulphide, contains aninfinite-chain cation, each sulphur atom being surroundedby six silver atoms in a distorted octahedron.l60by the action of hydro-gen on molten technical selenium a t 650", followed bydecomposition of the resulting hydrogen selenide at 1000".Fluorination ofselenium dioxide and oxychloride gives small yields of the compoundsF,Se-OF and F,Se*O*O*SeF,; the former is decomposed by water to oxygen,selenate, and fluoride, but the latter is inert.l@ The compound SeOCI,,Bpyhas a tetragonal pyramidal configuration round the selenium atom ; the oxygenatom occupies the apical position and chloride atoms and pyridine moleculestake up trans-positions in the basal plane; the molecules show a slighttendency to dimerisation by formation of weak chlorine bridges to othermolecules, thus giving the selenium atom a grossly distorted octahedral con-fig~rati0n.l~~ Selenium dioxide forms bright yellow solutions in sulphuricacid and is partially protonated to give [HSeO,]+[HSO,]- ; tellurium dioxideis ins01uble.l~~Group V1I.-Several addition compounds of chlorine trifluoride, iodineheptafluoride, sulphur tetrafluoride, or sulphur oxytetrafluoride, SOF,, andboron trifluoride, arsenic pentafluoride, or antimony pentafluoride havebeen described, those of boron trifluoride being the least, and those ofantimony pentafluoride the most, ~ t a b 1 e .l ~ ~ These addition compounds aredecomposed by potassium fluoride, e.g.,XNI IN/s\XS,N/SX( 1 0) Pure selenium may be madeSF,,BF8 + KF KBF, + SF,Studies of the temperature- and pressure-dependence of the infrared spectraof mixtures of hydrogen fluoride and chlorine trifluoride, sulphur dioxide ,carbon dioxide, carbonyl sulphide, or nitrogen indicate the formation of1 : 1 molecular complexes similar to those formed from hydrogen chlorideand sulphur dioxide or carbon dioxide.lssThe monohydrate of hydrogen chloride has been shown167 by X-ray167 J.Weiss, Angew. Chem., 1959, 71, 246.158 H. Schroder and 0. Glemser, Z. anorg. Chem., 1959, 298, 78.1.59 M. Becke-Goehring, " Progress in Inorganic Chemistry," 1959, 1, 207.I6O G. Bergerhoff, 2. anorg. Chem., 1959, 299, 328.161 S. Nielsen and R. G. Heritage, J . Electrochem. SOC., 1959, 106, 39.lea G. Mitra and G. H . Cady, J . Amer. Chem. SOL. 1959, 81, 2646.16s I. Lindqvist and G. Nahringbauer, Acta Cryst., 1959, 12, 638.164 R. H. Flowers, R. J. Gillespie, and E. A, Robinson, J . Inorg. Nuclear Chem.,165 F. See1 and 0. Detmar, 2.anorg. Chem., 1959,301, 113; F. A. Cotton and J. W.16' Y. I(. Yoon and G. R. Carpenter, Acta Cryst., 1959, 12, 17.1959, 9, 155.George, J . Inorg. Nuclear Chem., 1958, 7, 397.T. G. Burke and D. F. Smith, J . MoE. Sfiechoscopy, 1959, 8, 381SHARPE: TYPICAL ELEMENTS. 129analysis at -35" to be H,O+Cl-, each hydrogen atom being hydrogenbonded to the nearest chlorine, with 0-H - C1 2.95 A. The variation ofthe C1-0 bond length with change in the co-ordination number of the chlorinein the series of ions C10,-, ClO,-, and C10,- has been discussed : in ammon-ium chlorite, C1-0 is 1.57 k and LOClO 110", whereas in ClO,- the C1-0distance is only 1.44 A.Further work on the very unstable oxides of bromine has been re-ported; 169 the interaction of ozone and bromine has been stated to yieldthe oxide Br,O, in Pyrex, and (Br30& in quartz, apparatus.In trichloro-fluoromethane at -80" bromine dioxide is said to be formed.170 Brominetrinitrate, Br(NO,),, is reported171 to be formed by the interaction ofbromine trifiuoride and &nitrogen pentoxide in the same solvent at -30".A timely review of the structures of interhalogen compounds and poly-halides has been given by Havinga and Wiebenga,172 and important newwork an these substances has been published. The compound Me,NHBr, is[Me3NH] +2Br-Br3-.173 In tetraphenylarsonium tri-iodide the anion issymmetrical, with 1-1 = 2-90 A; 174 in tri-iodides of smaller cations the LIIIis the same (176") but the anion is by no means symmetrical. In the com-pound Me,NI, the nitrogen and iodine atoms are collinear, N-I being2.27 A and 1-1 2-83 A (0.17 longer than in molecular iodine).175 Thecompounds ISbCl, and IAlCI, contain IC&+ and SbC1,- or AlCl,- ions; theIC12+ ion is bent, with LClICl = 92.5" and 96.7" respectively. Eachiodine, however, has four chlorine atomsI I as near neighbours, the environment inshown in (11).These structures arerather like that of iodine trichloride;like the latter compound, ISbCl, is amoderately good conductor in the fusedstate ( K = lo-, ohmw1 cm.-l at 100'). Theequivalent conductivity in liquid sulphurdioxide is only 2% of that of potassiumhexachloroantimonate, suggesting disso-ciation in this solvent mainly into molecules.176Several new compounds containing bromine or iodine cations stabilisedby formation of complexes with pyridine have been prepared : the action ofbromine or iodine on dipyridinesilver fluoroantimonate, Ag(py),SbF,, indry acetonitrile at 0" gives the compounds Br(py),SbF6 and I(py),SbF,;,Cl-Al - .I the aluminium compound being as -At - CI,I2-86'>. n a"2.86', 85.3O ,a'9 0.6" I *,89 . I .\CI2.29 /.,y ( ' ' 2.26CI( 1 1)168 R. B. Gillespie, R. A. Sparks, and K. N. Trueblood, Acta Cyst., 1959, 12, 867.169 A. J. Arvia, P. J, Aymonino, and H. J. Schumacher, 2. anorg. Chem., 1959,170 M. Schmeisser and K. Joerger, Angew. Chem., 1959, 71, 623.171 M. Schmeisser and L. Taglinger, Angew. Chem., 1959, 71, 523.173 E. E. Havinga and E, €3. Wiebenga, Rec. Trav.chim., 1959, 78, 724.173 C. Romers and E. W. M. Keulemans, Proc. K. ned. Akad. Wetenschap., 1958,174 R. C. L. Mooney Slater, AcEa Cryst., 1959, 12, 187.175 K. 0. Stramme, Acta Chenz. Scand., 1959, 13, 268.176 C. G. Vonk and E. H. Wiebenga, Actu Cryst., 1959, 12, 867; Rec. Trav. chim.,298, 1.61, B, 345.1959, 78, 913.REP.-VOL. LVI z 30 INORGANIC CHEMISTRY.Br(py),F and I(py),F are obtained similarly from silver fluoride and yyridinein a~etonitri1e.l'~ In chloroform, however, iodine, pyridine, and silverfluoride are reported to give I(py)F; silver cyanide and the same reagentsyield the monopyridine adduct of iodine cyanide ; the infrared spectra ofthe compounds have been studied.178 The proton nuclear resofiancespectrum band for solutions of iodine in oleum is much broader than that foroleum alone, and is shifted to higher fields, the shift and broadening beingroughly proportional to the concentration of iodine.These changes areinterpreted in terms of the formation of a paramagnetic species of momentabout 1.5 B.M. and it is suggested that this is the iodine cation; the " spin-only " value for I+ with the electronic configuration 5s25P4 would, of course,be 2-83 B.M., but there is no compelling reason for assuming this value, sinceions of the heavier elements usually have moments which differ from thosecalculated on the " spin-only " basis.179 A comparison of the infraredspectra of several complexes of iodine cyanide (e.g., with benzene, ethanol,quinoline) shows that the decrease in the I-C stretching frequency is greatestfor the best donors; the C-N frequency, however, is little affected.lsOIodine, like silver ion, forms complexes with many cyclic olefins; theheats of complex formation in 2,2,4-trirnethylpentane are in the region of0.5-3-0 kcal./mole.lsl Formation constants for iodine-olefin complexesshow less dependence on ring size than those for silver-olefin complexes, afact which may indicate a difference in structure such as is already estab-lished for complexes of iodine or silver and aromatic hydrocarbons.The oxides I,O, and 1204 combine with sulphur trioxide to form thecompounds 1205,2S03 and 1204,3S0,, respectively; it is possible that thesemay have the structures (I02),S,07 and (10) (102)S,010.182 There is, how-ever, at present no evidence for the existence of the 102+ ion : iodyl fluoridedoes not combine with boron trifluoride in a manner analogous to nitryl andchloryl fl~orides.18~ The first product of the dehydration of periodic acidis reported to be the compound H71,014.184The preparation of the interesting compound CF,*IF2, by addition OCfluorine to trifluoroiodomethane in a freon solvent at -80", has been brieflyreported.lS5 A.G. S.3. THE TRANSITION ELEMENTSTHE transition elements will be considered in an order similar to thatadopted last year. Those aspects which are not necessarily characteristicof any single transition metal but which illustrate the general properties ofcomplexes or ligands are discussed first under the heading '' complexes."Organometallic compounds which contain a B metal-carbon bond are dis-177 H. Schmidt and H.Meinert, Angew. Chem., 1959, 71, 126.178 R. A. Zingaro and W. E. Tolberg, J . Amer. Chem. SOC., 1959, 81, 1353.179 T. M, Connor and M. C. R. Symons. J., 1959, 963.180 W. B. Person, R. E. Humphrey, and A. I. Popov, J . Amer. Chem. SOC., 1969,181 J. G. Traynham and J. R. Olechowski, J . Amer. Chem. SOL, 1959, 81, 571.182 H.-A. Lehmann and H. Hesselbarth, 2. anorg. Chem., 1959, 299, 51.*83 E. E. Aynsley and S. Sampath, J., 1959, 3099.I84 Z. Hauptman, Coll. Czech. Chem. Comm., 1959, 24, 2132.185 M. Schmeisser and E. Scharf, dngew. Chcm., 1959, 71, 524.81, 273SHARP f THE TIL4NSITION ELEMENTS. 131cussed next, and the chemistry of the elements is considered systematicallyin the ten transition groups.Complexes.-(a) General.The most important publication in this fieldhas been that of the Fai-aday Society Discussion on “ Ions of the TransitionElements ” which contains general surveys on ligand-field and molecular-orbital theories as applied to metal ions and includes many papers ondetailed applications of these theories to chemical and spectroscopic, mag-netic, and other physical phen0mena.l The proceedings of the InternationalConference 02 Co-ordination Chemistry, held in London in April, 1959, havebeen published as a Chemical Society Special Publication.2 The effect ofinner-orbital splitting on the thermodynamic properties of transition-metalcompounds has been re~iewed.~Radiochemical studies have shown differences in bond energies in thehalogenoplatinate series.The average Pt-Cl bond is12 kcal. stronger than the Pt-I bond and the averagePt-Br bond is 4-5 kcal. stronger than the Pt-I bond.6Cl- lies far to the right because of entropy andsolvation factors, but it is suggested that even incomplexes where the iodide is more stable than thechloride the Rl-C1 bond strength is, in fact, greater than the M-I band~trength.~ Co-ordination of an organic molecule as a ligand makes themolecule much more reactive. The reaction of nickel and palladiumacetylacetonates with nitrite ion gives complexes which probably havestructure (1). Potassium nitropalladite reacts with acetylacetone to givea 5-co-ordinate nitrosyl complex, and a similar cobalt complex is formedfrom cobalt(r1) acetylacetonate andnitric oxide.Copper( 11) acetyl-acetonate gives a 3-nitroacetylacetone /+ complex when treated with dinitrogentetroxide .5 Dihydroxymanganese ( IV)phthalocyanine and aquohydroxy-chromium(II1) phthalocyanine aret3) true 6-co-ordinate complexes and are /?/ = Mn phthalocyanine dibasic acids. It is considered thatthe anions are stabilised by con-jugation between the mutually perpendicular phthalocyanine and oxy-groups,such perpendicular conjugation being a new phenomenon in co-ordinationchemistry.6 Manganese(I1) phthalocyanine combines reversibly with oxygenwhen dissolved in pyridine; the product contains MnIV doubly bonded tooxygen (2) and is converted into a polymer (3) on heating.’ It was shown in1 Discuss. Faraduy SOC., 1958, 26.2 ‘ International Conference on Co-ordination Chemistry, ” Special Publication No.13, The Chemical Society, London, 1959.3 P. George and D.S. McClure, “ Progress in Inorganic Chemistry,” 1959, 1, 381.4 A. J. Po& and M. S. Vaidya, Nature, 1959, 184, 1139.5 C. Djordjevic, J. Lewis, and R. S. Nyholm, Chem. avtd Id., 1959, 122; R. Nast6 J. A. Elvidge and A. B. P. Lever, Proc. Chem. Soc., 1959, 123.7 J. A. Elvidge and A. B. P. Lever, Proc. Chem. SOL, 1959, 195.OHMeC=N, ,N=CAcHO/~ ~ ~ = ~ 0 1 M ;N=&.+ The overall equilibrium PtCls2- -1 61- --+ PtIG2- +(1)1 [& 0,&7 (2)and H. Bier, Ber., 1959, 92, 1858132 INORGANIC CHEMISTRY.1900 that silver ions produce colour changes with thiocyanato-complexes andthis observation has now been extended to a study of the interaction of silver(1)and mercury(11) ions with cis- and trans-[M1ll(NCS)ZRp]+ ions (MIII = Coor Cr, R = amine).Stable salts were not isolated, but evidence was foundfor the existence of several new species in solution and it is considered thatthe original complexes had an isothiocyanato-structure, the new complexeshaving in addition Ag-S or Hg-S bondss Structural studies have beenmade on Ni(H,O)H,Y, NH,CoY,2H20, and RbCoY,2H20 (Y4- = ethylene-diamine-NNN'N'-tetra-acetate ion). In the cobalt salts the ethylene-diaminetetra-acetate ion is acting as a hexadentate ligand but the H,Y2-ion is only acting as a quinquedentate ligand in the nickel salt, there beingone water molecule co-ordinated to the metal and one free CH2*C02H arm.9The thermodynamics of formation of ethylenediaminetetra-acetic acidcomplexes has been discussed by Staveley and Randall and changes inco-ordination number have been related to crystal-field effects.1°Details have been published of a method of determining magnetic sus-ceptibility by measuring shifts in the proton resonance lines of inert referencemolecules; less than 0.03 ml.of a dilute solution can be studied.ll Themagnetic susceptibilities of tetra- and hexa-co-ordinate cobalt (11) complexesand of copper(I1) complexes have been investigated in detail. The magneticmoments of the copper compounds are correlated on the basis of an octa-hedral or distorted octahedral (in the extreme case planar) configurationabout the copper.12 Numerous infrared studies on complexes have beenreported during the year.The transmission of electronic effects through ametal atom has been investigated by examining the effect of different ligandson the metal-hydrogen vibrations in hydrides and on N-H vibrations inammines. The changes seem to be mainly inductive in origin, but mesomericeffects and interaction between N-hydrogen atoms and the d orbitals of themetal are also important .13 The infrared spectra of compounds containingM=O groups (M = any transition metal) have a band between 900 and1100 cm.-lJ4 The infrared spectra of ethylenediamine complexes arebelieved to permit differentiation between those complexes in which theligand has cis- and those in which it has trans-c~nfigurations.~~ The infraredspectra of cobalt@), platinum(@, and palladium(11) ammines have alsobeen studied.l6 Complex fluorides show infrared absorption in the potassium8 W.C. Waggener, J. A. Mattern, and G. H. Cartledge, J . Amer. Chem. SOL, 1959,9 H. A. Weddiem and J. L. Hoard, J . Arnev. Chew. Soc., 1969, 81, 549; G. S. Smith10 L. A. K. Staveley and T. Randall, Discuss. Faraday Soc., 1958, 26, 157.11 D. F. Evans, J., 1959, 2003.12 B. N. Figgis and R. S. Nyholm, J., 1959, 338; B. N. Figgis and C. M. Harris,13 J. Chatt, L. A. Duncanson, B. L. Shaw, and L. M. Venanzi, Discuss. Faraday14 C. G. Barraclough, 3 . Lewis, and R. S. Nyholm, J., 1959, 3552.15 D. B. Powell and N. Sheppard, J., 1959, 791, 3089; see also K.Brodersen, 2.anorg. Chem., 1959, 298, 142.16 H. Siebert, 2. anorg. Chem., 1959, 298, 51; S. Mizushima, I. Nakagawa, M. J.Schmelz, C. Curran, and J. V. Quagliano, Spectrochim. Acta, 1958, 13, 31; H. Block,Trans. Faraday SOL, 1959, 55, 867.81, 2958.and J. L. Hoard, ibid., p. 556.J., 1959, 855.SOL, 1958, 26, 131SHARP: THE TRANSITION ELEMENTS. 133bromide or sodium chloride region and it is concluded that there is somecovalent bonding even in perovskites, KMF,.17Stereospecific influences in metal complexes containing optically activeligands have received considerable attention. Formation constants for thecomplexes formed from L- or racemic asparagine and cupric ions show thatthe formation of the non-mixed complex is favoured as compared with theformation of the mixed.ls The isolation of non-mixed complexes has beendemonstrated in several other experiments. Oxidation of a cobalt (11) saltin the presence of L-propylenediamine (pren) gives the pure D-ZZZ and L-111isomers; the base can be recovered from the complex optically pure.lgcis- or trans-[Co(en),Cl,]Cl (en = ethylenediamine) reacts with L-propylene-diamine to give C~(en),~+ and Co(~-pren),~+ ions with no mixed complexes:in this case a seven- or eight-co-ordinate cobalt(rr1) species is suggested asan intermediate.,O A demonstration that some of the optical isomers areless stable than others has also been given for cis-dinitro(ethy1enediamine)-(butane-2,3-diamine)cobalt (1rr)ions and a detailed study of the relativestability and reactivity has been given in terms of the stereochemistry of theindividual chelate rings.21 In platinum complexes, chloroplatinic acidreacts with D-propylenediamine to give a predominant yield of the L-dddand D-ddd isomers of the Pt(~-pren),~+ ion 22 but rather surprisingly thereaction of Pt(L-pren)CI, with ethylenediamine or of Pt(en)Clp with L-propylenediamine in dimet hylformamide gives a series of mixed complexeswhich are stable in aqueous solution.23Much has beenpublished on the kinetics of inorganic reactions and space permits onlythe briefest review of this field. Taube has written two reviews on thesubject 24 and there has been a report of a symposium on inorganic reactionmechanisms in which several aspects of the subject are reviewed and dis-cussed.25 Russian work on the kinetics of substitution in palladium andplatinum salts has also been summarised.26By making the assumption that relaxation occurs almost entirely in thefirst co-ordination sphere of cations, study of the 170 magnetic resonancespectrum of solutions of paramagnetic ions can give lower limits for the rateof exchange of bulk water molecules with those in the first co-ordinationsphere of the cations.Values found range from less than lo-' sec. forMn2+ to less than lo4 sec. for Ni2+. C P ions exchange water by a differentmechanism.27 The reaction between a quaternary ammonium chloride and(b) Mechanisms of reactions of inorganic complexes.17 R. D. Peacock and D. W.A. Sharp, J., 1959, 2762.18 W. E. Bennett, J . Amer. Chem. Soc., 1959, 81, 246.19 F. P. Dwyer, F. L. Garvan, and A. Shulman, J . Amer. Chem. SOC., 1959, $1, 290.20 F. P. Dwyer and A. M. Sargeson, J . Amer. Chem. SOC., 1959, 81, 5269.21 E. J. Corey and J. C. Bailar, jun,, J . Amer. Chem. SOC., 1959, 81, 2620; W. E.22 F. P. Dwyer and F. L. Garvan, J . Amer. Chem. SOL, 1959, 81, 1043.23 F. P. Dwyer and A. M. Sargeson, J . Amer. Chem. Soc., 1959, 81, 5272,24 H. Taube, Adv. Inorg. Chem. Radiochewt., 1969, 1, 1; also ref. 2, p. 57.2G J. Phys. Chem., 1959, 63, 321 et seq.26 A. A. Grinberg, Zhur. neorg. Khim., 1959, 4, 1517 [683].*37 R. E. Connick and R. E. Poulson, J. Chem. Phys., 1959, 30, 759; see also R. A.Bernheim, T. H. Brown, H. S. Gutowsky, and D.E. Woessner, ibid., p. 950.Cooley, Chui Fan Liu, and J. C. Bailar, jun., ibid., p. 4189.* Figures in brackets refer to the English translation134 INORGANIC CHEMISTRY.biscyclopentadienyltitanium(1v) bromide to give the corresponding chloridetakes place by a displacement (&2) process in tetrahydrofuran and benzene.The corresponding reaction with lithium chloride in tetrahydrofuran appearsto involve a nucleophilic displacement by the solvent.28 Contrary toprevious reports, the mechanism of electron exchange between uranium-@)and -(vI) species depends markedly upon the solvent.29 The reaction be-tween plutonium(1v) and uranium(1v) is very similar to the plutonium(1v)disproportionation and the Ce(Iv)-U(Iv) reactions and involves the form-ation of an intermediate deprotonated H2O-Pu(~v)-U(rv) complex, possibly[PU*O*U]~+.~~ Change of solvent from water to deuterium oxide decreasesthe rate of reaction of Cr2+ with (NH,),CO(OI--I,)~+ and (NH,),CO(OH)~'.The second reaction prcceeds by oxygen transfer and it is inferred that theformer proceeds by a similar mechanism; the decrease in rate is taken toindicate that the O-H bonds are stretched in the activated complex.31 Fromthe increase in rate of racemisation of (bipyridyl),Fe2+ and (o-phen-anthroline),Fe2+ ions with increase in the methanol content of the methanol-water solvent it is inferred that in alcohol-rich solution the racemisationtakes place by an intramolecular process.32 The racemisation of the[C0(en)~]3+ ion under forcing conditions proceeds by an SN2 mechanism:[C~(en)~],+ + en =+= primary intermediate.Hydroxide ion attacks the[Co(en),13+ ion at 85" to give [CO(~~),(OH)(H,O)]~+ but the hydroxide iondoes not play a key part in the overall racemisation process. The catalyticracemisation of this ion in the presence of charcoal, platinum, or silica geloccurs, with partial decomposition, through an activated six-co-ordinateintermediate; the [Rh(en),I3+ ion is not racemised under these conditions.%Electron exchange between cobaltous [containing species Co(NH3),,2+ andCo(NH,),,OH+ (n up to 6 or 5)] and cobaltic ammines proceeds through asymmetrical hydroxy-bridged complex.34 The oxidation of Cr2+ with[(NH,),Co(fumarate)]+ or its half ester proceeds through a bridge to thecarboxy-group of the acid.Electron transfer, which is accompanied byhydrolysis of the ester, takes place through the conjugated system of theester.35 Study of the rate of base-catalysed deuterium loss from deuterated[Co(NH3)J3+ and [Co(C,O,)(NH,),]+ ions has shown that these ions are acidsby virtue of their association and reaction with hydroxyl ions-not by theirability to act as proton donors.36 Isotopic exchange of chloride ion in the[NH,PtCl,]- ion shows that cis- and frans-chlorines in the complex are in-distinguishable; this result does not disprove the existence of a strong trans-effect since there may be internal rearrangements in the intermediate species.It is suggested that an Sx2 reaction in which Y replaces X, which is trans28 A.Jensen and F. Basolo, J . Amer. Chem. SOL, 1959, 81, 3813.D. M. Mathews, J. D. Hefley, and E. S. Amis, J . Phys. Chem., 1959, 63, 1236.30 T. W. Newton, J . Phys. Chem., 1959, 63, 1493.31 A. Zwickel and H. Taube, J . Amer. Chem. Soc., 1959, 81, 1288.32 L. Seiden, F. Basolo, and H. M. Neumann, J . Amer. Chem. SOC., 1959, 81, 3809.33 W. G. Gehmann and W. C. Fernelius, J . Inorg. Nuclear Chem., 1959, 9, 71;** E. Appelman, M. Anbar, and H. Taube, J . Phys. Chew., 1959, 63, 126.35 R. T. M. Fraser, D. K. Sebera, and H. Taube, J . Amer. Chem. SOC., 1959, 81,36 H. Block and V. Gold, J., 1959, 966.D. Sen and W. C. Fernelius, ibid., 1959, 10, 269.2906SHARP: THE TRANSITION ELEMENTS. 135to L, takes place as shown with a transition state which is symmetrical forboth the entering and the leaving group-a transition state which has beenutilised to account for the trans-effe~t.~'S: A i/ L-qt-x/ i5 A *4s: A i /L - P t - Y(c) CarbonyZs.Some theoretical aspects of metal carbonyls and of theproducts resulting froin the reactions between them and acetylenes havebeen considered during the year by Orgel,% and the use of metal carbonylsas catalytic intermediates in organic chemistry has also been reviewed.39An important new preparation for carbonyls has been reported. Sodiumbenzophenone ketyl reacts with chromic chloride in tetrahydrofuran to givean intermediate, probably chromium benzophenone ketyl, which reactsfurther with carbon monoxide under pressure at 100" to give chromiumhexacarbonyl in good yield.Manganese carbonyl was prepared similarly.@Molybdenum and tungsten carbonyls have been prepared by metatheticalexchange between iron pentacarbonyl and molybdenum pentachloride ortungsten he~achloride.~~ The trigonal bipyramidal nature of iron penta-carbonyl seems to be completely established by its Raman spectrum; 42 aresult confirmed by a comparison of the directly measured entropy with thatcalculated from spectroscopic data.43 However, the structure of cobaltcarbonyl is still unknown. By analogy with the structure of the complexCo,(CO),,HCiCH, a non-coplanar structure (4) has been proposed forCO,(CO),.~ This is in agreement with the infrared spectrumG and fits inwith the tendency for Co,(CO), to take up an extra carbonyl group under37 T.S. Elleman, J. W. Reishus, and D. S. Martin, jun., J . Amer. Chem. Soc., 1959,38 L. E. Orgel, ref. 2, p. 93.39 H. W. Sternberg and I. Wender, ref. 2, p. 35.40 R. D. Closson, L. R. Buzbee, and G. G. Ecke, J . Amer. Chem. Soc., 1958,80, 6167.4 1 A. N. Nesmeyanov, I<. N. Anisimov, E. P. Mikheev, V. L. Volkov, and 2. P.Valueva, Zlzur. neorg. Khim.. 1959, 4, 249 [107]; A. N. Nesmeyanov, E. P. Mikheev,I<. N. Anisimov, V. L. Volkov, and 2. P. Valueva, ibid., p. 503 [228].42 H. Stammreich, 0. Sala, and Y . Tavares, ./. Chem. Phys., 1959, 30, 856.43 A. J. Leadbetter and J. E. Spice, Canad. J . Chem., 1959, 37, 1923.44 0. S. Mills and G. Robinson, Proc. Chem. Soc., 1959, 156.45 G. Ror and I,. Mark6, Spertrorhim. Acta, 1959, 747.81, 10136 INORGANIC CHEMISTRY.pressure, the bonding of the extra group being to the vacant trigonal bridgingposition.It is possible, however, that when this extra carbon monoxidegroup is taken up the reaction CO + Co,(CO), + [Co(CO),]+ + [Co(CO),]-takes place.46Molybdenum and tungsten carbonyls react with sodium in liquidammonia to give Na,[M-II (CO),]; hydrolysis of the anion gives the species[Mo-I,(CO),H]-. Reduction of chromium carbonyl with sodium boro-hydride gives Na,[Cr-12(CO),,] which reacts with amines to give substitutedcarbonyls and carbonyl anions and can be reduced with sodium toNa,[Cr-II(CO),] .47 The broad-line proton magnetic resonance spectrum ofiron carbonyl hydride, Fe(CO),H,, gives an H-H distance of 1-88 & 0.05with an H-Fe-H angle of 109" to 125".The Fe-H distance is of the sameorder as the atomic radius of iron but the exact configuration of the moleculeis unknown.48 Dicarbonylcyclopentadienyliron chloride is reduced bysodium borohydride to dicarbonylcyclopentadienyliron hydride, an unstablecompound, m. p. -5", characterised by its nuclear magnetic resonancespectrum.49 Rhenium carbonyl reacts with alkali metals in tetrahydrofuranto give MRe(CO), derivatives (M = Li and Na). These are hydrolysed torhenium carbonyl hydride by phosphoric acid.60 Chromium, molybdenum,and tungsten hexacarbonyls react with hydroxide ions to give polynuclearanions which probably contain hydroxyl bridges ; hydride species areproduced from these anions by acids, substituted carbonyls by bases.51Biscyclopentadienyltitanium dicarbonyl, (C,H,),Ti(CO),, the first car-bony1 derivative of titanium, has been prepared by the action of carbonmonoxide and sodium cyclopentadienylide on biscyclopentadienyltitaniumdichloride. The compound forms reddish-brown, air-sensitive crystals.52Substituted chromium-group carbonyls have been prepared by reaction ofamines with alkali pentacarbonylchromates(- 11) ,= by reaction of triaryl andtriaryloxy-derivatives of Group V with the carbonyls,5q and by replacingthe arene group in arenechromium tricarbonyls or the cycloheptatrienegroup in C,H,MO(CO),.~~ These derivatives contain five, four, or threecarbonyl groups per molecule. Chromium and molybdenum carbonylsreact with 1 -met h ylp yridinium iodide to give iodopen t acarbonyl- 1 -methyl-pyridinium metallates(-I), (pyMe) [IM(CO),], which on gentle heating areconverted in to x- 1 -me thylpyridinium-me tal tricarbonyl~.~6 Thermal de-48 S.Metlin, I. Wender, and H. w. Sternberg, Nature, 1959, 183, 457.47 H. Behrens and J. Kohler, 2. Nutuvforsch., 1959, 14b, 463; H. Behrens and48 E. 0. Bishop, J. L. Down, P. R. Emtage, R. E. Richards, and G. Wilkinson, J.,49 M. L. H. Green, C. N. Street, and G. Wilkinson, 2. Naturforsch., 1959, 14b, 738.50 W. Hieber and G. Braun, 2. Naturforsch., 1959, 14b, 132.5 1 W. Hieber and K. Rieger, 2. unorg. Chem., 1959,300, 288; W. Hieber, K. Englert,62 J. G. Murray, J . Amer. Chem. SOC., 1959, 81, 752.58 H. Behrens and J. Kohler, 2. Nafuvforsch., 1959, 14b, 463.64 W.Hieber and J. Peterhans, 2. Nuturfovsch., 1959, 14b, 462; C. N. Matthews,T. A. Magee. and J. H. Wotiz, J . Amer. Chem. SOC., 1959, 81, 2273; A. Luttringhausand W. Kullick, Tetrdzedron Letters, 1959, No. 10, 13.66 E. W. Abel, M. A. Bennett, and G. Wilkinson, J., 1959, 2323.66 E. 0. Fischer and K. Ofele, 2. Nuturfursch., 1989, 14b, 736; see also B. MooreW . Haag, ibid., p . 600.1959, 2484.and K . Rieger, ibid., p p . 295, 304; W. Hieber and K . Englert, ibid., p. 311.and G. Wilkinson, Proc. Chem. SOC., 1969, 61SHARP: THE TRANSITION ELEMENTS. 137composition of manganese carbonyl halides gives bridged [Mn (CO),X],dimer~.~’ Many manganese carbonyls and manganese carbonyl halidessubstituted with Group V and VI ligands have been prepared by directinteraction between the ligand and the carbonyl, a carbonyl halide, or anarenemanganese carb0nyl.~5, 57-69 The substance resulting from theinteraction of triphenylphosphine and rhenium carbonyl chloride, previouslyregarded as [(Ph,P),Re(CO),] +C1-, is now considered from infrared andmolecular-weight evidence to be (Ph,P),Re(CO),Cl.Similar productsresult from the reaction between other Group V ligands and manganese andrhenium tetra- or penta-csrbonyl halides.57Iron carbonyls react with pyridines, pyridine N-oxides, and dimethylsulphoxides to give derivatives with anionic iron carbonyl species ; thecations consist of hexa-co-ordinated ferrous ions.60 Di(tertiary arsine)ironcarbonyls and carbonyl halides of the types Fe(CO),D, Fe(CO)D,,Fe(CO)DX, and Fe(CO),DX, (D = o-phenylenebisdimethylarsine, X = Bror I) have been prepared by interaction of iron pentacarbonyl and thearsine followed by oxidation of the products with iodine or bromine.61 The[Fe(C0),]2- anion reacts with oxides and other derivatives of arsenic,antimony, bismuth, tin, lead, and thallium to give complex non-ionic deriv-atives in which it is considered that iron tetracarbonyl groups are con-densed through the metals or metalloids.62(d) Cyanides and isocyanides.Little work on pure cyanides has beenreported this year and most aspects will be considered under the headingof the other ligands involved. Reduction of potassium cobalticyanidewith potassium in liquid ammonia gives pale yellow, very reactiveK,COI(CN),.~~ Further details have now been published of the high-resolution nuclear magnetic resonance studies on ions found in solutionscontaining cobalt (11) cyanide complexes.63a It is now considered that themain species present is [HCo1(CN),I3-; a similar ion, [HRh1(CN),I3-, isformed when rhodicyanide ions are reduced with sodium b~rohydride.~~From infrared studies it appears probable that the [COI(CN),(CO)]~- ion isplanar whilst the [CO~~(CN)~]~- ion has a symmetrical structure with ametal-metal bond 64 similar to that proposed for the [Ni2(CN),(CO)~4- ion.aThe isocyanide complexes of the transition metals have been reviewedduring the year.66 Isocyanide complexes of cobalt(x1) are formed in aqueoussolution ; reduction gives cobalt (I) complexes.The cobalt (11) complexesexist in two forms, red diamagnetic and blue paramagneti~.~~57 E. W. Abel and G. Wilkinson, J., 1959, 1501.58 W. Hieber and W. Freyer, Ber., 1959,92, 1765; W. Hieber and W. Schropp, jun.,59 R. S. Nyholm and D. V. R. Rao, Proc. Chem. Soc., 1959, 130.80 W. Hieber and A. Lipp, Ber., 1959, 92, 2075, 2085.61 H. Nigam, R. S. Nyholm, and D. V. R. Rao, J., 1959, 1397.62 W. Hieber, J. Gruber, and F. Lux, 2. anorg. Chew., 1959, 800, 275.63 G. W. Watt and R. J. Thompson, J . Inorg. Nuclear Chem., 1959, 9, 311.ma See Ann. Reports, 1958, 55, 148.64 W. P. Griffith and G. Wilkinson, J., 1959, 2757.66 W. P. Griffith, F. A. Cotton, and G. Wilkinson, J . Inorg. NucEear Chew., 1959, 10,66 L. Malatesta, ‘ I Progress in Inorganic Chemistry,” 1959, Vol.I, 283.2. Naturforsch., 1959, 14b, 460.23.A. Sacco and M. Freni, Gazzetta, 1959, 89, 1800138 INORGANIC CHEMISTRY.(e) Nztrosyls. Orange, deliquescent K5[V-1(CN)5(NO)],H,0 is preparedby reducing potassium vanadate in the presence of excess of base and ofcyanide with hydroxylamine hydroch1oride.a The anion is a member of theisoelec tronic series [V-I (CN), ( N0)l5-, [MnI (CN) (N 0)13-, [FeII( CN), (NO)] ,-.The CrO complex could not be isolated but green K3[Cr1(CN)5(NO)]was obtained under similar conditions. On the basis of chemical, spectro-scopic, and magnetic susceptibility data the previously reportedK,[MoO(CN),(NO)] ,2H20 is reformulated as K,[MO*~(OH),(CN>,(NO)] anda h ydroxy-cyanide previously reported as K, [MorV(OH),( CN), ( H,0)] ,2H,Oas K3[MoV(OH),(CN)4],2H,0 or K,[Mo~~~O~(CN),(H,O)],~H,O.In theselatter complexes molybdenum seems to attain its preferred co-ordinationnumber of eight.69 Oxidation of the [Mn*(CN),(NO)]3- anion with nitricacid gives the yellow [M~III(CN)~(NO)]~- anion.70 h complete structuraldetermination on [Ru(NH,),(NO) (OH)]Cl, has been described. Theruthenium atom is octahedrally co-ordinated with the hydroxyl and nitrosylgroups in trans-positions; the Ru-N-0 angle is 150°, and this complex mustbe compared with cobalt nitrosyl dithiocarbamate in which the Co-N-Osystem is also non-linear.'l Physicochemical studies have been made onthe nickel nitrosyl hydroxides which are prepared by the action of nitricoxide on nickel carbonyl in the presence of water and an alcohol.Thecomplexes, which have the general formula Ni(N0) (OR),(OH),-,, are con-sidered to contain dipositive nickel in tetrahedral co-ordination. These deepblue compounds slowly change to green nitro-complexes which areprobably polymeric, with octahedral co-ordination about the metal, e.g.,Ni(N0) (OH) (OMe), - Ni(N0,) (OMe) (MeOH). The iron complexes corre-sponding to the nickel nitrosyl hydroxideshave been reformulated (5) to contain tetra-ON% Fe do\ rr hedral iron(0). Nitrosyl halides of palladium,M&HN l o f F e k NO Pd(NO),C12, and rhodium, Rh(NO),Cl, have(') been reformulated to contain PdO and Rh(-I), thelatter compound being almost certainly polymeric. K [Co(-I>(CN) (NO) (CO),]is considered to have tetrahedral co-ordination about the cobalt, the nitrosylgroup donating as NO+.',Perfluoro-olefins such as tetrafluoroethylene andperfluorocyclohexadiene react with iron pentacarbonyl to give the complexes(C,F,),Fe(CO), and C,F,Fe(CO),.A complex analogous to Zeise's salt isformed in solution in aqueous ethanol from tetrafluoroethylene and sodiumchloroplatinite, but the solid complex could not be isolated. These are thefirst perfluoro-olefin-transition metal complexes and provide interestinggrounds for discussion of the effect of the electronegative fluorine on thestability of olefin complexes.73 Acrylonitrile, with an activated doubleHOMeMe(f ) OZe@ complexes.68 W. P. Griffith, J. Lewis, and G. Wilkinson, J., 1959, 1632.69 W.P. Griffith, J. Lewis, and G. Wilkinson, J., 1959, 872.70 F. A. Cotton, R. R. Monchamp, R. J. M. Henry, and R. C . Young, J . Inovg.71 G. B. Bokii and N. A. Paipiev, KrystaZlografya, 1958, 2, 691 ; cf. P. R. H. Alder-a W. P. Griffith, J. Lewis, and G. Wjlkinson, J. 1959, 1776.73 K. F. Watterson and G. Wilkinson, Chem. and Tnd., 1,959, 991.Nuclear Chem.. 1959, 10, 28.man and P. G. Owston, Nature, 1956, 178, 1071SHARP : THE TR.4NSITION ELEMENTS. 1.39bond, reacts with nickel carbonyl to give a red complex (6) which does notinvolve the lone pair of electrons on the nitrogen atom as in normal nitfilecomplexes. Bisacrylonitrilenickel is a very efficient polymerisation catalyst ;it is still electron-deficient and forms an adduct with/ triphen ylphosphine. 74 Substituted st yrene-platinumCH '.l-,C . H complexes, (X~C,H,*CH:CH,,PtCl,), (x = H, 3-C1,Q-CH,*O, %NO,, 4-N02, and 4-CH3), have been pre-. . . . pared by displacement of ethylene from ethylene-platinous chloride. When dissolved in alcoholic NC hydrogen chloride the dimers react to give ions(X*C,H,~CH:CH,,PtCl,), + 2HCl- 2H+(X*C,H,CH:CH,,PtCl3)-. In theolefin complexes all substituents are stabilising relative to styrene and thisfact is consistent with the presence of a double bond between platinum andthe ligand, the o and x bonds being affected approximately equally but inopposite directions by the s u b s t i t ~ e n t . ~ ~ It is pertinent to remark, how-ever, that the nature of the bonding in olefin complexes is still unknown;the infrared spectra of platinum ethylene complexes may be interpretedvery convincingly on the basis of Pt-C Q bonds.', In the " 0x0 " reactionfor the hydroformylation of olefins, studies of the rate of absorption ofcarbon monoxide have shown that it most likely that the reaction proceedsthrough an intermediate cobalt carbonyl hydride-olefin-carbon monoxidecomplex.77. *,CH- CHIConsiderable work has been published on the metal complexes of cyclicpolyenes. Norbornadiene (7) forms complexes with A&), CU(I) , Pd(11) ,Pt(II), Rh(I), and Ru(II). The last, a polymeric bridged complex, is thefirst olefin complex of r u t h e n i ~ r n . ~ ~ Other diene complexes describedinclude : the dimethyl acetylenedicarboxylate adduct of cyclo-octatetraene(8) with Rh(1) ; the maleic anhydride adduct of cyclo-octatetraene (9) withRh( I) ; 78 cyclo-oct a- 1,5-diene-molybdenurn and -tungsten tetracarbonylsand -ruthenium dihalides ; 79 and norbornadieneiron tricarbonyl.80 Fromthis fairly wide range of complexes it seems that conjugation is not a neces-sary requisite for the formation of diene complexes-even with iron-groupelements.81 Cyclo-octa-1,3,5- and -1,3,6-trienes (L) form the following74 G.N. Schrauzer, J. Amer. Chem. SOL, 1959, 81, 5310.75 J. R. Joy and M. Orchin, J. Amer. Chem. SOC., 1959, 81, 305.7' A. A. Babushkin, L. A. Gribov, and A. D. Gel'man, Zhur. neorg. Khim., 1959, 4,7 7 L. Kirch and M. Orchin, J. Amer. Chem. SOC., 1959, 81, 3597.78 E. W. Abel, M. A.Bennett, and G. Wilkinson, J., 1959, 3178.79 T. A. Manuel and F. G. A. Stone, Chem. and Ind., 1959, 1349; E. 0. Fischer andW. Frolich, Ber., 1959, 92, 2995; M. A. Bennett and G. Wilkinson, Chem. and Ind.,1959, 1516.80 R. Burton, M. L. H. Green, E. W. Abel, and G. Wilkinson, Chem. and Ind.,1958, 1592; R. Pettit, J . Amer. Chem. SOC., 1959, 81, 1266.81 Cf. B. F. Hallam and P. L. Pauson, J., 1958, 642.1542 [695]140 INORGANIC CHEMISTRY.complexes: LM(CO), (M = Cr, Mo, and Fe), L,M(CO), (M = Mo and W),and [LCo(CO),],. It seems likely that the two isomers may give complexesof different stoicheiometry and this may be related to the stereochemistryof the x bonds in the olefins (10, ll).s2 Cyclo-octatetraene complexes withRh(1) and iron carbonyls have been prepared.Normal cyclo-octatetraeneironcarbonyl has the formula C,H,Fe(CO), but reaction with excess of iron(10)carbonyl gives another complex in which the iron tricarbonyls are bonded toopposite sides of the octatetraene (12) .78983 All the complexes mentionedabove are prepared in the simplest possible way-by shaking, refluxing, orirradiating a mixture of the olefin with the metal halide or metal carbonyl.Complete structure determinations have been carried out for two complexesof this type. In the cyclo-octatetraene dimer (13)-silver nitrate structureeach silver atom is associated with two double bondsfrom different dimer molecules.84 The silver ioninteracts with two non-adjacent x bonds of eachcyclo-octatetraene molecule in the cyclo-octa-tetraene-silver nitrate complex.In this compound(13) there appears to be some interaction between the @ silver and nitrate i0ns.~5(g) Acetylene complexes. Acetylene complexes are now becoming dividedinto two distinct types: those in which the acetylene remains as a recognis-able entity in the complex, and those in which it has polymerised or hasreacted with the other ligands present.The acetylides of the transition metals have been reviewed by Nast.86K6[Ni1,(CzCR),] (R = H, CH,, C,H,) and K,Zn(C,H), have been preparedby the action of potassium acetylides in liquid ammonia on K,[NiI,(CN),(CO)Jand Zn(SCN),,2NH3 respe~tively.~~ The action of acetylene on pentacyano-cobaltate(11) species in aqueous solution gives the yellow saltK,[Co,(CN),,,C,H,] ,4H,O, a diamagnetic complex which is given the struc-ture (14) on the basis of spectroscopic measurements.8s Platinum acetylenecomplexes have been prepared by the reaction between an acetylene and82 E.0. Fischer, C. Palm, and H. P. Fritz, Bey., 1959, 92, 2645; E. 0. Fischer andC. Palm, 2. Nuturforsch., 1959, 14b, 598.88 T. A. Manuel and F. G. A. Stone, Proc. Chem. Soc., 1959, 90; M. D. Rausch andG. N. Schrauzer, Chem. and Ind., 1959, 957; A. Nakamura and N. Hagihara, Bull.Chem. SOC. Japan, 1959, 32, 880.84 S. C. Nyburg and J. Hilton, Acta Cryst., 1959, 12, 116.85 F. S. Mathews and W. N. Lipscomb, J . Phys. Chem., 1959, 83, 845.86 R. Nast, ref. 2, p. 103.87 R. Nast and H. Kasperl, Bey., 1959, 92, 2135; R. Nast and R. Miiller, ibid., 1958,88 W.P. Griffith and G. Wilkinson, J., 1959, 1629.91, 2861SHAKP: THE TRANSITION ELEMENTS. 141chloroplatinites or K [C,H,PtClJ. Monosubstituted acetylenes give in-definite products, but complexes of the types Y [acPtCl,], ac,Pt,Cl,, andtrans-[ac(pip)PtCI,] (Y = univalent cation,6 - ac = acetylene, pip = piperidhe) have beenisolated by using disubstituted acetyleness9Hydroxyacetylenes give stable complexes withplatinum, and it appears that there is con-electrons of the hydroxyl groups and the metalatom.g0 Cyclopentadienylnickel dicarbonylreacts with acetylenes to give complexes Cp,Ni,(RC,R') which are formulated(15) with the C-C bond at right angles to the Ni-Ni bond?l This structure issuggested by analogy with that found by X-ray analysis for diphenyl-111siderable interaction between the lone pairs of0ICO-c, Io'cOcO~0iacetylenedicobalt hexacarbonyl (16) ; X is the mid-point of the acetylenelinkage, the two phenyl groups being bent away from the cobalt atoms, andthe C-C bond of the acetylene being normal to the Co-Co bond.There isapproximately sixfold co-ordination about the two cobalt atoms.92 Reactionof dicobalt hexacarbonyl acetylenes with acid gives complexes of the typeHCo,(CO) ,,RC-CH. The suggested struc-ture involves three cobalt atoms in a ringwith three carbonyl groups on each metalatom, but there is no definite evidence asto the bonding of the acetylene0 0Qc/0Complexes of this type may shortly pro-vide models for the absorption of acetyleneon metal surfaces.The complex Co,(CO),,HCiCH has0 a structure involving a lactone ring'CI which must result from addition ofcarbon monoxide to acetylene.The twocobalt atoms are bridged by a carbon atom of the ring and a bridging car-bonyl; the two metal atoms and the bridging carbons are not co-planar (17) .aThe action of acetylenes on carbonyls or on organometallic compoundsgives wide ranges of complexes, many of which have been described duringthe year. Many of the structures are based on that found for the but-2-yne100(17)89 C. B. Bukhovets and H. K. Pukhova, Zhur. neorg. Khim., 1958, 3, 1714; J. Chatt,go J. Chatt, L. A, Duncanson, and R. G. Guy, Nature, 1959, 184, 526.O 1 J. F. Tilney-Bassett and 0. S.Mills, J . Amer. Chem. SOL, 1959, 81, 4757.92 W. G. Sly, J . Amer. Chem. SOL, 1959, 81, 18.93 R. Markby, I. Wender, R. A. Friedel, F. A. Cotton, and H. W. Sternberg, J .L. A. Duncanson, and R. G. Guy, Chem. and Ind., 1959, 430.Amer. Chem. SOL, 1968, 80, 6529142 INORGANIC CHEMISTRl-.complex of iron carbonyl hydride 93a and involve transition metal-carbonbonds with the further possibility of x bonding from the heterocyclic ringsystem containing a transition element. Alternatively, the acetylenes maybe polymerised to substituted butadienes or benzenes or may react withligands to form substituted pentadieneones. Any of these aromatic orpseudo-aromatic systems may act as x-bond donors. Thetulated for many of these complexes are supported by theirstructures pos-preparation bydirect interaction of the appropriate aromatic or olefinic system with themetal carbonyl.Thus diphenylacetylene reacts with iron pentacarbonyl inultraviolet light to give, among other products, the iron tricarbonyl complexof tetraphenylcyclopentadienone (18) ; this complex can also be preparedby direct interaction of iron pentacarbonyl and tetracyc10ne.~4 It will notbe possible to give details of all the reactions involved but systems studiedare : acetylene-iron carbonyls ; 949 95 cyclopentadienones with iron carbonyls,mercury cobalt carbonyl, cobalt carbonyl, chromium hexacarbonyl , molyb-denum hexacarbonyl, and manganese carbonyl ; g4-g6 acetylenes with(OC)3Fe--------~- p h c F e ( C O ) 3 + Ph.PCI2 -+- p h c P P hPh ’* Ph ‘ Ph Ph(20) (21)cobalt carbonyl, cyclopentadienylcobaIt dicarbonyl, and manganese carbonylLydride ; 97 acetylenes with organochromium derivative~.~B Oxidation ofiron hydi ocarbonyl-acetylene complexes eliminates one iron atom as Fez+and gives complexes which appear to be cyclic acyl derivatives of iron car-bony1 hydrid? (l!l).99 The reaction of some of the complexes describedabove kiith now-metallic halides offers a preparative route to new hetero-cyclic compounds. Pentaphenylphosphole (21) is formed by reaction ofFe,(CO),(PhG,Ph~, (20) with phenylphosphorus dichloride, and a hetero-cyclic system containing silicon [C,(C,H,),Si(C,H,)~ has also been synthesisedin this way.Pel? taphenylphosphole forms complexes with iron penta-93O Ann.Reports, 1955: 55; 150.94 G. N. Schrauzer, J . Arne#. Ciccx. Sor.. 1969, 81, 5307.95 W. Hubel, E. H. Braye, A. Clams, I<. Weiss, IT. Kruerke, D. A. Brown, G. S. D.King, and C. Hoogzand, J . Inrug. N z / c k n ~ C‘he???., 1959. 9, 204; W. Hubel and E. H.Braye, ibid., 1959 10, 250; W. Hiibel and E \G’elss, Chem. and Ind., 1959, 703; J. R,Let0 and F. A. Cotton, J . Amer. Chenz. So913 E. Weiss and W. Hubel, J . Iiaorg. N.tic /dL Y Chrnz., 2959, 11, 42.97 H. W. Sternberg, J. G. Shukys, C. n. I):)Ix-, I2 Markby, R. A. Friedel, andI. Wender, J . Amer. Chem. SOC., 1959, 81, 2339.08 G. Wilke and M. Kroner, Angew. Chew., 1939 7’1, 5 i l ; see also W. Metlesicsand H. Zeiss, J . Anzer. Chem. SOC., 1959, 81, 4117.99 J. R. Case, R. Clarkson, E.R. H. Jones, and 31. C. \f7!iitiii;, PYOC. Chem. Soc.,1939 81 2970.1959, 160SHARP THE TKANSITION ELEMENTS. 143carbonyl.loO The polymerisation of benzonitrile to triphenyltriazine byiron carbonyls is probably also an example of the type of polymerisationreaction that occurs with acetylenes.lo1Complexes with aromatic systemshave been reviewed twice during the past year.lo2 With the rapid develop-ment of the study of complexes derived from the reaction between acetylenesand metal carbonyls there is necessarily much overlap between the presentsection and the previous one. Tetramethylcyclobutadienenickel dichlorideis prepared by the action of tetramethyldichlorocyclobutene on nickelcarbonyl.lo3 The action of lithium amalgam on lJ2,3,4-tetrabromocyc1o-butane gives a mercury compound which affords what appears to be a silver-cyclobutadiene complex on reaction with silver nitrate.lM These complexesprovide the first example of the cyclobutadiene aromatic system , which seemsto be greatly stabilised when acting as a x-electron donor.New dicyclopentadienylides described during the year are dicyclopenta-dienylosmium,lo5 dicyclopentadienyl beryllium ,l06 and dicyclopentadienyl-zinc; lo' all of these complexes were prepared by standard procedures.Oxidation of dicyclopentadienylosmium gives an osmium (IV) species :(h) Complexes with aromatic systems.FeC1, 12 Cp20sIr - [Cp20srGOH]PF, ; Cp,0sI1 ___.jc [C~,OS~~I]PI;,Cp = cyclopentadienylNHIPFe NHIPF,It is considered that a vanadyl sandwich compound, possibly (C,H,),VO, isformed by oxidising dicyclopentadienylvanadium.108 On the structuralside there has been a complete structure determination of ruthenocene.Ruthenocene and osmocene are not isomorphous with ferrocene but thedetailed co-ordination about the metal is ~imilar.1~~ Dicyclopentadienylderivatives of Be, Mg, Sn, and Pb have finite dipole moments and it isapparent that the bonding in these compounds is different from that in thenon-polar ferrocene-type derivatives.The structure is interpreted byFischer as involving a a bond (22),106~110 but from additional spectroscopicevidence Wilkinson prefers a sandwich structure with the rings at an angle(23) .ll1 The reaction between dicyclopentadienylmagnesium and titanium100 E.H. Braye and W. Hubel, Claem. and Ind., 1959, 1250.101 S. F. A. Kettle and L. E. Orgel, Proc. Chem. SOC., 1959, 307.102 E. 0. Fischer and H. P. Fritz, Adv. Inorg. Chem. Radiochem., 1959, I, 5 5 ; F. A.103 R. Criegee and G. Schrader, Annalen, 1959,623,l; cf. Ann. Reports, 1958,55,269.104 M. Avram, E. Marica, and C. D. Nenitzescu, Ber., 1959, 92, 1088.105 E. 0. Fischer and H. Grubert, Ber., 1959, 92, 2302.106 E. 0. Fischer and H. P. Hofmann, Ber., 1959, 92, 482.107 E. 0. Fischer, H. P. Hofmann, and A. Treiber, 2. Naturforsch., 1959, 14b, 599.l08 H. M. McConnell, W. W. Porterfield, and R. E. Robertson, J. Chem. Phys., 1959,Io9 G. L. Hardgrove and D. I-I. Templeton, Acta Cryst., 1959, 12, 28; F. Jellinek,110 E. 0. Fischer and S. Schreiner, BEV., 1959, 92, 938.111 L.D. Dave, L). F. Evans, and G. Wilkinson, J., 1059, 3684.Cotton and G. Wilkinson, " Progress in Inorganic Chemistry," 1959, Vol. I, 1.30, 442.Z . Naturforsch., 1959, 14b, 737144 INORGANIC CHEMISTRY.tetrahalides gives cyclopentadienyltitanium trihalides and dicyclopenta-dienyltitanium dihalides.1l2 Reduction of dicyclopentadienyl-molybdenumand -tungsten halides with sodium borohydride gives the correspondinghydrides. These hyrides, containing metal-hydrogen linkages, sublimein v a c ~ 0 . ~ ~ However, the action of sodium borohydride on dicyclopenta-dienyl-cobalt and -rhodium halides results in the partial reduction of oneof the cyclopentadienyl rings to give cyclopentadienyl-metal cyclopenta-dienes, C5H5MC,H6.113 The rhodium compound and the correspondingiridium complex also result from the action of a mixture of potassiumcyclopentadienylide and cyclopentadiene on rhodium or iridium trihalides.l14Dicyclopentadienenickel(0) is formed by the reaction between nickel carbonyland cyclopentadiene.The nickel atom in this compound could be in almosttetrahedral co-ordination (24).l15 The nature of this type of complex hasbeen elucidated in a series of experiments including high-resolution infraredand nuclear magnetic resonance measurements. Deuterides and methyl(24) 0 Mderivatives corresponding to the parent complex C&?&OC5H6 have beenprepared, and it has been shown that dicyclopentadienylcobalt reacts withmethyl iodide to give cyclopentadienyl-l-endo-methylcyclopentadiene-cobalt (25) : (C5H5),Coo + Me1 + x-(C,H,)(1-endo-CH,*C5H,)Cor +(C5H5)CoI.The reaction between (C,H,),Co and carbon tetrachloride 116yields 113 the l-enndo-trichloromethylcyclopentadiene derivative which canbe reduced to the l-eutdo-dichloromethylcyclopentadiene complex. Thebonding in all these complexes appears to be from a symmetrical cyclopenta-dienyl ring plus bonding from two sets of x-electrons in a cyclopentadienering. In the cyclopentadiene compounds the endo-hydrogen is responsiblefor the low C-H stretch at -1850 cm.-lJ13 Triphenylphosphonium cyclo-pentadienylide (26) forms complexes with Group VI hexacarbonyls in whichthere is x bonding from the cyclopentadienyl ring.l17A partial structure determination on benzenechromium tricarbonyl hasshown that the benzene is symmetrically placed with respect to the chromiumatom and that the Cr-C-0 groups are linear.ll* This is in agreement withdipole-moment and microwave measurement^.^^**^^^ Reaction of the112 C.L, Sloan and W. A. Barber, J. Amer. Chem. Soc., 1959, 81, 1364.I14 E. 0. Fischer and U. Zahn, Ber., 1959, 92, 1624.1l6 S. Katz, J. F. Weiher, and A. F. Voigt, J. Amer. Chem. Soc., 1958, 80, 6459.11' E. W. Abel, Apar Singh, and G. Wilkinson, Chem. and I n d . , 1959, 1067.118 P. Corradini and G. Allegra, J. Amer. Chem. SOC., 1959, 81, 2271.1lP E. W. Randall and L. E. Sutton, Proc. Chem. SOC., 1959, 93; J. K. Tyler, A. P.M. L. €3. Green, L. Pratt, and G. Wilkinson, J., 1959, 3753.E. 0. Fischer and H.Werner, Ber., 1959, 92, 1423.Cox, and J. Sheridan, Nutwe, 1969,183, 1182SHARP : THE TRANSITION ELEMENTS. 145cobalt carbonyl-aluminium bromide complex or of a mixture of mercurycobalt carbonyl and aluminium chloride with aromatic hydrocarbons givesa trinuclear cobalt-carbon monoxide-arene cation, [Co,(Arene),(CO),] + or[Co,(Arene),(CO),]+ lZo This could be similar to the trinuclear nickel com-plex described last year.lZ0” Many complexes between silver perchlorateand polycyclic hydrocarbons such as chrysene and fluorene have beendescribed. 121The interaction of cyclopentadienylvanadium tetracarbonyl and cyclo-heptatriene gives x-cyclopentadienyl-x-cycloheptatrienylvanadium as purplecrystals. This is only the second preparation of a tropylium sandwichcompound.122 Tropyliumtricarbonylchromium(0) perchlorate (as 27) reactswith anions to give cycloheptatriene complexes (28).The cyclopenta-dienylide ion reacts with a simultaneous ring contraction and expansion togive arenechromium tri~arbony1s.l~~Organometallic Compounds of the Transition Elements.-There has been arapid growth of interest in the organometallic derivatives of the transitionelements. Many have already been mentioned under the general headingof complexes, but the present section deals with compounds containingmetal-carbon o-bonds. In general, the well-known organometallic deriv-atives of zinc, cadmium, and mercury have been excluded.Titanium halides react with methyl-lithium or methylmagnesium iodidein ether to give trimethyltitanium; a t low temperatures titanium tetra-chloride gives the tetramethyl derivative.Manganese iodide reacts in thesame way to give dimethylmanganese and diphenylmanganese and there isstrong evidence for the formation of di- and tri-methylchromium in similarreactions. Te t rame th ylt it anium reacts with titanium tetrachloride to givemethyltitanium trichloride, and methyl- and phenyl-manganese iodides areprepared similarly. Dimethylmanganese gives LiMnMe, on reaction withmethyl-lithium.124 Alkyltitanium halides are also formed in the reactionbetween titanium tetrachloride and lead tetra-alk~1s.l~~ Phenyl derivativesof chromium, molybdenum, and tungsten are obtained as phenyl-lithium-ether adducts by interaction of phenyl-lithium and the appropriate metal120 E. 0.Fischer and 0. Beckert, Awgew. Chern., 1958, 70, 744; P. Chini and R.121 G. Peyronel, I. M. Vezzosi, and S. Buffagni, Gazzetta, 1959, 89, 1863, 1869.122 R. B. King and F. G. A. Stone, J . Amer. Chem. Soc., 1959, 81, 5263.123 J. D. Munro and P. L. Pauson, Proc. Chem. Soc., 1959, 267.124 C. Beermann and K. Clauss, Angew. Chem., 1959, 71, 627; see also C. Beermann126 C. E. H. Bawn and J. Gladstone, Proc. Chem. Soc., 1959, 227.Ercoli, Gazzetla, 1958,88, 1170.Ann. Reports, 1958, 65, 152.and H. Bestian, ibid., p. 618146 INORGANIC CHEMISTRY.halides.126aryl hydrides : 127Reduction of the chromium compound gives a series of complexLi3CrPh,,2GEt,0 + Li,CrHPh5,3Et,0 ---t Li,CrH,Ph,,3Et20 .or Li3CrH,Ph,,3Et,O -+ Li,Cr,H,Ph6,3Et,0An organochromium cation is formed by the reduction of chloroforni bychromous chloride :CHCI, + 2Cr2+ + 10H,O --c, Cr(H,0),CHC1,2+ + Cr(H20)&l2+It is suggested that the reaction proceeds through CHCI, radicals.12s trans-[C,H,(PPh,)2],RuC1, reacts with aluminium alkyls to give halogenometalalkyls of the type [C2H,(PPh,),I2RuRC1 (R = Me, Et, Prn).Theseare converted into alkyl hydrides by lithium aluminium h ~ d r i d e . l ~ ~Reaction of the nickel and cobalt complexes, trans-R,MX, (R = alkyl- oraryl-phosphine, X = CI, Br), with Grignard reagents, aryl-lithiums, orsodium acetylides (in liquid ammonia) gives aryl or acetylide derivatives ofnickel or cobalt. The aryl derivatives are much more stable when the ringis ortho-substituted ; ethynyl derivatives of cobaltMe ,R are not ~ t a b 1 e .l ~ ~ Similar alkyl- or aryl-platinum(r1)derivatives were prepared (R = phosphine or 4 Pt’disulphide) in both the cis- and the tratzs-forms. Theaddition of methyliodide to trans-[(PR,),PtIIMeI]M~ gives [(PR,),PtIVMe,I,] .131 The compounds formedby the interaction of trimethylplatinum and p-(29) R‘ kc -o‘Ae’Me diketones have the structure (29) ; the platinumatom is bound directly to an active methyIenegroup.132 Many substituted platinum trimethyls [R,PtMe,]X (R = pyr-idine, amines, thiourea, X = halogen) have been prepared; the platinum-carbon bond is extremely stable.l=The Scandium Group and Lanthanides.-Scandium hydroxide gives truesolutions in concentrated sodium hydroxide and Na,[Sc(OH),] ,2H,O crystall-ises out. This hydroxy-complex is hydrolysed at sodium hydroxide con-centrations less than SM; the lithium salt is not ~ t a b 1 e .l ~ ~ Heating togetherthe appropriate oxides at high temperatures gives the compounds LiScO,,NaScO,, and LiYO,; these also are rapidly hydrolysed by water.l35 Somenew borides, MB, (M = Y, Nd, Tb, Dy, Ho, Lu) and MB, (M = Nd, Tb,Er, Lu), have been prepared but unfortunately there is not very good agree-126 F. Hein and R. Weiss, 2. anorg. Chem., 1958, 295, 145; H. Funk and \V. Hauke,127 F. Hein and R. Weiss, Naturwiss., 1959, M, 321.128 F. ,4. L. Anet, Canad. J . Chem., 1959, 37, 58; see also F. X. L. Anet and E.129 J. Chatt and R. G. Hayter, PYOC. Chem. SOC., 1959, 153.130 J.Chatt and B. L. Shaw, Chem. and ImL, 1959, 675.131 J. Chatt and B. L. Shaw, J., 1959, 705.132 A. C. Hazell, A. G. Swallow, and M. R. Truter, Chein. and Ind., 1959, 564.133 0. M. Ivanova and A. D. Gel’man, Zhzcr. neorg. Khirn., 1958, 3, 1334; R. A.134 B. N. Ivanov-Emin and E. A. Ostroumov, Zhur. neorg. IUzim., 1959, 4, 71 [27].135 13. Hoppe, Angew. Chein., 1959, 71, 457.‘‘C-HMe,I 0-Me7 ’ 0 - C ( \d/H-f-/C-o~Ptx,4ngew. Chem., 1959, 71, 408.Leblanc, J . Amer. Chem. SOC., 1957, 79, 2649.Golovnya and 0. M. Ivanova, ibid., p. 1347SHARP: THE TRANSITION ELEMENTS. 147ment between the lattice constants reported by the two sets of w0rkers.l3~Reaction of yttrium or samarium chlorides with lithium borohydride intetrahydrofuran gives the chloro-diborohydrides, MC1(BH4),.137 Reductionof anhydrous neodymium trichloride with metallic neodymium gives a darkgreen dichloride.This is a new oxidation state for neodymium; a darkpurple di-iodide has also been prepared.138 The action of fluorine on a mix-ture of alkali-metal chloride plus Pr6Oll gives hexafluoropraseodymates(1v) ,M,PrF, (M = Na, K, Rb, Cs). These are yellowish solids, immediatelyhydrolysed by water.139The Actinides.-Phases in which the components have the ratios 3 : 1,7 : 6, 1 : 2, and 1 : 4 have been isolated from the system LiF-ThF,; forNaF-ThF, the phases present are 4 : 1, 2 : 1, 3 : 2, 1 : 1, and 1 : 2 in the twocomponents.140 A quantitative comparison has been made of the extractionof niobium, tantalum, and protactinium from hydrochloric acid solution by 2,4-dimethylpentan-2-01 (di-isopropylcarbinol) and tributylamine.Varioushydroxy-chloride species from Pa(OH)Cl,+ to PaC1,2- are present in theprotactinium s01ution.l~~ The black solid which is formed when uraniummetal reacts with hydrochloric acid is an active form of U304.142 The addi-tion of alkali to a solution of uranyl nitrate and urea precipitates urea saltsof nitrouranic acid [UO,(NO,)OH] and of uranic acid [H,UO,,H,O]. This istaken to prove the existence of these acids as intermediates in the formationof ~ r a n a t e s . ~ ~ ~ Structural studies have been made on two uranyl salts.Sodium uranyl acetate has a linear 0-U-0 group, the uranium also beingsurrounded by three bidentate acetate ligands in the central ~lane.1~4 Thereis a very similar arrangement in bis(triethy1 phosphate)-uranyl nitrate, acomplex closely related to those used in the solvent extraction of uranium.145Phase studies on the BaF,-UF, and SrF,-ThF, systems have shown theexistence of a new compound, 2BaF,,3UF4, in the former; there is nosimilar compound in the latter.146There has been a noticeable decrease in the amount of published workon the chemistry of the transuranic elements this year.A series of shortreviews on these elements has been pub1i~hed.l~~ Full details of the prepar-ation and properties of neptunium hexafluoride-first prepared on a micro-gram scale in 1946-have now been given. It has m. p. 54.4", b. p. 55-2",136 G. A. Kudintseva, M. D. Polyakova, G.lr. Samsonov, and B. RI. Tsarev, Fiz.Metall. i 1Matallov., 1968, 6, 272; V. S. Neshpor and G. V. Samsonov, Zhur.fiz. Khim.,1958, 32, 1328; H. A. Eick and P. W. Gilles, J . Anzer. Cham. Soc., 1959, 81, 5030.137 A. Rrukl and K. Rossmanith, Monatsh., 1959, 90, 481.138 L. F. Drudingand J. D. Corbett, J . Amer. Chem. SOC., 1959 81 5512.139 R. Hoppe, Angew. Chem., 1959, 71, 457.140 R. E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes,J . Phys. Chem., 1959, 63, 1266; L. A. Harris, G. D. White, and R. E. Thoma, ibid.,p. 1974.141 A. T. Casey and A. G. Maddock, J . Inorg. Nuclear Chem.., 1959, 10, 289.142 R. C. Young, J . Iutorg. Nuclear Chem., 1958, 7, 418.143 P. S. Gentile, L. H. Talley, and T. J. Callopy, J . Inorg. Nuclear Chem., 1959,144 W. H.Zachariasen and H. A. Plettinger, Acta Cryst., 1959, 12, 526.145 J. E. Fleming and H. Lynton, Chem. and Ind., 1959, 1409.146 R. W. M. D'Eye and I. F. Ferguson, J., 1959, 3401.147 J. Chcm. Edztc., 1959, 36, 15, ct seq.10, 110148 INORGANIC CHEMISTRY.and is an orange solid which gives a colourless v a ~ 0 u r . l ~ ~ K,PuCl, andpossibly K,PuC15 have been shown to exist in the KCl-PuC1, ~ystem.14~Jorgensen has considered the spectra of actinide ions and concludes thatonly 5f electrons occur outside the radon shell for ions of charge greaterthan 3+. He points out that there is no necessary correlation between thepresence of f electrons and constant tervalency 150-a point which is veryrelevant in view of the increasing number of " anomalous " valency statesof the rare-earth elements.Titanium, Zirconium, and Hafnium .-The structure of baddeley it e-monoclinic 21-0,-has been redetermined and it has been shown that eachzirconium atom is surrounded by seven oxygen atoms at distances varyingfrom 2.04 to 2-22 A (30).Hafnium dioxide also has0 Zr one form which is isomorphous with badde1e~ite.l~~0 0 An X-ray and thermal analytical study of thesystems M,Ti205-TiO, has shown the existenceof the phases M,Ti,O,, M2Ti409, and M2Ti50,,(30) (M = Rb and Cs).15, In the system M,O-21-0,phases isolated are Li,ZrO,, Li,ZrO,, Li2Zr205, NaZrO,, three forms ofK,Zr,O,, and Rb2Zr205.163 In a preliminary account of the structure of(C,H5)TiCl2*O*TiC1,(C5H5)-prepared by the partial hydrolysis of cyclo-pentadienyltitanium trichloride-it has been stated that the Ti*-Ti linkis linear; d-p overlap between the orbitals of titanium and oxygen wouldprobably account for this type of structure.la A very complete study of thesulphides, selenides, and tellurides of titanium, zirconium, hafnium, andthorium has been reported this year.Phases present are MX, M2X3, andMX, (M = Ti, Zr, Hf, Th; X = S, Se, Te).15j The reaction betweenzirconium disulphide and zirconium dioxide gives 21-0S.l~~ Titaniumsulphochloride, TiSCI,, which has been postulated in several previousreactions, results from the reaction between titanium tetrachloride andhydrogen sulphide in the presence of carbon disulphide. The systemTiC1,-H2S may be summarised< 0" > 0" > 136"TiCl, + H2S .-> TiCl,,H,S - TiSCI, - TiS,.15'The reaction between titanium@) bromide and iodide and ammonia hasbeen studied in detail.In organic solvents 2- and 6-ammoniates result,but in liquid ammonia there is ammonolysis to [TiX,(NH,),-,]2- ions. At-36" compounds of stoicheiometry TiX4,8NH, are formed; these contain148 J. G. Malm, B. Weinstock, and E. E. Weaver, J . Phys. Chem., 1958, 62, 1506.149 R. Benz, M. Kahn, and J. A. Leary, J . Phys. Chem., 1959, 63, 1983.150 C. K. Jsrgensen, Mol. Phys., 1959, 2, 96; see also W. T. Carnal1 and P. R.151 J. D. McCullough and K. N. Trueblood, Actu Cryst., 1959, 12, 507; J. Adam152 0. Schmitz-DuMont and H. Reckard, Monatsh., 1959, 90, 134,153 H.-A. Lehmann and P. Erzberger, 2.unorg. Chem., 1959, 301, 233.154 P. Corradini and G. Allegra, J . Amer. Chem. Soc., 1959, 81, 5510.155 F. K. McTaggart and A. D. Wadsley, Austral. J . Chem., 1958, 11, 445; J. Bearand F. K. McTaggart, ibid., p. 458; F. K. McTaggart, ibid., p. 471; F. K. McTaggartand A. Moore, ibid., p. 481.156 A. Clearfield, J . Amer. Chem. Soc., 1958, 80, 6511157 P. Ehrlich and W. Siebert, 2. anorg. Chem., 1959, 301, 288.Fields, J . Amer. Chem. SOL, 1959, 81, 4445.and M. D. Rogers, ibid., p. 951SHARP : THE TRANSITION ELEMENTS. 149mainly ammonium halide and TiX(NH,), species. On thermal decom-position, TiBr4,8NH, gives TiBr4,2NH, as a red sublimate, with a residueof TiNBr ; TiI,,8NH3 gives TiN.158 Titanium and zirconium tetrachloridesreact with lithium dialkylamides to give compounds M(NR,),.The ethylderivatives are liquid a t room temperature ; they undergo aminolysis withhigher amines, e.g., piperidine, to give solidsC,HioNH Ti(NEt,), - Ti(NC5Hlo), + 4NHEt,Substituted piperidines show considerable steric effects, and the reactionbetween Ti(NMe,), and %met hylpiperidine yields Ti( NMe,) (NC,H,Me),The complexes Na3TiC16, K3TiCl6, K,TiCl,, and K,TiBr, have been foundin the systems NaC1-TiCl,, KCl-TiCl,, KBr-TiBr,.lGO Fluorination oftitanium alkoxides with antimony trifluoride gives esters of fluorotitanic acid,Ti(OR), + SbF, + Sb(OR),,3Ti(OR),F--t 3Ti(OR),F (R = Et, Pr, Bu).The intermediates have been isolated and the esters may also be preparedby the reaction between titanium alkoxides and acetyl fluoride.lslVanadium, Niobium, and Tantalum.-The structure of V,O, has beendescribed; the lattice consists of V06 octahedra joined together by sharingcorners, edges, and faces.Where the octahedra share faces the V-V dis-tance is 2-74 A (in metallic vanadium it is 2.62 A); the octahedra arejoined together by edges to give parallel rows.162 K,V& has a layerstructure in which vanadium atoms are surrounded by square or trigonalpyramids of oxygen atoms, the pyramids being joined by sharing basalcorners.163 pH measurements on rapidly hydrolysed vanadate solutionsshow that the only ions present are VlOO286-, HVl00,s5-, and H2VloOzs4-;in pyrovanadate solutions the V,0,4- and HVO,,- ions are in equi1ibrium.lMSpectrophotometric analysis also points to the presence of the H2V100,84-ion as a hydrolysis product of the vanadyl ion, in agreement with previousresults from potentiometric tit ration^.^^^ Use of an ultracentrifuge methodhas shown that decavanadate species are present in the orange-red isopoly-vanadates.166 A ternary nitride, Li,VN,, containing pentapositive vana-dium, is formed by heating lithium and vanadium nitrides under an atmo-sphere of nitrogen at 680".The structure is based on an anti-fluoritelattice ; the corresponding niobium and tantalum compounds were alsoprepared.167 Vanadium trichloride reacts with phosphine oxides to givecomplexes of the type VCl,(OPR,),. Tertiary aliphatic phosphines react15B G. W. A. Fowles and D. Nicholls, J., 1959, 990.159 D. C.Bradley and I. M. Thomas, Proc. Chem. Soc., 1959, 225.160 P. Ehrlich, G. Kaupa, and K. Blankerstein, 2. anorg. Chem., 1959, 299, 213.161 A. B. Bruker, R. I. Frenkel', and L. 2. Soborovskii, Zhur. obshchei Khim., 1958,lBZ S. Asbrink, S. Friberg, A. Magndi, and G. Anderson, Acta Chem. Scand., 1959,164 J. Meier and G. Schwarzenbach, Chimia (Switz.), 1958, 12, 328.165 L. Newman and K. P. Quinlan, J . Amer. Chem. SOL., 1959, 81, 547; see F. J. C.Rossotti and H. Rossotti, J . Inorg. Nuclear Chem., 1956, 2, 201.166 0. Glemser and E. Preisler, Naturwiss., 1959, 46, 474.167 R. Juza, W. Gieren, and J. Haug, 2. anorg. Chem., 1959, 300, 61.28, 2413.13, 603.A. Bystrom and €3. T. Evans, jun., A d a Chem. Scand., 1959, 13, 377150 INORGANIC CHEMISTRY.similarly, but tricyclohexyl- or triphenyl-phosphine gives products of varyingmolecular ratios which consist partially of dimers [VCl,PR,],.168The systems Li,O-Nb,O, and Ag,O-Nb,O, are very similar169 to thesystem Na,O-Nb,O, reported on last year.Tantalum pentachloride reactswith lithium dialkylamides to give volatile tantalum penta(dialky1amides) -159The niobium chlorides have received a thorough study. Niobium trichlorideexists over a composition range NbCl,.,, to NbCl,.,. Stoicheiometric nio-bium dichloride is formed by the reaction between niobium and NbC1,.67or NbCl, or by the reduction of the pentachloride with hydrogen. There isno evidence for a rnono~hloride.~~~ The oxyhalides of niobium and tantalumhave been reexamined and the existence of NbOCl,, NbOBr,, TaOBr,, andTaOCI, has been established.The first three are prepared by reactionbetween oxygen and the pentahalide; TaOCl, results from the pyrolysis oftantalum pentachloride m0n0etherate.l~~ Niobium tetraiodide has a struc-ture in which NbI, octahedra share opposite edges, the two niobium atomsbeing shifted from the centres of the octahedra towards each other to takepart in metal-metal bonding. The metal-metal distance is 3-2 A com-pared with the distance between octahedra centres of 3.83 A.172 Niobiumis effectively octahedrally co-ordinated in NbOCl,, the octahedra againsharing edges, but there is no evidence for metal-metal bonding.173M1MVC16 complexes have been studied for MV = Nb and Ta. All thepossible salts exist where MI is an alkali metal except for LiNbC1.,174 In thesystems H,O-NbF,-HF and H,O-TaF5-HF the following phases havebeen found to represent successive stages of hydrolysis : HNbF6,H20,HNb2Fl1,4H,O, Nb,05,2H20 ; HTaF5,1-5H,0, HTa2F,,,4.5H,0,T%O,, 1*4H,0.175Chromium, Molybdenum, and Tungsten.-The preparations of chromousoxide have been re-investigated, and a product with a CrN cubic structurehas been obtained by heating chromium carbonyl to between 250" and550°,176 The structure of black ferromagnetic chromium oxide, CrOrI4-prepared by thermal decomposition of Cr0,-has been confirmed as beingof the rutile type,177 but it is considered from magnetic evidence that thesolids of formal oxidation number -4.5 that result from the interaction ofCr(II1) and Cr0,2- in solution are hydroxy-complexes [Cr(OH),]HCrO, or[Cr(OH),],Cr04.178 KCr,08, which is prepared by melting chromium tri-166 K.Issleib and G. Bohn. 2. anorg. Chem., 1959, 301, 188.lbS A. Reisman and F. Holtzberg, J. Amer. Chem. Soc., 1958, 80, 6503; see Ann.170 H. Schafer and K.-D. Dohmann, 2. anorg. Chem., 1959, 300, 1.171 F. Fairbrother, A. H. Cowley, and N. Scott, J . Less Common Metals, 1959, 1,173 L. F. Dahl and D. L. Wampler, J . Amer. Chem. Soc., 1959, 81, 3150.173 D. E. Sands, A. Zalkin, and R. E. Elson, Acta Cryst., 1959, 12, 21.174 K. Huber, E. Jost, E. Neuenschwander, M. Studer, and B. Roth, Helv. Chim.Ada, 1958, 41, 2411; A. P. Palkin and N. D. Chikanov, Zhur. neorg. Khim., 1959, 4,898 [4Oi].175 N. S. Nikolaev and Y u .A. Buslaev, Zhur. neorg. Khim., 1959,4, 205 [84]; Yu, A.Buslaev and N. S. Nikolaev, ibid., p. 465 [210].H. Lux and G. Illmann, B e y . , 1959, 92, 2364.l77 K.-A. Wilhelmi and 0. Jonsson, Acta Chem. Scand., 1958, 12, 1532.178 H.-L. Krauss and G. Gnatz, B e y . , 1959, 92, 2110.Reports, 1958, 55, 155.206; W. A. Jenkins and C . M. Cook, jun., J . Inorg. Nuclear Cham., 1959, 11, 163SHARP: THE TR-4NSITION ELEMENTS. 151oxide with potassium dichromate, has tervalent chromium ions in octahedralco-ordination and sexavalent ions in tetrahedral co-0rdination.1~~ A com-plete structure determination has been carried out on monoclinic (NH,),CrO,.This compound contains a Cr2+ ion surrounded by a deformed pentagonalbipyramid of two superoxide ions and three ammonia molecules.l*O Thereaction of dibenzenechromium with di-t-butyl peroxide at 90" yieldsCr(OBu),, a deep blue solid, m.p. 37-38°.1s1 The oxidation of Cr2+ aquo-ions with certain reagents gives bridged binuclear Cr(m) cationic species ;similar binuclear ions are produced by boiling Cr(m) solutions.182Chomium(I1 and 111) complexes with phosphines and phosphine oxides -the complexes being of the types K,PH[Cr(SCN),(PK,)2], [(R,P),CrCI,],,Cr( SCN),( OPK,),, CrCl,( PR,) 2, CrCl,( OPR,),-have been described.lS3Acidification of molybdates is considered from pH curves to give aheptamolybdate, probably Mo70246- ; the mononuclear species present insuch solutions appear to be HMo0,- and hf0042-.184 However, from electro-metric and spectrophotometric studies it is considered that the main speciespresent is a tetram01ybdate.l~~ The presence of a Mo702,6- ion is in agree-ment with the existence of this ion in crystalline solids.The basicities ofheteropoly-acids have been measured by a spectrophotometric methodinvolving their influence on the ionisation of Methyl Orange. By usingresults from coagulation studies to establish the degree of agglomeration,the following formuk have been derived : H,COA!!O,O,,, H8CeMol,0,,,H,SiWl,O,,, H7P\V1,0,, H6p,~V,,0,,.1s6 Molybdenum hexacarhonyl doesnot give an arenemolybdenum tricarbonyl by reaction with henzoic acid butyields, instead, molybdenum( IT) ben20ate.l~~ A new molybdenum oxy-sulphide, MOOS,, results from the thermal decomposition of (NH4)2M~02S2.188The reactions of molybdenum dichloride have been extensively investigated.In general, it reacts as if it contained a quadrivalent cation, Mo,C184+, thereactions of this ion being very similar to those of the stannic ion.It isconcluded that in Mo,Cl,,, the molybdenum is effectively Mo(vI), employingall nine molybdenum orbitals, the complex cation thus having no reducingproperties.189 Two molybdenum oxybromides, Mo0,Br2 and MoOBr,,have been described; the latter is the compound previously described asMoBr4.190 Molybdenum pentachloride has a dimeric structure in the solidstate, the molybdenum having octahedral co-ordination.lgl The phases179 K.-A. Wilhelmi, A d a Clwm. S c a d . , 1958, 12, 1965; W. Klenim, 2. aizorg. Clzem.,180 E.H. McLaren and L. Helmholz, J . PJys. Chewz., 1959, 83, 1279.181 N. Hagihara and H. Yamazaki, J . Amer. Chem. SOC., 1959, 81, 3160.lE2 M. Ardon and R. A. Plane, J . Amer. Chem. Soc., 1950, 81, 3197; J. A. Laswickand R. A. Plane, ibid., p. 3564.Ia3 K . Issleib and A. Tzschach, 2. anorg. Chem., 1958, 297, 121; K. Issleib andH. 0. Frolich, ibid., 1959, 298, 84; K. Issleib, A. Tzschach, and H. 0. Frblich, ibid.,p. 164.1959, 301, 323.183 Y . Sasaki, I. Lindqvist, and L. G. Sillh, J . Inorg. Nuclear Chem., 1959, 9, 93.185 Y. Cannon, J . Inorg. Nuclear Chem., 1959, 9, 252.187 E. W. Abel, Apar Singh, and G. Wilkinson, J., 1959, 3097.188 G. Spengler and A. Weber, Ber., 1959, 92, 2163.189 J. C. Sheldon, Nature, 1959, 184, 1210.1*0 C. Durand, R.Schaal, and 1'. Souchay, Compt. rend., 1959, 248, 979.191 n. E. Sands and A . Zalkin, Acta Cryst., 1959, 12, 753.E. MatijeviC and M. Kerker, J . Arrzer. Chem. Soc., 1959, 81, 5560152 INORGANIC CHEMISTRY.present in the system HF-MoF,-H,O have been shown to be MoF,,H,MoO,F,, 1.5H20, H,MoO,F,,H,O, and MoO,,H,O.~~~There has been a chemical and physical investigation of the phasesprecipitated from tungstate solutions by acid. W03,2H20 and W03,H20have been identified as hydrates by comparison with the isomorphousmolybdenum compounds; a new compound, Na,O(WO,,H,O), (a = 4-10),has been isolated from this system.lg3 In aqueous solution 12-silicotungsticacid, H,SiW,,O,, has a molecular arrangement similar to that found for thes0lid.19~ Thallium-tungsten bronzes, Tl,WO, (x = 0-19-0*36), may beprepared by gentle reduction of thallium tungstate or mixtures of thalliumcarbonate and tungstic oxide. The univalent ion, M, in tungsten bronzesM,WO,, is considered to give rise to local energy levels in the forbidden gapbetween the conduction and the valency bands of tungsten trioxide.lg5The ammonolysis of tungsten hexackloride, either in liquid ammonia or inan inert solvent, gives WCl,(NH,),-, compounds; WCl,(NH,), reacts withammonium chloride to give [WC&(NH2),I2- ions. Thermal decompositionof the WCL(NH,),_, derivatives gives WC12(NH),.lg6Manganese, Technetium, and Rhenium.-Nuclear magnetic resonance andinfrared studies on precipitated manganese dioxide have shown the presenceof hydroxyl groups, and it is suggested that the observed non-stoicheiometryis due to replacement of oxide ion by hydro~y1.l~~ Manganous oxide be-comes non-stoicheiometric as the oxygen pressure is raised from 10-lo to 10-2atm.at 1500-1650". In this case the defect structure is considered to bedue to cation vacancies.1gs The blue solutions obtained by dissolvingmanganese dioxide in concentrated potassium hydroxide contain equimolarquantities of Mn(v) and Mn(I1r). Manganese(1v) appears to be thermo-dynamically unstable in such alkali solutions.199 Manganese oxysulphide,MnOS, is prepared by the action of oxygen on manganous sulphide; withhalogens, manganous sulphide gives halogeno-sulphides, MnSX,.200A review of the chemistry of technetium has been published this year.201Polarographic studies have established the existence of Tc(-I) in reducedpertechnetate solutions; the nature of this species is probably similar tothat of Re(-I) discussed below.202 Other new valency states of technetiumhave been characterised as resulting from the reaction between potassiumchlorotechnetate(1v) and o-phenylenebisdimethylarsine (D) (compounds31-35).," A reaction scheme for these changes is given opposite.Nuclear magnetic resonance studies have shown the presence of arhenium-hydrogen bond in rhenide solutions, and it seems likely that species192 N.S. Nikolaev and A. A, Opalovskii, Zhur. neorg. Khim., 1959, 4, 1174 [532].193 M. L. Freedman, J. Amer. Chem. SOL, 1959, 81, 3834.194 H. A. Levy, P. A. Agron, and M.D. Danford, J. Chem. Phys., 1959, SO, 1486.195 M. J. Sienko, J. Amer. Chem. SOC., 1959, 81, 5556.lg6 G. W. A. Fowles and B. P. Osborne, J . , 1959, 2275.197 0. Glemser, Nature, 1959, 183, 943.19* M. W. Davies and F. D. Richardson, Trans. Faraday SOC., 1959, 55, 604.199 K. A. K. Lott and M. C. R. Symons, J., 1959, 829.200 S. S. Batsanov and L. I. Gorogotskaya, Zhur. neorg. Khim., 1959, 4, 62 [24].201 G. E. Boyd, J. Chem. Educ., 1959, 36, 3.2O2 R. Colton, J . Dalziel, W. P. Griffith, and G. Wilkinson, Nature, 1959, 183, 1755.2O3 J, E. Fergusson and R. S. Nyholm, Nature, 1959,183. 2039SHARP THE TRANSITION ELEMENTS. 153such as [HRe(OH) (H20),]- or [H,Re(OH),(H,O)]- are present.202 Tri-methylsilyl per-rhenate, Me3Si*O*Re03, is prepared by the action of rheniumheptoxide on bistrimethylsilyl ether or by the interaction of silver per-rhenate and trimethylsilyl chloride.204 The per-rhenate ion is tetrahedralin aqueous solution but the existence of greenish-yellow Ba,(ReO,),, of un-known structure, has been confirmede205 Many complexes of rheniumtetraiodide and trichloride have been described; rhenium tetrabromide isprepared in the same way as the iodide205" and gives similar complexes.When the tetrabromide is heated in oxygen at 100-120" it gives colourless,volatile per-rhenyl bromide, Re0,Br.This sample appears more likely tobe true Re0,Br than the dark blue solid described previously.206 Darkgreen K5Re1(CN)6,3H20 may be prepared by reducing rhenium(&)with potassium amalgam.207solutionsD in refluxK,TcTVCI6 ____).~c~~~D,CI,ICI - CTC~~~D,BI-,]B~aq. EtOH orange (3 I ) LlBr In EtOH red (32)raflux Lil in EtOH / -reflux in excessTcTID,I, - [Tc~~'D,I,]I -+ [TC~~~D,~,]~,brown (34) EtOH or SOa deep red t o IP (35)black (33)Iron, Ruthenium, and Osmium.-Nuclear magnetic resonance and infra-red studies have shown that ferric hydroxide, Fe(OH),, cannot be precipitatedas a distinct phase, there being continuous loss of water and formation ofcondensed phases down to o(-Fe203.1g7 Schwertmann has made a verydetailed study of the conditions necessary for the formation of the variousiron oxides and oxy-hydroxides.208The infrared spectrum of ruthenium tetroxide is in agreement with atetrahedral structure for this molecule.209 Ruthenium(1v) species whichhave been prepared in aqueous solution by reduction of ruthenium tetroxideare generally polymeric, being of the form Ru(OH),,xH,O.Re-oxidationof these polymers requires up to eight equivalents of oxidising agent and itis suggested that there is induced oxidation of the bound water by ruthen-ium(Iv).210 Many ternary oxides of the alkaline-earth metals with Ru, Rh,M,DMIVO,, M,IIMrVO,, and M,11M2rV0,.211 The action of chlorine onruthenium trichloride gives a higher volatile chloride. The formula isunknown, but it has been suggested that it is the tetrachloride, RuCI4.212Ir, and Pt have been described this year; they are of the types MIIMIVO 3,204 M. Schmidt and H. Schmidbaur, Ber., 1959, 92, 2667.205 J. E.Earley, D. Fortnum, A. Wojcicki, and J. 0. Edwards, J . Amer. Chem. SOC,,205a Ann. RefJorts, 1958, 55, 161.206 R. Colton and G. Wilkinson, Chem. and Ind., 1959, 1314.207 D. Clams and A. Lissner, 2. anorg. Chem., 1958, 297, 300.208 U. Schwertmann, 2. anorg. Chem., 1959, 298, 337.209 R. E. Dodd, Trans. Faraday SOC., 1959, 55, 1480.210 F. P. Gortsema and J. W. Cobble, J . Amer. Chem. SOC., 1959, 81, 5516.211 J. J . Randall, jun., and R. Ward, J . Amer. Chem. SOL, 1959, 81, 2629; J. J.218 S. A. Shchukarev, N . I. Kolbin, and A. N. Ryabov, Zhur. neorg. Khim., 1959, 4,1959, 81, 1295.Randall, jun., and L. Katz, Acfa Cryst., 1959, 12, 519.1692 [763]154 INORGANIC CHEMISTRY.Reduction of cis-R,MX, [R = C,H,(PMe,),, C,H,(PEt,),, or o-C,H,(AsMe,),;M = Ru, 0 s ; X = halogen] with lithium aluminium hydride gives cis-R,MHX.The tram-complexes are not reduced, and the hitherto unknowncis-complexes were prepared for the first time. The hydrides are quitestable and can be stored out of contact with moisture and oxygen; theosmium derivatives are less stable than the ruthenium hydrides.129Cobalt, Rhodium, and Iridium.-Electron-diffraction studies have shownthat the substance precipitated from cobalt(I1) solutions by the action ofhydrogen sulphide is mainly Co&. When heated to 450" this changes toC O ~ S ~ . ~ ~ ~ It has previously been postulated that the peroxydicobalt coni-plexes, e.g., [(NH,),CO-O*O*CO(NH,),]~+ contain both ter- and quadri-valentcobalt, but electron-spin resonance studies have demonstrated theequivalence of the cobalt atoms.214 The first proof of the existence oftetrahedral co-ordination for cobalt(II1) ions has been given in the structureof the 12-tungstocobaltiate ion.The ease of reduction of the cobalt(II1)compound shows that this configuration provides relatively small stabilisationfor the 3+ state. The cobalt(I1) derivative also has tetrahedral co-ordin-ation.215 In the structure of bisacetylacetonecobalt(11) dihydrate there is atetragonally distorted octahedral co-ordination about the cobalt atom. Theorganic ligands are nearly planar but the cobalt is out of the plane.216 Sodiumchlorite is a good reagent for the oxidation of cobalt(11) to cobalt(II1) com-plexes; under suitable conditions chlorite-containing complex anions areformed.21' The action of potassium amide in liquid ammonia on cobalt-ammine hydrates has been studied.Various hydroxy-amido-complexesresult and these undergo further changes on treatment with the acidammonium nitrate.21* Complex cobalt (11) azide ions such as [CO(N,),]~-are formed in aqueous solution ; the tetraphenyl-phosphonium and -arsoniumsalts have been isolated.219 A complete structural study of trans-[Co(en),BrJBr,HBr,2HZ0 has shown the existence of [H20*H*OH2+] cations;the ethylenediamine is in the gazdche configuration.2Zo The deep green saltprepared by boiling ammonium chloroiridate( 111) with sulphuric acid has beenformulated as I<,[N(Ir(H,O) (SO,),),] on the basis of spectroscopic and mag-netic considerations; the nitrogen is three-covalent as in amines.221Nickel, Palladium, and Platinum.-Most of the work on nickel publishedthis year has been on various aspects of the co-ordination of the metal.The presence of the tetrahedral NQ2- ion has been established in solutionsof nickel chloride in fused pyridinium chloride, czesium chloride, and czesiumchlorozincate ; the ion is distorted in fused lithium chloride.222 Tetra-21s P.s. Aggarwal and A. Goswami, 2. Nalzarforsch., 1959, 14b, 419.214 E. A. V. Ebsworth and J. A. Weil, J . Phys. Chem., 1959, 63, 1890.215 L. C. W. Baker and V. E. Simmons, J . Amer. Chem. SOC., 1959, 81, 4744.216 G. J. Bullen, Acta Cryst., 1959, 12, 703.217 P. Spacu, C . Gheorghiu, M. Brezeanu, and S. Popescu, Rev. Chim. (Acad. R.P.R.),$18 0.Schmitz-DuMont and W. Hilger, 2. anorg. Chem., 1959, 300, 175.219 P. Senise, J . Amev. Ghem. SOC., 1959, 81, 4196.220 S. Ooi, Y . Komiyama, Y . Saito, and H. Kuroya, Bull. Chem. SOC. Japan, 1959,221 C. K. Jarrgensen, Actu Chem. Scund., 1959, 13, 196.225 D. M. Gruen and R. Id, McBeth, J . Phys. Chem., 1959, 63, 393.1958, 3, 127.52, 263SHARP : THE TRANSITION ELEMENTS. 155chloronickelates, R,NiCl, [R = Et4N+, Ph,MeAs+], have been preparedfrom alcoholic solution. From conductivity, spectroscopic, magnetic-susceptibility, and crystallographic studies it is concluded that there istetrahedral co-ordination about the nickel in these salts also.223 Stereo-chemical considerations would predict that the yellow complexes formed bythe action of triarylphosphine oxides on nickel(I1) salts should have tetra-hedral co-ordination about the metal; magnetic and spectroscopic data arein favour of this config~ration.~~~ The ligand-field theory has been appliedto the spectra of these tetrahedral complexes with very satisfactory results.225The position of the " planar " nickel complexes with anomalous magneticmoments has also reached a more satisfactory state.It is now believed thatdiamagnetic + paramagnetic transitions in these complexes are not dueto a change in stereochemistry but to a change in the strength of the fieldassociated with the ligands. The complexes are, in fact, pseudo-octahedral,the two apical ligands causing a perturbation from a singlet to a tripletground state.226 This perturbation can be effected merely by temperaturechanges ; this aspect of the problem has been studied for salicylaldiminederivative^.^^' Diamagnetic bis- (N-methylsalic ylaldimine)nickel(~r) , whichgives paramagnetic solutions, has a trans-planar arrangement about thenickel atom; there is no possibility of metal-metal bonding.228 It has beenshown that nickel@) forms a hexacyano-anion, [Ni(CN),]4-.229The absorption spectra of [PdX4I2- (X = C1, Br) and [Pd2X6I2- (X = C1,Br, I) ions depend upon the solvent and it is concluded that the ions areactually six-co-ordinate in solution.It appears possible that there is alsooctahedral co-ordination in the solid state.230 Platinic chloride has a tetra-hedral arrangement of chlorine atoms about the platinum; this seems to bethe first report of tetrahedral co-ordination for this element.231 The deepgreen colour of Pt (CH,NH,),PtCl, is associated with metal-metal interactionin the Physicochemical measurements have been made on thetwo chloro-acetylacetonates of platinum.It is concluded that the orangeform has the structure K[Cl,Ptac] and that the yellow form is K[C1Ptac2](ac = acetylacetone group). One of the acetylacetonate groups in theyellow form is m ~ n o d e n t a t e . ~ ~ ~ Further work has been published on thecomplexes that result in removal of protons from the amino-groups ofligands in platinum complexes. The reaction of bisethylenediamine-platinum(I1) iodide with excess of potassium amide in liquid ammonia givesKIPtxl(en-H) (en--2H)].The unstable species [Ptl(en) (en-H)] occurs223 N. S. Gill and R. S. Nyholm, J., 1959, 3997.224 F. A. Cotton, E. Bannister, R. Barnes, and R. H. Holm, Proc. Ckenz. Soc., 1959,22s A. D. Liehr and C. J. Ballhausen, Ann. Phys., 1959, 2, 134; B. R. Sundheim and228 G. Maki, J . Chem. Phys., 1958, 29, 1129; C. J. Ballhausen and A. D. Liehr,227 H. C. Clark and R. J. O'Brien, Canad. J . Chem., 1959, 3'9, 436.228 E. Frasson, C. Panattoni, and L. Sacconi, J . Phys. Chenz., 1959, 63, 1908.229 L. KiSovA and V. CuprovA,, Chem. Listy, 1958, 52, 1422.230 C. M. Harris, S. E. Livingstone, and I. H. Reece, J., 1959, 1606.232 M. T. Falqui, Ann. Chim. (Rome), 1958, 48, 1160.232 S. Yamada and R. Tsuchida, Bull. Chem. Soc. Japan, 1958, 31, 813,158.G.Harrington, J. Chem. Phys., 1959, 31, 700..J. Amer. Chem. SOL, 1959, 81, 538; see also C. Furlani, Gazzetta, 1958, 88, 279.A. A. Grinberg and I. N. Chapurskii, Zhur. neorg. Khim., 1959, 4, 314 [137]156 INORGANIC CHEMISTRY.transitorily in the reduction of [Pt(en)2]2+ with potassium in the presence ofpotassium amide.234Copper, Silver, and Gold.-The bonding in copper compounds continuesto excite considerable interest. The paramagnetic resonance spectrum ofcopper acetate is taken to confirm the existence of a &bond between themetal atoms in the binuclear molecule.235 The magnetic susceptibilitiesof cupric salts of substituted acetic acids and of cro-dicarboxylic acids alsofavour the existence of metal-metal bonding in the crystalline solids exceptin the case of cupric malonate. It is possible that geometrical considerationsrule out metal-metal bonding for copper salts of [CH2In-2(CO2H), acids whenn is As part of an extensive series of experiments on the variouscopper formates, it has been shown that the normal salt, which does nothave metal-metal bonding, can be “ conditioned ” into adopting a binuclearstructure with 6 bonding between the copper atoms by complexing the metalwith amines or di~xan.~,’ Green bis-salicylaldiminecopper(I1) is isomorphouswith the nickel complex, the atomic arrangement being such that the co-ordination about the copper is truly planar.238 The octahedron of fluorideions about the copper atom in K,CuF, is distorted to give four long (2-08 A)bonds in a plane, the two apical bonds being shortened (1.95 4.239 Crystal-field theory would predict a distorted octahedral co-ordination for copper@),and recent calculations have predicted that the distortion could give eitherfour long and two short bonds or four short and two long bonds as are morenormally found.240 A full structure has now been determined for anhydrouscupric nitrate.Each copper atom is eight-co-ordinate with respect tooxygen; there are two Cu-0 bonds linking Cu and NO, groups in infinitechains parallel to one axis; the other six bonds are to a distorted hexagonof oxygens at right angles to this axis, these oxygens being from nitrategroups which hold the infinite chains together. There is no obvious reasonwhy this structure should give rise to volatile monomers.241 A furtherunusual co-ordination arrangement for copper is found in bis(dimethy1-glyoxime)copper(II) .The structure consists of dimers, the copper atom beingslightly above the plane of four nitrogen atoms, and each copper atom beinglinked further to an oxygen of the other half of the molecule.242 In bothbis(succinonitri1e) copper (I) nitrate 243 and tristhioureacopper(r) chloride 244crystal structure determinations have shown tetrahedral co-ordination aboutthe copper atoms. In the former compound the succinonitrile acts as abidentate ligand and is joined to different copper atoms; the cations, there-fore, form chains through the structure. In the thiourea complex the copper234 G. W. Watt and J. W. Dawes, J . Amer. Chem. SOC., 1959, 81, 8.28s I. G. Ross, Trans. Faraday SOC., 1959, 55, 1057.286 M. Kondo and M. Kubo, J . Phys. Chem., 1958, 62, 1558; 0. Asai, M. Kishita,237 R. L. Martin and H. Waterman, J., 1959, 1359, 2960.238 J. M. Stewart and E. C. Lingafelter, Acta Cryst., 1959, 12, 842.239 K. Knox, J . Chem. Phys., 1959, 30, 991.240 A. D. Liehr and C . J. Ballhausen, Ann. Phys. (N.Y.), 1958, 8, 304; cf. U. dpikand M. H. L. Pryce, Proc. Roy. SOL, 1957, A , 238, 425.241 S. C . Wallwork, Proc. Chem. Soc., 1959, 311.242 E. Frasson, R. Bardi, and S. Bezzi, Acta Cvyst., 1959, 12, 201.243 Y. Kinoshita, I. Matsubara, and Y . Saito, BuK Chem. SOC. Jafian, 1959, 32, 741.244 C. B. Knobler, Y. Okaya, and R. Pepinsky, 2. Krist., 1959, 111, 385.and M. Kubo, ibid., 1959, 63, 96SHARP: THE TRANSITION ELEMENTS. 151shares sulphur atoms with neighbouring tetrahedra. Other cuprates,MCuO, (M = Na, Rb, Cs), have been prepared by heating a mixture of themetal oxide and cupric oxide in oxygen. Lithium oxide gives the loweroxides Li,CuO, and L~,CU,O,.~ Cuprates can also be prepared by oxidisingcupric salts with hypoclilorite.246Argentic oxide prepared by the normal methods has the zinc blendestructure, but it is generally contaminated with other oxides. The peroxy-nitrate, -sulphate, and -fluoride of silver are essentially Ag,O, containingoxide and acid salt impurities. Ag,O, has a cubic lattice with someoxygen defects.,,' Silver(1) NN'-dialkyldithiocarbamates react with thecorresponding thiuram disulphides to give blue solutions in benzene which,from electron-spin resonance studies, are considered to contain bivalentRSAgIISR species. Gold(1) species behave very similarly and, although thegold(m) compound results eventually, it is considered that there is definiteevidence for the presence of gold(I1) species in solution.248 The crystalstructure of aurous iodide shows that there are continuous Au-I chainsthroughout the crystal; the Au-I distance is very short (2-62 Therehas been considerable evidence this year to show that gold(m) can readilyachieve a co-ordination number of six in complexes. The bromoaurateion, AuBr,-, reacts with bromide ion in nitrobenzene and nitromethane to giveAuBrG3-, AuBr,2-, and Au2BrIo4- ions.250 1 ,lo-Phenanthroline and 2,2'-bipyridyl complexes of gold(II1) halides rearrange in non-aqueous solvents :2[Au(phen)X,]+ + 2X-+ [Au(phen)X,]+ + [AuX,]- + phen. It is con-sidered that the ready rearrangement is by way of an intermediate distortedoctahedral arrangement.251 Chloroauric acid reacts with alkali iodides togive complex iodides, MAuI, and M,AulAulIII, (M = Cs and Rb). Thelatter compounds are reminiscent of the complex chloride, Cs2Au2C16, re-ported many years Potassium fluoroaurate, KAuF,, is isomorphouswith the fluorobromate and it is possible that there is a distorted octahedralarrangement about the metal in this complex.253Zinc, Cadmium, and Mercury.-Cadmium alkyls react with molecularoxygen or alkyl hydroperoxides to give alkylperoxycadmium compounds.254Apart from this one paper, work on this group reported during the year has,been mainly concerned with the chemistry of mercury. ,4 combined X-rayand neutron-diffraction study QTI mercuric cyanide has shown that the,NC-Hg-CN groups are not linear and that the deviation from linearity canbest be explained in terms of interaction of the mercury atom with nitrogenatoms in neighbouring groups (36). Hg . N plane is a t an! The N245 W. Klemm, G. Wehrmayer, and H. Bade, 2. Elektrochem., 1969, 83, 56.246 A. Yu. Prokopchik and P. K. Norkus, Zhur. neorg. Khim., 1959, 4, 1359 [Sll].247 B. Stehlik and P. Weidenthaler, Chenz. Listy, 1958, 52, 402; B. Stehlik, P.248 T. Vanngard and S. Akerstrom, Nature, 1959, 184, 183; S. Akerstrom, Arkiv249 H. Jagodzinski, 2. Krist., 1959, 112, 80.250 C. M. Harris and I. H. Reece, Nature, 1958, 182, 1665.251 C. M. Harris, J., 1959, 682; C. 3%. Harris and T. X. Lockyer, ibid., p. 3083.282 A. Ferrari and M. E. Tani, Gazzetta, 1969, 89, 502.253 R. D. Peacock, Chew. and Ind., 1959, 904; see also ref, 17.254 €3. G. Davies and J. E. Packer, J., 1959, 3164.Weidenthaler and J. Vlach, ibid., p. 2230.Kemi, 1959, 14, 403158 INOKGANIC CHEMISTRY.angle of 92" to the plane through the Hg(CN), molecule.255 Complexes ofthe mercurous ion are little known, but it has been shown that oxyanionssuch as pyrophosphate, tripolyphosphate, oxalate, and succinate do formcomplexes.256 A solid which is probably a mercurous complex,Hg,phen,(NO,),, is precipitated from mercurous nitrate solution by o-phen-=N2.70 - -N (37)a n t h r ~ l i n e . ~ ~ ~ Mercurous nitrate also gives a complex with NN'-diacetyl-hydrazine ; this compound very probably has chains (37) running throughthe struc t ~ r e . ~ ~ ~ Bis (trifluoromethylthio)mercury, Hg(S*CF,),, is obtainedin high yield from mercuric fluoride and carbon disulphide at 250". Whenheated to higher temperatures it breaks down to give CF,*SCF, andCF,*S-S*CF,. The mercurial reacts with metallic copper to give (Cu*S*CF&and in aqueous solution reacts with silver nitrate to give Ag*S*CF3. I tundergoes many metathetical reactions with organic halides.259D. W. A. S.A. G. SHARPE.D. W. A. SHARP.255 J. Hvoslef, Acta Chem. Scand., 1958, 12, 1568.2 j 6 T, Yamane and N. Davidson, J . Amer. Chem. SOC., 1959, 81, 4438.257 G. Anderegg, Helv. Chim. Acta, 1959, 42, 344.258 K. Brodersen and L. Kunkel, BEY., 1958, 91, 2698.239 E. H. Man, D. D. Coffmann, and E. L. Muetterties, J . Amer. Chew. SOC., 1959,81, 3575

ISSN:0365-6217    

DOI:10.1039/AR9595600111

出版商:RSC    

年代:1959

数据来源: RSC

摘要:

ORGANIC CHEMISTRYI. INTRODUCTIONAMONG the topics reviewed in the theoretical section of this Report are thechemistry of carbanions and carbenes, where valuable stereochemical in-formation has recently been obtained, and oxidation by ch-amic acid,permanganate, and other oxidants.There has been much progress in the assignment of absolute configur-ations. Conformational, mechanistic, and theoretical approaches to thisproblem are discussed. Much promise attaches to a procedure for the com-putation of molecular rotations from the polarisabilities of the componentsof asymmetric groups. A second example is recorded of a compound owingits optical inactivity to a four-fold alternating axis of symmetry. Theimportance of entropy in determining equilibria and rates of isomerisationhas been emphasised in a number of investigations.Among general synthetic methods, hydroboronation, followed by re-placement of boron by hydroxyl (H,O,) or hydrogen (H+) affords, respec-tively, means for anti-Markovnikov hydration and non-catalytic reductionof olefins.Serviceable procedures are described for stereospecific synthesisof trisubstituted ethylenes, and for repeated chain-lengthening by three-carbon units and by isoprene residues.Advances continue in the synthesis and identification of naturally occur-ring unsaturated acids. Much work has been done on acetylenes, on theone hand in exploiting the reactivity of halogeno- and alkoxy-acetylenes,and on the other in elucidating the structures of natural poly-ynes.Tri-merisation of hexa-1,5-diyne gives a partly conjugated cyclo-octadeca-hexayne, which by prototropic rearrangement followed by reduction givescyclo-octadecanonaene. This monocyclic olefin with 18 conjugated x-elec-trons would, according to Hiickel’s (4n+2) rule, be expected to have aromaticcharacter; it is at least not evidently unstable.Observations on non-benzenoid aromatic systems include niuch work oncyclopentadienyl anions and tropylium cations, the production of tetra-methylcyclobutadiene as its complex with nickel chloride, and the prepar-ation of new metallocenes. Several new boron-containing hetero-aromaticsystems have been described, as also has the first isothiazole (1-thia-2-aza-cyclopentadiene) .A new biosynthetic theory challenges the view that alkaloids arise in themain from amino-acids.Total syntheses of colchicine, cinchonamine, anddihydrocorynantheine are reported. The constitution and configuration ofaconitine have been elucidated.Recent developments in the chemistry of nitrogen-containing derivativesof sugars, of sugar anhydrides, and of deoxy- and branched-chain sugars arereviewed.New amino-acids have been isolated of the most diverse structures,including the first naturally occurring yyrazole. A process has been devise160 ORGANIC CHEMISTRY.which breaks a peptide chain at a tyrosine or tryptophan residue. Muchimportant work has been done on amino-acid sequences in normal andabnormal hanoglobin and on the structure and synthesis of biologicallyactive peptides.A total synthesis of coenzyme A has been effected.P. B. D. DE LA M.T. s. s.2. THEORETICAL ORGANIC CHEMISTRYEiectrophilic Aromatic Substitution.-This subject was not reviewed lastyear, and so the present report covers both 1955 and 1959.General theory. In recent years, the reactivity of aromatic compoundsto electrophilic reagents (e.g., X+) has generally been discussed in terms ofthe Wheland transition state (1) or a related unsymmetrical structure inwhich the C-X bond is only partly formed and in which the cyclic delocal-isation of the x-electrons is partly retained.l These approaches do notdistinguish between the effects of x-electrons in different molecular orbitals.At the same time there has been a growing body of evidence, supplied(1) (2)mainly by K.Fukui and his collaborators,2 indicating a relation betweenthe orientation of electrophilic substitution and the x-electron distributionin the highest filled molecular orbital of the aromatic compound. Relatedcorrelations have been made for nucleophilic and homolytic reactions, andthe whole has been termed the frontier orbital theory of aromatic sub-stitution.2 This approach has recently met considerable criticism,3 but itsimplication that the higher-energy molecular orbitals of the aromatic com-pound are particularly important in determining the reactivity has appar-ently influenced several new interpretations of the reaction path.435 Oneof these, by R. D. Brown,5 starts with the assumption that aromatic sub-stitution proceeds through two unsymmetrical charge-transfer complexes,e.g., (2) ; calculations suggest that in these complexes the charge is effectivelytransferred to the aromatic ring and the reagent is above one of the carbonatoms.For certain reactions, including nitration, it is assumed that thefirst step (a) is rate-determining, and calculations on this basis are in goodagreement with the relative reactivities in a series of polycyclic hydro-1 M. J. S. Dewar, Ann. Reports, 1956, 53, 133.3 K. Fukui, T. Yonezawa, and C. Nagata, J . Chem. Phys., 1957, 26, 831; K. Fukui,T. Yonezawa, C. Nagata, and H. Shingu, &id., 1954, 22, 1433, and references therequoted.K. Fukui, T. Yonezawa, and C. Nagata, J . Chem. Phys., 1959, 31, 550, and follow-ing letters.4 K.Fukui, T. Yonezawa, and C. Nagata, Bull. Chern. SOC. Japan, 1954, 27, 423;J . Cbem. Phys., 1957, 27, 1247; S. Nagakura and J. Tanaka, Bull. Chem. SOC. Japan,1959, 52, 734.6 R. D. Brown, J., 1959, 2224THEOKETICAL ORGANIC CHEMISTRY. 161carbons.6 However, rather similar results can be obtained by the calcul-ation of localisation energies (cf. ref. l), and methods for such calculationscontinue to be developed.'The equilibrium studies by Mackor and his co-workers * throw some lighton the possible intermediates in aromatic substitution. In ionising solvents(dimethyl sulphate, nitrobenzene, etc.) some aromatic compounds (ArH)react with Lewis acids (e.g., BF,, SO,) to form the corresponding aromaticcations (ArH+); in solvents of lower dielectric constant, addition canoccur to form compounds of type (3).In sulphuric acid alone, oxidationH H(3)to the cation is now known to occur,phatic character " of the CH, group(4)as well as protonationin compounds related(4). The " ali-to (4) has beenindicated by nuclear magnetic resonance measurement^.^Empirical rules related to the Hammett equation continue to be de-veloped. The " selectivity relationship " between the partial rate factorsfor substitution at the m- and the $-position of a monosubstituted benzenederivative has been re-examined for substitution in toluene lo and appliedwith less success to substitution in t-butylbenzene.ll Further considerationhas been given to the Hammett o-values12 and to their interpretation interms of separate contributions from the inductive and conjugative inter-action of substituents with the aromatic ring.ls The application of theo+-values to electrophilic substitution has been discussed in detail l4 anda critical analysis of the above approximations has been p~b1ished.l~At the recent Hyperconjugation Conference, de la Mare presentedevidence for the importance of O-H and N-H hyperconjugation in thereactions of phenols and amines,16 and in other papers the reactivity of thealkylbenzenes was discussed with special reference to the relative importanceof C-H and C-C hyperc~njugation.~~ Further work has been done on thesteric inhibition of mesomerism in substituted benzene derivatives.l*R.D. Brown, J., 1959, 2232.D.Peters, J., 1958, 1028.W. I. Aalbersberg, G. J. Hoijtink, E. L. Mackor, and W. P. Weijland, J., 1959,C. MacLean, J. H. van der Waals, and E. L. Mackor, Mot. Phys., 1958, 1, 247.lo L. M. Stock and H. C . Brown, J . Amer. Chem. SOC., 1959, 81, 3323.l1 L. M. Stock and H. C. Brown, J . Amer. Chem. SOC., 1959, 81, 5621.l2 M. M. Fickling, A. Fischer, B. R. Mann, J. Packer, and J. Vaughan, J . Amer.la R. W. Taft and I. C. Lewis, J . Amer. Chem. SOC., 1958, 80, 2436; 1959, 81, 5343,l4 H. C. Brown and Y . Okamoto, J . Amer. Chem. SOC., 1958, 80, 4979.l5 H. van Bekkum, P. E. Verkade, and B. hl. Wepster, Rec. Trm. chim., 1959, 78,l6 " Conference on Hyperconjugation," Pergamon Press, 1959, p. 126.l7 R. W. Taft, I. C. Lewis, ref. 16, p. 24; E. Berliner, 09.cit., p. 143.l8 T. C . van Hock, P. E. Verkade, and B. M. Wepster, Rec. Trav. chim., 1958, 77,559; H. Kafod, L. E. Sutton, P. E. Verkade, and B. M. Wepster, ibid., 1959, 79, 790.REP.-VOL. LVI F3049, 3055.Chem. SOC., 1959, 81, 4226.5352.815I 62 ORGAN I C CHEM I SllZY.Hydrogen-isotope exchange. Recent work is consistent with the theorythat hydrogen-isotope exchange in aromatic compounds can occur througha preliminary protonation, as suggested by Gold and Satchell and illustratedbelow. Thus the rate of detritiation of (~-~H)-p-cresol in D,O is greater( A 1 mechanism).than that in H,O by a factor of 1.6 (both media contained 4~-hydrochloricacid).l9 The variation of rate with composition in H,O-D,O mixtures isnot linear and is as expected for a preliminary protonation equi1ibri~m.l~The effect of zinc chloride and stannic chloride on the rate of hydrogen-isotope exchange of $-deuteroanisole in acetic acid containing hydrogenchloride parallels the effect of these salts on the protonation of anilinederivativesm However, there is also evidence that exchange can occur bya mechanism involving a Bronsted acid in the rate-determining step.Kresgeand Chiang 21 have shown that the detritiation of labelled 1,3,5-trimethoxy-benzene in acetate buffers is catalysed by molecular acetic acid, and thedetritiation of labelled 1,2,3-trimethoxybenzene in trifluoroacetic acid givessome evidence for the same effect.22 The importance of this mechanism(presumably A-SE2) (cf. ref. 23) relative to the A 1 mechanism mentionedabove is not yet understood, and it is possible that some of the facts usedin support of the A1 mechanism may permit other interpretation~.~3Primary hydrogen-isotope effects in these exchanges have been studiedby comparing the relative rates of displacement of deuterium and tritiumby h y d r ~ g e n .~ ~ , ~ ~ The values of kDlkT are all about 2, but their relativevalues show evidence of an increase with the reactivity of the positionsubstituted.Partial rate factors 25 have been obtained for the deuteration of alkyl-benzenes in trifluoroacetic acid containing D,O. Some work has beenreported on the orientation and rate of deuteration of benzene derivativesin the presence of platinum.26 Substituent effects have been reported forthe protodetritiation of a number of benzene derivatives in several acidicmedia, including aqueous sulphuric acid and trifluoroacetic a ~ i d .~ 7 Second-ary isotope effects (studied by comparing -CH3 and -CD, substituents) donot appear significant in aromatic hydrogen-isotope exchange.28Is V. Gold, R. W. Lambert, and D. P. N. Satchell, Chem. and Ind., 1959, 1312.2O D. P. N. Satchell, J., 1958, 1927, 3910.21 A. J. Icresge and Y . Chiang, J . Amer. Chem. SOC., 1959, 81, 5509.2z D. P. N. Satchell, J., 1958, 3904.29 F. A. Long and M. A. Paul, Chem. Rezi., 1957, 51, 935; cf. L. Melander and P. C.24 S . Olsson, Zrliiv Kemi, 1959, 14, 85.25 W. M. Lauer, G. W. Matson, and G. Stedman, J . Amer. Chem. SOC., 1958, 80,26 W. G. Brown and J.L. Garnett, J . Amer. Chem. SOC., 1958, 80, 8272.27 C. Eaborn and R. Taylor, Chem. and IBd., 1959, 949.28 A. J. Kresge and D. P. N. Satchell, Tetrahedron L e f f e r s , 1959, 13, 20; W. &I.Myhre, Arkiv Kemi, 1959, 13, 507.6433, 6437, 6439.Lauer and C. B. Koons, J . Org. Chem., 1959, 24, 1169THEOI<BTICAL ORGANIC CHEhIISTRY. 163'I'hie zeroth-order nitration obtained by E. I>. Hughes, SirChristopher Ingold, and others in nitromethane has now been extended tothe N-nitration of N-methyl-2,4,6-trinitroaniline 29 and to the O-nitrationof methyl alcohol, 4-nitrobenzyl alcohol, ethylene glycol, trimethyleneglycol, and glycerol.30 The zeroth-order rates are the same as for C-nitration,and the interpretation is also the same-a slow rate-determining formationof NO,+ followed by a fast reaction with the substrate.On the additionof sufficient water, the kinetic form of these reactions becomes first-orderwith respect to the substrate, and the relative reactivity of these substratesand of water towards NO2+ can then be obtained. Values on the scalebenzene = 1 are : H,O, 0.1--0*01; N-methyl-2,4,6-trinitroaniline, 1.4;methyl alcohol, 30.The comparison of the rates of nitration and l*O-exchange in aqueoussolutions containing nitric acid has now been extended to the nitration of2-mesitylethanesulphonic acid 31 (the most reactive substrate yet studiedin this way); the nitration still appears to involve NO2+. A kinetic studyof the nitration of benzene by nitric acid in acetic anhydride is inconsistentwith nitration by dinitrogen pentoxide and suggests that this reactionoccurs by the rapid formation of NO,+ in a pre-equilibrium step; thereaction is catalysed by added sulphuric acid and anticatalysed by nitrateions.32 The difference in isomer proportions sometimes observed betweennitrations in acetic anhydride and in sulphuric acid has been ascribed33to the increased electrostatic interaction between the electrophilic reagentand the molecular dipole of the substrate as a result of the low dielectricconstant of acetic anhydride.The orientation of nitration has been re-examined for substitution intoluene,M +-nitrotol~ene,3~ o-nitrotol~ene,~~ ethyl ben~oate,~' and benzo-nitrile.38 In the nitration of ethyl benzoate, the entropy of activation isthe same for substitution a t the o-, m-, and +-positions.37 In the nitrationof benzonitrile the o : p-ratio is 3-3; this is discussed with reference to themechanism by which -T substituents give high o :$-ratios (see also p.238).Partial rate factors have been published for the nitration of diphenyl-methane, fluorene, diphenyl ether, dibenzofuran, diphenylamine, carbazole,39and various nitro biphenyl^.^^ The partial rate factors for 4-nitrobiphenylNitration.hexanones besides the expected epoxides. Oxidation of cyclohex-2-enonewith trifluoroperoxyacetic acid 33 affords 2-hydroxyadipic acid, via theexpected hex-2-enolactone. Perhydrofluorenone is produced on thermalreaction of carbon monoxide and cy~lohexene,~4 and cyclopentene behavesanalogously.(29) (30) (31) (32)Pyrolysis of xanthates 35 or acetates 36 of tertiary alcohols of the type (30)yields both exo- and endo-cyclic olefins.The latter type of reaction involvesa cis-elimination.37 Pure methylenecycloalkanes are formed 38 whenhydroxy-acids (31; n = 1 4 ) are heated with copper in quinoline. 3,6-Dimethylenecyclohexene arises 39 from the pyrolysis of the acetate (32).1,2,4 and 1,3,5-Trimethylenecyclohexane and 1,3,5,7-tetramethylenecyclo-octane are produced by catalytic cyclopolymerisation of allene; and allenewith acetylene cyclopolymerises, according to the conditions, to 3,5- or3,6-dimethylenecyclohexene and 3,5,7-trimethylenecyclo-octene. The cyclo-hexene derivatives readily arornati~e.~~Hydration of cyclic olefins, via alkylborons, involves cisaddition of theelements of water.41 Cyclohexa-3,5-diene-l,2-diol (" benzene glycol ")has been prepared 42 from 3,4,5,6-tetrachlorocyclohexane-I,2-diol.l-Formylcyclo-hexene and -pentene have been togetherANSELL : ALICYCLIC COMPOUNDS. 223The action of zinc, in the presence of EDTA, on pentaerythritol tetra-bromide produces53 pure spiropentane.The spiran (42) is formed by theaddition of tetracyanoethylene to the diene (43; R = H), but with the diene(43; R = Me) addition occurs to the endocyclic double bond to form thebicyclo [2,2 ,O]hexane (44) .M Similar reactions are described by Blomquistand Mein~ald.~5 Syntheses of 6,9-methylenespiro[4,5]decane and spiro[5,6]-dodecane 66 are reported.Me.C(CHBr .CO,Et ) 2----.- ----_HOIC OZH (47)ICH,.CO,EtCOZH(46)The reported 57 formation of three isomeric bicyclobutanecarboxylicacids (45) from the ester (46) could not be sub~tantiated.~~ The structure(47) of the " cage compound " derived from one such acid is therefore ques-tionable. Ethyl bicyclo[l,l,0]butane-l-carboxylate, obtained from ethyl3-bromocyclobutane-l-carboxylate and triphenylmethylsodium, is the firstauthenticated member of this series.59The dione (48) is readily available 60 from methyl vinyl ketone and2-methylcyclopentane-lJ3-dione.Silver perchlorate with the chloride (49)forms the perchlorate of the ion (50).Ph. .(48) (49) (50)Claisen rearrangement of the ether (51) to the aldehyde (52;13 = CH,CHO) is a stereospecific method62 of introducing an angular sub-stituent. 9-Acetyldecalin and the ketone (52; R = COMe) are amongthe products from Friedel-Crafts acetylation of decalin.63224 ORGANIC CHEMISTRY.Norcaradienecarboxylic acid (and the derived nitrile) yield 64 phenyl-acetic acid when heated with sulphuric acid, and the dichloride (53) yields 65cycloheptatriene and toluene on pyrolysis.Dehydrative cyclisation of 2-3'-oxoalkylcyclohexanones yields bi-cycle [3,3,1] nonenones .66The free-radical halogenation of norbornane 67 gives mainly the 2-halide.Bromination of both norbornane-exo- and -endo-2-carboxylic acid yieldsem-2-bromobornane-l-carboxylic acid, whereas either acid chloride yieldsexo-2-bromonorbornane-endo-2-carboxylic acid.68 The novel rearrangementof 5-nitronorbornene to the oxazinone (54) has been des~ribed,~~ and amechanism proposed for it.The adamantane derivative (56) has been obtained '* by condensationof 4-dichloromethyl-4-methylcyclohexa-2,5-dienone and acetonedicarboxylicester, followed by ketonic hydrolysis to the diketone (55) and condensationwith nitromethane.The ketone formed by the action of boron trifluoride on endrin (57a) isconsidered'l to have structure (58), and not structure (57b) as suggestedprevio~sly.~~The sign and magnitude of optical rotation of some cyclic compoundsmay be estimated 73 by the use of the principles of conformational asym-metry and certain empirical constants. a-Axial and a-equatorial chloro-and bromo-ketones can be distinguished by measurement of their optical134 M, J.S. Dewar and C. R. Ganellin, Chem. and Ind., 1959, 458.65 €3. E. Winberg, J. Org. Chem., 1959, 24, 264.66 S. Julia and D. Varech, Bull. Soc. chim. France, 1959, 1127.67 E. C. Kooyman and G. C. Vegter, Tetrahedron, 1959, 4, 382,68 W. R. Boehme, J . Amer. Chem. SOC., 1959, 81. 2762; H. Kwart and G. Null,69 W. E. Noland, J. H. Cooley, and I?. A. McVeigh, J . Amer. Chem. Soc., 1959, 81,70 H. Stetter and J. Mayer, Angew. Chem., 1959, 71, 430.71 R. C. Cookson and E. Crundell, Chem. and Ind., 1959, 703.73 E. J . Skerrett and E. A. Baker, Chem. and Ind., 1959, 639.7 3 J . H. Brewster, J . Amer. Chem. SOL, 1959, 81, 6483, 5493.ibid., p. 2765.1209ANSELI. ALICYCLIC COMPOllNDS. 326rotatory disper~ion.'~ 2-Fluorocyclohexanone exists 75 in the theoreticallyless stable axial conformation. The absolute configurations of cis- and trans-( a ) x = 60( b ) X =(57)1,4dimethylcyclohexane have been established 75a by correlation with meso-and racemic-ad-dimethyladipic acid respectively.The cyclohexa-1 ,Pdiene molecule is considered 78 to be folded along the3,6-axis.The preferred conformations for cycloheptane (59) and (60) andcyclo-octane (61) and (62) have been predicted, and the last pair sub-stantiated by evidence based on the dipole moments of cyclo-octanonederivative^.^^ The conformation (59) has also been deduced on spectro-scopic grounds and those of cyclononane and cyclodecane have been dis-cussed.78 cis-Cyclodecene is less stable than its tra~~s-isomer.~~ The four-membered ring in pino- or isopino-camphone is consideredso to be planar,the strain of the system being accommodated in the six-membered ring.Further examples 81 of the stereospecificity of micro-organisms arepresented, e.g., A9-octalin-1,5-dione is reduced stereospecifically by CurvuZariafalcata and Rihizopus nigricans to (55)-5-hydroxy-As-octal-l-one.The stericeffect of 4-substituents in the mercuration of cyclohexene is reported; 82thus replacement of a l-hydroxy-l-methylethyl group by an isopropylgroup reverses the direction of addition. Norbornane-elzdo-2-carboxylicacid has been resolved and stereochemically correlated with the exo-isomerand with norborn-5-ene-exo- and -endo-2-carboxylic acid.On the basis of ultraviolet and infrared absorption 2-, 3-, and 4-acet-amido- and -benzamido-pyridine exist predominantly in the acylamino-form.84 o-, m-, and p-Aminophenyl 4-pyridyl ether (56) are rearranged byacids to N-4-pyridyl-o-, -m-, and -$-aminophenol (57). An essential stepin the proposed mechanism for the transformation is quaternisation of thepyridine-nitrogen atom.%With sodium hydrogen sulphite some pyridine quaternary salts yieldaddition compounds which are readily decomposed by alkali into alkyiaminesand diketones; the latter cyclise under acid conditions to phenoIs, asillustrated.s6+ NHzMe Me MeThe addition of ammonia to glutaronitrile yields glutarimidine (58).The imino-groups are reactive, undergoing displacement reactions with, forexample, water, hydroxylamine, and aniline.Glutarimidines are regardedas di-iminopiperidines or amino-imino-piperidehes, and not as diamino-dihydropyridines.87 Glutardialdehyde and ammonium cyanide react inaqueous solution, to yield 2,6-&~yanopiperidine.~82 Z. Arnold, Experientia, 1959, 15, 415.83 K. Mecklenborg and M. Orchin, J . Org. Chem., 1958, 25, 1591.84 R. A. Jones and A. R. Katritzky, J., 1959, 1317.85 D. Jerchel and L. Jakob, Chem. Ber., 1959, 92, 724.86 R. LukeS and J. Jizba, CoZZ. Czech.. Chem. Comm., 1959, 24, 1868.87 J. A. Elvidge, R. P. Liastead, and A. M. Salaman, J., 1959, 208.88 R. A. Henry, J . Org. Chem., 1959, 24, 1363PINDER: HETEROCYCLIC COMPOUNDS. 26 1Dieckmann cyclisation of the ester (59f yields, of the two possible isomers,A similar the p-keto-ester (60), the structure being proved by ozonolysis.cyclisation of the appropriate unsaturated diester affords the oxopiperideine(61).89The hydrochlorides of 1-methyl-3- and -4-oxopiperidine crystallise withone molecule of water. Infrared measurements show the water molecule ispresent as a hydrate of the carbonyl group, there being no carbonyl absorp-tion.w With the free bases, the carbonyl infrared absorption band appearsat a slightly higher frequency than that of cyclohexanone.A similar, butmore marked, difference is observed between 1-methyl-3-oxopyrrolidine andcyclopen tan~ne.~lActiphenol, a metabolic product of actinomycetes, is formulated as 4-(2-hydroxy-3,5-dimethylphenacyl)-2,6-dioxopiperidine (62), on the basis ofphysical and chemical properties and partial synthesis from the closelyrelated actidi0ne.9~Oxygen heterocycles. A synthesis of dkyl- and aryl-4-pyrones fromcarboxylic acids and anhydrides, by heating them at 220-300", is de-scribed.93 The photo-dimer of 2,6-dimethyl-4-pyrone has been assigned thecage-structure (63).The compound forms a bis-2,4-dinitrophenylhydrazone,and the other two oxygen atoms are ethereal, on infrared evidence.saturated, and reverts to the pyrone with dilute acid. Treatmentperbenzoic acid yields first a ketd-iactone, and finally two isomeric dilactones :hydrolysis of one of the latter affords isodehydroacetic acid (64) and thecyclobutanetetrol (65). The second dilactone yields, after several stages,the keto-lactone (66).The ultraviolet absorption of the dimer (Amx at233 mp, E 6600) is anomalous, probably having its origin in transannularIt iswithint e r a c t i ~ n s . ~ ~89 H. Plieninger and S. Leonhauser, Chem. Ber., 1959, 9Q, 157991 J , B. Jones and A. R. Pinder, J., 1959, 615.9% R. J. Highet and V. Prelog, Helv. Chim. Actu. 1959, &, 1523.93 J. D. von Mikusch, Angew. Chem., 1959, 11, 311.94 P. Yates and M. J. Jorgenson, J . Amar. Chem. SOL, 1958, 80, 6160.R. E. Lyle, R. E. Adel, and G . G. Lyle, J . Org. Chem., 1959, 24, 342263 ORGANIC CHEMISTRY.2- and 4-Pyrans can be prepared in good yield by the reaction of Grignardreagents with 2- and 4-pyrones respe~tively.~~Both kojic acid (67; X = OH) and a-deoxykojic acid (67; X = H)react with acrylonitrile, the former to yield a nitrogen-free productCl5Hl4O9,~ and the latter a compound formulated on chemical and physico-chemical grounds as (68) ,97The met hylat ion with diazome t hane of 6-substitut ed 3,4-dihydro-2,4-dioxo-2H-pyrans (69) leads to a mixture of the 2-methoxy-4-pyrone and the4-methoxy-2-pyrone , easily distinguished by their infrared spectra.Q8The ethylene ketal (70), derived from benzoin, undergoes an interestingmolecular rearrangement to 2,3-diphenyl-1,4-dioxen (71) with toluene-p-sulphonic acid.9QGeminal cyanonitrosoparaffins react readily with dienes to form dihydro-1,2-oxazines.100Diazines and triazines.Condensation of p-dialdehydes with guanidine,urea, and thiourea yields pyrimidines with a carbon-substituent at position 5,and an amino-, hydroxy-, or thiol group at position 2.The dialdehydes areprepared in situ from a-alkyl-p-chloroacrylaldehydes.101"XHCI.CH=CR'CHO - HO*CH=CR.CHO OHC.CHR.CHO &Reagent: I , (NH,),C=X (X = NH, 0, or S).The chlorinated enols of P-keto-aldehydes, obtained from cyclic ketoneswith the Vilsmeier reagent (H*CO*NMe,-POCl, or H*CO*NMe,-COCl,) , givewith formamide at 180-190" 4,5-disubstituted pyrimidines.lo22 Ha CO. N H2-95 R. Gompper and 0. Christmann, Angew. Chem., 1959, 71, 32.913 C. D. Hurd. R. T. Sims, and S. Trofimenko, .T. Amer. Chem. Soc., 1959, 82, 1684;cf. Ann. Reports, 1958: 55, 291.97 C. D. Hurd and S. Trofimenko, J . Amer. Chem. SOC., 1959, 81, 2430.98 D. Herbst, W. B. Mors, 0. R. Gottlieb, and C.Djerassi, J. Amer. Chem. SOC., 1959,81, 2427.99 R, K. Summerbell and D. R. Berger, J . Amer. Chem. Soc., 1959, 81, 633.100 0. Wichterle and V. Gregor, CoEZ. Czech. Ckem. Cowzm., 1959, 24, 1158.101 L. Rylski, F. Sorm, and 2. Arnold, Coll. Czech. Chem. Comm., 1959, 24, 1667.102 W. Ziegenbein and W. Franke, Angew. Chem., 1959, 71, 628PINDER HETEROCYCLIC COMPOUNDS. 263Malonamides condense with ethyl carbonate in liquid ammonia in thepresence of sodium hydroxide to give good yields of barbituric acids.lo3 Asynthesis of thymidine has been described.104Piperazine and 1-phenylpiperazine find use in the characterisation andidentification of perfluoro-organic acids as salts.lWSeveral 2-cyanopyridines have been trimerised in the presence of base to1,3,5-triazines of basic skeleton (72).A similar reaction with 2-cyano-pyrimidine yields the compound (73). Many of these compounds with6 (72)N A N u (73)ferrous ions yield deep blue chelate complexes.los The chlorine atoms inchloro-1,3,5-triazines can be replaced by fluorine by treatment of the tri-azines with antimony tri- or penta-fluoride; side-chain halogen atoms arcalso replaced.107 phcTo E t NHPh. CH I1f HS\ C=NH ‘“Cx:”’ !!&IEt Et-C I‘C02R NH20 0Sul’kur compounds. Thiourea reacts with trans-ac-ethylcinnamic acid orits ethyl ester to yield a 1,3-thiazan.l0*Butyl-lithium and methyl sulphate eliminate the sulphur atoms pro-gressively from 1,4-dithiins, yielding ultimately acetylenic hydrocarbons.SAXTON : ALK-iLOIDS. 279Uleine, the principal base of A .uulei, contains an exocyclic methylene groupconjugated with an indole ring. Two Hofmann degradations furnished3-ethyl-I-methyl-2-vinylcarbazole, which was degraded to the known3-ethyl-l-methylcarbazole. Since uleine contains C-ethyl and N-methylgroups, the only structure consistent with these results is (20).49 Twoalkaloids related biogenetically to uleine are ellipticine (21; R = Me,R' = H) 50 and olivacine (guatambuinine) (21; K = H, R' =which have been isolated from other Aspidosperma species; ellipticine alsooccurs in Ochrosia species, together with a methoxyellipticine,B and itsconstitution has been proved by a somewhat unconventional synthesis.501,2,3 ,4-Tetrahydro-N3-mcthylellip t kine (U-alkaloid R) 509 54 and ( + ) - 1,2,3,4-tetrahydro-N3-methylolivacine (guatambuine, U-alkaloid C) 52955 occur widelyin A spidosperma species.Ochrosia elliptica also contains elliptine (isoreser-piline) , which is structurally related to ajmali~ine.~~The bark of Hunteria eburnea, which has a marked hypotensive action,contains four alkaloids whose skeletal structures are clearly reminiscent ofaspidospermine. Eburnamine and isoeburnamine are stereoisomers (22) ,and they yield the same lactam, eburnamonine, on oxidation with chromicacid; dehydration of either stereoisomer gives the fourth alkaloid, eburna-menine. Wolff-Kishner reduction of eburnamine (22) , followed by racemis-ation at the asterisked carbon atom (via the tetradehydro-derivative), yieldsthe (&)-base (23), which was identified by total synthesis.56Curare groztp.The Proceedings of an International Symposium oncurare and curare-like agents have been published ; these contain discussionson the chemistry and pharmacology of all types of curare alkaloids.57 Anadmirable and comprehensive review of the calabash curare alkaloidssummarises this field up to the beginning of 1959.57 Diaboline, the tertiarybase which occurs in Strycktnos diaboli, is now known to be the N(a)-acetylderivative of the Wieland-Gumlich aldehyde.68 Most of the investigationsreported during this year have been concerned with establishing earlierstructural pr0posals,5~ and extending and amplifying interconversions inthis series. The structure of fluorocurarine (24) has been confirmed by tworoutes,GO one of which involves a direct synthesis from the Wieland-Gumlichaldehyde (24a; R = OH).Reduction of fluorocurarine with zinc and acid49 G. Biichi and E. W. Warnhoff, J . Atner. Chem. SOC., 1959, 81, 4433.50 R. B. Woodward, G. A. Iacobucci, and F. A. Hochstein, J . Amer. Chem. SOC.,1959, 81, 4435.51 J. Schmutz and F. Hunziker, Pharm. Acta Helv., 1958, 53, 341.52 M. A. Ondetti and V. Deulofeu, Tetrahedron Letters, 1969, No. 7, 1; G. B. Marini-Bettblo and J. Schmutz, Helv. Chim. Ada, 1959, 42, 2146; G. B. Marini-Bettblo andP. Carvalho-Ferreira, Ann. Chim. (Italy), 1959, 49, 869.53 S. Goodwin, A. F. Smith, and E. C . Homing, J . Amer. Chem. SOL, 1959, 81, 1903.54 J. Schmutz and F. Hunziker, Helv.Chim. Acta, 1958, 41, 288.55 P. C. Ferreira, G. R. Marini-Bettblo, and J. Schmutz, Exfierientia, 1959, 15, 179.56 F. Bartlett, W. I. Taylor, and R. Hamet, Comfit. rend., 1959, 249, 1259.57 " Curare and Curare-like Agents," ed. D. Bovet, F. Bovet-Nitti, and G. B.I\llarini-Bettblo, Elsevier, Amsterdam, 1959 ; K. Bernauer, Fortschr. Chem. org. Natur-sioffe, 1959, 17, 183.58 A. R. Battersby and H. I?. Hodson, Proc. Chem. SOC., 1959, 126.59 Cf. Ann. Reports, 1958, 55, 310.60 H. Fritz, E. Besch, and T. Wieland, Angew. Chem., 1959, 71, 126; N7. von Philips-Ilorn, K. Bernauer, H. Schmid, and P. Karrer, Nelzi. Chim. A d a , 1859, 42, 461280 ORGANIC CHEMISTRY.gives a dihydro-derivative by saturation of the 2,16-double bond; in bufferedsolution at pH 5 this intermediate dimerises to give dihydrotoxiferine (24b;R = R' = H).BO The latter has also been obtained from caracurine V,itself obtained by the dimerisation of the Wieland-Gumlich aldehyde.61The analogous dimerisation of the N(b)-metho-salts of this aldehyde yieldsR ' 0 CH * HC'CH.CH 2 R oc1Me, ,OHO\Me H OzC Me CI 0- coCOZH oc- /HOzC Me-$H-CTC!+- CHMeTC- Mea mixture of C-toxiferine I, diacetyl-C-toxiferine I, and N(b)-dimetho-caracurine V; this mixture can be converted without separation intoC-toxiferine I (24b; R = R' = OH) in an overall yield of 62y0.62 Theunsymmetrical bis-quaternary ion (24b; R = H, R' = OH) is the curare-alkaloid C-alkaloid H; this has been synthesised by a mixed condensationof heminordihydrotoxiferine (24a; R = H) with the N(b)-methochlorideof the aldehyde (24a; R = OH).Quaternisation of the tertiary basiccentre in the product then gives (24b; R = H, R' = OH), identical with61 I<. Bernauer, I?. Berlage, W. von Philipsborn, H. Schmid, and P. Karrer, Hetv.Chim. Acta, 1969, 42, 201.68 F. Berlage, K. Bernauer, W. von Philipsborn, P. Waser, H. Schmid, and P.Karrer, Helv. Chim. Ada, 1959, 42, 394SAXTON : ALKALOIDS. 281natural C-alkaloid H. Since photochemical oxidation of the latter givesC-alkaloid G and aerial oxidation in acetic acid-pyridine at elevated tem-peratures yields C-alkaloid F, these two “ dimeric ” alkaloids are alsoavailable by total synthesis.85The CM formulation of C-curarine I has received additional confirmation,since the Hofmann degradation to a ditertiary base can be achieved in twostages, via a monoquaternary ion containing a tertiary basic centre.64Pyrrolizidine Group.-The major alkaloid of Crutalaria anauruides hasbeen identified as l-methylenepyrrolizidine.a The evidence relating to thestructures of jacobine, jacoline, jaconine, and their hydrolysis products hasbeen re-examined and re-interpreted ; the new structures proposed removethe apparent anomalies in the chemistry of these substances.6s Jacobine isnow formulated as the epoxide (25), jacoline is the related 7,8-glycolJ andj aconine is the corresponding chlorohydrin containing the chlorine atom atposition 8.The two acids, jaconecic (26) and isojaconecic (27), are pre-sumed to be formed by nucleophilic attack on the oxide function in (25) bythe free 2-hydroxyl group and hydrolysis of both ester groups; the newformulations are confirmed by the results of the oxidative degradation ofthese two acids. The chlorodilactone, obtained from jacobine by the actionof hydrochloric acid, is the bis-&lactone (28) ; the infrared absorption at1781 cm.-l, earlier regarded as diagnostic of a y-lactone, is also exhibitedby a model bis-8-lactone.66The absolute configuration deduced earlier by Warren and Klemperer forposition 1 in (-)-heliotridane , and therefore in (-)-retronecanone, has beenconfirmed by the stereochemical correlation of the latter with (-)-methyl-succinic acid.67 Accordingly, the absolute configuration at Cc8) in (-)-retronecanone and the pyrrolizidine alkaloids, e.g., monocrotaline, shouldbe as shown in (29) and (30) respectively.This has been corroborated bythe degradation of monocrotaline (30) to the amino-alcohol (31), which wasidentical with that synthesised from ( -)-proline.68 Syntheses of heliotrineand supinine have been reported; heliotrine (32; R = OH, R’ = Me) wasobtained by preferential replacement of the allylic hydroxyl group in helio-tridine with chlorine, followed by reaction with the sodium salt of heliotricacid. Supinine (32; R = R’ = H) was synthesised in an exactly analogousmanner from supinidine and sodium trache1anthate.mPhenanthridine Group.-The constituents of further species belonging tothe family Amaryllidaceae have been examined.’* Of the new bases isolated,parkamine is the principal alkaloid of AmaryZZis parkeri.On the basis of itsconversion by sodium and pentyl alcohol into a mixture of caranine (33;63 F. Berlage, K. Bernauer, H. Schmid, and P. Karrer, Hetv. Chim. Acta, 1969, a,64 V. Boekelheide, 0. Ceder, M. Natsume, and A. Ziircher, J . Amer. Cheem. SOL,*ti C. C. J. Culvenor and L. W. Smith, Austral. J . Chem., 1959, 12, 255.T. A. Geissman, Austrul. J . Chem., 1959, 12, 247; R. B. Bradbury and S. Masa-67 R. Adams and D. Me& J. Amer. Chem. SOC., 1959, $1, 4946.R. Adams and D. Fle3, J . Amer. Chern. SOC., 1959, $1, 5803.6s C. C. J, Culvenor, A. T. Dann, and L. W. Smith, Chern. and Ind., 1959, 20.70 H.-G. Boit and W. Dopke, Naturwiss., 1969, 46, 228, 475; Chem. Ber., 1969, 92,2650.1959, 81, 2256.mune, J.Amer. Chem. SOL, 1959, 81, 5201.m a , 2582282 ORGANIC CHEMISTRY.R = OH, R’ = R” = H), dihydrocaranine, and deoxycaranine (33; R =R‘ = R” = H), and also the formation of anhydrofalcatine lactam by theaction of hot mineral acid, parkamine is formulated as (33; R = OH,R’ = R“ = OMe). Arnaryllidine, which occurs in A . behdonna, is prob-ably the corresponding glycol (33; R = R‘ = OH, R” = OMe).70 TheCH2*O-CO*$-CHMe H? ?R’ ,O & ’CHMe, o \(33)“Ci?3r-R”(32)position of the aromatic methoxyl group in these alkaloids is still sub judice.The position of the phenolic hydroxyl group in pseudolycorine (34; R = H,R’ = Me, R” = OH) has been established by ethylation and degradationto the phenanthridone (35; R = Et, R = Me), which was also obtainedby ~ynthesis.7~ Norpluviine (34; R = Me, R’ = R” = H) and demethyl-homolycorine (36), two new phenolic alkaloids from Lycoris radiata, have theH .OMeM e 0 / 6 0 @ Z e ’ H2Cb ,oa$;HO \ 0 H2C,o \ \(36) R (37) (3 8) 0o ; .- C H 2 -‘?HZ(3 9) HO2C-”‘Mefree phenolic group in the alternative position; the structures of both baseswere proved by degradation to the isomeric phenanthridone (35; R = Me,A comparatively abundant source of the hitherto rare alkaloid crinamine(37; R = H) has been found in several Crinum species, which also containa new alkaloid, 6-hydroxycrinamine (37; R = OH).72 The structure ofthe latter was confirmed by its ready conversion into apohaemanthidine,R’ = Et).7171 S.Uyeo and N. Yanaihara, J . , 1959, 172.72 H. M. Fales, D. H. S. Horn, and W. C. Wildman, Chew. aid Ind., 1959, 1416SAXTON ALKALOIDS. 283and by the rearrangement of its methiodide with alkali, which affordedcriwelline (38).72Diterpene Group.-Atisine has been degraded to a non-nitrogenous acid,which should have the structure and stereochemistry indicated in (39).This product is of interest in connection with the possible stereochemicalcorrelation of atisine with the diterpene~.~~The constitutions of hypognavine 74 and heti~ine,~~ which probablycontain the same ring system, have been discussed. The structure proposedearlier for hetisine 76 has been shown to be untenable, and a modified struc-ture has been suggested.75The combined efforts of two groups of investigators have resulted in theclarification of the structure of aconitine (40; R = Et, R’ = OH, R” =OH).77778 In another outstanding example of the application of X-raycrystallographic methods, Przybylska and Marion have deduced that thestructure and absolute configuration of (+)-demethanolaconinone are as@;: o@f% / *: * - --..f OH OHN E t N*o / 8OH HOOAc NR: I R’ 37OMe ’. OMe OMeCH OMe CH2*OMe CH2.0Me(40) (41) (4 2)given in (41).’8 Consequently, aconitine must be (40; R = Et, R’ = OH,R” = OH) or the isomer in which the benzoyl group is attached to theneighbouring tertiary alcohol function. This formulation explains satis-factorily the non-formation of a carbinolamine ether on oxidation (cf.delcosine and delsoline with OH at C,,), and also the significant reductionin basicity which accompanies the formation of aconitoline (the chromic acidoxidation product), which is an +unsaturated p‘-amino-ketone (ring A asin 41).Pyraconitine, the pyrolysis product of aconitine, behavesin the Wolff-Kishner reduction as an a-methoxy-ketone; hence thisprovides additional evidence for the presence in aconitine of the systemAcO-C-CH(OH) 1 -L The relationship of the nitrogen atom to theI Iacetoxy-group has been confirmed by the pyrolysis of aconitine N-oxide,which affords the nitrone (42); the latter can be reconverted into aconitineby reduction followed by ethylation. This behaviour is best explained bythe presence in aconitine of the system N-C(17)-C(7)-Cts)-OA~, which is73 0.E. Edwards and R. Howe, Proc. Chem. SOC., 1959, 62.74 S.-I. Sakai, Chem. Pharm. Bull. (Japan), 1959, 7 , 55.75 A. J. Solo and S. W. Pelletier, J. Amer. Chem. Soc., 1959, 81, 4439.76 K. Wiesner and 2. Valenta, Fortschr. Chem. wg. Naturstofle, 1958, 16, 62.77 I<. Wiesner, M. Gijtz, D. L. Simmons, L. R. Fowler, F. W. Bachelor, R. I?. C.78 H. Mayer and L. Marion, Canad. J. Chem., 1959, 37, 856; M. Przybylska andBrown, and G. Buchi, Tetrahedron Letters, 1959, No. 2 , 15.L. Marion, ibid., pp. 1116, 1843; D. J. McCaldin and L. Marion, ibid., p. 1071284 ORGANIC CHEMISTRY.sufficiently close to being planar to allow a concerted elimination duringpyrolysis.77 In detailed discussions on the structures of aconitine anddelphinine, Wiesner and his collaborators have established the substitutionpattern in rings c and D, and have deduced the constitution (40; R = Me,R = R" = H) for del~hinine,~~ in which C(3) is a possible alternative sitefor the methoxyl group of ring A.The complex Hofmann degradationwhich delphonine methiodide undergoes is at last given a rational explan-ati0n.7~In the lycoctonine series, the constituents of Imda roykana (fam.Compositae) have been investigated.*O Royline is identical with lycoctonine,and inuline is its anthranoyl derivative. This plant appears to be therichest known source of lycoctonine, and its occurrence here is the first to berecorded outside the Ranunculaceae.go Hydroxylycoctonine, the silveroxide oxidation product of lycoctonine, is now formulated as the semiacetal(43) ; its salts have an anhydronium structure, and contain a 7-keto-gro~p.~~~ OMe(4 4) (4 5 )The lycoctonine-type formulz for deltaline and delpheline have beenrejected, and have been replaced by perhydrophenanthrene structures.82Deltaline is formulated as (44; R = OAc, R' = OH) and delpheline as(44; R = OH, R' = H).The conversion of delpheline into deoxylycocton-ine involves, in the last stage, the acid-hydrolysis of the methylenedioxy-function; it is now suggested that this proceeds with simultaneous Wagner-Meerwein rearrangement of the 13,8-bond into the 13,9-positionJ to give thelycoctonine skeleton.82Miscellaneous.-Nitidine, the alkaloid of Zauzthoxylum nitidzcm (fam.Rutaceae) , is the quaternary benzophenanthridine derivative (45) .a Itoccurs in association with oxynitidine, the related benzophenanthridone,7s K.Wiesner, F. Bickelhaupt, and D. R. Babin, Experientia, 1959, 15, 93; I<.Wiesner, F. Bickelhaupt, D. R. Babin, and M. Gotz, Tetrahedron Letters, 1959, No. 3,11.80 0. E. Edwards and M. N. Rodger, Canad. J . Chem., 1959, 37, 1187; S. K. Tala-patra and A. Chatterjee, J . Indian Chsm. SOL, 1959, 86, 437.81 0. E. Edwards, M. Los, and L. IVfariorl, Proc. Cham. Soc., 1959, 192; Canad. J .Chem., 1959, 37, 1996; 2. Valenta, Chem. and Ind., 1959, 633.8% M. Carmack, D. W. Mayo, and J. P. Ferris, J . Amer. Chem. SOL, 1959, 81, 4110.8s H. R. Arthur, W. H. Hui, and Y . L. Ng, J., 1959, 1840SAXTON : ALKALOIDS. 285Purpurogall in A'0,4Me0 :93 r C02Me C02MeC I H2C0 94 (4 8)0Me0 \Me0 -OH(4 9) 0 OMe (50)Synthesis of colchicine by Eschenmoser and his colleagues.88Reagents: I, (a) Me$04-NaOH; (b) H2-Ni; (c) LiAIH,; ( d ) H3P04-k180.2, (a) HC-C.CO,Me-NEt,-C,Hll*OH, then C,Hll*OK; (b) MeI-K,CO,.3, Chlorornethylmaleic anhydride a t 175O.4, (a) MeOH-H,S04; (b) CH8N2.5, (a) C,HIl.0K-C6H,; (b) NaOH-MeOH.6, (a) OsO,; (b) NaHC0,-MeOH-0,; (c) NaOH; (d) Quartz powder a t 260'.7, (a) p-Me-C,ii,*SO,CI-pyridine; (b) NH,-EtOH a t 100"; (c) NaOH.8, (a) CH,N2; (b) separation of isomeric methyl ethers; (c) N-bromoruccinimide;9, NaOH.(d) NH3-EtOH at 1000.[Caption continued on p .286286 ORGANIC CHEMISTRY.Synthesis of colchicine by van Tarnelen etReagents: i, (a) CH,=CH*CN-KOBU~; (b) Zn-Br*CH,*CO,Me; (c) KOH; (d) dicyclohexycarbodi-imide; (e) CH2N2.ii, Na-NH,-ether.i i i , (a) Cu(OAc),-MeOH; (b) p-Me*C6H,*S0,H-C&t6; (c) N-bromosuccinimide.iv, (a) CH,N2; (b) N-bromosuccinimide; (c) NaN,; (d) H2-Pd; (e) H20-H+.Conversion of (49) into (-)-colchicine (50).*O10, (a) (+)-Camphor-I0-sulphonic acid; (b) Ac20-pyridine; (c) CH2N,.but the latter is probably an artifact.These are the first natural productsto contain this particular orientation of substituents ; the benzophen-anthridine alkaloids previously encountered have substituents in positions 7and 8 in ring A.Actinidia PoZygama contains two physiologically active substances , ofpresumably terpenoid origin. The basic component is actinidine (46) ;the other is a neutral lactone, matatabilactone.84The structure proposed for n~pharidine,~~ deduced from the results ofdegradation, has now been confirmed by the synthesis of (5)-deoxy-nupharidine.86 Nupharamine (47) , a companion alkaloid of the roots ofNuphar japonicum, possesses the same sesquiterpenoid skeleton.87Probably the most outstanding achievements in alkaloid synthesisduring the year under review are two total syntheses of (-)-colchicine,which were carried out according to the reactions outlined in the accompany-ing charL88 Both the Swiss and the American synthesis start from a deriv-ative of trihydroxybenzosuberone, and proceed, by different routes, todeacetylaminocolchiceine (48) , which was used as the relay compound, andthence to (&)-deacetylcolchiceine (49).Since the latter has already beenreconverted into (-)-colchicine (50),s9 the synthesis of the alkaloid iscomplete.J. E. S.10. CARBOHYDRATESAmino-sugars and Other Sugar Derivatives Containing Nitrogen.-The bio-logical importance of amino-sugars is becoming increasingly evident and sotheir chemistry is being rapidly developed.to have structure (1).Methanolysis of the substance resulted in scission at (a) to yield paromamineand an anomeric mixture of methyl paromobiosaminides.2 Paromamine wasshown to be a 2-amino-2-deoxyglucoside. The parent disaccharide (paromo-biosamine) of methyl paromobiosaminide is composed of a 2,6-diamino-2,6-84 T. Sakan:A. Fujino, F. Murai, Y . Butsugan, and A. Suzui, Bull. Chem. Soc.Japan,1959, 32, 315.85 M. Kotake, S. Kusumoto, and T. Ohara, Annalen, 1957, 606, 148.86 T. Kaneko, I. Kawasaki, and T. Okamoto, Chem. and Ind., 1959, 1191.Y. Arata and T. Ohashi, J . Pharm. Sac. Jafian, 1959, '79, 127.88 J. Schreiber, W. Leimgruber, M. Pesaro, P. Schudel, and A. Eschenmoser, Angew.Chem., 1959, 71, 637; E. E. van Tamelen, T. A. Spencer, D. S. Allen, and R. L. Orvis,J . Amer. Chem. SOC., 1959, 81, 6341.89 H. Corrodi and E. Hardegger, Helv. Chim. Actu, 1957, 40, 193.1 T. H. Haskell, J. C. French, and Q. R. Bartz, J . Amer. Chem. Soc., 1959,81, 3482.2 T. H. Haskell, J. C. French, and 9. R. Bartz, J . Amer. Clzem. Soc., 1959,81, 3480.The antibiotic paromomycin has been showOVEREND : CARBOHYDRATES. 287dideoxyhexosyl residue united to position 3 of a D-ribose unit.3 Synthetic2-amino-l,6-anhydro-2-deoxy-p-~-gulopyranose hydrochloride has beenshown to be identical with the amino-sugar derivative isolated from strepto-thricin and streptolin B.4 2-Acetamido-2-deoxy-~-galacturonic acid is acomponent of an antigenic polysaccharide isolated from Escherichia coZL5Much effort is concentrated on developing methods for the synthesis ofamino-sugars and derivatives.Conventional methods have been extendedand new routes devised. Enzymic conversions of N-acetylhexosamines into N-acetylhexosaminic acidsand of glucosamine into galactosamine have beenH,OH reported. The valuable reference compound (2) hasbeen prepared by Stoffyn and Jeanloz 8 who have also+NH, CI- reviewed the methyl ethers of 2-amino-2-deoxy-~ugars.~ The hydrochlorides of D-[ l-14C]glucosamineand ~-[l-~~C]galactosamine have been synthesised lofor use in metabolism experiments, and preparations of 2-acetamido-4,6-0-benzylidene-2-deoxy-glucose l1 and methyl 2-amino-4,6-0-benzylidene-2-deoxy- p-D-glucoside hydrochloride l2 have been described.The alkalineepimerisation of 2-acetamido-2-deoxy-~-glucose has been developed to yieldgram quantities of 2-acetamido-2-deoxy-~-mannose~~ Stereospecific addi-tion of ammonia to D-arabo-tetra-acetoxy-1-nitrohex-l-ene affords N-acetyl-l-deoxy-l-nitro-D-mannosamino1 which is convertible into 2-amino-2-deoxy-o-mann0~e.I~ The L-isomer was prepared similarly. Cramer et aZ.15 havedescribed syntheses of 6-amino-6-deoxy-~-glucose and derivatives thereof,and Muber et a2.le have converted methyl 3-amino-4,6-0-benzylidene-3-(2)T. H, Haskell, J.C . French, and Q. K. Bartz, J . Amer. Chem. Soc., 1959, 81, 3481.4 R. W. Jeanloz, J . Amer. Chem. SOC., 1959, 81, 1956.I<. Heyns, G. Kiessling, W. Lindenberg, H. Paulsen, and hi. E. Webster, Chent.6 L. I. Hochstein, J. B. Wolfe, and H. I. Nakada, J . Amer. Chent. SOC., 1950, 81,F. Maley and G. F. Maley, Biochim. Biophys. Acta, 1959, 31, 577.8 P. J. Stoffyn and R. W. Jeanloz, J . Anzer. Chem. SOC., 1958, 80, 5690.9 R. W. Jeanloz, Adv. Carbohydrate Chem., 1958, 13, 189.10 R. Kuhn, H. J. Leppelmann, and H. Fischer, Annalen, 1959, 620, 15.l1 H. Masamune, T. Okuyama, and H. Sinohara, TGhoku J . Exp. Med., 1958, 68,12 S.Akiya and T. Osawa, Chem. Pharm. Bull (Japan), 1959, 7, 277.l3 S. Roseman and D. G. Comb, J . Amer. Cham. SOL, 1958, 80, 3166; C . T. Spivak14 A. N. O'NeilI, Canad. J . Chem., 1959, 37, 1747.l6 G. Huber, 0. Schier, and J. Druey, HPIv. China. A d a , 1959, 42, 2447.Ber., 1959, 92, 2435,4111.181.and S . Roseman, ibid., 1959, 81, 2403.I?. Cramer, H. Otterbach, and H. Springmann, Chem. BEI., 1959, 92, 384288 ORGANIC CHEMISTRY.deoxy-a-D-altroside into 3-amino-3,6-dideoxy-~-altrose hydrochloride byconventional methods.Reduction of the hydrazino-compounds formed by replacement ofsulphonyloxy-groups in the sugar series provides a convenient approach tothe synthesis of amino-sugars.17 By this method methyl 3,4-0-isopropyl-idene-2-0-tosyl-p-~-arabinoside, lJ2-0-isopropylidene-3 ,5-di-O-tosyl-cc-~-xylofuranose, 1,2-O-isopropy~dene-5-0-tosy~-a-~-xy~ofuranose, methyl 3,5-O-isopropylidene-2-O-tosy~-or~-~-xylofuranoside , and methyl 3,4-O-iso-propylidene-6-0-tosy1-cr-~-galactoside have been converted via the hydr-azino-derivatives into amino-sugar derivatives.ls Crystalline 2-amino-2-deoxy-~-ribose and 2-amino-2-deoxy-~-~yxose (as hydrochlorides) wereprepared by this route.lB In 1938 Peat and Wiggins l9 showed that ammono-lysis of a tosyloxy-group proceeds through an epoxide intermediate when asuitably situated hydroxyl group is available; this results in retention ofconfiguration at the original site of the tosyloxy-group because of two suc-cessive inversions at this point.Using 1,2:5,6-di-O-isopropylidene-3-0-tosyl-D-glucofuranose (3) Lemieux and Chu 2o have now demonstrated that(3) MeCH2-0AcO AcHN Q I I (7)CH~*OACAcO 0 H,OAcAcHN(8)I(4) Me CH2.OH(5)JCH(SEt)ZCH (SO,Et),_2, H o g A c 4 OH HO Q HO NHAcCH2 *OH(9) (6)when the tosyloxy-group is not adjacent to free hydroxyl groups ammono-lysis or hydrazinolysis proceeds with Walden inversion to give a derivativeof 3-amino-3-deoxy-~-allose (4; R = H or NH, respectively).Oxidationwith peroxypropionic acid of 3-acetamido-3-deoxy-~-allose diethyl dithio-acetal(5) [obtained by treating compound (4; R = Ac) with ethanethiol andhydrochloric acid] yielded the cyclic disulphone (6) together with diethyl-17 M. L. Wolfrom, F. Shafizadeh, and R. K. Armstrong, J.Amer. Chem. Soc., 1958,80, 4885.18 M. L. Wolfrom, F. Shafizadeh, R. K. Armstrong, and T. M. Shen Han, J. Amer.Chema. SOC., 1969, 81, 3716.19 S. Peat and L. F. Wiggins, J., 1938, 1810.20 R. U. Leinieux and P. Chu, J . Amer. Chenz. SOL, 1958, 80, 4745OVIJHICNI) CAKHOHY DHA'lXS. 2 89sulplionylme thane and 2-acetamido-2-deoxy-D-ribose.21 The disulphone (6)could also be obtained by the sequence of reactions (7) + (8) ---;)- (9) --+c(6) (1, acetolysis; 2, de-0-acetylation and diethyl dithioacetal formation;3, oxidation with peroxypropionic acid). Both conversions (5) -+ (6)and (9) --t (6) proceed via the unsaturated intermediate (10). Theoxidation of the dithioacetal (9) also gave rise to 2-acetamido-2-deoxy-~-ribose. These results confirm the concIusion of Lemieux and Chu20 thatreplacement of the 3-tosyloxy-group in compound (3) by ammonia andhydrazine residues proceeds with inversion of configuration./SO,Et\SO,Et I HOCH, - 'i' 'i' 'i' CH=C I l lOH OH NHAc i (10)The epoxide route to amino-sugars has been further extended. Com-mencing with methyl 2,3-anhydro-4,6-0-benzylidene-a-~-alloside (1 1) Fosteret aZ.22 have carried out the sequence of reactions (11) ---t (14) to prepare2-amino-l,6-anhydro-2-deoxy-~-~-altropyranose hydrochloride.(14). The0- 0-Ph- CH-O I <&Me Ph . Cti-0 I <>MeLHO q.$oHe 3, Hoqy CI-HO (12)CH2.0H //;/ CH2-0( 1 1 ) O(13) HO HO (14)Reagents: I, MeOH-NH,, followed by N-acetylation. 2, Partial hydrolysis. 3, Total hydro-lysis.ammonolysis of methyl 2,3-anhydro-a- and -p-D-ribofuranoside has beeninve~tigated.~,~* With each anomer attack occurred almost exclusively atposition 3 and in this way methyl 3-amino-3-deoxy-CC- and -P-D-XylOfUran-oside were obtained. In the course of the synthesis of the P-epoxide (16)it was found that treatment of methyl 2-0-benzoyl-3-0-methanesulphonyl-Fi-O-trity~-~-~-xylofuranoside (15; Ms = MeSO,) with hot 80% acetic acid21 B.Coxon and L. Hough, Chem. alzd Id., 1969, 1249.22 A. B. Foster, M. Stacey, and S. V. Vardheim, Acta Chem. Scand., 1958, 12, 1605.23 C. D. Anderson, L. Goodman, and B. R. Baker, J . Amer. Chem. SOL, 1958, 80,24 R. E. Schaub and M. J. Weiss, J . ,4mer. Chem. SOC., 1958, 80, 4683.5247.REP.-VOL. LVI 2!)0 ORG.4NIC CHEMISTRY.resulted, not only in detritylation, but also in ring expansion of some of theproduct to the corresponding pyranoside which after oxide formation andammonolysis afforded methyl 3-amino-3-deoxy-P-~-xylopyranoside (17)The same results were obtained in the a-series.Thus by this novel ring-expansion with retention of configuration all four possible methyl 3-amino-3-deoxy-D-xylosides were obtained. Whitehouse and Kent 25 have preparedcrystalline methyl 2-acetamido-2-deoxy-p-D-glucofuranoside by treating2-acetamido-2-deoxy-D-glucose diethyl dithioacetal with mercuric oxide inmethanol. Aqueous mercuric chloride in the presence of mercuric oxidegives with 2-acetamido-2-deoxy-D-galactose diethyl dithioacetal a mixturefrom which by column chromatography on, successively, carbon, cellulose,and silicate it is possible to separate ethyl 2-acetamido-2-deoxy-l-thio-a-and -p-D-galactofuranoside and -/3-D-galactopyranoside.36 Ethyl 2-acet-CH1.OH (18) (19) (20) (2')Reagents: I, 10,.2, NaBH,. 3, HCI.amido-2-deoxy-l-thio-a-D-galactofuranoside (18) was converted into %amino-2-deoxy-L-arabinose (2 1) (isolated as the hydrochloride) by the annexedsequence of reactions.27Lindberg and Theander 28 have prepared an oxime (23) from the keto-glycoside (22) and this on hydrogenation in presence of Adams catalystCHl-OH2Lo?OPle Ho<o?OMeHOOH HO-N OHafforded methyl 3-amino-3-deoxy-~-~-allopyranoside (24) in 85% yield.Reduction of compound (23) with sodium amalgam yielded methyl 3-amino-3-deoxy-~-~-glucopyranoside (25) in 45% yield ; the presence of the amine(24) in the mother-liquors being demonstrated by paper chromatography andionophoresis.Baer and Fischer 29 have described a novel method for the synthesis of25 M.W. Whitehouse and P. W. Kent, Tetrahedron, 1958, 4, 425.26 34. L. Wolfrom and 2. Yosizawa, J . Arner. Chem. SOC., 1969, 81, 3474.27 M. L. Wolirom and 2. Yosizawa, J . Amer. Chem. SOL, 1959, 81, 3477.28 B. Lindberg and 0. Theander, Acin Chem. Scand., 1959, 13, 1226.28 H. H. Baer and H. 0. L. Fischer, Proc. Nat. Acad. Sri. C . S . A . , 1958, 44, 991;J . Amer. Chem. SOC., 1959, 81, 5185OVEKEND : CARBOHYDRATES. 29 I3-amino-3-deoxyribose. Cleavage with periodate of the methyl pento-pyranosides affords the dialdehydes (26) and (27) and it has been shown that10,- Meo-CHO 0 (26)Methyl /I-D- or a-L-pentopyranoside j-CHo i i CH2-'10,- CHO T H-C-OMeMethyl a-D- or p-L-pentopyranoside 0 (27) i"" 1 CH,-these can be cyclised with nitromethane and sodium methoxide, in yieldsup to 40%, to give intermediates which can be converted into amino-sugars.Thus the dialdehyde (26) is so converted into the sodium salt (28) of the3-acinitro-pyranoside which on dry acidification by grinding with solidpotassium hydrogen sulphate gives mainly methyl 3-deoxy-3-nitro-p-~-ribopyranoside (29) ; the configuration of this is shown by catalytic reduc-tion to a methyl 3-amino-3-deoxypentoside (30) from which crystalline3-amino-3-deoxy-~-~bose hydrochloride (31) can be obtained by hydrolysiswith hydrochloric acid. Reduction of the synip (29) remaining after < '?OMe O?OMe '?OMe '?OHHOOCN OH OIN OH HIN OH H,N+ OHCI' + 0- N3+(28) ( 2 9 ) (30) (31)crystallisation afforded up to 5% of methyl 3-amino-3-deoxy-p-~-xylo-pyranoside (32; X = NH,), but so far methyl 3-deoxy-3-nitro-p-~-xylo-pyranoside (32; X = NO,) has not been isolated in pure form from the dry-acidification mixture.The same sequence of reactions has been carried outwith the dialdehyde (27). In this series the amount of the xylose isomerwas greater (up to ll%), but the main final product was 3-amino-3-deoxy-a-L-ribose hydrochloride. Using thiourethane derivatives Baker et nZ.30developed a new synthesis of amino-sugars. Reaction of the sodio-derivative of methyl 4,6-O-benzylidene-cw-~-glucoside with phenyl iso-thiocyanate afforded an amorphous 2-phenylthiourethane (33) (53%) andthe crystalline %-isomer (34; R = €3) (21%).The 2-O-methanesulphonylderivative (34; R = Me-SO,), on treatment with methanolic sodium meth-oxide, underwent ring closure to give compound (35) whence alkaline hydro-lysis yielded methyl 2-anilino-4,6-O-benzylidene-2-deoxy-a-~-rnann0~ide30 B. R. Baker, K. Hewson, L. Goodman, and A. Renitez, J . Amer. Chem Soc.,1958, 80, 6577292 ORGANIC: CHIIMISTKY.(36). In view of Liebermann’s results 31 on the S-alkylation of the N-phenyl-thiourethane (37) to compound (38) it is surprising that the alkylation of0-Q”‘ 1 <aMe ]3c+) O-C*NHPhI {+ 1HO Ph-CH-0 Ph * C H - 0 OMe0 ORI(32) (33) SZC-NHPh (34)0- 0-Ph-CH-0 OMe Ph-CH -0(35) (36)the derivative (34; R = MeoSO,) proceeded by nitrogen-attack to lead tocompound (35) rather than by sulphur-attack to give compound (39).Onenoticeable difference in the two procedures is Liebermann’s use of the silversalt of the urethane (37) in contrast to the sodium salt used in the cyclisationof the 2-O-methanesulphonyl derivative (34; R = MeOSO,). This syntheticPhaNH*C.OEtII5(37)Ph.N=C*OEtISMe(38)pathway, whereby a 1 ,Z-frans-glycol system of a sugar can be convertedinto a 1,2-cis-amino-alcohol system, has considerable potentialities. Byuse of N-substituted thiourethane groups other than N-phenyl it should bepossible to prepare a variety of N-alkyl-, N-aryl-, and N-arylalkyl-amino-sugars.If an N-benzylthiourethane is employed it should be possible toremove the N-benzyl group by hydrogenolysis, thereby achieving thesynthesis of amino-sugars without a substituent on the nitrogen atom.Synthesis of the interesting disaccharide, 2-acetamido-6-0-(2-acetamido-2-deoxy-~-~-g~ucosy~)-2-deoxy-~-glucose has been described.32The order has been determined 33 in which amino-sugars are eluted withacid from columns of ion-exchange resin. These results coupled with aconsideration of the orders of separation of the N-acetylated sugars on paperchromatograms and pherograms, and of data on the estimation of thesesugars, make it possible to judge more accurately than by paper chromato-graphy alone the identity of certain sugars, without recourse to authenticmaterial as a standard €or comparison.Further investigations of theN-acetylation and estimation of hexosamines have been reported's andsome studies have been made of the effect of electronegative N-substituents81 C. Liebermann, Annalen, 1881, 207, 121.32 W. Yu and T. Hsing-I, Acta Chim. Sinica, 1959, 25, 50.33 M. J. Crumpton, Biochem. J , , 1958, 69, 25P; 1959, 72, 479.s4 G. A. Levvy and A. McAllan, Bioclzem. J., 1959, 71, 127OVEREND: CARBOHYDRATES. 293on the hydrolysis of 2-amino-2-deoxy-glucosides.35 By comparing theproducts of degradation of hexosamines by ninhydrin with those of briefoxidation of the corresponding hexoses by periodate it was concluded thatin both cases the 4-formic esters of the lower pentoses are produced and arehydrolysed to the pentoses.38 Some odd reactions have been noted.Period-ate oxidation of various 3-amino-3-deoxyribofuranosyl derivatives and ofone 3-amino-3-deoxyarabinofuranosyl compound resulted in the uptake oftwice the expected amount of oxidant .37 Two 5-amino-5-deoxyribo-furanosides each reacted with 4 molar equivalents of periodate, but various2- and 3-aminodeoxypyranosides behaved " normally." The bis-aldehydewhich is obtained on oxidation of the corresponding non-amino-furanosidesis neither an intermediate nor the final product of the oxidation of %amino-3-deoxypentofuranosides. Consequently the convenient periodate-molarrotation procedure 38 for the determination of anomeric configuration isinapplicable to nucleosides containing 3-amino-3-deoxypentofuranosylmoieties. Care must be exercised in the selection of the amine-protectinggroup in amino-sugar syntheses when the use of alkaline reagents is con-templated since it has been found 39 that aqueous-ethanolic sodium hydr-oxide converts methyl 2-benzyloxycarbonylamino-2-deoxy-6-O-tosyl-cr-~-glucopyranoside (40) into methyl 2-amino-3,6-anhydro-N2,0*-carbony1-2-deoxy-a-D-glucoside (41).2-Amho-2-deoxy-D-glucose has been transformed into oxazolone andoxazoline derivatives.@ Treatment of the N-benzoyl derivative withacetone and an acid catalyst produces a compound with structure (42).1,3,4,6-Tetra-O-acetyl-2-benzyloxycarbonylamino-2-deoxy-~-glucose witheither titanium tetrachloride or aluminium trichloride-phosphorus penta-,CII 1 I N H-CO.0- CHzPhAcO 0CHI.OAC(43)CHI. OAC(44)35 W. Yu and H. Ching, A d a Chim. Sinica, 1958, 24, 413.36 P. J. Stoffyn, J . Org. Chein., 1959, 24, 1360.37 M. J. Weiss, J. P. Joseph, H. M. Kissman, A. M. Small, R. E. Schaub, and F. J.38 J. Davoll, B. Lythgoe, and A. R. Todd, J., 1946, 833.39 A. B. Foster, M. Stacey, and S. V. Vardheim, Acta Chem. Scand., 1959, 13, 281.40 S. Konstas, I. Photaki, and 1,. Zervas, Chem. Ber., 1959, 92, 1288.McEvoy, J . Amer. Chem. Soc., 1959, 81, 4050294 ORGANIC CHEMISTRY.chloride gives a l-chloro-derivative (43) from which benzyl chloride is elimin-ated to yield the oxazolone derivative (44). From 1,3,4,6-tetra-0-benzoyl-2-benzyloxycarbonylamino-2-deoxy-cc~-~-glucose and hydrogen bromide inacetic acid it is possible to obtain 2-amino-3,4,6-tri-0-benzoyl-l-bromo-2-deoxy-a-D-glucose hydr~bromide.~~ With alcohols both this salt and tbefree base give satisfactory yields of the hydrobromides of 2-amino-3,4,6-tri-0-benzoyl-2-deoxy-P-~-glucosides.The preparation of genuine 2-acet-amido-3,4,6-tr~-0-acetyl-l-bromo-2-deoxy-cc-~-glucose has been outlined; 42this substance rearranges in the presence of water to the known 1,3,4,6-tetra-O-acety~-2-amino-2-deoxy-a-~-gl~~0~e hydrobromide. The glycosyl-ation of acetohalogeno-derivatives of 2-amino-2-deoxy-~-glucose by Grignardreagents has been studied.43 The compound known in the literature as2-benzamido-l,3,4,6-tetra-0-benzoyl-2-deoxy-a-~-glucose is in fact an ano-meric mixture consisting mainly of the p-form; 44 with hydrogen bromidein acetic acid it affords 2-benzamido-3,4,6-tri-O-benzoyl-l-bromo-2-deoxy-a-D-g1UCOSe which will react readily with alcohols and thiols to give p-glucos-aminides or p-thioglucosaminides ; in moist ether it rearranges to 2-amino-1,3,4,6-tetra-O-benzoyl-2-deoxy-cr-~-glucose hydrobromide, the free base ofwhich can be smoothly benzoylated to give authentic 2-benzamido-I ,3,4,ci-tetra-0-benzoyl-2-deoxy-~e~-glucose.~~~~ By using only the first step, amperometric titration of liberated thiol groupspermits the determination of disulphide bonds in intact proteins.3' Oxid-ation of cysteine to cystine by Cu2+ ions,= iodosobenzoate, or tetra-thionate 38b during this fission, converts all cysteine-cystine residues intoS-sulphocysteine in the otherwise intact This sulphite fissionmay prove more useful than oxidation by performic acid for degradingproteins to single peptide chains for sequence determination, since otheramino-acids such as methionine and tryptophan are unaffected.Thebehaviour of cysteine in proteins has been of interest from other viewpoints.%The presence of a 2-thiazoline ring in bacitracin A has given credeme to thesuggestion 39 that these heterocyclic compounds, formed by condensationbetween the thiol group of cysteine and the carbonyl group of an adjacentamino-acid, may be normal features of protein structure. Although gluta-thione rearranges to the thiazoline in strongly acid solution, there is noevidence for cyclisation in solutions less acid than pH 1.40 This observation,as well as a detailed kinetic study of the interconversion of 2-methylthiazoline39 (a) L.Josefsson and P. Edman, Acta Chem. Scand., 1956,10, 148; ( b ) L. Josefsson,34 K. Narita, J . Amer. Chem. SOC., 1959, 81, 1751; J. L. Rabinowitz, Acta Chem.85 L. B. Smillie and H. Neurath, J . Biol. Chem., 1959, 234, 355.313 (a) D. T. Elmore and P. A. Toseland, J., 1957, 2460; ( b ) D. T. Elmore, J., 1959,3152.37 S, J. Leach, Biochim. Biophys. Acta, 1959, 33, 264; J. R. Carter, J. Biol. C h e w ,1959, 234, 1705.38 (a) J. M. Swan, Nature, 1957, 180, 643; (b) J. L. Bailey and R. D. Cole, J . Biol.Chem., 1959,234,1733; ( c ) J.-F. Pechhre, G. H. Dixon, R. H. Maybuky, and H. Neurath,J .Biol. Chem., 1958, 233, 1364; Biochim. Biophys. Acta, 1959, 31, 259; L. Weil andT. S. Seibles, Arch. Biochem. Biophys., 1959, 84, 244.39 K. Linderstram-Lang and C. F. Jacobsen, Compt. rend. Trav. Lab. Carlsberg,Ser. chim., 1940, 23, 289.40 R. B. Martin and J. T. Edsall, Bull. SOC. Chim. biol., 1958, 40, 1763.Arkiv Kemi, 1958, 12, 183.Scand., 1959, 13, 1463ELMOKE : AMINO-ACIDS, PEPTIDES, AND PROTEINS. :JOYand N-a~etyl-2-mercaptoethylamine,4~ has led to the conclusion that 2-thiazoline rings are not likely to be a normal feature of protein structure.Identification of C-terminal residues by fission with hydrazine has beenimproved. The reaction is accelerated by addition of hydrazine salts,42while separation of amino-acid hydrazides from amino-acids is more com-plete if polyacraldehyde, instead of a simple aliphatic or aromatic aldehyde,is added to the solution produced.&The unexpected formation ofcomplexes between N-benzyloxycarbonylamino-acids and their sodiumsalts 44 offers an explanation for discrepant melting points in the l i t e r a t ~ r e .~ ~Fortunately, formation of these complexes can be avoided by addition ofthe alkaline solution of N-benzyloxycarbonylamino-acid to an excess ofacid at 0". N-Benzyloxycarbonyl groups have been used to protect theguanidino-group of arginine 46 and the imidazole ring of histidineJ4' though ,for the latter, N-benzyl groups may be better as they are stable to bases.Removal of N-benzyloxycarbonyl groups from methionine peptides byhydrogen bromide or chloride has been troublesome owing to formation ofsulphonium C O ~ ~ O U ~ ~ S , ~ ~ ~ but addition of ethyl methyl sulphide preventsthis side-reacti~n.~~~ Boiling trifluoroacetic acid, a new reagent for remov-ing N-benzyloxycarbonyl groups, is claimed not to split peptide bonds orcause racemisation.M The chromophoric N-4-phenylazobenzyloxycarbonyland related groups, which can be removed by the usual methods, are usefulvariant^,^^^,^^ especially in syntheses where purification of intermediatesdemands chromatography or counter-current distribution. Although form-amido-acids tend to give racemic peptides, the carbodi-imide methodafforded optically pure products from which the formyl group was removedwith methanolic hydrogen chloride.62 N-Trityl groups may be used in theazide method under carefully controlled conditions,53u but N-tritylamino-acids, prepared by partial hydrogenolysis of their benzyl esters or directlyfrom amino-acids, gave only moderate yields of dipeptides in a variety of41 R.B. Martin, S. Lowey, E. L. Elson, and J. T. Edsall, J . Amer. Chem. Soc., 1959,81, 5089.4a J. H. Bradbury, Nature, 1956, 178, 912; Biochem. J., 1958, 68, 475, 482.43 T. Kauffmann and F.-P. Boettcher, An.nalen, 1959, 625, 123.44 E. P. Grommers and J. F. Arens, Rec. Trav. chim., 1959, 78, 558.46 W. Grassman and E. Wiinsch, Chem. Ber., 1958, 91, 462.46 L. Zervas, M. Winitz, and J. P. Greenstein, J. Org. Chem., 1957, 23, 1515; L.Zervas, T. Otani, M. Winitz, and J. P. Greenstein, Arch.Biochem. Biophys., 1958, 75,290; J. Amer. Chem. SOC., 1959, 81, 2878.47 A. Patchornik, A. Berger, and E. Katchalski, J . Amer. Chem. Soc., 1957, 79,6416; S. Akabori, K. Okawa, and F. Sakiyama, Nature, 1958, 181, 772; F. Sakiyama,K. Okawa, T. Yamakawa, and S. Akabori, Bull. Chem. SOC. .Japan, 1959, 31, 926.48 (a) D. Theodoropoulos and G. Folsch, Acta Chem. Scand., 1958, 12, 1955; D.Theodoropoulos, ibid., p. 2043; (b) R. Schwyzer and C . H. Li, Nature, 1958, 182,1669.49 (a) 0. Gawron and F. Draus, J. Org. Chem., 1958, 23, 1040; (b) R. A. Boissonnasand St. Guttmann, Helv. Chirn. Acta, 1959, 42, 1257.6o F. Weygand and W. Steglich, 2. Naturforsch., 1959, 14b, 472.61 (a) R. Schwyzer, P. Sieber, and K. Zatsk6, Helv. Chim. Acta, 1958, 41, 491;( b ) R.Schwyzer and F. Sieber, ibid., 1959, 42, 972.62 J. C. Sheehan and D.-D. H. Yang, J . Amer. Chem. SOC., 1958, 80, (a) 1164, (b)1158.68 (a) B. M. Iselin, Arch. Biochem. Biofihys., 1958, 78, 532; (b) G. C. Stelakatos,D. M. Theodoropoulos, and L. Zervas, J . Amer. Chem. Soc., 1959, 81, 2884.Peptide Synthesjs.-Protecthg grozlps310 ORGANIC CHEMISTRY.methods.53b A hydrazide may be covered by a N-trityl group when theazide method is to be used in a subsequent step.=t-Butyl esters of amino-acids, although less readily prepared in good yieldthan lower homologues, may occasionally be useful. The ester group can bepreferentially cleaved in presence of a N-benzyloxycarbonyl group byhydrogen chloride in benzene, or both groups may be removed by hydrogenbromide in acetic acid.55 4-Nitrobenzyl esters of amino-acids have beenrecommended in preference to the corresponding benzyl esters, since theirgreater stability to hydrogen bromide facilitates the selective removal ofN-benzyloxycarbonyl groups ; 51b356 hydrogenolysis of the ester group isstraightforward.Excess of alkali should be avoided in the hydrolysis ofN-benzyloxycarbonylpeptide esters, especially when glycine is adjacent tothe N-termin~s,~~ otherwise rearrangement to a hydantoin or urea derivativemay result (this reaction was employed by Wessely for the stepwise degrad-ation of peptides).Several methods have been reported for protecting the thiol group ofcysteine. N-Formyl-2,2-dimethylthiazolidine-4-carboxylic acid, obtainedfrom cysteine by successive condensation with acetone and formylation,gives peptide derivatives from which protecting groups are removed simul-taneously by aqueous-methanolic hydrogen The conventionalS-alkylcysteines have been made in good yield by a simplified method,58while S-(benzylthiomethy1)cysteine offers interesting possibilities, since theprotecting group is removed by mercuric chloride.59 S-(Tetrahydro-2-pyranyl)cysteine, from which the covering group is removed by silver ionsat 0", is unfortunately obtained in poor yield and has two asymmetriccentres.60Formation ofpeptide bond.The value of a method of peptide synthesisdepends chiefly on the yield and optical purity of the product.1a*2c Bodanszkyand du Vigneaud have critically discussed the various methods of formingpeptide linkages and favour the reaction of p-nitrophenyl esters of N-benzyl-oxycarbonylamino-acids with amino-esters.61 The tendency for racemis-ation may be assessed by the synthesis of Z.gly.-L-phe.gly.0Et,62 sincecrystallisation from ethanol at 0" can detect and separate the racemate evenwhen <1% is present.Success with the carbodi-imide method seems todepend on experimental conditions such as temperature and solvent.During the synthesis of the dipeptide derivatives (15; R = H,R' = H or [CHJ,=CO,Et), by the carboxylic-carbonic anhydride pro-cedure, reaction at the urethane-nitrogen atom led to by-products (15 ;R = CH,Ph*O*CO*NH-CH,-CO, R' = H or [CHJ,=CO,Et).@ In addition5* F. Weygand and W.Steglich, Chem. Ber., 1959, 92, 313.55 R. W. Roeske, Chem. and Ind., 1959, 1121.5G H. Schwarz and K. Arakawa, J. Amer. Chent. Soc., 1959, 81, 5691.57 J . A. Maclaren, Austral. J. Chem., 1958, 11, 360.58 D. Theodoropoulos, Acta Chent. Scand., 1959, 13, 383.59 P. J . E. Pimlott and G. T. Young, Proc. Chem. Soc., 1958, 257.Go G. F. Holland and L. A. Cohen, J. Amer. Chem. SOC., 1958, 80, 3765.62 G. W. Anderson and F. M. Callahan, J. Amer. Chem. Soc., 1958, 80, 2902.G3 K. D. Kopple and R. J . Renick, J . Org. Chenz., 1959, 23, 1565; P. SchellenbergM. Bodanszky and V. du Vigneaud, J , Amer. Chem. SOC., 1959, 81, 5688.and J . Ullrich, Chcnz. BPY., 1959, 92, 1256ELMORE : AIMINO-ACIDS, PEPTIDES, AND PROTEINS. 31 1the anhydrides RCO-O*CO,Et are prone to attack by secondary amines atboth carbonyl-carbon atoms, and the ratio of products depends on theamine and the group R, especially their steric effects.64 This may be im-portant in the synthesis of peptides of sarcosine, proline, and hydroxy-proline. The use of ethoxyacetylene in peptide synthesis has been furtherstudied,65 and experimental conditions have been improved.65b TheCH,Ph.OCO*N RCH,*CO*NHCH R’*CO,Et(15)R’*N HaR.CO,H + HCEC-OEt __+ CH,=C(OEt)*O*CO*R -+ R.CO*NHR’ 3- AcOEt(16)Anderson-Callahan test 62 was satisfactory, and the method deserves widerapplication.The mechanism does not necessarily involve formation of ananhydride; an O-acylketen hemiacetal (16) is a likely intermediate, and theO-(N-phthaloylglycyl) derivative [lS; R = o-C,H,(CO),N*CH,] has beenisolated.65u Related methods employ l-chlorovinyl ethyl ether or 1,l-dichloroethyl ethyl ether, and in these cases acyl chlorides are probablyint ermediat es.66It has been reported briefly that 1,l-carbonyldi-imidazole (17) gives agood yield of simple peptides with negligible racemisation at low temper-a t u r e ~ .~ ’ ~ The method depends on the formation of an N-acylimidazole (18)and its reaction with an amino-e~ter.~’~ In an ingenious, related method,reaction between N-acylamino-acid hydrazides and acetylacetone givescrystalline N-acylaminoacylpyrazoles (19 ; Tos = +-C,H,Me*SO,), whichgive peptides with amino-esters.68TO^ - NH-CH R - co .N H R‘EcO, FNP-NJ -EtO’EtO,HO’P 0 *NH.CHR. COzEtReagents: I , RC0,H; 2, R’*NH,; 3, CH,Ac,.Various methods which involve phosphorus compounds have receivedattention. Addition of imidazole during syntheses with tetraethyl pyro-phosphite accelerates the reaction and improves yields; it is suggested that64 N.*\. Leister and D. S. Tarbell, J . Org. Chem., 1958, 23, 1152.88 (a) J. C. Sheehan and J. J. Hlavka, J . 0t.g. Chem., 1958, 23, 635; (b) 13. J. Panne-man, A. F. Marx, and J. I;. Arens, Rec. Trav. chinz., 1969, 78, 487.O6 L. Heslinga and J. F. Arens, Rec. z’rav. chim., 1957, 76, 952.67 (a) G. W. Anderson and R. Paul, J . Anzer. Cheun. Soc., 1958, 80, 4423; (b) T.68 W. Reid and B. Schleimer, i I ~ i n ~ ! l c i ? , 19.58, 619, 43.lf-ielaiid anti G. Schneider, Annulen, 1063, 580, 1.59312 ORGANIC CHEMISTRY.N-(diethoxyphosphino)imidazole (20) is an intermediate.69 Bis-o-phenylenepyrophosphite has been recommended, since it is more readily prepared thantetraethyl pyroph~sphite.~~ Although syntheses of dipeptides were satis-factory, extensive racemisation occurred when N-acylpeptides were used asstarting materials.A thorough examination of the Goldschmidt andLautenschlager method 71 has revealed the same defect.72 A related methodinvolves reaction of phosphoric oxide with diethyl hydrogen phosphite at100” and then addition of an amino-ester. The mixture, which probablycontains a phosphoramidate (21), reacts with an N-acylamino-acid to give adipeptide.73 Advantage can be taken of the reactivity of enol phosphates(22) ZON H-CH WCO-NH R’Z-NHCH R.COIH RNHS(EtO),PO*O*C(OEt)=CH.CO,Et _____t Z*NH*CHR.CODO*PO(OEt)z -WCeH,,*N=C=N.CaH,,Z.NHCHR.CO2H + NH,’CHR’.CO,.C,H,.NO2-~ _______t(23) Z*NHCH R.CO.NH*CH R’CO2*C6H,*NO,-P(Z = CH2PhoO*CO-)to synthesise peptides.N-Acylamino-acids and (l-ethoxy-2-ethoxy-carbonylvinyl) diethyl phosphate (22) give unsymmetrical anhydrides,which react with esters or salts to give peptide derivative^.^^ Since carbodi-imide and unsymmetrical anhydride syntheses are considerably faster thanthose involving p-nitrophenyl esters, tripeptides can be obtained fromamino-acid derivatives without isolation of dipeptide interrnediate~.~~ AnN-acylamino-acid and a @-nitrophenyl ester of an amino-acid (23) arecoupled by one of the faster methods, and, without isolation, an alkyl esterof an amino-acid is added.Di- and tri-peptides of ory-diaminobutyric acidmay be synthesised easily 76 through the key intermediate L-S-amino-l-tosyl-pyrrolid-2-one (24). The aminoacyl insertion reaction has been reviewed :Tos*NHIRCO-NH N-Tos p 1 2R”O.CO.NH.CH.CO.NHR’ c Tos*NH I L4R - co -N H . c H - co - N H R ’ [y,04, R’-NH,.Reagents: I, HBr-AcOH-PhOH; 2, COCl2, then R”OH; 3, R.C02H, [(EtO),P]20;6g G. W. Anderson, A. C. McGregor, and R. W. Young, J . Org. Chem., 1958,23, 1236.70 P. C. Crofts, J. H. H. Markes, and H. N. Rydon, J., 1958, 4250; 1959, 3610.71 S. Goldschmidt and H. Lautenschlager, Annalen, 1953, 580, 68.7* W. Grassmann and E. Wiinsch, Chem. Ber., 1958, 91, 449; W. Grassmann, E.73 G. Schramm and H.Wissmann, Chem. Ber., 1958, 91, 1073.l4 F. Cramer and K.-G. Gartner, Chew. Ber., 1958, 91, 1562.75 M. Goodman and K. C . Stueben, J . Amer. Chem. Soc., 1959, 81, 3980.76 K. PoduSka and J. Rudinger, Coll. Czech. Chew. Comm., 1069, 24, 3449.Wunsch, and A. Riedel, ibid., p. 455ELMORE : AMINO-ACIDS, YEPTIDES, AND PROTEINS. 313more recent experiments have shown that the rearrangement is intra-molecular and proceeds without racemisation.''Cyclopeptides and Related Antibiotics.*-N-Cyclopeptides and antibioticshave been reviewed recently.2eJ Kenner and his have syn-thesised N-cyclopentapeptides from the diastereoisomers ofH .gly . leu. gl y . leu. gly . S . C6H,*N0,-pand correlated the yields with the lengths of the acyclic peptides as deter-mined by measurement of their dielectric increments.Synthesis of N-cyclo-peptides by procedures involving unsymmetrical anhydrides or phospho-amides 79 suffers from the risk of racemisation. One of the most interestingmethods of synthesis is the doubling reaction, in which a reactive ester of apeptide forms a N-cyclopeptide containing twice as many amino-acid residuesas the acyclic peptide. Schwyzer 8o has considered the factors which favourthis reaction. Thus, anti-parallel doubling assists the synthesis of grami-cidin S and of its homologue,81u in which lysine replaces ornithine, giving akind of anti-parallel pleated sheet. The configurations of the amino-acidsenable all their side-chains to be axially disposed. N-Cyclopeptides con-taining 2(2n + 1) residues (n = 1, 2, etc.) can be made by the doublingreaction. Bishomogramicidin S has an antibiotic activity comparable withthat of the parent compound.81 Various acyclic analogues of gramicidinSS2 and an acyclic pentapeptide sequence of tyrocidine A51b have beensyn thesised.A decapeptide corresponding to one of the possible structures for poly-myxin B, has been synthesised and is active against Brucella bronchisepti~a.~~This is a notable achievement, for the synthesis required three differentmethods of protecting amino-groups.The method of Podugka and Rudin-ger 76 may provide an alternative and simpler route to this compound.Rotatory dispersion studies have enabled Konigsberg and Craig@ todelineate partial structures for bacitracin A (25a-e), which may account forthe hitherto ill-defined linkage between phenylalanine and isoleucine as wellas their easy racemisation.Reduction of esterified bacitracin A with lithiumborohydride, followed by hydrolysis, revealed that both carboxyl groups ofL-aspartic acid were blocked, one with the c-amino-group of lysine, and thatthe 8- and y-carboxyl groups of D-aspartic acid and D-glutamic acid respec-tively were free.8577 Ref. 2e, p. 157; M. Brenner and J . P. Zimmermann, HeZv. Chim. Acta, 1958, 41,79 M. Rothe, I. Rothe, H. Briinig, and K.-D. Schwenke, Angew. Chem., 1959, '71, 700.81 R. Schwyzer and P. Sieber, HeZv. Chim. Ada, 1958, 41, (a) 2186, ( b ) 1582.82 B. F. Erlanger, W. V. Curran, and N. Kokowsky, J . Amer. Clzem. SOC., 1958, 80,8s K.Vogler, P. Lanz, and W. Lergier, Experientia, 1959, 15, 334.84 Ref. 2e, p. 226; W. Konigsberg and L. C. Craig, J . Amer. Chem. SOL, 1959, 81,85 D. L. Swallow and E. P. Abraham, Biochem. J., 1959, 72, 326.* Cyclic peptides, in which amino-acids are linked only through peptide bonds, areIf the ring contains an ester or disulphide linkage, the terms467; H. Dahn, R. Menass6, J. Rosenthaler, and M. Brenner, ibid., 1959, 42, 2249.G. W. Kenner, P. J. Thomson, and J. M. Turner, J., 1958, 4148.Ref. 2e, p. 171.1128; 1959, 81, 3051, 3055.3452.called N-cyclopeptides.0- or SS'-cyclopeytide are applied314 ORGANIC CHEMISTRY.Two antibiotics from different strains of Streptomyces are O-cyclo-peptides. Etamycin (26) contains allohydroxy-D-prolinc , a-phenyl-L-I i"' c p ,ssarcosine, and p ,N-dimethyl-L-leucine , which previously were not known tooccur naturally.86 Catalytic hydrogenation of the pyridine ring, followedby opening of the lactone, permitted sequence determination 86u by theQOH ~O-NH-CHB"~.CO-N CO-?Me/ CO-NH-CH CH2 ICHMe coI IO-CO-CHPh *NMe*CO - CHMe.NH*CO-CH*NMeIEtamycin (26) Me2CH-CHMe u:lco*NHEdmaii method. A penetrating degradative study led to the structure (27)for echinomycin, and the authors suggest that the unusual 1,4-dithian ringmay have been overlooked in other polypeptide^.^^Evolidine,ss from the leaves of Evodea xanthoxyloides, is an N-cyclo-85 (a) J.C. Sheehan, €1. G. Zachau, and W. B. Lawson, J . Amel.. Clzem. SOC., 1957,79, 3933; 1958, 80, 3349; ref.2e, p. 149; (b) R. B. Arnold, A. W. Johnson, and A . B.Mauger, J . , 1958, 4466.87 W. Keller-Schierlein, M. Lj. MilhailoviC, and V. Prelog, I€ch. Clzinz. i f cfa, 1959,42, 305ELMORE AMINO-ACIDS, PEPTIDES, AND PROTEINS. 315heptapeptide with the sequence asp.NH,.leu.ser.phe.leu.pro.val. In viewof its amino-acid composition, it would be interesting to lmow if it has anystrepogenin activity (see below).New Peptides.-In addition to ophthalmic and norophthalmic acid, bovinelens contains S-sulphogl~tathione.~~ y-Glutamyl-S-methylcysteine has beenisolated from lima and kidney beans; S-methylation of glutathione, fol-lowed by degradation with carboxypeptidase, gave an identical product andconfirmed the structure. Other new peptides of glutamic acid includey-glutamylvalylglutamic acid 91 from the rush, Junczis conglomeratus, andarginylglutamine 92 from the green alga Cladophora.A peptide from themycelium of Penicillium chrosogenuwz, which is probably a-aniinoadipyl-cysteicylvaline, is of interest because it is biogenetically related to cephalo-sporin N.93 Pencillin may arise by cyclisation of the corresponding cysteinetripeptide to cephalosporin N, followed by exchange of the side-chain for acarboxylic acid. Pyroglutamylglutaminylalanine has been synthesised andis identical with eisenin from the marine alga Eisenia b i c y ~ l i s . ~ ~ The re-lated pyroglutamylglutaminylglutamine,g4b~ gs however, apparently is differ-ent from fastigiatine from the brown alga Peluetia fasfigiata, which wasbelieved to have that s t r u ~ t u r e .~ ~Strepogenins.-A variety of peptides has been synthesised or isolatedfrom protein hydrolysates, having strepogenin activity. Merrifield andWoolley 97 have tentatively suggested that, for high activity, the peptideshould contain at least five amino-acid residues including either serine orcysteine, and the latter should preferably not be N-terminal. The presenceof amino-acids with lipophilic side-chains seems to be advantageous for highactivity. The sequence of amino-acids is not critical, since bothH.ser . his. leu.va1. glu. OH and H .Val. his.glu. ser .leu. OH were highly active .The related peptide, H.thr.his.leu.val.glu.OH was inhibitory to L. caseieg8From hydrolysed casein, a hexapeptide containing no serine or cysteine hasbeen isolated and was highly active.99 The relation between structure andactivity thus seems as elusive as ever.Mypertensins.-Full details have appeared of the syntheses of va15-hypertensins I and I1 (28; X = val), and the repeated and successful useof the carbodi-imide method is noteworthy.loO Tryptic degradation of a88 H.D. Law, I. T. Millar, H. D. Springall, and A. J. Birch, €'roc. Chenz. Soc., 1958,198.89 S. G. Waley, Biochem. J., 1959, 71, 132.I-I. Rinderknecht, D. Thomas, and S. A s h , Helu. Chiwz. Acta. 1968, 41, 1; 13. hl.91 A. I. Virtanen and T. Ettala, Actn Chenz. Sraizd., 1958, 12, 787.ga S. Makisumi, J . Biochem. (Japan), 1959, 46, 63.93 H. R. V. Arnstein, D. Morris, and E. J.Toms, Biochim. Bioplzys. A d a , 1959,35, 561.g4 (a) T. Kaneko, T. Shiba, S. Watarai, S. Imai, T. Shimada, and I<. Ueno, Cheni.upad I n d . , 1957, 986; (b) J. Rudinger and 2. Pravda, Coll. Cz~clz. Chem. Comm., 1958,23, 1947.g5 T. Shiba, S. Imai, and T. ICaneko, Bull. Clzem. SOC. Japan, 1958, 31, 244.96 C. A. Dekker, D. Stone, and J. S. Fruton, J . Eiol. Chem., 1949, 181, 719.97 R. B. hlerrifield and D. W. Xf-oolley, J . Ameu. Chem. SOC., 1958, 80, 6635.98 R. B. Merrifield, L. Biol. Chem., 1058, 232, 43.99 0. Mikeg, and F. Sorm, Coll. Czech. Chenz. Comm,, 1959, 24, 1897.loo R. Schwyzer, B. Iselin, €I. Kappelcr, B, Riniker, W. Rittel, and f l . Ziiher, ZIi~kv.I IZacharius, C. J. Morris, and J. F. Thompson, Arch. Biochem. Biophys., 1959, 80, 199.( ' h i m .Llctn, 1958, 41, 1273, 1287316 ORGANIC CHEMISTRY.plasma-protein fraction has furnished a tetradecapeptide (28; X = ileu) ,which is further hydrolysed by rennin to ileu5-hypertensin I. Degradativeevidence of structure of the rennin substrate has now been confirmed bysynthesis.lOlH.asp.arg.val.tyr.X.his.pro.phe.his.leu .leu.val.tyr.ser.OH/-Hypertensin I- ,-b4-,Hypertensin II+ TI 28; X = val o r ileu)Plasma RenninenzymeOxytocin and Vasopressin.-Improved methods for the isolation ofoxytocin and vasopressin have been described.lo2 Horse oxytocin andvasopressin are identical with the bovine horniones.lo3 New syntheses ofoxytocin have been announced; 61~104 one is of particular interest, since itinvolved starting with the C-terminal amino-acid and adding one residue ata time by reaction with a N-benzyloxycarbonylamino-acid 9-nitrophenylester.61 An analogue of oxytocin , in which phenylalanine replaced tyrosine,has been synthesised in two laboratories; lo5 bioassay revealed that thehydroxyl group of tyrosine is favourable, but not essential, for hormonalactivity.The isoasparagine isomer of oxytocin,lo6 like the isoglutamineisomer,lo7 is inactive, but unlike the latter, does not inhibit arginine-vasopressin.lo8 An improved synthesis of arginine-vasopressin , whichavoided exposure of peptide derivatives containing C-terminal asparagine totetraethyl pyrophosphite or carbodi-imide, obviated possible contaminationwith an anhydro-derivative, and gave a highly active product.log Ananalogue of vasopressin, in which histidine replaced lysine or arginine hadfeeble activity.ll0 The attenuation of pressor activity with decreasingpK,’ of the basic amino-acid is remarkable, and this relationship is furtherexemplified by the relatively high pressor activity of arginine-vasotocin,lllwhich is composed of the SS’-cyclopeptide fragment of oxytocin and thebasic side-chain of arginine-vasopressin.Pharmacological evidence has101 L. T. Skeggs, J. R. Kahn, K. E. Lentz, and N. P. Shumway, J . Exp. Med., 1957,106, 439; L. T. Skeggs, K. E. Lentz, J. R. Kahn, and N. P. Shumway, ibid., 1958, 108,283.102 R. Acher, A. Light, and V. du Vigneaud, J . Bid. Chem., 1958, 233, 116;A. Light, R. 0. Studer, and V. du Vigneaud, Arch.Biochern. Biophys., 1959, 83, 84;A. V. Schally, H. S. Lipscomb, and R. Guillemin, Biochim. Biophys. A d a , 1959,31, 252.10s R. Acher, J. Chauvet, and M.-T. Lenci, Bull. Soc. Chim. b i d , 1959, 40, 2005.104 &I. Bodanszky and V. du Vigneaud, J . Amev. Chem. Soc., 1959, 81, 2504.105 M. Bodanszky and V. du Vigneaud, J . Amer. Chern. Soc., 1959, 81, 1258, 6072;106 W. B. Lutz, C. Ressler, D. E. Nettleton, and V. du Vigneaud, J . Amer. Chem.107 C. Ressler and V. du Vigneaud, J , Amer. Chenz. SOC., 1957, 79, 4511.lo8 C. Ressler and J. R. Rachele, Pmc. SOL. Exptl. Bid. Med., 1958, 98, 170.lo9 P. G. Katsoyannis, D. T. Gish, G. P. Hess, and V. du Vigneaud, J . Amer. Chem.Soc., 1958, 80, 2558; V. du Vigneaud, D. T. Gish, P. G. Katsoyannis, and G. P.Hess,ibid., p. 3355.110 P. G. Katsoyannis and V. du Vigneaud, Arch. Bkochem. Biophys., 1958, 78,555.P.-A. Jacquenoud and R. A. Boissonnas, Helv. Chim. Acta, 1959,42, 788.SOC., 1959, 81, 167.P. G. Katsoyannis and V. du Vigneaud, J . BUioZ. Chem., 1958, 233, 13552I< T,MO KE : AM I NO --4CI DS , 1'K PTI DES , A N I) PHOTE I N S , 3 17subsequently indicated that arginine-vasotocin is a natural hormone of certaincold-blooded vertebrates.l12Melanocyte-stimulating Hormones (MSH) .-This subject has receivedconsiderable attention since it was last reviewed.wg Full details of sequentialstudies on the a- and p-porcine hormones have appeared.l13 In addition, thestructure of human p-MSH has been determined.l14 Three schoolshave synthesised biologically active peptides. The pentapeptideH.his.phe.arg,try.gly.OH had weak hormonal a ~ t i v i t y .~ ~ J ~ ~ A trideca-peptide derivative, differing from a-MSH in having a N-benzyloxycarbonylinstead of an N-acetyl group on the N-terminal serine residue, glutamine inplace of glutamic acid, and an N'-tosyl group on lysine, had about 1% ofthe activity of the natural hormone.l16 The corresponding N-acetyl deriv-ative, reported more recently, had 25% of the activity of the honnone.ll7ct-MSH itself has been brilliantly synthesised by Boissonnas, Guttmann, andtheir colleag~es.4~b N-Acetyl-~-seryl-~-tyrosyl-~-seryl-~-methionyl-~-glut-amic acid y-benzyl ester 118 and L-histidyl-L-phenylalanyl-L-arginyl-L-tryptophyl- L - glycyl - (N" - benzyloxycarbonyl- L - lysyl) - L - prolyl- L - valineamide 118 were condensed by the carbodi-imide method; removal of protect-ing groups required very carefully controlled conditions.Finally,Schwyzer's group have synthesised a protected octadecapeptide with thecomplete amino-acid sequence of bovine p-MSH, which has about 1% ofthe biological activity of the natural horrnone.ll9 The N-terminal aspartylis replaced by a N-benz yloxycarbonylasparaginyl residue, lysine has anN'-toluene-9-sulphonyl substituent, glutamine replaces glutamic acid, andthe C-terminal aspartic acid is diesterified.I 2 3 4 5 6 7 8 9 1011 1213Ac.ser.tyr.ser.met.glu.his.phe.arg.try.gly,lys.pro.vai.~H2I 2 3 4 5 6 7 8 9 10 I 1 12 13 14 I 5 16 17 18 s (0x1 H.asp.ser.*gly.pro.tyr.lys.met.g lu.his.phe.arg.try.gly.ser.pro.pro.lys.asp.0HI 2 3 4 5 6 7 8 9 10 i I 12 13 14 15 16 I7 18 19 20 21 22a(human) H.ala.glu.lys.iys.asp.glu.gly.pro.tyr.arg,met.glu.his.phe.arg.try,gly.ser.pro.pro.lys.asp.OHa- and ~-Melanocyte-stimulating hormones. (* glu in porcine a-MSH.)112 B. T. Pickering and H. Heller, Nutwe, 1959, 184, 1463; W. H. Sawyer, R. A.113 J. I. Harris and P. Roos, Biochern. J., 1959, 71, 434, 445; J. I. Harris, ibid.,114 J. I. Harris, Nature, 1959, 184, 167.115 K. Hofmann, M. E. Woolner, G. Spuhler, and E. T. Schwartz, J . Awer. Chem.SOC., 1958, 80, 1486.116 K. Hofmann, M. E. Woolner, H. Yajima, G. Spiihler, T. A. Thompsoh, and E. T.Schwartz, J . Amer. Chem. SOC., 1955, 80, 6458.117 K. Hofmann, H. Yajima, and E. T. Schwartz, Biochim.Biophys. Acta, 1959, 38,252.l18 St. Guttmann and K. A. Boissonnas, Helv. Chim. A d a , 1958, 41, 1852; R. A.Boissonnas, St. Guttmann, R. L. Huguenin, P.-A. Jacquenoud, and E. Sandrin, ibid.,p. 1867.119 R. Schw!rzer, H. Kappeler, €3. Iselin, W. Rittel, and H. Zuber, Helv. Chim. Acta,1959, 42, 1702.Munsick, and H. B. van Dyke, ibid., p. 1464.p. 45131 s ORGANIC CHEMISTRY.Haemog1obins.-There are three recent reviews of hzemoglobins. 120 Thestructural comparison of normal adult (A) or normal foetal (F) with abnormalhaemoglobins (C, E, G, H, I, S, etc.), by electrophoretic and chromatographicexamination of enzyme digests of the proteins (" fingerprinting "),121 hasrecently provided results of profound significance to the study of the chemicalbasis of gene mutations.The cc- and the P-chains (two of each) 122 of humanhzmoglobin A may be separated chromatographically or electrophoretic-ally.123 The P-chains have the N-terminal sequenceH.val. hisleu. thr.pro.glu.glu.ly~,1~~~ 124whereas the a-chains begin with H.val.le~.I~~ Present evidence suggeststhat the C-terminal sequence of P-chains is tyr.his.0H.126 Haemoglobin Sand C are identical with hzmoglobin A except that glutamic acid at position 6of the N-terminal sequence of the two P-chains is replaced by valine andlysine ~ e v e r a l l y . l ~ ~ J ~ ~ Hzmoglobin G also differs from hamoglobin A a tone position; glycine replaces glutamic acid at position 7 of the N-terminalsequence of the p-chains.128 In hzmoglobin E, a further variation of asingle amino-acid has been demonstrated at a point remote from the N -termini of the p-chains.One of the peptides resulting from tryptic degrad-ation of haemoglobin A has the sequence:H.val.asp.val.asp.glu.val.gly.gly.gIu.ala.leu.gly.arg.0Hwhereas, in hzmoglobin E, lysine replaces glutamic acid at the ninth residuefrom the N-terminus of this p e ~ t i d e - l ~ ~ Normal foetal hzmoglobin F con-sists of 2a- and 2y-chains; the former are identical with the a-chains ofhzemoglobin A,130 while the latter have N-terminal g1y~ine.l~~ " Finger-printing " revealed many differences between the y-chains and the p-chainsof hzmoglobin A.130 An abnormal fatal haemoglobin (" Barts ") consistsof 4 y-cliains.132 Hzmoglobin H consists of 4 p-chains, identical with thoseof hzmoglobin A.lS A structural change in the a-chains is found in haemo-globin I ; one tryptic peptide contains tryptophan, unlike the correspondingpeptide from hzemoglobin A.lM120 H.A. Itano, A h . Protein Chem., 1957, 12, 215; H. K. Prins, J . Chromatog.,1959, 2, 445; W. A. Schroeder, Fortschr. Chem. org. Naturstoffe, 1959, 17, 322.121 V. M. Ingram, Biochim. Biophys. Acta, 1958, 28, 539.122 H. S. Rhinesmith, W. A. Schroeder, and N. Martin, J . Amer. Chem. SOC., 1958,80, 3358.123 S. Wilson and D. B. Smith, Canad. J . Biochem. Physiol., 1959, 37, 405; V. M.Ingram, Nature, 1059, 183, 1795.124 J. A. Hunt and V. &I. Ingram, Nature, 1959, 184, 640.125 H. S. Rhinesmith, W. A. Schroeder, and L. Pauling, J . Amer.Chem. SOC., 1957,79, 600.126 K. Hike and G. Braunitzer, 2. Naturforsch., 1959, 14b, 603; T. Kauffmann andF.-P. Boettcher, ibid., 1959, 13b, 467; Chem. Bey., 1959, 92, 2707.137 J. A. Hunt and V. M. Ingram, Nature, 1958, 181, 1062; Biochim. Biophys. Acta,1958, 28, 546; V. M. Ingram, ibid., 1959, 36, 402.128 R. L. Hill and H. C. Schwartz, Nature, 1959, 184, G41.1ZD J. A. Hunt and V. M. Ingram, Nature, 1959, 184, 870.130 J. A. Hunt, Nature, 1959, 183, 1373.131 W. A. Schroeder and G. Matsuda, J . Amer. Chem. SOC., 1958, 80, 1521.132 J. A. Hunt and H. Lehrnann, Nature, 1959, 184, 872.13* M. Murayama and V. M. Ingram, Nature, 1959, 183, 1798.R. T. Jones, W. A. Schroeder, J. E. Balog, and J. R. Vinograd, J . Amer. Chem.Soc., 1959, 81, 3161TSlMORE AM I N O-_L\C I 13s , I T P'TI I)E S , AND PH OlE I N S .319Phosphopeptides and Phosphopr0teins.-Phosphoproteins are increasinglybecoming a focus of attention. One reason is the elucidation of the amino-acid sequences at the " active centres " of a number of hydrolytic enzymes,which have been inhibited by phosphorylation with compounds such as di-isopropyl phosphorofluoridate (see Table). Some phosphate-transferringenzymes and phosphatases are phosphorylated at the hydroxyl group of aAmino-acid sequences in Phosllhorylated enzymes.Phosphoryl-EnzymeTrypsinChymotrypsinThrombinHorse-liver ali-esterase dHorse-serum pseudo-choline-esteraseElastaseRabbit-muscle phos-phoglucomutaseMuscle phosphorylaseBone or intestinal alk-aline phosphataseHexokinase JAcetylcholinesterasea (- b)atingreagentii, iiii11111 ...ivVviiStructure a t site of phosphorylationAsp.ser.cys.glu.gly.asp.se~.gly.pro.val.cys.ser.gl~.lys.gly.asp.ser.gly.gly.pro.leu.gl y .asp. ser . gl y . glu .ah.gly .asp. ser.gly .gl y . glu ser. g1 y . gl y . (glu , ser)phe.glp.glu.ser.ala.gly. (ala,,ser)*{gly.asp.ser.gly.asp.ser.gly.glu.ala.va1.lys .gluNH,.ileu. ser.val.arg.ser.ser.ser.* There is no satisfactory explanation for the different results.Reagents : i, (PrfO),PO*F; ii, (Pri0)MePO-F; iii, glucose 1- or 6-[32P]phosphate;iv, ATP + M P + " converting enzyme "; v, inorganic [32P]phosphate; vi, S2P-ATPor glucose 6-[32P]phosphate.References: a, G. H.Dixon, D. L. Kauffman, and H. Neurath, J . BioE. Chew., 1958,233, 1373. b, R. A. Oosterbaan, P. Kunst, J. van Rotterdam, and J. A. Cohen, Biochinz.Biophys. Acta, 1958, 27, 556; N. K. Schaffer, L. Simet, S. Harshman, R. R. Engle, andR. W. Drisko, J . Bid. Chem., 1957,225, 197; N. K. Schaffer and R. P. Lang, Fed. PYOC.,1959, 18, 317. c, J. A. Gladner and K. Laki, J . Amer. Clzem. Soc., 1958, 80, 1263.d , H. S. Jansz, C. H. Posthumus, and J, A, Cohen, Biochisn. Bioghys. Acta, 1959, 33,396. e, H. S. Jansz, D. Brons, and M. G. P. J. Warringa, Biochim. Biophys. Acta, 1959,34, 573. f, B. S. Hartley, M. A. Naughton, and F. Sanger, Biochim. Biophys. Acla,1959,34, 243. g , D. E. Koshland and M. J. Erwin, J . Amev. Chem. Soc., 1957, 79, 2657.h. E. H. Fischer, D.J. Graves, E. R. S. Crittenden, and E. G. Krebs, J . Bid. Chem.,1959, 234, 1698. i, G. Agren, 0. Zetterqvist, and M. Ojamae, Acta Ckem. Scand., 1959,13,1047; L. Engstrom and G. Agren, ibid., 1958,12,357. j , G. Agren and L. Engstrom,Acla Chew. Scand., 1056,10, 489. k , N. K. Schaffer, S. C. May, and W. H. Summerson,J . Bid. Chem., 1954, 206, 201.serine residue by incubation with substrate (see Table). O-Phosphoryl-serine and -threonine and several simple peptide derivatives have been syn-the~ised.l~~ Protected peptides have been synthesised and then phosphoryl-ated with diphenyl or dibenzyl phosphorochloridate. Hydrogenolysis isfavoured for the removal of protecting groups, since the phosphate grouptends to undergo p-elimination in alkali.Lombricine, isolated from earth-135 ( a ) D. Theodoropoulos, H. Bennich, G. Folsch, and 0. Mellander, Nature, 1959,184, 187; ( b ) G. Folsch, A c f a Chew. S c a d , 1055, 9, 1039; 1955, 12, 561; 1959, 13,1407, 1422; G. Riley, J. H. Turnbull, and If'. Wilson, J., 1957, 1373:I20 OKGANIC CHEMISTKY.w o r r ~ i s , ~ ~ ~ has been proved to be 0-(O’-(2-guanidinoethyl)phosplioryl)-u-serine by degradation and synthesis.137 N-Phosphoryl-lombricine, a naturalphosphagen of earthworm muscle, has also been synthesised.Evidence has accumulated, which weakens Perlmann’s 13* claim that, ofthe phosphorus present in a-casein, 40% is phosphoamide and 20% is pyro-phosphate. It is also unlikely that all the phosphorus of p-casein is in theform of phosphodiester linkages. Alkaline dephosphorylation of casein inH,180 gave unlabelled inorganic phosphate, and therefore represents ap-elimination ; N-P bonds were thereby ex~1uded.l~~ Degradation of CC-and p-casein with proteolytic enzymes, especially trypsin, produced phospho-peptones, in which the number of phosphate groups equalled the total numberof serine and threonine residues.lM titration of the phospho-peptones revealed that all phosphoric acid groups were monoesterified.Moreover, the phosphopeptide from p-casein is probably N-terminal in theprotein and contains all the phosphorus. The resistance of a-N-ethoxy-carbonyl-L-lysyl-(O-phosphoryl-L-sery1)glycine to trypsin is interesting inview of the limited attack on casein by this enzyme.135a It appears thatseveral consecutive residues of O-phosphorylserine occur in some phospho-proteins.141 Partial acid-hydrolysis of casein afforded HfP-ser],*OH(n = 1, 2, 3), while phosvitin furnished an even larger range (n = 1-6).Such accumulations of phosphoric acid groups may explain the slow hydro-lysis of casein by certain phosph~monoesterases,~~~ since similar observationshave been recorded with nucleosides bearing more than one phosphomono-esterRibonuc1ease.-Final elucidation of the complete amino-acid sequence isstill awaited. At least two differences between beef- and sheep-pancreaticribonucleases have been found; residues 3 and 37 are threonine and lysinein the former, and serine and glutamic acid in the latter.lM Attempts havebeen made to identify the “active centre’’ of the enzyme. Inhibition byiodoacetate at pH 5-5-6.0, followed by chromatographic purification andhydrolysis, gave one mol. of im-carb~xymethylhistidine.~~~ Subtilisincleaved the ala-ser linkage, but the two fragments remained stronglybound, so that chromatography and dialysis failed to separate them. Care-ful fractionation with trichloroacetic acid succeeded, however, and the twoIn onea0 21136 N. Van Thoai and Y . Robin, Biochiw. Biophys. Acta, 1954, 14, 76; R. Pant,137 I. M. Beatty, D. I. Magrath, and A. H. Ennor, Nature, 1959, 183, 591; I. M.138 G. Perlmann, Adv. Protein Chem., 1955, 10, 1.139 L. Anderson and J. J . Kelley, J . Amer. Chem. Soc., 1959, 81, 2275.140 (a) R. &kerberg, Arkiv Kemi, 1959, 13, 409; (6) R. F. Peterson, L. W. Nauman,and T. L. McMeekin, J . Amer. Chem. Soc., 1958, 80, 95; H. Bennich, B. Johansson, andK. Osterberg, Acta Chem. Scand., 1959, 13, 1171.141 J. Williams and F. Sanger, Biochim. Biophys. Acta, 1959, 33, 294; N. J . Hipp,M. L. Groves, and T. L. McMeekin, J. Amer. Chem. Soc.. 1957, ‘79, 2559.148 T. Hofmann, Biochem. J . , 1958, 69, 139.145 J: Baddiley, J . G. Buchanan, and R. Letters, J., 1958, 1000; C. A. Dekker,A, M. Michelson, and A. R. Todd, J . , 1953, 947.144 C. B. Anfinsen, S. E. G. Aqvist, J. P. Cooke, and B. Jonsson, J . Bid. Chem.,1959, 234, 1118.145 H. G. Gundlach, W. E. Stein, and S. Moore, J . Biol. Chem., 1959, 234, 1754.Biochern. J . , 1959, 73, 30.Beatty and D. I. Magrath, ibid., p . 591ELMOKE : AMINO-ACIDS, PEPTIDES, AND PROTEINS. 32 1fragments were separately inactive, but fully active when mixed.146 Sormhas made an interesting comparison of peptide sequences in ribonuclease,trypsinogen, chymotrypsinogen, and in~u1in.l~~D. T. E.M. F. ANSELL.C. A. BUNTON.A. G. DAVIES.P. D. B. DE LA MAKE.D. T. ELMORE.J. MCKENNA.W. G. OVEREND.A. R. PINDER.Y. POCKER.J. H. RIDD.J. E. SAXTON.T. S. STEVENS.J. TEDDER.G. H. WHITHAM.146 F. M. Richards, Proc. Nut. Acud. Sci. U.S.A., 1958, 44, 162; F. M. Richards,147 F. Sorm, Coll. Czech. Chem. Comm., 1959, 24, 3169.and P. J. Vithayathil, J . Bid. Chew., 1959, 234, 1459.

ISSN:0365-6217    

DOI:10.1039/AR9595600159

出版商:RSC    

年代:1959

数据来源: RSC

摘要:

BIOLOGICAL CHEMISTRY1. INTRODUCTIONTHE ramifications of biochemistry are now so extensive that it probablycomes as no surprise that one of the topics considered in this year’s Reporthas not been dealt with previously. A considerable amount of work iscurrently being undertaken on mineral metabolism with special reference toteeth; much of the information available is the result of fruitful co-oper-ation between scientist and clinician and is thus often published in journalsnot on the reading list of more chemically minded biochemists. A review ofthis work in Anlzual Reports will remedy this; furthermore, it is importantto have available the chemical and biochemical facts on such emotionallycharged problems as 9*Sr fall-out and fluoridisation of drinking water.The discovery that p-carotene was converted into vitamin A in the in-testinal mucosa of aninials and not in the liver was made during 1946-48.When it was iurther shown that the conversion in vivo proceeded easily, onefelt that the mechanism of the reaction would soon be revealed.Theproblem has, however, proved most complex and a stocktaking at the presenttime after 10 years’ endeavours seems appropriate.Progress in the study of muscular contraction has continued steadilyduring the past few years, but an important recent development in musclebiochemistry has been the attempt to elucidate the chemistry of relaxation.The characteristic cycle of normal muscle fufiction embraces both contractionand relaxation, and the chemical events associated with these are comple-mentary and equally important aspects of muscle biochemistry. Thisyear’s Report discusses modern aspects of both features in relation to earlierobservations.The discovery of new amino-acids is but one aspect of biochemistrywhich has been enormously aided by chromatography in all its variousaspects, and applications of these techniques to a study of higher plants haverevealed a number of interesting new compounds.Most of these have nowbeen well characterised chemically and the biosynthesis and metabolism .ofsome are now reasonably clear. However, the biochemistry of many ofthese new amino-acids remains to be investigated. ‘r. w. G.2. CHEMISTRY OF BONE AND TOOTH MINERALSTHERE has been a reawakening of interest in the chemistry of mineralisedtissues during the last decade.The skeleton is not merely a convenient framework upon which musclescan act and from which viscera depend. It is a vast storehouse which pro-vides minerals to the body in times of stress and is replenished in times ofplenty.The minerals of bone are distributed in an organic matrix, about70% by wt. of mature bone being inorganic. The tooth consists of twomajor tissues, enamel which is the most highly mincralised tissue in the bodyHARTLES: CHEMISTKY OF BONE AND TOOTH MINERALS. 323containing less than l:/b of organic matter, and dentine, which containsabout 7Sy0 of minerals. The third mineralised dental tissue, the cementum,covers the roots of teeth in a thin layer and is chemically similar to bone.Perhaps the most important physical characteristic of the mineralcrystals of bone and teeth is their smallness.Early workers,l basing theirestimates on X-ray-diffraction studies, deduced that the length of the crystalwas of the order of to 104 cm. Measurements based on the deter-mination of total surface area of powdered bone by gas-adsorption tech-niques have produced results supporting earlier estimates of size. Suchparticles are well beyond the range of the light-microscope and it is onlywith the aid of the electron-microscope that actual crystals have beenvisualised.3 Using a combination of microdiffraction of X-rays and electron-microscopy, Engstrom and Zetterstrom estimated that the crystals were200 A in width. Robinson and Watson 5 produced electron micrographs ofintact bone showing crystals 350400 A long, almost as wide, and 25-50 Athick.The crystals appeared to be oriented with their long axes in thedirection of the collagen fibres. It seems established, therefore, that bonemineral is crystalline and that the crystals are very small indeed.Composition of the Crystals.-The main mineral constituents of bone andteeth are calcium, phosphate, carbonate, hydroxyl ions, and water, withsmaller amounts of magnesium, sodium, potassium, and chloride.The main component of the solid phase is undoubtedly some form ofbasic calcium phosphate. If the major component were tricalcium ortho-phosphate Ca3(P0&, then the molar Ca : P ratio would be 1-5. Manyworkers have shown that the Ca : P ratios of samples of human bone are ingeneral higher than 1.5, the most usual values being around 1.66, but valuesabove and below this figure are quite commonly found. Dallemagne andFabry6 are of the opinion that bone salt may be considered as having afundamental unit which is tricalcium phosphate combined with excess ofcalcium.In view of the similarity of the X-ray-diffraction patterns of bone andnaturally occurring apatites, many workers have concluded that bonemineral is an apatite.This is, however, inconclusive evidence, since anyunignited precipitate of calcium phosphate gives the X-ray diffraction pat-tern of an apatite. Neuman and Neuman,' in an excellent review, discussthis problem fully and conclude that the apatite pattern of X-ray diffractionis given by almost any sample of calcium phosphate with a molar Ca : Pratio lying between 1.33 and 2.0.Thus, on this basis, any unignited calciumphosphate sample with a Ca : P within 20% of the theoretical value of 1-66could be classified as hydroxyapatite. It is not justifiable, therefore, to1 W. F. De Jong, Rec. Trau. chim., 1926, 45, 445; W. F. Bale, H. C. Hodge, andS. L. Warren, Amer. J . Roentgenol., 1934, 32, 369; J. Thewlis, Proc. Phys. SOC., 1939,51, 99.N. V. Wood, Science, 1947, 105, 531.A. Engstrom and R. Zetterstrom, Exptl. Cell. Res., 1951, 2, 268.R. A. Robinson and M. L. Watson, Anat. Bec., 1952, 114, 383.3 R. A. Robinson, J . Bone and Joiizt Surg., 1952, 34, A , 389.6 M. J. Dallemagne and C.Fabry, in Ciba Foundation Symposium on Bone Struc-7 W. F. Neuman and M. W. Neuman, Chem. Rev., 1953, 53, 1.ture and Metabolism, Churchill, London, 1956324 BIOLOGICAL CHEMISTRY.visualise the main component of bone salts as a compound of fixed com-position such as hydroxyapatite, 3Ca,(PO,),,Ca(OH),.Neuman and Neuman7 conclude that the fundamental bone salt is acompound of calcium, phosphate, hydroxyl ions, and water which exhibitsa Ca : P ratio of approximately 1.5 and diffracts X-rays to give a character-istic apatite pattern. It represents only one small region of an indefiniteseries, the transition from one end of which to the other is associated withisomorphic substitution of hydrogen ions and water for calcium. This viewis in accord with the concept of the dynamic state of the bone minerals.Fabry has introduced the term pseudoapatite to describe the fundamentalcompound of bone salt.The best estimate of the bone salt therefore seems to be that it consistsof a crystal lattice containing mainly calcium, phosphate, and hydroxyl ions,the outer components of which are in equilibrium with a surface hydrationshell containing calcium and other ions and also in equilibrium with theinterior ions of the crystal.The hydration shell in turn is considered to bein rapid equilibrium with the tissue fluids in the bone. This concept is notcompletely irreconcilable with the views of Dallemagne and his colleagues 8who have always opposed the idea that bone was essentially hydroxyapatite,nor does it jettison completely the idea of an " apatite-like " structure.Carbonate of Bone Mineral.-The mineral portion of bone contains about5% of carbon dioxide.One of the difficulties in the study of bone salts isthat the preparation of samples for investigation necessitates destruction ofthe organic phase; this gives rise to the possibility of producing changes inthe mineral fraction. Dallemagne and his co-workers have investigatedthe carbonate content of bone salts obtained from whole bone by the re-moval of the organic material with ethylene glycol. They consider thatcalcium carbonate has-an independent existence in bone salt, and that it isnot part of the crystal lattice. It has been shown that the thermal extrac-tion curve for carbon dioxide of bone salts is similar to that for decom-position of calcium carbonate.When bone salts are dissolved in dilute acids,carbon dioxide is released faster than phosphate is dissolved. In youngrats,lo experiments with l*CO, have shown that skeletal carbon dioxide is incomplete equilibrium with blood, which would be unlikely if the carbonatewere situated deep in the crystal lattice. These observations provided cir-cumstantial evidence for considering that the carbon dioxide is surface-bound but, as Neuman and Neuman7 point out, they do not necessarilyprove the independent existence of calcium carbonate. Dallemagne andFabry 6 proposed that basic tricalcium phosphate may be bound to carbondioxide via an additional calcium atom.Size of Bone Crystal.-Bone crystals are so small that they present a vastsurface area. Robinson,3 on the basis of average crystal dimensions, hascalculated that the specific surface in autoclaved bone varies from 84 to106 sq.m./g. Thus in an average man the total bone crystal surface would8 C. Fabry, Biochim. BioFhys. Acta, 1954, 14, 401.9 W. F. Neuman, T. Y . Toribara, and B. J. Mulryan, .J. Amer. Chem. SOG., 1953, 75,10 b. L. Buclianan and A. Nakao, Fed. PYOC., 1952, 11, 19.4239HARTLES: CHEMISTRY OF BONE AND TOOTH MINERALS. 326be of the order of 100 acres. The few litres of body fluid flowing over thesurfaces could therefore be in intimate contact with the solid phase, thusfacilitating the rapid exchange so often observed in physiological studies.Tooth Minerals.-The fundamental difference between the tooth of non-persistent growth and bone is that once the tooth is formed it does notundergo the biological remodelling which can take place in bone.Localfactors may cause small variations in the composition of teeth during theirformation and these variations will then persist throughout the life of thetoo th.llThe individual crystals in enamel and dentine are much larger than inbone.12 The total surface area presented by the crystals is therefore muchless, values of 1-8 and 2.4 sq. m./g. have been reported for enamel and dentine,respectively2 (cf. 84-106 sq. m./g. for bone). In general, however, thecomposition of the fundamental tooth salt is believed to be similar to thatof bone, but much work remains to be done on minor differences in com-position, particularly in relation to the problem of dental caries.There issome evidence to suggest that, in the cotton rat, teeth with a high carbonatecontent are more liable to decay than those with a lower carbonate content.11Influence of Diet on Composition of Bones and Teeth.-Severe changes inthe mineral content of the diet are reflected in the composition of bone ofany age, but are most noticeable in young growing bone. Dietary changescan only influence the tooth during its formative period. An importantseries of papers have been published by Sobel and his colleagues during thelast few years.11J2" They have shown that in the rat and the cotton ratthere is a relation between the composition of bone and tooth minerals andthe fluid from which they are deposited, and that the composition of the fluidis in turn related to that of the blood serum.Animals reared from weaningon a diet high in calcium and low in phosphorus bad a blood-calcium concen-tration 10% above normal, a blood carbon dioxide level about 10% belownormal, and a blood-phosphorus value only 40% of normal. On a diet lowin calcium and high in phosphorus the blood-calcium concentration was about60% of the normal, blood carbon dioxide about 4% above normal, andblood-phosphorus about 17% above normal. These changes in blood com-position were reflected in different ways in the different mineralised tissues.In the normal cotton rat the PO, : ZCO, ratio is highest in enamel, lower indentine, and lowest in bones.The Ca : PO, ratio of the tissues shows muchless variation, although in enamel it is still slightly higher than in dentine orbone.In the tibia and femur, and in the enamel and dentine of the incisor andmolar teeth, the PO, : XO, ratio is directly related to that of the serum.In contrast, the Ca : PO, ratio of enamel and dentine is hardly affected bychanges in blood Ca : PO, ratio, whereas the ratio in bone varies with that11 A. E. Sobel, Ann. N . Y . Acad. Sci., 1955, 60, 713.12 R. F. Sognnaes, D. B. Scott, M. J. Ussing, and R. W. G. Wyckoff, J . Dent. Bes.,1952, 31, 85.125 A. E. Sobel, M. Rockenmacher, and B. Kramer, J . Bid. Chem., 1945, 158, 475;1945, 159, 159; A. E. Sobel and A. Hanok, ibid., 1948, 176, 1103; A.E. Sobel, A.Hanok, H, Kirschner, and I. Fankuchen, ibid., 1949, 179, 205; A. E. Sobel and A.Hanok, J . Dent. Res., 1958, 37, 632326 HIOLOGICAL CHEMISTRY,in the serum. These resuIts refer to growing bones and growing teeth andindicate differences in composition related to differences in dietary intake ofcalcium and phosphorus. The major changes arising from alteration in dietare in the PO, : 2C0, ratios. The changes in Ca : PO, are smaller, thoughsignificant, in bone and not significant in teeth. These observations areinterpreted by Sobel as indicating the governing influence of " local factors,"acting a t the site of formation, upon the composition of the bone and tooth.It is also apparent that the "carbonate" fraction of the tooth is morereadily susceptible, to dietary influence than is the calcium or phosphateportion.This in turn suggests that the " carbonate " of the tooth is notincorporated in the crystal lattice but is situated at the surface or in thehydration cell.Moisture Content of Mineralised Tissues.-The water content of bonevaries with the source of bone and with its age. Human bone from thenewborn has been reported to contain 30% of water, compared with 20% inold age.13 Other workers have found values of 13-22y0 of water in humancortical bone and 32-52% in cancellus bone.14 The water content ofpowdered bone equilibrated in air for 48 hours and then heated for 24 hoursat 105" was found l5 to be 8%. Cortical bone from young dogs contains asmuch as 540h of water compared with 21% in older dogs.16Le Fevreand Manly l7 reported that enamel contained an average of 2.3% of water(range 1-5%) and that dentine had an average water content of 13.2%(range 10.8-15.7 %) .Deciduous enamel (2.8%) contains slightly morewater than permanent enamel (2.3%). Deciduous dentine, on the otherhand, contains less water (11.2y0) than permanent dentine (13.2%). In arecent study Burnett and Zenewitz l8 found that the maximum water con-tent of freshly extracted whole teeth and dentine was 9-32 and 10.Oyo,respectively. Rehydration a t 98" F and lOOyo humidity restored some, butnot all, of the moisture content.Earlier work has shown that minerals in fresh untreated bone, althoughcontaining considerable amounts of water, are not as highly hydrated as anequilibrated synthetic hydroxyapatite.This has led to the tentative con-clusion that not all the crystal surface of intact bone is available for hydr-ation, perhaps owing to its bonding with the organic phase.' From this itmay be inferred that with increasing age a larger proportion of adult compactbone may be in less intimate contact with water, either as a hydration shellor as circulating fluid. For example, it is now well established' that theuptake of 45Ca and 32P is greatest in young growing bone. This may dependa t least in part on the degree of hydration of the bone crystals.Association of Mineral Crystal with the Organic Phase.-Electron-micro-graphs 3~19 of intact sections of bone show an intimate contact between theIn general, the water content of teeth is less than that of bone.13 J .H. Vogt and A. Tonsager, A d a Med. Sand., 1949, 135, 231.14 I. S. Edelman, A. H. James, H. Baden, and F. D. Moore, J . Clin. Invest., 1954,33, ;522.J . E. Eastoe and B. Eastoe, Biochem. J., 1954, 57, 453.16 R. A. Robinson and S. R. Elliott, J . Bone and Joint Surg., 1957, 39, A , 167.17 M. L. Le Fevre and R. S. Manly, J . Amer. Dent. Ass., 1938, 25, 233.18 G. W. Burnett and J . Zenewitz, J. Dent. Res., 1958, 37, 581IIARTLES: CHEMISTRY OF BONE AND TOOTH MINERALS. 327suriaces of the crystals and the collagen fibres. The problem arises,what if any is the nature of the linkage between the mineral and organicphase?Robinson and Watson l9 review existing information and present con-vincing evidence for the association of mineral crystals with the bandregions of collagen fibrils of bone. In human infant bone, a small 100-120 Aperiod banding is observed.In mature bone the spacing alters and a pair ofbands appears at 640 The diameter of the fibril also increasesirom 150 A in very young infants to about SO0 A in middle-aged adults.The inorganic crystals are found in association with these bands. Thecrystals in young bone are very small, -100 A in length; in mature bonethey are larger, 200-300 A long, and span the doublet band of the fibril.In senile bone the diameter of the collagen fibril increases, to 1500 A, andthe crystals are large enough to spread over two or more doublet bands,thus obscuring the fibril period.The first appearance of inorganic crystalsis associated with the appearance of the collagen fibrils; there does there-fore seem to be an intimate link between the two structures. The differencein size of crystals from young and adult bone may be a further factor in thegreater isotope-exchange which occurs in newly formed bone.Role of Citrate.-Bone and dentine contain almost 1% of citrate, andenamel contains nearly 0.1yo.20 Little is known of the function of citratein a mineralised tissue. Dixon and Perkins 21 suggest that bone citrate isformed in bone cells by normal metabolic activity and is coprecipitated withminerals during calcification of the tissue. This is a reasonable suggestionsince a coprecipitate is formed from solutions of inorganic and citrate ionssimilar to those found in a serum ultra-filtrate.22 Armstrong and Singer 23believe that a t least some, if not the major portion, of bone citrate is ofpurely adventitious origin owing to the continuous presence of citrate inbody fluids.Bellin and Steenbock 24 found that administration of vitamin Dto previously depleted animals caused an increase in bone citrate but con-cluded that the amount of citrate in bones was related to the calcium nutri-tion of the animal rather than to the rachitic state per se. Nicolaysen andEeg-Larsen 25 consider that there may be a dual effect, that vitamin D doesinfluence the accumulation of citrate in bones but that over longer periods adefect arising from deficiency of the vitamin may be ameliorated when thediet is rich in calcium and phosphorus.When whole bone or dentine is treated with dilute hydrochloric acid theportion dissolving contains the minerals, about 5% of the nitrogenous com-pounds, and all the citrate (06--0.9%).Recent work has suggested theintervals.19 R. A. Robinson and M. L. Watson, Ann. N.Y. Acad. Sci., 1955, 60, 596.20 F. Dickens, Biochem. J., 1941, 52, 260; A. H. Free, J . Dent. Res., 1943, 22, 477;I. Zipkin and I<. A. Piez, ibid., 1950, 29, 498; M. V. Stack, Brit. Dent. J., 1951, 90, 173.21 T. F. Dixon and H. R. Perkins, Biochem. J., 1952, 52, 260.22 A. C. Kuyper, J . Biol. Chem., 1945, 159, 411.23 W. D. Armstrong and L. Singer, in Ciba Foundation Symposium on Bone Struc-24 S.A. Bellin and H. Steenbock, J . Biol. Chem., 1952, 194, 311; H. Steenbock and25 R. Nicolaysen and N. Eeg-Larsen, in Ciba Foundation Symposium on Boneture and Metabolism, Churchill, London, 1956.S. A. Bellin, ibid., 1953, 205, 988.Structure and Metabolism, Churchill, London, 1956328 BIOLOGICAL CHEMISTRY.association of citrate with a peptide.Z6 When dentine from human teeth isdemineralised the solution contains the minerals and the citrate-peptidecomplex. If minerals are reprecipitated by raising the pH, the citratecomplex is adsorbed or coprecipitated with the minerals. Lowering the pHto redissolve the minerals releases the citrate complex. Precipitation ofcalcium as sulphate at an acid reaction does not cause coprecipitation of thecitrate complex.Thus, over the physiological range of pH, citrate is firmlyassociated with the mineral phase. This linkage of citric acid with mineraland a peptide is of interest since it suggests that not all the citrate presentin a mineralised tissue is of adventitious origin. Analysis has shown thatthe peptide associated with the citrate is highly basic, containing a largeproportion of arginine and ammonia, with aspartic acid, valine, Ieucine, andisoleucine as major cornponent~.~~ There is, as yet, no evidence that thecomplex is associated with the collagenous constituents of dentine, unlessby ionic linkage.goStrontium and Mineralised Tissues,-The increased concentration ofbone-seeking alkaline-earth nuclides arising from nuclear fission provides arecent alteration in the general environment which requires careful study.Among these baleful products of man's ingenuity are B9Sr and 90Sr; thelatter is widely distributed in human bone and is potentially noxious owingto its comparatively long half-life of 28 yearsa8Stable strontium is a normal minor constituent of bone.ee Using animproved method of determination by radioactivation analysis, Sowdenand Stitch 30 found that samples of bone from normal persons of both sexesand different ages contained about 100 pg./g.of ashed tissue. There is noevidence that quantities of strontium of this order are harmful to bone.The possible hazard to health from ingestion of 90Sr would therefore be dueto its radiation activity and not to its chemical toxicity.QOStrontium is de-posited in the United Kingdom approximately in proportion to the rainfallin a given area. The greatest uptake of the nuclide is by vegetation of hillpastures where the soil is acidic and often deficient in calcium and phos-phorus.31 Hill sheep which graze on these pastures are therefore sensitiveindicators of the degree of contamination of a particular area.Biochemically, strontium behaves very like calcium,32 but there is adefinite discrimination against strontium in the presence of an adequatecalcium intake. Thus, calcium is preferentially absorbed from the gut,and strontium is more readily excreted via the urine than is calcium. Thereis therefore preferential utilisation of calcium in bone formation and inlactation.Two recent papers are of particular interest; Morgan and26 R. L. Hartles and A. G. Leaver, Arch. Oral Biol., 1960,1, in the press.27 A. G. Leaver, J, E. Eastoe, and R. L. Hartles, Arch. Oral Biol., 1960, 1, in the28 J. L. Kulp, W. R. Ecklemann, and A. R. Schubert, Science, 1957, 1245, 219;2s R. M. Hodges, N. S. MacDonald, R. Nusbaum, R. Steams, F. Ezmirlian, P. Spain,80 E. M. Sowden and S. R. Stitch, Biochem. J . , 1959, 67, 104.31 F. J. Byrant, A. C. Chamberlain, A. Morgan, and G. S. Spicer, J . Nuclear Energy,32 H. G. Jones and W. S. Mackie, Brit. J . Ntctr., 1959,18, 355.press.W. R. Ecklemann, J. L. Kulp, and A. R. Schubert, ibid., 1958, 12'9, 266.and C. McArthur, J . Bid. Chem., 1950, 186. 619.1967, 6, 22HARTLES: CHEMISTRY OF BONE ,4ND TOOTH MINERALS.329Wilkins 33 analysed the carcass of a yearling sheep reared on hill pasture inan area of high rainfall. The animal was killed in 1957, and analysis showedthat the average activity of the whole skeleton was 182 strontium units(1 S.U. = c per g. of calcium), the level in the teeth was lower (135 S.U.)and that in the pelvis was 203 S.U. Jones and Mackie 32 carried out experi-ments on Scottish Blackface wethers aged 12-15 months; they adminis-tered 89Sr and 45Ca simultaneously to their animals and found that theproportion of the dose absorbed and deposited in the skeleton was for 4Tafour times that for 89Sr. They found that the major discrimination against89Sr was in absorption and urinary excretion. There appeared to be littleor no discrimination in rate of excretion into the intestine or in transfer ofnuclides from serum to bone.An interesting experiment is reported by Holgate.= Rabbits were givena single injection of 90Sr c per 100 g.of body weight), and the uptakewas determined for teeth and femur, Rabbits have teeth which are con-tinuously growing, but they remain constant in length owing to attrition.The 90Sr content of the femur was maximal eight hours after injection andthen fell steadily to a minimum after 30 days, this level was then maintainedalmost constant until the last animals were killed at 180 days. This suggeststhat most of the 90Sr is rapidly adsorbed on the surface of the bone crystalsor stays in the hydration shell. Most of the 90Sr in the bone then returns tothe tissue fluids and blood as their content of %r falls.A smaller portionpenetrates to the interior of the crystal lattice, possibly by a recrystallisationprocess, and is only slowly removed as remodelling occurs, In teeth (con-tinuously growing) the picture was quite different. The gOSr in teeth in-creased steadily for 30 days after the injection and then fell to a smallervalue than in bone after 100 days. This can be explained by the liberationof 90Sr from bones into the blood stream in the days following injection, thusproviding a continuously available t hougb decreasing supply of nuclide forincorporation into teeth. Once formed, tooth mineral is much more resistantto change than is bone, and the gOSr burden remains until the tooth is wornaway by normal attrition.Thus the amount of 90Sr in the tooth willincrease until the first deposit reaches the biting surface and begins to wearaway. In an animal with teeth of non-persistent growth, such as themonkey or man, 90Sr taken up by the developing teeth after exposure to asingle high dosage is retained for a very long time. Thus a child exposed toa high level of 90Sr might expect to have radioactive teeth so long as thoseteeth remained in sit%, whereas the level in the bones would begin to decreaseshortly after exposure.Information concerning the 90Sr content of human bone is not easilyobtained; Holgate 34 quotes the annexed data as the latest available figures.1 month t o 1 year ..................... 0.70 S.U.1-1 S.U.1 year to 5 years ........................ 0.83 S.U. 1.2 S.U.5 years to 20 years 0.25 S.U. 0.45 S.U.Over 20 years ........................... 0.11 S.U. 0.1 S.U.Age March, 1956 July, 1956.................................... Stillborn 0.44 S.U. 0-55 S.U......................33 A. Morgan and J. E. Wilkins, Biochem. J., 1959, 71, 419.34 W. Holgate, Brit. Dent. J., 1959, 107, 131330 BIOLOGICAL CHEMISTRY.The largest rise is in children under 5 years of age. The Medical ResearchCouncil suggested that the burden of gOSr in human bone should not beallowed to rise above 100 S.U., and that if the level reached 10 S.U., then theproblem should receive immediate consideration.Status of Fluoride in Bones and Teeth.-Attention has been focusedrecently on problems associated with the skeletal deposition of fluoride sincemany communities are consuming water which naturally contains fluoride,and others are drinking water to which fluoride has been added to bring theconcentration up to one part per million (1 p.p.m.).The latter measurehas been adopted in certain areas in the United States and in three demon-stration areas in the United Kingdom, for it has been shown that the con-sumption of such a drinking water results in about a 50% reduction indental-caries experience. The topic of the relation of fluoride to dentalcaries has been extensively re~iewed.~5Fluoride is bone-seeking and all bones appear to contain some fluoride.Its concentration in the skeleton increases with advancing years and in somemeasure with dietary intake.36 Jackson and Weidmann 37 have recentlyexamined the fluoride content of human bone in relation to age and watersupply in three areas in the United Kingdom, where the water contained(0.5, 0.8, and 1.9 p.p.m.of fluoride respectively. They found that in allinstances the amount of fluoride in bone increased with age up to a maximumat about 55 years. At this point bones from the three areas contained 190,245, and 400 rng. per 100 g. of dry, fat-free material.In the case of teeth, fluoride is deposited systematically only during theirformation. It has been found that the fluoride content of enamel increaseswith the fluoride content of the water supply.37 Brudevold and his col-leagues 38 have suggested that fluoride deposition in enamel takes place inthree stages, during enamel formation, after mineralisation is complete butbefore eruption of teeth, and after eruption during the life span of the tooth.The last two methods of deposition are due to physicochemical changes inthe outermost layers of the formed enamel. The maximum concentrationof fluoride (3370 p.p.m.) was in the outer enamel from teeth formed in anarea where the drinking water contained 5.0 p.p.m. The correspondinginnermost enamel contained 570 p.p.m.Comparative figures from areaswhere the water contained 1.0 and 0.1 p.p.m. were 889 and 129 p.p.m., and499 and 42 p.p.m., respectively.The fixation of fluoride is believed to be by exchange with hydroxyl inthe crystal lattice or a t the crystal ~urface.3~ McCann,4O studying the up-take of fluoride by a synthetic hydroxyapatite over a wide range, concluded55 ’‘ The Fluoridation of Domestic Water Supplies in North America,” H.M.S.O.,London, 1953; H.H. spnes, Brit. Dent. J., 1954.96, 173; W. F. Stilwell, N. L. Edson,and P. V. E. Stainton, The Fluoridation of Public Water Supplies,’’ 1957, GovernmentPrinter, Wellington, N.Z. ; Wld. Hlth. Org., Techn. Rep. Ser., 1958, No. 146.s6 G. E. Glock, F. Lowater, and M. M. Murray, Biochem. J., 1941, 35, 1235.57 D. Jackson and S. M. Weidmann, J. Path. Bact., 1958, 76, 451.58 S. Isaac, F. Brudevold, F. A. Smith, and D. E. Gardner, J . Dent. Res., 1958, 37,SB W. F. Neuman, M. W. Neuman, E. R. Main, J. O’Leary, and F. A. Smith,40 H.G. McCann, J . Biol. Chem., 1953, 201, 247.318.J. Biol. Chem., 1950, 187, 655CLOVER : META~lROLISM OF P-CAROTENE AND RELATED PROVITA4MIKS A. 331that a t levels of a few parts per million fluorapatite was formed exclusively;with increasing concentration of fluoride a mixture of fluorapatite andcalcium fluoride was formed, until at concentrations above 0.2% calciumfluoride is the main product. The uptake of fluoride by the enamel surfacehas been studied by using lSF, and a method has been developed for theanalysis of small quantities of stable fluoride using an isotope-dilutiontechnique .*IFrom the dental point of view the important observations have beenmade that the solubility of surface enamel at pH 4 - 6 decreases as thefluoride content increases.42 Much more information is required concerningthe manner in which fluoride is deposited in a mineralised tissue.Conclusion.-The study of the chemistry of bone and teeth bears a directrelation to three major problems.First, in an ageing population where anincreasing number of individuals is surviving beyond three score years andten, consequences of bone fracture are serious; the chemistry of ageing andsenile bone must receive greater attention if the reasons for the slow healingof fractures of aged bone are to be understood. Secondly, the incidence ofdental caries in young children is distressingly high ; an increased knowledgeof the intimate chemistry of the tooth may provide information concerningthe decay process. Thirdly, the recently increased concentration of bone-seeking nuclides in the general environment requires that the pattern of theirskeletal deposition be studied.R.L. H.3. METABOLISM OF JS-CAROTENE AND RELATED PROVITAMINS AALTHOUGH 30 years have passed since Moorel demonstrated that p-caro-tene (1) was transformed into vitamin A (13) in the animal body, the mech-anism of this process represented by route A of Chart 1 is still unknown.The structural relation of the two compounds suggested to Karrer and hisco-workers 2 that p-carotene might undergo hydrolysis of the central doublebond to form two molecules of vitamin A, but attempts to elucidate thedetails of the biological system have been fruitless. Consequently, parallelwork on the structural features required for provitamin A and vitamin Aactivity has received more attention.This has been reviewed by Heilbronet aZ.,3 Ze~hmeister,~ B a ~ t e r , ~ Goodwin,6 and, more recently, by Isler andZeller.’The chemistry and biochemistry of the various carotenoids and related4 1 J. H. Fremlin, J. L. Hardwick, and J. Suthers, Nature, 1957, 180, 1,179; J. L.p 2 S. B. Finn and C. de Marco, J . Dent. Res., 1956, 35, 185; S. Isaac, F. Brudevold,Hardwick, J. H. Fremlin, and J. Mathieson, Brit. Dent. J., 1958,104, 47.F. A. Smith, and D. E. Gardner, ibid., 1958, 3’4, 254.T. Moore, Biochem. J., 1930, 24, 692.2 P. Karrer, R. Morf, and K. Schopp, Helv. Chim. Ada, 1931, 14, 1036, 1431.3 I. M. Heilbron, W. E. Jones, and A. L. Bacharach, Vitamins and Hormones, 1944,4 L.Zechmeister, Vitamins and Hormones, 1949, 7, 57.J. G. Baxter, in ‘ I Progress in the Chemistry of Organic Natural Products,” 1952,T. W. Goodwin, “ The Comparative Biochemistry of the Carotenoids,” Chapman &2, 156.Vol. IX, p. 41 (ed. L. Zechmeister), Springer-Verlag, Vienna.Hall Ltd., London, 1952.7 0. Isler and P. Zeller, Vitamins and Hormones, 1957, 15, 31332 BIOLOGICAL CHEMISTRY.compounds have also been described in considerable detail by Karrer andJucker * and G o o d ~ i n , ~ , ~ respectively. Again, work on the chemicalsynthesis of vitamin A and various carotenoids and larger homologues hasalso been reviewed r e ~ e n t l y , ~ ~ * J ~ J ~ but detailed knowledge regarding theirmetabolism is still lacking. By newly developed methods of chemicalsynthesis, a variety of compounds, intermediate in size between P-caroteneand vitamin A, can be prepared which should assist the biochemist indetermining the nature of enzymic attack on molecules such as carotenoidswhich possess long, conjugated double-bond systems. The present Reportdiscusses work carried out during the last few years towards this end withparticular reference to the provitamin A-vitamin A transformation.( 1 ) 4 f\1- [Unknown i n t e r m e d i a t e dCHART 1.Suggested routes for eonvevsion of @-carotene into vitamin A .* P. Karrer and E. Jucker, “ Carotenoids,” transl. E. Braude, Elsevier, Amsterdam,@ T. W. Goodwin, Ann. Rev. Biochfm., 1955, 24, 497.10 H. H. Inhoffen and H. Siemer, Progress in the Chemistry of Organic Naturall1 0.Isler, H. Lindlar, M. Montavon, R. Riiegg, G. Saucy, and P. Zeller, Chem. SOC.1950.Products,” 1952, Vol. IX, p. 1 (ed. L. Zechmeister), Springer-Verlag, Vienna.Special Publ. No. 4, 1956, p. 47GLOVER: METABOLISM OF @-CAROTENE AND RELATED PROVITAMINS A. 333Provitamin A-Vitamin A Conversion.-Structurally, it would appear that,if P-carotene were oxidised a t the central double bond, two molecules ofretinene (vitamin A aldehyde) (11) might be formed which could be imme-diately reduced to vitamin A.12 On the other hand, if an excentric bondis attacked, only one molecule of vitamin A would result from the furtherdegradation of the larger fragment (see Chart 1). The evidence for andagainst these two views has been outlined p r e v i o u ~ l y .~ ~ ~ ~ ~ ~ ~ A major diffi-culty of the problem is that the conversion of p-carotene into vitamin Atakes place only on a small scale in experimental animals and relativelyslowly. Further, it has not yet been possible to prepare an enzyme systemwhich will carry out the reaction in vitro, so the possibility of obtainingsufficient intermediates to allow their proper characterisation seems remote.An alternative approach is to synthesise substances closely related tobiological intermediates indicated by some hypothetical scheme such asterminal fission followed by p-oxidation (route B in Chart 1). Here eitherthe fhapocarotenals (2, 5, 7, and 9) or the related series of p-apocarotenoicacids (4, 6, 8, and 10, respectively) would be possible intermediates.Therewere several reasons for considering this possible, e.g. : (a) Most biologicalassays l5 suggest that only one molecule of vitamin A is formed per moleculeof p-carotene, although perhaps two may be obtained in the presence ofoptimal amounts of to~opherol.l6~~~ No intermediate values have beenobtained. (b) Two yellow pigments were isolated18 from the lipids of thehorse intestine and tentatively identified 19 as p-apo-10’- (5) and p-apo-12’-carotenal (7) ; these must have resulted from terminal oxidation ofp-carotene. They had not hitherto been detected ih plant extracts, so itwas assumed they were formed in the animal. (c) Chemical oxidation of@-carotene begins at one end of the conjugated double-bond system {seebelow) , and often there is an overall parallelism between chemical and bio-logical oxidations.(a) 16,16’-Bishomo-~-carotene (14) is biologicallyactive 20 (20% as active as all-trans-@-carotene) although it does not possessa central double bond. (e) Substances such as a-“ vitamin ” A 2 l or 3-hydr-oxy-“ vitamin ” A z2 which would arise in addition to vitamin A fromla R. F. Hunter, Nature, 1946, 158, 257; J. Glover, T. W. Goodwin, and R. A.l a J. S. Lowe and R. A. Morton, Vitamins and Hormones, 1956, 14, 97.14 T. Moore, “ Vitamin A,” Elsevier, Amsterdam, 1957.15 F. M. M. Hume, Brit. J . Nutrit., 1951, 5, 104.l6 C. J. Koehn, Arch. Biochem. Biophys., 1948, 17, 337.1’ M. J. Burns, S. M. Hauge, and F. W. Quackenbush, Arch. Biochem.Biophys.,18 G. N. Festenstein, Ph.D. thesis, Liverpool, 1951.Is E. R. Redfearn, Ph.D. thesis, Liverpool, 1954.Zo H. J. Deuel, jun,, H. H. Inhoffen, J. Ganguly, L. Wallcave, and L. Zechmeister,21 S. R. Ames, W. J. Swanson, and P. L. Harris, J. Amev. Chew SOL, 1955, 77, 4136.22 R. H. Painter, Ph.D. thesis, Liverpool, 1955.Morton, Biochem. J., 1948, 43, 109.1951, 30, 341.Arch. Biochem. Biophys., 1952, 40, 352334 BIOLOGICAL CHEMISTRY.central fission oi dietary or-carotene or cryptoxanthin, respectively, and areknown to be stored in the liver, have never been detected in rats.p-Apo-B’-carotenal (2) had been reported 23 to be vitamin-A-active, sothe remaining members of the series were prepared by oxidising p-carotenewith hydrogen peroxide in the presence of osmium tetroxide.24 Morerecently they have been elegantly synthesised by Ruegg and his col-league~.~~.26In studying the metabolism of p-apo-8’-, -lo’-, and -12’-carotenal in therat, it was observed19 that small amounts of some were oxidised to thecorresponding carboxylic acids ; consequently the higher vinylogues ofvitamin A acid were also prepared.Preparation of p-Apocarotenals-Oxidation of p-carotene. When p-caro-tene is oxidised with chromium trioxide, the double bonds of the @-iononerings are preferentially attacked and the end products are semi-p-carotenoneand p-~arotenone.~’ Alkaline permanganate, on the other hand, appears toattack the terminal double bonds of the central chain yielding p-apocaro-tenals (2, 5, 7) having one @-ionone ring intact, but it does not appear toform retinene 28 (1 1).With hydrogen peroxide alone, however, retinene isformed in small yield 29 (ca. 1%), though with osmium tetroxide as cata-lyst 24930 a moderate yield (cn. 30%) i: obtained. When a solution of hydro-gen peroxide in t-butyl alcohol is used,31 the progress of the reaction couldbe followed with time and the p-apo-8’-, -lo’-, and -12’-carotenal as well asretinene were isolated in chromatographically pure form.lg Grob andButler 32 also reported finding these aldehydes. More recently a smallamount of the P-apo-l4‘-carotenal (9) has also been found% in the reactionmixture, Dialdehydes, having 3,4, 5, and 6 ethylenic bonds in conjugation,and corresponding to segments of the central chain of p-carotene, are alsopre~ent.1~ The pattern of the rates of production of the various aldehydesby osmium tetroxide-hydrogen peroxide pointed to a progressive removalof the ends of the conjugated system rather than random reaction along it.19The reagent attacks the penultimate double bond in the conjugated system;semi-p-carotenone or P-carotenone have never been detected among theproducts.Further, the yields of pure retinene or higher aldehydes fromp-carotene were found never to exceed 10-12y0.In one procedure (Chart 2) for the synthesis of p-apo-12’-carotenal (C25) (7), Ruegg and colleagues 25 used as starting point theDirect synthesis.2s H. von Euler, P. Karrer, and U. Solmssen, Helv. Chim Acta, 1938, 21, 211.24 N.L. Wendler, C. Rosenblum, and N. Tishler, J . Amer. Chenz. SOC., 1950, 72,25 R. Ruegg, H. Lindlar, M. Montavon, G. Saucy, S. F. Schaeren, U. Schwieter, and26 R. Riiegg, M. Montavon, G. Ryser, G. Saucy, U. Schwieter, and 0. Isler, Helv.27 R. Kuhn and H. Brockmann, Annulen. 1935, 516, 95.28 P. Karrer and U. Solmssen, Helv. Chim. Acta, 1937, 20, 682; P. Karrer, U.29 R. F. Hunter and N. E. Williams, J., 1945, 554.30 G. C. L. Goss and W. D. Macfarlane, Science, 1947, 106, 375.31 N. A. Milas and S. Sussman, J . Amer. Chem. SOC., 1936, 58, 1302.32 E. C. Grob and R. Butler, Helv. Chinz. Acta, 1954, 37, 1908.33 U. Liithi, M. J. Fishwick, and J. Glover, unpublished work (1957).234.0. Isler, Helv. Chim. Acta, 1959, 42, 847.Chim. Acta, 1959, 42, 854.Solmssen, and W.Gugelmann, ibid., p. 1020GLOVER : hIET.4I30LISM OF @-CAROTENE .4ND RELATED PKOVI‘TAMINS A. 336C,, p-aldehyde (15) which is an intermediate in the industrial synthesis ofp-carotene. This was condensed with lithium acetylide in liquid ammoniato form the C,, acetylenic alcohol (16). The latter without purification was(19)CHART 2. Synthesis of ~-apo-l2’-caroteizul.coupled with methylmalondialdehyde enol-benzoate (17) in a Grigiiardreaction, giving the ester (18), which with acetic acid in propan-2-01 undernitrogen yielded 15,15‘-didehydro-~-apo-12’-carotenal (C,,) (19). Partialhydrogenation with a Lindlar catalyst 35 and isomerisation of the 15,15’-HO - Y C H ( O E t ) ,H C ~ C L ~ + OHCyCH*OEt + 9 C ; ; P E t(20) (22)(15)CHO - CH (OEt)j R+ CH (OEt),4- H,C:CH.OEt (+ZnC12)(25) 6R Y C H ( O E t )(2 4)CHART 3.Synthesis of 15,15’-didehydro-/3-apocarotenals.cis-p-apocarotenal intermediate produced a good yield of the all-trauts-p-apo-l2’-carotenal (7).Sodium or lithiumacetylide was first condensed with the methylmalondialdehyde enol-ether(20) to form the ether (21). This with ethyl orthoformate produced the34 0. Isler, H. Lindlar, 31. Montavon, R. Ruegg, and P. Zeller, Helv. Chinz. A r f a ,1956, 39, 249.35 H. Lindlar, Hrlu. CJCiwE. ilcfn, 1952, 35, 446.An improved procedure was followed later (Chart 3)336 BIOLOGICAL CHEMISTRY.acetal (22) which is a useful new building unit for branched polyenes. Con-densation of C,, p-aldehyde and this compound by means of lithium amidein liquid ammonia afforded a C,, hydroxy-acetal (23) which was readilyconverted by acid into the free aldehyde (19).The higher vinylogues were prepared 26 by using this aldehyde as startingmaterial. The diethyl acetal (24) was condensed with ethyl vinyl ether inthe presence of zinc chloride, to form the dehydro-p-C,, ether acetal (25),which on acid hydrolysis gives the free aldehyde in good yield.Repetitionof these steps using alternately ethyl propenyl ether and ethyl vinyl etherfor the condensation with the appropriate 15,15’-didehydro-p-apocarotenalacetals enabled Riiegg and colleagues 26 to synthesise the higher membersof the series up to C4,,. Reduction of the acetylenic bonds in each of thesevarious 15,15’-didehydro-~-apocarotenals with a Lindlar catalyst, followedby isomerisation of the cis-derivatives by heat, gave the all-trans-p-apo-carotenals which are listed with their ultraviolet absorption maxima inTable 1.Further reduction of the aldehydes with lithium aluminiumhydride affords the corresponding series of p-apocarotenols.TABLE 1. Ultraviolet absorption maxima (m p) of p-apocarotenoids inC0,Melight petrolewt (for R see Chart 1).Compound X=CH,*OH CHO CO,H326 367343, 355 385377, 393 414376, 393 410403, 424 435426, 453 457443, 471 473a Ref. 36.350376 373 li325-400327 @430 426 28448 445, 471 26458, 495 464, 491 28Synthesis of p-Apocarotenoic Esters.-Two of this series, ethyl p-apo-14’-carotenoate (28) and p-apo-l2’-carotenoate (31) containing 22 and 25carbon atoms respectively, were synthesised from retinene 36 (see Chart 4).In a modification of the Reformatsky reaction,37retinene was condensed with ethyl bromoacetate in refluxing pyridine-benzene (5% vlv) in the presence of zinc dust to form the C,, 15-hydroxy-ester (27) in 80--85~0 yield.Dehydration with freshly prepared aluminiumEster of the C,, acid.38 S. Fazakerley, Ph.D. thesis, Liverpool, 1957.37 R. L. Shriner, “ Organic Reactions,” John Wilcy & Soils Inc., New York, 1042,VOl. IGLOVER: METABOLISM OF p-CAROTENE AND RELATED PROVITAMINS A. 337phosphate then gave a variable yield (30-60y0) of ethyl P-apo-l4’-caro-tenoate.Reduction of the ester (28) with lithium aluminiumhydride formed the C,, alcohol (29) which was readily converted into thealdehyde P-apo-l4’-carotenal (30) by manganese dioxide.38 A similar con-densation of the latter with ethyl bromopropionate followed by dehydration,again with aluminium phosphate, enabled ethyl P-apo-12’-carotenoate (31)to be obtained.Condensation of retinene with ethyl y-bromotiglate wasused in the preparation of the 15-hydroxy-ester (32), but dehydration of thiscompound always yielded the retro-acid, a difficulty often experienced inchain-lengthening of polyene~.~~Ester of the C,, acid.CHART 4. C,, and C,, /%apocaroterioids.The isomeric C,, acid (33) having a methyl group in the F-position to thecarboxyl group was synthesised by Redfearn 40 using a procedure similar tothat of Robeson et aL4I for vitamin A.It involved the condensation ofretinene with methyl P-methylglutaconate to form a diester which on hydro-lysis and decarboxylation gives the C,, mono-acid (33).C,, to Cm acids. The higher vinylogues containing 27-40 carbons (e.g.,torularhodin) have been recently synthesised by Isler and colleagues 42by the Wittig reaction.& The chain-lengthening was carried out as follows :methyl bromoacetate and triphenylphosphine gave the phosphoniumbromide which with sodium methoxide or aqueous sodium hydroxide yieldedthe phosphorane (34). This compound reacted smoothly with 15,15’-di-dehydro-P-apo-lZ’-carotenal (C,J (19) ; the resulting ester (35) was partiallyhydrogenated and isomerised as described above, giving methyl all-trans-P-apo-10’-carotenoate (36) (C27).Saponification liberates the free acid.The higher members, e.g., p-apo-8’-carotenoic acid (39), were prepared byusing the same sequence of reactions with the various 15,15’-didehydro-P-apocarotenals and the appropriate phosphorane (34 or 37) (Chart 5).38 S. Ball, T. W. Goodwin, and R. A. Morton, Biochem. J . , 1948, 42, 516.39 0. Isler, W. Huber, A. Ronco, and M. Kofler, Helv. Chim. Acta, 1947, 30, 911;H. 0. Huisman, A. Smit, S. Vromen, and L. G. M. Fischer, Rec. Trav. chim., 1952, 71,899.4 O E. R. Redfearn, 1957, personal communication.4 1 C. D. Robeson, J. D. Cawley, L. Weisler, M. H. Stern, C. C. Eddinger, and A. J.42 0. Isler, W. Guex, R. Hiiegg, G. Ryser, G. Saucy, U. Schwieter, M. Walter, and43 G.Wittig and U. Schollkopf, Chem. Bcr., 1054, 87, 1964; G. Wittig and W. Haag,Chechak, J . Amer. Chem. Soc., 1955, 77, 4111.A. Winterstein, Helv. Chim. Acta, 1959, 42, 864.ibid., 1955, 88, 1664338 BIOLOGICAL CHEMISTRY.The absorption maxima of the series of aldehydes, acids, esters, andalcohols are given in Table 1.Provitamin-A Activity of p-Apocarotenoids.-The availability of the abovecompounds has enabled the terminal oxidation hypothesis to be examined.Preliminary results with the @-apocarotenals suggested to Glover and Red-fearn 44 that if oxidative fission of the 7',8'-double bond of p-carotene occurredTie., fission at (b) in formula (l)], the larger p-apo-8'-carotenal fragment mightbe degraded by @-oxidation. The 9'- and 13'-methyl groups lie in or-positionsto the potential carboxyl groups; they would slow the process but not stopit.It would, however, be stopped at the central carbon atoms because ofmethyl substitution in the @-position, at C(13). Again, if the normal p-oxid-ation were involved, one might also expect the activated forms of the p-apo-carotenoic acids to be intermediates.l e(3 9 )CHART 5 . Synthesis of ,!l-apocarotenoic acids.The metabolism of these synthetic compounds in rats has been ex-amined 44245 in two ways. First, the minimum daily requirement to promotesteady growth of vitamin-A-deficient rats at a rate at least equal to thatproduced by 1 pg. of vitamin A was determined under standard dietaryconditions. Secondly, lipids mainly from livers and intestines of groupsof vitamin-A-deficient rats dosed with the various P-apocarotenoids wereexamined for metabolites, in particular for vitamin A.I t is necessary todo this because growth-activity could mean merely conversion into vitamin Aacid and not vitamin A alcohol, which is the main product of @-carotenemetabolism. Not all the p-apocarotenoids have yet been tested in this way,but the results for some of the lower members of the series are set out inTable 2, together with those for vitamin A and its aldehyde and acid, as \Yellas for p-carotene.Recently, the biological activity of the @-apocarotenals containing25-32 carbons has been determined by Maurisch et al., using the U.S.P.rat curative growth assay.46 The results, which are included in Table 2, givea more precise measure of activities in relation to that of P-carotene.It is clear that all the compounds examined are vitamin-A-active, but44 J.Glover and E. R. Redfearn, Biochem. J., 1954, 58, xv.a5 S. Fazakerley and J. Glover, Biochem. J., 1967, 65, 3 8 ~ .46 Personal communication from Dr. M. Montavon (Messrs. Hoffmann-La Roche,Switzerland), regarding results reported by W. Maurisch, E. de Ritter, J. Vreeland,and R. Krukar at an Amer. Chem. SOC. meeting, September, 1959GLOVER: METABOLISM OF p-CAROTENE AND RELATED PROVITAMINS A. 339to varying degrees, confirming the earlier work of von Euler et aZ.23 Allthe compounds, except vitamin A acid, were converted in vivo into vitamin A,which was characterised by its chromatographic behaviour on alumina,ultraviolet absorption, and antimony trichloride colour r e a c t i ~ n .~ $ * ~TABLE 2. Provitamin A activity of some p-apocarotenoids in the rat.Biological activityfi-Apocarotenoid *c2() -R/CH2'OHR/CHO(vitamin A)/ CO2H Rp-CaroteneRef.a12b44--1944-494919---Dailyrequire-ment11123050-1005-1021< 2(tLg.)-5-10--5-0 Y* For R see Chart 1.'Vitamin Aformation all-trans-Activity (%) 46 v zDose15(mg. /rat)1.7-8.010-2.52.50.9{ ;:;2-51-101-101.60.6-1 4A7 fi-carotene -VitaminA (yo) Mean40-7060-700434 126-0.5 (24 hr.)7.0 (60 hr.)2130.2Trace3 d-10-15f P = 0.05.5.87240Range t86-18248-7065-8029-58a E.Le B. Gray, K. C. D. Hickman, and E. F. Brown, J. Nutrition, 1940, 19, 39.# I . M. Sharman, Brit. J. Nutrition, 1949, 3, viii. Ref. 23. Ref. 19.Whether the minimum daily requirements or the activities relative tothat of p-carotene are compared, the C,, compounds are superior to the othermembers so far examined and as good as or better than 6-carotene in sup-porting growth; so they could be related to intermediates in the metabolismof p-carotene or of the higher vinylogues. However, the low biologicalactivity of the C,, group, varying from one-fifth to one-fiftieth of the C,group, means that they are unlikely to be intermediates in the metabolismof the latter. The absence of any C,, compound in the lipids of animalsdosed with the various C,, compounds tends to confirm this.The lowe340 BIOLOGICAL CHEMISTRY.biological activities for the higher p-apocarotenals (C2, to C32) implies thatthey also are not intermediates in the main pathway for the formation ofvitamin A from p-carotene: however, they could be intermediates in aminor route.With regard to the ability of the various p-apocarotenoids to producevitamin A in vivo after single doses, only the ester of the C,, acid was superiorto p-carotene. When, therefore, the growth tests and the speed of conver-sion into vitamin A are taken into account, only the C25 15-hydroxy-acidreally behaves as if it were closely related to an intermediate on the mainroute of conversion of p-carotene into vitamin A.All these aldehydes appear to bewell absorbed by the rat.A portion of each is immediately reduced to thecarotenol in the intestine and another portion is oxidised to the acid; someof the latter then becomes esterified. In the lipids from rats dosed withp-apo-10‘-carotenal, a little p-apo-l2’-carotenol was found. Its formationmust be somewhat analogous to that of vitamin A alcohol from the esterof the C,, acid (see below). However, no compound with a carbon skeletonintermediate in size between either p-apo-8’-carotenal or p-apo- 12’-carotenaland vitamin A was detected in the lipids from animals dosed with thosealdehydes.Both these esters are well ab-sorbed and are stored in the fat depots as well as in the liver, whereas thefree acids tend to be metabolised quickly.This difference was also notedby Redfearn ** in studies with the C25 p-apo-l2’-carotenoic acid isomer (33)and vitamin A acid, and their esters: these three cannot be reduced to thecorresponding P-apocarotenols in vivo. Some of the C2, acid is convertedinto vitamin A in the intestine during absorption and the process iscompleted in the liver. If p-oxidation were involved in this step, thenvitamin A acid would be the main product and not vitamin A alcohol; soprobably a different enzyme system is utilised. Similuly, the C, acid oralcohol has not been detected among the metabolites of the ester of the C,acid.Chromatography of the recovered @-apo-IY-carotenoic ester fractionfrom the tissue lipids resolved it into two zones, both containing esters.Onecorresponded to the compound administered, having Amax. 396 mp, but thesecond had A,, 400 mp. This bathochromic shift is characteristic of thechange of a cis-compound into the more stable all-trans-f0rm,~*47 involvingthe double bond adjacent to the carbonyl group. About 40% of the totalester fraction was in the trans-form in the wall of the small intestine, whereasin the liver this proportion had risen to 93-94y0, indicating a progressivechange to the all-trans-f~rm.~~ This change probably accompanies hydro-lysis and re-esterifitation of the acid with either glycerol or a higher alcohol..The C,, acid isomer behaved similarly. Whether this change is necessarybefore conversion into vitamin A or merely coincidental is not known.Themetabolism of the higher P-apo-10’- and -8’-carotenoic acids or esters hasnot yet been fully investigated.47 H. 0. Huisman, A. Smith, P. H. van Leeuwen, and J, H. van Rij, Rec. Truu. chirra.,1956, 76, 977.p-A$o-8’-, -lo’-, and -12’-carotenaZs.p-Apo-14’- and -12‘-carotenoic estersGLOVER: METABOLISM OF @-CAROTENE AND RELATED PROVITAMINS A. 341The C,, isomer was studied 48 to determine the effect of methyl-substitu-tion in the @-position to the terminal carboxyl group on conversion of thecompound into vitamin A. Metabolism of this compound by the @-oxid-ation system is blocked, yet vitamin A alcohol is formed in small amounts.The yield was only slightly less than that from the normal @-apo-l2’-carot-enoic ester; so another enzyme system must be operative.Both the C,, (27) and the C,, acid (32) with a 15-hydroxyl group were converted into vitamin A, the latter in a yield (21% ofvitamin A in 19 hr.after a single dose) which is greater than can be obtainedfrom a single dose of P-carotene.As the C25 group of compounds proved the most active of the seriestested, they were examined further for participation in the p-carotene-to-vitamin A transformation. p-Apo-l2’-carotenal was selected first as repre-sentative of the group because it is readily converted into the acid andalcohol and would probably have the best chance to enter the enzymesystem responsible for metabolising @-carotene. The aim of the work wasto use the aldehyde as a trapping agent for any similar radioactive aldehydederived from the metabolism of specifically labelled [15,15’-14C]-@-carotenein the rat.Metabolism of [15,15’-14C]-@-Carotene.-Specifically labelled p-car0 tenewas synthesised 49 and a small sample * was mixed with an excess of @-apo-12‘-carotenal and administered to vitamin-A-deficient rats.The animalswere killed 5 hr. after dosing, when absorption across the intestine would beoptimal, and the lipids from the intestine and liver were examined.50 Un-changed @-apo-l2’-carotenal and @-apo-l2’-carotenoic acid were isolated andpurified chromatographically. The fraction containing the aldehyde wastreated with hydroxylamine and the oxime crystallised. The acid fractionwas too small for crystallisation even as a derivative, but it was purified byquantitative conversion into the ester followed by either rechromatographyor reduction with lithium aluminium hydride, the resulting alcohol beingisolated chromatographically. The specific activities of the various frac-tions were measured and compared with those of the original [15,15’-l4C]-P-carotene and the [1-14C] vitamin A isolated from the liver.The re-isolatedp-apo-l2’-carotenal and its metabolite, the corresponding acid, were labelled,indicating that a little @-carotene had been degraded to the aldehyde. Asthe aldehyde and acid had approximately the same specific activity, theformer must have become labelled first since the action of aldehyde-oxidaseis irreversible. Again, the agreement in their specific activities suggeststhat little or no [15,15’-14C]-@-apo-12’-carotenoic acid could have beenderived from a higher homologue by @-oxidation. The aldehyde re-isolatedfrom the lumen was radioactive, so presumably the [15,15’-14C]-P-carotenewas first attacked there.Comparison of the specific activities of the twocompounds shows that the amount formed was quite small (<3% of the48 E. R. Redfearn, Biochem. J., 1957, 66, 3 9 ~ .49 H. H. Inhoffen, U. Schwieter, C. 0. Chichester, and G. Mackinney, J. Amer.60 J. Glover and P. P. Shah (1958), unpublished work.* The Reviewer is grateful to Professor G- Mackinney for the gift of this material.15-Hydroxy-esters.Chew. SOC., 1955, 77, 1053342 BIOLOGICAL CHEMISTRY.dose). The specific activity of the [l-14C]-vitamin A was higher than thatexpected from the specific activities of the [15,15’-14C]-labelled p-apo-carotenoids and so must have been derived mainly by another route.Thisresult confirms earlier observations that, while a small amount of P-carotenemay be metabolised via carotenals, this is certainly not the main route.Metabolism of [U-14C]-p-Carotene and [U-14C]-Retinene.-An attempt 5lwas made to answer the problem of central fission versus terminal oxidationby comparing the metabolism of [U-l*C]-p-carotene and -retinene duringtheir absorption across the intestine of the rat. It was considered thatoxidative attack on a terminal bond in P-carotene, followed by degradationof the larger fragment to retinene or vitamin A, would lead to small fragmentswhich on entering the various metabolic pools would rapidly release 14C0,into the respired air.Central fission, on the other hand, would produce[U-14C]-retinene or [U-14C]-vitamin A directly, which being quickly ab-sorbed would perhaps not be appreciably metabolised until they reached theliver later. In this event, the pattern of release of 14C0, would be moregradual.[U-f4C]-p-carotene has been prepared 52953 in two laboratories and itsmetabolism studied in the rat. It was found to be degraded extensively tosmall fragments; 14C02 appeared quickly in the respired air, the amountbeing maximal 5 hr. after dosing (when absorption across the intestine isoptimal) and declining. This was consistent with the above hypothesis.However, when [U-14C]-retinene was used,64 the pattern of release of14C02 was almost identical, indicating that this molecule can also be rapidlydegraded in transit across the intestine.Conclusions.-(a) The general conclusion is that terminal oxidation ofp-carotene, followed by progressive removal of the side chain of the largerfragment until retinene or vitamin A is left, is not the main metabolicroute to vitamin A.(b) When such an oxidation does occur, however, thelarger fragment can give vitamin A, but not necessarily by p-oxidation.(c) The very strikingly greater biological activity of the C,5 p-apocarotenoidsthan of their homologues indicates that the former best provide the type ofsubstrate which the enzyme system requires for fission. The relatively lowyield of vitamin A obtained after single doses of P-apo-l2’-carotenal, com-pared with the biological activity at low dose level, is difficult to understand.It may be that when it is administered in small doses the yield of vitamin Ais better; or that vitamin A acid is produced to an appreciable extent. Thisacid would be difficult to trace chemically in vim, but is biologically active.J.G.Note added in proof. An exhaustive study by Worker 5 5 with whole organs andtissue preparations to find a suitable system for studying the conversion of /?-caroteneinto vitamin A has had little success.51 M. J. Fishwick and J. Glover (1958), unpublished work.52 J..Glover and E. R. Redfearn, Biochem. J., 1953, 54, viii; J. Glover and P. P.53 J. S. Willrner and D.H. Laughland, Can. J . Biochern. Physiol., 1957, 35, 819.54 M. J . Fishwick, Ph.D. thesis, Liverpool, 1958.65 N. A. Worker, Brit. J . Nutrition, 1959, 18, 400.Shah, abzd., 1957, 67, 1 5 ~ PERRY THE CHEMISTRY OF MUSCLE CONTRACTION AND RELAXATION. 3434. THE CHEMISTRY OF MUSCLE CONTRACTION AND RELAXATIONIN view of the long interval since any aspect of muscle biochemistry has beenreviewed in these Reports1 the present discussion will refer to recent ad-vances in the field set against the background of relevant earlier work.Contraction.-Structzcre of contractile system. Like many biologicalprocesses the chemical events associated with contraction take place in aheterogeneous phase. Presumably, metabolites and cofactors, both ofwhich are soluble and of relatively low molecular weight, interact with theinsoluble contractile system within the cell, causing it to shorten and tobring about contraction of the tissue as a whole.To understand thisZA1 P(4) (b) (aFIG. 1. Structure of the myofibril.(a) .4ppearance of myofibril of the striated muscle cell as seen with the ordinary light-(b) Diagrammatic representatio.pz of longitudinal section through myofibril i n the direction(c) Diagrammatic representation of a cross-section of the A band showing the hexagonalNote that the appearance of a longitudinalmicroscope. Diameter of myofibril, 1-2p.A-A (Fig. 1 6 ) .array of thick (A) and thin (I) filaments.section depends on the angle of sectioning.process detailed knowledge of the chemistry of the myofibril, the contractileunit, is not in itself enough; an understanding of the ultrastructure down tothe molecular level is also required.When examined in the light-microscopethe myofibril from striated muscle is characterised by dark and light bands,the A (anisotropic) and I (isotropic) bands respectively, which alternatealong its length (Fig. 1). Electron-microscopy has proved an invaluabletool for studies of ultrastructure and in the case of the striated myofibriltwo main filament types can be identified. The larger of these, the so-calledA filaments, about 100 A in diameter, are found in the A band arrangedparallel to the myofibril axis. I filaments, about 50 A in diameter, are the1 I<. Bailey, ,4nn. Reports, 1946, 43, 280; D.M. Needham, ibid., 1952, 49, 275.2 S. V. Perry, in “ Comparative Biochemistry,” ed. M. Florkin and H. S. Mason,Academic Press, New York, 1960, Vol. 11, p. 245; idem, Physiol. Rev., 195G, 36, 1;A. F. Huxley, Progr. Rioph?sics Biophys. Cham., 1957, 7, 255344 BIOLOGICAL CHEMISTRY.main components of the I band and continue into the A band to form aninterlocking hexagonal array with the A filaments 394 (Fig. 1).Although isolated myofibrils can shorten by about 75--80~0 of theiroriginal length, in vivo under physiological conditions contraction rarelyexceeds 40% of the resting length. Recent studies of band changes occur-ring during contraction over the physiological range have indicated thatthe A band remains unchanged in length. The whole of the shortening inthis range occurs in the I band, which ultimately disappears when the myo-fibril has contracted by about 35--40y0 of its resting length.To explainthese band changes it has been suggested 3 ~ 5 that the myofibril contracts byvirtue of the I filaments’ moving further into the A band along the spacesbetween the A filaments, thus bringing about the shortening and final dis-appearance of the I band. On relaxation when the myofibril returns to itsoriginal length the reverse process takes place.The problem is to devise a satisfactory physicochemical mechanismwhich will explain how one protein filament system can be drawn deeperinto the other with which it forms an interdigitating hexagonal array. Themechanism must be reversible and be correlated with the chemical changesknown to accompany contraction.All workers agree that the myofibril isbuilt of longitudinal filaments, but although the evidence for the two-fila-ment system described above is excellent for rabbit skeletal muscle,* a num-ber of workers have not been able with the electron-microscope to demon-strate such a two-filament system in certain other striated muscles.6~7 Like-wise in smooth muscle some workers claim that only one type of filament ispresent.* Contraction is characteristic of all types of muscle and, althoughthe ultrastructure of the muscle tissues so far examined consists of fila-mentous protein elements, the electron-microscope evidence available to datedoes not permit us to say that the arrangement of these filaments is identicalin every case.It seems, however, that all muscles contain a commonspecialised biochemical system. The precise proportions and performanceof this system depend on the type of muscle, but it might be supposed thatthe mechanism of contraction at the molecular level is similar in all suchtissues.Chemical natuure of contractile system. The muscle tissues so far examinedcontain three proteins, myosin, tropomyosin, and actin ; these proteins areobtained only from muscle and in the limited studies of isolated myofibrilsthey have been shown to be localised in these contractile elements in thecell and to make up about 85-90y0 of the myofibrillar dry weight. Certainother components are also said to be present in the myofibril and accordinglypresumed to have some special role in contraction.These are usually notwell defined and are present in relatively small amounts2 At presentnothing is known of their function, nor have any special features in their3 J. Hanson and H. E. Huxley, Symposia SOC. Exp. Biol., 1955, 9, 228.4 H. E. Huxley, J . Biophys. Biochem. Cytol., 1957, 3, 631.6 J. L. Farrant and E. H. Mercer, Ex$. Cell Res., 1952, 5, 553.7 A. J. Hodge, J . Biophys. Biochem. Cytol., 1955, 1, 361.8 C. F. Shoenberg, J . Biophys. Biochem. Cytol., 1958,4, 609,A. F. Huxley and R. Niedergerke, Nature, 1954, 173, 971; H. E. Kuxley and J.Hanson, ibid., p. 973PERRY: THE CHEMISTRY OF MUSCLE CONTRACTION AND RELAXATION. 345properties which may play a role in contraction yet been recognised.Pre-cise analysis of the myofibril in terms of its protein components is still notpossible, owing to difficulties of determination, but provisional figures forthe rabbit myofibril are given in the Table.Approximate protein composition of the isolated rabbit myojbril.% Total NMyosin .......................................... 50-55Actin ............................................. 20-25Tropomyosin .................................... 10-15Other components.. ............................ 5-10By selective extraction and use of fluorescent antibodies lo it has beenshown that myosin is localised in the A band, that actin and tropomyosinare certainly present in the I band, and that both are probably present inthe A band.If the model proposed by Huxley et aL4y5 is accepted and ifeach filament system is assumed to have a constant protein composition, it-/,so0 il a23ii Myosin400i - - ISX 7i o p o myosin- 241 Actin dimerS d-/&oooi A Filament - - N O i< * 4 o i-20,000~ T FiIomontFIG. 2. Diagram to illustrate the relative dimensions of filaments of the rabbit myojibriland the molecules of its three main protein components (vertical and horizontai scabsnot identical).follows that myosin is localised in the A filaments and that actin and tropo-myosin are associated with the I filaments. There is some electron-micro-scopic evidence *y7 for interfilamentous material in the A band but nothingis known about its nature.Comparison of the molecular sizes and shapes of the myofibrillar proteinswith the dimensions of the contractile system indicate that they are similar.The molecules are presumably aligned along the axes of the filaments whichcan be at most only a few molecules thick (Fig.2).Of the three major protein components, only actin and myosin havephysicochemical properties which can be readily related to the contractileprocess. The role of tropomyosin is not known but, since the originalisolation from vertebrate muscle of the soluble form, tropomyosin B,ll it9 W. Hasselbach, 2. ges. Naturw., 1953, 86, 449; J. Hanson and H. E. Huxley,10 H. Finck, H. Holtzer, and J. M. Marshall, J . Biophys. Biochem. Cytol,, 1956, 211 K. Baiiey, Biochem. J., 1948, 43, 271.Nature, 1953,172, 530; A.Corsi and S. V. Perry, Biochem. J., 1958, 08, 12.suppl., 175346 BIOLOCICAI. CHBMISTRY.has been shown l2 that certain invertebrate muscles contain an insolubleform known as tropomyosin A, in addition to the soluble type. Tropo-myosin A is found in large amounts in molluscan adductor muscles (up to30% of the total protein) and it has been suggested that it may be respon-sible for the characteristic tonic properties of these m~sc1es.l~ Although thesolubility properties of the tropomyosins are different, the amino-acidanalyses of the two types are fundamentally similar and for this reason theseproteins are known collectively as tropomyosins.Myosin. Myosin has been the subject of considerable physicochemicalinvestigation. Although the most highly purified preparations, L- andcrystalline myosin, used in these studies appear monodisperse on ultra-centrifugation or electrophoresis, evidence is accumulating that they maybe far from satisfactory in this respect.Most work has been carried out onpreparations of rabbit skeletal-muscle myosin which are well known to becontaminated with 5'-adenylic acid deaminase and small amounts of nucleicacid. According to some workers the standard preparations of L-myosincontain 10-15% of impurities,14J5 and very recently Kominz et aZ.16 suc-ceeded in separating from myosin by dialysis against O-lM-sodium carbonatea distinct electrophoretic component of molecular weight 29,000 whichamounts to about 14% of the original myosin. The relation of this proteinto other so-called sub-units of myosin obtained by urea I5,l7 and other treat-ments 16 is not clear.Treatment with urea would not be expected to destroycovalent linkages but the units obtained in this way are smaller than theL- and H-meromyosin produced by tryptic or chymotryptic digestion. Con-trolled heat-denaturation of myosin also facilitates the separation of addi-tional components.l8 It is worth speculating whether L- and H-mero-myosin 19 represent true covalently bound sub-units rather than componentswhich pre-existed in the myosin molecule and whose separation is facilitatedby predigestion.2°*21 Such a consideration may involve a fine distinctionof what constitutes a sub-unit, but recent work on the chromatography ofmyosin on diethylaminoethylcelulose indicates that myosin preparationscontain components of different ATP-ase activity.21 In contrast, H-mero-myosin appeared to be homogeneous with respect to ATP-ase activity.22As yet there has been no clear demonstration of the separation of an ATP-ase of high activity from myosin.When fractionation of the protein occurs12 I<. Bailey, Pubbl. Stax. Zool. Nupoli, 1956. 29, 96; Biochim. Biophys. Ada, 1957,24, 612; D. R. Kominz, F. Saad. J. A. Gladner, and K. Laki, Arch. Biochem. Biophys.,1957, 70, 16; D. R. Kominz, F. Saad, and K. Laki, Conference on the Chemistry ofMuscular Contraction, Japan, 1957, p. 66.13 J. C. Ruegg, Biochim. Biophys. Actu, 1959, 35, 278.14 W. F. H. M. Mommaerts and R. G. Parrish, J , Bid.Chem., 1951, 188, 645.15 T. C. Tsao, Biochim. Biofihys. Ada, 1953, 11, 368.16 D. R. Kominz, W. R. Carroll, E. N. Smith, and E. R. Mitchell, Arch. Biochent.17 A. G. Szent-Gyorgyi and M. Borbiro, Arch. Biochern. Biophys., 1956, 60, 180.18 R. H. Locker, Biochim. Biophys. Acta, 1959, 32, 189.19 A. G. Szent-Gyorgyi, Arch. Biochem. Biophys., 1953, 42, 306; J. Gergely, M. A.20 W. R. Middlebrook, Abs. 4th Internat. Congr. Biochem., Vienna, 1958, p. 84.21 S. V. Perry, Biochenz. J., 1960, 74, 94.25 H. Mueller and S. V. Perry, Biochim. Biophys. Acta, in the press.Biophys., 1959, 79, 191.Goiivea, and D. Karibian, J . BioE. Chem., 1955, 212, 165PERRY: THE CHEMISTRY OF MUSCLE CONTRACTION AND RELAXATION. 347the enzymically active portion represents the major part of the originalprotein.Notwithstanding these reservations about their nature a considerableamount of precise physicochemical study has been applied to myosin pre-parations, Up to recently a molecular weight of 840,000 was accepted23but with clear evidence now available for aggregation in myosin solutionsunder certain conditions 24 this value has become the subject of contro-versy.25 Application of the Archibald approach to sedimentation equili-brium has given values in the region of 420,000,26 and similar values havebeen obtained by the sedimentation-diffusion method at low protein con-centration.Such figures would fit well the present views on the sub-unitcomposition of myosin derived from investigations on the meromyosins.26aPhysicochemical study of N-ethylmaleimide-poisoned myosin in 5~-guan-idine hydrochloride has indicated that the myosin molecule consists of threepolypeptide chains each wound in a tight a-helix, these chains together form-ing a three-stranded rope-likeActiuz.Actin is of particular interest as a myofibrillar component in thatit combines with myosin to form the complex, actomyosin, which possessesthe special property of responding to the addition of ATP under certain ionicconditions by contraction. Russian workers 28 have made the interestingclaims (although recently with some reservation 29) that this property residesin the myosin alone and that the role of actin is to alter and stabilise the pH-dependence of the ATP-ase. Such claims do not fit in with conventionalviews, nor are they supported by the observation of Hayashi et thatactin is an essential requirement for contraction at both pH 7.6 and 9-0.Some further work has been carried out on the nature of the processinvolved in the polymerisation of G(globu1ar)-actin 31 (considered to be adimeric form of particle weight 140,000) to the F(fibrous)-form which isextremely viscous in solution and combines with myosin to form contractileactomyosin.Conventional views would regard this as a linear polymeris-ation of G-actin dimers but polarisation-fluorescence studies 31 suggest thatsome caution must be exercised before this model is adopted. Although thepolarisation-fluorescence studies give a molecular weight for the polymerisedF-actin no greater than that of the dimer, application of the light-scatteringtechnique suggested that it may reach a value of several millions.32From a systematic study of the polymerisation of G-actin, Oosawa and23 H.H. Weber and H. Portzehl, Adv. Protein Chew., 1952, 7, 161.24 A. Holtzer, Arch. Biochem. Biophys., 1956, 64, 507.25 H. H. Weber, Ann. Rev. Biochem., 1957, 26, 667.s6 P. H. Von Hippel, H. K. Schachman, P. Appel, and M. F. Morales, Biochim.Biophys. Acta, 1955, 28, 504; X7. F. H. M. Mommaerts and B. B. Aldrich, ibid., p . 627.865 Cf. S. Lowey and A. Holtzer, Biuckim. Biuphys. Acta, 1959, 34, 470.27 W. W. Kielley and W. F. Harrington, Fed. Proc., 1959, 18, 259.z8 W. A. Kafiani and V. A. Engelhardt, Doklady Akad. Nauk S.S.S.R., 1953, 92, 385.29 W.A, Engelhardt, Conference on the Chemistry of Muscular Contraction, Japan,30 T. Hayashi, R. Rosenbluth, P. Satir, and M. Vozick, Biochim. Biophys. Acta,81 T . C . Tsao, Biochim. Biophys. Acta, 1953, 11, 227.32 J. Gergely and H. Kohler, Conference on the Chemistry of Muscular Contraction,1957, p. 134.1958, 28, 1.Japan, 1957, p. 14348 BIOLOGICAL CHEMISTRY.his co-workers conclude that it can be regarded as a reversible ‘‘ fibrouscondensation.” A critical actin concentration, determined by conditions inthe medium, is required before polymerisation occurs. Above the criticalconcentrations excess of G-actin is converted into the F-form. These in-vestigations suggest that all preparations of F-actin contain both F- andG-actin which are in equilibrium and undergo continuous interconversion.The fact that G-actin preparations contain a small but persistent amountof ATP, which is converted into ADP on polymeri~ation,~~ has stimulatedspeculation on the role of this nucleotide and the G-F transformation inrelation to the contractile process.An implication of these nucleotidechanges during G-F interconversion on the theory of Oosawa et al. is thatdephosphorylation of ATP occurs continuously in F-actin solutions. Theseauthors have claimed that added ATP is slowly dephosphorylated by F-actinsolutions.=As yet there is no direct evidence of participation of the G-F trans-formation in contraction. It would be attractive to consider the nucleotidewhich is bound to the myofibri136 as a built-in acceptor for the phosphatebond energy used in contraction, but such a view is not supported by thefact that the phosphorus of this nucleotide only slowly equilibrates withthat in the nucleotide pool of the muscle cell after injection of inorganicP2PJorthopho~phate.~~ The equilibration is not speeded up significantlyby activity of the muscle.Although the bound nucleotide of the myofibrilis rather inert so far as enzymes are concerned, Strohman 38 has found thatthe nucleotide associated with isolated actin can participate in reactionsinvolving the creatine-phosphokinase system. Pertinent to the problem aresome interesting observations on the localisation of nucleotide metabolismwithin the I band, as revealed by autoradi~graphy.~~Actomyosin. The interaction of actin and myosin and the effects ofATP on it are perhaps the most striking phenomena of muscle biochemistry.Combination of these two proteins causes a marked increase in viscosity..On addition of low concentrations of ATP this is reduced to a value whoselogarithm equals the sum of the logarithms of the viscosities of actin andmyosin, measured separately. Szent-Gyorgyi 40 first explained this effectas a simple dissociation of the complex into actin and myosin, but it hasbeen suggested41 as a result of light-scattering studies that a change inmolecular shape rather than dissociation is responsible for it. This inter-pretation of the light-scattering data is, however, not supported by allinvestigator^,^^ and certainly separation of actin and myosin can be demon-33 S.Askura, K. Hotta, N. Irnai, T. Ooi, and F. Oosawa, Conference on the Chemistryof Muscular Contraction, Japan, 1957, p. 57.34 F. Oosawa, S. Askura, K. Hotta, N. Imai, and T. Ooi, J . Polymer Sci., 1959, 37,323; F. Oosawa, ibid., 1957, 26, 29.85 F. B. Straub and G. Feuer, Biochim. Bio9hys. Acta, 1950, 4, 455.36 S. V. Perry, Biochem. J., 1952, 51, 495.87 A. Martonosi, M. A. Gouvea, and J. Gergely, Fed. PYOC., 1959, IS, 283.38 R. C . Strohman, Biochim. Biophys. Ada, 1959, 32, 436.89 D. K. Hill, J . Physiol., 1959, 145, 132.40 A. Szent-Gyorgyi. Acta Physiol. Scund., 1945, 9, Suppl. No. 25.4 1 J. J. Blum and M. F. Morales, Arch. Biochem. Biophys., 1953, 43, 208.‘2 J. Gergely, J . Biol. Chem., 1956, 220, 917; H.Nuda and K. Maruyama, Biochim.Bio@ys. Acta, 1959, 30, 598PERRY: THE CHEMISTRY OF MUSCLE CONTRACTION AND RELAXATION. 349strated 43 by ultracentrifugation of actomyosin solutions in the presence ofATP.Whereas the interaction of actomyosin and ATP can be more readilyinvestigated by physicochemical methods when it occurs in solution, studyof the reaction ilz v i m , occurring as it does in a heterogeneous system, presentsgreater difficulties. The contracting effect of ATP on actomyosin gels insuitable ionic environment can readily be compared with the behaviour ofmore physiological models such as isolated myofibrils or glycerated musclepreparations.& Any differences which are apparent are probably due todifferences in the degree of orientation of the protein filaments in the twotypes of system.In actomyosin solutions the dissociating action of ATPis reflected in the change of viscosity. Presumably dissociation of the com-ponents on addition of ATP also occurs in the gel but is then followed bycontraction of the system. Any mechanism proposed for contraction in themyofibril system with its precise orientation of filaments and localisation ofprotein must apply also to the randomly oriented actomyosin gel precipitatedfrom a solution of the complex.Protein-protein interactions are not unusual in biological systems but,unlike actomyosin formation, most are non-specific. Myosin thiol (SH)groups are essential for both ATP-ase and actomyosin-forming activity,45and for a number of thiol reagents there is a close correlation between thedegree of inhibition of both properties. With several types of inhibitor thegeneral pattern of behaviour suggested that the same active centres wereessential for actin-combination and enzynie-substrate complex-formationalthough there was some indication that with iodoacetamide the ATP-aseactivity of myosin was less sensitive to this reagent than was the acto-myosin-forming property.Using very high concentrations of the inhibitor,BMny 46 succeeded in treating actomyosin with iodoacetamide and isolatingfrom it a myosin component which had no ATP-ase activity but combinednormally with actin. These results and those obtained with other thiolreagents are taken4' to indicate that different thiol groups on the myosinmolecule are necessary for the interaction with ATP and with actin, but thatthe " pyrophosphate binding " part shares in both activities.Actin alsocontains thiol groups, which are involved in the G-F transformation,48 butthe ability of F-actin to combine with myosin is relatively independent ofthiol reagents.45Adenosine tripkcosphatase. The other aspect of the interaction of myosinwith ATP which seems important for the contractile process is the hydrolysisof the nucleotide :ATP + H,O I_e ADP + H,PO,45 A. Weber, Biochim. Biophys. Acta, 1956, 19, 345; J. Gergely and A. Martonosi,43 H. H. Weber and H. Portzehl, Prop. Biophysics Biophys. Chem., 1954, 4, 60.45 K. Bailey and S. V. Perry, Biochim. Biophys.Acta. 1947, 1, 506.46 M. B&r.r&ny, 4th Internat. Congr. Biochem., Vienna, 1958, Abs., p. 84.47 M. BQrAny and K. B&r&ny, Biochim. Biophys. Acta, 1959, 35, 293.48 G. Feuer, F. Molnar, E. Pettk6, and F. B. Straub, Acta Physiol. Acad. Sci. Hung.,Fed. Proc., 1958, 17, 227.1948, 1, 160; G. ICuschinsky and F. Turba, Biochim. Biophys. Acta, 1961, 6, 426350 BIOLOGICAL CHEMISTRY.The enzyme concerned is perhaps more accurately described as a nucleosidetriphosphatase rather than an ATP-ase as it will also split the triphosphatesof inosine, guanine, uridine, and cytidine at high rates. Inorganic tri-phosphate is hydrolysed slowly. Detailed investigation of the enzyme 2 9 4 4 ~ 4 9has revealed many unusual properties, but despite the mass of experimentalfacts a satisfactory picture of the mechanism of ATP hydrolysis has yet toemerge.Myosin ATP-ase is atypical in its activator requirement in that it isactivated by calcium and not by magnesium although the latter is usuallymore effective with enzymes using ATP as substrate.Magnesium, alone orin the presence of calcium, inhibits the enzyme,50 and in the latter caseantagonism between the ions is a~parent.~l The thiol nature of the enzyme iswell e~tablished,~~ and it is thus surprising that under certain conditions lowconcentrations of specific thiol reagents increase the hydrolysis catalysed bycalcium-activated A T p - a ~ e . ~ ~ Another apparently paradoxical effect isthat a t high ionic strengths low concentrations of ethylenediaminetetra-acetate (EDTA) stimulate the enzyme53 whereas a t low ionic strengthsimilar concentrations inhibit 55 2,4-Dinitrophenol also stimulates thecalcium-activated ATP-ase of myosin 52,56 and it is of interest to comparethis system with the mitochondrial ATP-ase which is likewise sensitiveto dinitr~phenol.~' Earlier ideas 57958 that the mitochondrial ATP-ase mightbe associated with a contractile system regulating volume changes of mito-chondria have recently been discussed further.59Although most of the above observations apply to actin-free myosinpreparations, the presence of actin profoundly affects the enzymic behaviourof the system.In strong contrast to their effect on myosin, both magnesiumand calcium at low ionic strength markedly activate actomyosin ATP-ase;55y60the ions are no longer antagonistic and under certain conditions may besynergic.55 At higher ionic strengths (> 0.15) magnesium-activation dis-appears and the enzymic behaviour more closely corresponds to that of49 D.M. Needham, Adv. E.ttzymoZ., 1952, 13, 151; H. H. Weber and H. Portzehl,Adv. Protein Chem., 1952, 7, 161; A. G. Szent-Gyorgyi, Adv. Enzymol., 1955, 16, 313;K. Bailey, in " The Proteins " (eds. H. Neurath and K. Bailey), Academic Press, NewYork, 1954, Vol. IIB, p. 951; M. F. Morales, J. Botts, J. J. Blum, and T. L. Hill, Plzysiol.lieu., 1955, 35, 475.60 I. Banga and A. Szent-Gyorgyi, Stud. Imt. Med. Chem. Szeged, 1943, 3, 72.51 &I. F. H. M. Monimaerts and K. Seraidarian, J . Gen. PhysioZ., 1947, 30, 401.52 G.D. Greville and D. M. Needham, Biochim. Biophys. Acta, 1955, 16, 284; J. 13.Chappell and S. V. Perry, ibid., p. 285; W. W. Kielley and L. B. Bradley, Fed. Proc.,1955, 14, 235.53 E. T. Friess, Arch. Biochem. Bioflhys., 1954, 51, 17; E. T. Friess, M. F. Rlorales,and W. J. Bowen, ibid., 1954, 53, 311; G. D. Greville and E. Reich, ibid., 1957, 20,440.54 W. J. Bowen and T. D. Kerwin, J . Biol. Chem., 1954, 211, 237.55 S. V. Perry and T. C. Grey, Biochem. J., 1956, 64, 184.66 H, C. Webster, Ph.D. thesis, Cambridge, 1953; S. V. Perry and J. B. Chappell,67 S. V. Perry, Conferences et Rapports, 3rd Internat. Congr. Biochem., Brussels,58 J. B. Chappell, Ph.D. thesis, Cambridge, 1954.59 A. L. Lehninger, Symposium on Molecular Biology (ed.R. E. Zirkle), Univ.60 S. V. Perry, Biochem. J . , 1951, 48, 257.Biochem. J., 1957, 65, 469.1055, p. 365.Chicago Press, Chicago, 1959, p. 122PERRY 1 THE CHEMISTRY OF MUSCLE CONTRACTION AND RELAXATION. 351myosin at a similar ionic strength. These effects apply to actomyosin madeby combination of the separately isolated proteins and to more physiologicalsystems such as isolated myofibrils. Despite the fact that purified myosinis not activated by magnesium this ion is clearly important far functioningof myosin in situ as it is essential for the contraction and relaxation 62 ofisolated myofibrils.With actomyosin systems marked differences occur in the temperaturecoefficient of the calcium- and magnesium-activated action of A T p - a ~ e .~ ~Analysis of the Arrhenius plot for the hydrolysis of ATP by myosin in thepresence of magnesium (a reaction which can hardly be called activated asthe rate is very slow) in the absence and presence of 2,4-dinitrophenol sug-gests that the enzyme-substrate complex with substrates lacking the 6-amino-group may have a conformation which is particularly sensitive tochange a t about 16". Although this phenomenon does not occur with ATPalone, yet if dinitrophenol is added the behaviour now resembles that withITP, suggesting that the dinitrophenol may be strongly attracted to thegroup or groups on the protein which normally bind the amino-group inRTP.63Kinetic analysis of calcium-activated hydrolysis of ATP by L-myosindoes not allow a clear distinction between two possible mechanisms, namely,those wherein (i) the substrate is Ca-ATP and free ATP is inhibitory, or(ii) calcium myosinate is the activated form of the enzyme which splits freeATP, and Ca-ATP is inactive.The latter mechanism has been consideredmore acceptable because of the simpler postulates.M Similar hypotheseshave been put forward 55,65 to explain the experimental findings withmagnesium as the activator for actomyosin ATP-ase. Certain features ofthe latter system, namely, inhibition by EDTA at a concentration one-fiftiethof that of the r n a g n e ~ i u m , ~ ~ * ~ ~ and the relief of inhibition induced by excessof ,4TP by very low concentrations of calcium,55 imply that for the activationby magnesium small amounts of some cation (e.g., Ca2') are required whichcan be selectively removed by the binding action either of EDTA or of ATP.Mreber's recent study 67 of the myofibrillar ATP-ase supports such an ex-planation.This hypothesis can be used as the basis of a plausible theoryof the mechanism of inhibition of ATP-ase which occurs during relaxation(see below).An unusual feature of the hydrolysis of ATP by L-myosin or actomyosinis that the reaction begins with a high initial rate which over the first 10-20sec. may be up to five times as high as the stationary value reached within1-2 m i n u t e ~ . ~ * ~ ~ ~ EDTA eliminates this effect, whereas both the initial61 C. A. Ashley, A. -4rasimavicius, and G. ill. Hass, Exp. Cell. Res., 1956, 10, 1 .62 J.R. Bendall, J. Physiol., 1953, 121, 232.63 H. M. Levy, N. Sharon, and D. E. Koshland, Biochi-m. Biophys. Acta, 1959, 33,,288.64 L. B. Nanninga, Biochim. Biophys. Acta, 1959, 36, 191; Arch. Bioclzem. Biophys.,66 G. Geske, M. Ulbrecht, and H. H. Weber, Arch. Ex$. Pathol. Phaumahol., 1957,1957, 70, 346.230, 301.66 S. V. Perry and T. C. Grey, Biorhenz. J., 1956, 64, 5 ~ .G7 A. Weber, J. Biol. Chem., 1959, 234, 2764.68 ,4. Weber and W. Hasselbach, Biochim. Biophys. Actn, 1964, 15, 237.G9 Y . Tononiura and S. ICitagawa, Hioch~nz. Htophys. d c f a , 1957, 26, 15352 BIOLOGICAL CHEMISTRY.and the stationary phase are enhanced by 9-chloromercuribenzoate and2,4-dinit~-ophenol.~~ If the hydrolysis of ATP is essential for the develop-ment of tension this initial phase of high activity may be of physiologicatsignificance.It would be of great advantage for the myofibril to hydrolyseATP veryrapidly for a few milliseconds during the initial stage of a muscletwitch.Some light has been thrown on the mechanism of ATP hydrolysis bystudying the reaction catalysed by myosin systems in the presence of H,180.When the activator used with actomyosin is calcium, one atom of 180, isintroduced into each molecule of inorganic orthophosphate produced.'* Inthis respect the mechanism of the splitting of ATP is similar to that occurringin phosphokinase systems.71 The value of the ratios of the reactivities ofwater and methanol €or enzymic compared with non-enyzmic hydrolysis ofATP are of a very different order, which suggests that the mechanism ofenzymic hydrolysis involves a specific myosin-water interaction.72 How-ever, if the magnesium-activated hydrolysis by L-myosin, intact lobstermuscle, or actomyosin is studied, appreciable exchange of 1802 betweenH2180 and the inorganic orthophosphate formed is apparent.73 This findingis interpreted as indicating that a phosphorylated intermediate which iscapable of exchanging oxygen with water is formed in these systems.Evi-dence of another kind, namely, the binding of inorganic orthophosphate byH-meromyosin during ATP hydrolysis, has also been taken as evidence fora phosphorylated intermediate.74When 32P was used the evidence found for a phosphorylated intermediatewas somewhat controversial. No exchange between inorganic 32P and ATPor between AD3,P and ATP was observed by Koshland et aZ.,70 whereasWeber 75 reported that with '' Fuadin "-poisoned myosin such an exchangecan be demonstrated.An exchange of 32P between AD32P and ATP whichis stimulated by magnesium has been demonstrated with preparations ofactomyosin extracted as the complex (" natural " actomyosin), and withm y ~ f i b r i l s , ~ ~ ~ ~ ~ This exchange also occurred with myosin extracted selec-tively from whole myofibrils, but not with L-myosin or preparations of" synthetic " actomyosin from purified actin and myosin. The granularATP-ase of muscle actively catalysed this transfer,77 but although thisenzyme contaminates " natural " actomyosin and myofibril preparations itwas considered that the major part of the exchange studied was catalysedby the actomyosin system.So f a r as L-myosin is concerned there is generalagreement that with this protein alone it has not so far been possible todemonstrate any exchange of 32P between AD32P and ATP.70 D. E. Koshland, 2. Budenstein, and A. Kowalsky, J . Biol. Chzem., 1954, 211, 279.71 B. Axelrod, Adv. Enzymol., 1956, 17, 159.73 D. E. Koshland and E. B. Herr, J . Biol. Chem., 1957, 228, 1021.73 H. M. Levy and D. E. Koshland, J . Amer. Chsm. SOC. , 1958, 88, 3164.74 J. Brahms and C. Rzysko, Abs. 4th Internat. Congr. Biochem., Vienna, 1958,75 H. H. Weber, Conferences et Rapports, 3rd Internat. Congr. Biochem., Brussels,76 G. Ulbrecht and M. Ulbrecht, Biochim. Biophys.Ada, 1957, 25, 100.77 G. Ulbrecht, M. Ulbrecht, and H. J. Wustrow, Bioclainz. BiopJays. Acta, 1957, 25,p. 83.1955, p. 356.110PERRY: THE CHEMISTRY OF MUSCLE CONTRACTION AND RELAXATION. 353ATP and contraction. Two important aspects of the interaction of ATPwith the actomyosin system, namely, the mechanical changes and thehydrolysis of ATP, have to be related to the events occurring in vivo. Thereis little doubt that the contraction which can be induced by ATP in acto-myosin systems in vitro is the counterpart of contraction in living muscle.Striking confirmation of this is shown by treating myofibrils with ATPunder controlled conditions : these structures then contract and exhibitthe same band changes as take place in contracting living m u ~ c l e .~ ? ~ ATPis not unique in producing contraction, for other nucleoside triphosphatescan bring about this change; nevertheless the latter are present in musclein concentrations much lower than that of ATP which, if it is not separatedfrom the site of action by some physical barrier, would be expected to be theactive agent purely on mass-action considerations.The question whether ATP is split during contraction, quite apart fromthe fact as to whether it is the contractile agent, is also controversial. As aconsequence of prolonged activity in excess of what the particular muscle isnormally called upon to perform, inorganic orthophosphate accumulates, thelevel of creatine phosphate falls, and subsequently so does the ATP con-centration.2~78 Some investigators 79 have felt that to prove that ATP isthe primary source of energy for the contractile system it is necessary todemonstrate a fall in the level of this substance during the initial stages of asingle twitch, the whole event normally lasting about 100 milliseconds.This is undoubtedly an ideal requirement but the possibility of being ableto demonstrate such a change is doubtful.It is estimatedso that theorthophosphate liberated would represent a very small fraction of the ATPpresent. Hydrolysis of ATP would be occurring under conditions wherethe whole metabolism of the cell is poised ready to rephosphorylate any ADPproduced. Certainly the inability to show an appreciable drop in ATPmust not in itself be taken to exclude the possibility of ATP splitting duringcontraction without ensuring that the enzyme systems concerned withrephosphorylation are ineffective.With in vitro systems considerable correlation between contraction andsplitting occurs.2~23*49 Although there are occasions when correlation isnot satisfactory these may arise because the contractile process is moresensitive to the physical state of the systems than is the enzymic activity.Contraction obviously will not be apparent when the actomyosin is in solu-tion, but such conditions certainly favour ATP-ase activity.A more seriousobjection would be the demonstration that contraction can be induced byATP in a model system without its being hydrolysed. Evidence of thiskind has yet to be obtained.It may be concluded that studies with in vitro systems, in which it ispossible to evaluate accurately the ATP level and the rate of its hydrolysis,there is reasonably good correlation between contraction and tension de-veloped on the one hand and simultaneous hydrolysis of ATP on the other.78 W.F. H. M. Mommaerts, “ Muscular Contraction,” Interscience Publ. Inc., New79 E.g., A. V. Hill, Nature, 1949, 163, 320.80 W. F. H. M. Mommaerts, Amer. J . Physiol., 1955, 182, 585.York, 1950.REP.-VOL. LVI 354 RIOLOGICAL CHEMISTRY.Some exceptions exist, but in the opinion of the Reporter these are notserious objections to this hypo thesis.With intact living muscle, measurement of chemical change during asingle twitch presents considerable difficulties.They arise because of therelatively small change which may be expected, its extremely short duration,and problem of fixing the muscle at a given time (measured in milliseconds)to prevent further chemical change. Chemical reactions in the restingmuscle approach a steady state and it is impossible to predict the preciseeffect of a single twitch on this condition. It is conceivable that thenucleoside-polyphosphate level is relatively insensitive to a low level ofactivity. Within the last 10-15 years a number of attempts have beenmade to tackle this problem and, except in two recent investigations,s0S8lsome evidence for ATP breakdown has been presented. It is, however,difficult to compare all the investigations because the conditions and degreeof activity to which the muscle was subjected were somewhat variable.Theexperiments of Fleckenstein et aZ.B1 and of Mornmaerts:O involving directanalysis of the phosphate compounds of muscle most likely to be hydrolysedduring contraction, have shown that various skeletal muscles of the turtleand frog rectus abdominis can undergo a single twitch without significantchange being apparent in the ATP, ADP, or creatine-phosphate levels. Onthe other hand, indirect determination of nucleotide changes during contrac-tile activity in intact living muscle by spectrophotometric means has pro-vided evidence for a small increase of ADP level after a single twitch. Thisincrease is estimated to be 2% of what would be expected on the assumptionthat the energy required for the work done by the muscle during contractionwas derived from ATP.82Even if breakdown of ATP in living muscle is masked by the efficiency ofrephosphorylation systems, activity should give rise to an increased turnoverin the phosphate atoms of creatine phosphate and of the muscle nucleotides.As yet, however, tracer studies have failed to reveal a transfer of phosphatefrom phosphocreatine to ATP either during drug-induced contracture offrog muscles 83 or during tetanic contracture of cat ga~trocnernius.~~ Evenmore difficult to reconcile with the hypotheses that ATP is dephosphorylatedduring contraction is the further finding g5 that after injection of inorganic[32P]orthophosphate stimulation more than 10,000 times in one hour didnot cause a significant change from the normal resting condition in thedistribution of 32P between creatine phosphate, the terminal phosphate ofADP, and the terminal and middle phosphate of ATP. In neither restingnor stimulated muscle were any of the organic phosphates in equilibriumwith the total orthophosphate.Difficulties arise in interpreting suchstudies, for much of the injected isotope is in the extracellular spaces andnot in metabolic contact with the nucleotides within the cell. This heavilylabelled extracellular phosphate will form part of the orthophosphate81 A. Fleckenstein, J. Janke, R. E. Davies, and H. A. Krebs, Natztre, 1954,174, 1081.82 B. Chance and C. M. Connelly, Nature, 1957, 179, 1235.S3 A. Fleckenstein, J. Janke, R. E.Davies, and W. Richter, Arch. Ex*. Pnthol.8s J. Sacks, Nrrfure, 1959, 183, 825.Phavmakol., 1956, 228, 596.G. J. Dixon and J. Sacks, Amer. J . Physiol., 1958, 193, 129PERRY: THE CHEMISTRY 01; MWSCLE CONTRACTION AND RELAXATION. 355fraction separated from the muscle. As perfusion of the muscle to removeextracellular phosphate also causes changes in the intracellular organo-phosphates some workers 86 consider that it is not possible to determine theabsolute turnover rate of any organophosphate compound which has in-organic phosphate as its immediate source of phosphorus. Equilibrationbetween injected inorganic p2Plphosphate and muscle nucleotides is rela-tively slow compared with that in other tissues; 87 even so it has been con-cluded 86 that the speed at which the terminal phosphate of ATP is replacedin resting muscle is such as to preclude any attempt to measure differencesin rates in working muscle.Nevertheless, if the results obtained by Sacksand other workers are valid, then it is clear that dephosphorylation of ATPis not the direct source of energy for muscle activity.Some effort has been directed towards a search for alternative sourcesof energy, but as yet such a compound has not been discovered. It is un-likely that carnosine phosphate is present in muscle in appreciable a m o u n t ~ , ~ ~ aand the recently discovered phosphorylated guanidino-compounds 87b foundin some invertebrates are of the phosphagen type rather than substanceswhich directly supply energy for contraction.Relaxation.-When the stimulus reaches the muscle the electrical changesoccurring a t the membrane initiate in some way the chemical changes whichtake place at the myofibril and contraction results.These changes continuefor only a limited period after a single stimulus; in a matter of millisecondsthe tension in the contractile unit drops. There is good evidence 88 thatrelaxation is a passive process and extension to the resting length follows asa consequence of the load on the muscle when the contracting force nolonger acts. It seems likely that in resting muscle the enzyme systemswhich play a part in contraction are in steady-state equilibrium. Theelectrical changes occurring a t the membrane as a consequence of the nerveimpulse reaching the cell initiate some slight but significant change, possiblyionic in nature, which completely alters the enzymic balance at the myofibril.A view which has much to commend it is that the myofibrillar ATP-ase isgreatly activated above the low basic level characteristic of the resting myo-fibril, and that shortening then ensues.The initiating electrical changes a tthe membrane are of short duration and, once they are over, the tendencyis for the system to return to the condition characteristic of resting muscle;tension falls and the myofibril extends to its resting length.In earlier work with actomyosin model systems and glycerated fibres 2$ 23949conditions were devised in which previously contracted actomyosin systemscould be made to relax. Usually this occurred in the presence of ATPand various enzyme inhibitors such as EDTA, I ‘ Salyrgan,” etc., whichbrought the ATP-ase activity of the system to a low level.In some casesrelaxation could be obtained in the absence of ATP but in the presence of86 E.g., A. H. Ennor and H. Rosenberg, Biochem. J., 1954, 56, 308.87 K. K. Tsuboi, Arch. Biochem. Biophys., 1959, 83, 445.87b N. V. Thoai, J. Roche, Y . Robin, and N. V. Thiem, Compl. read. SOC. Biol., 1953,147, 1241; N. V. Thoai and Y. Robin, Biochim. Biophys. Acla, 1954, 14, 76; G. E.Hobson and K. R. Rees, Biochem. J . , 1955, 61, 549.88 A. V. Hill, Proc. K0-v. Soc.. 1949, R, 136, 420.D. F. Cain, A. M. Delluva, and R. E. Davies, Nature, 1958, 182, 720356 BIOLOGICAL CHEMISTRY.pyrophosphate and triphosphate 23 which dissociate actomyosin but are notthemselves split. From such studies with model systems the concept hasemerged of the dual role of ATP, i.e., it is able to act, depending on theconditions, as both a contracting and a relaxing agent.When ATP-aseactivity is high, ATP acts as a contracting agent; when it is low, ATPplasticises the system, presumably by breaking the link between actin andmyosin, the tension drops, and the actomyosin fibre relaxes.An important step towards more physiological systems was made whenit was shown that addition of ATP to crude muscle-cell fragments SB and topartly washed glycerated fibres produced an elongation rather than a con-traction. If the systems were more highly purified, addition of ATP pro-duced the well-known contraction.The implication was that these crudepreparations contained some factors which modified the effect of ATP onthe actomyosin system. This factor (known variously as the Marsh factor,Marsh-Bendall factor, or relaxing factor) is considered to be effective inliving resting muscle and prevents contraction from taking place, althoughthe ATP concentration irt sit% in the absence of such a factor would causethe myofibrils to contract.Ideally, the relaxing factor should be studied in systems in which itseffect on the tension of the contracted system can be measured directly.This involves using fibres with which, unless they are extremely thin, itseems impossible to maintain the ATP Concentration constant throughoutthe fibre. ATP is diffusing into the fibre and at the same time being brokendown by the ATP-ase activity of the actomyosin component.For thisreason certain phosphorylase preparations such as creatine phosphokinase 91and myokinase 92 have been claimed to possess relaxing-factor activity. Itseems possible that these phosphokinases may act by keeping the ATP at asufficiently high concentration throughout the system.* Pertinent to thisquestion are the findings of Japanese workersg3 that in addition to thephosphokinase system another muscle fraction, which appeared to be relatedto the granular fraction of muscle sarcoplasm, was necessary. Portzehl 94also found the relaxing factor in the granular fraction which could be sedi-mented completely from sarcoplasm by high-speed centrifugation.Apartfrom causing relaxation of fibre models, relaxing-factor preparations inhibitin a parallel manner the ATP-ase activity of myofibrils 94 and of actomyo~in,~~and the synzeresis of actomyosin gels.g6 Whenever relaxation occursin vitro the evidence so far indicates that ATP-ase activity is low, whichsuggests that inhibition of the enzymic activity brings about the loss in89 B. B. Marsh, Nature, 1951,167, 1065; idem., Biochim. Biophys. Acla, 1952, 9, 247.90 E. Bozler, Amer. J . Physiol., 1951, 167, 276.91 M. C. Goodall and A. G. Szent-Gyorgyi, Nature, 1953, 172, 84; L. Lorand, itid.,p. 1181; E. Bozler, J . Gen. Physiol., 1954, 37, 63.92 J. R. Bendall, Proc. Roy. Soc., 1954, B, 142, 409.93 H.Kumagai, S. Ebashi, and F. Takeda, Nature, 1955, 176, 166; S. Ebashi,F. Takeda, M. Otsuka, and H. Kumagaia, Symposia on Enzyme Chem., Japan, 1956,94 H. Portzehl, Biochim. Biophys. Acfa, 1957, 26, 373.D. J. Baird and S. V. Perry, Biochem. J., in the press.H. Mueller, Biochim. Biophys. Ada, in the press.11, 11.* At high ATP concentrations the magnesium-activated ATP-ase is inhibitedPERRY: THE CHEMISTRY OF MUSCLE CONTRACTION AND IIELAXAllON. 357tension and resulting relaxation of the system.97 Portzehl 98 concluded thatif sufficiently thin fibres were used there was no requirement for a phospho-kinase system as well as the granular preparation of the relaxing factor,either to bring about relaxation in fibres or to inhibit the ATP-ase activityof myofibrils.More recently, however, Molnar and Lorand 99 have providedfurther evidence for the potentiating action of pyruvic phosphokinase withrelaxing-factor preparations. Nevertheless, other workers 1oo-102 considerthe phosphokinase function in the system to be non-specific, but theirexperiments suggest that there is a requirement for a dialysable cofactor inthe system.The precise centrifugal force required to sediment granules (or possiblyreticular material) with relaxing-factor activity from muscle homogenatesdepends somewhat on the species and type of muscle used.95 In the liter-ature the activity is often considered to be associated with the microsomefraction, but studies on the distribution in rabbit skeletal muscle render thisless certain.The bulk of the activity in rabbit skeletal muscle is sedimentedbelow 20,000 9, and the fraction rich in oxidative activity is also the mostconcentrated with respect to relaxing factor. The factor is less easily sedi-mented from pigeon breast-muscle homogenates than from similar prepar-ations of rabbit skeletal muscle, and there is a sharper distinction betweenit and the fraction rich in oxidative activity. In any case muscle is poor ina granular fraction rich'in nucleic acid and corresponding to the conventionalmicrosome fraction of other ti~sues.10~The factor preparations are lipoprotein in nature and possess ATP-aseactivity 9591019104 which is not derived from myosin and is now known to beassociated with the granular components of s a r c ~ p l a s m .~ ~ ~ Both ATP-aseand relaxing-factor activity are destroyed by phospholipase, but undercertain conditions the relaxing-factor activity can be preferentially de-stroyed.lo6 As yet there has been no report of the preparation of therelaxing factor in a soluble form. A significant finding is that relaxing-factor activity of these preparations is readily abolished by low concen-trations of c a l c i ~ m . ~ ~ ? ~ ~ ~ When assayed in the presence of 5-millimolarsodium oxalate, preparations are effective in extremely low concentrations,which suggests that the function of oxalate is to remove some substance(perhaps calcium) present in the preparation and inhibiting their a~tivity.~5For example, with preparations of granules from rabbit muscle 50% in-hibition of the myofibrillar ATP-ase associated with 1 mole of myosinPhysiol., 1953, 37, 53.n7 J.X. Bendall, J. Physiol., 1953, 121, 232; E. Bozler and J . '1'. Prince, J . Gen.ga H. Portzehl, Biochim. Biophys. .4cta, 1957, 24, 474.gg J. Molnar and L. Lorand, Nafuve, 1959, 183, 1032.loo F. N. Briggs, G. Kaldor, and J. Gergely, Biochim. Biophys. Acta, 1959, 34, 211.lol J. Gergely, G. Kaldor, and F. N. Briggs, Biochim. Biophys. Acta, 1959, 84, 218.lo2 G. Kaldor, J. Gergely, and F. N. Briggs, Biochim. Biophys. Acla, 1959, 84, 224.lo3 S. V. Perry and M. Zydowo, Biochem. J., 1959, '72, 682.lo8 L. Lorand, J. Molnar, and C. Moos, Conference on the Chemistry of Muscularlo5 W. W. Kielley and 0. Meyerhof, J . Biol. Chewz., 1948, 176, 591; S.V. Perry,lo6 S, Ebashi, Arch. Biochem. Biophys., 1958, 76, 410.lo' E. Bozler, Amer. J . Physiol., 1952, 168, 760.Contraction, Japan, 1957, p. 85.Biochim. Biophys. A d a , 1952, 8, 499358 BIOLOGICAL CHEMISTRY.(molecular weight 420,000) is obtained when 20 kg. of total microsomalprotein is present, of which the relaxing factor probably represents only asmall part .95In the absence of oxalate much larger amounts of granules are requiredto bring about inhibition and under such conditions activity falls off onageing at 0°.g5 Such a loss in activity is evident only when assays arecarried out in the absence of oxalate. These results are compatible with theslow liberation, in relaxing-factor preparations, of an ion such as calciumwhich inactivates the preparation unless chelating agents are present.Pyrophosphate behaves in a similar manner to oxalate and to the cofactorreported by Kaldor et aL102If speculation is justified at this stage the following mechanism appearsplausible.In view of the inhibition of the magnesium-activated myo-fibrillar ATP-ase with low concentration of EDTA or higher concentrationsof ATP,55366 it is possible that traces of calcium or of a similar cation areessential in some way for the enzyme.67 The relaxing factor may inhibitmyofibrillar ATP-ase in a similar way to these substances by binding tracesof a cation (perhaps calcium) essential for enzymic activity. Further sup-port for this hypothesis would come from the demonstration that relaxingfactor preparations have a strong affinity for calcium.It is striking that theinsoluble granular preparations can exert their influence on the splittingof ATP which occurs on another insoluble system, the myofibril. Thissuggests that the relaxing factor brings about inhibition, not by direct inter-action at the active centres of the enzyme, but rather by changing thecommon soluble environment of the two systems to one which is unfavour-able for ATP hydrolysis by the magnesium-activated enzyme. The actionsof oxalate and the soluble cofactor lo0-lo2 are sufficiently similar to suggestthat their function is to bind the cation (perhaps calcium) present, whichwould otherwise inactivate the relaxing factor. As a physiological counter-part of oxalate the cofactor could have this function in resting muscle, butcould lose it momentarily when muscle is stimulated so that the myofibrilcan hydrolyse ATP at a high rate and hence contract.Conclusions.-The theories which have been proposed (see Perry for areview) to explain the mechanism of contraction usually involve two mainassumptions about the ultrastructure of the contractile unit. These arethat it consists of a single-filament system which shortens by folding in someway or that it is a two-filament system in which one type of filament movesalong the The latter mechanism has much to commend it; but,although the evidence is good for its occurreiice in rabbit skeletal muscle,conclusive evidence for a similar system in other types of muscle has yet tobe produced.It seems reasonable to suppose that the mechanism of con-traction a t this level of organisation is common to all muscle tissues. Bothactin and myosin (and possibly other myofibrillar proteins) appear to beactive participants in contraction, and the two-filament mechanism utilisesthe interaction between the two proteins in a convincing way to explain bothcontraction and relaxation. ATP is usually given a role in modern theorieslo8 €1. H. Weber, ‘‘ The Motility of Muscle and Cells,” Harvard Univ. Press, Cam-bridge, Mass., 1958FOWDEN NEW AMINO-ACIDS FROM PLANTS. 359but not all workers consider its dephosphorylation to occur simultaneouslywith contraction. Present views on enzymic activity during relaxationstrengthen the case for this hypothesis; and, in addition, ATP has uniqueproperties as a relaxing agent compared with other nucleoside triphos-phates.log Much of the work at the growing points of muscle biochemistrymay seem imprecise by purely physicochemical standards, but this is aconsequence of the complexity of the systems studied and the problems in-volved.It can be said, however, that progress in this field towards a mole-cular biology-the integration of the chemical events and the ultrastructureof a complex biological system-is certainly as well advanced here as any-where in biochemistry, s. v. P.5. NEW AMINO-ACIDS FROM PLANTSDURING the last decade about fifty amino- or imino-acids have been newlyidentified as components of higher plants. About twenty more have beenrecognised either as constituents of micro-organisms or as fragments ofantibiotics excreted by them.As a group, these newly discovered acidshave no striking chemical or physiological properties, and their rapid dis-covery is the result of the application of paper and ion-exchange chromato-graphy to the examination of plant extracts. Brief accounts of the chemistryof some of the newly recognised acids have appeared in earlier Reports,l andtheir biological importance has been considered in other reviews.2 Only afew of the acids are distributed widely in plants; the majority are found onlyin occasional plant species. Their distribution follows no rules. Certaincompounds are characteristic of particular plant families, e.g., azetidine-2-carboxylic acid for the Liliaceae.The distribution of many others is hap-hazard, i.e., they are accumulated in high concentration by only a fewspecies that are botanically quite unrelated. The random distribution hasfavoured the idea that they are unimportant and perhaps ‘ I accidental ”products of metabolism ; however, this concept may prove unacceptablewhen inore plant species have been examined and when more crucial inform-ation is available concerning their metabolic relationships. This Reportwill consider recent contributions to our knowledge of the chemistry andbiochemistry of each of the main types of acid.Dicarboxylic Acids-The only new dicarboxylic amino-acid identified asa constituent of higher plants since the last Reports 1 is a-m-carboxyphenyl-gly~ine,~ which was isolated from the acid fractions of an extract of Irisbulbs.Comparison with synthetic material prepared from m-carboxy-benzaldehyde by a Strecker reaction proved its identity.Two acids have been identified as products of microbial metabolism.@-Methylaspartic acid was formed as an intermediate in the reversibleanaerobic conversion of glutamate into mesaconate and ammonia by Clostri-.IDS W. Hasselbach, Biochim. Biophys. Acta, 1956, 20, 355.Ann. Reports, 1955, 52, 271; 1957, 54, 276.F. C. Steward and J. I<. Pollard, Ann. Rev. Plant. Physiol., 1957,8,65; L. Fowden,C. J. Morris, J. 17. Thompson, S. Asen, and F. Irreverre, J . Anzep. Chenz. Soc.,BioE. Rev., 1958, 33, 393.1969, 81, 6069360 BIOLOGICAL CHEMISTRY.diwn tetanomorphum extract^.^ The acid was provisionally assigned theL-tho-configuration.After growth of Streptomyces ~imosus,~ an actino-mycete better known as the producer of the antibiotic terramycin, substantialquantities (1-2 g./l.) of (+)-Ed-diaminosuccinic acid were isolated from thefermentation medium. New syntheses of meso- and racemic ad-diamino-succinic acids have been published.6Synthetic y-hydroxyglutamic acid has been resolved into its four opticalisomers.' One pair of diastereoisomers formed a lactone very easily andthis provided a basis for their separation. After conversion into chloro-acetyl derivatives, the resolution of each pair of diastereoisomers into D-and L-forms was undertaken by using a hog renal L-acylase preparation.The specific rotations of all the isomers were given.By comparison ofspecific rotations in water and 5~-hydrochloric acid, the natural acidisolated from Hemerocallis was shown to be L-allohydroxyglutamic acid.*A new synthesis for my-methyleneglutamic acid has been published andthe racemic mixture has been res~lved.~ The synthetic method of Hellmannand Lingens lo has been shortened by substituting ethyl a-iodomethyl-acrylate (prepared from a-iodomethylacrylic acid 11) for the analogousbromo-compound. The modified synthesis was used to prepare DL-Y-methylene[a-14C]glutamic acid by condensation of the iodo-intermediatewith diethyl acet amido [ a-14C] malonate. *The metabolism of these glutamic acid derivatives has been studiedrecently.When plants assimilate 14C02 photosynthetically, glutamic acidnormally becomes labelled rapidly, but when 14C02 was supplied to leavesof Phlox decussata,l2 Adiantum j5edatum,12 Lilium regale,13 or tulip l4 littleincorporation of the carbon-14 into y-hydroxyglutamic acid, y-methylene-glutamic acid, or y-hydroxy-y-methylglutamic acid was observed. Experi-ments with [carboxy-14C]pyruvate have provided more definite informationabout the biosynthetic pathways leading to the acids. After labelledpyruvate had been supplied to the fern, Asplepziurn septentrionale, the specificactivity of y-hydroxy-y-methylglutamic acid was higher than that of otherfree amino-acids; l5 a similar result was obtained for y-methyleneglutamicacid and y-methyleneglutamine in ground-nut leaves.16 These facts suggestthat the basic carbon skeleton may be produced by condensation of twomolecules of pyruvate (De Jong17 observed an analogous slow chemical4 H.A. Barker, R. D. Smyth, E. J. Wawszkiewicz, M. N. Lee, and R. M. TVilson,Arch. Biochem. Biophys., 1958, 78, 468.6 H. McKennis and A. S. Yard, J . Org. Chem., 1958, 23, 980.7 L. Benoiton, M. Winitz, S. M, Birnbaum, and J. P. Greenstein, J . Amev. Chew.8 L. Fowden, unpublished result.Y. Nakagawa and T. Kaneko, J . Chem. Soc. Jafian, 1957,78, 232; T. Kaneko andlo H. Hellmann and F. Lingens, Chem. Ber., 1956, 89, 77.l1 K. N. Welch, J., 1930, 257.12 G. E. Hunt, Plant Physiol., 1958, 33, suppl., xii.14 L. Fowden and F. C. Steward, Ann. Bot. N.S., 1957, 21, 69.15 P.Linko and A. I. Virtanen, Acla Chem. Scand., 1958, 12, 68.16 L. Fowden and J. A.- Webb, Ann. Bot. N.S., 1958, 22, 73.17 A. W. K. De Jong, Rec. Trav. chim., 1900, 19, 259.F. A. Hochstein, J . Oyg, Chern., 1959, 24, 679.Soc., 1957, 79, 6192.Y . Nakagawa, ibid., p. 1216.M. E. Wickson and G. H. N. Towers, Canad. J . Biochern. Physiol., 1956, 34, 502kOWDEN: NEW AMINO-ACIDS FKOM PLANTS. 361condensation of pyruvic acid in the presence of gaseous hydrogen chloride).Certainly one molecule of pyruvate must enter y-hydroxy-y-methylglutamicacid and y-methyleneglutamic acid intact and not after conversion intoacetyl-CoA. y-Hydroxyglutamic acid may be formed by condensation ofpyruvate with glycine or glyoxylic acid, but negative results were obtainedwhen labelled substrates were supplied to P.decussata.15When y-methylene[a-14C]glutamic acid was supplied to leaves of pea,tulip, or peanut, carbon-14 was incorporated fairly quickly into a varietyof amino-acids, sugars, and organic acids.8 The relative constancies of theconcentrations of y-methylene-glutamic acid and -&tarnine present inexcised tulip leaves during storage l4 must then be maintained by dynamicequilibria and not by the metabolic inertness of the two substances.The degradation of y-hydroxyglutamic acid in plants has not beeninvestigated, but when y-hydr~xy[a-~~C]glutamic acid was supplied to rats,substantial amounts of the original 14C activity appeared rapidly in glutamicand aspartic acid.18 Enzymes present in extracts of animal livers converthydroxyproline into y-hydroxyglutamic acid via its y-semialdehyde in amanner analogous to that involved in the interconversion of proline andglutamic acid.It is possible that the proline-glutamic acid enzymes actin a non-specific manner by catalysing the conversion of the hydroxy-corn pound^.^^y-Hydroxy- and y-methylene-glutamic acid readily donate their amino-group to a-oxoglutarate in the presence of extracts of Phlox 2o and peanut 21leaves respectively. Ellis 22 has shown that both transamination reactionsare catalysed by a purified aspartate-glutamate transaminase prepared fromcauliflower buds. Since this plant material is not known to contain eithery-hydroxy- or y-methylene-glutamic acid, the reactions catalysed by extractsof Phlox and peanut may be the result of non-specific enzyme action.Both y-methylglutamic and a-aminoadipic acid occur in certain higherplants. The structural relation existing between the two acids is the sameas that between (3-methylaspartic and glutamic acids, and therefore inter-conversion of the six-carbon acids may be shown ultimately to proceed by amechanism similar to that observed for the five-carbon acids in C.tetano-rnorph~m.~Imino-acids.-Three new derivatives of proline have been isolated fromseaweeds. 3-Carboxymethyl-4-isopropenylproline occurs in two forms(L-a-kainic acid, and L-a-allokainic acid; I) in Digenea simplex.* InL-a-kainic acid, the 2- and 3-substituents are trans to one another and thoseat C(,) and C(4) are cis; both configurations are trans in L-a-allokainic acid.The substances have been ~ynthesised.~~ 3-Carboxymethyl-4-(2-carboxy-Is L.Benoiton and L. P. Bouthillier, Canad. J . Biochem. Physiol., 1956, 34, 661.l9 E. Adams, R. Friedman, and A. Goldstone, Biochim. Biophys. Acta, 1958, 30, 212.2o A. I. Virtanen and P. K. Hietala, Acta Chem. Scand., 1955, 9, 549.21 L. Fowden and J. Done, Nature, 1953, 171, 1068.22 R. J. Ellis, personal communication.23 S. Murakami, T. Takemoto, and 2. Shimuzu, J . Pharm. SOC. Japan, 1953,73, 1026.24 Y. Ueno, K. Tanaka, J. Ueyanagi, H. Nawa, Y . Sanno, 5%. Honjo, R. Nakamori,T. Sugawa, M. Uchibayashi, K. Osugi, and S. Tatsuoka, Proc. Japan Acad., 1957, 33,53; K. Tanaka, &I. Miyamoto, M.Honjo, H. Morimoto, T. Sugawa, and M. Uchi-bayashi, ibid., p. 47362 BIOLOGICAL CHEMISTRY.l-methylhexa-l,3-dienyl)proline (domoic acid; 11) was obtained fromChondria a ~ r n a t a . ~ ~ The three substances have useful anthelminthic pro-perties.Hydroxypipecolic acids have received considerable at tention in the pasttwo years. 4-Hydroxypipecolic acid was isolated first from Acacia penta-dena.26 A hydroxypipecolic acid, isolated from Armeria mnritirna,27 wasprovisionally assigned the 3-hydroxy-configuration. Comparisons of thetwo materials showed them to be very similar, if not identical. Subsequentisolations from Acacia willardia and Lysilornn bahamense 28 have providedadditional support for the 4-hydroxy-structure. More recently a hydroxy-pipecolic acid was isolated from A.ecelsn, and evidence supporting a trans-4-hydroxy-configuration was 0btained.2~ 4-Oxopipecolic acid has beenshown to occur in the antibiotic, staphylomycin; 30 on catalytic hydrogen-ation ~-cis-4-hydroxypipecolic acid was formed. cis-3-Hydroxypipecolicacid has been prepared31 and shown to be separable from the imino-acidof Armeria by paper chromatography.8 The position regarding the naturaloccurrence of the 3-hydroxy-compound is now uncertain. However,3-hydroxypicolinic acid occurs in the antibiotics etamycin 32 and staphyl-om ycin .31The trans-configuration assigned to 4-hydroxypipecolic acid brings thiscompound into line with natural 5-hydroxypipecolic acid isolated fromdates; the trans-configuration of hydroxyl and carboxyl groups in the lattercompound is established unequi~ocally.~s A new method of obtaining thediastereoisomeric mixture of (&)-5-hydroxyallo(cis)- and (&)-5-hydroxp-pipecolic acid from kojic acid is available.= (&)-5-Hydroxypipecolic acidwas prepared essentially free from the allo-isomer by reduction of 5-OXO-piperidine-2-carboxylic acid (obtained from glutamic acid) with sodiumb~rohydride.~~ The related dehydro-derivative, baikiain (1,2,3,6-tetra-hydropyridine-2-carboxylic acid), has also been synthesised by a newmethod.After hydrolysis of the benzoyl group from cis-5-benzamido-l-bromopent-3-yne-l-carboxylate, base-catalysed elimination of hydrogenbromide and ring closure gave b a i k i a i ~ ~ ~ Unexpected difficulties were25 K.Daigo, J . Pharm. SOC, Japan, 1959, 79, 353, 356.26 A. I. Virtanen and S. Kari, Acta Chem. Scand., 1955, 9, 170.27 L. Fowden, Biochem. J., 1958, 70, 629.28 A. I. Virtanen and R. Gmelin, A d a Chem. Scand., 1959, 13, 1244.$9 J. W. Clark-Lewis and P. I . Mortimer, Nature, 1959, 184, 1234.80 H. Vanderhaeghe and G. Parmentier, Symposium on Peptide Antibiotics, 17th,31 H. Plieninger and S. Leonhauser, Chem. Ber., 1959, 92, 1579.8% J. C. Sheehan, H. G. Zachau, and W. B. Lawson, J . Amer. Chem. Soc., 1958, 80,53 B. Witkap and C. M. Foltz, J . .4nzer. Chem. SOC., 1957, 79, 192.H. C. Beyerman, Rec. Tvav. chim., 1958, 77, 249.95 H. C. Beyerman and P. Boekee, Rec. Trav. chtm., 1959, 78, 648.36 N. A. Uobson and R. A. Raphael, J., 1958, 3642.Congr.Pure Appl. Chem., 1059, p. 56.3349FOWDEN : NEW AMINO-ACIDS FROM PLANTS. 363found when attempts were made to cause the cyclisation of other 1,5-sub-stituted cis-pent-3-ene-l-carboxylic acids.The biogenetic pathways leading to the heterocyclic ring systems ofproline and pipecolic acid have common features. The possible pathwaysby which pipecolic acid may be formed are illustrated in the annexed chart.The conversion of lysjne into pipecolic acid has been demonstrated byisotopic tracer experiments with higher plants, Neurospora, and intact rats.Reaction (4) is probablyCH ZH2C' '7H2IH02C ,CH-C02HNH2CHZHO-H2C )CH.C02H\H2t/\CHz 2,NH2the primary one occurring i n Neurospora 37 andReactions: ( I ) +2H. (2) -2H.(3) Transaminase or amine oxidase. (4) a-Amino-acidoxidase. (SC) Spontaneous cyclisation. (5) +2H. (6) +2H.rats.38 Loss of the c-amino-group of lysine [reaction (3)] is catalysed by aplant amine oxidase from peas; 39 transamination could also yield cc-amino-adipic 8-semialdehyde. The reduction of l-amino-5-hydroxyhexanoic acid(hexahomoserine) by extracts of N . cyassa [reaction (2)] also produced thealdehyde; DPNH acted as a better hydrogen donor than TPNH.40 a-Amino-8-hydroxyvaleric acid is reduced to glutamic y-semialdehyde undersimilar conditions. As yet, reaction (1) does not appear to have beendemonstrated with certainty, but the analogous conversion of glutamic acidinto its y-semialdehyde is well established.Enzymic reduction of 3,4,5,6-tetrahydropyridine-2-carboxylate intopipecolic acid [reaction (6)] has been observed.41 Extracts of rat organs, ofN .crassa, and of seedlings of pea and green gram (Phaseolus radiatus) aregood sources of the dehydrogenase, which can use either DPNH or TPNH.Reaction (5) is not proved but the corresponding reduction of A4-pyrroline-2-carboxylic acid has been demonstrated for N . crassa 42 and crude extractsof rat organs.41 Ultimately, reaction (5) may be shown to occur in higher37 R. S. Schweet,.J. T. Holden, and P. H. Lowy, J . Biol. Chem., 1954, 211, 517.s8 M. Rothstein and L. L. Miller, J . Amer. Chem. SOL, 1954, 76, 1459.3B P. J. G. Mann and W. R. Smithies, Biochem. J., 1955, 61, 89; A. J. Clark and40 T. Yura and H. J. Vogel, J , Biol. Chem., 1959, 234, 339.41 A.Meister, A. N. Radhakrishnan, and S. D. Buckley, J . Biol. Chem., 1957, 229,T. Yura and 11. J. Vogel, J . Bid. Chenz., 1959, 234, 335.P. J. G. Mann, ibid., 1959, 71, 596.789364 BIOLOGICAL CHEMISTRY.plants since the necessary substrate, 2,3,4,5-tetrahydropyridine-Z-carboxylicacid, is presumably produced by the action of plant amine oxidase.The degradation of pipecolic acid has not been studied extensively.After [l*C]- and pH]-pipecolic acid had been supplied to phyllodes of AcaciahomaZophyUa, radioactivity appeared quickly in various amino-acids, sugars,and organic acids. 4-Hydroxypipecolic acid and a compound presumed tobe 5-amino-l-hydroxyhexanoic acid were amongst the first compounds tobecome labelled in the tritium experiments.* a-Aminoadipic acid and lysinelater became labelled and so some of the above reactions are probablyreversible.Two general mechanisms can be postulated for the biogenesis of thehydroxy-imino-acids.The first requires that the heterocyclic ring is formedonly after the hydroxy-group has been introduced into an appropriate open-chain amino-acid. y-Hydroxyglutamic acid and 6-hydroxylysine, both ofwhich occur naturally, could then yield hydroxyproline and 5-hydroxy-pipecolic acid by reactions analogous to those involved in the synthesis ofproline and pipecolic acid. However, there is no evidence that the con-version of hydroxyproline into y-hydroxyglutamate (see above 19) can bereversed, even in animal tissues. The metabolism of 6-hydroxylysine hasnot been investigated.According to the second mechanism the hydroxyl group is introducedafter the formation of the heterocyclic ring.This mechanism for hydroxy-proline synthesis has now been shown to occur in animal and plant tissues.Hydroxyproline is a rare component of plant proteins but occurs as a char-acteristic component of the protein present in abnormally growing cells,e.g., in tissue cultures and plant tumours. By using cultures of carrot root,it has been shown that hydroxyproline is produced by hydroxylation ofproline only after the latter imino-acid has been incorporated into the cellprotein.& Free hydroxyproline causes inhibition of growth by suppressingthe incorporation of proline into protein.The experiments in which labelled pipecolic acid was supplied to Acacia 8(see above) indicated that 4-hydroxypipecolic acid was formed directly fromthe parent imino-acid.When [14C]lysine was supplied, labelled pipecolicacid was formed very rapidly; the carbon-14 was intraduced subsequentlyinto the 4-hydroxy-compound. No active hydroxylysine could be detected.Degradation of hydroxyproline has been reported for two systems. TheD-amino-acid oxidase of sheep kidney converted either D-hydroxyproline orD-allohydroxyprohe into pyrrole-2-carboxylic acid ; presumably 4-hydr-oxy-A1-pyrroline-2-carboxylate is an intermediate which then spontaneouslyloses water.& A strain of Pse.udmmas, isolated from soil, also producedpyrrole-2-carboxylic acid from L-hydroxyproline or ~-allahydroxyproline,which were interconverted by an epirnerase.44 An alternative degradativepathway was present in Pseudamoaas; the A1-pyrroline ring could open and,after loss of ammonia and subseqaent oxidation, a-oxoglutarate wasformed, as shown opposite.45* J.K. Pollard and F. C. Steward, J. Ex$. Bot., 1959, 10, 17.44 A. N. Radhakrishnan and A. Meister, J . Biol. Chem., 1957, 226, 569.45 E. Adams, J . Biol. Chem., 1869, 234, 2073FOWDEN NEW AMINO-ACIDS FROM PLANTS. 365The biosynthetic mechanism leading to azetidine-2-carboxylic acid isstill not clear. Aspartic acid, ay-diaminobutyric acid, and homoserine arepossible precursors, but when these acids were supplied as 14C-labelled com-pounds to leaves of Co.tzvaZlaria. majalis (lily-of-the-valley), which containedconsiderable amounts of azetidine-2-carboxylic acid, only slight incorpor-ation of radioactivity into the imino-acid was observed.46 Diaminobutyrategave a labelled compound that could be catalytically hydrogenated to yieldazetidine-2-carboxylic acid ; by analogy with proline and pipecolic acidmetabolism, this compound may be Al-azetidine-2- or -4-carboxylic acid.Later work showed that roots, and not leaves, may be the main site forsynthesis of azetidine-2-carboxylic acid in these plants.47Only slight degradation of [14C]azetidine-2-carboxylic occurred inC.maj'alis leaves in 48 hours.46 In contrast, a soil yeast degraded azetidine-2-carboxylic acid rapidly with initial formation of y-amino-or-hydroxy-butyric acid; this was subsequently converted into p-alanine, possibly wiuy-amino-a-o~obutyrate.~8Diamino- and Basic Acids.-Recently several additions have been madeto this group of naturally occurring acids.ap-Diaminopropionic and ory-diaminobutyric acid, both previously recognised only as components ofantibiotics, have now been identified as products from higher plants. Theformer was isolated from seeds of Mimosa palmeri; 49 the latter was presentin traces in the rhizome of Polygonaturn multijfor~rn.~~ New chemical syn-theses are available for diaminopropionic acid 51 and for diaminobutyricacid.52Derivatives of ap-diaminopropionic acid and the homologous acids,ornithine and lysine, have been isolated. L-( -)-a-Amino-13-ureidopropionicacid (albizziine, the lower analogue of citrulline) occurs in large quantitiesin seeds of various Albixxia species and those of other Mimosa~eae.~~953Albizziine was converted into diaminopropionic acid by treatment withboiling 48% hydrobromic acid.The isomeric L- (3-amino-a-ureidopropionicacid has been ~ynthesised.~~8-Acetylornithine occurs in ferns, grasses, and many members of the*6 L. Fowden and M. Byrant, Biochem. J., 1959, 71, 210.47 L. Fowden, Biochem. J., 1959, 71, 643.48 H. Vinson and L. Fowden, unpublished result.*9 R. Gmelin, G. Straws, and G. Hasenmaier, 2. physiol. Chem., 1959, 814, 28.50 L. Fowden and M. Bryant, Biochem. J., 1958, 70, 626.51 H. Hellmann and G. Haas, Cheun. Ber., 1957, 90, 1357.53 G. Talbot, R. Gaudry, and L. Berlinguet, Canad.J . Chem., 1958, 36, 593; M.Fraenkel, Y. Knobler, and T. Sheradsky, Bull. Res. Council Israel, Sect. A. Chem., 1958,7, 173; M. Zaoral, Chem. Listy, 1958, 52, 2338.53 A. Kjaer, P. 0. Larsen, and R. Gmelin, Experientia, 1959, 15, 253366 RIoLocIc.u, CHEMISTRY.Fumariaceae.u The flagellar proteins of the bacterium, SaZmoneZZa typhi-murium, yield E-N-methyl-lysine on hydrolysis ; 55 this amino-acid was notdetected in the protein component of the remainder of the bacterial cell.y-Guanidinobutyric acid is present in a variety of plant tissues; 56 from1 to 20 pg./g. fresh weight occur in the fruit of many species. The acid maybe formed by transamidination known to occur in animal tissues; can-avanine, arginine, or guanidinoacetic acid can donate their amidine groupto ornithine, canaline, glycine, or hydr~xylamine.~~ The formation ofy-guanidinobutyrate from y-aminobutyrate and arginine is catalysed byextracts of rat or pig kidney.58 Glycine was better than, and P-alanineinferior to, y-aminobutyrate as an acceptor of the transferred amidine group.A deguanidinase, differing in its properties from arginase, has been found invarious fish livers ; this enzyme hydrolytically splits y-guanidinobutyric acid,yielding urea and y-amin~butyrate.~~Canavanine, an important constituent of jack-bean seeds (Canaualiaensiformis), has now been shown to occur in a wide variety of other legu-minous seedsm A new type of cleavage of canavanine to homoserine andhydroxyguanidine occurs in a pseudomonad.61 Kalyankar et aL61 alsosummarise the other known degradative reactions of canavanine that yielda variety of products including O-ureidohomoserine, guanidine, canaline, andCC-oxo- 8-guanidinox ybut yric acid.Another guanidino-compound, y-hydroxyarginine, has been isolated fromthe marine animal, Polycheira rufescens (the sea-cucumber) .62 Alkalinehydrolysis produced y-hydroxyornithine, an amino-acid whose naturaloccurrence would not be unexpected, and which bears the same structuralrelationship to hydroxyproline as 8-hydroxylysine does to 5-hydroxy-pipecolic acid.Acids derived from A1anine.-Amino-acids containing a benzenoid orheterocyclic ring attached to the @-carbon atom of an alanine residue featureas protein components (e.g., phenylalanine, tyrosine, tryptophan, andhistidine).Recently several additional alanine derivatives have beenisolated from higher plants; they appear to occur only as free amino-acids.2,4-Dihydroxy-6-methylphenylalanine (111) has been obtained fromseeds of Agrostemma githago (corn cockle).63 The acid was synthesised bythe annexed route.An amino-acid (stizolobic acid) containing a y-pyrone nucleus has beenisolated from Stizolobium hassjoo,64 a shrubby legume; the plant also con-tains 3,4-dihydroxyphenylalanine. The new acid, p- (3-carboxy-y-pyron-54 A. I. Virtanen and P. Linko, Acta Chem. Scand., 1955,9,531; L. Fowden, Nature,1958, 182, 406; R. H. S. Manske, Canad. J . Res., 1937, 15, B, 86; G. Reuter, Flora,1957,145, 326.55 R. P. Ambler and M.W. Rees, Nature, 1959, 184, 56.5g F, Irreverre, R. L. Evans, A. R. Hayden, and R. Silber, Nature, 1957, 180, 704.1: 3 . 1. Pisano, C. Mitoma, and S. Udenfriend, qdzkre, 1997, 180, 1125.59 R. Baret and M. Mourgue, Compt. rend. SOC. R i d , 1957, 358, Flj.61.6o E. A. Bell, Biochem. J., 1958, 70, 617.61 G. D. Kalyankar, M. Ikawa, and E. E. Snell, J . Biol. Chem., 1958, 239, 1175:6* Y . Fugita, Bull. Chem. SOC. Japan, 1959, 82, 43.9.63 G. Schneider, Biochem. Z . , 1958, 330, 42B:64 S. Hattori and A. TGpmrnipe, Nptu-fe, 1959, 183, 1136., B. Walker, J . Biol. Chem., 1957, 224, 57FOWDIJN : NEW AhiTh’O--4.\C‘IDS 1;EOkl PLAKTS. 3675-y1)alanine (IV), is only a minor component and was isolated from theexudate flowing from cut sterns of seedlings. Ozonolysis of stizolobic acidgive a mixture of aspartic, oxalic, and formic acid.eo -0H=C: IN-CFhHO G C H ; .CH. I CO2HMe N% (111 1Another heterocyclic ring (the pyrazole nucleus) is present in p-pyrazol-1 -ylalanine (V), an amino-acid isolated from seeds of Citn.zZZus vulgaris(watermelon). This is the first report of a naturally occurring pyrazolederivative. Smaller quantities of the acid are present in seeds of relatedcucurbitaceous plants. The acid was synthesised by refluxing s i l ~ e rpyrazole with ethyl a-amino-p-chloropropionate. The infrared spectrum ofthe synthetic material was identical with that of the natural acid after itsra~emisation.~~ The compound isolated from watermelon juice, and pro-visionally identified as p-imidazol-l-ylalanine,66 was probably the abovepyrazole derivative.A new hetero-cyclic alanine derivative recently isolated fromA .willardia has been identified as L-p-uracil-3-1 ylalanine (willardiine; VI).66n The new acid is anisomer of mimosine (leucanol), first isolated fromNH2 Mimosa pudica.66b Willardiine and mimosine mayboth be regarded as derivatives of ap-diamino-propionic acid.The biosynthesis and biodegradation of these alanine derivatives havenot been investigated.Hydroxy-amino-Acids.-Certain hydroxy-amino-acids have been de-scribed under earlier headings. Two further hydroxy-acids have beenobtained from higher plants. y-Hydroxyvaline was isolated from Kalanchoedaigremoiztiana; its presence in other Kalanchoe species could not be con-but by paper chromatography small amounts of its lactone wereThe genus Albixxia is a rich source of newer amino-acids.N‘COHc\ ,N*CH2-CH’Co2H ICH(VI)c3 I;.I:. No6 and L. Fonden, Naizwe, 1959, 184, ~ . 4 . 69.66 S. Shinano and T. Kaya, J . Agric. Chem. SOC. Japaw, 195i, 31, 759.66n R. Gmdlin, 2. phvsiol. CItem., 1969, 316, 164.G6b J: Renz, %. phyiiol. Chem., 1936, 244, 153;67 J . K. I’ollard. E, Sondheimer, and F. C . Steward, Na144re, 1958, 182. 1360,R. -4dams and J. I,. Johnson, J .Anirv. Chem. Sor., 1949, 71, 705368 BIOLOGICAL CHEMISTRY.identified in extracts of K . daigremontiana. y-Hydroxyvaline was syn-thesised by catalytic hydrogenation of P-methyl-a-oxo-y-butyrolactone togive its a-hydroxy-lactone ; this was converted into the a-chloro-derivativeby treatment with thionyl chloride in pyridine, and y-hydroxyvaline wasthen obtained after treatment with concentrated ammonia.The stereo-isomeric composition of the product was not investigated.The second compound isolated was O-acetylhomoserine ; 68 like homo-serine, it was isolated from pea plants. The function and metabolism of thetwo hydroxy-acids have not been studied.p-Hydroxyleucine has been identified as a component of a peptide-typeantibiotic produced by a strain of PaeciZ0myces.6~Aminobutyric Acids.--Aminobutyric acid is plresent in the soluble-nitrogen fraction of almost all plants. It may be formed from glutamic acidby the action of glutamic decarboxylase, an enzyme widely distributed inplants.y-Aminobutyrate is produced by other pathways in micro-organisms , e.g. , by transamination from succinic semialdehyde in Pseudo-monas juorescens 70 and ToruZopsis ~ t i l i s , ~ ~ by hydrolysis of the lactam ringof 2-pyrrolidone in P. aer~ginosa,~~ and by oxidation of pyrrolidine orputrescine via y-aminobutyraldehyde in P. f l ~ o r e s c e n s . ~ ~ It is doubtfulwhether these mechanisms are of any importance for the synthesis of y-amino-butyric acid in higher plants, but putrescine, and possibly succinic semi-aldehyde, have been identified in some plants.The suggestion has been made that y-aminobutyric acid may be re-carboxylated to yield glutamic acid. Comparison of the metabolism ofy-amino[I4C] butyrate and [14C]glutamine in tissue culture of carrot roothas lent support to this idea,73 but only slight reversal of normal glutamic-decarboxylase activity has been dem~nstrated.~~ However, when theenzymic re-carboxylation of y-aminobutyric acid was studied in the presenceof an anion-exchange resin, larger proportions of glutamic acid were pro-duced (the glutamate formed was absorbed by the resin and rendered un-available to the enzyme).75 A similar situation may be operative in livingtissues where cellular organisation may ensure that newly formed mole-cules of glutamic acid are removed immediately from the site of enzymeaction.It is more probable that y-aminobutyric acid is converted into succinicsemialdehyde by a transamination and that the aldehyde is then oxidised tosuccinic acid.Many micro-organisms, including yeast, bacteria, andunicellular algae, contain transaminases capable of catalysing the reactionbetween y-aminobutyrate and a-oxoglutarate. The properties of theenzyme present in P. $uorescens have received detailed study.7o The sameN. Grobbelaar and F. C. Steward, Nature, 1958, 182, 1358.69 G. W. Kenner and R. C. Sheppard, Nature, 1958, 181, 48.70 E. M. Scott and W. B. Jakoby, J . Bid. Chew., 1959, 234, 932; W. B. Jakoby7 1 R. Pietruszko and L. Fowden, unpublished result.73 F. C. Steward, R. G. S. Bidwell, and E. W. Yemm, J. Exp. Bot., 1958, 9, 11.74 R. Koppelman, S. Mandeles, and M. E. Hanke, J . Biol, Chew., 1958, 233, 73.75 J. K. Pollard, personal communication,and J. Fredericks, ibid., p. 2145.F.F. No6 and W. J. Nickerson, J. Bad., 1958, '45, 674FOWDEN: NEW AMLNO-ACIDS FROM PLANTS. 369authors studied the properties of succinic semialdehyde dehydrogenase,isolated from this organism.76The metabolism of y-amin~[carboxy-~~C]butyric acid has been studied inthe organism, Bacillus ~ ~ m i l u s , ~ 7 which produces and excretes large amountsof glutamic acid into the culture medium. If glutamic acid was formedprimarily by direct carboxylation from this specifically labelled y-amino-butyrate, then the o-carboxy-group would have carried the heaviest label-ling. But over 99% of the activity present in the glutamate was associatedwith the a-carboxy-group, which is in accord with its formation from thecarbon skeleton of y-aminobutyric acid via the reactions of the tricarboxylicacid cycle.When the organism was grown in the presence of some of theorganic acid intermediates of this cycle, the glutamate excreted had, asexpected, a lower specific activity.y-Amino[l4C]butyric acid was metabolised quite readily when suppliedto pea leaves; aspartic acid, alanine, and glutamic acid became radio-active in succession,78 as would be expected if the carbon skeleton wasmetabolised via the tricarboxylic acid cycle. This sequence of labellingsuggests that the initial degradation of y-aminobutyrate involved a trans-amination; direct carboxylation would give glutamic acid as the primarylabelled compound.Convincing demonstrations of a y-aminobutyrate-transaminase in higherplant tissues are, however, rare, A transaminase, catalysing a reactionbetween y-aminobutyrate and a-oxoglutarate, was found in extracts ofnodulated pea but further experiments have shown that the enzymeactivity is confined to the nodules.78 Since the microbial symbiont, Rhizo-biz~um, contains an active y-aminobutyrate-transaminase, the transaminationobtained u7ith nodulated roots may have been caused entirely by the infectiveorganism.A similar transaminase has been reported in a potato tuberextract,80 but this observation is of doutbful value because microbial con-tamination was not excluded during the long, 24 hour, reaction period. Withmitochondria from peanut seedlings, definite transamination betweeny-aminobutyrate and either a-oxoglutarate or pyruvate has been obtainedin 3 hours.78 Pyruvate was approximately five times more efficient thana-oxoglutarate as an amino-group acceptor.Oxidative degradation of y-aminobutyric acid has not been demonstratedas yet in plants, but oxidative mechanisms operate in brain tissue and leadto the formation of y-amino+- and -cc-hydroxybutyric acid.81 Eventuallythese mechanisms may be shown to be widely distributed.By the pro-duction of these p- and a-hydroxy-acids, y-aminobutyrate metabolism usesintermediates common to degradation of hydroxyproline 4* and azetidine-2-carboxylic acid,48 respectively. Mutant strains of Escherichia coli alsoproduce y-amino-cc-hydroxybutyric acid by decarboxylation of y-hydroxy-76 W. B. Jaboby and E. M. Scott, J . Biol. Chem., 1959, 284, 937.77 T.Tsunoda and I. Shiio, J . Biochem. (Japan), 1959, 4$, 1011, 1227.78 R. 0. D. Dixon and L. Fowden, unpublished result.79 J. I<. Miettinen and A. I. Virtanen, Acta Chem. Scand., 1953, 7, 1243.80 T. Suzuki, A. Maekawa, T. Hasegawa, M. Ito, H. Honda, T. Nagano, S. Saito,and Y . Sahashi, Bull. Agric. Chem. SOC. Japan, 1958, 22, 39.81 K. Inui Med. J . Osaka Univ., 1959, 11, 681; S. Sao, ibid., 1957, 7, 833370 I~TOI~OGICAL CHEMISTRY.glutamic acid,82 and the 8-hydroxy-acid similarly from allo-p-hydroxy-glu tamate .83Onemethod used y-aminobutyrate which, after N-acetylation, was brominatedon the cc-carbon atom. The bromine atom was replaced by a hydroxylgroup and acid-catalysed de-acetylation yielded the required a ~ i d . 8 ~ It hasalso been prepared by treating ay-diaminobutyric acid with nitrous acid.48a- and p-Aminoisobutyric acid are both known as plant products.Thep-amino-compound was isolated recently from the bulbs of I ~ i s tingitana; 8ssynthetic and racemised natural material gave identical infrared spectra.A new synthesis of the acid from glycine involving Wolff rearrangement ofthe diazoethyl ketones has been described.g6 a-Aminoisobutyric acid is acomponent of the antibiotic produced by Paecilomy~es.~~ The metabolismof these acids has not been investigated.Acids derived from Cysteke.-The isolation of (+)-S-methyl-L-cysteinesulphoxide from cabbages and turnipss7 has been followed by that of itsprobable biological precursor (-)-S-methyl-L-cysteine. The latter acid wasisolated from seeds of Phaseolus vulgaris (kidney beans),88 and occurs as ametabolite of N.crassa. It can act as a sole source of nutrient sulphur forthis organism.8g A transmethiolase, isolated from yeast, has been partlypurified and shown to catalyse the formation of S-methyl-L-cysteine fromL-serine and methanethi01,~O No other amino-acid tested could substitutefor L-serine as an acceptor of the MeS group. Ethanethiol reacted a t about60% of the rate observed for methanethiol. y-L-Glutamyl-S-rnethyl-L-cysteine has also been obtained from kidney-bean seeds; 91 and the corre-sponding sulphoxide occurs in the Lima bean.g2The seeds of Albixzia julibrissin contain S-2-carboxyethyl-~-cysieine inamounts equal to 0.3% of their dry weight.93 The acid has been synthesisedfrom L-cysteine and p-bromopropionic acid.94 A crude enzyme preparationfrom A .lophantha seeds causes hydrolysis of S-2-carboxyethyl-~-cysteine toammonia, pyruvic acid, and p-mercaptopropionic acid.93 S-2-Carboxy-propyl-L-cysteine has been identified tentatively as a component of ,4.willadia.66aCycloalliin (5-methyl-l,4-thiazan-3-carboxylic acid l-oxide) (VII), iso-lated recently from onion bulbs (Allium ~ e p a ) , ~ ~ may be regarded as a cyclisedy-Amino-a-hydroxybutyric acid has been synthesised only recently.82 A. I. Virtanen and P. K. Hietala, Acta Chem. Scand., 1955, 9, 549.83 W. W. Umbreit and P. Heneage, J . Biol. Chem., 1953, 201, 15.84 A. Mori, J . Biochem. (Japan), 1959, 46, 59.85 S. Asen, J. F. Thompson, C . J. Morris, and F. Irreverre, J . Bid. Chem., 1959, 234,86 K. Balenovie, I. JambreSiC, and I. Ranogajec, Croat Chem. Acta, 1957, 29, 87.87 R. L. M. Synge and J. C. Wood, Biochem. J . , 1956, 64, 252; C. J. Morris andJ. F. Thompson, C. J. Morris, and R. M. Zacharius, Nature, 1956, 178, 593.89 J. B. Ragland and J. L. Liverman, Arch. Biochem. Biofihys., 1956, 65, 574.E. C . Wolff, S. Black, and P. F. Downey, J. Amer. Chem. SOC., 1956, 78, 5958.91 R. M. Zacharius, C. J . Morris, and J. I;. Thompson, Arch. Riochenz. BioFhp., 1959,343.J. F. Thompson, J . Sac, Chem. Ind., 1955, 951.80, 199.H. Rinderknecht, J . Soc. Chem. Iltd., 1957, 1354.R. Gmelin, G . Strauss, and G. Hasenmaier, 2. Nafwforsch., 1958, 13b, 252%94 A. Schoberl and A. Wagner, Z . physiol. Chew., 1956, 304, 97.95 A. I . Virtanen and E. J . Matikkala, Acin Chfwz. Scnizd., 1959, 13, 623Some properties of recently isolated amino- and imino-Amino- and imino-acid M. p.*m-Carboxyphenylglycine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . .(+)-aa'-Diaminosuccinic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . 240-290 dL-y-Allohydroxyglutamic acid , . . . . . . . . . . . . , , . . . . . . . . . 187 dL-y-Methyleneglutamic acid , . .. .... . .. . . . .. . . . . . . . . . . . 195-197 dL-a-Kainic acid .. ... . ... . ... . . . . . . . ... .. . ... . ..... ...... . . .. 251 dL-a-Allokainic acid ... . ... . . . . . . . ... .. . ... ..... . .... .. .. .. 237 dDomoic acid ................................................ 217 dL-5-Hydroxypipecolic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235 d~-trans-4-Hydroxypipecolic acid . , . . . . . . . . , . , . . . . . . . . 294 dL-ay-Diaminobutyric acid dihydrochloride . . . . . . . . . 197-198L-ap-Diaminopropionic acid monohydrochloride . . . 237 dalbizziine . . . . . . . . . . . . . . . . , , . . . . . . . . . . . . . . . . . . . . . . , . . . . , . . . . . 2 17 d6-Acetylornithine . . . . . . . . . . . , . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . 266 dy-Hydroxyarginine monohydrochloride . . . . . . . . . . . . 190-191 d/3-(2,4-Dihydroxy-6-methylphenyl)alanine . . . . . . . . . 252 dStizolobic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231-233j?-Pyrazol-l-ylalanine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236-238 d~-fl-Uracil-3-ylalanine . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . 204-205 dy-Hydroxyvaline .......................................... 228/3-Aminoisobutyric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183S-Methyl-L-cysteine . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , 169-1 70S-Methyl-L-cysteine sulphoxide . . . . . . . . . . . . . . . . . . . . . . . . 220 dy-Glutamyl-S-methyl-L-cysteine . . . . . . . . . . . . . . . . . . . . . 165-173 dS-2-Carboxyethyl-~-cysteine . . . . . . , . . . . . . . . . . . . . . . . . . , . 2 18 d215" dL-threo-fl-Methylaspartic acid . . , . . . . . . . . . . . .. . . . , , .. . . . , -O-Acetylhomoserine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -Cycloalliin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -[.ID inH2O- 10"- 12- 15+8 - 109.6-23.1- 13.1---+ 13.3 -- 67 + 13.1 ---- 73+ 10- 13- 26 + 125- 21----fa]^ in HC1(normality inparentheses)Approx.in phenol-H'ZO3-13.3" (5N)3-59 ( 1 . 5 ~ )-1-3 (5N)+14 (3N) ---9 (N) -0*0.82(+)0.33(-)0.31(-)0.43(0-0.86(+)0-0.80(-)0.56(0.16(-)0*0.69(0.82(-)0.710.62(0*0.35(@* bl. p.'s associated with decomposition are indicated as d. t Phenol-H,O mixtures normally contain 75--80% (w/w) of phenol.$ Composition of solvent mixture used varies slightly between different laboratories,+ or - in parentheses indicatesabsence of NH, respectively.Colour symbols: Y, yellow; Br, brown; R, red; V, violet; B, blue; P, purple; G, green372 BIOLOGICAL CHEMISTRY.form of alliin, S-allyl-L-cysteine sulphoxide, obtained earlier from garlic(AZZium s a t i ~ u m ) . ~ ~ Cycloalliin was synthesised by the following stages : 95L-cysteine, S-allyl-L-cysteine, S-2-bromopropyl-L-cysteine, 5-methyl-1,4-thiazan-3-carboxylic acid (VIII) (by ring closure involving elimination ofhydrogen bromide in pyridine) , cycloalliin [formed from (VIII) by treatmentwith hydrogen peroxide]. Cycloalliin was decomposed by refluxing it withG~-hydrochloric acid, and oxidised and reduced products were obtained(see formulae).SO3H SO3HI II IQ I 1H2C/Sx7H2 + CHI + CHIN H26N-IH2C s, CH 2I INMe-CH C HsC02H Me-HC, ,CH.C02H HC' Me*HC ,N,CH.C02HH H NH2(VII1) g - M e t h y l - Cysteictaurine a c i dThe biosynthesis of cycloalliin may proceed by hydration of alliin toyield S-2-hydroxypropyl-~-cysteine sulphoxide ; then elimination of waterfrom the hydroxyl and a-amino-groups may cause ring closure.Summary of Properties.-The Table annexed lists some of the physicalproperties of amino- and imino-acids isolated recently. Unfortunately,complete data are frequently not published, sometimes owing to lack ofmaterial. To the biologist, RF values are often more useful than m. p.'s anddata are given here for two commonly used solvents. Differences in theexperimental procedures used in various laboratories cause minor variationsin these values, and, in order to minimise these variations, RF values obtainedwith butan-l-ol-acetic acid-water mixtures are based upon that of alanine(Ralsnine). The colour produced from each amino-acid spot on paperchromatograms treated with ninhydrin is somewhat variable; as far aspossible those given in the Table are quoted from the original literature.L. F.L. FOWDEN.J. GLOVER.T. W. GOODWIN.R. L. HARTLES.S, V. PERRY.96 A. Stoll and E. Seebeck, Experientia, 1947, 3, 114

ISSN:0365-6217    

DOI:10.1039/AR9595600322

出版商:RSC    

年代:1959

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY1. INTRODUCTIONONCE again it has to be said that this Report is in the main concerned withoriginal papers rather than abstracts. The division into sections is on thesame general lines as last year and, as before, we have tended to mentioninorganic applications first followed by organic applications. In preparingthis Report we have, of course, noted certain matters which appear to us tomerit special attention. Repeatedly, in analytical work, and particularlyin titrimetry, we note a tendency to carry out chemical operations auto-matically and to make instrumental recordings of the results. There arecertain dangers that must, however, be watched. The chemical procedureson which the tests are based must be thoroughly sound, because if record-ings are made based on uncertain chemical operations, then many of thegreat advantages of these procedures will be lost.There seem to be a large number of papers appearing on non-aqueoustitrimetry and this field has expanded to include potentiometric and coulo-metric methods as well as conventional volumetric procedures.The numberof publications on gas chromatographic and particularly gas-liquid chromato-graphic methods continues to increase, and there are welcome signs that thisprocedure is finding application in many industries, other than the petroleumindustry, which has borne the brunt of the development work. In workon the micro-scale the oxygen-flask combustion method is being used to anincreasing extent in the preliminary opening up of organic substances.Thefact that only oxygen is used in the combustion process along with simpleabsorbents makes the procedure clean and acceptable in a large number ofcases.Analytical chemists who wish, on occasion, to read reviews on particularaspects of their work will find it worth while to follow the articles which areappearing in The Analyst at two-monthly intervals. These articles arewritten critically, and during the past year have included reviews on suchdiverse topics as the Analysis of Synthetic Detergents, The Infra-red Analysisof Solid Substances, X-Ray Fluorescence Analysis, Ferrous MetallurgicalAnalysis, and Gas Chromatography and its applications.Finally, we draw the attention of analytical chemists to the address ofthe retiring president of the Society for Analytical Chemistry, Dr.J. H.Hamence. In this address (Analyst, 1959, 84, 271), he describes in detailsome of the important events and developments which have taken place inthe Society over the past two or three years. Moreover, the address in-cludes some most interesting philosophical observations on the future ofanalytic a1 chemistry 374 ANALYTICAL CHEMISTRY.2. GENERALACCURACY, a subject of prime interest to all analysts, has been speciallystudied by Bishop,l who has recorded the conclusions reached after hiscritical re-examination and assessment of the mechanical precision intitrimetric procedures. He has paid particular attention to such matters asdrainage errors in burettes, and suggests that the pipette-dilution methodoffers some improvement in the precision of volumetric methods. Anyfurther increase in mechanical precision, it is said, affords little or no im-provement in the accuracy of determination owing to problems of end-pointdiscrimination and limits in the purity of normal reagents.In a secondpaper the same author describes his findings on weight titrimetric analysis,using a form of needle-valve weight burette. Even under most favourableconditions there appears to be a limit to the accuracy of the analyticalresults, which is governed by physicochemical considerations and is at leastone power of 10 less than the maximum attainable mechanical precision ofmeasurement .Electrodes sensitive to specific elements are a great help in many ana-lytical problems.Bower has described the results obtained with an experi-mental sodium aluminosilicate glass electrode manufactured by BeckmanInstruments Inc. The electrode was insensitive to calcium and magnesiumbut sensitive to sodium, potassium, and hydrogen ions, giving theoreticalrelationships between E.M.F. and cationic activity. The author alsodescribes a procedure using the electrode for the determination of sodiumin waters. The water sample is diluted if necessary, the pH adjusted to 7,and any potassium precipitated as the tetraphenylboron derivative, beforemaking the E.M.F. measurements.On the use of high-frequency measurements in analysis, the work ofWeber and Cruse 4 indicates that such measurements are of particular valuein the registration of phase changes and hence in the plotting of phasediagrams.They illustrate this by observations on the systems tin-zinc,lead-tin, and bismuth-antimony. Another topic of general interest hasbeen discussed by Fischer et a2.,6 who have shown that variations in thephysical form of precipitates can be tolerated better in turbidimetrk titra-tions than in turbidimetric determinations involving comparison of turbidi-ties with standards. They find that the addition of a non-ionic surface-active reagent enhances nucleation at the expense of crystal growth in some,but not in all, precipitation reactions.Bagshawe 6 has contributed an excellent review on the determinationof about 25 elements in steel. These elements may be added intentionallyas alloying constituents or be present inherently as native impurities.Thereview is written critically and with a nice sense of balance. It should beread by analysts not directly concerned with the steel industry because it1 E. Bishop, Analyt. Chim. Acta, 1959, 20, 315.2 E. Bishop, Analyt. Chim. Acta, 1959, 20, 405.a C. A. Bower, Proc. Soil Sci. SOC. Amer., 1959, 23, 29.4 Th. Weber and K. Cruse, 2. analyt. Cham., 1959, 166, 333.6 R. B. Fischer, M. L. Yates, and M. B. Batts, Analyt. Chim. Acta, 1959, 20, 501.B. Bagshawe, Analyst, 1959, 84, 475HASLAM AND SQUIRRELL: GENERAL. 375contains a great deal of useful information which the author has been ableto sift very carefully as an active member of the B.I.S.R.A. Methods ofAnalysis Committee.Solvent extraction methods for the determination ofmetals are becoming more numerous. Khorasani and Khundar' havedeveloped a procedure for the rapid determination of antimony in theantimonates of lead, tin, mercury, nickel, and chromium. The method isbased on the selective extraction of antimony@) from a hydrochloric acidsolution with ethyl acetate. The antimony in the extract is determinediodometrically. Iron(m), cobalt(zI), cadmium(II), and large amounts ofcopper and tin interfere with the extraction. Jantik and Korbl,* however,have described a new extraction method for the separation of copper. Thecopper is converted into its complex pyridino-bromide or -iodide and is thenextracted with chloroform before determination by a complexometricprocedure.The interference of zinc can be masked by the addition ofiminodiacetic acid but this procedure fails in the case of cadmium andmercury.Ehrlich and ICeil have developed a useful method for the determinationcf small amounts of silica in oxides such as TiO,, Al,O,, V,O,, and ZrO, andin certain metallic salts such as ferric salts. In the presence of hydrofluoricand sulphuric acid and in a silver flask the silicon is volatilised as hexa-fluorosilicic acid, the distillate being collected in a polythene receiver. Thesilica in the distillate is determined by a procedure involving stannouschloride reduction of silicomolybdate. For the rapid determination ofchloride in silica and other solids, Robinson lo prefers to heat the sample ina combustion tube with sulphuric-nitric acid in a stream of nitrogen.Thechloride evolved is collected in a sodium carbonate or a de-ionised waterscrubber and may then be determined by potentiometric titration or by acolorimetric procedure if the amount is very small. Advantages of themethod are that, when required, up to 1.5 g. of sample can be used and ananalysis can be completed in 20 minutes.Hoffmann l1 has put forward a very ingenious method for the determin-ation of traces of sulphide in paint films. The film is treated with sodiumazide and iodine solution, a control on the same reagents being run alongside.Owing to the catalytic effect of sulphide on the iodine-azide reaction, nitrogenis produced with a paint film containing sulphide.The experiments areconducted in such a way that this difference between sample and controlsides, i.e., due to nitrogen, exerts a pressure which can be measured. A mostuseful method l2 for the determination of small amounts of organically boundsulphur in non-olefinic hydrocarbons has also been worked out. Thesulphur compound is reduced to nickel sulphide with Raney nickel and afteracidification the liberated hydrogen sulphide is absorbed in a mixture ofsodium hydroxide solution and acetone before titration with standardmercuric acetate solution, dithizone being used as indicator. An analysisS. S. M. A. Khorasani and M. H. Khundar, Analyt. Chim. Acta, 1959, 21, 24.F. JanCik and J. Korbl, Talanta, 1958, 1, 55.P. Ehrlich and Th.Keil, 2. analyt. Chem., 1959, 166, 254.lo J. W, Robinson, Analyt. Chim. A d a , 1959, 20, 256.l1 E. Hoffmann, 2. arzalyt. Chem., 1959, 166, 168.l 2 T,. Granatelli, Ana.lj*t. Chern., 1959, 31, 434376 ANALYTICAL CHEMISTRY.takes less than 16 hours and good accuracy is obtained for as little as 5 y ofsulphur. As much as 50 g. of sample can be used.F. L. Hahn l3 has developed an ingenious method for the rapid deter-mination of carbonates. The sample is contained in a flask under reducedpressure, and strong acid is added, carbon dioxide being evolved from thesample. Momentary equilibration with the external atmosphere is nowmade so that the pressure within the flask is atmospheric. Sodium hydr-oxide solution is now allowed to flow into the flask, and this proceeds untilequilibrium between the external atmosphere and that in the flask is re-established.The volume of sodium hydroxide solution sucked into theflask is equivalent to the volume of carbon dioxide evolved from the sample.The Metal Impurities Sub-committee of the Analytical Methods Com-mittee of the Society for Analytical Chemistry has carried out a consider-able amount of work on various methods of destruction of organic matterbefore determination of trace elements. This sub-committee has publisheda very useful note l4 on perchloric acid and its handling in analytical work;this acid is used in appreciable quantities in wet digestion procedures. Thenote draws attention to the properties, uses, storage, and handling of theacid as well as the dangers which may occur in wood fume cupboards ifperchloric acid is in regular use in such surroundings.The determination of materials present in the air of chemical plants andin the atmosphere in general is of ever-increasing importance, and severalpapers on this subject have been published throughout the year.Gage,15for example, has described an indicator tube method for the determinationof trichloroethylene vapour in air. The sample of air is drawn through twotubes which are joined in series immediately before test. The first tubecontains silica gel impregnated with potassium permanganate and ortho-phosphoric acid. The second tube contains silica gel impregnated witho-tolidine hydrochloride and serves to measure the chlorine liberated in thefirst tube.Detector tubes have many advantages but, unfortunately, thereagent systems employed are not always extremely stable. Grosskopf l6has overcome some of these difficulties, e.g., in the determination of form-aldehyde. He provides a tube in which the carrier material is impregnatedwith sulphuric acid. Just before the test is commenced an ampoule con-taining a solid solution of a xylene isomer in paraffin is broken above thecarrier material. The air under test is drawn through the detector tube,carrying with it the xylene and any formaldehyde to the sulphuric acid.Under these conditions, reaction is instantaneous, and a red colour is obtainedproportionate to the formaldehyde concentration, In the determination ofozone in the air of rooms, it seems desirable to carry out the test by passingthe air at a definite rate through a solution of potassium iodide containingaluminium chloride and ammonium chloride a t pH 4-4.The flasks usedmust be blackened and great care must be taken over the purity of thedistilled water used. In this test, due to Hunold and Pietrulla,17 the blankl3 F. L. Hahn, Z. analyt. Chem., 1969, 166, 243.l4 Analyst, 1959, 84, 214.16 J . C. Gage, Analyst, 1959, 84, 609.l6 H. Grosskopf, 2. analyt. Chem., 1959, 170, 271.1' G. A. Hunold and MT. Pietrulla, Z. analyt. Chem., 1959, 165, 20HASLAM ANL, SQUIRKELL: GENERAL. 377is very important and is apparently best determined by passage of a knownvolume of air, freed from ozone by passage over Hopcalite, through a similarpotassium iodide solution to that described above.Included in the papers of general interest in organic analysis is that ofAdey and Cox18 who have put forward a method for the determination ofup to 2% of a-picoline in pyridine on the assumption that the impurities inthe pyridine are a-picoline and water. A definite weight of the pyridinesample under test is added to a precise amount of a 20% (w/w) solution ofpotassium chloride.The clear mixture is heated until the lower solutiontemperature is reached as indicated by the appearance of turbidity. Underthe conditions used, pure pyridine gives a solution temperature of 27.0".A mixture of 1% (w/w) a-picoline and 99.0% (w/w) pyridine gives a solutiontemperature of 26.3".Macdonald's work19 has led to the production of a neutral reagent forthe determination of fat in milk and milk products.The reagent containstrisodium citrate, sodium salicylate, and disodium ethylenediaminetetra-acetate which dissolve the solids other than fat, a polyoxyethylene derivativeof sorbitol trioleate and alcohol which assists in the fat separation, and a smallamount of butyl alcohol which ensures that the results are the same as bythe conventional Gerber procedure.Mixtures of sulphanes and sulphur have been analysed by Schmidt andTalsky.20 The sulphanes are determined by estimation of the hydrogensulphide produced by attack on this mixture with excess of cyanide, whilstthe sulphur is found by difference between the thiocyanate produced byhomogeneous and heterogeneous cyanide reaction on the mixture.In thedetermination of nitrogen in organic compounds by the Kjeldahl method,Schulek et aLZ1 make out a strong case for the collection of ammonia, distilledfrom Kjeldahl digestion products, in cold boiled-out water rather than inacid.An official method is available in this country for the determination ofalkylbenzene sulphates in river waters and sewage. It is believed, however,that various organic substances present in natural waters are liable tointerfere with the official test. Webster and Halliday22 have sought toovercome these difficulties in a procedure in which the sample is first sub-jected to acid hydrolysis. A definite process is then employed for theisolation of the detergent-l-methylheptylamine complex from the neutralisedhydrolysate.The final Methylene Blue test is carried out by the principleof the official method.The analysis of rubbers and elastomers containing acrylonitrile copoly-merised with styrene and vinylpyridines is becoming an important task inthe plastics and rubber industries. Three important papers on this subjecthave appeared in Analytical Chemistry this year. The first 23 describes thedetermination of residual acrylonitrile monomer in acrylonitrile-styreneI<. A. Adey and J. D. Cox, Analyst, 1959, 84, 414:l9 F. J. Macdonald, Analyst, 1959, 84, 287.2o M. Schmidt and G. Talsky, 2. anaZyt. Ckem., 1959, 166, 274.21 E. Schulek, K. Burger, and M. Feher, 2. analyt. Chem., 1959, 167, 28.22 H.L. Webster and J. Halliday, AnaZyst, 1959, 84, 562.28 G. Claver and M. E. Murphy, Analyt. Chem., 1959, 31, 1682378 ANALYTICAL CHEMISTRY.copolymers. The sample is dissolved in NN’-dimethylforniamide, and thefree acrylonitrile determined by a direct polarographic test after the additionof tetrabutylammonium iodide electrolyte. The presence of styrenemonomer does not affect the test. Burleigh, McKinney, and Barker 24are concerned with the determination of vinylpyridine, acrylonitrile, andacrylic acid in elastomeric polymers. By use of a selected Kjeldahl catalystcontaining potassium sulphate, selenium, mercury, and mercuric oxide anda long digestion time they are able to determine the nitrogen due to bothpyridyl and nitrile groups, with considerable accuracy, The basic nitrogenis determined by titration with perchloric acid in non-aqueous media, andacrylic acid is titrated with sodium methoxide solution also in non-aqueousmedia.The authors give useful information on the choice of solvents forboth sample and titrant for use in the non-aqueous titration methods.The analysis of acrylonitrile-methylvinyipyridine copolymers has beenapproached from rather a different angle by Stafford and T ~ r e n . ~ ~ Thenitrile is hydrolysed by boiling with concentrated sulphuric acid, and theammonia from the salts so produced distilled from the solution after theaddition of alkali by the conventional Kjeldahl procedure. The pyridine isconveniently determined by ultraviolet spec trophotome tric measurementsmade on a sulphuric acid solution of the sample after sufficient hydrolysisto solubilise the polymer.Fischer’s reagent for the determination of water may readily be preparedwater-free and of good stability by a simple process due to Eberius andBohnes.26 Methanol and pyridine, which may each contain up to 0.2% ofwater are first mixed, then sulphur dioxide is added, followed by a smallamount of iodine.Liquid bromine is nowadded until the mixture shows the presence of free bromine by its browncolour. Under these conditions the preparation is free from water andappropriate amounts of iodine and sulphur dioxide are now added to com-plete the final preparation of the reagent. The process is just as effectivewhen ‘‘ methyl cellosolve ” is substituted for the methanol.Also on thesubject of water determination, Jordan and Fischer 27 make some interest-ing observations on two methods of determination of the water content ofacetone. The first method, which they modify, depends on the reactionbetween the water in the acetone and acetyl chloride, in pyridine; the acidproduced is titrated. In their second method, a mixture of the acetonewith an equal volume of petroleum is heated and the clearing temperatureis observed. This temperature depends on the water content of the acetone.Interesting observations are made on the drying of acetone and on thehygroscopic character of dry acetone.Acetyl determinations in organic compounds are usually carried out byhydrolysis with alkali, followed by addition of sulphuric or phosphoric acidand subsequent steam-distillation of the acetic acid produced.To speed upthe test it is necessary to keep the volume low, and, in the past, it has beenPyridinium iodide is produced.24 J. E. Burleigh, 0. F. McIGnney, and M. G. Barker, Analyt. Chenz., 1959, 31, 1684.25 C. Stafford and P. E. Toren, Analyt. Chem., 1959, 31, 1687.2* E. Eberius and H. Bohnes, 2. analyt. Chem.. 1959, 168, 330.27 I<. Jordan and W. R. Fischer, %. atzalyt. Clzem., 1959, 168, 182HASLAM AND SQUIRHELL: GENERAL. 379necessary to make small batchwise additions of water in the steam-distill-ation process. Kainz 2* has now put this part of the test on an automaticbasis, as a result of which much time is saved.Motor-driven syringe burettes have been commonly incorporated inautomatic titration equipment and recording apparatus has also beenwidely used.Miller and Thomason29 have developed a method for theautomatic thermometric titration of free acids in aqueous solutions of suchmetal ions as zirconium, uranium, copper, and thorium. The free acid,which may be hydrofluoric, sulphuric, or nitric acid, is determined by titra-tion with a standard base, delivered from a motor-driven syringe andrecording of the change in temperature as detected by a thermistor duringthe titration. The end-point of the titration is obtained by extrapolationof the straight-line portions of the curves to their point of intersection. Bythis method milliequivalent quantities of free acid can be determined withreasonable accuracy.Williams and his co-workers 30 have designed a simple and highly accuraterecording titration apparatus for the automatic titration a t constant pH ofthe acidic or basic compounds liberated by the reaction of hydrolysis enzymes.The titrant, to maintain constant pH, is delivered from a micrometer syringedriven by a servo-motor which simultaneously operates the pen of therecorder along one axis.The pen carriage is moved along the other axis atconstant speed which can be varied by use of a five-speed gear box.A simple automatic apparatus has been described by Haslani andSquirrell 31 for recording full-scale potentiometric titration curves. Theapparatus combines three pieces of commercially available equipment whicha t any time can be used independently.These consist of a constant-speedinjection apparatus driving a hypodermic syringe to deliver titrant a t adefinite rate, a pH meter for indicating pH or E.M.F. change produced bythe addition of titrant, and a recorder for registration of the output fromthe pH meter. The apparatus has great versatility in speed of injection andin sensitivity control; examples are given of its use in conventional potentio-metric titrations.Thoburn and his co-workers 32 have described an automatic colorimetrictitrimeter. The titration is monitored by a light beam passing through theglass titration beaker and falling on a photo-cell. A series of 8 filters coversthe entire visible range and can be selected for use with individual indicators,At the end-point the sharp change in transmittance, recorded by the photo-cell, causes a meter relay to operate, which in turn stops delivery of titrantfrom a motor-driven syringe.An automatic counting device on the syringedrive-motor records the titration in terms of counts which can be calibratedfor each syringe. In general the delivery rate is of the order of 2-4 ml. perminute with 288 counts per ml.Calcium and magnesium have been determined by Malmstadt and28 G. Kainz, 2. analyt. Chenz., 1959, 166, 32.2D F. J. Miller and P. F. Thomason, Analyt. Chem., 1959, 31, 1498.30 R. C. Williams, R. S. Ruffin, and L. A. Mounter, Analyt. Chem., 1959, 31, 611.31 J . Haslam and D. C. M. Squirrell, J . AppZ. Chem., 1959, 9, 65.32 J.M. Thoburn, C. M. Jankowski, and M. S. Reynolds, Analyt. Chem., 1959, 31,12438 0 ANALYTICAL CHEMISTRY.Hadjiioannou= in dolomites and limetones by using a direct automaticderivative spectrophotometric titration procedure with EDTA as titrant.Calcium is automatically titrated at pH 13 with Calcon as indicator, andthe total calcium plus magnesium are titrated at pH 10 by using EriochromeBlack T as indicator; the normal and second derivative spectrophotometrictitration curves can be recorded, and the titration automatically terminatedat the end-point. A 650 mp filter is used for both indicators.Matthews and Patchan% have developed a method for the automatictitration of peroxides in petroleum products. The sample is treated withpotassium iodide, and the iodine liberated titrated with standard sodiumthiosulphate solution automatically.The method is also applicable tohydroperoxides and diacyl-type peroxides. An advantage of the method isthat the iodine liberated is immediately and continuously reduced as it isformed back to iodide by the addition of the standard thiosulphate. Theiodine concentration is rarely allowed to exceed a very small value and thenonly momentarily.The coulometric principle has been applied to the determination of waterby the Karl Fischer method. Meyer and Boyd35 have determined thewater content of organic solvents containing as little as 5 y per ml., usingtheir apparatus which utilises electrically generated iodine in a solution ofdepleted Karl Fischer reagent in ethylene glycol.Kelley and his co-workers 36 have described an automatic cut-off attachment for the pHindicator unit so that it can be used to control this titration automatically.This control unit can also be used to control other pH, millivolt, or dead-stop titrations.A new continuous chloride-ion analyser has been described by Jones aridKehoe 37 which is easy to standardise and which has applications in qualitycontrol and for monitoring the chloride-ion concentration in industrialwastes. The principle is very similar to that for pH measurement, a con-ventional reference electrode being used in conjunction with a specialsensing electrode, basically silver-silver chloride. The potential developedat the sensing electrode depends directly on the concentration of chlorideions in the solution in which the electrodes are immersed, and this potentialdifference is amplified and recorded.For the automatic and continuousdetermination of uranium in a radioactive process stream, an automaticplant-type polarograph 38 has been designed, The uranium(v1) is reducedto uranium(v) at a dropping mercury electrode in a nitric acid electrolyte,and the resultant polarograni recorded every 74 minutes. A manuallyoperated feed for the standardisation solution is incorporated in the design.This minimises interfering side reactions.33 H. V. Malmstadt and T. P. Hadjiioannou, Analyt. Chim. Acta, 1958, 19, 563.34 J. S. Matthews and J. F. Patchan, Analyt. Chem., 1959, 31, 1003.35 A.S. Meyer, jun., and C. M. Boyd, Analyt. Chern., 1959, 31, 215.36 M. T. Kelley, R. W. Stelzner, W. R. Laing, and D. J. Fischer, Analyt. Chem.,57 R. H. Jones and T. J, Kehoe, I n d . Eng. Chem., 1959, 51, 731.313 G. J. Alkire, K. Koyama, K. J. Hahn, and C . E. Michelson, Analyt. Chern., 1958,1959, 31, 220.30, 1912IIASLAM AND SQUIRKELL QUALITATIVE AND QUANTITATIVE. 38 13. QUALITATIVE AND QUANTITATIVE INORGANIC AND ORGA NICQualitative.-Many new qualitative tests have been devised during theyear and a remarkable feature has been the extremely simple nature of thetests, no doubt facilitated by the introduction of new reagents. For example,Clark et aZ.S9 have extended the field of usefulness of zinc dithiol by devisingmany simple tests for the field testing of innumerable ores and minerals.Usually a solution of part of the ore is first prepared from a few fragments ofthe ore, and zinc dithiol or a solution of dithiol freed from zinc is applied,under particular conditions, to test portions of the solution.The coloursand reactions obtained are often quite revealing. Very few reagents havebeen proposed which are specific for iron(I1). It is suggested, however,4Othat if the test solution is maintained in a special Thunberg tube which canbe evacuated before addition to cacotheline reagent, then the blue colourobtained is quite stable a t pH 7.4 and, moreover, it is said to be specific foriron(r1).At the 1958 Microchemistry Symposium held in Birmingham, a new testfor fluoride was demonstrated. It is this test which forms the basis of anew spot test for the fluoride ion 41 which, it is claimed, is the only reactionof the fluoride ion responsible for the production of a new coloured species.In this test, in an acetate buffer, the fluoride ion produces a lilac blue doublecomplex with a red cerium ( ~ v ) alizarin-complexone complex.Weisz et aZ.,42 in their ring-oven procedure, have often made use ofsulphides in determinations of separated metals.The metal is precipitatedin the paper as its sulphide, then converted into the appropriate amount ofsilver sulphide by treatment with silver nitrate, etc. In estimating theamount of silver sulphide and hence of the metal in question, only one scaleis used, i.e., the silver sulphide scale prepared by application of the test toknown amounts of copper; calibration factors for use with other elementsare available in terms of the equivalent amount of copper.As a further aidin the use of the ring-oven method, Ballezo 43 has developed a simplifiedform of the oven in which the filter-paper, on which the various analyticalseparations are carried out, is mounted on a glass plate, held at a particulartemperature by the vapour of a boiling solvent in contact with it.In the organic field, a useful method44 has been developed for theidentification of the n-alkyl groups present as side chains in alicyclic andaromatic hydrocarbons, i.e., in such substances as alkylcyclohexenes, alkyl-benzenes, and alkylcyclohexanes. The side chain is split by the oxidativeaction of a definite chromic acid-sulphuric acid mixture.The resultingacids are distilled in steam, converted into their corresponding ethyl-ammonium salts, then separated and identified by paper-chromatographicANALYSIS39 R. E. D. Clark and C. E. Tamale-Ssali, Analyst, 1959, 84, 16.40 G. G. Rao, V. N. Rao, and G. Somidevamma, 2. analyt. Chem., 1959, 166, 11.41 R. Belcher, PI. A. Leonard, and T. S. West, Talunta, 1959, 2, 92.42 H. Weisz, M. B. Cklap, and V. V. Almatan, Mikyochim. Acta, 1969, 36.43 H. Ballezo, Mikrochzm. Acta, 1959, 314.44 M. JureCek, hf. SouCek, J. ChurACek, and F. Renger, 2. analyt. Chem., 1959, 65,109382 ANALYlICAL CHEMISTRY.test. It would appear, from the work of Tisler,46 that 9-chlorobenzoylisothiocyanate has outstanding advantages as a reagent for the character-isation of aromatic and aliphatic primary and secondary amines.Reactionusually takes place in the cold and the solid products, i.e., substitutedthioureas are usually very easily crystallised.A reaction given by aliphatic and aromatic polycarboxylic acids, aryl-allryl carboxylic acids, and aromatic monocarboxylic acids which can beused for the qualitative detection of these compounds in the presence ofother carboxylic acids and sulphonic acids has been detailed by Feigl andStark-Ma~er.~~ The acids when heated at 160" with alkali or ammoniumhalides yield halogen hydracids which can be detected with indicator paperor by the demasking of silver ferrocyanide. o-Nitrophenol also gives thisreaction and hence the test is useful for distinguishing this compound fromits isomers.Instead of using an interfacial test, Turney4' claims to haveextended the general utility of the Molisch carbohydrate test by adding adefinite weight of the substance under test to a definite weight of l-naphthol,then adding sulphuric acid and mixing immediately.Advantage has been taken of the condensation reaction between aliphaticketones containing the structure R*CH,-CO*CH,R' and 2-hydroxy-l-naphthaldehyde in a method due to Sawicki and Stanley@ for the colori-metric detection of small amounts of such ketones. The reaction is carriedout under special conditions in the presence of aluminium chloride with2-methoxyethanol as the reaction medium.It is the exothermic reactionbetween the 2-methoxyethanol and the reagent powder containing thealuminium chloride that provides the heat necessary for colour development.The test appears extremely simple to carry out, and a positive blue colourA,, 598 mp) can be obtained with amounts of ketone as low as 1-5 y in0.5 ml. of 2-methoxyethanol solvent.Feigl and Jungreis49 have utilised work previously carried out by Duffto develop new spot tests for phenols and dialkylanilines. The phenol isheated with a mixture of oxalic acid and hexamine; fonnylation takes place'and an o-hydroxyaldehyde is produced. This is detected by its reactionwith hydrazine to yield a fluorescent aldazine. The alkylated aniline istreated initially in the same way as the phenol with the production of a9-dialkylaminobenzaldehyde or a 9-monoalkylaminobenzaldehyde.Thisreaction product is detected by the formation of an orange-coloured Schiff'sbase with benzidine. Another useful test has been described by Pesez andBartos 5O for m-biphenols. These compounds form a red complex in highlyacid alcoholic media with diphenylacraldehyde. The sensitivity of the test issuch that 1 pg. of biphenol can be detected in 5 ml. of final coloured solution.Reaction also takes place with compounds having a methylene group inthe a-position to a carboxyl and with primary aromatic amines; in thesecases the reaction products are yellow.45 M. Tisler, 2. analyt. Chem., 1959, 165, 272.46 F. Feigl and C. Stark-Mayer, Talanta, 1958, 1, 252.47 T.A. Turney, Analyst, 1959, 84, 194.48 E. SaN-icki and T. W. Stanley, Analyt. Chem., 1958, 31, 122.49 F. Feigl and E. Jungreis, Analyst, 1958, 83, 666.60 M. Pesez and J. Bartos, Analyt. Chim. ,4cta, 1959, 20, 187TIASLA4M AND SQUIRREtL QUALITATIVE AND QUANTITATIVE. 383Knight and House 51 have tackled the complex problem of characteris-ing or analysing surface-active agents by a novel procedure. They preferto decompose the sample with phosphoric acid and examine the non-surface-active hydrophobic oil so produced. This examination involves gas-liquidchromatography and infrared spectroscopy. Aromatic, sulphonated,straight-chain alkyl sulphates, amides, and esters are decomposed to givegood yields of the parent hydrophobic materials. Dioctyl sulphosuccinategives a mixture of octyl alcohols and olefins and ethylene oxide; alcoholcondensates give olefins derived from the starting hydrophobic materials.Much other useful information on the classification of surface-active agentsby qualitative tests is given in the previously mentioned review by Smith.52Amin 53 has used the p$’-nitrophenylazobenzoyl derivative for the char-acterisation of thiols.He has prepared the derivatives of some nine thiolsin reasonable yield and found that they crystallise well and have well-definedmelting points. The derivatives can also be separated chromatographicallywhich is of great advantage when mixtures of thiols have to be characterised.Quantitative (Gravimetric).-A rapid gravimetric method for the deter-mination of aluminium in titanium and other alloys which is applicablewithout preliminary separation from such elements as manganese, vanadium,tin, chromium, iron, etc., has been described by Pender.54 The sample isdissolved in dilute hydrofluoric acid and oxidised with hydrogen peroxidebefore precipitation of the aluminium as sodium fluoroaluminate by additionof sodium fluoride.This salt is isolated, reprecipitated, washed, and driedunder specified conditions. The method requires only half the time neededby other methods and gives results comparable with those obtained by the8-hydroxyquinoline method. Ziegler and Horn% have shown that, at anappropriate pH value, molybdate may be separated from vanadate byextraction of the tributylammonium molybdenum thioglycollate complexof the molybdenum with methylene chloride as solvent.The methylenechloride extract is wet-digested, and the molybdenum finally determined aslead molybdate.2-Aminopicolinic acid, prepared by oxidation of 8--hydroxyquinoline,appears to be a very selective reagent for the precipitation of palladium.56This element is precipitated quantitatively over the pH range from normalwith respect to hydrochloric acid, to pH 12.5. It is possible to precipitatepalladium free from most of the common ions and the interference of coppermay be avoided by the use of EDTA, and that of silver by working at apH of 7 or above. After precipitation, the determination may be completedby solution of the palladium-containing precipitate in excess of potassiumcyanide solution and back titration of the excess cyanide with standardsilver solution.An interesting separation of silver from lead has beenproposed by Ziegler ef aL5’ The solution, at an appropriate pH, is treated51 J. D. Knightand R. House, J . Amer. Oil Cliemists’ SOL, 1959, 36, 195.53 W. B. Smith, Analyst, 1959, 84, 7 7 .F , ~ El S. Amin, J., 1958, 4769.54 H. W. Pender, Analyt. Cltem., 1959, 31, 1107.55 M. Ziegler and H. G. Horn, 2. analyt. Chem., 1959, 166, 362.56 A. I<. Majumdar and S. P. Bag, %. analyt. Chem., 1958, 164, 394.57 hf. Ziegler, H. Sbrzesny, and 0. Glemser, 2. nncrlyt. Chem., 1969, 167, 96384 ANALYTICAL CHEMISTRY.with isopropenylacetylene, silver isopropenylacetylide being produced.This substance is extracted with methylene chloride.On treatment of thesolvent layer with hydrochloric acid solution the silver is converted intochloride and is finally weighed as such. Miller and Thaw 58 have establishedconditions for the quantitative determination of tungsten. These involvethe addition of orthophosphate to the tungstate solution, after which theacidity is adjusted by the addition of hydrochloric acid. Tri-n-butyl-ammonium chloride is used as precipitant, and the precipitate of tris-tri-n-butylammonium 12-tungstophosphate is recovered, washed, and dried at 210".m-Ethylphenoxyacetic acid is understood to be a very selective reagentfor the determination of zirconium.59 The precipitation suffers no interfer-ence from most cations and even chromium and vanadium can be removedby reprecipitation.The precipitate is of variable composition and containsboth the mono- and the semi-hydrate of rn-Et~C,H,~O~CH,~CO~O.ZrO(OH).Hence the determination must be completed by ignition of the precipitateto zirconium dioxide.In a method which appears satisfactory for use in a plant-control labor-atory, Lysyj and his co-workers 6o determine carbon monoxide by a gravi-metric procedure. They prefer to convert the monoxide into the dioxideby passage over thermally decomposed silver permanganate as catalyst ; thedioxide thus formed is absorbed in a weighed Ascarite tube. Carbon mon-oxide concentrations between 0.1 and 1.5% (vlv) can be determined whenusing only 500 ml. of gas sample.Quantitative (Volumetric) .-Of the large number of conventional volu-metric methods described in 1959 we are able to mention but a few.Acompound called Siloxen,G1 which is readily prepared by the action of hydro-chloric acid on calcium silicide, has proved to be a chemiluminescent end-point indicator of considerable value in redox titrations where the colour ofthe solution or the reaction products causes difficulties in the titration. Itis particularly useful in the direct permanganornetric titration of iodides,ferrous iron, stannous, molybdenum(IrI), arsenite, and oxalate ions andhydrogen peroxide. It may also be used in the indirect permanganometrictitration of iodates, silver and vanadium(v) ions. Improved indicators forEDTA titrations are still being produced, and Omega Chrome Fast Blue 2G 62is now proposed for the direct titration of calcium, magnesium, manganese,and nickel and for the direct displacement titration of lead and cadmium.I t is suggested that improvements in cerrain EDTA spot tests may beeffected by the addition of fenugreek mucilage, a colourless polysaccharide.Yalman and his co-workers63 prefer to use an indirect method for thedetermination of calcium in the presence of phosphate.A 15-20% excessof standard EDTA solution is added to a hydrochloric acid solution of thesample containing phosphate. The solution is made alkaline with sodium58 C . C . Miller and D. H. Thaw, Aulalyst, 1959, 84, 440.59 A. B. Sen and S. Misra, 2. analyt. Chem., 1959, 168, 343.60 I. Lysyj, J.E. Zarembo, and A. Hanley, Analyt. Chem., 1959, 31, 902.61 L. Erdley, I. BuzBs, and L. Pdos, 2. analyt. Chem., 1959, 169, 187.62 A. A. Abdel el Raheem, 2. analyyt. Chem., 1959, 167, 98.63 R. G. Yalman, W. Bruegemann, P. T. Baker, and S. M. Garn, Analyt. Chem. ,1959, 31, 1230HASLAM AND SQUIRRELL: QUALITATIVE AND QUANTITATIVE. 385hydroxide, and the excess of EDTA back-titrated slowly with calciumchloride solution to the yellow-green colour of Calcein indicator. Morestandard EDTA is now added until the true pink brown Calcein end-point isobserved. Conventional iodide procedures for the determination of copperin carbonatite ores are not very satisfactory, and particularly so in thepresence of large mounts of calcium. In his proposed method, Toerien 134dissolves the ore in a mixture of nitric, orthophosphoric, and perchloric acidsand readily obtains a clear solution. Permanganic acid is reduced by oxalicacid solution, and iron complexed with sodium fluoride.The pH of thesolution is adjusted to between pH 2.5 and 3 with sodium acetate solution,before the final iodimetric determination of the copper.Ferric salts, a t the appropriate degree of sulphuric acid acidity, arespeedily reduced by hydroxylamine hydrochloride solution. This forms thebasis of a method of determination of iron,% the resulting ferrous solutionbeing titrated with sodium vanadate, N-phenylanthranilic acid being usedas indicator. Precautions have to be taken in the presence of tungsten andvanadium. A rather novel procedure has been devised by Jackwerth andSpecker 66 for the determination of bivalent mercury which does not sufferinterference from chlorides and bromides and the great majority of heavy-metal ions. Bismuth(II1) is added to the mercury(x1) solution which is thentitrated with standard iodide solution in the presence of cyclohexanone.Whilst the mercury(I1) is being complexed the organic layer is colourless oryellow, but at the end-point it becomes orange owing to the production andsolution in the organic phase of the bismuth complex.Rao and Suryana-rayanaG7 have put forward what they describe as a new method for thedetermination of molybdenum(v1). They rely on the fact that molyb-denum(v1) compounds, in hydrochloric acid at loo", are reduced immediatelyby hydrazine sulphate only to the molybdenum(v) condition; the molyb-denum(v) compounds may then be titrated with standard solutions ofvanadate or ceric sulphate.In connection with work on Ziegler catalysts it is often desirable to beable to express opinions about the proportion of Ti(I1) compounds presentin particular circumstances.To do this it is necessary to be able to realisethe two reduction equivalents of Ti@). It has been shown by Martin andStedefeder 68 that this may be accomplished by reaction with ferric chlorideat -50" to -70" in alcohol and in an atmosphere of carbon dioxide. If acatalyst contains both Ti@) and Ti(Ix1) compounds then by oxidation a tlow temperatures and later at 20-80" both reduction equivalents of theTi(@ are realised in a preliminary titration.Before a second titration,which determines total titanium, the catalyst containing Ti(I1) and Ti(II1)compounds is treated with S~-hydrochloric acid at room temperature, theTi@) being converted into Ti@); the total Ti@) is then determined bytitration with ferric chloride. The results of the two tests enable theproportions of Ti(I1) and Ti(II1) in admixture to be determined.64 F. v. S. Toerien, Analyst, 1959, 84, 565.65 G. G. Rao and G. Somidevamma, 2. analyt. Chem., 1959, 165, 432.66 E. Jackwerth and H. Specker, 2. analyt. Chem., 1959, 167, 269.67 G. Gopala Rao and M. Suryanarayana, 2. analyt. Chem., 1959,168, 177.68 H. Martin and J. Stedefeder, Annalen, 1958, 618, 17.REP.-VOL. LVI 386 ANALYTICAL CHEMISTRY.Much attention has been directed to the volunietric determination ofanions.For example, Szekeres and Bakkcs-Polgar 69 have suggested amethod of examination of alkali carbonates and bicarbonates in whichalcohol is added to a solution of the sample and the carbonate then titratedwith barium chloride to the phenolphthalein end-point. Excess of bariumchloride is now added, and the mixture boiled to break down the bicarbonate.The excess of barium is now titrated with sodium carbonate solution (phenol-phthalein indicator). In this way a measure of the bicarbonate is obtained.The problem of the determination of bromate and periodate in thepresence of one another has been solved in two ways.’O (a) After determin-ation of the total periodate and bromate iodometrically, a fresh portion ofthe material is titrated with bromide in hydrochloric acid solution.Theperiodate is reduced to iodate and the bromate to bromine. Sodiumhydrogen carbonate is now added and the hypobromite produced is allowedto react with urea solution. When this reaction is complete, the iodate isdetermined by reaction with iodide and acid. (b) The total periodate andbromate is determined as above. In a second portion of the sample theperiodate is reduced to iodate with hydrogen peroxide in sodium hydrogencarbonate solution. *4fter removal of excess of peroxide, the sum of theiodate plus bromate is determined iodometrically. Appropriate calculationsnow yield figures for the proportions of periodate and bromate in the originalmixture.The old Fajans titration, in which chloride ion is titrated with silvernitrate solution using fluorescein as adsorption indicator, is not alwayssuccessful with certain organic base hydrochlorides.This is due to the factthat in aqueous media the silver chloride formed in the course of the titrationmay be peptised by the associated cations to the almost clear highly dispersedsol. These difficulties may be avoided 71 by titration of the hydrochloridesin 70% methanol solution. Previous work by Erdey and Svehla72 onoxidising agents has now been extended to the determination of free halogens,hypohalogenites, halogenites, and halogenates, etc. In this method theoxidising agent first oxidises ferro- to ferri-cyanide, which is then determinedby titration with ascorbic acid solution, 2,6-dichlorophenolindophenol beingused as indicator.Also on the subject of oxidising agents, there is no doubtthat a method proposed by Rao and Laddha73 for the determination ofchlorate in the presence of perchlorate will prove to be controversial. Theseauthors suggest, though not with complete conviction, that the chloratemay be determined by titration of the acid solution with standard titanoussolution in the cold and in the presence of bromide with Quinoline Yellowas indicator.As a result of the work of E. BakLcs-Polgar 74 it is now possible to deter-mine phosphate volumetrically in the presence of otherwise interfering ions.The solution under test is first treated with 1,2-diaminocyclohexane-NNN’N’-69 L.Szekeres and E. BakBcs-Polgar, 2. anal-~t. Chem., 1959, 165, 85.70 L. Szekeres, 2. analyt. Chem., 1959, 165, 32.7 1 Th. Eckert, Arch. Pharm., 1959, 292, 320.72 L. Erdey and G. Svehla, 2. analyt. Chem., 1959, 167, 164.73 B. K. Sadananda Rao and G. S. Laddha, 2. analyt. Chem., 1959, 167, 410.74 E. BakBcs-Polgar, 2. analyt. Chem., 1959, 167, 353HASLAM AND SQUIRRELL : QUALITATIVE AND QUANTITATIVE. 387tetra-acetate (DCTA) which masks iron and aluminium at the appropriatepH. A.fter formation of these complexes excess EDTA is added to complexcalcium and magnesium. The excesses of EDTA and DCTA in the presenceof buffer and indicator are titrated with magnesium chloride solution.Alcohol is now added, after which the phosphate ion is titrated with standardmagnesium solution.Riedel 75 has also developed an interesting procedurefor the determination of phosphate. After removal of sulphate as thebarium salt, the phosphate is precipitated in perchloric acid medium by theaddition of a known amount of bismuth solution. The excess of bismuth isthen back titrated with EDTA in acid solution and in the presence of thebismuth phosphate. The test may be carried out in solutions containingphosphate and ferric salts; in that case the ferric salts are reduced at asuitable stage in the process.In a method again due to Bakiics-Polgar and Szekeres 76 for the deter-mination of phosphate and sulphate in the presence of one another, thephosphate is first titrated in aqueous-alcoholic medium a t pH 10 with stan-dard magnesium chloride as titrant and Eriochrome Black T as indicator.The magnesium is precipitated as magnesium ammonium phosphate andslight excess of magnesium ions is indicated by the colour change of theindicator.This excess of magnesium is removed by addition of EDTAsolution and this is accompanied by appropriate colour change. The sul-phate is now titrated with standard barium chloride solution, which at theend-point produces a final colour change because the excess of barium dis-places the magnesium from the magnesium complexone. H. Plaetschke 77has developed a rapid and simple method for the determination of sulphatein aluminium sulphate solutions. He uses an indicator solution preparedfrom the disodium salt of tetrahydroxybenzoquinone, potassium chloride,and sodium nitrite and to this is added a known volume of standard bariumchloride solution.A deficiency of the aluminium sulphate solution undertest is added, and the titration then completed by the addition of standardpotassium sulphate solution to the change point, i.e., rose to orange-white.Conditions have also been worked out 78 which are suitable for the titrimetricdetermination of 2-200 mg. of sulphate. The titration is carried out in50% propan-2-01 solution with lead nitrate as titrant; dithizone and 4-2'-pyridylresorcinol are used as indicators at pH values of 4 and 6 respectively.Contributing to the numerous volumetric methods applied to organicanalysis, Koszegi and Salg6 79 have shown that it is possible to determinehexamethylenetetramine, formaldehyde, and inorganic ammonium com-pounds by quantitative oxidation with bromate in acid solution at 100".The flasks used are designed to avoid loss of bromine in the test, and aniodometric titration procedure is employed in the determination of thebromate consumption.For the determination of acetyl groups in organiccompounds, Miizor and Meiselso prefer to dissolve or suspend the material75 K. Riedel, 2. analyt. Chem., 1959, 168, 106.76 E. Bakacs-Polgar and L. Szekeres, 2. analyt. Chem., 1959, 166, 406.77 H. Plaetschke, 2. analyt. Chem., 1959, 168, 264.78 R. Puschel, E. Lassner, and P. L. Reiser, 2. unaZyt. CJzevn., 1959, 166, 401.79 D. Koszegi and E. Salg6, 2. analyt.Chem., 1958, 184, 320.L. MAzor and T. Meisel, Amdyf. Chim. Acta, 1959, 20, 130388 ANALYTICAL CHEMISTRY.in absolute methanol and saponify with a known amount of potassiummethoxide solution. The excess of methoxide is then hydrolysed, and theresulting potassium hydroxide determined by titration with standard acidand an appropriate indicator.Kavaranaa finds that for the assay of acetylsalicylic acid in tablets, atitration with sodium methoxide solution in an anhydrous pyridine mediumto a phenolphthalein end-point, gives excellent results. The method hasthe great advantage that ather constituents usually associated with acetyl-salicylic acid in tablets, viz., phenacetin, caffeine (or caffeine sulphate),phenobarbitone, quinine sulphate, and excipients, do not appear to interferein the test.West and Skoog 82 have shown that acidic solutions of vanad-ium(v) are moderately strong oxidising agents for certain organic corn-pounds. Oxidation of a-hydroxy-acids produces carboxylic acid and carbondioxide, whilst oxidation of ethylene glycol, glycerol, and 1,3-propanediolyields formic acid. These authors also use the principle of the test in amethod 83 for the determination of glycerol. The excess of oxidant is titratedwith ferrous solution, N-phenylanthranilic acid being used as indicator.In the presence of zinc sulphate, hydroxylamine is oxidised to nitric acidand water, and hydrazine to nitrogen, by alkaline ferricyanide. In theabsence of zinc sulphate, however, hydrazine and hydroxylamine are bothconverted i - to nitrogen.Sant has utilised both these reactions in amost useful method for the determination of milligram quantities ofhydrazine and hydroxylarnine either alone or in admixture. The end-pointin the titration of ferricyanide with hydrazine and hydroxylamine sulphatesis denoted by the appearance of a clear white precipitate of zinc potassiumferrocyanide. Fritz and Schenk 85 prefer to use perchloric acid as catalystin the acetylation of hydroxy-compounds. The acetylation of alcohols withacetic anhydride in ethyl acetate solution is complete in 5 minutes at roomtemperature by this methad, and pyridine can also be used as solvent.When acetylation i s complete the excess of anhydride is decomposed withpyridine and water and determined with standard alkali in the normal wayagainst a blank on the reagents alone.Hindered alcohols, glycols, somesugars, and hydroperoxides also react quantitatively.Jaselkis 86 has detailed two useful procedures for the determination ofthe components of alkanethiol-dialkyl sulphide and -dialkyl disulphide mix-tures. In the first case the thiol in an aliquot part of the test solution istitrated with iodine, arid the dialkyl sulphide + thiol in a second aliquotpart are titrated with bromide-bromate solution in the presence of alkalineacrylonitrile to convert the thiol into sulphide. In the second case the thiolalone is titrated first, and then after reduction of the alkyl disulphide tomore thiol with zinc in acetic-hydrochloric acid-alcohol, the total thiols areagain titrated iodometrically.The method is quantitative for alkyl disul-phides of molecular weight higher than propyl disulphide.81 H. H. Kavarana, Indian J. Phavm., 1958, 20, 248.82 D. M. West and D. A. Skoog, Analyt. Chern., 1959, 31, 583.83 D. M. West and D. A. Skoog, Analyt. Chem., 1959, 31, 586.84 B. R. Sant, Analyt. Chim. Aeta, 1959, 20, 371.85 J. S. Fritz and G. H. Schenk, Analyt. Chem., 1959, 31, 1808.86 B. Jaselkis, Analyt. Chem., 1969, 31, 928HASLAM AND SQUIRRELL : QUALITATIVE AND QUANTITATIVE. 389A method which is said to be of wider application than others has beendescribed by Johnson and Fletcher 87 for the determination of vinyl ethersand other olefinic unsaturation. The sample is allowed to react with anexcess of mercuric acetate in methanol to form the addition compound,with the liberation of acetic acid.Sodium bromide is added to convert theexcess of mercuric acetate into the bromide, which permits direct titrationof the acetic acid with alcoholic potassium hydroxide solution. The wideapplicability of the method is demonstrated by results obtained on 16 vinylethers and 27 miscellaneous olefinic compounds. Wehle has put forwarda method for the determination of propan-2-01 which may be useful in theexamination of cosmetic preparations. The procedure is based on oxidationof the propan-2-01 to acetone by a solution of bromine in phosphoric acid.The excess of bromine, and any bromine which may have entered intocombination with the acetone, are determined by reaction with potassiumiodide solution a t appropriate temperature followed by titration of theliberated iodine with standard thiosulphate solution.Schulek, Burger, andFeh6r g9 are concerned with the alkali hydrolysis of organic nitro-compoundsand with the determination of ammonia, cyanide, nitrite, and nitrate in thehydrolysis products which are obtained. They rely on distillation a t acontrolled pH to separate the ammonia and cyanide from the nitrate andnitrate. The ammonia in the distillate is determined by titration, and thecyanide by application of the cyanogen bromide reaction. In the residualsolution nitrite is determined by application of the iodide reaction andnitrate by Devarda’s alloy reduction.Caso and Cefola9* havefound that sulphamic acid is an excellent primary standard for use in suchtitrimetry. It can be purified easily, dissolves readily in basic solvents suchas dimethylformamide and n-butylamine, and gives no gels or precipitatesin the course of titration with lithium methoxide in benzene-methanolsolution.It can also be used as a standard in conductometric titrations insuch media as dimethylformamide and glacial acetic acid, in which solventit is possible to titrate with perchloric acid in glacial acetic acid. Barnes 91has described a method for the non-aqueous determinatioh of acetylenichydrogen which is based on reaction of the monosubstituted acetylenic com-pound with silver perchlorate, with a subsequent liberation of hydrogen ions.The acid produced as a result of acetylide formation is titrated with a stan-dard solution of tris(hydroxymethy1)methylamine in methanol to screenedThymol Blue indicator.This method permits direct determination ofacetylenic hydrogen in water-immiscible solvents and easily hydrolysedesters.Amongst the other interesting papers on non-aqueous titrimetry that ofReiss 92 should be noted. He shows that substances such as quinine hydro-chloride and antipyrine, soluble in acetic anhydride, can be readily titratedWe turn now to work in non-aqueous media.87 J. B. Johnson and J. P. Fletcher, Analyt. Chem., 1959, 31, 1563.88 H. Wehle, Z . analyt. Chem., 1959, 169, 241.89 E. Schulek, I<. Burger, and M. FehPr, 2. anatyb. Chem., 1959, 167, 423.90 M.M. Caso and M. Cefola, AnaZyt. Chiwr. Acta, 1959, 21, 205.91 L. Barnes, jun., Autalyt. Chsh,, 1959, 31, 405.92 R. Reiss, 2. analyt. Chem., 1969, 167, 16390 ANALYTICAL CHEMISTRY.in that medium with solutions of perchloric acid in glacial acetic acid; thesame applies to substances such as hyoscyamine hydrobromide and nico-tinic acid, soluble in the course of the titration. Difficulty soluble substancessuch as aneurin hydrochloride and caffeine can be dissolved in formic acidbefore application of the test. Metal halides such as sodium chloride,strontium chloride, and potassium bromide respond to this latter test.Patchornik and Rogozinski 93 have presented a method for the determin-ation of the individual components of complex mixtures of organic andinorganic acids, acyl halides, anhydrides, and alkyl halides.The method isof high accuracy and is based on titration of the components in non-aqueousmedia with three standard base solutions, namely, sodium methoxide,tributylamine, and benzyltrimethylammonium hydroxide. The sameindicator is used for all titrations. Finally, Small 94 claims to obtain excel-lent results in the direct determination of active hydrogen in ethanolamine-type compounds. The sample is dissolved in tetrahydrofuran and titratedwith lithium aluminium di-n-butylamide in an atmosphere of nitrogen.4-Phenylazodiphenylamine is a satisfactory end-point indicator.4. PHYSICAL METHODSElectrical.-In this section we deal with electrical methods of all kinds,starting with the inorganic and organic applications of potentiometry.Standardisation in pH work is of interest to all, and Keyworth and Hahn 95are in favour of sodium hydrogen diglycollate as a reference buffer for thestandardisation of electrode systems and for other buffer purposes. Thematerial is non-hygroscopic and readily available in a primary standardgrade. A 0.2~-solution has a pH of 3-40 & 0.02 over a wide temperaturerange and dilution by a factor of two does not affect the pH by more than0.02 unit.Khalifa et aLg6 have extended their previous work on EDTA titrations,using mercuric nitrate as back titrant in alkaline medium, to problemsinvolving the analysis of binary mixtures of bismuth with such elements ascalcium, strontium, copper, zinc, cadmium, lanthanum, lead, nickel, ormanganese.In such cases two titrations are performed: (a) a titration ofthe bismuth alone with EDTA at pH 2.5, potassium iodide being used ascolorimetric indicator; and (b) a second titration at pH 8-5-9-5 in whichexcess of EDTA is added, and this excess back-titrated potentiometricallywith standard mercuric nitrate, using a silver amalgam indicator electrode.The second titration gives a measure of the total bismuth plus the otherconstituent of the binary mixture. Saxena and Bhatnagar 97 have madepotentiometric studies of the precipitation of copper ferrocyanide by titra-tions of copper sulphate with potassium ferrocyanide at various concen-trations, using a ferri-ferro-cyanide electrode system. As a result of thiswork they find that the sharp potentiometric end-point corresponds with93 A.Patchornik and S. E. Rogozinski, Analyt. Chem., 1959, 31, 985.94 L. A. Small, Analyst, 1959, 84, 117.95 D. A. Keyworth and R. B. Hahn, Talanta, 1951, 1, 41.96 H. Khalifa and A. Soliman, 2. analyt. Chem.. 1959, 169, 109.97 R. S. Saxena and C. S. Bhatnagar, Analyt. Chim Ada, 1959, 20, 494HASLAM AND SQUIRRELL : PHYSICAL METHODS. 39 1the formation of a compound K,Cu,[Fe(CN),],. The titration curves areregular and reproducible and thus the system presents a useful method forthe determination of copper in solution.Gansel 98 has described both macro- and micro-procedures for the directdetermination of silver in such materials as photographic films, emulsions,etc. He wet oxidises the organic matter and halides by treatment withsulphuric-nitric acid and finally titrates the silver sulphate so produced withstandard potassium bromide solution potentiometrically.An advantage ofthe method is that the complete process is carried out in the same vessel. Animportant advance in the determination of halogens in organic compoundshas been made by Menville and Parker.s9 The sample in a suitable solventis decomposed by the addition of dispersed sodium reagent and propan-2-01.When decomposition is complete (after 5 minutes) the excess of sodium isdestroyed with methanol, and the solution acidified with nitric acid beforepotentiometric titration of the ionised halide in the aqueous phase withsilver nitrate solution. Results of quite good accuracy have been obtainedon a wide range of organic halides.The determination of small amounts of chloride has been dealt with byseveral workers.For example, a new method which is both rapid andaccurate has been presented by Malmstadt and WinefordnerlOO for thedetermination of chloride in the range 10-6-10-1~. The method is basedon null-point potentiometry and uses two similar silver chloride electrodes,one of which is in contact with the test solution and the other with a knownreference solution contained in an isolation compartment or cell linked tothe solution under test by an asbestos fibre or similar contact. The methodconsists simply of changing the chloride concentration of the unknownsolution whilst maintaining the ionic strength constant until the concen-tration is identical with the known reference and a null reading on thepotentiometer is obtained.The total ionic strength is kept constant byusing large but identical quantities of electrolyte in both reference sampleand titrant solution. Very small amounts of chloride, i.e., less than 1 p.p.m.,in ethylene glycol have been titrated potentionietrically by Hanna andJura.lol The electrode system is simply a silver indicator electrode and acalomel electrode with the saturated potassium chloride solution replacedby potassium nitrate solution, as reference. The titration is carried outwith 0.0005~-silver nitrate solution in propan-2-01, conventional potentio-metric titration curves being obtained.The difficult problem of the determination of small amounts of chloridein titanium and zirconium has been dealt with quite successfully by Priceand Coe.lo2 In the final titration two identical silver-silver chloride elec-trodes are used, and a small e.m.f.is applied across the two electrodesimmersed in the stirred solution, containing chloride, under test. Chlorideions from the solution being tested and silver ions from the titrant, reactreversibly at the electrodes. The resulting current falls to a minimum at the98 E. E. Gansel, Analyt. Chem., 1959, 31, 1366.loo H. V. Malmstadt and J. D. Winefordner, A~zalyt. Chim. Ada, 1959, 20, 383.Io1 J. G. Hanna and J. Jura, Analyl. Claem., 1959, 31, 1820.lo3 D. Price and F. R . Coe, Annlyyt, 1959, 84, 65.R.L. Menville and W. E. Parker, Analyt. Chem., 1959, 31, 19013 92 ANALYTICAL CHEMISTRY.end-point of the titration and rises when excess of silver titrant is added.The authors have extended the principle of the test to the correspondingdetermination of chloride in paper.lo3In the organic field, Fritz and his co-workers l0Q have presented a methodfor the determination of carbonyl compounds which gives distinct end-points whether carried out with a potentiometric or indicator titrationfinish. The carbonyl compound is treated with 2-dimethylaminoethanoland hydroxylamine hydrochloride in methanol-propan-2-01. The excess ofhydroxylamine is then determined by titration with a standard solution ofperchloric acid in methyl cellosolve. Martius Yellow indicator mixed witha little Methyl Violet is used in the visual end-point procedure, the colourchange corresponding exactly with the point of maximum inflection in theconventional potentiometric titration curve.Sass loti has put forward aninteresting method for the identification and quantitative examination ofmixtures of saturated fatty acids from octanoic to stearic acid. These acidsare converted into the corresponding potassium salts, which are thendifferentiated by potentiometric titration with standard silver nitratesolution. Advantage is taken of the different solubility products of thesilver salts of the various acids.Willemart and FabrelOG have described a method for the analysis ofmixtures of thiols and organic disulphides.The total of thiols plus di-sulphides is determined by titration with a standard solution of potassiumbromide after the addition of potassium bromate and mineral acid to thesample solution. The following reactions occur :R.SH + 3Br, + 2H20 RS02Br + 5HBrR S 9 R + 5Br, + 4H,O -E 2R*SO,Br + 8HBrThe thiol alone can be selectively titrated in another aliquot part of thesample solution with the same solution of potassium bromate. In this,however, potassium bromide is replaced by potassium iodide and underthese conditions the thiol alone is titrated:HBrO, + 6HI + 6Hf ---+ HBr + 318 + 3H,OThe end-point in the titrations can be satisfactorily detected potentio-metrically under standard polarisation conditions, and from the titrationfigures obtained the proportion of thiol and disulphide in the mixture canbe calculated.Potentiometry in non-aqueous media has become a very valuable ana-lytical tool.Malmstadt and Vassallo lo' have combined the use of theirderivative potentiometric and spectrophotometric titration procedure andtri-n-butylmethylammonium hydroxide titrant, in a most useful method forthe titration of hydrochloric-sulphuric acid and nitric-sulphuric acid mix-tures in acetone. Under the conditions of the method, two end-points areobtained, the first corresponding to the hydrochloric or nitric acid and the103 D. Price and F. R. Coe, Analyst, 1959, 84, 62.lo4 J. S. Fritz, S. S. Yamamura, and E. C . Bradford, Analyt. Chem., 1959, 31, 260.106 C. Sass, Fette u. Seijen, 1959, 61, 93.106 R.Willemart and P. Fabre, Ann. Phurm. f r a q . , 1958, 16, 676.107 H. V. Malmstadt and D. A. Vassallo, Analyt. Chem., 1969, 31, 200HASLAM AND SQUIRRELL : PHYSICAL METHODS. 393first hydrogen of the sulphuric acid, and the second to the second hydrogenof the sulphuric acid. Both end-points are sharp and can be easily discernedfrom normal potentiometric curves or by visual detection. Considerationsof other titrants and solvents are given. Das and Mukherjee lO8 also titratesulphuric acid as a mono- or di-basic acid in a glycol-isopropyl alcohol mediumusing sodium hydroxide or an organic base, e.g., piperidine, as titrant. Thetitration is carried out potentiometrically or conductometrically and is usefulfor the quantitative evaluation of mixtures of sulphuric with other acidsincluding hydrochloric, nitric, perchloric, phosphoric, and acetic acids.Cundiff and Markmaslog have extended their work on the differentialtitration of strong acids with tetrabutylammonium hydroxide.They alsoinclude in their latest study the titration of mixtures of sulphuric acid withnitric, hydrochloric, perchloric, phosphoric, or sulphonic acids and theresolution of a typical mixture of a strong, weak, and very weak acid.They again emphasise the great versatility of this titrant.The application of constant-current potentiometry to the non-aqueoustitration of weak acids has been described by Shain and Svobodal10 whouse tetrabutylammonium hydroxide as titrant and acetone as solvent.Two platinum electrodes are used with a polarising current of 1 PA through-out the titration, whilst the potential difference between the electrodes isregistered by a pH meter or voltameter.In most cases a typical peak-shaped titration curve is obtained permitting extremely easy recognition ofthe end-point. Mathews and Welch l l 1 7 l l 2 have also critically examinedpotentiometric methods €or the titration of weak acids and phenols inseveral solvents and have discussed the relative merits of some electrodesystems.Van Meurs and Darmen 113 have made an extensive study of the conducto-metric and potentiometric titration of nitrogen bases in non-aqueous mediawith, for example, perchloric acid. They have discussed the factors govern-ing the shape of the titration curves, uiz., nature of solvent and titrant,temperature, etc. They present useful conclusions on this method ofde t ei-mination, and prefer pot en tiome t ri c t itration rat her than conducto-metric, especially when dealing with mixtures.A chemically inert mediumof low solvating power, but of sufficient conductivity to permit titration,gives best results and hence nitrobenzene is an excellent solvent. Streuli 114has correlated the potentiometric titration behaviour of different types oforganic bases in nitromethane with their structure. He finds that althoughamines give normal-type titration curves, yet monosubstituted and un-substituted amides and ureas show extremely steep titration curves, probablydue to hydrogen bonding. Equations are presented relating basicity of thevarious compounds in nitromethane and water.Other electrical methods include a continuous process described bylo8 M.N. Das and D. Mukherjee, Analyt. Chem., 1959, 31, 233.lo0 R. H, Cundiff and P. C. Markunas, Analyt. Chim. A d a , 1939, 20, 506.110 I. Shain and G. R. Svoboda, A~zalyt. Chem., 1959, 31, 1857.111 D. H. Mathews and T. R. Welch, J . Appl. Chem., 1958, 8, 701.112 D. H. Mathews and T. R. Welch, J . Appl. Chem., 1958, 8, 710.11s N. Van Meurs and E. A. M. F. Darmen, Analyt. Chim. Acta, 1959, 21, 193.lI4 C. A. Streuli, Arzalyt. Chem., 1959, 81, 1662394 ANALYTICAL CHEMISTRY.Eckfeldt 115 which may have future application in the analysis of flowingsample streams. The procedure introduces a new method of electro-chemical analysis in which the reaction is brought about by allowing thesample to flow through a cell in contact with a large working electrode at apre-determined potential.The potential of this electrode is so chosen as tobring about the required electrochemical reaction excluding as far as possibleside reactions. In measurements of sample solutions containing iodide,iodine, and oxygen the electrode efficiency varied with the solution flow rateand the conditions at the working electrode but was largely independent ofthe concentration of the material being analysed. Hochmann and Bayer 116have developed an interesting method for the determination of oxytetra-cyclin. They rely on the fact that with ferric salts oxytetracyclin reactsin 1 : 1 molecular proportions.Excess of ferric salt is added to the sampleunder test, and the excess of iron determined by high-frequency titrationwith EDTA. Alfonsi 117 has extended his work on controlled electrolysisto the analysis of tin base alloys, leaded bronzes, silver solder, and copper-cadmium alloys.A subject of some interest has been described by Mather and Anson 118who have devised a method for the coulometric generation of hydrogen ionsin anhydrous acetic acid containing sodium perchlorate by anodicallyoxidising a mercury electrode. The method of titration should be applicableto many basic substances normally titrated by volumetric and potentio-metric methods in acetic acid. Accurate results have been obtained forthe titration of sodium acetate and potassium hydrogen phthalate.Po1arography.-Baumgarten and his co-workers 119 have extended thevaluable information on the polarographic characteristics of many metalions in hydroxy-acid supporting electrolytes including ammonium citrate,malonate, and tartrate and also ammoniacal ammonium oxalate. Thepaper also includes data obtained in weakly acidic citrate media.The determination of nitrate in meat and meat-curing brines suffersinterference in many conventional methods because of the presence ofprotein and other organic matter.Dhont l20 has overcome these difficultiesby ensuring that the nitric acid, equivalent to the nitrate, nitrates phenol-disulphonic acid, with the production, in the main, of B-nitrophenol-2,4-di-sulphonic acid.As might be expected from the presence of the nitro-group, this acid is capable of polarographic reduction and determination.By covering the electrodes with a polyethylene membrane, Carritt andKanwisher 121 have perfected a polarographic method for the determinationof dissolved oxygen in fluid systems, which is much more selective to oxygenthan previously described methods. The membrane also prevents electrodepoisoning and the system is temperature-compensated by means of a thermi-stor incorporated in the electrode. The instrument can be used with115 E. E. Eckfeldt, Analyt. Chem., 1959, 31, 1453.116 K. Hochmann and I. Bayer, 2. analyt. Chem., 1959, 166, 88.117 B. Alfonsi, Anulyt. Clzim. Acta, 1958, 19, 569.116 W. B. Mather, jun., and F.C. Anson, Analyt. Chim. Acta, 1959, 21, 468.119 S. Baumgarten, R. E. Cover, H. Hofsass, S. Karp, P. B. Pinches, and I,. Meites,120 J. 13. Dhont, Analyst, 1959, 84, 372.121 n. E. Carritt and J. W. Kanwisher, AnaZyt. Chem., 1959, 31, 6.Analyt. Chim. Acta, 1959, 20, 397HASLAM AND SQUIRRELI. PHYSICAL h1ETHOT)S. 395continuous recording devices or as a portable apparatus with a micrometerscale indicator.It appears that 1,4-benzoquinone and its simple homologues react withsecondary 2-hydroxyethylamines of the general formula R*NH*CH,*CH,*OHto yield substituted benzoquinones of the type C,H,O,*NR*CH,-CH,OH,where R may be aliphatic, arylaliphatic, aromatic, or hydroxyalkyl. Konigand Berg122 show that this reaction, followed by the examination of thepolarographic and fluorescent behaviour of the reaction products, may beused with advantage in the characterisation of secondary 2-hydroxyethyl-amines.A procedure originally put forward by Kemula for the separationof organic nitro-compounds has now been applied with success by Skndi lZ3to the separation of thiophosphoric acid esters used as insecticides and theirbreakdown products. The separation is carried out on a polythene columnand the progress of the separation is followed polarographically.A method has been presented by Keily et aZ.124 for the assay of high-purity chromium metal and chromium oxide. The metal is oxidised to thesexavalent state and a weighed excess of solid ferrous ammonium sulphateis added. Reduction of the chromium occurs and the excess of ferrous ironis then measured by amperometric titration with ceric ammonium sulphatesolution. The method is capable of a precision of 3-45 parts in 10,000.Zittel and his co-workers125 have modified the original method due toHeyrovsky and Berezicky for the amperometric titration of barium.Theyhave altered the titration medium to tetraethylammonium bromide inaqueous ethyl alcohol and use lithium sulphate as titrant. Under theseconditions, and with the dropping-mercury electrode as the indicatorelectrode, they are able to titrate solutions as low as 5 x 1 0 - 5 ~ in bariumwith reasonable accuracy.For the direct titration of potassium with sodium tetraphenylboron,Amos and Sympson 126 use an amperometric method of end-point detectionobtained with a conventional dropping-mercury electrode.The anodicdepolarisation current of the tetraphenylboron a t this electrode is measuredat intervals throughout the titration, and the results are plotted; there isthe usual sharp increase in current when the end-point is passed. Chlorideinterferes at concentrations of 3 0 . 3 2 ~ . Den Herder and Van Pinxteren 127have used a rotating platinum electrode with a saturated calomel referencefor the amperometric titration of fluoride with a standard solution of ferricchloride. Satisfactory current voltage curves are obtained for the titrationof 38-950 pg. of fluoride in a 5-10 ml. volume of aqueous ethanol saturatedwith sodium chloride, and the method is thus most useful for the examinationof water samples.Chromatography .-The last year has seen significant advances in allbranches of chromatography, and under this heading we have selectedpapers which we consider to be of the widest general interest.These papers**2 K. H. Konig and H. Berg, 2. analyt. Chem., 1959, 166, 92.123 E. Sandi, 2. analyt. Chem., 1959, 167, 241.l24 H. J. Keily, A. Edridge, and J. 0. Hibbits, Analyt. Chim. Acta, 1959, 21, 135.H. E. Zittel, F. J. Miller, and P. F. Thomason, AnaZyt. Chem., 1959, 31, 1351.126 W. R. Amos and R. F. Sympson. Analyt. Chem., 1958, 31, 133.I z 7 J . J. Den Herder and J. A. C . Van Pinxteren, Pharm. Weekblad, 1958, 93, 1013396 ANALYTICAL CHEMISTRY.have been grouped together in sections dealing with paper chromatographyand electrophoresis, column chromatography, ion-exchange chromatography,and finally gas-solid and gas-liquid chromatography.disAcusses some of the basic considerations which must be borne in mind indesigning electrophoretic apparatus.He concerns himself with the main-tenance of buffer stability and of stable electrical test conditions and withthe stabilisation and formation of starting boundaries. He makes observ-ations on the matrix, the stabilising media, the selection of buffers, and thejdentification and analysis of separated substances, as well as temperaturecontrol. McDonald and his co-workersla9 have been able to reduce thedevelopment time for paper chromatograms by use of a simple apparatuswhich applies centrifugal force to the paper being developed.The chromato-grams obtained in this apparatus are similar to those obtained by normalmeans. By combinifig the centrifugal force with a high-voltage, direct-current electrical field one is also able to increase the speed of planar electro-phoretic separations.On the theoretical aspect of partition chromatography, Franc andJokl130 have made a study of the R, values given in the literature of alarge number of organic compounds including alcohols, ketones, etc., forminghomologous series. They have proposed what might be a most usefulequation relating R, value [ = log(l/Rf) -11 to the number of carbon atomsin the members of a homologous series.The detection of spots due to organic compounds, e.g., lipids and alkaloids,on paper chromatograms by the iodine vapour method has always had thedisadvantage that, owing to the high background stain, the detection ofweak or tailing spots has been difficult.Pan 131 has shown that if thechromatogram is first sprayed with a solution of aluminium sulphate anddried before being hung in the iodine vapour then the background stainingis much less than by the usual method. After this treatment the chromatodgram can be sprayed with starch solution, and the iodine-stained spotsappear deep blue against a light blue background. Such coloured spotsremain visible for over 1 month. Wegmann la* has also described a usefulidea for spraying chromatograms with marker reagents. He suggests theuse of Aerosol spray bottles, which can be easily manipulated with one handand give a more uniform distribution of spray reagents. The author isaware of the limitations of the method, in that it might be dangerous to useit with caustic alkalis in alcohol and that the aerosol container might suffercorrosion.He still feels, however, that the introduction of aerosol sprayreagents should be promoted by research institutes and industrial labora-tories. It is probable that Miss and Segal 133 have put forward an importantimprovement in Rutter’s well known method of paper chromatography.They thread a small piece of thread through the middle of the filter-paper,825.In a general article on the subject of zone electrophoresis Martin128 N. H, Martin, Artalyst, 1939, 84, 89.120 H. J. McDonald, L.P. Ribeiro, aild L. J. Banaszak, Analyt. Chem., 1W9,180 J. Franc and J. Jokl, J . ChWmdog., 1959, 2, 423.Is1 S. C. Pan, J. Chrornatug., 1969, 2, 433.1sz K. Wegmann, J. Chro+watog., 1959, 8, 321.188 A. Miss and F. Segalk Z . analyt. Chsm., 2959, 165, 1HASLAM AND SQUIRRELL: PHYSICAL METHODS. 397then feed the eluting liquid through this thread in order to develop thechromatogram. The thread can be varied and hence changes may be madein the rate of development of the chromatogram.Interesting observations have been made on the characterisation of fattyacids, resin acids, and naphthenic acids which are used in the soap-makingindustry. The acids are oxidised with chromic-sulphuric acid, and theresulting steam-volatile acids titrated. Acetic, propionic, and butyric acidsare readily identified in the steam-volatile matter by the chromatographicbehaviour of their ethylammonium salts.laAnalytical chemists concerned with the examination of anti-oxidants,whether natural or synthetic, will be well advised to study in detail a veryinteresting report of the vitamin E panel of the Analytical Chemists Com-mittee of the Society for Analytical Chemistry.135 This report is concernedwith the determination of tocopherols which are natural antioxidants inoils, foods, and feeding stuffs, and several useful principles are involved.After preliminary separation from interfering matter the tocopherols areseparated from one another by two-dimensional paper chromatography.The separation in the first dimension is effected on paper impregnated withzinc carbonate, and in the second dimension, the second separation is subse-quently effected on the same paper impregnated with paraffin. The separ-ated tocopherols are determined by taking advantage of the fact that, beingreducing substances, they reduce ferric salts, and the ferrous salts producedreact with bipyridyl to give appropriate colours, suitable for measurement.D e h ~ r i t y , l ~ ~ in a communication on the chromatographic separation of anti-oxidants, describes three basic methods.In two of these, partially acetyl-ated paper is used, and in the third the separation is achieved on papercoated with cotton-seed oil. The developing solvents used are conventional.Toxicologists may be concerned with the analytical separation of sulphon-amide drugs and the examination of alkaloidal residues obtained from suchmaterials as viscera, stomach washes, and urine by application of the Stas-Otto process of preliminary extraction.They will find the circular paper-chromatographic method employed by Tewari and Tripathi137 to be ofinterest. Langford and Vaughan have obtained excellent separationof mixtures of polymers including polyvinyl acetate, polyvinylbutyraldehyde,polystyrene, and polyvinyl chloride, by paper chromatography using isobutylmethyl ketone as developing solvent. When required, even greater separ-ation can be obtained by development in a second direction using a mixtureof this ketone and methanol. The spots are made visible by spraying witha universal indicator solution.Two very simple column chromatographic methods have been devisedby Smith 139 for the separation and determination of adipic, glutaric, andsuccinic acids.A novel feature is the inclusion of an internal indicator inthe silicic acid-water column which permits convenient tracing of the134 M. JureEek and P. Kozkk, 2. andyt. Chem., 1959, 167, 32.135 Analyst, 1959, 84, 356.13' S. N. Tewari and D. N . Tripathi, 2. analyt. €hem., 1959, lM, 356.138 W. J. Langford and D. J. Vaughan, J . Chromatog., 1959, 2, 564.1SB A. I . Smith, Analyt. Chewa., 1959, 31, 1621.B. A. Dehority, J . Chromatog., 1959, 2, 384398 ANALYTICAL CHEMISTRY.separated acid bands. In the first procedure the column is developed witha butanol-chloroforrn solvent and then extruded for separation of thedeveloped bands.In the second procedure the column is developed withthree -butanol-chloroform mixtures, and the acids are collected individuallyas they are eluted from the column. Forstner and Rogers,l40 in work onthe separation and study of 2- and 4-nitroso-l-naphthol, have described theapplication and use of chemisorption in chromatographic separations oforganic isomers and homologues. Their results show that in such caseschemisorbent columns can show greater efficiency than mere physical sorp-tion columns and they point out the particular usefulness of low capacitysalts and impregnated high capacity oxides as chromatographic sorbents.In thedetermination of cobalt in the presence of nickel advantage may be takenof the fact that, from a solution of both the metals containing excess ofpotassium cyanate and ammonium acetate buffer, Dowex 1-X8 ion-exchangeresin selectively holds the c0ba1t.l~~ The cobalt may afterwards be extractedfrom the resin with hydrochloric acid solution and subsequently determinedby the colorimetric cyanate procedure.Wilkins and Hibbs 142 have de-scribed a simple method for the determination of nickel in gold-nickelalloys. The sample is dissolved in aqua regia and, after evaporation to dry-ness to remove nitric acid, the residue is re-dissolved in hydrochloric acid.This acid solution is passed down a Dowex 1-X5 ion-exchange column, andthe gold chloro-complex is strongly absorbed. The nickel is determined inthe eluate by an EDTA titration procedure.has presented a rather novel ion-exchange method for theanalysis of two ions, for example, Na and K present as chlorides in aqueoussolution.An aliquot part of the solution is evaporated to dryness underdefinite conditions, and the residue weighed. A similar aliquot part ispassed through a cation-exchange column saturated with one of the ionsbeing determined. The eluate and washings are then evaporated, dried, andweighed as before. From the two weights obtained the composition of theoriginal mixture can be calculated, to give a result within a 2% error. Themethod may also be used for anions, if an anion-exchanger is used, but in bothcases the salts must be capable of being dried to constant weight.A variationof the method using a cation-exchanger in the hydrogen form with a titrimetricfinish is also described, but by this method the relative error is greater.In analytical work on plating baths, etc., it is often desirable to removelarge amounts of chromic acid before the determination of certain cations.Although ion-exchange resins have been suggested for the purpose, thedifficulty is that most of them are insufficiently stable and produce un-desirable Cr3+ ions. According to the work of Weiner and Schiele,l44 how-ever, Amberlite 1.R.A.-410 ion-exchange resin does not suffer from thesedisadvantages. Prochkzkov5 145 has developed a process which overcomesIon-exchange resins are of increasing service to the analyst.Gabrielson140 J.L. Forstner and L. B. Rogers, Alzalyt. Chew., 1959, 31, 365.141 M. Ziegler and W. Rittner, 2. analyt. Chem., 1959, 165, 197.112 D. H. Wilkins and L. E. Hibbs, AnaZyl. Chim. A d a , 1959, 20, 273.143 G. Gabrielson, AnaZyt. Cltim. Ada, 1959, 20, 146.144 R. Weiner and C. Schiele, 2. analyt. Chem., 1959, 169, 271.145 L. ProchAzkovA,, 2. anaZyt. Chem., 1959, 167, 254HASLAM A4ND SQUIRRELL: PHYSICAL METHODS. 399many of the difficulties previously encountered in the determination ofnitrates in water. Interfering cations are first removed by passage througha suitably prepared active carbon column. The nitrate is reduced withhydrazine in the presence of a definite proportion of copper before colori-metric determination of the nitrite obtained by the sulphanilic acid-wnaphthylamine test.Nitrate, sulphate, and chloride may be determined in the same sampleof water by a simple procedure developed by Ceausescu.1Q6 The water isfirst passed through an ion-exchange resin whereby all the cations are re-placed by hydrogen ions.In the eluate the total acidity due to nitric,sulphuric, and hydrochloric acids is determined by titration with alkali,using sodium alizarinsulphonate as indicator. The titrated solution is nowtreated with barium sulphate suspension, alcohol, and a further amount ofsodium alizarinsulphonate solution. The sulphate is now determined bytitration with standard barium perchlorate solution , the sodium alizarin-sulphonate this time functioning as adsorption indicator.Desorption ofthe sodium alizarinsulphonate is now accomplished by the addition ofsulphuric acid followed by titration of the chloride with mercuric nitratesolution , diphenylcarbazone being used as indicator. The nitric acid isdetermined by difference.ResS and Straka147 have developed a useful method for the determin-ation of sulphur in pyrites concentrates. The sulphur is converted intosulphate by heating with a mixture of manganese dioxide and potassiumhydroxide. The product is leached with water, and the sulphate in theextract determined by passage of an aliquot part of the solution through acation-exchange resin before titration of the resulting sulphuric acid withstandard alkali. The method may be applied to the determination ofsulphur in certain organic compounds containing sulphur, sulphur andnitrogen, or sulphur and chlorine. In the last case allowance has to hemade for the chlorine ionised in the process.On the organic side, difficulties encountered in the determination offluorine in organic compounds also containing phosphorus , by the mercuricnitrate-alizarinsulphonate method, after Parr bomb fusion, have been over-come by Eger and L i ~ k e .l ~ ~ These authors absorb the fluoride and phos-phate on an ion-exchange column and separate them by selective elutionbefore individual determination. Bromine , chlorine, and sulphur can alsobe determined simultaneously with the fluorine and the phosphorus.Fluorine in many fluoro-compounds and chlorine and fluorine in certainchlorofluoro-compounds can often be determined quite readily if the sub-stance is soluble in di-isopropyl ether.149 The solution of the test substancein this ether is treated with a biphenyl sodium dimethoxyethane complexand the resulting sodium salts are converted into the corresponding halogenacids by passage through an ion-exchange resin in the hydrogen form.When chlorine and fluorine are both present, titration of the total acids in146 D.Ceausescu, 2. analyt. Chem., 1959, 165, 424.147 2. fiezbi: and K. Straka, 2. analyt. Chem., 1959, 166, 161.148 C. Eger and J. Lipke, AIzaZyt. Chim. Acta, 1959, 20, 548.149 P. Johncock, W. R. Musgrave, and A. Wiper, Aizalyst, 1059, 84, 245400 ANALYTICAL CHEMISTRY.the eluate gives a measure of both; chloride may be determined inde-pendently in the eluate by application of the mercury oxycyanide method.A combination of ion-exchange chromatography and ultraviolet spectro-scopy enables Shelley and Umberger lm to differentiate and determine acidicaromatic and heterocyclic compounds.A strongly basic resin is used andthe acidic compounds are subsequently eluted with ethyl alcohol or acidifiedalcohol and examined by ultraviolet-spectrophotometry. The method isalso applicable to phenols and such compounds as codeine phosphate.Sherma and Rieman,lsl in further work on solubilisation chromatography,have separated mixtures of aliphatic and aromatic ethers, saturated fattyacids, and substituted benzenes and naphthalenes by elution throughcolumns of ion-exchange resins with aqueous solutions of acetic acid.Ginn and Church lS2 have described two new ion-exchange methodsfor the analysis of surface-active mixtures containing non-ionic and anion-active constituents.In a two-stage method the mixture is passed down astrongly acid cation-exchange column, and the effluent contains the un-changed non-ionic and the anionic component in its acid form. This effluentis now passed through an acid-absorbing, weakly basic, anion-exchangeresin, whereupon the anionic component is absorbed, and the non-ionicpasses through to be recovered from the effluent. The anion-active com-pound is now eluted from the column with alcoholic sodium hydroxide andis recovered from the alkaline eluate. A single-stage mixed-bed method isalso described for the more rapid recovery.of non-ionic surface-active agentsfrom such mixtures.Many review papers on subjects of interest to analytical chemists merelyconsist of very brief descriptions of large numbers of original analyticalpapers. It is refreshing, therefore, to read the critical review by Rose 153on an up-to-date topic, e.g., " Gas Chromatography and its Analytical Applica-tions. "The gas-liquid chromatographic separation of mixtures of compoundshaving a widely varying boiling range has often presented dificulties inchoosing a practicable column temperature. These difficulties have beenovercome by Sullivan and his co-workers 154 and by Nogare and Harden.155The former workers utilise a non-linear temperature programming methodbased very simply on starting the run at room temperature and switchingthe column heater to full heat.This results in a slow increase in temper-ature over the first 10 minutes of run, followed by a rapid increase to say150" in 30 minutes. The reproducibility of the temperature programme a ta fixed heater setting is surprisingly good. Nogare and Harden1% uselinear temperature programming facilitated by a proportional controllerand low heat capacity column and heater. Detector stability is main-tained by the incorporation of a buffer block between the column and thethermal conductivity detectors.150 R. J. Shelley and C . J. Umberger, Analyt. Chem., 1959, 31, 593.151 J. Sherma and Wm. Rieman, tert., Analyt. Chim. Ada, 1959, 20, 357.152 M.E. Ginn and C. L. Church, AnaZyt. Chem., 1959, 31, 551.155 B. A. Rose, Analyst, 1959, 84, 574.154 J. H. Sullivan, J. T. Walsh, and C. Merritt, jun., Analyt. Chem., 1959, 31, 1826.155 S. D. Nogare and J. C. Harden, Analyt. Chem., 1959, 31, 1829HASLAM AND SQUIRRELL: PHYSICAL METHODS. 401A large amount of identification work in gas-liquid chromatography hasbeen based on elution times. It has been inferred that a substance is cor-rectly identified because its corrected relative retention time with referenceto a standard substance is the right one for the substance in question underparticular column conditions or sets of column conditions. This is notalways the case, and the alternative w,ethod of identification which Ander-son 156 has put forward is likely to have far-reaching effects.He describesmethods by which gas-liquid chromatographic fractions issuing from acolumn are collected in cold traps. The material in a given cold trap isthen transferred quantitatively to a previously evacuated infrared gas celland identified by infrared methods.By combining a suitably modified " time of flight " mass spectrometerwhich scans a mass range from m/e = 1 to m/e = 6000 at the rate of 2000times per second, with a gas-liquid partition chromatographic apparatus,Gohlke l57 has produced an apparatus which is capable of separating andpositively characterising organic mixtures boiling below 350". The massspectrometer is connected to the gas-liquid chromatographic apparatusbetween the column exit and the thermal conductivity cell.Such mixturesas acetone, benzene, toluene, ethylbenzene, and styrene can be rapidyseparated and identified.Karchmer 158 has set out the gas-liquid partition characteristics of someeleven sulphur compounds in the boiling range 58-126" on a column ofPP'-iminodipropionitrile on Celite. He finds that, with a helium carrier gasa t 84", this column resolves the compounds on the basis of their electrophiliccharacter. By logarithmic plot of the retention times on this column againstthose obtained on a volatility delineating column (e.g., white oil on Celite), aseries of straight lines corresponding to tertiary thiols, iso-primary thiols,primary normal thiols, aromatics, and thiophens are obtained. Membersof a homologous series tend to lie on their respective straight lines, Usefulgas-liquid chromatographic data have also been published by Chang andKarr 159 on the identification of some 52 aromatic hydrocarbons boiling upto 218" present in a low-temperature bituminous coal tar.The resultsindicate that alkylbenzenes with an equal number of carbon atoms in theiralkyl groups show a linear relationship between the logarithm of the relativeretention time and normal boiling point, whilst C,, C,, C,,, C,,, and C,,alkylbenzenes lie on 5 parallel lines whose separation from each other isrelated to the logarithm of the number of carbon atoms in the alkylgroup.Kratzl and Gruber lrn have developed an ingenious method which islikely to be of interest to analysts concerned with the determination ofalkoxyl groups.By means of hydriodic acid, the alkoxyl groups are con-verted into the corresponding iodides which are quantitatively absorbedon a short column. The iodides are then transferred to a gas-liquidchromatographic column where they are separated on a tritolyl phosphate156 D. M. W. Anderson, Analyst, 1959, 85, 50.157 R. S. Gohlke, Analyt. Chem., 1959, 31, 535.158 J. H. Karchmer, Analyt. Chern., 1959, 31, 1377.159 Ta. Chuang Lo Chang and C. Karr, jun., Analyt. Chim. Acta, 1959, 21, 474.160 K. Kratzl and K. Gruber, Monatsh., 1958, 89, 618403 ANALYTICAL CHEMISTRY.stationary phase. The separated iodides are determined by the conventionalbromination procedure. In addition, it has been shown by Spingler andMarkert that acetyl and formyl groups may be determined and differenti-ated in organic compounds by a rather novel process.The substance isfirst heated with methanol and hydrogen chloride and the methyl acetateand methyl formate produced are separated from the methanol and hydro-chloric acid, etc., by gas chromatography.The selective reactivity of silver nitrate with 2-bromobutane has beenused by Harris and McFadden 162 in a gas-liquid chromatographic methodfor the determination of 2-bromobutane and l-bromo-2-methylpropane.An additional tube packed with crushed firebrick impregnated with silvernitrate is inserted into the feed tube to the chromatographic column. Thisabsorbs the 2-bromobutane at room temperature and the l-bromo-2-methyl-propane is registered on the chromatogram.The analysis can be repeatedwithout the absorption tube, both compounds then being registered andeach component can thus be determined by difference. Brealey et ~ ~ 1 . l ~ have developed a useful method for the gas-liquid chromatographic deter-mination of chloroform in aqueous pharmaceutical preparations. Theessential features of their test are that (a) n-propanol as internal marker isadded to the sample under test, (b) a high molecular-weight polyethyleneglycol is used as stationary phase, and (c) the column is operated at 88";the injection system is designed to avoid fouling of the column. n-Propanol,chloroform, and water are satisfactorily separated and the proportion ofchloroform in a particular preparation is deduced from the peak heights dueto chloroform and n-propanol.A polyethylene glycol of high molecular weight has been found to beparticularly useful for the separation of the products arising from the high-temperature coking of coal,l6* and this has enabled valuable information tobe gained about the benzene, toluene, xylene, styrene, and trimethyl-benzene contents of light oils.The picrate method for the determination ofnaphthalene in coke-oven gas is not particularly satisfactory because thepicrate precipitate is contaminated with the picrates of hydrocarbons otherthan naphthalene. If, however, the impure picrate is decomposed withacetic acid and then extracted with benzene, the benzene extract may thenbe examined by gas-liquid chromatographic test to give a true measure ofthe naphthalene.Vacuum pyrolysis or depolymerisation and gas-liquid chromatographicexamination of the products obtained have for some time been used for theidentification of acrylate and methacrylate polymers.Radell and Strutz 165have designed a method whereby the controlled-temperature pyrolysis iscarried out in an apparatus attached directly to the chromatographiccolumn. This permits the complete analysis to be carried out on about5 mg. of sample and has the advantage that conditions can be made stableand reproducible. By repeating the analysis on two columns with different161 H. Spingler and F. Markert, Mikrochim. Ada, 1959, 122.162 W. E. Harris and W. H. McFadden, Analyt.Chem., 1958, 31, 114.163 L. Brealey, D. A. Elvidge, and K. A. Proctor, Analyst, 1959, 84, 221.164 H. Ritter and H. Schnier, 2. analyt. Chem., 1959, 170, 310.165 E. ,1. Radell and H. C. Strutz, Analyt. Chem., 1959, 31, 1890HASLAM AND SQUIKRELL: PHYSICAL METHODS. 403retention characteristics, qualitative identification of the components of thepyrolysis products can be made.Langer and his co-workers 166 have overcome difficulties in the gas-liquidseparation of phenols by converting them into their trimethylsilyl ethersbefore chromatographic test. Chromatograms showing clear separationswith no tailing of the peaks are obtained, and the method can be applied toaqueous solutions since water is converted into hexamethyldisiloxane andtrimethylsilanol in the conversion reaction and these are eluted initiallyfrom the column.A method, which is also applicable to other anti-oxidants and maskingagents, has been presented by Jennings and his co-workers 167 for the deter-mination of 2,6-di-t-butyl-~-cresol in paperboard. The anti-oxidant isextracted with cyclohexane-propan-2-01 and concentrated, followed bygas-liquid chromatographic test of an aliquot part of the concentrated ex-tract.The column used is propylene glycol on C22 firebrick, with heliumas carrier gas at a temperature of 200". The relative retention times ofvarious anti-oxidants when using the above column and a silicone columnare given, and it is evident that such data can be used for the qualitativeexamination of anti-oxidants.Absorption Spectroscopy.-In this section we have tried to cover as widea range as possible of the large number of excellent papers published in 1959on all branches of absorption spectroscopy.There are very few analysts who have not, a tsome time or other, felt the need of an effective method for the extractionof calcium from solutions in such a way that the calcium may be determinedin the extracted phase.Umland and Meckenstock 168 have shown that, inthe simultaneous presence of both n-butylamine and 8-hydroxyquinoline,calcium may be quantitatively extracted by chloroform from a solution ofpH 11-12. Moreover, the calcium may be determined in the chloroformextract by photometric 'measurement at 370-380 mp. The procedure maybe adapted to the determination of calcium in a whole host of technicalproducts.Copper forms a stable greenish-yellow complex with Tiron (disodiumsalt of 4,5-dihydroxybenzene-1,3-disulphonic acid) and Majumdar and Sava-riar 1G9 have taken advantage of this in a spectrophotometric method forthe determination of small amounts of copper.The complex is formedat a pH of 6.1-6.9 and is measured at its absorption maximum of 375 mp.Jacobs and Yoe 170 have studied the complexes formed by copper, cobalt, andnickel with NN'-bis-(3-dimethylaminopropyl)dithio-oxamide. Cobalt formsa yellow, nickel a reddish-orange, and copper an olive-green complex, andalthough these complexes are themselves insoluble in water, the use of aprotective colloid enables solution to be effected over a required concen-tration.By measurement at 500, 430, and 315 mp of the complexes166 S. H. Langer, P. Pantages, and I. Wender, Chevn. and Ind., 1958, 1664.167 E. C. Jennings, jun., T. D. Curran, and D. G. Edwards, ,4naZyt. Chem., 1958, 30,168 F. Umland and I<. U. Meckenstock, 2. andyyt. Chem., 2959, 165, 161.IG9 A. K. Majumdar and C. P. Savariar, Andyt. Chim. Actn, 1959, 21, 53.170 \V, D. Jacobs and J . H. Yoe, Analyt. Chiin. Ada, 1969, 20, 435.Inorganic applications.1946404 ANALYTICAL CHEMISTRY.formed at pH 9 and application of a spe.ctrophotometricic equation, allthree elements can be determined when present together in the test solution.Small amounts of ferric iron have been titrated at pH 3.5 with ethylene-diamine-(o-hydroxyphenylacetic acid) to a photometric end-point.Themethod 171 can cover a wide range of iron concentrations, for by decreasingthe volume of solution and titrant strength, microgram quantities can betitrated. To decrease the sensitivity for the titration of milligram amountsof iron, the wavelength chosen for photometric measurement is adjustedaccordingly away from 470 mp, at which wavelength the red ferric chelateshows maximum absorption.Ducret and Maurel have carried out much work on the analysis ofminerals, using extraction methods and coloured cations. In the firstmethod 172 for the determination of traces of gold in solution, gold chlorideis complexed with Methyl Violet and the complex is quantitatively extracteda t a low pH with trichloroethylene. The colour of the extract is measuredat 600 mp.In the second method,173 in which Crystal Violet is used ascomplexing agent, traces of tin can be determined by extraction of thecoloured complex with dipropylacetone and measurement at 595 mp. Athird method174 can be used for the determination of traces of phosphatein the form of phosphomolybdate. The phosphomolybdate is complexedwith safranine, and the colour extracted with acetophenone at pH 1-5 beforespectrophotometric measurement at 532.5 mp. Finally, these authors havedescribed a method for the indirect determination of traces of sulphate bymeans of an ion-exchange resin.175 The sulphate ions are exchanged withan equivalent amount of thiocyanate ions, and these are determined byextraction with dichloroethane after forming a complex with MethyleneBlue.Molybdates may be separated from vanadates by taking advantage ofthe fact that, with excess of thioglycollic acid, molybdates produce a molyb-denum(II1) complex of dithioglycollic acid.176 At the appropriate pH thiscompound is selectively absorbed on a Dowex resin, and the vanadium inthe eluate then determined by colorimetric measurement of the blue reactionproduct obtained by the action of excess of thioglycollic acid on the vanadiumcompound.The molybdenum may then be eluted from the column anddetermined as its 8-hydroxyquinoline complex. The determination of smallamounts of magnesium in the presence of large amounts of zinc is carried outby Maurice177 by a method which involves a preliminary removal of thezinc and some other interfering elements by a controlled electrolysis using amercury cathode.Any aluminium is then removed by a chloroform extrac-tion with 8-hydroxyquinoline, and the magnesium finally determined colori-metrically at 505 mp as the complex formed at pH 8.95 with 3-(2,4-dimethyl-phenylcarbamoyl) - 2-hydroxy- 1 - o - hydroxyphenylazonaphthalene. A most171 A. L. Underwood, Analyt. Chim. Acta, 1959, 20, 228.172 L. Ducret and H. Maurel, AnaZyt. Cham. Acta, 1959, 21, 74.173 L. Ducret and H. Maurel, Analyt. Chim. Ada, 1959, 21, 79.174 L. Ducret and M. Drouillas, Analyt. Chim, Ada, 1959, 21, 86.175 L. Ducret and M. Ratouis. Analyt. Chim. Acta, 1959, 21, 91.176 M. Ziegler and W. Rittner, 2.analyt. Chem., 1958, 164, 310.17' hl. J . Maurice, Analyt. Chzm. Ada, 1969, 20, 181HASLAM AND SQUIRRELL: PHYSICAL METHODS. 405useful method has been described by Monnier and Haerdi 178 for the deter-mination of microgram amounts of nickel in the presence of large amountsof other cations. The nickel is precipitated as its nioxime complex andextracted with organic solvent, when, after preliminary procedures toseparate it from foreign cations, it is determined by colorimetric measure-ment in quinoline solution.Sonnenschein’s procedure 179 for the determination of traces of silicon inwater follows fairly conventional lines in the initial production of silico-molybdenum-blue. After that an oxyethyl lauryl amine of this kind offormula is used, where x + y = ca.16:This amine combines with the silicomolybdenum blue to yield a chloroformsoluble complex, suitable for photometric measurement. Ringbom andhis co-workers 180 have also described a method capable of high precision forthe determination of silicon, this time in insoluble silicates, clays, etc. Thesample is fused with sodium hydroxide, and the melt dissolved in watercontaining EDTA. Silicomolybdic acid is now formed by reaction withammonium molybdate in a monochloroacetic acid-ammonium chloroacetatebuffer a t a pH of 3.0-3.7, and the yellow colour produced, which is stablefor almost 2 days, is measured at 390 mp.Everest and Martin181 have developed a useful method for the deter-mination of thorium in medium-grade ores. In the presence of mesotartaricacid, which complexes any zirconium present, the thorium is separated froma nitric acid solution by extraction with a solvent containing tri-n-butylphosphate and ethyl methyl ketone as diluent.Aluminium nitrate is usedas a salting-out agent. The thorium in the organic phase is extracted withwater, followed by absorptiometric determination with l-(o-arsonophenyl-azo)-2-naphthol-3,6-disulphonic acid. Two turbidimetric procedures havebeen devised for the determination of 0.001-@4~0 of tin in copper basealloys.ls2 The first method, applicable in the presence of small amounts ofiron, utilises phenylarsonic acid as reagent. In the examination of samplescontaining large amounts of iron and small amounts of tin the more sensitivereagent 4-hydroxy-3-nitrophenylarsonic acid is recommended, more especiallywhen the tin content is below O .O l ~ o . The methods appear relatively freefrom interference except froin iron.Titanium can be extracted as its thiocyanate complex from sulphate orchloride acidic solutions by tri-n-octylphosphine oxide dissolved in cyclo-hexane. The complex in this medium exhibits a molar absorbance indexof 41,000 at lmX. = 432 mp, and the principle outlined above has beenused in a most simple and sensitive method for the determination of titanium,described by Young and White.183 Neither quadrivalent metal ions nor178 D. Monnier and W. Haerdi, Analyt. Chim. A d a , 1959, 20, 444.179 W. Sonnenschein, 2. analyt. Chem., 1959, 168, 18.180 A.Ringborn, P. E. Ahlers, and S. Siitonen, Analyt. Chim. A d a , 1959, 20, 78.181 D. A. Everest and J. V. Martin, Analyst, 1959, 84, 312.182 H. J. G. Challis and J . T. Jones, Analyt. Chim. Acta, 1969, 21, 58.183 J . P. Young and J. C. White, Analyt. Chem., 1959, 81, 393406 ANALYTICA4L CHEMISTRY.large amounts of Fe(n) or U(VI) interfere in the test. Strocchi and ReboralMhave made strong claims that the dihydroxylamine salt of dihydroxymaleicacid is an extremely sensitive and specific reagent for the colorimetric deter-mination of titanium. The test has to be carried out at a definite pH valueand with a specific time of colour development.Maeck and his co-workers 185 have devised two spectrophotometricmethods specific for uranium. They are based on extraction of the uraniumas tetrapropylammonium uranyl trinitrate with isobutyl methyl ketone, froman acid-deficient aluminium nitrate salting solution.Milligram amounts ofuranium are determined in the extract by direct spectrophotometric measure-ment of the complex at 425 mp. Microgram amounts are determined byadding dibenzoylmethane to the solution in an ethyl alcohol-pyridinemixture and measuring the absorption of the chelate so formed at 415 mp.Vanadium has often been determined in the past by oxidation with hydrogenperoxide in sulphuric acid solution and measurement of the resulting colouredsolution at 460 mp. At this wavelength the concentrations of sulphuric acidand hydrogen peroxide are critical. Harthamp,ls6 however, has shown thatby working at the isosbestic point, vix., 405 mp, the determination may bemade virtually independent of sulphuric acid and hydrogen peroxidecontents.A useful solvent-extraction method for the determination of zinc hasbeen described by Scroggie and Dean.ls7 The zinc is quantitatively ex-tracted from a hydrochloric acid solution of the sample with a 5% (w/v)solution of tri-iso-octylamine in isobutyl methyl ketone.The zinc is thendetermined in situ in the organic phase by using 2-carboxy-2’-hydroxy-5’-sulphoformazylbenzene (Zincon) colorimetric measurement being made at620 mp. o-Carboxyphenylazo-l,8-dihydroxynaphthalene-3,6-disulphonate(sodium salt) prepared by diazotisation of anthranilic acid and couplingwith chromotropic acid, has been shown by Majumdar and Savariar 188 toform soluble coloured complexes with thorium and zirconium.Thesecomplexes obey Beer’s law over convenient concentration ranges and hencecan be used for the determination of traces of these elements. The azo-dyehas also proved to be an excellent complexometric indicator for thesemetals.The coloriinetric determination of halides has received much attention,and a method which may well have other applications has been worked outby Geld and SternmanlS9 for the determination of small amounts ofchloride in hydrogen peroxide. After careful decomposition and evapor-ation of the sample, the residual chloride is treated with mercury thio-cyanate, with consequent liberation of an equivalent amount of thiocyanateions, which form a reddish-orange complex with ferric iron.This colour,which is proportional to the chloride, is suitable for colorimetric measurement.184 P. M. Strocchi and P. Rebora, 2. analyt. Chem., 1959, 169, 1.185 W. J. Maeck, G. L. Booman, M. C. Elliott, and J. E. Rein, Analyt. Clzem., 1959,186 H. Harthamp, 2. analyt. Chem., 1959, 169, 339.187 L. E. Scroggie and J. A. Dean, Analyl. Chim. Acta, 1959, 21, 282.188 A. K. Majumdar and C . P. Savariar, Naturwiss., 1959, 46, 323.189 I. Geld and J. Sternman, Analyt. Chem., 1959, 31, 1662.31, 1130I-IASLAM AND SQUIRRELL : PHYSICAL METHODS. 407Chemists concerned with the analysis of brine will be interested in thework of Collins and Watkins,lgo who have described a rapid and precisemethod for the determination of iodides and bromides in oil-field brines.Iodides are oxidised to iodine with nitrite and extracted with carbon tetra-chloride.The absorbance of this solution at 517 mp is a direct measure ofthe iodide present. After removal of iodides, the bromide is oxidised tobromine with hypochlorite, and the bromine is extracted with carbontetrachloride, and its absorption measured at 417 mp. The method isespecially useful when the concentration ratio of chlorides to the otherhalides is too large to permit determination of bromides and iodides bypotentiometric and other instrumental methods.An improved method for the determination of fluoride in blood serum,which is obviously applicable to other samples, has been presented by Singerand Armstrong.lgl The sample is ashed at a low temperature in the presenceof specially prepared magnesium oxide, and the ash transferred to a micro-distillation apparatus. The perchloric acid distillation of the fluoride iscarried out with a stream of nitrogen passing through the apparatus to sweepthe fluoride from the microcell to the receiver, which markedly reduces thedistillation volume required. The fluoride in the distillate is determined bytreatment with a reagent lake consisting of a mixture of EriochromeCyanine R solution and zirconyl chloride solution under defined conditions,and measurement of the resulting colour at 568 mp.A new colorimetricmethod for the determination of low concentrations of fluoride has beendescribed by Kamada and Onishi.lg2 They use the zirconium lake of theazo-dye, 9-dimethylaminoazophenylarsonic acid, which reacts with fluorideto give the zirconium fluoride complex ion, liberating an equivalent of theazo-dye, which is separated from the unreacted insoluble lake and measuredspectrophotometrically at 500 mp.The reaction of nitrate and nitrite with brucine hydrochloride in thepresence of sulphuric acid has been used by Fischer et dlg3 in two usefulmethods for the colorimetric determination of these ions.For the deter-mination of nitrite alone, even in the presence of nitrate, the reaction iscarried out with a total concentration of 17% sulphuric acid. When theacid concentration is increased to 5oy0, both nitrate and nitrite react andthe total is determined.The colorimetric measurements are made at410 mp. For the assay of sulphuric acid solutions in the concentrationrange 85-99y0 of acid to within &0-3y0, Zimmerman and Brandt 194 havedeveloped a spectrophotometric procedure. The method takes advantageof the fact that quinalizarin when dissolved in various concentrations ofsulphuric acid shows absorption maxima at 537, 575, and 605 mp and anisosbestic point a t 585 mp. The ratio of the absorbance of the solution at535 mp and 630 mp is determined and the concentration of the acid solutionobtained from a previously prepared calibration graph.190 A. G. Collins and J . W. Watkins, Analyt. Chem., 1959, 31, 1182.191 L. Singer and W. D. Armstrong, Analyt. Chem., 1958, 31, 105.192 M. Kamada and T.Onishi, J. Chem. SOC. Japan, 1959, 80, 275.193 F. L. Fisher, E. R. Ibert, and H. F. Reckman, ,4nalyt. C h ~ m . , 1958, 30,1972.194 E. Zimmcrmsn and W. W. Rrandt, Tnlantcz, 1958, 1, 374408 ANALYTICAL CHEMISTRY.Dunstone and Paynelg5 have developed an interesting method for thespectrophotometric determination of zinc, magnesium, cadmium, calcium,strontium, and barium with et hylenediamine-NNN'N'- t e t ra-ace tic acid ;e.g., in the case of zinc the test is based on the fact that, the optical densityof an EDTA solution both in the presence and in the absence of zinc beingknown, the optical density difference may be used as a measure of the zinc.It is necessary, of course, that the zinc must form a chelate with the EDTAand that this chelate has very little absorption at the wavelength used.Chenglg6 has shown that the selectivity of the cupferron method for thedetermination of titanium may be greatly increased by adding EDTA asmasking agent and extracting the complex with 4-methylpentan-Z-one,followed by absorptiometric measurement in the near ultraviolet and theultraviolet region.Under these conditions, titanium, uranium, and ceriumgive yellow complexes, and tin, beryllium, aluminium, iron, hafnium,zirconium, niobium, tantalum, and the rare earths give colourless complexes.The sensitivity of the test to uranium and cerium is not great, and hencetitanium can be determined in the presence of traces of these elementswithout previous separation.A fluorimetric determination which might well be applicable in appro-priate circumstances has been outlined by Rao and A~pa1araju.l~' Itdepends on the blue fluorescence produced by boric acid with resaceto-phenone in sulphuric or phosphoric acid.It may be possible to utilise thisreaction in the determination of boric acid in particular circumstances. Onthe subject of X-ray fluorescence analysis, Brown lQ8 has concluded his mostuseful review with the forecast that the method will find increased applicationto routine and non-routine analytical problems. Advantages are that themethod is rapid, independent of the chemical combination of the element,and non-destructive in that the sample examined is not destroyed during test.The review by Duyckaerts lB9 on the infrared analysis of solid substanceshas set out the physical and chemical factors affecting the spectra.Thelatter include adsorption of substance on particles of dispersing medium,chemical reaction of substance with medium, polymorphism of substance,mixed crystal-formation, distortion of the crystalline structure, and form-ation of complexes between substance and medium.The growing use of infrared spectroscopy in inorganic analysis is demon-strated in a paper by Tuddenham and Lyon,200 who have shown that un-known chlorite minerals can be classified by infrared spectroscopy alone.By relating the infrared data with the chemical analysis of some 21 chloritesand related minerals, both the degree of substitution of aluminium forsilicon and the total iron content of the mineral can be estimated and thestructural type can also be readily deduced.Also in the inorganic fieldNeeb 201 has developed an interesting method of examination of binarylg5 J. R. Dunstone and E. Payne, Analyst, 1959, 84, 110.lu6 K. L. Cheng, Analyt. Chew, 1958, 30, 1941,197 G. Gopala Rao and N. Appalaraju, 2. malyt. Chem., 1969, 167, 325.198 F. Brown, Analyst, 1959, 84, 344.lg9 G. Duyckaerts, Analyst, 1959, 84, 201.200 W. M. Tuddenham and R. J. P. Lyon, Analyt. Chtm., 2959, 81, 377.201 R. Neeb, 2. analyt. Chem., 1959, 170, 95HASLAM AND SQUIRRELL : PHYSICAL METHODS. 409mixtures of aluminium , gallium , and indium. Precipitation with 8-hydroxy-quinoline gives a measure of the total constituents- in the binary mixture,The dried 8-hydroxyquinoline precipitate is mixed with casium bromideand examined as a czesium bromide disc in the infrared regioh of the spec-trum.The individual oxinates have characteristic absorption bands.Particular care is necessary in the preparation of the ccesium bromide discs.A useful method has been devised by Starkeg 202for the colorimetric determination of acetylacetone. This p-diketohe isallowed to react with cupric acetate under specific pH conditions. Theblue chelate thus formed is extracted with chloroform before absorptio-metric measurement at 650 mp. Nicksic and Juddao3 have utilised thegeneral reaction of primary and secondary arylamines with furfuraldehydeto give highly coloured reaction products, in a method for the determinationof $$'-dioctyldiphenylamine in hydraulic fluids.The sample in solution inpropan-2-01 is treated with 18N-sulphuric acid and filtered. The furfur-aldehyde reagent is added to an aliquot part of the filtrate, and the colourmeasured against a similar aliquot part containing no added furfuraldehydeat 385 mp. Degradation products of the amine do not interfere, but adisadvantage of the method is that the reaction does not go to completionand calibration is required with each set of samples tested.A simple method for the determination of small amounts of such per-oxides as benzoyl peroxide , lauroyl peroxide , and cumene hydroperoxidedescribed by Eiss and Giesecke204 takes advantage of the reaction withbenzoyl-leuco-Methylene Blue to form a characteristic Methylene Bluecolour suitable for colorimetric measurement at 662 mp.Zirconiumnaphthenate is used to accelerate the peroxide decomposition in trichloro-acetic acid-benzene solution and thereby increase the leuco-dye reactionrate. The time for complete colour development at 25" varies with theperoxide under test from 30 minutes in the case of t-butyl hydroperoxideto 30 hours for benzoyl peroxide, but once developed, the colours appearstable for several days if kept in the dark at this temperature. Johnsonand Savidge 205 have investigated the use of 4-aminophenazone as a couplingreagent in the presence of an oxidising agent for the determination ofphenols. Suitable conditions of test have been outlined, and the reagentappears useful for the determination of several phenols of pharmaceuticalinterest.A novel test, which may have far-reaching consequences, has beendeveloped by Saville 206 for the colorimetric determination of microgramamounts of thiols.The thiol solution is first treated with nitrous acid toform the S-nitrosothiol. Excess of nitrous acid is now removed by am-monium sulphamate , and an acid solution of sulphanilamide containingmercuric chloride is added. Under these conditions the S-hitmsothiol ishydrolysed to yield nitrous acid, which in its turn diazotises the sulphanil-amide. This diazotised base is coupled with N-l-naphthylethylenediamineOrganic applications.202 R. J. Starkey, Analyst, 1959, $4, 517.203 S. W. Nicksic and S. H. Judd, Analyt. Chem., 1958, 30, 2002.204 M. I.Eiss and P. Giesecke, Analyt. Chew., 1M9, 81, 1558.206 E. Saville, Analyst, 1968, 83, 070.C. A. Johnson and R. A. Savidge, J . Pharm. Pharmacol., 1958, 10, 1713410 ANALYTICAL CHEMISTRY.hydrochloride to yield an intensely coloured azo-dye, suitable for colori-metric measurement and proportionate to the amount of thiol originallysubmitted to the test.Preliminary tests with diazotised dianisidine and Gibbs’s reagent suggestthat these reagents cannot be used very effectively in the separation of thevarious tocopherols. Marcinkiewicz and Green 207 have subsequentlydeveloped a procedure, however, for the separation of the six nitrosotoco-pherols, ie., the two nitrosotocopherols derived from y-tocopherols and theindividual nitroso-derivatives of p-, y-, E-, and q-tocopherol.The separatednitroso-derivatives may then be determined by application of the ferricchloride-bipyridyl reaction. The procedure has been showii to be of valuein the analysis of synthetic mixtures of tocopherols and in the determinationof p- and &-tocopherols in natural oils.Determinations of biuret in commercial samples of urea2W have beenaccomplished by reaction of the biuret with alkaline nickel tartrate solutionand measurement of the absorption of the resulting nickel complex at465 mp. This method seems to suffer much less interference from the pre-sence of ammonium compounds than does the corresponding methodinvolving the preparation of the copper complex.In order to obtain the required accuracy in absorptiometric measure-ments in the far ultraviolet region, Hansen and Buell2Og have developed aspectrophotometer for use in the range 194-225 mp.The instrument has ahalf-intensity band width of 1.5 mp and has good sensitivity. The sameauthors 210 have described the use of the instrument for obtaining absorptionspectra of some biologically important compounds in the far ultravioletregion.A considerable amount of work has been carried out by a joint com-mittee of the Pharmaceutical Society and the Society for AnalyticalChemistry211 which has led to the development of methods for the deter-mination of the capsaicin content of capsicum and its preparations. Afterpreliminary preparation of the sample, the capsaicin is extracted eitherchromatographically or by an ether-alkali partition method.The directspectrophotometric method may then be used to determine the capsaicin.Alternatively, advantage may be taken of the fact that capsaicin, i.e., thevanillylamide of isodecenoic acid, is, in effect, a phenolic substance, and, assuch, couples with a diazotised base. Further, in the preferred method, itproduces a phenoxide when treated with alkali solution. At the same time,this production of phenoxide is accompanied by a precise and definite shiftin the ultraviolet absorption. McKinney and Reynolds 212 have also takenadvantage of the shift in absorption of phenols to longer wavelengths whenconverted into their phenoxide ions in a photometric titration method for theirdetermination.The absorption spectra of both phenol and its ion aremeasured, and a wavelength is selected where only the phenoxide ion shows207 J. Green and S. Marcinkiewicz, Analyst, 1959, 84, 297,208 J. Sverak, 2. analyt. Ckem., 1959, 169, 178.200 R. E. Hansen and M. V. Buell, Analyt. Ckem., 1959, 31, 878.2lO R. E. Hansen, J . Bid. Ckem., in the press.211 Analyst, 1959, 84, 603.212 R. w. McKinney and C. A. Reynolds, Talnnta, 1958, 1, 46JIASLAM AND SQUIRRELL PHYSICAL METIIOI>S. 41 1absorption. The phenol in butylamine solution can now be titrated withalcoholic potash solution, the end-point being determined by plottingabsorbance a t the selected wavelength against the volume of titrant addedand observing intersection of the straight line drawn through the linearportions of the plot.The determination of copolymerised styrene in copolymers containingcarbon black and other fillers, and in insoluble polymers presents greatdifficulty.Hilton et aL213 have overcome this difficulty by nitrating asuitably extracted sample of the polymer with nitric acid under reflusconditions. The styrene yields reproducible amounts of $-nitrobenzoicacid, which is extracted from the nitration products and examined in sodiumhydroxide solution by ultraviolet absorption measurements at 265, 273.75,and 285 my, from which the styrene content can be calculated. The methodhas an accuracy of about 0.2%.Infrared examinations of many organic substances are often made by thepotassium bromide disc method.Quantitative measurements by thisprocedure are not always as accurate as could be wished, and Ileller andWagner 214 claim to have obtained results of better accuracy in the examin-ation of steroid mixtures by melting the mixture between sodium chloride orpotassium bromide plates before the infrared test. For this procedure it isnecessary, of course, that the steroid mixture does not decompose on melt-ing. Chemists concerned with the identification of anionic surface-activeagents will be interested in the paper by Jenkins and K e l l e n b a ~ h . ~ ~ ~ Theseauthors have prepared the barium salts of some 10 organic sulphates andsulphonates and have found that the infrared spectra of these water-insolublesalts serve as an excellent means of identification.They give details of themethod of preparation and ashing of the salts in addition to the procedure forobtaining the infrared spectrum by the potassium bromide disc technique.The use of Alodan, 5,6-bischlorome thyl- 1,2,3,4,7,7-hexachlorobi-cyclo[2,2,l]hept-Z-ene, as a contact insecticide to guard against the ravagesof corn beetle has necessitated the development of a very accurate methodfor its determination in grain. The direct determination cannot be accom-plished, but it is possible by Paulig's method216 to extract the grain withcarbon tetrachloride, to purify this carbon tetrachloride extract by chromato-graphic treatment, then to convert the Alodan in the extract into 5,6-di-met hylene- 1,2,3,4,7,7-hexachlorobicyclohept ene, which is readily deter-mined by infrared measurement.The conversion is accomplished with theaid of alcoholic potash.Lee Smith and McHard 217 have presented much useful infrared spectro-photometric data on organo-silicon compounds. They are able by thismethod satisfactorily to characterise materials whether they be in themonomeric or polymeric state. The method of examination and sometypical spectra of chlorosilanes and silicon polymers are shown, and theinterpretation of these spectra in terms of group frequencies is explained.213 C. L. Hilton, J, E. Newell, and J. Tolsma, Analyt. Chem., 1959, 31, 915.214 I<. Heller and U. Wagner, 2. analyt. Chem., 1959, 16'4, 90.215 J. W. Jenkins and I<. 0. Kellenbach, Andyt. Chem., 1959, 31, 1056.917 A. Lee Smith and J.A. McHard, Analyt. Chem., 1959, 31, 1174.G. Paulig, 2. analyt. Chem., 1959, 168, 401412 ANALYTICAL CHEMISTRY.Lady and his co-workers218 have also used infrared spectroscopy for theanalysis of silicon polymers. They are able to determine the ratio of methylto phenyl groups in such polymers by measuring the intensity of the methyl-silicone and phenylsilicone compounds at 7.92 and 6.97 microns respectively.Most of the standard spectra are prepared from methylphenyldichlorosilaneand methyltrichlorosilane mixed in the appropriate proportions, and in-fluences due to polymeric structure on deviations from this calibration arediscussed.Two useful methods for the identification and analysis of polyurethanerubbers by ihfrared spectroscopy have been detailed by P.J. Corish.219 Inthe first method the rubber is examined as such, in the form of a microtomedsection. The use of crystallinity bands to characterise the acid portion ofthe polyester is discussed, together with the characterisation of di-isocyanatesby their absorption in the skeletal region. In the second method the rubberis hydrolysed in a stainless-steel tube with aqueous sodium hydroxide. Thediamine resulting from the original di-isocyanate is extracted with ether, theaqueous layer then filtered free from disubstituted ureas, and the filtrate dis-tilled substantially to dryness. By drying the distillate in a vacuumdesiccator over phosphoric oxide the glycol resulting from the hydrolysis canbe isolated. The dicarboxglic acids produced are isolated from the distill-ation residue after acidification with hydrochloric acid.The s0dil.mchloride formed in the neutralisation of the excess of alkali, of course, has noeffect in the subsequent infrared examination.In other papers concerned with the infrared examination of plastics,Rohmer 820 has stated that difficulties which arise in the determination ofmethyl groups in polyethylene are often bound up with the method ofstandardisation. He has suggested that many of these difficulties may beavoided by the use of appropriate standards prepared from polyethylene-polypropylene mixtures. Luther, Meyer, and Loew 221 have studied theinfrared spectroscopy of polyvinyl chloride plasticiser films, prepared fromdifferent dialkyl phthalates and different kinds of polyvinyl chloride.Theyconclude that there are two key frequencies, 1430 crn.-l for the polyvinylchloride and 1728 crn.-l for the phthalates, which follow the Beer-Lambertlaw in a concentration range of technical interest, and hence are suitablefor the determination of phthalate plasticiser in polyvinyl chloridefilms.Emission Spectroscopy.-In a most interesting article on Accuracy inSpectrochemical Analysis, Arrak and Mitteldorf 222 have discussed thesubject under six main headings, viz., sampling, spark source, electrodes,spectrograph, photometry, and calcdations. They also mention newtechniques for reducing variables, including special optics for reducing theeffect of arc wander, the packing of electrodes with powder samples, anddevices for mechanically traversing a flat sample during sparking.31, 1100.218 J.H. Lady, G. M. Bower, R. E. Adams, and F. P. Byme, Analyt. Chem., 1959,210 P. J. Corish, Analyt. Chem., 1959, 31, 1298.220 M. Rohmer, 2. analyt. Chem., 1959, 170, 147.221 H. Luther, H. Meyer, and H. Loew, 2. analyt. Chem., 1969, 170, 155.222 A. Arrak and A. J. Mitteldorf, A$$J~. Spectroscopy, 1969, 18, 86HASLAM AND SQUIHRELL : PHYSICAL METHODS. 413Kelley, Fischer, and Jones z23 have described the constructioii and useof 3 high-sensitivity recording flame spectrophotometer which has exceptionalperformance in the red spectral region, Special features and advantages ofthe instrument include high precision and dependability combined withgreat sensitivity.As a result, anion and salt interferences can be minimisedby working at estreme dilution. Reduction of spectral and flame back-ground interferences are achieved by use of a good monochromator. A new" vacuum cup " method has been proposed by Zink 224 for the handling ofsolution samples in spectrochemical analysis. In the method, which avoidstrouble due to boiling over, the sample is contained in a plastic cup surround-ing a centre bored graphite electrode which also has a transverse cut, toallow flow of sample into the centre bore. The sample is sucked into theanalytical gap for excitation by means of the rcduced pressure created inthe spark gap by each discharge pulse.The micro-sampling and -analysis of metals present as tiny specks onthe sample surface has been reviewed by Kunge and Bryan.225 They de-scribe the niethods for the removal of millimicrogram quantities of thesemetallic constituents from the sample by means of special drills as smallas 6.3 microns in diameter. The drilling is performed under a stereoscopicmicroscope, and the drillings obtained are transferred to ultra-pure electrodesfor spectrographic examinat ion.A method has been described by Baird 226 for the spectrochemical analysisof very pure samples of chromium.The chromium is volatilised as chromylchloride and the impurities are collected on a calcium sulphate matrix.This matrix containing the impurities is now burned in a d.c. arc, and theamount of the impurities calculated from measurement of the impurity lineintensities, with indium as an internal standard; Mg, Pb, Fe, Al, Cu, andAg have been satisfactorily detcrmiricd in chromium by this method in therange 0.005-0.0001 yo.A method developed by Radmacher and H e s s l i i ~ g ~ ~ ~ for the spectro-analytical determination of trace elements in coal is really a method for theirdetermination in the carefully prepared ash of the coal.The method isbased on the behaviour on excitation of a mixture of the ash, ammoniumchloride, and carbon powder of very high purity. In the examination ofslags, a preliminary fusion with borax is first effected. Rekus 2% prefersto use indium as the internal standard for the spectrographic determinationof potassium in coal ash. Its advantages are that it is usually absent fromcoal and, spectrographically, it is a compatible partner for potassium, theindium line being approximately 60 A removed from the potassium line, andsuffers no interference from other elements present in coal ash.Indium alsohas the merit that its excitation potcntial is similar to that of potassiumand its ionisation potential is not too far removed from that of potassium.A very useful step which has as its object the preliminary concentration223 31. T. Ketley, I). J . Fischer, and H. C. Jones, AnaZyt. Clzem., 1959, 31, 178.224 T. H. Zink, Appl. Spectroscopy, 1959, la, 94.228 E. F. Kunge and I;. R. Bryan, AppZ. Spectroscopy, 1959, 13, 74.226 C. G. Baird, Appl. Spectroscopy, 1959, $3, 29.227 'CV. Radmacher and H.Hcssling, Z . analyt. Chem., 1959, 167, 172.228 A. F. Rekus, Appl. Spectroscopy, 1958, 18, 141414 ANALYTICAL CHEMISTRY.of small amounts of thallium present in test substances has been proposed.229Advantage is taken of the relatively high vapour pressure of thallium and itscompounds and the thallium is volatilised in a stream of oxygen or hydrogen,the products being collected on a metallic cold finger before spectrographicdetermination of the thallium.It is fairly obvious that there are likely to be important developments inthe use of atomic absorption spectroscopy in the determination of metalsin solution. The principle of the test was outlined in our previous Report(1958) and this principle has now been extended to the determination ofsilver, gold, platinum, rhodium, and palladium in solution.B0 It is probable,however, that the early papers concerned with analytical determinations byatomic absorption spectroscopy stressed the specific character of the testrather too strongly.David,=l in his paper, points out that phosphorus,aluminium, silicon, sodium, and potassium will all interfere in the deter-mination of calcium in the wet digestion products of plant material byatomic absorption spectroscopy. These interferences may be avoided, ie.,that of phosphorus, aluminium, and silicon by the addition of magnesiumand sulphate to both sample and standard, and that of sodium and potassiumby addition of these elements in excess to both sample and standard.Products obtained by the wet digestion of plant material appear to bevery suitable for the determination of zinc and magnesium by atomicabsorption spectroscopy.In a method also due to D a ~ i d , ~ ~ 2 a hollowcathode discharge tube emits intermittent light of the element to be deter-mined at a particular frequency. Between this discharge tube and the slitof a medium quartz spectrograph there is a Lundegiirdh air-acetylene flameassembly into the base of which a fog of the solution under test may beintroduced. The plate holder of the spectrograph is replaced by a slit andphotomultiplier assembly so arranged that this latter slit is placed on theresonance line of the element being determined. The signal from thephotomultiplier is fed to an a.c. amplifier and the rectified output is measuredwith a millivoltmeter.5.MICRO-ANALYSISNEUMAYER~~ has described what might be an important advance in themicro-determination of molecular weights. He has modified Muller andStolten’s apparatus, utilising thermistors as temperature-sensing elements, sothat maximum temperature is registered in only 3 minutes. By using thisapparatus, which operates on the principle that a. solution when exposed tovapours of the same solvent assumes a temperature higher than the solventalone exposed to the same vapour atmosphere, a molecular weight can bedetermined on less than 5 mg. of sample with a relative error of less than 2%.Roth 234 has described some rather interesting methods of determinationz2Q W. Geilmann and K. Heinz Neeb, 2.analyt. Chern., 1959, 165, 251.230 R. Lockyer and G, E. Hames, Analyst, 1959, 84, 385.231 D. J. David, AnaZyst, 1959, 84, 536.232 D. J . David, Analyst, 1958, 83, 655.233 J. J. Neumayer, Analyt. Chim. Acta, 1959, 20. 519.234 H. Roth, Mikrochinz. Actu, 1958, 6, 766HASLAM AND SQUIRRELL : MICRO-ANALYSIS. 415of certain organic functional groups. He details procedures for determiningthe amount of alkali which reacts with acid anhydrides and lactones, aswell as a method for the determination of acid anhydrides by reaction with2,4-dichloroaniline to produce a 2,4-dichloroanilide ; the excess of 2,4-di-chloroaniline is determined by a bromination procedure. Many thiols maybe determined by a method involving reaction with copper(I1) butylphthalate.The excess of copper is determined by reaction with iodide.Disulphides and dialkyl sulphides may be satisfactorily determined byoxidation by bromine to the corresponding sulphones. Isocyanates andisothiocyanates may be readily determined by reaction with amines to yieldsubstituted ureas or thioureas; the excess of amine is determined by titrationwith acid.Filipovic and StefanacS35 have pointed out that some high results ob-tained in the Zeisel method of determination of methoxyl and ethoxylvalues may be due to insufficient purification of the alkyl iodides liberatedby reaction with hydriodic acid. They have overcome this difficulty byreplacing the usual liquid-filled washers with a solid Ascarite purifying tubeand carrying out the reaction in a stream of nitrogen or air.By also in-cluding a layer of " anhydrone '' in the purificatioii tube, the iodides areobtained in a sufficiently pure state to permit direct carbon and hydrogendeterminations to be carried out. The data thus obtained are of obviousqualitative and quantitative use when the organic compound under in-vestigation might contain methoxyl or ethoxyl groups or possibly both.The separation and estimation of methoxyl and ethoxyl groups presenttogether in organic compounds has also been carried out by Makens et aLm6The methyl and ethyl iodides liberated in the conventional way are passedinto a solution of trimethylamine in nitrobenzene, and the ethyltrimethyi-and tetramethyl-ammonium iodides are formed. These iodides have widelydifferent solubilities in this medium and hence can be separated by filtrationand individual determination by a modified Volhard or other methods.A method has been devised by Ashworth 237 for the determination ofvery small amounts of t-butyl alcohol in aqueous solution.He uses amercuric sulphate-sulphuric acid reagent similar to DenigWs reagent and isable to determine concentrations of t-butyl alcohol as low as 1-6 mg. perlitre with about 5% error.Kainzm has developed an interesting method of automatic control ofthe combustion of organic compounds in organic analysis. The apparatusincorporates a flow-meter which is provided with electrodes ; the operationof a relay is the governing factor in controlling the heating of the organicsubstance.Every organic substance is dealt with as an individual andprevious information about its behaviour on combustion is not necessary.A speedy method has been devised for the micro-determination of chlorine,bromine, and fluorine in organic substances.239 The substance is volatilisedin hydrogen, then combusted in an oxy-hydrogen flame. The combustion is235 L. Filipovic and 2. Stefanac, Croat. Chem. A h , 1959, 30, 149.236 R. F. Makens, R. L. Lothringer, and R. A. Donia, Anal;)& Chern., 1959, 31, 1265.237 M. F. R. Ashworth, Mikrochim. Ada, 1959, 506.238 G. Kainz, 2. analyt. Claem., 1959, 188, 427.239 F. Ehrenberger, Mikrochim. A d a , 1959, 192416 ANALYTICAL CHEMISTKY.particularly effective in breaking down organic fluorine compounds.Thetitration methods used for finishing are conventional, i.e., potentiometricfor the halides, and the thorium alizarin-red S method for fluorine.In order to use the Schoniger method of combustion for the determinationof phosphorus in motor oils and additives, Barney and his co-workers2ahave modified the combustion vessel and sample container, so that up to200 mg. of sample can be combusted. They use a one-litre reagent bottleas the combustion vessel and their sample container is fashioned from amicro-extraction thimble held in a simple platinum-wire support. Aftercombustion, the products are absorbed in dilute nitric acid and the phos-phorus is determined colorimetrically as the phosphomolybdovanado-complex. Rogers and Yasuda 241 have used the Schoniger combustionmethod for the determination of fluorine in organic compounds, After thedecomposition of the sample the ionised fluoride is determined by an im-proved ferric salicylate colorimetric method, which is carried out at a con-stant pH of 1.9-2-1.The method appears to give results with an accuracyadequate for the calculation of empirical formulz.have developed a sorting test for the preliminary qualit-ative detection of fluoride in foods and waters. The ash of the food-stuff,or a suitable solution of the substance under test, is treated with tartaricacid and sulphuric acid, and the mixture heated to a temperature sufficientto cause the tartaric acid to turn brown. The volatile products, containinga t this stage only about one third of the total fluoride in the sample, arecollected in a drop of water in a modified Feigl apparatus.The amount offluoride in this drop is determined by application of the reaction withzirconium-alizarin reagent on a spotting plate and comparison with knownstandards.By a combination of solvent extraction and ring-oven methods, West andMakherji 2@ have worked out a scheme for the separation and identificationof 35 metallic ions in a single drop of unknown solution. The unknown isdivided into 4 groups by placing the non-aqueous extract of the metalchlorides, thiocyanates, acetylacetonates, and diethyldithiocarbamates onfilter-paper and depositing them as rings by means of a ring-oven. Anothergroup is obtained by similar treatment of an aqueous solution of residualions.The individual ions are subsequently identified by spot-test methodsapplied to sectors cut from the separated rings of'deposited salts. Budd-hadev Sen 244 has used a reaction of gold(II1) with phenyl2-pyridyl ketoximeto form an orange-yellow chelate as the basis of a new spot test for gold.This coloured chelate is very soluble and can be extracted from aqueoussolutions with chloroform in the pH range 3-9. The limit of identificationis approximately 0-5 pg. of gold. The author details the precautions takenin the detection of gold in the presence of the pIatinum metals, copper,nickel, and cobalt.Quentin et240 J. E. Barney, J . G. Bergmann, and W. G. Tuskan, Analyt. Chem., 1959,31, 1394.241 R. N. Rogers and S.K. Yasuda, Analyt. Chem., 1959, 31, 616.2423 K. E. Quentin, J. Indinger, and S. W. Souci, 2. Lebeizsm.-Untersuch., 1959, 109,249 P. W. West and A. K. Makherji, Analyt. Chern., 1959, 31, 947.244 Buddhadev Sen, Mikrochinz. Acta, 1959, 513.213HASLAM AND SQUTRRET,L : RADIOCHEMICAL METHODS. 4176. RADIOCHEMICAL METHODSIN 1956 the Society for Analytical Chemistry broke new ground byappointing their first Analytical Chemistry Research Scholar in the personof T. T. Gor~uch.2~5 He was given the job of investigating an old problemby a new procedure. In the determination of trace elements in organicmaterials it is usually necessary to effect a preliminary destruction of theorganic matter by wet or dry oxidation processes and, in the past, manycontroversies have arisen about the loss of trace elements in these preliminarytests. GorsuchB5 has brought a new weapon to bear on this problem byadopting a radiochemical approach.In the main, his recovery experimentshave been concerned with the following elements : lead, mercury, zinc,selenium, arsenic, copper, cobalt, silver, cadmium, antimony, chromium,molybdenum, strontium, and iron. Most attention has been paid to lossesof lead and mercury in these preliminary oxidation processes.In radiochemical tracer analysis, Lambie B6 has made a new approachwhich, he claims, results in increased accuracy. He indicates that the errorsinherent in radioactive tracer analysis may be reduced by measuring theunseparated rather than the separated fraction of the radioactivity.Williams 247 has developed a novel method for the determination of verysmall proportions of tin in iron and alloy steels.The sample is first sub-mitted to neutron irradiation in such a way that the product contains thedesirable tin isotope lHSn of convenient half-life and, moreover, long-lived isotopes, l13Sn and 121Sn, are produced in only small quantities. Decayof the irradiated sample for a convenient period enables any 125Sn producedto be converted into 125Sb which is removed in the subsequent chemicaloperations. After this preliminary, tin is added as carrier, and a wholeseries of chemical purifications carried out which have as their purpose thefinal production of a purified stannic oxide containing the active lzlSn andsuitable for counting.Control experiments are carried out on pure tin,The method is capable of determining quite accurately amounts of tindown to 0.0001% in alloy steels and 0-0005% in iron.A radiochemical method described by Morris and Killick248 for thedetermination of small amounts of silver in galena and blendes uses theradionuclides lloMAg and ll0Ag. The silver is separated after the addition ofcarrier, mainly as chloride, sulphide, oxide, and iodate. The final countingis carried out on the silver as iodate, from the weight of which the chemicalyield is determined gravimetrically. Amounts of oxygen of the order of0.01-2% have been determined in beryllium metal by a procedure Zg9 inwhich the metal is first irradiated in a 14.5-Mev neutron flux and the residualactivity is counted with a Geiger counter. The 7.4-second P-activity from16N, which is produced from oxygen in the course of the test, is comparedwith calibration data obtained on known beryllium-beryllium oxide mix-tures.e45 T. T. Gorsuch, Analyst, 1959, 84, 135.e46 D. A. Lambie, AnaZyst, 1959, 84, 173.247 A. I. Williams, Analyst, 1959, 84, 433.248 D. F. C. Morris and R. A. Killick, AIzalyt. Claim. Ada, 1959, 20, 587.249 R. F. Coleman and J. I,. Perkin, Analyst, 1969, 84, 233.REP.-VOL. LVI 418 ANALYTICAL CHEMISTRY.Finally, a method which can be used for the particle-size analysis ofany sub-sieve particles which have a y-ray absorption coefficient significantlydifferent from that of the suspending liquid, has been presented by Ross,=in particular for the analysis of uranium oxide particles. The particles inuniform suspension are allowed to settle and their concentrations at afixed depth in the suspending liquid are continuously determined andrecorded by measuring the transmittance of 7-rays through the solutionfrom an %lAm source. The method can be readily calibrated, and thedata converted to a standard curve of (particle fractions under a certainsize) vmszGs (diameter) obtained from Stokes's law.7. APPARATUSThroughout the year, many excellent pieces of apparatus and manyanalytical instruments have been described. In this short Report, however,we have concentrated largely on general aids to the analyst that can befairly easily constructed in the laboratory.The need for a simple means of indicating and recording the changes inthe composition of the eluate from liquid-solid chromatographic columns hasbeen satisfied in an apparatus due to C l a ~ t o n . ~ ~ ~ This detector depends onthe differences in the heat of absorption of liquids on suitable absorbents.The eluate from the main column is passed through a cold capillary columnsuitably protected from outside temperature changes and fitted with thesame absorbent as the main column. The temperature variation a t a pointin the small cold column is detected by a thermocouple, the output fromwhich can be supplied to a suitable galvanometer or recorder. The detectorcan also be used for separations made on ion-exchange columns, when thedetector is again filled with the resin being used. Peterson and Sober 252have described an apparatus which will be of real value to those engaged ingradient-elution chromatographic separations. The apparatus, whichconsists of a series of identical mixing chambers containing eluant of varyingcomposition in hydrostatic equilibrium , can be adjusted to produce nearlyany concentration gradient without change in the apparatus. The initialconcentration of each eluant and its position in the series control the shapeof the gradient. The authors give details of qualitative relationships andconstruction of the apparatus.The conventional method, originally due to Eschka, for the determinationof mercury by volatilisation and formation of an amalgam with gold, whichis subsequently weighed, has been improved by He has designeda simple apparatus which eliminates errors due to loss of mercury vapour andgives excellent results. The sample is mixed with iron powder and coveredby a layer of zinc oxide in a small silica combustion flask. The flask isfitted by a standard cone joint to a silica tube containing gold foil. Thistube is easily removed complete with gold foil for weighing purposes.A melting point apparatus which is particularly suitable for use with150 C. P. Ross, Analyt. Chem., 1959, 31, 337.261 G. Claxton, J . Chromatog., 1959, 2, 136.s1 E. A. Peterson and H. A. Sober, Analyt. Chem., 1959, 31, 857.'5s J. Lacy, Analyt. Chinz. Actu, 1959, 20. 195HASLAM AND SQUIRRELT. : APPARATUS. 419explosive materials has been designed by Ungnade et aZ.254 The apparatusutilises an electrically-heated copper block, and an optical system is providedwhich projects on to a screen at the rear of the apparatus both transmittedand reflected images of the melting point tube. In this way a completestudy of the phase transition before and during melting is possible.Patterson and Rabouin 255 have devised an all-glass capillary viscometerwhich permits the solution of a polymer sample a t high temperature, filtra-tion, and measurement of the solvent and solution efflux flow times withoutremoval from the vapour heating bath. The advantage of the apparatus isthat it permits safe handling of liquids at high temperatures without thedifficulties of oxidative degradation and precipitation usually encounteredin other methods of examining the viscosity of polymer solutions at elevatedtemperatures.Copies of infrared spectra can be obtained at the same t h e as theoriginal spectrum is being traced by using the mechanical auxiliary recorderdesigned by Watt.256 The apparatus employs a double pen arm by whichone small copy of the spectrum can be made on standard chart for recordfiling and another made on gummed paper, 8" x 24", for sending to theworker initiating the analytical sample. This copy may be easily fixed intoa working notebook opposite the details of the sample tested.J. HASLAM.D. C . M. SQUIRRELL.254 H. E. Ungnade, E. A. Igel, and B. B. Brixner, Analyt. Chem., 1959, 31, 1432.255 G. D. Patterson, jun., and L. H. Rabouin, tert., Rev. Sci. Instr., 1958, 29, 1086.256 P. R. Watt, Chem. and Ind., 1959, 44

ISSN:0365-6217    

DOI:10.1039/AR9595600373

出版商:RSC    

年代:1959

数据来源: RSC

摘要:

INDEX OF AUTHORS’ NAMES.Aalbersberg, W. I., 161.Abdel el Raheen, A. A.,Abd Elhafez, F. A., 190.Abe, T., 44.Abegg, R., 99.Abel, E. W., 136, 137, 139,144, 151, 249.Abendroth, H. J., 204.Abkin, A. D., 20.Abraham, E. P., 313.Abraham, M. H., 202.Abraham, N. A., 221.Abraham, R. J., 79, 83,Abthren, I., 244.Accasiscina, F., 33.Acher, R., 316.Acker, D. S., 211, 268.Ackermann, D., 305.Ackerman, Th., 35, 36.Adam, J., 148.Adams, A., 259.Adams, E., 361, 364.Adams, G. E., 18.Adams, R., 281, 367.Adams, R. E., 412.Adamsky, R. F., 120.Adel, R. E., 261.Adey, K. A., 377.Adler, E., 186.Aebi, A., 191, 228.Aggarwal, P. S., 154.Agranoff, B. W., 213, 226.Agren, G., 319.Agron, P. A., 152.Ahlers, P. E., 405.Ahlquist, L., 214.Ahluwalia, V.K., 269, 270.Ahmed, S. R., 193, 263.Ahramjian, L., 177,Ahrens, E. H., 214.Ahrens, K. H., 88.Ahrland, S., 99, 102.Akabori, S., 305, 300.Akerstrom, S., 167.,4khtar, M., 211.A4kiga, S., 287.Aksnes, G., 42, 170.Albanesi, G., 208.Albert, A., 108, 252.Albert, N., 113.Alberty, R. A., 44.Albrecht, R., 180.illbright, L. F., 19.i\lder, B. J., 35.*4lder, K., 267.Alderman, P. R. H., 138.Xldrich, B. B., 347.384.255.Aldrich, P. E., 196, 230,Aleksanyan, V. T., 68.Alfonsi, B., 394.Ali, M. A., 251.Ali, S. M., 119.Alikhanov, P. P., 46.Alkire, G. J., 380.Allegra, G., 144, 148, 249.Allen, A. O., 11, 15, 18.Allen, D. S., 286.Allen, G., 75.Allen, M., 197.Allen, R. H., 238.Alley, P. W., 258.Allinger, J., 177.Allinger, N.L., 192, 194,Allred, E. L., 199.Almaian, V. V., 381.Alpert, N., 67.Altman, A,, 24.Altshuller, A. P., 34.Amberger, E., 120.Ambler, R. P., 305, 366.Ambros, D., 172, 195.Amdur, I., 23, 24.Ames, S. R., 333.Amiel, Y., 222, 246, 278.Amin, El. S., 383.Amis, E. S., 36, 90, 134.Amos, W. R, 395.Anand, N., 235.Anbar, M., 44, 134.Anderegg, G., 91, 106, 107,Anderson, A. G., 244.Anderson, B. C., 211, 221.Anderson, C. D., 268, 289,,4nderson, C. J., 203.Anderson, D. H., 80.Anderson, 1). M. W., 401.Anderson, I). R., 17.Anderson, G. J., 203.L4nderson, G. W., 310, 311,Llnderson, I,., 320.i1ndersoii;L. C., 21,Andersson, G., 140.Andersson, S., 119.Andreas, H., 205.Andrei, F., 212.Andrews, L. J., 164.And, E.F. T,. J., 295.-\net, F. A. Id., 146.Anfinsen, C. B., 320.Angyal, S. J., 185.Anisimov, K. N., 135.267, 276.195, 225.108, 158.300.312.42 1Anjaneyulu, B., 276.Ansell, M. F., 220, 230.Anson, F. C., 394.Anta, M. C., 17.Anthony, W. C., 265.Antmann, R. C., 35.Aoki, T., 275.Apar Singh., 151.Appalaraju, N., 408.Appel, H. H.. 228.Appel, P., 347.Appelman, E., 134.Apple, E. F., 118.Applequist, D. E., 223.Aqvist, S. E. G., 320.Arai, G., 278.Arakawa, K., 310.Arasimavicius, A., 351.Arata, Y., 286.Archer, G., 47.Ardon, M., 151, 183.Arens, J. F., 208, 218, 257,Arigoni, D., 234, 235, 236.Anson, B. H.. 213, 214.Aritomi, M., 236.Arkell, A., 216.Allinger, J., 225.Rrmitage, D. M. A., 257.Armstrong, D.A., 10, 11.Armstrong, R. K., 288.Armstrong, W. D., 327,Arnett, E. M., 196.Arnold, R. B., 314.Arnold, R. T., 190.Arnold, Z., 260, 262.Arnstein, H. R. V., 315.Aroney, M., 195.Arrak, A., 412.Arthur, H. R., 284.Arthur, J. C., 20.Arthur, W. R. B., 50.Artyukhin, P. I., 107.Arvia, A. J., 129.Arya, V. P., 234.Asai, O., 156.Asbrink, S., 149.I2sen, S., 359, 370.Ash, B. D., 201.Ashby, E. C., 115, 199.Ashley, C. A., 351.Ashmore, P. G., 50, 68, 59.Ashworth, M. F. R., 415.Askura, S., 348.Xslin, S., 315.Asselineau, C., 214.Asselineau, J., 214.Aston, J , G., 192.309, 311.407422 INDEX OF AUTHORS’ NAMES.Atoji, M., 113, 114.Atteberry, R. W., 116.Attix, F. H., 22.Aubrey, D. W., 117.Audrieth, L. F., 124, 125.Augenstine, L., 17.Ausloos, P., 20.Austin, A.T., 306.Austin, J. M., 100.Autrey, R. L., 235.Avram, M., 143, 245.Axelrod, B., 352.Axtmann, R. C., 87.Axworthy, A. E., 56.Aymonino, P. J., 129.Aynsley, E. E., 119, 130.Ayres, D. C., 229.Baaz, M., 112.Babicky, A., 17.Babin, D. R., 284.Babko, A. K., 99.Babushkin, A. A., 139.Bach, N. A., 7.Bacharach, A. L., 331.Bachelor, F. W., 283.Bachmann, G. B., 217.Back, R. A., 10, 20.Baddeley, G., 44, 223.Baddiley, J., 320.Badding, V. G., 200.Bade, H., 157.Baden, H., 326.Bader, F., 211.Bader, R. F. W., 53.Badger, R. M., 113.Baer, D. B., 220.Baer, H. H., 290.Bag, S. P., 383.Bagdasar’yan, K. H. S.,Bagger, J. B., 108.Bagshawe, B., 374.Bai, C. C., 276.Bailar, J.C., jun., 133.Bailey, A. S., 214.Bailey, J. L., 299, 308.Bailey, K., 343, 345, 346,Bailey, W. J., 205, 221.Baird, C. G., 413.Baird, D. J., 356.Bak, B., 83.Bakkcs-Polgar, E., 386,Baker, B. R., 268, 289, 291,Baker, E. A., 224.Baker, L. C. W., 154.Baker, P. T., 384.Bakker, G. H., 238.Balazs, E. A., 16.Baldwin, R. R., 59.Bale, W. F., 323.BalenoviC, K., 370.Balestic, P., 21.20.349, 350.387.300.Ball, D. J., 299.Ball, S., 337.Ballezo, H., 381,Ballinger, P., 46, 53, 175.Ballhausen, C. J., 109, 155,Bamdss, E. M., 297.Ban, Y., 274.Banaszak, L. J., 396.Banga, I., 350.Bank, J., 217,Banks, C. V., 107.Banks, R. E., 240.Bannick, W. M., 105.Bannisten, E., 120, 156.BbrAny, K., 349.BBrbny, M., 349.Barash, L., 191.Barber, G.A., 299.Barber, M. S., 212.Barber, W. A., 144, 250.Barbour, A. K., 240.Barcel6, J. R., 77.Barclay, R., jun., 221.Bardi, R., 156.Bareis, D. W., 21.Baret, R., 366.Bark, R. A., 63.Barkemeyer, H., 252.Barker, G. R., 186, 304.Barker, H. A., 360.Barker, M. G., 378.Barker, R., 8.Barker, S. A., 16, 77, 257.Barltrop, J. A., 190, 230,Barnes, A. J., 277.Barnes, L., jun., 389.Barnes, R., 155.Barnes, R. Ar, 168, 259.Barney, J. E., 416.Barr, N. F., 11, 13.Barr, S. J., 194.Barraclough, C. G., 132.Bartell, L. S., 197.Bartels-Keith, J, R., 218.Barth, C. A., 63.Bartlett, F., 279.Bartlett, P. D., 169, 172,Barton, D. H. R., 195, 196,Bartos, J., 382.Bartz, Q. R., 218, 286.Barua, A. K., 27, 236.Bascombe, K.N., 49.Basmanova. V. M., 45.Basolo, F., 104, 109, 134.Bassett, J. Y., 181, 239.Bassi, D., 74.Batsanov, S. S., 152.Battersby, A. R., 272, 274,Battiste, M., 219, 244, 257.Batts, M. B., 374.Bauer, L., 222.156.234, 265.202.235, 236.279.Bauer, M., 206.Bauer, R. S., 210.Baumann, M., 274.Baumann, P., 225.Baumgarten, F. , 249.Baumgarten, S., 394.Baumgartner, G. J., 257.Bawn, C. E. H., 145, 206.Baxendale, J. H., 11, 17,Baxter, E. F., 19.Baxter, J. G., 331.Bayer, I., 394.Baylouny, R. A., 221.Bazilevich, G. If., 73.Bazhulin, P. A., 69, 77.Beachell, H. C., 77.Bear, J., 148.Beatty, I. M., 320.Beck, F., 38.Becker, A., 221, 222.Becker, E. D., 81, 83, 86.Becker, O., 249.Becke-Goehring, M., 125,Beckers, H.G., 124.Beckert, O., 145.Beckman, H. F., 407.Bednar, J., 15, 16, 21.Bedniagina, N. E., 242.Beenakker, J. J. M., 25.Beer, C. T., 277.Beermann, C., 145.Beesley, R. M., 223.Begun, G. M., 72.Behr, 0. M., 207.Behrens, H., 136.Behrens, 0. K., 304.Behringer, H., 258.Behringer, J., 71, 72.Belcher, R., 381.Belford, G., 91.Belford, R. L., 91.Bell, E. A., 366.Bell, F., 194.Bell, P. H., 304.Bell, R. M., 218.Bell, R. P., 41, 45, 47, 49,Bellemans, A., 32.Bellin, S. A., 327.Bel’skii, I. F., 219, 257.Benck, R. F., 37.Bendall, J. R., 351, 356,Bender, M. L., 45, 55, 179.Bender, P., 267.Bendz, G., 209.Benedict, I., 304.Ben-Efraim, D. A., 173,BeneSova, V., 228, 237.Benitez, A., 291.Benjamin, B.M., 173.Benjamin, L., 33.Benkeser, R. A., 167, 221.18.128.61, 164, 175, 176.357.225IBenn, M. H., 296.Bennett, M. A., 136, 139.Bennett, W., 16, 17.Bennett, W. E., 107, 133.Bennich, H., 319, 320.Benning, W. F., 49.Benoiton, L., 360, 361.Benson, R. E., 210, 221.Benson, S. W., 45, 56.Bentley, K. W., 270.Benz, E., 239.Benz, R., 148.BerAnek, J., 256.Berchtold, G. A., 204.Berg, H., 395.Bergeon, R., 28, 29.Berger, A., 309.Berger, A. W., 31.Berger, D. R., 262.Bergerhoff, G., 128.Bergmann, E. D., 221, 222,Bergmann, G., 67.Bergmann, J. G., 416.Bergmann, M., 296.Bergson, R., 23,Berkenhoff, H. O., 120,Berker, U., 220.Berkheimer, H. E., 50.Berkowitz, L. M., 203.Berkoz, B., 216.Berlage, F., 280, 281.Berliner, E., 53, 161, 165.Berlinquet, L., 365.Bernardini, F., 201.Bernasconi, R., 236.Bernath, G., 196.Bernauer, K., 279, 280,Bernhard, C., 244.Bernhardt, H.A., 10.Bernheim, R. A., 133.Bernstein, H. J., 67, 68, 77,79, 82, 83, 84, 86, 215.Bernstein, I. A., 299.Berson, J. A., 173, 197,225, 226.Bertho, A., 294.Berti, G., 50.Bertoluzza, A., 76.Besch, E., 279.Bessho, K., 275.Bestian, H., 145.Bethell, D., 60, 166, 168,Betts, R. H., 106.Bewick, A,, 40.Bewick, A,, 40.Beyer, A., 124.Beyer, E., 202.Beyerman, H. C., 273, 306,Bezzi, S., 156.Bhatia, Y. R., 210.Bhatnagar, S. S., 277.Bhatnager, C. S., 390.227.281.171.362.DEX OF AUTHORS’ NAMES. 423Bhatt, hl. V., 225.Bhattacharya, A. , 270.Bhattacharyya, S.C., 227,Bickelhaupt, F. , 284.Bidwell, R. G. S., 368.Biemann, K., 265.Bier, H., 131.Bierman, W. J-, 35.Bigeleisen, J., 51.Bigley, D. B., 190, 230,Billeter, E., 194.Binkley, W. W., 16.Binks, R., 274.Birch, A. J., 226, 229, 316.Birchall, J. M., 240.Bird, C. W., 209.Bird, R. B., 23.Birkenshaw, J. H., 258.Birks, F. T., 214.Birnbaum, S. &I., 197, 360.Bishop, E., 374.Bishop, E. O., 136.Biss, J. W., 201.Bithos, 2. J., 274.Bjermm, J., 91, 92, 98, 104.Bjerrum, N., 169.Blacet, F. E., 177.Black, J. F., 19.Black, S., 370.Blackall, E. L., 163.Blackhurst, J. D., 15.Blackie, M. S., 102.BlBha, K., 272.Blanchard, E. P., jun., 176.Blanchard, L. P., 177.Blankerstein, K., 149.Blaser, B., 124.Blau, E. J., 77.Bloch, K., 226.Bloching, H., 127.Block, B.P., 104.Block, F. B., 221.Block, H., 45, 132, 134.Blomquist, A. T., 194, 219,Bloom, S. M., 220.Bloomer, 0. T., 31.Bloomfield, J. J., 219.Bloomquist, C. A. A., 222.Blum, J., 201.Blum, J. J., 348, 350.Bly, R. S., jun., 172.Boag, J. W., 22.Bobbitt, J. M., 186, 274.Boberg, F., 256.Bobovich, I. S., 69, 71.Bobovich, Ya. S., 76.Bockris, J. O’M., 39, 40,Bodanszky, M., 310, 316.Bodea, C., 212.Bodlander, G., 99.Bohme, H., 239.Boehme, W. R., 224.228.234.223.113.Boekee, P., 306, 362.Boekelheide, V., 265, 281.Boettcher, F.-P., 309, 318.Bognar, R., 298.Bohlmann, F., 210.Bohn, G., 150.Bohnes, H., 378.Boissonnas, R. A., 300,Boit, H.-G., 281.Bokii, G. B., 138.Bolto, B.A., 166.Bonavent, G., 219.Bond, G. C., 50, 198.Bonham, R. A., 197.Bonino, G. B., 74, 75.Bonner, T. G., 42, 50.Bonner, W. A., 173, 198.Bonnett, R., 270.Booman, G. L., 406.Boone, J. L., 116.Booth, F., 36.Boothe, J. H., 242.Bor, G., 135.Borbiro, Ill., 346.Borer, K., 120.Borowiechi, L., 227.Bos, €3. J. T., 208.Bose, A. K., 189.Bose, J. L., 187.Bosshard, H. H., 204, 239.Bottini, A. T., 197.Botts, J., 350.Boulter, D., 226.Bourne, E. J., 77.Bouthillier, L. P., 361.Bouy, P., 122,Bovey, I?. A., 80, 84.Bowen, W. J., 350.Bower, C. A., 374.Bower, G. AT., 412.Bowman, R. E., 52,62,174.Bowmann, N. S., 173.Boyce, C. B. C., 223.Boyd, C. M., 380.Boyd, G. E., 152.Boyd, G. V., 244.Boyle, J. W., 12.Bozler, E., 356, 357.Bracha, P., 227.Bradbury, J.H., 309.Bradbury, R. B., 281.Bradford, E. C., 392.Bradley, A., 183.Bradley, D. C., 149.Bradley, L. B., 350.Bradley, M. J., 117.Bradley, R. B., 83.Bradsher, C. K., 264.Bradt, P., 63.Brady, G., 36.Brady, G. W., 120.Brady, R. O., 215.Brandhn, C.-I., 126.Brahms, J ., 352.Brand, J. C . D., 53.316, 317424 INDEX OF AUTHORS' NAMES.BrandmtilIer, J., 67, 71.Brandt, L. W., 31.Brandt, W. W., 106, 407.Brasch, J ., 264.Brattain, W. H., 39.Braude, E. A., 174.Braun, F., 273.Braun, G., 136.Braunitzer, G., 318.Braye, E. H., 142, 143.Brealey, L., 402.Bredig, M. A., 126.Breene, R. G., 90.Bremer, R. F., 183.Brenner, G., 230.Brenner, M., 313.Breslow, D. S., 119.Breslow, R., 178, 219, 224,Breton, J.L., 236.Breuer, H., 295.Brewer, F. M., 119.Brewster, J. H., 189, 224.Brewster, R. Q., 197.Brey, M., 228.Brezeanu, M., 164.Brice, V. D., 214.Bridoux, M., 70.Briggs, F. N., 357.Briggs, L. H., 233.Brimacombe, J. S., 181,Bringi, N. V., 272.Brink, N. G., 270.Britt, J. J., 234.Britton, D., 67.Brixner, B. B., 419.Broadbent, H. S., 198.Brock, W., 296.Brockmann, H., 243, 334.Brodersen, K., 132, 158.Brodersen, S., 68.Brodsky, A. M., 17.Bromer, W. W., 304.Brons, D., 319.Brook, P. R., 278.Brooke-Hoey, G., 165.Brooks, C. J. W., 228.Brooks, J. W., 194.Brossi, A., 274.Brotherton, T. K.. 119.Browder, H. P., 163.Brower, K. R., 49.Brown, B. R., 267.Brown, C., 31.Brown, D.A., 142.Brown, E. F., 339.Brown, F., 408.Brown, H. C., 114, 161,165, 166, 198, 199, 200,208, 221, 238.Brown, J. H., 205.Brown, L. C., 86.Brown, P. K., 197.Brown, R. D., 160, 161,167, 168, 266.257.257.Brown, R. F. C., 270, 283.Brown, T. H., 133.Brown, T. L., 264.Brown, W. B., 29, 32.Brown, W. G., 162.Brownstein, S., 82.Broyde, B., 22.Brudevold, F., 330, 331.Bruegemann, W., 384.Brunig, H., 313.Bruice, T. C., 45, 179.Bruker, A. B., 149.Brukl, A., 147.Brun, M., 19.Brutcher, F. V., jun., 194.Bryan, F. R,, 413.Bryant, F. J., 328.Bryant, M., 253, 365.Bryce-Smith, D., 243.Buchanan, D. L., 324.Buchanan, J. G., 320.Buchowski, H., 50.Buchta, E., 212.Buck, J. S., 267.Buckenstein, S., 170.Buckingham, A.D., 25, 98.Buckley, S. D., 363.Buddhadev Sen, 416.Buderstein, 2.. 352.Budzikiewicz, H., 251.Biichi, G., 229, 230, 279,Biihler, W., 255.Buell, M. V., 410.Butler, R., 334.Buffagni, S., 145.Buist, G. J., 185.Bujwid, 2. J., 239.Bukhovets, C. B., 141.Bulewicz, E. M., 57, 64.Bulgrin, V. C., 185.Bullen, G. J., 154.Bullock, E., 255.Bunker, D. L., 57.Bunn, D., 11.Bunnett, J. F., 44, 165,181, 239.Bunton, C. A., 46, 122, 163,181, 185.Burch, P. R. J., 16.Burg, A. B., 116, 123, 124,Burge, D. E., 127.Burger, K., 377, 389.Burgstahler, A. W., 223,Burke, T. G., 128.Burkett, H., 47, 167.Burkhardt, K., 273.Burkhardt, L., 116.Burkus, J., 44.Burleigh, J. E., 378.Burnett, G. W., 32G.Burns, M. J., 333.Burns, W.G., 21.Burr, J. G., 19, 21.283.126.274.Burrell, J. W. K., 212.Burske, N. W., 175.Burstein, S., 228.Burswasser, H., 17.Burton, M., 8, 10, 13, 17,Burton, R., 139.Bushbek, G. V., 275.Buslaev, Yu. A., 150.Butement, F. D. S., 41.Butler, A. R., 64.Butler, G. C., 299.Butsugan, Y., 286.Buttery, R. G., 177.BUZ~S, I., 384.Buzbee, L. R., 135.Bykova, E. V., 170.Byrne, F. P., 412.Byron, S. R., 65.Bystrom, A., 149.Bystroff, R. I., 106.Cadotte, J. E., 302.Cadwick, J., 119.Cady, G. H., 127, 128.Cafrey, J. M., 13.Cagle, F. W., 194.Caglisti, V., 74.Cahn, R. S., 188.Cain, B. F., 233.Cain, D. F., 355.Cais, M., 233.Calderazzo, F., 249.Caldin, E. F., 44.Califano, S., 77.Callahan, F. M., 310.Callear, A. B., 60, 61.Callis, C.F., 101, 123.Callopy, T. J,, 147.Calvin, M., 91, 93.Cambie, R. C., 233.Camera, B. R., 221.Campaigne, E., 204.Campbell, G. W., 115.Campbell, I. G. M., 197.Cannon, G. W., 219.Cannon, P., 151.Canonica, L., 236.Canterino, P. J., 119.Cantley, M., 303.Cantrall, E. W., 235.Carbon, J. A,, 304.Carey, J. G., 241.Carleson, R. G., 99.Carlin, R. B., 266.Carlson, D. P., 266.Carmack, &I., 204, 254.Carnall, W. T., 106, 148.Carnie, W. W., 45.Caron, A. P., 124.Carpenter, D. R., 83.Carpenter, G. B., 128.Carr, M. D., 164.Carrington, T., 65.Carritt, D. E., 394.Carriuolo, J., 55.18ICarroll, W. R., 346.Carson, G. L., 67.Carson, H. O., 203.Cartledge, G. H., 132.Carter, J. C., 115.Carter, J.R., 308.Carvallo, J. daS., 298.Carvallo-Ferreira, P., 279.Case, F. H., 263.Case, J. D., 265.Case, J. R., 142, 208.Case, L. C., 254.Caserio, F. F., 124.Caserio, M. S., 206.Casey, A. T., 147.Casey, E. J., 12.Cashion, J. K., 60, 62.Caso, M. M., 389.Castellano, S., 83.Castle, J. E., 268.Cava, M. P., 234, 245.Cavallini, D., 17.Cawley, J. D., 337.Ceausescu, D., 399.Ceder, O., 281.Cefola, M., 389.cekan, Z., 277.Celap, M. B., 381.Cels, J. P., 40.Cervinka, O., 256.Chaberek, S., 106.Chain, E. B., 304.Chakrabarti, J. K., 83, 278.Chakravarty, K. K., 228.Challis, H. J. G., 405.Chamberlain, A. C., 328.Chamberlin, J. W., 232.Chambers, R. D., 239.Chance, B., 354.Chandrasekharan, V., 75.Chanduri, N. J., 177.Chaney, A., 297, 298.Chang, J., 18.Chang, P.C., 20.Chang Shih, 52.Chanley, J. D., 299.Chantry, G. W., 70.Chapiro, A., 20.Chaplen, P., 258.Chappell, J. B., 350.Chapurskii, I. N., 155.Charles, R. G., 93, 108.Charlesby, A4., 8, 18.Charman, H. B., 46, 175.Chatt, J., 91, 99, 102, 109,Chatterjee, A., 270, 284.Chatterjee, S. K., 235.Chaundy, T. W., 32.Chauvet, J., 316.Cheaney, D. E., 66.Chechak, A. J., 337.Cheek, C. H., 9.Chen D. T. Y., 49, 171.Chen, M. C. M., 107.Chen, Y. T., 104.132, 141, 146.DEX OF AUTHORS’ NAMES. 425Cheney, G. E., 92, 108.Cheng, C. C., 268.Cheng, K. L., 408.Cherniak, E. A., 19, 20.Chernova, A. I., 15.Chernova, I. I., 275.Chernyak, N. Y., 17.Chia, Y.-T., 35.Chiang, Y., 46, 162.Chichester, C.O., 341.Chikamoto, T., 226.Chikanov, N. D., 150.Ching, H., 293.Chini, P., 145.Chiorboli, P., 71, 74, 75, 76.Chirkov, N. M., 49, 50.Chisholm, M. J., 214.Chisler, E. V., 71.Chiurdoglu, G., 225, 229.Cholnoky, L., 212.Chong Ng, C., 20.Cho, A. K., 263.Chopard-dit- Jean, L. H.,274.Chou, T.-T., 274.Choudhuri, S. N., 234.Chow, S. W., 229.Christ, R. E., 227.Christensen, B. E., 306.Christie, J. B., 263.Christie, M. I., 61.Christie, W. H., 263.Christmann, O., 262.Chu, P., 288.Chu, T. L., 118.Chui Fan Liu, 133.Chumaevskii, N. A., 77.ChurA,Eek, J., 381.Church, C. L., 400.Ciampolini, M., 104Ciccone, S., 45.Ciganek, E., 172, 195.Cini, R., 109.Cipollini, E., 123.Ciula, R. P., 223.Claes, P., 10.Clancy, M.J., 303.Clapp, L. B., 49.Clar, E., 241, 242.Clark, A. J., 363.Clark, A. M., 30.Clark, C. G., 104.Clark, H. C., 109, 155.Clark, K. J., 265.Clark, L. W., 45.Clark, R. E. D., 381.Clark, V. M., 251, 270.Clark-Lewis, J. W., 362.Clarkson, R., 142, 208.Clauss, A.. 142.Clauss, D., 153.Clauss, H., 74.Clauss, K., 145.Claver, G., 377.Claxton, G., 418.Clay, P. G., 17.Clearfield, A., 148.Cleaver, A. J., 303.Clement, R. A., 42.Closs, G. L., 218.Closson, R. D., 135.Closson, W., 195, 234.Closson, W. D., 173.Cloutier, G. G., 9.Clusius, K., 24.Cobble, J. W., 153.Cocker, W., 230.Coe, F. R., 391, 392.Coffman, D. D., 127, 158.Cohen, A., 66.Cohen, A. D,, 79.Cohen, D., 54.Cohen, L. A., 307, 310.Cohen, J.A., 319.Cohen, S., 220.Coke, J. L., 192.Colburn, C. B., 122.Cole, R. D., 308.Cole, S., 16.Coleman, R. F., 417.Coller, B. A. W., 167, 168.Collette, J. W., 239.Collins, A. G., 407.Collins, C. H., 221.Collins, C. J., 52, 173.Collins, D. J., 244.Collinson, E., 11, 12, 19, 20.Colomb, D., 171.Colton, R., 152, 153.Comb, D. G., 287.Comin, S., 273.Cone, N., 278.Cone, N. J., 277.Conger, R. L., 38.Connelly, C. M., 354.Connick, R. E., 34, 35, 38,Connolly, J. D., 227.Connor, T. M., 82, 130.Conrow, K., 244.Conroy, H., 83, 278.Conway, B. E., 40.Cook, A. H., 304.Cook, C. M., 150.Cooke, J. P., 320.Cooke, N. J., 214.Cookson, R. C., 196, 224.Cooley, J. H., 224.Cooley, W. E., 133.Cooper, W., 20.Cope, A. C., 172, 193, 195.Coppinger, G.M., 55, 170.Coppola, J., 278.Corbett, J. D., 147.Corbett, W. M., 296.Cordier, P., 20.Cordner, J . P., 52.Corey, E. J., 133, 231, 232,Corio, P. L., 83.Corish, P. J., 412.Corner, J., 27.87, 99, 133.235, 307426 INDEX OF AUTHORS’ NAMES.Cornforth, J . W., 191, 201,Cornforth, R. H., 191, 201,Corradini, P., 144, 148, 249.Corrodi, H., 286.Corsi, A., 345.Costoulas, A., 76.Cosway, H. F., 31.Cotter, J. L., 169.Cotton, F. A., 74, 85, 128,137, 138, 141, 142, 143,155, 207, 247, 248, 249.205, 210, 213, 235.205, 210, 213.Cotton, R., 250.Cottrell, T. L., 25.Courtney, H. C., 103.Courtois, J . E., 304.Couture, A. M., 34, 35.Cover, R. E., 394.Coverdale, C. E., 173.Cowan, M. J-. 105.Cowley, A.H., 120, 150.Cowley, B. R., 240.Cox, A. L., 31.Cox, A. P., 144.Cox, J. D., 377.Cox, J. R., 180.Cox, J. S. G., 235.Coxon, B., 289.Coyle, T. D., 115.Crabb6, P., 213.Cracco, F., 10.Craig, D. P., 90.Craig, L. C., 313.Cram, D. J., 52, 173, 175,177, 190, 246.Cramer, F., 287, 312.Cramer, R. D., 208.Craven, J. M., 42.Crawford, R. A., 127.Criegee, R., 143, 187, 201,208, 220, 245.Cripps, H. N., 220.Crisan, C., 218.Cristiani, G. F., 254.Crittenden, E. R. S., 319.Crofts, P. C., 312.Crombie, L., 215.Crook, E. H., 113.Cross, B. E., 252.Crow, W. D., 273.Crum, J. D., 299.Crumpton, M. J., 292.Crundell, F., 224.Cruse, K., 374.Culbertson, T. P., 215.Cullen, W. R., 125.Cullis, C. F., 181, 183.Culvenor, C. C.J., 281.Cundiff, R. H., 393.CuprovA, V., 155.Curran, C., 132.Curran, T. D., 403.Curran, W. V., 313.Curry, T. H., 193.Curtin, D. Y., 84, 195, 222.Curtiss, C. F., 23.Cutts, J . H., 277.Cymerman-Craig, J ., 210.Czapski, G., 12.Dagliesh, C. E., 252.Dahl, L. F., 150.Dahler, J. S., 23.Dahlgard, RI., 197.Dahlgren, G., 185.Dahlinger, 0. F., 106.Dahlmann, S., 202.Dahn, H., 180, 185, 313.Daigo, K., 362.Dainton, F. S., 7, 11, 12, 19,Dale, W. BI., 17.Dallemagne, &I. J., 323.Daly. J. J., 205.Daly, J. M., 105.Daly, L. H., 77.Dalziel, J., 152.Danford, M. D., 152.Daniels, F., 59.Daniels, R., 222.Dann, A. T., 281.D’Ans, J., 202.Dapoigny, J., 29.Darling, S. F., 219, 257.Darmer, E. A. M. F., 393.Darnell, A.J., 126.Darwent, B. de B., 60.Darwish, D., 43, 170.da Settino, A., 50.Datta, S. P., 107.Dauben, C. H., 106.Dauben, H. J., 206, 250.Dauben, W. G., 173, 239.Dave, L. D., 143.David, D. I., 414.David, S., 299, 300.Davidson, G. C., 274.Davidson, J. DI., 118.Davidson, N., 57, 87, 158.Davies, A. G., 202.Davies, D. A., 66.Davies, H. G., 157.Davies, J. E., 231.Davies, J. V., 17.Davies, M. W., 152.Davies, N. R., 99, 102.Davies, R. E., 354, 355.Davis, A., 66.Davis, B. R., 233.Davis, D. A,, 166.Davis, S. B., 304.Davis, T. W., 12.Davis, W., jun., 10.Davis, W. H., 9.Davison, W. H. T., 18, 19.DavoIl, J., 293.Dawes, J. W., 156.Dawson, J., 28.Dawson, J. P., 192.Day, A. C., 230.20.Das, M. N., 393.Day, L.A., 238.Dean, J. A., 406.Deans, F. B., 167, 168.de Bell, A., 67.Debouille, L., 77.de Bethune, A. J., 33.Decius, J. C., 68.Decker, 114.Dsdek, V., 254, 255.Defilippes. F. M., 17.De Geiso, R. C., 40.de Gaudemaris, G., 20.de Gorski, E., 20.De Graaff, W., 25.de Halas, D. R., 21.Dehority, B. A., 397.Ue Jong, A. W. I<., 360.De Jong, W. F., 323.Dekker, C. A., 315, 320.Delahay, P., 41.de la Mare, P. B. D., 164,168, 175, 181, 194, 238,252.Delhaye, M., 68.Delhaye-Buisset, M. B., 68.Delluva, A. M., 355.Delwaulle, M. L., 70.de Marco, C., 17, 331.Demarteau-Ginsburg, H.,Demint, R. J., 20.Den Herder, J. J., 396.den Hertog, H. J., 259.Denncy, D. B., 53, 55, 166,Denney, D. Z., 184, 206.Denning, G. S., 204.Denny, D.B., 170.Deno, N. C., 50, 170.De Puy, C. H., 204, 220,Derauche, R., 300.de Renzo, E. C., 304.de Ritter, E., 338.de Ropp, R. S., 304.Dersin, H., 127.DeSa, J., 277.Descamps, M., 229.Desirant, Y., 240.Dessy, R. E., 49, 85.Detmar, O., 128.Deulofeu, V., 273, 270.Deuel, H. J., jun., 333.DeVilliers, J. P., 237.de Vries, A. E., 18.DeVries, T., 31.Dewar, M. J. S., 160, 163,168, 224, 244, 271.Dewhirst, K. C., 246.Dewhurst, 13. A., 16, 18.Dey, A. K., 101.D’Eye, R. W. M., 147.Dhar, ill. L., 216, 235.Dhont, J. H., 394.Diaper, D. G. M., 204.Diara, A., 234.214.184, 206.2211 [NDEX OF AUTHORS, NAMES. 427Diassi, P. A., 276.Dibeler, V. H., 63.Dickel, D. F., 276.Dickens, F., 327.Diehl, H. W., 299.Diels, O., 267.Dietl, A., 168.Dietrich, P., 202.Dietz, R., 271.Dilgren, R.E., 174.Dillon, R. L., 175.Dills, C. E., 172.Di Milo, A. J., 52.Din, F., 28, 29, 30, 31.Dingwall, A., 47.Dinh-nguyen, Ng, 215.Dinu, D., 245.Dion, H. W., 218.DiPaulo, F. S., 30, 31.Ditter, J. F., 116.Diveker, P. V., 251.Dixon, G. H., 308, 319.Dixon, G. J., 344, 354.Dixon, R. N., 72.Dixon, R. 0. D., 369.Dixon, T. F., 327.Djerassi, C., 191, 195, 213,216, 225, 228, 233, 234,236, 262, 270, 306.Djordjevic, C., 131.Dmitriev, M. T., 10.Dobbs, E. R., 27.Dobbs, F. W., ‘79.Dobson, N. A., 362.Dodd, R. E., 119, 153.Doehaerd, Th., 225.Dopke, W., 281.Doering, W. von E., 174,177, 179, 217, 257.Dohmann, K.-D., 160,Dokoupil, Z., 25.Dolejs, L., 229.D o h , P.I., 12.Dolle, L., 10.Dolphin, G. W., 22.Domb, C., 27.Donaldson, D. M., 11, 13.Donath, W. E., 194.Dondes, S., 10.Done, J., 361.Donia, R. A., 415.Donne, C. D., 142, 208.Doody, E., 107.Dorfman, L. M., 9, 10.Dorzd, V. N., 247.DostAl, K., 125.Douglas, B. E., 108Douglas, J. E., 166.Douglas, K. J., 163, 238.Douslin, D. R., 192.Dowden, D. A., 198.Dowell, A. N., jun., 178.Dower, M. J. S., 193.Dowling, J. M., 68.Down, J. C., 136.Downes, J. E., 259.Downey, P. F., 370.Draber, W., 251.Draganic, I., 16.Dragut, A., 19.Drake, J. F., 105.Drake, J. M. F., 105.Drakin, S. I., 34.Draus, F., 309.Drenchko, P., 255.Dresdner, R. D., 124.Drimus, I., 19.Drinkard, W., 86.Drisko, R. R., 319.Drouillas, M., 404.Druding, L.F., 147.Druey, J., 215, 287.Dryden, H. L., jun., 172.Drysdale, J. J., 220.Ducker, J. W., 220.Ducret, L., 404.Dudek, G. O., 180.Dudley, F. B., 127.Duffey, D. C., 178.Duffy, R., 121.Duke, F. R., 183, 185.Dumitresco, V., 19.Dummer, G., 273.Duncan, J. F., 91.Duncan, P. M., 45.Duncanson, L. A., 132, 141.Dunitz, J. D., 245.Dunning, H. N., 17.Dunstone, J. R., 408.Dupont, J. A., 117.Durand, C., 151.Durup, J., 19.Durup, M., 19.Durynina, L. I., 299.Dutta, P. C., 230.Dutton, G. G. S., 302.Dutton, W., 63.du Vigneaud, V., 307, 310,Dwyer, F. P., 133.Duyckaerts, G., 408.Duynstee, E. F. J., 43,Dyall, L. K., 187.Dyanslrov, I. A., 178.Dylion, C. M., 276.Dyne, P. J., 15.Dyrssen, D., 109.Eaborn, C., 162, 167, 168.Eaglioti, E., 235.Eakin, B.E., 31.Earley, J. E., 49, 119, 153.Eastoe, B., 326.Eastoe, J. E., 326, 328.Ebashi, S., 356, 357.Eberius, E., 378.Eberson, L., 197.Ebnother, A., 253.Ebsworth, E. A. V., 72, 73,83, 120, 154.Ecke, G. G., 135.316.171.Eckert, Th., 386.Eckfeldt, E. E., 394.Ecklemann, W. R., 328.Eddinger, C. C., 337.Eddy, N. B., 252.Edelman, I. S., 326.Edman, P., 304, 308.Edridge, A., 395.Edsall, J. T., 70, 105, 108,Edson, N. L., 330.Edwards, B. E., 204.Edwards, D. G., 403.Edwards, J. O., 49, 153,Edwards, L. J., 114.Edwards, 0. E., 232, 283,Edwards, T. P., 274.Eeg-Larsen, N., 327.Efimov, E. A., 39.Efrain, D. A., 197.Eger, C., 399.Egerton, A. C., 59.Egerov, Y. P., 73.Eggerer, H., 213, 226.Eglinton, G., 207.Ehrenberger, F., 415.Ehrenson, S. J., 80, 178.Ehrlich, P., 148, 149, 375.Eick, H.A., 147.Eigen, M., 169.Eigenman, G. W., 190.Eilers, K. L., 220.Einarsson, P., 126.Eisch, J., 168, 267.Eisenbraun, E. J., 213, 216.Eiss, M. I., 409.Ekstrom, B., 208.Elad, D., 231.Elagina, N. V., 223.Elias, L., 62.Eliason. M. A., 57.Eliel, E. L., 52, 84, 195,200, 243.Eliezer, I., 21.Elion, G. B., 268.El Khadem, H., 297.Elleman, T. S., 135.Ellington, E. V., 304.Ellington, R. T., 31.Elliott, J. J., 55.Elliott, M. C., 406.Elliott, S. R., 326.Ellis, A. J., 49.Ellis, C. P., 25.Ellis, R. J., 361.Ellman, G. L., 70.Elmore, D. T., 306, 308.El Sawi, M. M., 295.El-Shafei, 2. M., 297.Elson, E. L., 309.Elson, R.E., 150.Elvidge, D. A,, 402.Elvidge, J. A., 84, 105, 131308, 309.179.284.260, 271428 INDEX OF AUTHORS’ NAMES.Emelitus, H. J., 111, 117,Emmett, P. H., 198.Emmons, W. D., 44.Emtage, P. R., 136.Engelhardt, V. A,, 127,Engelhardt, W. A., 347.England, B. D., 164.Engle, R. R., 319.Englert, K., 136.Englert-Chwoles, A., 32.Engstrom, A., 323.Engstrom, L., 319.Ennor, A. H., 320, 355,Ennor, K. S., 298.Enslin, P. R., 237.Entschel, R., 212.Enzell, C., 228.Ephstein, Ya. V., 299.Ercoli, R., 145, 249.Erdey, L., 384, 386.Erdtman, H., 228.Erickson, L. E., 44.Erickson, R. E., 213, 214.Erlanger, B. F., 313.Ermolaev, K. M., 297.Ernest, I., 276.Ernst, F., 202.Ernst, R., 53, 165.Ershler, B.V., 15.Erusalimchik, I. G., 39.Erwin, M. J., 319.Erxleben, H., 270.Erzberger, P., 148.Eschenmoser, A., 286.Eschinazi, H. E., 226.Espy, H. H., 173.Ettala, T., 315.Ettlinger, L., 242.Ettlinger, M. G., 219.Evans, A. G., 50, 169.Evans, B. L., 122.Evans, D. E. M., 240.Evans, D. F., 132, 143.Evans, F. E., 253.Evans, H. T., jun., 149.Evans, I. J., 101.Evans, J. C., 70, 72, 76.Evans, M. G., 100.Evans, R. L., 366.Evans, R. M., 181, 203.Evans, W. C., 272.Evans, W. L., 50.Everest, D. A.. 405.Evers, E. C., 115.Evstigneeva, R. P., 276.Ewald, A, H., 49.Eyring, H., 194.Ezmirlian, F., 328.123, 125.208, 347.Fabbri, G., 74, 75.Fabre, P., 392.Fabry, C., 323, 324.Fairbrother, F., 120, 150.Falbe, J., 265.Fales, H.M., 282.Falqui, M. T., 155.Fan, C., 277.Fankuchen, I., 325.Fanshawe, F. A., 304.Fanta, G. F., 223, 258.Farhat-Aziz., 42Farmer, D. W. A,, 298.Farmer, R. C., 44.Farnow, H., 228.Farrant, J. L., 344.Farrell, P. G., 53, 164.Fassnacht, J. H., 207.Fastovskii, V. G., 30, 31.Fava, G., 121.Fawcett, F. S., 127.Fazakerley, S., 336, 338.Fazakerley, H., 235.Feairheller, W. R., jun., 77.Feates, F. S., 35.Fedeli, E., 236.Federova, T. I., 101.Fedotova, A. Z., 39.Feher, F., 68.Feher, M., 377, 389.Feifer, J. P., 186.Feig, G., 184, 206.Feigl, F., 382.Feldman, A., 188.Feldman, T., 67.Fells, I., 178.Feltkamp, H., 225.Feng, M. S., 55.Feng, P. Y., 21.Ferimore, C. P., 64.Ferguson, I. F., 147.Fergusson, J. E., 120, 152.Fernandes, F., 277.Fernando, Q., 92, 108.Fernelius, W.C., 91, 93,103, 104, 108, 134.Fernez, A., 298.Ferradini, C., 14.Ferrari, A., 157.Ferreira, P. C., 279.Ferrier, F. J., 187.Ferris, A. F., 306.Ferris, J. P., 284.Fessenden, R. W., 19, 79.Festenstein, G. N., 333.Fetter, M. E., 253.Fetter, N. R., 116.Feuer, G., 348, 349.Feuer, H., 217.Fickling, M. M., 161.Fiecchi, A., 236.Field, F. H., 8.Fields, B. R., 148.Fields, P. R., 106.Fields, T. L., 242.Figgins, B, F., 27, 28.Figgis, B. N., 132.Filatova, E. D., 17.Filipovik, L., 415.Filipovich, G., 46, 84, 85,175.Finch, A., 123.Finck, H., 345.Finkbeiner, H. L., 203.Finlayson, A. J., 173.Finn, S. B., 331.Finnegan, R. A., 270.Fischer, A., 49, 161.Fischer, A.K., 248.Fischer, D. J., 380, 413.Fischer, E. H., 319.Fischer, E. O., 136, 139,140, 143, 144, 145, 247,248, 249, 250.Fischer, F. G., 235.Fischer, H., 40, 287.Fischer, H. 0. L., 290.Fischer, L. G. M., 337.Fischer, R. B., 374.Fischer, W. R., 378.Fischmeister, I., 232.Fisher, F. L., 407.Fisher, R. D., 70.Fishwick, M. J., 334, 342.Fitch, S. J., 116.Fitzpatrick, T. J., 306.Fitzsimmons, R. V., 72.Flagg, J. F., 16.Flanberg, F., 118.Flanders, D. A., 14.Flautt, T. J., 85.Fleckenstein, A., 354.Fleischer, D., 107.Fleming, J. E., 147.Fle3, D., 281.Fletcher, G,, 17.Fletcher, H. G., jun., 299,Fletcher, J. P., 389.Fletcher, W. H., 72.Fleury, P., 304.Flexser, L. A., 47.Flood, A. E., 299.Florin, R.E., 240, 241.Flowers, H. M., 215.Flowers, R. H., 128.Flubacher, P., 75.Fodor, G., 196.Folsch, G., 309, 319.Forster, W., 73, 120.Folkers, K., 213, 214, 270.Foltz, C . M., 306, 362.Fontanella, L., 254.Forbes, E. J., 240.Forbes, M., 270.Ford, J. F., 202.Ford, T. A., 208.Formica, J . V., 215.Fornaguera, I., 225.Forrest, H. S., 269.Forsen, S., 86.Forst, W., 61.Forstner, J. L., 398.Fortnum, I). H., 74.Fortnum, D., 153.Foster, A, B., 181, 187, 257,289, 293, 303.300IFoster, R., 44.Fournier, J. , 228.Fowden, L., 253, 304, 359,360, 361, 362, 365, 366,367, 368, 369.Fowles, G. W. L4., 120, 149,152.Fox, R. C., 264.Fraenkel, M., 365.Fraisse, R., 219.Franc, J., 396.Francis, P. S., 182.Frank, H. S., 34.Franke, W., 262.Frankel, M., 306.Frankel, M. B., 217.Franklin, J.L., 63.Franz, I<., 249.Franzen, V., 217.Franzus, B., 119.Fraser, R. R., 222.Fraser, R. T. M., 43, 134.Frasson, E., 112, 155, 156.Fray, G. I., 265.Frazer, J. W., 122.Fredericks, J. , 368.Fredga, A., 306.Free, A. H., 327.Freed, S., 36.Freedman, M. L., 152.Freeman, M. P., 30.Freiser, H., 92, 107, 108.Freitag, W. O., 115.Fremlin, J. H., 331.French, C. M., 118.French, J. C., 218, 286.Freni, M., 137.Frenkel’, R. I., 149.Freund, H., 102.Frey, H. M., 177.Freyer, W., 137.Friberg, S., 149.Fricke, H., 14, 17.Fried, J. H., 175.Friedel, R. A., 141, 142,Friedman, H. A,, 147.Friedman, H. L., 12.Friedman, L., 8.Friedman, R., 361.Friedman, S., 198.Friess, E.T., 350.Frilley, M., 22.Fritz, G., 120, 168.Fritz, H., 279.Fritz, H. P., 140, 143, 247,Fritz, J. S., 388, 392.Frizel, D. E., 50.Frolich, H. O., 151.Frolich, W., 139, 249.Froling, A., 218.Froling, M., 218.Froemsdorf, D. H., 221.Frohardt, R. P., 218.Frow, F. R., 192.208.250.DEX OF AUTHORS’ NAMES. 429Frowein, R., 295.Frumkin, A. N., 40.Fruton, J. S., 315.Frye, C. L., 120, 206.Fuchs, R., 219.Fugita, Y., 366.Fuhlhage, D. W., 255.Fujino, A., 256.Fujita, J., 102.Fujiwara, S., 83.Fukui, K., 160.Fuller, R., 221.Funabashi, K., 8.Funk, H., 146.Fuoss, R. M., 33, 169.Furlani, C., 74, 155.Fuson, R. C., 238.Futami, S., 20.Fyfe, W. S., 49.Gabrielson, G., 398.Gadsby, B., 230.Gartner, F.-G., 312.Gaumann, E., 242.Gage, J.C., 376.Gal, R., 219, 244.Galatry, L., 28.Galbraith, A., 265.Galik, V., 232.Gallaghan, J . , 11 6.Gallup, G. A., 178.Gambaryan, N. P., 177.Gami, D. C., 31.Gamlen, G. A., 102.Gandhi, R. P., 226.Ganellin, C. R., 224, 244.Ganguly, B. K., 230.Ganguly, J., 215, 333.Gansel, E. E., 391.Gant, P. L., 10.Gaoni, Y., 222.Garber, R. A., 49.Gardner, D. E., 330, 331.Garfinkel, D., 70.Garg, C. P., 200.Garn, S. M., 384.Garner, C. S., 104.Garnett, J. L., 162.Garratt, S., 274.Garrett, C. G. B., 39.Garrison, W. M., 16, 17.Garton, G., 119.Garvan, F. L., 133.Garvin, D., 62.Gascoigne, R. M., 194.Gatzke, A. L., 55, 170.Gaudemer, M., 211.Gaudry, R., 365.Gawron, O., 309.Gaydon, A.G., 65.Geering, E. J., 257.Gehmann, W. G., 134.Geilmann, W., 414.Geissman, T. A., 263, 281.Geld, I., 406.Gellerman, J. L., 214.Gelles, E., 106, 171.Gel’man, A. D., 107, 139,Gender, W. J., 234.Gentile, P. S., 147.George, J . H. B., 98.George, J. W., 85, 128.George, P., 88, 92, 99, 105,George, R. S., 108.Georgian, V., 201.Gercke, R. H. J., 21.Gergely, J., 346, 347, 348,Gerischer, H., 38, 40, 41.Gerovich, M. A., 34.Gerrard, W., 206, 239, 271Gerri, N. J., 62.Gerson, F., 49.Geske, D. H., 243.Geske, G., 351.Gething, B., 240.Gevantman, L. H., 22.Ghatak, W. R., 230.Gheorghiu, C., 154.Gibbins, S. G., 85.Giddey, A., 270.Gieren, W., 149.Giesecke, P., 409.Giesemann, H., 258.GiguGre, P. A., 7, 60.Gilat, Y., 16.Gil-Aviv, E., 195.Gilbert, B., 270.Gilham, P.T., 268.Gill, E. K., 56, 61.Gill, N. S., 155.Gilles, P. W., 147.Gillespie, R. B., 129.Gillespie,R. J., 112,128,168.Gillis, H. A., 19.Gilman, H., 120, 267.Gilmour, J. B., 35.Ginn, M. E., 400.Ginsburg, D.. 272.Giovanella, B., 17.Gish, D. T., 316.Givens, W. G., 65.Gjertsen, L., 43.Gladner, J. A., 319, 346,Gladstone, J., 145.Glasson, W. A., 179.Glatzer, G., 71.Glemser, O., 120, 128, 149,Glick, R. E., 80.Glock, G. E., 330.Gloor, U., 213.Glover, J., 334, 338, 341,Glover, T. W., 333.Gloss, G. L., 196.Glueckauf, E., 37.Glushkova, M. A., 119.Gmelin, R., 305, 362, 365,146.131.349, 357.152, 383.342.367, 370430 INDEX OF AUTHORS, NAMES.Gnatz, G., 150.Gobreclit, H., 39.Godsall, J.A., 240.Goebel, W., 22.Goering, H. L., 173, 174,Gijtz, M., 283, 284.Goggin, P., 239.Gohlke, R. S., 401.Gold, H., 202.Gold, V., 33, 43, 45, 50, 53,54, 102, 134, 162, 166,168, 171.Coldberg, D. E., 91, 104.Goldberg, S. I., 247.Goldman, K., 31.Goldschmidt, S., 312.Goldstein, I. J., 302.Goldstein, J. H., 82.Goldstone, A., 361.Golomb, D., 54.Golova, 0. P., 299.Golovnya, B. A., 146.Golub, A. M., 102.Golubovic, A., 202.Gom6z Herrera, F., 77.Gompper, R., 262.Gonick, E., 108.Gonikberg, M. G., 68.Gonzalez, A. G., 235.Goodall, M. C., 356.Goodgame, D. M. L., 119.Goodman, I., 268.Goodman, L., 268, 289,Goodman, Ri., 304, 312.Goodwin, S., 83, 273, 274,Goodwin, T. W., 331, 332,Gopala Rao, G., 385, 408.Gopinath, K.W., 275,276.Gorbacheva, I. N., 275.Gordon, D. A., 176.Gordon, J. J., 243.Gordon, S., 12, 15.Gore, P. H., 174.Gorman, M., 277, 278.Gorogotskaya, L. I., 152.Gorsich, R. D., 250.Gorsuch, T. T., 417.Gortsema, F. P., 153.Goss, G. C. L., 334.Goswami, A., 154.Gottlieb, 0. R., 262.Goubeau, J.. 74, 115.Goubeaud, H.-W., 239.Gould, I?. E., 306.Goulden, J. D. S., 122.Goutarel, R., 277.Gouvea, M. A,, 346, 348.Govenstein, E., jun., 176.Govindachari, T. R., 244,Gowenlock, B. G., 217.Goyal, K., 112.Grace, J. A., 170,291, 300.279.337.275, 276.Graham, G. E. T., 182.Graham, W. H., 43.Grahame, D. C., 36.Granatelli, L., 375.Grant, D. K., 120.Grant, D. M., 81.Grant, L. R., 126, 199.Grant, M.S., 166.Grant, P. K., 233, 234.Grant, P. M., 16.Grant, W. K., 207.Grashey, R., 240.Grassman, W., 309, 312.Graves, D. J., 319.Gray, E. Le B., 339.Gray, P., 60, 122, 192.Graybill, B. M., 43.Greaves, J. C., 62, 66.Green, B., 234.Green, L. G., 118.Green, J., 269, 410.Green, M., 39, 206.Green, M. L. H., 136, 139,Greenberg, S., 225.Greenburg, S. M., 268.Greene, F. D., 181.Greenlee, T. W., 198.Greenough, W. B., 204.Greenstein, J. P., 197, 305,Greenwood, N. N., 118,Gregor, V., 262.Greiner, R. W., 174.Greville, G. D., 350.Grevendonk, W., 28.Grewe, R., 267.Grey, T. C., 350, 351.Gribov, L. A., 139.Gribova, E. I., 56.Griffin, B. P., 215.Griffith, J. S., 92.Griffith, W. P., 137, 138,Gnffiths, J.V., 116.Grimes, W. R., 147.Grimison, A., 165, 168.Grimme, W., 258.Grimshaw, J., 229.Grinberg, A. A., 155.Griot, R., 255.Grisebach, H., 272.Gritter, R. J., 203.Grob, E. C., 334.Grobbelaar, N., 368.-Grobe, G., 120.Groger, D., 272.Groenewege, M. P., 118.Grommers, E. P., 309.Gronowitz, S., 83.Grosse, A. V., 126.Grosskopf, H., 376.Grove, J. F., 218.Groves, M. L., 320.Groves, P. T., 170,144, 248.309, 360.125, 199.140, 152.Grovenstein, E. , 165.Grovenstein, E., jun., 176.Grubb, H. M., 243.Gruber, J., 137.Gruber, K., 401.Grubert, H., 143, 247, 248.Gruen, D. M., 154.Gruen, H., 84.Grussner, A,, 274.Grundmann, C., 263.Grundyrev, A. A., 73.Grunwald, E., 43, 171.Grunze, H., 125.Grzybowski, A.K., 107.Gualandi, C., 71.Gubisch, N., 201.Guddal, E., 210, 257.Gubeli, O., 1133.GuCgan, R., 205, 212.Giinthard, H. H., 194.Giinther, K., 112.Guentner, W. S., 18, 22.Guex, W., 337.Guffy. J. C., 60.Gugelmann, W., 334.Guggenheim, E. A., 28, 30.Guild, W. R.. 17.Guillemin, 316.Gundlach, H. G., 320.Gunn, S. R., 118.Gunstone, F. D., 214.Gupta, V. N., 270.Gurney, R. W., 34.Gus'kova, L. V., 101.Gustafson, R. L., 103, 107.Guthrie, R. D., 302.Gutmann, V., 112.Gutowsky, H. S., 81, 133.Guttmann, S., 44.Guttmann, St., 309, 317.Guy, R. G., 141.Gyimesi, J., 252.Gyorgy, P., 270.Haag, W.. 136, 337.Haas, G., 365.Haber, R. G., 195.Hadjiioannou, T. P., 380.Haefele, L. F., 307.Halschke, G., 258.Haerdi, W., 405.Hafner, K., 220, 244, 246.Hagemann, G., 295.Hagihara, N., 140, 151.Hahn, F.L., 376.Hahn, K. J., 380.Hahn, R. B., 390.Hahn, W., 265.Haines, R. L., 12.Haissinsky, M., 7, 16.Hale, W. F., 221.Halevi, E. A., 55.Hall, C. D., 202.Hall, D. M., 193, 263.Hall, J. R., 72.Hallam, B. F., 139INDEX OF AUTHORS’ NAMES. 43 1Hallgren, B., 215.Halliday, J., 377.Halmann, M., 54.Halpern, J., 45, 54, 112,Halpern, O., 216.Halsall, T. G., 230, 235,Halsay, G. D., jun., 30.Ham, N. S., 67, 76.Hames, G. E., 414.Hamet, R., 279.Hamill, W. H., 8.Hamilton, G. A., 42, 54,Hamilton, J. K., 303.Hamilton, R. A,, 25.Hammett, L. P., 47, 49.Hammick, D. Ll., 267.Hammond, G. S., 163, 221,Hamrick, P. J., jun., 222.Han, Y. W., 166.Hanania, G.I. H., 105.Hance, P. D., 276.Hanke, M. E., 368.Hadey, A., 384.Hanna, J. G., 391.Hanok, A., 325.Hansen, R. E. , 410.Hansen, R. P., 214.Hanson, J., 344, 345.Hanson, J. B., 272.Happe, J. A., 86.Harbottle, G., 111.Harcourt, R. D., 168, 266.Hardegger, E., 286.Harden, J. C., 400.Harder, R., 106.Hardgrove, G. L. , 143.Hardwick, J. L., 331.Hardwick, T. J., 11, 12, 18,Hare, D. G., 202.Harlan, J. T., 22.Harnish H., 124.Harper, B. J. T., 272.Harper, R. C., 25.Harper, S. H., 219.Harrand, M., 71.Harrington, G., 155.Harrington, W. F., 347.Harris, C. If., 132, 155, 157.Harris, G., 304.Harris, J. I., 317.Harris, L. A., 147.Harris, L. E., 235.Harris, M. M., 194.Harris, P. L., 333.Harris, T. M., 204.Harris, W.E., 402.Harrison, A. J., 61.Harrison, K., 251.Harrison, R., 201.Harrison, W. F., 244.Harrod, J. V,, 112.183.236.171.238.22.Harshman, S., 319.Hart, E. J., 7, 12, 13, 14,15, 21, 22.Hart, H., 180.Harteck, P., 10.Harthamp, H., 406.Hartles, R. L., 328.Hartley, B. S., 319.Hartley, G. S., 43.Hartzler, H. D., 217, 219.Hasegawa, T., 369.Hasek, W. R., 127.Hasenmaier, G., 305, 365,Haskell, T. H., 286.Haskins, R., 251.Haslam, J., 379.Hass, G. M., 351.Hassall, C. H., 304.Hassan, M., 164.Hasselback, W., 345, 351,Hasselmeyer. G., 266.Hasted, J. B., 36.Haszeldine, R. N., 178,Hatt, H. H., 215.Hattori, S., 83, 304, 366.Hauck, F., 177.Haug, J., 149.Hauge, S. M., 333.Hauke, W., 146.Hauptman, Z., 130.Hauptmann, S., 246.Hauser, C.F., 222.Hauser, C. R., 44, 176, 204,Havinga, E., 194.Havinga, E. E., 129.Hawthorne, M. F., 44, 117,Hayashi, S., 83.Hayashi, T., 347.Hayashi, V. K., 20.Hayden A. R., 366.Hayes, K. T., 168.Hayman. H. J. G., 21.Haymond, H. R., 16.Haynes, L. J., 251.Haynie, R., 219, 244.Hayon, E., 11.Hays, H. R., 203.Hayter, R. G., 146.Hayward, L. D., 298.Hazato, G., 83.Hazdra, J. J., 221.Hazebroek, P., 192.Hazel, J. F., 21.Hazell, A. C., 146.Hazlehurst, D. A., 40.Heacock, R. A., 252.Head, A. J., 195.Heastie, R., 30.Heath, C. E., 10.Heck, G., 77.Hedberg, K., 127.370.359.240.222.199.Hedges, R. M., 238.Hedgley, E. J., 303.Heffernan, M. L., 168.Hefley, J. D., 134.Heiba, E. I., 21.Heidt, L.J., 95.Heikes, R. R., 113.Heilberger, P., 163.Heilbron, I. M., 331.Heilbronner, E., 49, 50.Hein, F., 146.Heine, H. W., 253.Heine, K., 19.Heinz Neeb, K., 414.Heinzelman, R. V., 265.Heitsch, C. W., 116.Helbig, R., 221.Heller, H., 317.Heller, K., 41 1.Hellerbach, J. , 274.Helling, J. F., 247.Hellman, M., 240.Hellmann, H., 360, 365.Helmholz, L., 151.Hely Hutchinson, M., 211.Henbest, H. B., 216, 225.Henderson, I. H. S., 12.Henderson, L. M., 272.Hendrickson, J. B., 226.Heneage, P., 370.Henery-Logan, K. R., 265.Henglein, A., 7, 19.Henick, E. C., 178.Henley, E. J., 20.Hennig, G. R., 111.Henning, U., 213, 220.Hennion, G. F., 195.Henrich, G., 204.Henrikson, B. W., 223.Henry, R. A., 260.Henry, R.J. M., 138.Hepler, L. G., 99.Heppolette, R. L., 42, 171.Herbst, D., 262.Herbst, P., 210.Herbstein, F. H., 195, 225.Heritage, R. G., 128.Herman, J. A., 7.Herout, V., 210, 227, 228,Herr, E. B., 352.Herrick, E. C., 218.Herron, J. T., 63.Herscovici, J., 10.Hersh, C. K., 31.Herz, W., 254, 255.Herzfeld, K. F., 58.Heslinga, L., 311.Hess, G. I?., 316.Hess, H. J., 232.Hess, K., 272.Hesse, G., 200.Hesselbarth, H., 130.Hessling, H., 413.Hester, J. B., 274, 276.Heubach, E., 74.229, 237432 IHeusinger, H., 21.Hewson, K., 291.Hey, D. H., 52.Heyns, K., 287, 295.Hibbits, J. O . , 395.Hibbs, L. E., 398.Hickford, R. H., 120.Hickinbottom, W. J., 166.Hickling, A., 121.Hickman, K. C. D., 339.Hickner, R.A., 167.Hieber, W., 136, 137.Hiebsch, J., 244.Hietala, P. K., 361, 370.Highet, R. J., 261.Hildebrand, R. P., 227,Hilger, W., 154.Hilgetag, G., 202, 206.Hill, A. V., 353, 355.Hill, D. G., 44, 176.Hill, D. K., 348.Hill, R. L., 304, 318.Hill, T., 204.Hill, T. L., 350.Hiller, L. A., 56.Hilse, K., 318.Hilton, C. L., 411.Hilton, J., 43, 140.Hindman, J. C., 54.Hine, J., 175, 178.Hine, M., 175.Hinshelwood, C. N., 56,62.Hinton, I. G.. 266, 268.Hipp, N. J., 820.Hirose, L. Y., 228.Hirota, K., 20.Hirschfelder, J. O., 23, 57.Hisature, I. C., 72.Hitzemann, G., 68.Hlavka, J. J., 311.Hoard, J. L., 107, 132.Hoare, D. E., 56.Hoare, T. E., 66.Hobson, G. E., 355.Hochanadel, C. J., 12.Hochmann, K., 394.Hochstein, F.A., 279, 360.Hochstein, L. I., 287.Hock, H., 202.Hodge, A. J., 344.Hodge, H. C., 323.Hodges, R., 233, 236.Hodges, R. M., 328.Hodgkin, D., 102.Hodnett, E. M., 51, 55,Hodson, H. F., 165, 279.Hoeksema, H., 268.Hoffman, R. A., 83.Hoffmann, C. W. W., 113.Hoffmann, E., 375.Hoffmann, H., 205.HoffmannovA, J.. 277.Hoffmeister, W., 19.IIofmann, 13. P., 143, 248.229.182.DEX OF AUTHORS’ NAMES.Hofmann, K., 317.Hofmann, T., 320.Hofsass, H., 394.Hoijtink, G. J., 161.Hokama, T., 217.Hoke, D. I., 167.Holden, J. T., 363.Holden, K. G., 274.Holgate, W., 329.Holland, G. F., 310.Holleck, L., 40, 106.Holliday, A. K., 121.Holly, F. W., 270.Holm, R. H., 155.Holmes, F., 105.Holmquist, H. E., 208.Holroyd, R. A., 177.Holt, R.B., 59.Holtzberg, F., 150.Holtzer, A,, 347.Holtzer, H., 345.Holum, L. B., 268.Honda, H., 369.Honeyman, J., 185, 302,Honjo, M., 361.Honnen, L. R., 250.Hood, G. C., 70, 86.Hoogzand, C., 142.Hopkins, C. Y., 214, 215.Hopkins, L. O., 230.Hoppe, R., 146, 147.Horkk, A., 228.Horkk, M., 228, 256.Horiuti, J., 175.Horn, D. H. S., 282.Horn, H. G., 383.Horne, M. G., 214.Horner, L., 205.Hornig, D. F., 66.Horning, E. C., 273, 274,Horning, W. C., 53.Horrocks, W. D., 207.Horvat, R., 197.Horyna, J., 50.Hossenlopp, I. A., 192.Hotta, K., 348.Hough, L., 289, 303.House, R., 383.Hovorka, F., 40.Howard, J., 306.Howe, A. I?., 16.Howe, R., 232, 283.Howell, C. F., 172, 195.Howk, B. W., 208, 209.Howlett, K.E., 194.Hsing-I, T., 292.Hubbard, W. N., 192.Huber, G., 287.Huber, K., 150.Huber, M., 24.Huber, W., 337.Huber-Emden, H., 216.Hudec, J., 209.Hudson, G. V., 44.303.279.Hudson, R. F., 206.Hiibel, W., 142, 143.Huebner, C. F., 276.Hiickel, W., 225.Hiinig, S., 214.Hiitler, R., 242.Huttel, R., 44.Huffman, G. W., 303.Huggins, C. M., 83.Hughes, E. D., 163, 169,Hughes, G., 11.Hughes, N. A., 277.Hugo, J. M., 237.Huguenin, R. L., 317.Hui, W. H., 284.Huisgen, R., 179, 196, 216,Huisman, H. O., 337, 340.Hulett, J. R., 51, 175.Hume, F. M. M., 333.Humphrey, R. E., 130.Hunold, G. A., 376.Hunsberger, I. M., 203.Hunt, G. E., 360.Hunt, J. A., 318.Hunter, R. F., 333, 334.Huntsman, W. D., 193.Hunziker, F., 279.Hurd, C.D., 227, 262.Hurst, J. J., 227.Husain, D., 57.Hush, N. S., 90.Huston, J. L., 112.Huston, R. C., 253.Hutchings, G. H., 268.Hutchinson, F., 17.Huxley, A. F., 343, 344.Huxley, H. E., 344, 345.Huyskens, P., 10.Huzan, E., 28.Hvoslef, J., 158.Hyman, H. H., 49.Hyne, J. B., 86.Iacobucci, G. A., 279.Ibert, E. R., 407.Ichishima, I., 78.Igel, E. A., 419.Ikawa, M., 366.Illmann, G., 150.Illuminati, G. , 164.Imai, N., 348.Imai, S., 315.Impasato, F. J,, 177, 191,Inagaki, H., 20.Indelli, A., 42.Indinger, J., 416.Ingles, D. L., 294, 295.Ingold, (Sir) C. K., 163,169, 171, 188, 192.Ingram, V. M., 318.Inhoffen, H. H., 332, 333,Inowye, Y., 226.171.217, 240.21 9.341INDEX OF AUTHORS’ NAMES. 433Insley, H., 147.Inui, K., 369.Ioan, Y., 166.Ionad, G., 19.Ironside, C.T., 241.Irreverre, F., 359, 366, 370.Irvine, D. H., 105.Irving, H., 89, 91, 99, 105.Isaac, S., 330, 331.Isaacs, N. S., 253, 297.Isbell, H. S., 301.Iselin, B., 315, 317.Iselin, B. M. , 309.Ishikawa, M., 276.Isler, O., 211, 213, 331, 332,334, 335, 337.Issleib, K., 150, 151.Itano, H. A., 318.Ito, K., 89, 275.Ito, M., 369.Itoh, J., 87.Itoh, N. , 268.Iurygina, E. V., 45.Ivanov, Iu. B., 41.Ivanova, 0. M., 146,Ivanov-Emin, B. N., 119,Ives, D. J. G., 35.Iwasaki, T., 20.Iyoda, J., 115.Izadian, H., 15.Izrailevich, Ye. A., 45.Jache, A. W., 113.Jackman, L. M., 84, 212.Jackson, D., 330.Jackson, M., 298.Jackwerth, E., 385.Jacobs, T. L., 210.Jacobs, W.D., 403.Jacobsen, C. F., 308.Jacquenoud, P.-A., 316,Jacquier, R., 219.Jacura, Z., 172, 195.Jaeger, E., 274.Jager, H., 200.Jaeger, R. H., 265.Janecke, L., 270.JaffC, H. H., 49, 85.Jager, H., 235.Jagodzinski, H., 157.Jain, A. C., 271.Jain, T. C., 228.Jakob, F., 240.Jakob, L., 260.Jakoby, W. B., 368, 369.Jakubowski, 2. L., 218.Jakuszewski, B., 33.JambrSiE, I., 370.James, A. H., 326.James, B. R., 105.JanEik, F., 375.Jander, G., 112.Janke, J., 354.Jankowski, C. M., 379.146.317.Janot, M.-M., 277.Janson, J., 298.Jansz, H. S., 319.Jantos, N., 258.Jantzen, E., 205.Jardetzky, C. D., 84.Jardetzky, 0. , 84.Jarvie, A. W. P., 53.Jarvis, N. L., 198.Jaselkis, B., 388.Jaymond, P., 299, 300.Jeanloz, R.W., 287, 294.Jeener, J., 30.Jefferies, P. R., 229.Jefferson, E. G., 43.Jeffrey, G. A., 278.Jeger, O., 235.Jellinek, F., 143.Jencks, W. P., 44, 55.Jenkins, A. C., 31.Jenkins, J. W., 411.Jenkins, W. A., 150.Jennings, E. C., jun., 403.Jensen, A., 134.Jensen, F. R., 165, 166.Jensen, S. L., 212.Jenny, E. F., 207.Jenny, E. J., 215.Jenssen, H., 307.Jepsen, D. W., 57.Jerchel, D., 252, 260.Jilek, J. O., 276.Jillot, B. R. , 105.Jirousek, L., 252.Jizba, J., 260.Johl, A., 304.Jonsson, B., 320.Joerger, K., 129.Johannin, P., 29.Johansson, B., 320.John, D. I., 304.Johncock, P., 399.Johnson, A. M., 95.Johnson, A. W., 271, 314.Johnson, C. A., 409.Johnson, C. D., 238.Johnson, C. E., 80.Johnson, G.R. A., 15, 17.Johnson, G. S., 306.Johnson, J., 115.Johnson, J. B., 389.Johnson, J . L., 367.Johnson, L. F., 83, 274.Johnson, R. E., 20.Johnson, R. R., 55, 170.Johnson, S., 113.Johnson, W. S., 206.Johnston, T. P., 268.Johnston, W. D., 113.Johnstone, R., 274.Jokl, J., 396.Jolly, W. L., 113, 121,Jonassen, H. B., 106.Jones, A. C., 70, 86.Jones, A. S., 296.125.Jones, E. R. H., 142, 208,209, 235.Jones, F., 105.Jones, G. O., 27, 28, 30.Jones, G. W., 64.Jones, H. C., 413.Jones, H. G., 328.Jones, J. B., 261.Jones, J. G., 91.Jones, J. K. N., 299.Jones, J. M., 55.Jones, J. T., 405.Jones, M., 217, 257.Jones, R., 85.Jones, R. A., 260.Jones, R. H., 380.Jones, R. T., 318.Jones, W. E., 331.Jones, W.H., 49, 77.Jones, W. I., 203.Jones, W. J., 203.Jones, W. M., 258.Jonsen, J., 300.Jonsson, O., 150.Jrargensen, C. K., 89, 92,95, 104, 148, 154.Jorgenson, M. J., 261.Jordan, J . E., 23.Jordan, K., 378.Jortner, J., 12.Josefsson, L., 308.Joseph, B. J., 17.Joseph, J . P., 293.Jost, E., 150.Joy, J. R., 139.Jucker, E., 211, 253, 332.Judd, S. H., 409.Julia, M., 205, 212.Julia, S., 205, 212, 224.Jungreis, E., 382.Jura, J., 391.JuraCka, F., 206.JureCek, M., 381, 397.Jurkowitz, L., 197.Jutz, C., 211.Juza, R., 113, 149.Kabayama, M. A., 193.Kaesz, H. D., 115, 121.Kafiani, W. A.. 347.Kafod, H., 161.Kagawa, M., 227.Kahn, J. R., 316.Kahn, M., 42, 148.Kainz, G., 379, 415.Kaizerman, S., 184.KakAE, B., 276.Kaldor, G., 367.Kalinachenko, V. R., 45.Kalkwarf, D. R., 17.Kallfass, H., 115.Kalyankar, G. D., 366.Kamada, M., 407.Kamat, V. N., 277.Karnenetskaya, S. A., 56.Kaminsky, M., 34434 INDEX OF AUTHORS’ NAMES.Kaneko, T., 286, 315, 360.Kaneko, Y., 175.Kanwisher, J. W., 394.Kaplan, J., 63.Kaplan, J. I., 81.Kappeler, H., 315, 317.Kapustin, A. P., 170.Kapustinskii, A. F., 35, 36.Karagounis, G., 206.Karakhanav, R. A., 219,Karchmer, J. H., 401.Kari, S., 362.Karibian, D., 346.Karp, S., 394.Karplus, M., 80, 81.Karr, C., jun., 401.Karrer, P., 212, 279, 280,281, 331, 332, 334.Kasansky, B. A,, 223.Kaskan, W. E., 63, 64.Kasper, J. S., 114.Kasperl, H., 140.Kassalin, H. G., 249.Kassel, L. S., 56.Katayama, M., 83, 175.Katchalski, E., 309.Katritzky, A.R., 260.Katsoyannis, P. G., 316.Katsuda, Y., 226,Katz, D. L., 31.Katz, L., 153.Katz, S., 144.Katz, T. J., 193.Kaufman, J. V. R., 252.Kaufmann, F., 62, 64.Kaufmann, H. P., 214.Kauffmann, D. L., 319.Kauffmann, T., 259, 269,Kaupa, G., 149.Kavarana, H. H., 388.Kavstov, V. I., 40.Kawaj, K., 72.Kawasaki, I., 286.Kay, I. T., 271.Kaya, T., 367.Kaye, I. A., 52, 173.Kazama, Y., 204.Kecki, Z., 75.Keefer, R. M., 164.Keen, R. T., 183.Keenan, V. J., 17.Kehoe, T. J., 380.Keil, Th., 375.Keith, J. N., 115.Kelkar, G. R., 227.Kellenbach, K. O., 411.KeIler-Schierlein, W., 242,Kelley, J. J., 320.Kelley, M. T., 380, 413.Kempter, G., 244.Kemula, W., 50.Kende, A. S., 225, 242.Kennedy, A., 122.257.309, 318.314.Kennedy, F., 219.Kennedy, J.M., 15.Kennedy, T., 123.Kenner, G. W., 271, 304,Kent, J. A., 240.Kent, P. W., 290, 298.Kenttamaa, J., 170.Kerker, M., 151.Kerr, J. A., 45.Kerwin, T. D., 350.Ketley, A. D., 53.Kettle, S. F., 121.Kettle, S. F. A., 143.Keulemans, E. W. M., 129.Kewlen, E., 125.Keyworth, D. A., 390.Khalifa, H. , 390.Kharasch, M. S., 184, 206.Khastgir, H. N., 234, 237.Khorana, H. G., 268.Khorasani, S. S. M. A., 375.Khundar, M. H., 375.Kiamud-din, M. , 168.Kido, K., 90.Kieff er, J., 29.Kielley, W. W., 347, 350,Kiely, H. J., 395.Kieso, A., 256.Kiessling, G., 287.Kihara, T., 23.Kikkawa, I., 275.Kikuchi, T., 275.Kilby, D. C., 165.Killick, R. A., 417.Kim, 3.-Y., 49.Kimmel, J.R., 304.Kimura, M., 83.Kinell, P.-O., 75, 76.King, E. L., 98, 100, 102.King, F. E., 235.King, F. T., 67.King, G. S. D., 142.King, J., 87.King, P. A., 47.King, R. B., 145, 248.King, T. J., 235.Kingsbury, C. A., 177.Kinoshita, Y., 156.Kirby, G. W., 251.Kirch, L., 139.Kirkwood, J. G., 32.Kirschfeld, S., 299.Kirschner, H., 325.Kirshenbaum, A. D., 31,Kishita, M., 156.KiSovA, L. , 155.Kissman, H. &I. , 293.Kistiakowsky, G. B., 177.Kitagawa, S., 351.Kivelson, D., 79, 86.Kivelson, M. G., 79.Kivestroo, W., 194.Kjaer, A., 305, 365.313, 368.357.126.Klaboe, P., 76.Klages, F., 204, 216.Klahre, G., 205.Klanberg, F., 121.Klein, E., 33.Klein, J., 222.Kleiner, E. M., 275.Kleinschmidt, G., 272.Klemchuk, P.P., 53, 166.Klement, R., 125.Klemm, W., 151, 157.Klezl, P., 250, 251.Klikorka, J., 112.Klinot, J., 236.Klocking, €3.-P., 296.Kloubek, J., 272.Klove, M. S., 249.Klyne, W., 187, 189, 194,Kmet, T. J., 52, 174.Knabe, J., 276.Knapp, H., 31.Kneller, M. T., 263.Knight, J. D., 175, 383.Knobler, C. B., 156.Knobler, Y., 306, 365.Knollmiiller, K. O., 125.Knox, G. R., 247.Knox, H. J., 177.Knox, K., 156.Knox, L. H., 217, 257.Knunyants. I. L., 177.Kobe, K. A., 163.Kober, E., 263.Koch, K. F., 214.Kochetkova, N. S., 247.Koczka, K., 196.Kodama, G. , 115.Kodama, H., 204.Kochling, H., 294.Kogl, F., 270.Kogler, H. P., 248.Kohler, J., 136.Koehn, C. J., 333.Konig, E., 105.Kohler, J., 136.Konig, K.H., 395.Korbl, J., 375.Koerner, W. E., 59.Koster, R., 198, 272.Koszegi, D., 387.Kofler, M., 213, 337.Koft, E., 263.Kohltoff, I. M., 170.Kohler, H., 347.Kohnstam, G., 43, 171.Kojima, K. , 77.Kokes, R. J., 198.Kokowsky, N., 313.Kolbanovsky, Yu. A., 17.Kolbin, N. I., 153.Kolotyrkin, Y. M., 12.Kolousek, J., 17.Komamine, A., 304, 366.Komendatov, M. I., 178.Kominz, D. R., 346.228INDEX OF AUTHORS, NAMES. 435Iiomiyama, Y., 154.Kondilenko, I. I. , 72.Kondo , M. , 156.Kondratiev, V. N. , 59.Konigsberg, W., 313.Konstas, S. , 293.Koons, C. B., 55, 162.Kooyman, E. C., 224.Kopecky, K. R., 173, 177,Kopelman, R., 241, 368.Kopoldova, J., 17.Koppel, H. C., 268.Kopple, K. D., 310.Korableva, V. D., 101.Koreslackov, Iu.D., 244.Kornblum, N., 203.Korotov, I?. A., 72.Korshak, V. V., 111.Korte, F., 252, 265.Korte, I., 252.Korzun, B., 276.Koshland, D. E., 319, 351,Koski, W. S., 116.Koskikallio, J., 48, 49.Kosmatyi, Yu. V., 102.Kosower, E. M. , 172.Koster, G. F., 95.Kotake, M., 286.KovAcs, K., 259.KovA?, J., 272.Kowelsky, A., 352.Koyama, K., 380.Koz&k, P., 397.Kozikowski, J., 249.Koziollek , D. , 294.Kradolfer, F. , 242.Kramer, B., 325.Krarner, G. M. , 25.Krapcho, A. P., 220.Krasnanslry, V. J. , 60.Krasokee, I?., 109.Kratzer, J., 44.Kratzl, K., 401.Kraus, C. A., 170.Kraus, K. A., 70.Krause, J, T., 36.Krause, L., 68.Krause, M., 41.Krauss, H.-L., 150.Krebs, E. G., 319.Krebs, H. A.. 354.Krecker, B.D. , 104.Kreevoy, M. M., 46, 53,Kresge, A. J. , 46, 58, 162.Krestinskii, Ya. A., 31.Kriegsman, H., 73, 74.Kriegsman, K., 120.Kriner, W. A., 115.Krishnamurti, D., 75.Kristal’nii, E. V., 20.Kristen, H., 299.Krivis, A. , 265.Kroner, M., 142, 248.190.352.175.Krongauz, V. A., 20.Kriierke, U., 142.Krukar, R., 338.Krupicka, J. , 182.Krupowicz, J., 227.Kruschinski, L. , 72.Kubba, V. P., 168.Kubo, M., 156.Kuchen, W., 124.Kudintseva, G. A., 147.Kuehl, F. A., 270.Kuehne, M. E., 276.Kuffer, F., 19.Kugo, T., 275.Kuhn, R., 287, 334.Kuhn, S. J., 166.Kuhnkies, R., 39.Kuivila, H. G., 46, 167.Kuksis, A., 204.Kulka, M., 241.Kullick, W., 136.Kullnig, R. K., 84.Kulp, J. L., 328.Kumagai, H. , 356.Kumli, K.F., 206.Kunkel, L. , 158.Kunst, P., 319.Kuntze, H., 217.Kupperman, A., 8, 10.Kurien, K. C., 13, 17.Kuroya, H. , 154.Kursanov, D. N., 170,Kury, J. W., 99.Kuschinsky, G., 349.Kusomoto, S., 286.Kuthan, J., 232.Kuwata, K., 20.Kuyper, A. C., 327.Kuzina, L., 71.Kwart, H., 182, 183, 224,244.305.Labes, M. M., 217.Lacam, A. , 28.Lacher, J. R., 220.Lack, R..E., 210.Lacy, J., 418.Ladbury, J. W., 181, 183.Laddha, G. S., 386.Lady, J. H., 412.Lafont, R., 75.Lagowski, J. J., 111.Lahey, F. N., 229, 236.Lahrmann, E., 250.Laidler, K. J., 34, 35, 36,49, 56, 61, 171.Laine, N., 82.Laing, W. R., 380.Laki, K. , 319, 346.Laland, S., 300.Lambert, R. W., 63, 162.Lambie, D. A., 417.Lamchen, M. , 270.Lampe, F.W., 8, 9.Landau, B. S., 147.Landau , L. , 58.Landesman, H. , 85.Landmann, W., 17.Landor, P. D., 210.Landor, S. R., 188, 210.Lane, T. J., 102, 105.Lang, R. P., 319.Lange, E. , 33.Lange, R. F., 265.Langemann, A., 177, 213.Langer, F. , 250, 251.Langer, S. H., 403.Langford, P. B., 178.Langford, P. D., 175.Langford, W. J., 397.Langhoff, J., 19.Lansbury, P. T., 221.Lanz, P., 313.Lappert, M. I?., 117, 206,239, 271.Large, W. , 268.Larkworthy, L. F., 105.Larsen, H. O., 223.Larsen, P. O., 305, 365.Lasocki, 2. , 167.Lassner, E., 387.Lassettre, E. N., 8.Laswick, J. A,, 151.Latimer, W. M., 34.Latourette, H. K., 306.Laubengayer, A. W., 116.Lauer, J. L., 77.Lauer, W. M., 55, 162.Langhland, D. H., 342.Laughlin, R.G., 177.Laughton, P. M., 54, 171.Laurent, T. C., 16.Lau tenschlager , H . , 3 1 2.Lauterbach, R. , 270.Lavie, D., 237.Law, H. D., 315.Lawes, B. C. , 49.Lawrence, R. V., 233.Lawson, W. B., 307, 314,Lawton, E. A., 122.Lazarev, A. N., 73.Leach, S. J., 308.Leadbetter, A. J., 75, 135,Leah, A. S., 29.Leake, W. W., 203, 239.Leal, G., 223.Leane, J. B., 82, 83.Leary, J. A., 42, 148.Leaver, A. G., 328.Leberman, R., 105, 107.Leblanc, E., 146.LeBleu, R. E., 264.Lecocq, A., 29.Ledeen, R., 299.Lederer, E., 214, 234.Le Dizet, L. , 304.Ledwith, A., 41, 206, 218.Lee, C. C., 172, 173.Lee, J.. 84.Lee, J. B., 295.362436 INDEX OF AUTHORS’ NAMES.Lee, M. N. , 360.Lee, W. H., 122.Leeding, M. V., 236.Lee Smith, A., 411.Le FBvre, C.G., 189,Le FBvre, R. J. W., 189,Le Fevre, M. L., 326.Leffler, J. E., 43.Lefort, M., 13, 22.Le Goff, P., 177.Le Hir, A., 277.Lehmann, G. , 206.Lehmann, H., 318.Lehmann, H.-A., 130, 148.Lehner, H. , 278.Lehninger, A. L., 350.Leibbrand, K. A., 221.Leibowitz, J., 298.Leimgruber, W., 286.Leisten, J. A., 47, 180.Leister, N. A., 311.Le Men, J., 277.Lemieux, R. U., 84, 288.Lempert, C. , 252.Lenci, M.-T., 316.Lengyel, S., 36.Lenk, W., 243.Le Noble, W. J., 163.Lentz, K. E. , 316.Leonard, M. A., 381.Leonard, N. J., 264.Leone, C., 17.Leonhauser, S., 261, 362.Leppelmann, H’. J., 287.Leppla, W. , 304.Lergier, W. , 313.Lerner, A. B., 265.Lester, C. T., 173.Leto, J. R., 142, 249.Letsinger, R.L., 271.Letters, R., 320.Levand, O., 203.Levelt, J. M., 25, 28.Lever, A. B. P., 106, 131,Levich, V. G., 41. . Levin, S. H., 230.Levine, R., 203, 239.Levitt, B. P., 59.Levitt, L. S., 184.Levy, H. A., 152.Levy, H. M. , 351 , 352.Levy, S., 220.Levvy, G. A., 292.Lewak, S. , 300.Lewicka, K. , 259.Lewis, B. A., 302.Lewis, E. S., 55, 170.Lewis, I. C., 161.Lewis, J., 131, 132, 138.Lewis, K. G., 235.Lewis, R. E., 55, 180.Li, C. H., 304, 309.Li, N. C., 107.194.194, 195.271.Lichtin, N. N., 20, 60, 169,Liebenthal, J. L., 19.Lieber, E., 258.Liebermann, C. , 292.Liebster, J., 17.Liehr, A. D., 109, 155,Ligett, W. B., 240.Light, A., 316.Liler, M., 40.Liley, P. E., 23.Lincoln, R. M., 17.Lindars, F. J., 62.Lindberg, B., 290, 298.Lindemann, L.P., 60.Lindenberg, W. , 287.Linderstram-Lang, K. ,Lindgren, V. V., 240.Lindler, H., 211, 332, 334,Lindqvist, I., 75, 76, 126,Lindsey, R. V., 204, 205,Lindsay, R. V., jun., 221.Lingafetter, E. C. , 156.Lingens, F., 360.Linko, P., 360, 366.Linnenbom, V. J. , 9.Linnett, J. W., 59, 62, 66,Linstead, R. P., 260.Linton, H. R., 73.Lipke, J., 399.Lipp, A., 137.Lippincott, E. R., 28, 67,Lippold, G., 206.Lipscomb, H. S., 316.Lipscomb, W. N., 114, 116,Lipsky, S., 18.Lissner, A., 153.List, P. H., 305.Little, R., 119.Littler, J. S., 183, 203.Liu, L. H., 276.Liu, S., 213.Liverman, J. L., 370.Livingston, R., 7.Livingstone, S. E., 155.Llewellyn, D. R., 122.Lloyd, D.G., 18.Locker, R. H., 346.Lockhart, J. C., 42.Lockyer, R. , 414.Lockyer, T. N., 157.Loeb, J. N., 197.Loew, H., 412.Loewe, L., 185.Loewenthal, H. J. E., 198.Lombardo, G., 103.Long, F. A., 8, 46, 53, 162,170.156.308.335.128, 151.210.92, 104.70, 77.140.175, 177.Long, H. M., 30.Long, L. H., 115.Longi, P. , 201.Longone, D. T., 219.Longuet-Higgins, H. C.,Loo, Y. H., 272.Looy, H. V., 49.Lorand, L. , 356, 357.Lord, R. C., 73, 74.Lorenz, W., 40.Lorette, N. B., 205.Los, M., 244, 284.Lothringer, R. L., 415.Lott, K. A. K., 152.Loudon, J. D., 181.Lovell, F. M., 278.Lovering, E. G., 12.LovreEek, B., 39.Lowater, F. , 330.Lowe, J. S., 333.Lowen, A. M. , 50.Lowey, S., 309, 347.Lowy, P. H., 363.Lozer, S.A., 65.Lucchesi, P. J., 10.Luck, S. M., 176.Ludlum, K. H. , 116.Liithi, U., 334.Luttke, W., 217.Liittringhaus, A., 136, 265.Luke& R., 254, 255, 256,259, 260, 272.Lukhtanova, V. D., 40.Lusi, A., 264.Lustig, M., 117.Luther, H., 412.Lutz, E. F., 254.Lutz, W. €3. , 316.Lux, F., 137.Lux, H., 150.Lyle, G. G., 261.Lyle, R. E., 261.Lynds, L., 200.Lynen, F., 213, 226.Lynn, J. W., 119.Lynton, H., 147.Lyon, R. J. P., 408.Lysyj, I., 384.Lythgoe, B., 293.McAllan, A., 292.McArthur, C., 328.McBee, E. T., 240, 241.McBeth, R. L., 154.McCabe, L. J., 16.McCaldin, D. J., 283.McCann, H. G., 330.McCarthy, P. J., 103.McCasland, G. E., 197.McClure, D. S., 88, 99,Maccoll, A., 90, 193.McCollum, J.D., 243.McConnel , H. M. , 81 , 143.McCoy, L. L., 206, 219.244.131INDEX OF AUTHORS’ NAMES 437McCullogh, J. P., 192.McCullough, J. D., 148.MacDiarmid, A. G., 115,MacDonald, D. L., 300.Macdonald, F. J., 377.McDonald, H. J., 396.MacDonald, N. S., 328.McDonald, R. N., 244.McElhinney, R. S., 225.McElvain, S. M., 218.McEvoy, F. J., 293.McEwen, W. E., 206.McFadden, W. H., 402.McFarland, J. W., 217.Macfarlane, W. D., 334.McGarvey, B. R., 79, 84.McGlashan, M. L., 28.McGregor, A. C., 312.McHale, D., 269.McHard, J. A., 411.Maciak, G., 277.McIntyre, G. H., 104.McKean, D. C., 72, 73.McKennis, H., 360.Mackenzie, N., 198.McKerns, K. W., 304.Mackie, W. S., 328.Mackillop, M. J., 72.Mackinney, G., 341.McKinney, 0.F., 378.McKinney, R. W., 410.Mackor, E. L., 82, 161.McKusick, B. C., 21.Mchchlan, A. D., 126.McLaren, E. H., 151.Maclaren, J. A., 310.Maclean, C., 82, 161.McLeod, J. B., 32.McMeekin, T. L., 320.McMurry, T. B. H., 230.McNabb, W. M., 21.MacPhillamy, H. B., 276.McTaggart, F. K., 148.McVeigh, P. A., 224.McWeeny, R., 80.Madan, M. P., 27.Maddock, A. G., 147.Maeck, W. J., 406.Maeda, N., 20.Maekawa, A., 369.Magat, M., 19, 21.Magee, J. L., 8, 14.Magee, T. A., 136.Maginn, R. E., 249.Magndi, A., 149.Magnusson, E. A., 90.Magnusson, R., 186.Magrath, D. I., 320.Mahan, B. H., 177.Mahler, W., 123.Mahlman, H. A., 16, 22.Maimind, V. J., 297.Main, E. R., 330.Maisch, W. G., 28.Maitlis, P. M., 168.120.Majumdar, A.K., 383,403,Makens, R. F., 415.Makharji, A. K., 416.Maki, G., 155.Makino, K., 20.Makisumi, S., 315.Malatesta, L., 137.Maley, F., 287.Maley, G. F., 287.Maley, L., 93.Malinowski, E. R., 184.Malm, J. G., 148.Malmstadt, H. V., 380, 391,Mamalis, P., 269.Man, E. H., 158.Manabe, T., 20.Mancera, O., 225.Mandelcorn, L., 111, 188.Mandeles, S., 368.Mandell, L., 82.Manelis, G. B., 49.Manhas, B. S., 112.Manly, R. S., 326.Mann, B. R., 161.Mann, F. G., 266, 268.Mann, P. J. G., 363.Mannerskantz, C., 173.Manno, P. J., 9.Manske, R. H. S., 366.Mantica, E., 249.Manuel, T. A., 139, 140.Mao, T. J., 124.Maranville, L. F., 70.March, J., 218.Marcinkiewicz, S., 269,410.Mares, F., 183.Marica, E., 143, 245.Marini-Bettblo, G.B., 279.Marino, G., 165, 166.Marion, L., 273, 283, 284.Markby, R., 141, 142, 208.Markert, F., 402.Markes, J. H. H., 312.Markham, R., 268, 271.Markley, F. X., 228.Mark6, L., 135.Markova, S. V., 77.Markunas, P. C., 393.Marsden, D. G. H., 66.Marsh, B. B., 356.Marshall, B. A., 240.Marshall, J. M., 345.Marshall, R., 305.Marshall, T. W., 80.Martell, A. E., 91, 103, 106,Martin, A. J. P., 214.Martin, D. L., 103.Martin, D. S., jun., 135.Martin, E. L., 210.Martin, H., 385.Martin, J. D., 258.Martin, J. V., 405.Martin, N., 318.406.392.107, 271.Martin, N. H., 396.Martin, R. B., 44, 103, 105,Martin, R. L., 156.Martin, W. B., 304.Martonosi, A., 348, 349.Maruyama, K., 348.Marx, A. F., 311.Masamune, H., 287.Masamune, S., 281.Mashiko, T., 83.Mason, E.A., 23, 24, 27, 28.Mason, J., 122.Mason, S. F., 53, 55, 164.Mateos, J., 173.Mateos, J. L., 177.Matikkala, E. J., 305, 370.MatijeviC, E., 151.Mather, W. B., jun., 394.Matheson, M. S., 7, 17.Matheson, R. A., 100.Mathew, K. K., 191, 201.Mathews, D. H., 393.Mathews, D. M., 134.Mathews, F. S., 140.Mathieson, D. W., 234.Mathieson, J., 331.Mathieu, J.-P., 72, 74.Mathot, V., 30, 31.Matousch, W. R., 109.Matsen, F. A., 80.Matson, G. W., 162.Matsubara, .I., 156.Matsuda, G., 318.Matsuda, H., 41.Matsuki, Y., 83.Matsuoka, S., 83.Matsuura, T., 229.Mattern, J. A., 132.Matthews, C. N., 136.Matthews, D. L., 65.Matthews, J. S., 380.Mattock, G. L., 16.Mattsson, E., 39.Mauger, A.B., 314.Mauli, R., 228.Maurel, H., 404.Maurice, M. J., 404.Maurisch, W., 338.Maxwell, C. R., 17.May, A. D., 67, 75.May, P. J., 195.May, S. C., 319.Maya, W., 195.Maybury, R. H., 308.Mayer, H., 283.Mayer, J., 224.Mayer, R. P., 174.Mayo, D. W., 74, 247, 284.Mayor, L., 59.Mazaki, T., 236.Mhzor, L., 387.Mazumdar, M., 78.Mazur, J., 56, 57.Mazur, R. H., 172.108, 125, 308, 309.205, 210, 213438 INDEX OF AUTHORS’ NAMES.Mazur, Y., 199.Mazzanti, G., 119, 201.Meaburn, G. M.,’ 19, 20.Mead, J. F., 17.Meckenstock, K. U., 403.Mecklenborg, K., 260,Medrud, R. C., 114.Mehl , W. , 40.Mehne, A., 113.Mehta, A. C., 269.Meier, J., 149.Meier, K. D., 207.Meijer, F. A., 194.Meinert, H., 130.Meinwald, Y.C., 194, 223.Meisel, T., 387.Meisels, A., 231.Meisels, G. G., 9.Meisinger, M. A. P., 270.Meister, A., 363.Meites, L., 394.Melander, L., 162.Melchior, N. C., 93.Melera, A., 237.Mellander, O., 319.Mellor, D. P., 93, 109.Melrose, G. J. H., 229.Melton, C. E., 8, 9.Menass6, R., 180, 313.Menssen, €I. G. , 305.Menville, R. L., 391.Menzies, A. C., 67.Mercer, E. H., 344.Mergault, P., 15.Merlis, N. M., 299.Merrifield, R. B., 315.Merritt, C. , jun., 400.Merz, K. M., 120.Meschi, D. J., 127.Meschke, R. W., 221.Meshitsuka, G., 18, 20.Messerly, J. E., 192.Metlesics, M., 142.Metlesics, W.. 209, 251.Methin, S., 136, 198.Metzger, G., 40.Meyer, A. S., jun., 380.Meyer, H., 412.Meyerhof, O., 357.Meyerhoff, K., 113.Meyerson, S., 243.M’Hirsi, A,, 28.Miarka, S.V., 222.Miasishcheva, G. G., 15.Micheel, F., 294, 295, 298.Michelakis, A. M., 16.Michels, A., 25, 28, 29.Michels, J. G., 168.Michelson, A. M., 320.Michelson, C. E., 380.Middlebrook, W. R. , 346.Middleton, W. J., 207.Miettinen, J. K., 369.M!ge!’, P. K., 104.Mlhail, R., 10.MikeS, O., 315.Mikhailov, G. V., 68.Mikhailov, V. A. , 34.Mikheev, E. P., 135.Milas, N. A., 202, 334.Milburn, R. M., 181.Miles, J. H., 185.Miles, J. M., 185.MilhailoviC, M., Lj., 314.Miliayeva, N. M., 49.Mill, T., 182.Millar, I. T., 315.Millen, D. J,, 122.Miller, A. E. G., 201.Miller, C. C., 384.Miller, C. E., 20.Miller, D. G. , 36.Miller, I;. A., 67.Miller, F. J., 379, 395.Miller, G., 267.Miller, G.T. , 114.Miller, H. C., 85.Miller, I. T., 241.Miller, J. B., 299.Miller, J. G., 25.Miller, L. L., 363.Miller, N., 10, 11, 13, 20,Miller, R. E., 44.Miller, R. R., 105.Miller, W. T., jun., 175.Milligan, T. W., 264.Mills, J. F. D., 278.Mills, J. S., 236.Mills, 0. S., 135, 141.Minc, S., 75.Mino, G., 184.Minoura, Y., 253.Minton, R. G., 42.Mironov, K. E., 121.Mirra, J., 219, 244.Misra, S., 384.Miss, A., 396.Mita, I., 20.Mitchell, E. R., 346.Mitchell , M. J. , 245.Mitchell, P. C. H., 101.Mitoma, C., 366.Mitra, G., 128.Mitra, S. S., 77, 255.Mitscher, L. A., 233.Mitteldorf, A. J., 412.Miyake, A., 78.Miyamoto, M., 361.Miyazawa, T., 78, 192.Mizuno, Y., 163, 164.Mizushima, S., 78,102, 132.Mocek, M., 55, 170.Modena, G., 184.Modic, F. J. , 238.Mohlmann. E., 269.Moeller, C. W., 118.Moelwyn-Hughes, E. A.,Morikofer, A., 49, 50.Moslein, E. M., 213, 226.Moffatt, J. G., 268.50.42, 178.Moir, R. Y., 197.Mok, S. F., 169.Molnar, B., 252.Molnar, F., 349.Molnar, J. , 357.Molter, R. F., 218.Mommaerts, W. F. H. M.,346, 347, 350, 353.Monchamp, R. R., 138.Mondon, A., 266.Mondovi, B., 17.Monk, C. B., 101.Monnier, D., 405.Montarnal , R. , 19.Montavon, M., 211, 332,334, 335, 338.Montgomery, J. R., 268.Montroll, E. W., 57.Moodie, R. B., 82.Moody, G. J., 16.Mooney, R. W., 113.Mooney Slater, R. C. L.,Moore, A., 148.Moore, B., 136.Moore, C. E., 88.Moore, F. D., 326.Moore, J. W., 17.Moore, P.T., 172, 193.Moore, R. C. , 167.Moore, R. N., 233.Moore, R. W., 233.Moore, S., 307, 320.Moore, T., 331, 333.Moore, W. R., 172, 193.Moores, M. S., 266.Moos, c., 357.Morales, M. F., 347, 348,Moran, T. I., 24.Morf, R., 331.Mori, A., 370.Morimoto, H., 361.Moritani, I., 172.Morgan, A., 328, 329.Morgan, D. J. , 205.Morgan, L. O., 87.Morozov, N. M. , 56.Morris, C. J., 315, 359, 370.Morris, D., 315.Morris, D. F. C., 417.Morris, J. H., 199.Morris, L. J., 214.Morrison, J. A., 75.Morrison, J. S., 113.Mors, W. B., 262.Mortensen, J. P., 249.Mortimer, F. S., 79, 82.Mortimer, P. I., 362.Morton, R. A., 333, 337.Mory, R., 204.Mosby, W. L., 198.Moschel, A., 208, 220, 245.Moskvin, A. I., 107.Mothes, K., 272.Motl, O., 229.129.350INDEX OF AUTHORS’ NAMES.439Mounter, L. A., 379.Mountfield, B. A., 271.Mourgue, M., 366.Mousseron, M., 219.Moyer, J. R. , 76.Mozgova, K. K., 111.Muccini, G. A., 18.Miihlbauer, E., 204.Miiller, E., 206.Miiller, I?., 107.Miiller, H., 273, 346, 356.Miiller, P., 211.Miiller, R., 140.Muetterties, E. K., 85, 127,Mukherjee, D., 393.Mukherjee, S. L., 230.Mukherji, S . M., 226.Muller, E., 216,Muller, N.. 81.Muller-Schiedmayer, G. IMulyran, B. J. , 324.Munk, S., 17.Munro, J. D., 145, 250.Munsick, R. A:, 317.Murai, F., 286.Murakami, M. , 172.Murakami, S., 361.Muramatsu, N., 294.Murata, H., 102.Murayania, M., 318.Murman, R. K., 104.Murphy, M. E., 377.Murphy, R. B., 42, 47, 167.Murray, D.H., 299.Murray, J, G., 136.Murray, K., 199.Murray, M. A., 50.Murray, M. M., 330.Murrya, R. W., 217.Musgrave, W. R., 399.Musgrave, W. K. R., 239.Musher, J., 82.Myers, R. Y., 127.Myhre, P. C., 162, 167.Nace, H. R., 203, 205.Nageli, P., 107.Nasanen, R., 103.Nagakura, S., 160.Nagano, T. , 369.Nagata, C., 160.Naghizadeh , J . N. , 42.Nagri, S. M., 221.Nahabedian, K. V., 46,Nahringbauer, G., 128.Nair, C. P. N., 277.Nair, V. S. K., 101.Nakada, H. I., 287.Nakagawa, I., 78, 132.Nakagawa, Y. , 360.Nakajima, A. , 20.Nakajima, M., 221.Nakamori, R. , 361.158, 239.123.167.Nakamoto, K., 102, 103.Nakamura, A., 140.Nakao, A., 324.Nakatsuka, T., 228.Nakazaki, M., 192.Nambury, C. N. V., 258.Nametkin, N.S. , 73.Nancollas, G. H., 100, 101,Nanninga, L. B., 351.Narasimhan, N. S., 237.Narasimhan, P. T., 80, 82.Nardelli, M., 121.Narita, K., 308.Nascimento, J. M., 235.Nast, R., 131, 140.Natsume, M., 281.Natta, G., 119, 201, 249.Naughton, M. A., 319.Nauman, L. W., 320.Naumann, P.. 120.Naves, Y., 226.Nawa, H., 361.Naylor, P. G. , 175.Nazy, J. R., 271.Neeb, R., 408.Needham, D. M., 343, 350.Neipp, L., 242.Nejak, R. P., 18.Nekrasov, L. N., 40.Nelson, F., 70.Nelson, N. A., 207.Nemodruk, A. A. , 239.Nenitzescu, C. D., 143, 166,Nerdel, F., 77, 254.Neshpor, V. S., 147.Nesmeyanov, A. N., 135,Nettleton, D. E., 316.Neuberger, A., 187.Neuenschwander, E. , 150.Neuman, M. H. , 330.Neuman, M. W., 323.Neuinan, W.F., 323, 324,Neumann, H. M., 134.Neumayer, J. J., 414.Neupert, H.-J., 244.Neurath, H., 308, 319.Neureiter, N. P., 259.Neuss, N., 277, 278.Nevell , T. P. , 303.Nevitt, T. D., 19.Newbould, J., 267.Newburg, N. R., 119.Newell, J. E., 411.Newman, H., 226.Newman, L., 149.Newman, M. S., 170, 211,Newns, G. R., 121.Newth, F. H., 297, 298.Newton, T. W., 54, 134.Nezhevenko, M. A., 15.Ng, Y. L., 284.106.245.247.330.216, 270.Nicholls, B., 225, 249.Nicholls, D., 149.Nicholson, E. M., 253.Nickerson, W. J., 368.Nicksic, S. W. , 409.Nicoara, E., 212.Nicolaysen, R., 327.Niedergerke, R. , 344.Nield, E., 241.Nielsen, J. R., 76.Nielsen, S., 128.Nielsen, W. D., 177.Nigan, H., 137.Nightingale, E. R., 37.Nightingale, E.R., jun.,Nigrelli, R. F., 299.Nikitin, E. E., 58.Nikolaev, N. S., 150, 152.Nishida, S., 172.Nishimura, S., 83.Nixon, E. R., 73.Noble, P. C. , 9.Noble, R. L., 277.No6, F. F., 304, 367, 368.Noell, C. W. , 268.Nogare, S. D., 400.Noland, W. E., 224, 265.Nolle, A. W., 87.Noller, C. R. , 237.Nordin, I. C., 223.Nordlander, J. E., 82, 211.Nordmann, C. E., 115, 116.Norkus, P. K., 157.Norman, R. 0. C., 240.Normant, H., 218.Norris, T. H., 112, 127.Norrish, R. G. W., 61, 65.Nortia, T., 107.Norton, K. B., 237.Noury, J., 28.Novhk, L., 276.Novotnjr, L., 229, 255.Nowacki, E., 272.Noyce, D. S., 44, 47.Noyes, R. M., 50.Nozaki, H., 204.Nuda, H., 348.Null, G., 224.Nusbaum, R. , 328.Nwsim, M., 55, 199.Nyberg, D.D., 306.Nyburg, S. C., 140, 278.Nyholm, R. S., 90, 105,131, 132, 137, 152, 155.Nyilas, E., 272.Nystrom, R. F., 200.O’Brien, D. E., 268.O’Brien, R. J., 109, 155.Ochiai, E., 276.Odan, K., 20.afele, K., 136, 249.opik, U., 156.herberg, R., 107, 320.Ogata, Y., 44, 184.34440 INDEX OF AUTHORS’ NAMES.Ogle, J. R., 306.Ognajanov, I., 228.Ogryzlo, E. A., 62, 63.Ohara, T., 286.Ohashi, S., 125.Ohashi, T., 286.Ohlberg, S. M., 126.Ohloff, G., 228.Ojamae, M., 319.Oka, S., 41.Okada, S., 17.Okamoto, T., 286.Okamoto, Y., 161.Okamura, S., 20.Okawa, K., 305, 309.Okaya, Y., 156.Oki, M., 264.Okuyama, T., 287.Olah, G. A., 166, 200.Oldenberg, O., 59.Oldershaw, G. A., 65.Olechowski, J. R., 130.Olivier, K.L., 174.Ollis, W. D., 243.Olovsson, I., 121.Olsson, S., 63.O’Leary, J., 330.Onak, T. P. , 85, 277.Ondetti, M. A., 279.O’Neill, A. N., 287.Onishi, T., 407.Ooi, S., 154.Ooi, T., 348.Oosawa, F., 348.Oosterbaan, R. A., 319.Oosterhoff, L. J., 192.Opalovskii, A. A., 152.Opekunov, A. A., 68.Opitz, H. E., 74.Orchin, M., 139, 178, 218,Ordyntseva, N. D., 72.Orekhov, V. D., 15, 17.Orgel, L. E., 86-92, 102,104, 135, 143, 244.Orgler, K., 208.Ormand, F. T., 80.O’Rourke, C. E., 49.Orvis, R. L., 286.Osawa, T., 287.Osbond, J. M., 214.Osborne, A. G., 244.Osborne, B. P., 152.O’Shea, E. X., 195.Osiecki, J., 196, 234.Osiecki, S., 75.Oster, G., 22.Ostroumov, E. A., 146.Osugi, K., 361.Otani, T., 309.Otani, T.T., 305.Otero, C., 77.Otsuka, M., 356.Ott, H., 179, 196, 216.Otterbach, H., 287.260.Otto, H.-W., 267.Overberger, C. G., 264.Overend, J., 72.Overend, W. G., 187, 299,Overton, K. H., 227, 228.Owen, H. F., 72.Owen, J., 90.Owston, P. G., 138.Oxman, A., 222.Ozitjanskaja, L. , 71.Packer, J., 161, 202.Packer, J. E., 157.Paddock, N. L., 123.Padley, P. J., 65.Pages, M., 16.Pai, B. R., 275, 276.Painter, R. H., 333.Paipiev, N. A., 138.Paleolog, E. N., 39.Palkin, A. P., 150.Palko, A. A., 114.Palm, C., 140, 250.Palm, D., 55.Palmer, H. B., 66.Palmer, W. G., 111.Pan, S. C., 396.Panattoni, C., 112, 155.Panchenkov, G. M., 73.Panfilov, G. A., 242.Panneman, H. J., 311.Pant, R., 320.Pantages, P., 403.Paoletti, P., 103, 104, 109.Pappalardo, L.R., 95.Parent, J. D., 31.Parham, W. E., 218, 263.l’arikh, J. R., 197.Park, J. D., 220.Parker, A. C., 71.Parker, R. E., 253, 207.Parker, W., 273.Parker, W. E., 391.Parmentier, G., 362.Parrish, F. W., 303.Parrish, R. G., 346.Parry, R. W., 114, 115,Parsonage, N. G., 31.Parsons, M. A., 302.Parsons, R., 37.Parton, H. N., 100.Patai, S., 169.Patchan, J. IT., 380.Patchornik, A., 309.Patrick, C. R., 60, 61, 240.Patrick, J. B., 216.Pattermann, F., 251.Patterson, D., 193.Patterson, G. D., jun., 419.Patterson, J. M., 256.Patton, R., 216.Paul, A. D., 99.Paul, M. A., 162, 163.Paul, R., 311.Paul, R. C., 112.303.116.Paulig, G., 411.Paulin, D., 74.Pauling, A., 318.Paulsen, H., 287.Pauncz, R., 55.Pausacker, K.H., 187.Pauson, P. L., 139, 145,Pavlik, I., 112.Payne, D. A. , 207.Payne, D. S., 123.Payne, E., 408.Peacock, R. D., 133, 157.Peake, J. S., 74.Pearson, N., 194.Pearson, R. B., 163.Pearson, R. G., 175.Peat, S., 288.Pechhre, J.-F., 308.Pecsok, R. L., 104, 108.Pelletier, S. , 107.Pelletier, S. W., 283.Pender, H. W., 383.Penfold, B. R., 125.Penney, W. G., 92.Pennington, R. E., 192.Pepinsky, R., 156, 278.Peppel, W. J., 258.Perekalin, V. V., 76.PergB1, M., 259.Perkin, J. L., 417.Perkins, H. R., 327.Perkins, N. A., 243.Perlmann, G., 320.Perlmutter-Hayman, B.,Perrin, D. D., 103.Perry, S. V., 343, 345, 346,348, 349, 350, 351, 356,357.Person, W. B., 130.Pesaro, M., 286.Pesez, M., 382.Pestaner, J.F., 22.Peter, G., 17.Peterhans, J,, 136.Peters, C. R., 115.Peters, D., 161, 167, 220,Peters, E., 240, 263.Peters, R. A., 214.Peters, T., 307.Petersen, H., 204.Peterson, D. C., 17.Peterson, D. L., 22.Peterson, E. A., 418.Peterson, H. J., 50.Peterson, M. L., 204, 205.Peterson, K. F., 320.Petrovskii, Ya. V., 30, 31.E’etru, I?., 232.Pettit, R., 139, 223.Pettk6, E., 349.I’eyronel, G., 145.I’Aeiderer, W., 268.Pfeiffenschneider, K., 127.250.42.243IPhilbin, E. M., 194.Philipp, W., 228.Phillips, C. S. G., 120.Phillips, B., 201.Phillips, G. O., 16.Phillips, J. R., 121.Phillips, W. D., 85, 127.Photaki, I., 293.Phung, P. V., 17.Piacenti, F., 77.Picard, J. P., 252.Pickering, B. T., 317.Pictet, A., 299.Pidacks, C., 304.Yiercey, I).C., 27.Pietrulla, W., 376.Pietruszko, R., 368.Piette, L. H., 85.Piez, K. A., 327.Pigman, W., 295.Pillay, P. P., 277.Pimlott, P. J. E., 310.Pinches, P. B., 394.Pinder, A. R., 261.Pines, H., 259.Pinkard, R. M., 77.Pinner, S. H., 19.Pino, P., 201.Piontelli, R., 40.Pisano, J. J., 366.Pitkethly, R. C., 202.Pitochelli, A. R., 117, 125.Pittet, A. O., 303.Pittman, R. A., 20.Pitzer, K. S., 23, 33, 192,Pivovarov, V. M., 69, 72.Placzek, G., 71.Plaetschke, H., 387.Plane, R. A., 70, 151.Plate, A. F., 77.Platford, R. F., 21.Plazek, E., 259.Pleskov, Iu. V., 39.Pleszke, K., 249.Plettinger, H. A., 147.Plieninger, H., 222, 255,261, 362.Pliml, J., 256.Plimmer, J.R., 304.Pliva, J., 67.Poclter, Y., 42, 43, 51, 53,54, 169, 171, 174, 175,176.194.Podkowka, J., 163.Podlovchenko, R. I., 78.PoduSka, K., 312.Po&, A. J., 131.Potzscher, G. , 77.Pogany, J., 245.Pol, E. H., 268.Polak, L. S., 8, 17.Polanyi, J. C., 57, GO, 62.Polgar, N., 214.Poli, G., 40.Poliakova, I . D., 76.DEX OF AUTHORS’ NAMES. 441Pollard, C. B., 263.Pollard, J. K., 305, 359,364, 367, 368.PSos, L., 384.Polyakova, M. D., 147.Pomerants, G. H., 102.Pompa, F., 123.Ponder, B. W., 204.Pongor, G., 298.Pool, R. A. H., 30, 31.Poole, J. B., 91.Popescu, S., 154.PopjAk, G., 213.Pople, J. A., 79, 80, 82, 84,Popov, A . I., 130.Popper, ‘1. L., 229.Porai-Koshits, M. A., 109.Porter, G., 61.Porter, J.J., 178.Porter, W. L., 306.Porterfield, W. W., 143.Portzehl, H., 347, 349, 350,Posthumus, C. H., 319.Postmus, C., 102.Postovski, I. Ia., 242.Pottie, R. F., S.Poulet, H., 72, 74.Pouli, D., 47.Poulsen, K. G., 104.Poulson, R. E., 38, 87, 99,Powell, D. B., 132.Powell, R. E., 34.Powers, J. W., 203.Pracejus, G., 191.Praill, P. F. G., 259.Prasad, R. N., 263.Pratt, L., 144, 248.Pratt, M. W. T., 192.Pravda, Z., 315.Pregaglia, G., 119.Preisler, E., 149.Prelog, V., 188, 190, 191,Preobrazhenskii, N. A.,Price, A. L., 267.Price, C. C., 253.Price, D., 391, 392.Price, E., 55, 170.Price, J. K., 273, 274.Price, R., 271.Prigogine, I., 32.Prince, J. T., 357.Prince, R. H., 120.Prins, D. A., 278.Prins, H.K., 318.Prins, W., 298.Pritchard, D. E., 81.Pritchard, H. O., 57.Prinzbach, H., 179, 217,ProchAzka, Z., 265.l’rochAizko\~A, T,. , 398.86.356, 357.133.225, 242, 261, 314.275, 276.265.Proctor, K. A., 402.Proctor, Z., 253.Prokopchik, A. Yu., 157.Proskow, S., 197, 232.Proskurnin, >I. A., 12, 15,Protheroe, J., 66.Protheroe, J. B., 56.Protiva, M., 276.Prue, J. E., 42, 179.Prushothaman, K. K., 244.Pryce, M. H. L., 90, 166.Pryor, vCT. A., 47,Przybylska , M., 283.Pshezhetskii, S. Ya., 10.Pshezhetskii, Ya., FA;.Pucheault, J . , 14.Puciles, J., 234.Piischel, R., 387.Puisieux, F., 277.Pukhova, H. I<., 141.Pullman, B., 167.Pummer, W. J., 240, 241.Puranik, P. G., 76.Purlee, E. L., 53.Pushnyak, A.N., 104.Puterbaugh, W. H., 203,17.211.Quackenbush, F. W., 333.Quagliano, J. V., 102, 132.Queen, A., 43, 171.Quentin, K. E., 416.Quinlan, K. P., 149.Raab, N., 278.Raabe, B., 120.Rabideau, S. W., 54.Rabin, B. R., 105, 107.Rabinovich, E. A., 45.Rabinowitz, J. L., 308.Rabouin, L. H., tert., 419.Rabovik, Y. I., 119.Rachele, J. R., 316.Radell, E. A,, 402.Radhakrishnan, A. N., 363,Radmacher, W., 413.Ragland, J. B., 370.Rainey, Wr. T., 52, 173.Rajadurai, S., 244, 275.Raniachandran, J., 70.Kamachandran, I,. K., 307.Ramadas, C. V., 275.Ramaiah, K., 76.Raman, S. P., 236.Ramiah, K. V., 76.Ramirez, F., 220.Ramsay, 0. B., 204.Ramsden, E. N., 164.Ramsperger, H. C., 56.Randall, E. W., 144, 249.Randall, J.J., 44.Randall, J. J., jun., 153.Randall, T., 106, 132.Randles, J . E. R., 33.364442 INDEX OF AUTHORS’ NAMES.Rangachari, P. N., 307.Ranogajec, I., 370.Rao, A. S., 227.Rao, B. P. , 194.Rao, C. N. R., 70.Rao, D. V. R., 137.Rao, G. G., 381, 385.Rao, K. S., 68.Rao, V. N., 381.Raphael, R. A., 207, 229,Rapkin, E., 241.Rapoport, H., 274, 277.Rapoport, L., 252.Raskin, S. S., 76.Rasmussen, E., 184.Ratouis, M., 404.Rauch , J. , 68.Rausch, M. D., 140.Raution, S. G., 69.Raw, C. J. G., 25.Real D. G., 69.Read, G., 251, 270.Read, J., 13.Readshaw, R. L., 203.Rebora, P., 406.Reckard, H. , 148.Redfern, E. R., 333, 337,Reddy, J. van der M.,Reddy, M. P., 18.Reece, I. H., 155, 157.Reed, R. I., 8, 178.Reed, W.L., 44.Rees, A. H., 263.Rees, K. R., 355.Rees, M. W., 305, 366.Reeves, L. W., 86.Reich, E., 350.Reichstein, T., 235.Reid, W., 311.Reilly, C. A., 70, 86.Reimann, C., 116.Rein, J. E., 406.Rein, R., 44.Reinert, K., 272.Reiser, P. L., 387.Reisfeld, M. J., 23.Reishus, J. W., 135.Reisman, A., 150.Reiss, R., 389.Reist, E. J., 268, 300.Rekus, A. F., 413.Rembarz, G., 302.Renger, F., 381.Renick, R. J., 310.Renner, U., 278, 304.Rennhard, H. H., 229.Renz, J., 367.Ressler, C., 307, 316.Reuben, B. G., 62.Reusch, W. H., 235.Reuss, J.. 25.Reuse, P., 242.Reuter, G., 366.273, 362.338, 342.116.Reuwer, J. I;., jun., 51,Reyle, K., 304.Reynolds, C. A., 410.Reynolds, G. F., 49.Reynolds, G. R., 85.Reynolds, M.S., 379.Reynolds, T. M., 295.RezAE, z., 399.Rhinesmith, H. S., 318.Ribeiro, L. P., 396.Rice, M. R., 42.Rice, 0. K., 56, 58.Rice, S. A., 32.Rice, W. E., 27.Richard, C. F., 107.Richards, C. G. , 265.Richards, F. M., 321.Richards, R. E., 82, 83,Richards, T. A., 211.Richardson, A. C. B., 24.Richardson, E. H., 68.Richardson, F. D., 152.Richardson, M. J., 23.Richardson, R. D. , 240.Richey, H. G., jun., 172.Richter, W., 354.Richtmyer, N. K. , 298.Rickborn, B., 177.Rickes, E. L., 270.Ridd, J. H., 165, 168, 238,Rieche, A. , 202.Riedel, A., 312.Riedef, K., 387.Rieger, K., 136.Rieman, W. , tert. , 400.Riemschneider, R., 220,Riess. W. , 267.Riesz, P., 15.Rietvald, 0. A., 27.Riley, D. P., 27.Riley, G., 319.Riley, T., 50, 171.Rilling, H.C., 226.Rimington, C., 252.Rinderknecht , H., 370.Rinehart, K. L., 215, 247.Ringbom, A., 405.Riniker, B. , 315.Rinzena, L. C., 218.Ripamonti, A., 123.Rissi, E., 253.Rittel, W., 315, 317.Ritter, H. , 402.Rittner, W., 398, 404.Rivolta, B., 40.Robb, E. W., 276.Robb, J., 30.Robb, J. C., 60, 61.Roberts, C. W., 268.Roberts, J. D., 82, 172,173, 197, 206, 211.Roberts, J. E., 127.175.127, 136.252, 304.249.Roberts, R. M., 163, 166.Roberts, T. , 194.Robertson, A. J. B., 60.Robertson, A. V., 273.Robertson, R. E., 42, 54,Robin, Y.. 320, 355.Robins, R. K., 268.Robinson, D. W., 72, 73.Robinson, E. A., 112, 128.Robinson, G., 135.Robinson, G. C., 174.Robinson, J. W., 375.Robinson, (Sir) R., 265,Robinson, R.A., 32, 36,Robinson, R. E., 77.RoEek, J., 182, 183.Roche, J., 355.Rockenmacher, M., 325.Roderick, G. W. , 36.Rodewald, W. J. , 230.Rodger, M. N., 284.Rodin, J. O., 270.Roeske, R. W., 310.Roger, D. J., 105.Rogers, L. B., 40, 398.Rogers, M. D., 148.Rogers, M. T., 80, 82,Rogers, N. A. J., 230.Rogers, R. L., 17.Rogers, R. N., 416.Rogozinski, S. E., 390.Rohlin, E. M., 177.Rohmer, M. , 412.Roland, C. C., 105.Rolle, M., 295.Rollins, 0. W., 119.Romanenko, L. I., 102.Romafiuk, M., 210.Romanzo, J., 67.Romers, C., 129.Ronco, A. , 337.Rooda, R. W., 273.Roos, P., 317.Ropp, G. A. , 50.Ropp, R. C., 113.Rose, B. A., 400.Roseman, S., 287.Rosen, L., 295.Rosenbaum, J., 170.Rosenberg, H., 355.Rosenblum, C., 334.Rosenbluth, R., 347.Rosenstock, P. D., 236.Rosenthaler, J. , 313.Ross, C. P., 418.Ross, D. A., 17.Ross, I. G., 156.Ross, L., 114.Ross, L. 0. , 268.Ross, S. B., 101.Ross, S. D. , 44.Rossmanith, I<. , 147.143, 171.267, 270.323, 326, 327.84INDEX OF AUTHORS’ NAMES. 443Rossotti, F. J. C., 88, 103,Rossotti, H., 149.Rossotti, H. S., 91.Rotblat, J., 22.Roth, B., 150.Roth, H., 414.Roth, M. R., 197.Rothe, I., 313.Rothe, M., 313.Rothstein, M., 363.Rottenberg, M., 179, 182.Rourke, F. M., 9.Rowlinson, J. S., 22, 23, 28,Roy, R. S. , 61.Roychaudhuri, D. K., 276.Rubin, R. J., 57.Rudinger, J., 306, 312, 315.Rudolph, P. S., 8, 9.Riidorff, W., 111.Riiegg, R., 211, 213, 332,Ruff, O., 122.Ruffin, R.S., 379.Rule, N. G., 166.Rundel, W., 206, 216.Rundle, R. E., 112, 113.Runge, E. F., 413.Russell, D. M. , 265.Russell, G. A. , 176.Russell Jones, A., 10.Rustogi, C. L., 269.Rutherford, R. I., 49.Rutschmann, J., 253.Rutskov, A. P., 35.Ruzicka, L., 188, 226, 232.Ryabov, A. N., 153.Ryan, J. A., 102.Ryback, G., 265.Ryder, A., 218.Rydon, H. N., 312.Ryhage, R., 214, 215, 216.Rylander, P. N., 203, 243.Rylski, L., 262.Ryschkewitsch, G. E., 117.Ryser, G., 211, 334, 337.Ryskin, Y. I., 73.Rzysko, C., 362.Saad, F., 346.Sable, H. Z., 299.Sacco, A., 137.Sacconi, L., 103, 101, 109,Sacks, J., 354.Sadananda Rao, €3. K.,Safir, S. R., 304.Sager, W. F., 183.Saha, N. N., 230.Sahashi, Y., 369.Saines, G., 170.Saito, S., 369.Saito, Y., 154, 156, 175.Sakai, S.-I., 283.149.29, 30.334, 335, 337, 346.155.386.Sakan, T., 286.Sakshita, K., 77.Sakiyama, F., 309.Sakurada, I., 20.Sala, O., 74, 135.Salaman, A. M., 260.Salg6, E., 387.Salmon, G. A., 11.Salsburg, 2. W., 32.Salvetti, O., 74.Salzwedel, M., 214.Sambeth, J., 125.Samoilenko, V. M., 102.Samoilov, 0. Ya., 37, 38.Sampath, S., 130.Samsonov, G. V., 147.Samuel, A. H., 14.Sanderson, R. T., 207.SAndi, E., 395.Sandri, J. M., 180.Sandrin, E., 317.Sands, C. A. , 199.Sands, D. E., 150, 151.Sandu, S. S., 112.Sanger, F., 319, 320.Sang-up Choi, 166.Sanno, Y., 361.Sant, B. R., 388.Santambrogio, E., 249.Santilli, A. A., 219.Santos, M.L. R., 17.Sao, S., 369.Sarel-Imber, M. , 298.Sargeson, A. M., 133.Sartori, G., 74.Sartori, P., 122.Sasaki, Y., 151.Sass, C., 392.Satchell, D. P. N., 53, 55,Satir, P., 347.Sato, &I., 305.Sato, T., 294.Saucy, G., 211, 332, 334,Sauer, J,, 217.Sauer, J. C.. 21, 208, 209.Sauers, R. R., 227, 231.Saunders, M., 86, 217.Saunders, VV. H., 173.Saunders, W. W., 265.Saurel, J., 29.Savarier, C. P., 403, 406.Savidge, R. A., 409.Saville, E., 409.Sawicki, E., 382.Sawyer, D. T., 108.Sawyer, W. H., 317.Saxena, R. S., 390.Saxena, S. C., 23, 24, 27.Sayer, G. C., 236.Sayre, E. V., 36.Sazonova, V. A., 247.Sbrzesny, H., 383.Schaad, L. J., 51, 175.Schaal, R., 151.162.337.Schachman, H. K., 317.Schade, G., 228.Schade, W.J., 63.Schafer, H., 150.Schafer, K., 30.Schaefer, R. W., 116.Schaefer, T., 82.Schaeffer, A. O., 9.Schaffer, C. E., 89, 95, 101.Schaeffer, H. J.. 268.Schaeffer, R., 85, 114.Schaeren, S. F., 211, 334.Schaffer, N. K., 319.Schaffer, R., 301, 302.Schaffner, K., 235.Schally, A. V., 316.Schamp, H. W., 24.Scharf, E., 130.Schatzki, T. F., 24.Schaub, R. E., 280, 293.Scheibe, G., 267.Scheiber, G., 67.Schellenberg, P., 310.Schenk, G. H., 388.Schenk, P. W., 127.Scherba, L. D., 35.Scherrer, H., 190.Scheurch, C., 298.Schiele, C., 398.Schier, O., 287.Schiff, H. I., 9, 62, 63,Schiff, S., 270.Schiflett, C. H., 10.Schinzel, E., 251.Schittler, E., 276.Schlafer, H. L., 91, 106.Schlegel, W., 237.Schleimer, B., 311.Schlenk, H., 214.Schleyer, P., 172.Schlogl, I<., 208.Schmeisser, M., 122, 129,Schmelz, M. J., 132.Schmid, C.H., 166.Schinid, H., 279, 280, 281.Schmid, H. J., 172.Schmid, M., 204.Schmidbaur, H., 153.Schmidt, B. H., 85.Schmidt, G., 19.Schmidt, H., 130.Schmidt, M., 127, 153, 377.Schmiechen, R., 301.Schmir, G. L., 307.Schmitz, E. , 202, 353.Schmitz-DuMont, 0.. 148,Schmutz, J., 275, 278, 279.Schmutzler, R., 122.Schnabel, W., 19.Schnapp, O., 241.Schneider, B., 67, 228.Schneider, C. R., 102.Schneider, Ch., 19.Schneider, F., 274.130.154444: INDEX OF AUTHORS' NAMES.Schneider, G., 305, 311,Schneider, J., 246.Schneider, K., 222.Schneider, W., 91, 108.Schneider, W. G., 27, 79,Schnider, O., 274.Schnier, H., 402.Schmoyer, L.F., 254.Schoberl, A., 370.Schollkopf, U., 205, 337.Schoeneck, W., 259.Schopf, C., 273.Schopp, K., 331.Scholes, G., 7, 13, 15.Schott, G. L., 57.Schowtka, K. H., 73.Schramm, G., 202, 312.Schrauzer, G. N., 139, 140,Schreiber, J., 286.Schreier, E., 253.Schreiner, F., 35.Schreiner, S., 143.Schrodell, R., 200.Schroder, G., 143, 245.Schroder, H., 119, 128.Schroeder, W., 167, 268.Schroeder, W. A., 318.Schropp, W., jun., 137.Schroth, W., 244.Schubert, A. R., 328.Schubert, W. M., 42, 47,Schudel, P., 286.Schiitte, H. R., 272.Schulek, E., 377, 389.Schuler, K. E., 57, 58.Schuler, R. H., 13, 18,Schuller, W. H., 233.Schulte, K. E., 258.Schultz, F., 47, 167.Schumacher, H.J., 129.Schumb, W. C., 73.Schwartz, E. T., 317.Schwartz, H. C., 318.Schwarz, H., 310.Schwarz, H. A., 13, 15.Schwarzenbach, G., 88, 91,98, 103, 107, 108, 149.Schwartzmann, L. H., 201.Schweet, R. S., 363.Schwenke, K.-D., 313.Schwertmann, U., 153.Schwieter. U., 211, 213,Schwyzer, R., 309, 313,Scott, D. B., 325. *Scott, E. M., 368, 369.Scott, J. M. W., 42, 171.Scott, N., 120, 150.Scott, R. L., 30, 32.Scroggie, L. E., 406.366.82, 84, 86.142, 208.167.19.334, 337, 341.315, 317.Seaforth, C. E., 304.Searcy, A. W., 111.Searle, H. T., 123.Searles, S., 203, 254.Sebban-Danon, J., 20.Sebera, D. K., 43, 134.Sedgwick, R. D., 18.Seebeck, E., 372.Seel, F., 122, 128.Seelig, H. S., 19.Segel, F., 396.Seibles, T.S., 308.Seidel, C . F., 226.Seidel. M., 217.Seiden, L., 134.Seiler, N., 235.Seiter, H., 40.Seltzer, S., 54, 55.Selwood, P. W., 38.Semenov, A., 172.Semenov, N. N., 58.Semmhouze, W., 249.Sen, A. B., 384.Sen, D., 134.Senda, K., 83.Sengupta, P., 234, 237.Sengupta, S. K., 237.Senise, I?., 154.Senn, H., 91, 108.Senvar, C. B., 14. 'Seraidarian, K., 350.Serat, W. F., 17.Seshadri, T. R., 252, 269,Sesonske, A., 19.Seth, R. L., 101.Setkina, V. N., 170.Settine, R. L., 255.Seyferth, D., 83, 211.Shabarova, 2. A., 252.Shabtai, J., 195.Shaeffer, H. J., 173.Shafizadeh, F., 288.Shah, P. P., 341.Shain, I., 393.Shamma, M., 236.Shandon, K., 45.Shapatyi, V. A., 15.Shapiro, B. L., 216.Shapiro, D., 215.Shapiro, I., 84, 86, 116,Sharkey, W.H., 207, 210,Sharman, I. M., 339.Sharon, N., 351.Sharp, D. W. A., 99, 133.Shashoua, V. E., 305.Shatenshteh, A. I., 45.Shaw, B. L., 132, 146.Shaw, C. J. G., 185, 303.Shaw, D. F., 186, 304.Shaw, G., 263.Shaw, K. B. , 271.Shaw, R. A., 123.Shchukarev, S. A,, 153.270.117.219, 220.Shechter, H., 247.Sheehan, J. C., 265, 309,311, 314, 362.Sheffield, J. C., 9.Sheinker, A. P., 20.Sheldon, J. C., 151.Shelley, R. J., 400.Shemyakin, M. M., 297.Shen Han, T. M., 16, 28Shenian, P. , 219.Sheppard, N., 72, 79, 80,Shepparcl, R. C., 368.Sheradsky, T., 365.Sheridan, J., 144.Sherma, J., 400.Sherman, G. M., 234.Shiba, T., 315.Shiihara, I., 115.Shiio, I., 269.Shillaker, B., 43, 171.Shillington, J.K., 204.Shilov, E., 165.Shilov, Ye, A., 53.Shimada, T., 315.Shimadina, L. G., 99.Shimanouchi, T., 78.Shimizu, H., 83.Shimo, K., 263.Shimuzu, Z., 361.Shinano, S., 367.Shine, H. J., 204, 221.Shiner, V. J., 186.Shingu, H., 160.Shirley, D. A., 258.Shoaf, C. J., 200.Shoenberg, C. F., 344.Shoolery, J. N., 83, 84, 85,Shorland, F. B., 214.Shorter, J., 164.Shorygin, P. P., 71, 72.Shoulders, B. A., 84.Shriner, R. L., 336.Shriver, D., 121.Shubin, V. N., 12.Shuikin, N. I., 219, 257.Shukys, J. G., 142, 208.Shulman, A., 133.Shulman, R. G., 38, 87.Shulov, L. M., 275.Shumway, N. P., 316.Shunk, C. H., 213, 214.Shuttleworth, S. G., 107.Shvo, Y., 237.Sibilia, J. P., 70.Sicher, J., 193, 225.Sidgwick, N. V., 99.Sieber, P., 309, 313.Siebert, H., 74, 132.Siebert, W., 148.Siegel, B., 116.Siemer, H., 332.Sienko, M. J., 152.Siitonen, S., 405.Silber, R., 366.83, 132.274'INDEX OF AUTHORS' NAMES. 445Silbert, L. S., 201.Sillen, L. G., 98, 101, 109,Silver, M. S., 172.Silvestromi, P., 105.Simamura, O., 163, 164.Simet, L., 319.r:-flkins, R. J. J., 50..;~:naonds, D. H., 307.Simmons, D. L., 283.Simmons, H. E., 218.Simmons, V. E., 154.Simon, H., 55.Simon, W., 49.Simons, J. H., 21.Simons, J. P., 41.Simonsen, J. L., 227.Sims, P., 108.Sims, R. J. , 262.Singer, L., 177, 327, 407.Singh, A., 249.Singh, D., 112.Singh, J., 112.Singh, M., 226.Singley, J. E., jun., 178.Sinohara, H., 287.Sirrenberg, W., 256.Siryatskaya, V.N., 56.Sisido, K., 204.Sisler, H. H., 117.Sitz, H., 216.Sjoberg, B., 306.Skattebarl, L., 210, 257.Skeggs, L. T., 316.Skell, P. S., 178, 207,Skerrett, E. J., 224.Skinner, G. B., 66.Skinner, H. A., 30.Sklarz, B., 270.Skoog, D. A., 388.Slack, R., 259.Slansky, C. M. , 33.Slater, G. P. , 173.Slater, N. B., 56.Slaugh, L. H., 198.Slaughter, J. I., 59.Sloan, C. L., 144, 250.Slomp, G., 79, 84.Sly, W. G., 141.Small, A. M. , 293.Small, L. A. , 390.Small, T., 265.Smillie, L. B., 308.Smissman, E. E., 221,Smit, A,, 337.Smith, A., 340.Smith, A. F., 279.Smith, A. I., 397.Smith, C. R, 214.Smith, D. B., 318.Smith, D. F., 128, 218.Smith, E. A., 85.Smith, E. L,, 304.Smith, E. N., 346.111, 151.217.222.REP.-VOL. LVISmith, F., 302, 303.Smith, F.A., 330, 331.Smith, F. T., 57.Smith, G. F., 105.Smith, G. S., 107, 132.Smith, H. E., 191.Smith, H. M., 70.Smith, J. C., 192.Smith, J. D., 123.Smith, L. W., 281.Smith, M. A., 186.Smith, M. J., 176.Smith, R. D., 218.Smith, S., 43, 170.Smith, T. S., 85.Smith, W. B., 52, 173, 174,Smith, W. C., 127.Smithies, D. , 17.Smithies, W. R., 363.Smolin, E. M., 252.Smrt, J., 256.Smyth, R. D., 360.SnaveIey, F. A., 104.Sneddon, W., 8.Snell, E. E., 366.Snyder, R. H., 221.Sobel, A. , 325.Sober, H. A., 418.Soborovskii, L. Z., 149.Sobotka, H., 299.Soddy, T. S., 267.Soffer, M. D., 228.Sognnaes, R. F., 325.Sokolov, N. O., 68.Sokolovskaya, A. I., 69.Soliman, A., 390.Solmssen, U., 334.Solo, A.J., 283.Soloway, A. H., 272.Somidevamma, G., 381,Sommer, L. H., 120, 206.Sondheimer, E., 305, 367.Sondheimer, F., 199, 207,222, 230, 231, 246.Sonesson, A., 106.Sonnenberg, J., 199.Sonnenschein, W., 405.Soolery, J. N., 35.Sarensen, N. A. , 210, 257.$om, F., 210, 227, 228,229, 237, 262, 316, 321.Sosnovsky, G. , 184, 206.SouEek, M., 227, 229, 381.Souchay, P., 151.Souci, S. W., 416.Sowden, E. M., 328.Sowerby, D. B., 124.Spackman, D. H., 307.Spacn, P., 154.Spain, P., 328.Spanagel, E. W., 219, 257.Spandau, H., 124.Sparks, R. A., 129.Speake, R. N., 229.383.385.Speakman, J. C., 113, 207,Specht, W., 250.Specker, H., 385.Spector-Shefer, S., 215.Spencer, M. S., 58.Spencer, R.R., 268, 300.Spencer, T. , 45, 164, 175.Spencer, T. A., 286.Spengler, G., 151.Speranza, G., 258.Speroni, G., 77.Spice, J. E., 135.Spicer, G. S., 328.Spielman, J. R., 116.Spingler, H., 402.Spinks, J. W. T., 10, 21.Spinner, E., 77.Spiteller, G., 251.Spitter, G., 251.Spivak, C. T., 287.Springall, H. D., 315.Springmann, H., 287.Spuhler, G., 317.Spurny, Z., 16.Squirrell, D. C. M., 379.Srinivasan, R., 227.Srinivasan, V. R., 76.Srivastava, B. N., 24, 25,Srivastava, H. C., 203.Srivastava, K. P., 25, 27.Stabnikova, T. V., 223.Stacey, F. W., 21.Stacey, M., 16, 181, 240,289, 293, 303.Stack, M. V., 327.Stallberg-Stenhagen, S.,Stafford, C., 378.Stafford, W. H., 20, 244.Stahnecker, E., 175.Stainton, P.V. E., 330.Stamm, 0. A., 53, 165.Stammreich, H., 67, 72, 74,St. And&, A. F., 276.Stankk, J., 300.Stange, H., 306.Starko, V. I., 77.Stanley, G., 164.Stanley, T. W., 382.Stansbury, E., 67.Stanton, H. E., 9.Starcher, P. S. , 201.Starer, I., 207, 217.Starkey, R. J., 409.Stark-Mayer, C. , 382.Staub, L., 122.Staveley, L. A. K., 30, 31,106, 132.Stearns, R., 328.Stedefeder, J., 385.Stedman, G., 122,162, 163.Steele, D., 77, 240.Steele, J. W., 227.241.27.214, 216.135.446 ISteenbock, H., 327.Stefanac, Z., 415.Steglich, W., 309, 310.Stehlik, B., 157.Stein, G., 12, 16, 17, 21,Stein, W. E., 320.Stein, W. H., 307.Steiner, R., 253.Stekharov, A. I., 71.Stelakatos, G. C., 309.Stelzner, R. W., 380.Stenhagen, E., 214, 215,Stenlake, J.B., 227.Stepaniants, A. Us., 50.Stephens, R., 241.Stephens, R. W., 187, 303.Stephenson, J. , 209.Sterin, K. E., 68.Stern, D. R., 200.Stern, K. H., 36, 90.Stern, M. H., 337.Sternbach, B., 120.Sternberg, H. W., 135, 136,141, 142, 208.Sternman, I., 406.Stetter, H., 224.Stetter, R., 270.Stevens, B., 65.Stevenson, D. P., 8.Stevenson, H. B., 220.Stevenson, R. W., 176.Steward, F. C., 305, 359,360, 364, 367, 368.Stewart, A. T., jun., 176.Stewart, J. M., 156.Stewart, R., 50,55, 82, 170,Stewart, W. E., 82.Stiehl, R. T., 209.Stiles, M., 44, 174, 203.Stilwell , W. F. , 330.Stirm, S., 300.Stitch, S. R. , 328.Stivers, E. C., 51, 175.Stock, L. M., 161, 166,238.Stoffel, W., 214.Stoffelsma, J., 218.Stoffyn, P.J., 287, 293,Stoicheff , B. P. , 68, 75.Stokes, R. H., 32, 36.Stokr, J., 67.Stoll, A., 270, 372.Stoll, W. G., 278, 304.Stolow, R. D., 195.Stone, D.. 315.Stone, F. G. A., 115, 121,Stones, H. H., 330.Storey, B. T., 202.Stork, G., 226, 231.Storni, A., 226.Stowe, B. B., 252.Straka, K. , 399.42.216, 232.183.298.139, 140, 145, 248.DEX of; AUTHORS’ NAMES.Strand, A. , 300.Straub, F. B., 348, 349.Strauss, G., 305, 365, 370.Strauss, U. P., 101.Street, C. N., 136, 248.Strehlow, R. A. , 66.Streitwieser, A., jun., 171,Streng, A. G., 31, 126.Streuli, C. A., 393.Stricker, K., 211.Strocchi, P. M., 406.Stroh, H. H., 296.Stroh, R. , 265.Strohman, R. C., 348.Strrzrmme, K. O., 129.Strong, J.D., 19.Strong, L. E., 170.Stroud, L., 31.Strouf, O., 277.Strutz, H. C., 402.Stryland, J. C., 67, 75.Studer, M., 150.Studer, R. O., 316.Stueben, K. C., 312.Sturtevant, J. hl., 45, 179.Subba Rao, B. C., 198.Suchy, M., 237.Sud, R. K., 214.Siiess, R., 253.Sugasawa, S., 255, 267,Sugawa, T., 361.Sugden, T. M., 57, 64, 65.Suh, J. T., 222.Suhadolnik, R. J., 272.Sujishi, S., 115.Sukhotin, A. M. , 35.Sullivan, E. A., 113.Sullivan, J. C., 54.Sullivan, J. H.. 58, 400.Summerbell, R. K., 262.Summerson, W. H., 319.Sundheim, B. R.. 155.Surve, K. L. , 228.Suryanarayana, M., 385.Sushchinskii, M. M., 69, 76,Sussman, S., 334.Sutcliffe, L. H., 84.Sutherland, I. O., 243, 270.Sutherland, J. W., 21.Sutherland, M.D., 227,Suthers, J. , 331.Sutin, N., 111.Sutton, L. E., 90, 93, 144,161, 211, 249.Suzui, A., 286.Suzuki, S. , 226.Suzuki, T., 369.Svedi, A., 198.Svehla, G., 386.Sverak, J., 410.Sverdlov, L. M., 78.Svirbely, W. J., 42.173.268.78.229.Svoboda, G. H. , 277.Svoboda, G. R., 393.Svoboda, M. , 193, 225.Swain, C. G., 51, 52, 53,Swallow, A. G. , 146.Swallow, A. J., 8.Swallow, D. L., 313.Swan, E. P., 297, 298.Swan, G. A., 20, 21.Swan, J. M., 304, 308.Swanson, L. W., 19.Swanson, W. J., 333.Sweet, D., 299.Swenker, M. D. P., 25.Swern, D., 201.Swett, L. R., 304.Sworski, T. J., 16.Sykes, P., 259.Sykes, R. L., 107.Sfkora, V., 227, 229.Symons, M. C. R., 113, 126,130, 152, 170.Sympson, R. F., 395.Synge, R.L. M., 370.Szab6, L., 300.Szabolcs, J. , 212.Szekeres. L.. 386. 387.175.Szent-Gyord, .A. , 348,350.Szent-Gyorgyi, A. G., 346,350, 356.Szmuszkovicz, J. , 265.Szutka, A., 21.Taber, W. A., 272.Taborsky, R. G., 263.Tabushi, I., 184.Tachikawa, R., 267.Ta. Chuang Lo Chang.,Tadanier, J., 52, 173.Taft, R. W., 161.Taft, R. W., jun., 50, 176.Taglinger, L., 129.Taimuty, S. I., 22.Tajmr, L., 300.Takahashi, K., 83.Takebayashi, M. , 253.Takeda, F., 356.Takei, S. , 221.Takemoto , T. , 361.Talapatra, S. K., 284.Talbot, G., 365.Talbott, R., 47, 167.Talley, E. A., 306.Talley, L. H., 147.Talsky, G., 127, 377.Tamale-Ssali, C. E., 381.TFimas, V., 212.Tamir, H., 272.Tamm, C., 180, 235.Tamm, R., 211.Tanaka, J., 160.Tanaka, K., 361.Tani, M. E., 157.401INDEX OF AUTHORS’ NAMES. 447Tarasiejska, Z., 294.Tarbell, D. S., 311.Tarimu, C. L. , 215.Tarnawski, A., 163.Tarno, J. V., 180.Tarrago, X., 13.Tashlick, I., 264.Tatevskii, V. A., 77.Tatlow, J. C., 240, 241.Tatsuoka, S., 361.Taube, H., 38, 43, 54, 111,133, 134, 181.Taubinger, R. P., 25.Tausend , A. , 39.Tavares, Y., 72, 74, 135.Tawney, P. 0. , 221.Taylor, E. C., 268.Taylor, E. H., 21.Taylor, M. D., 199.Taylor, N. F., 298.Taylor, R., 73, 120, 162.Taylor, R. C., 77.Taylor, R. D., 55, 180.Taylor, S. M., 54, 183.Taylor, W. I., 278, 279.Taylor, W. J., 77.Taylor-Smith, R., 188, 210.Tchernysheva, A. S., 17.Tedder, J. M., 239.Teller, E., 68.Temkin, A.Ia., 8.Templeton, D. H., 106,121,Tener, G. M., 268.Teodorescu, L., 166.Teply, J., 15, 21.Terandy , J . , 2 1.Terashima, M. , 274.Testa, E., 254.Tester, H. E., 28.Tewari, S. N., 397.Thachuck, R., 173.Thaller, V., 216.Thaw, D. H., 384.Theaker, G. , 239.Theander, O., 290, 298.Theimer, R. , 76.Theodoropoulos, D. , 310,Theodoropoulos, D. M. ,Thesing, J., 256.Thewlis, J., 323.Thiem, N. V., 355.Thilo, E., 123, 125.Thoai, N. V., 355.Thoburn, J. M., 379.Thoma, R. E., 147.Thomas, D., 315.Thomas, D. W., 271.Thomas, I. M., 149.Thomas, K., 252.Thomas, 0. H., 167.Thomason, P. F. , 379, 395.Thompson, A., 118, 125,143.319.309.298, 299.Thompson, J. F., 315, 350,Thompson, R. J., 137.Thompson, S. O., 9.Thompson, T.A., 317.Thomson, J. B., 247.Thomson, P. J., 226, 313.Thorp, N., 30.Thorpe, J. F., 223.Thrush, B. A. , 61.Thiirkauf, M., 182.Thyagarajan, B. S., 177,Thyagarajan, G., 69, 70.Tieckelmann, H. , 263.Tien, J. M., 203.Tierney, P. A., 114.Tiers, G. V. D., 46, 81, 84,Tillett, J. G., 181.Tilney-Bassett, J. F., 141,Timmons, P. S., 20, 21.Tipper, C. F. H., 41.Tipping, A. E. , 240Tishler, M., 334.Tisler, M., 254, 382.Titeica, S. , 166.Tobey, S. W., 16.Todd, (Sir) A. R., 251, 270,274, 293, 320.Todd, J. E., 116.Todd, S. S., 192.Toerien, F. v. S., 385.Tolberg, W. E., 130.Tolkachev, 0. N., 276.Tolsma, J., 411.Tomashov, N. D., 39.Tomboulian, P., 222.Tomida, I., 221.Tomita, M., 275.Tomkinson, J. C., 91,Toms, E.J., 315.Tonomura, Y., 351.Tonsager, A. , 326.Tootal, C. P., 59.Topchiev, A. V., 17, 73.Topping, R. M., 44.Toren, P. E., 378.Toribara, T. Y., 324.Tormo, J.-V., 55.Toropova, V. F., 102.Toseland, P. A., 308.Tovaglieri, M. , 208.Towers, G. H. N., 360.Towle, L. H.. 22.Townley, J. R., 28.Townsend, M. G., 126.Toy, M. S., 297.Trager, L., 299.Trafimenko, S., 262.Tramer, A., 75.Traynham, J. G., 130.Treiber, A., 143, 248.Treibs, A., 168.370.181.85, 175.240.105.Treibs, W., 210, 221, 244,Trenner, N. B., 213, 214.Trifan, D., 173.Triffett, A. C. K., 215.Trilling, C . A., 21.Tripathi, D. N., 397.Trippett, S., 307.Tristram, E. W., 49.Trojhek, J., 256, 277.Trotman-Dickenson, A. F.,Trueblood, K.N. , 129, 148.Trumbore, C. N., 13, 20, 21.Truter, M. R., 146.Tsao, T. C., 346, 347.Tsarev, B. M., 147.Tschesche, R., 307.Tsin, N. M., 31.Tsuboi, K. K., 356.Tsuchida, M. , 44.Tsuchida, R., 156.Tsukamoto, A., 200.Tsunoda, T., 369.Tsutsui, M., 209, 248.Tuddenham, W. M., 408.Tullock, C. W., 127.Tulub, T. P., 71.Tunkel, N., 56, 170.Tuppy, H., 304.Turba, I?., 349.Turnbull, J. H., 319.Turner, D. W., 174.Turner, J. J., 79, 80.Turner, J. M., 313.Turney, T. A., 382.Tursch, B. , 225.Tuskan, W. G., 416.Tweit, R. C., 173.Tyler, J. K., 144.Tzschach, A., 151.246.8, 45, 65, 177.Ubbelohde, A. R. , 30.Uchibayashi, M., 361.Udenfriend , S. , 366.Ueno, K., 315.Ueno, Y., 361.Ueyanagi, J., 361.Ukholin, S. A., 68.Ulbert, K., 67.Ulbrecht, G., 352.Ulbrecht, M., 351, 362.Ulbricht, T.L. V., 188.Ullman, E. F., 219, 304.Ullrich, J., 310.Umberger, C. J., 400.Umbreit, W. W., 370.Umland, F., 403.Underwood, A. L., 404.Ungelenk, J., 113.Ungnade, H. E. , 419.Urbanek, L. , 229.Urch, D. S., 163.Uri, H., 19.Ushioda, S., 255.Ussing, M. J., 325448 INDEX OF AUTHORS’ NAMES.Utianskaya, E. Z., 50.Utvary, K., 112.Uutsilia, E., 93.Uyeo, S., 282.Vanngard, T., 157.Vaidya, M. S., 131.Vainshtein, F. M., 53.Vajda, T., 259.Valenta, Z. , 283, 284.Valentin, F., 67.Valentine, L., 50.Valkanas, G., 174.Valueva, 2. P., 135.van Ammers, M., 259.Van Baalen, C,, 269.van Bekkum, H., 161.van Cleve, J. W., 302.van Dael, W., 28.Vanderhaeghe, H., 362.Vanderslice, J.T., 28.Van der Waals, J. H., 82,VanderWerf, C. A., 206,van Dyke, H. B., 317.van Hock, T. C., 161.van Itterbeek, A., 27, 28.van Leeuwen, P. H., 340.van Leusen, A. M., 208.Van Meter, J. C., 304.Van Meurs, N., 393.Vannerberg, N.-G., 113.van Panthaleon van Eck,Van Pinxteren, J. A. C.,van Rij, J. H., 340.van Rotterdam, J., 319.van Soest, G., 25.\‘an Tamelen, E. E., 230,267, 274, 276, 286.Vanterpool, A., 266.Van Thoai, N., 320.Van Uitert, L., 93.Van Wazer, J. R., 101, 123,Vardheim, S. V., 289, 293.Varech, D., 224.Varga, L., 16.Varnakova, L. P., 276.Vasilesco, P., 19.Vasil’yev, V. P., 101.Vassallo, D. A., 392.Vaughan, D. J., 397.Vaughan, J., 49, 161.Vaz, A., 277.Vedeneev, A. V., 45.Vegter, G.C., 224.Venanzi, L. M., 132.Venkataraman, K. , 252.Venketeswarlu, K., 69, 70.Verghese, J., 227.Verkade, P. E., 161.Vezzosi, I. M., 145.161.255.29.c. L., 93.396.125.Videla, G. J., 117.Viehe, H. G., 207.Vieregge, H., 208.Vig, B., 226.Vig, 0. P., 226.Vilkas, M., 201, 221.Vincent, J., 17.Vining, L. C., 251,270, 272.Vinnik, M. I., 49, 50.Vinograd, J. R., 318.Vinsom, H., 365.Virtanen, A. I., 305, 315,360, 361, 362, 366, 369,370.Viscontini, M., 268, 269.Viswanathan, N., 275.Vithayathil, P. J., 321.Vittimberga, B., 238.Vlach, J., 157.Vodar, B., 28, 29.Vopel, K. H., 220,Vogel, A., 253.Vogel, H. J., 363.Vogler, K., 313.Vogt, J. H., 326.Voigt, A. F., 144.Voipio, A., 45.Volger, H.C., 308.Volkov, V. L., 135.Vollema, G., 257.Volman, D. H., 19, 61.Volodina, 2. V., 299.Vol’pin, M. E., 244.Von Egidy, A. I., 118.von Euler, H., 334.Von Hippel, P. H., 347.von Holt, C., 304.von Holt, L., 304.Vonk, C. G., 129.von Mikusch, J. D., 261.von Philipsborn, W., 279,von Rudloff, E., 214.von Sydow, E., 214.von Wittenau, M. S., 229,Voronin, V. G., 276.Voronkov, M. G., 73.Vos, A,, 125.Vozick, M., 347.Vreeland, J., 338.Vromen, S., 337.Vryskii, Iu. P., 46.Vystrcil, A., 236.Wacker, A., 299.Waddington, G., 192.Waddington, T. C., 111,Wadsley, A. D., 148.Wadsten, T., 119.Wakamatsu, S., 263.Wakelin, R. W., 214.Wakil, S. J., 215.Waggener, W. C., 132.Wagner, A., 370.280.230.118, 121.Wagner, A.F., 270.Wagner, C . D., 20.Wagner, J. G., 236.Wagner, R. I., 124.Wagner, U., 411.Wagner, W. M., 178, 217.Wagner- Jauregg, T., 255.Wahl, A. C., 9, 43.Waight, E. S., 174.Wailes, P. C., 215.Walborsky, H. M., 177,191, 219.Wald, G., 197.Waley, S. G., 315.Walker, D. C., 20.Walker, J. B., 366.Walker, P. A., 28.Walker, R. E., 25.Wall, F. T., 56.Wall, L. A., 240, 241.Wall, R. E., 180.Wallace, T. J., 203.Wallbillich, G., 217.Wallbridge, M. G. €I., 115-Wallcave, L., 333.Wallenfels, K., 251.Walling, C., 49.Walling, J. F., 30.Wallwork, S. C., 156.Walsh, A., 67.Walsh, A. D., 56, 66.Walsh, J. T., 400.Walsh, P. D., 22.Walter, M., 337.Walton, E., 270.Wampler, D. L., 150.Wannagat, U., 127.Ward, E. R., 238.Ward, R., 111, 153.Ward, R.B., 16, 298.Warhurst, E., 75.Warnhoff, E. W., 279.Warren, B. E., 59, 66.Warren, S. L., 323.Warrener, R. N., 263.Warringa, M. G. P. J., 319.Wartik, T. K., 118.Wasem, K., 122.Waser, P., 280.Wassenaar, T., 28, 29.Wassermann, A., 170.Wassmuth, C. R., 186.Watanabe, T., 90.Watarai, S., 315.Waterman, H., 156.Waters, 0. J., 227.Waters, W. A., 181, 183,Watkins, J. D., 163.Watkins, J. W.. 407.Watson, D., 177.Watson, J. S., 60.Watson, M. L., 323, 327.Watson, P. K., 16.Watson, W. W., 24.Watt, G. W., 40, 137, 156.203, 240Watt, P. R., 269, 419.Watters, I. I., 104.Watterson, K. F., 138.Waugh, J. S., 79, 83, 85.Waudszkiewicz, E. J., 360.Wax, J., 299.Weakliem, H. A. , 107, 132.Weaver, E.E. , 148.Weaver, H. E., 85.Weaver, J. R., 116.Weaver, W. M., 203.Webb, J., 214.Webb, J. A., 360.Webb, J. S., 216.Webb, R. L., 21.Weber, A., 151, 349, 351.Weber, H. H., 347, 349,Weber, J. Q., 122.Weber, 0. A., 105.Weber, Th. , 374.Webster, D. E., 167.Webster, E. R., 172.Webster, H. C., 350.Webster, H. L., 377.Webster, M. E., 287.Weedon, B. C. L., 211, 212.Wegmann, K., 396.Wehle, H., 389.Wehrmayer, G., 157.Wehrmuller, J. 0. , 297.Wehrt, H., 306.Weidenthaler. P. , 157.Weidmann, H., 294.Weidmann, S. M., 330.Weiher, J. F., 144.Weijland, W. P., 161.Weil, J. A., 154.Weil, L., 308.Weilenmann, H. R., 268.Weimar, R. D., 268.Weinberg, I., 83.Weiner, M. A., 211.Weiner, R., 398.Weiner, S., 12,Weinstein, B. , 234.Weinstein, F., 165.Weinstock, B., 148.Weisberg, H.E., 42.Weisblat, D. I., 299.Weisenborn, F. L., 276.Weisler, L., 337.Weismann, T. J., 118.Weiss, E., 142.Weiss, J., 7, 11, 13, 15, 17,Weiss, M. J., 289, 293.Weiss, R., 146.Weisz, H., 381.Welch, K. N., 360.Welch, T. R., 393.Wellendorf, M., 272.Wellings, I., 181.Wells, R. R., 238.Welsh, H., 67.Welsh, H. L., 67, 75.350, 351, 352, 358.128.INDEX OF AUTHORS’ NAMEWelvart, Z., 52.Wender, I., 135, 136, 141,142, 198, 208, 403.Wendler, N. L. , 334.Wendt, H. J., 272.Wenkert, E., 232, 272, 276.Wen-Yang Wen. , 34.Wepster, B. M., 161.Werner, H., 144, 249.Wessely, F. , 250, 251.Wessely, K., 299.West, D. M., 388.West, P. W., 416.West, T. S., 381.Westenberg, A.A., 25.Westerman, L., 104.Westheimer, F. H., 54, 180,Weston, R. E., jun., 55.Westoo, G. , 264.Westplial, 0. , 300.Wethington, J. A. , 263.Weyerstahl, P., 254.Weygand, E., 272.Weygand, F., 297, 301,Weyna, P. L., 218.Whalley, E., 24, 48, 49.Whalley, W. B., 234.Wheeler, T. S., 194.Whelan, W. J. , 303.Wheland, G. W., 163.Whiffen, D. H., 77, 240,Whipple, E. B., 82.Whiston, J., 17.White, A. W., 197.White, C. E., 77.White, D. E., 229.White, D. M., 230.White, F. A., 9.White, G. D., 147.White, J., 67.White, J. A., 45.White, J. C., 405.White, J. M., 107.White, R. F. M., 168, 304.White, W. B., 67.White, W. N., 172.Whitear, A. L., 259.Whitehouse, M. W., 290.Whitehurst, J. S., 223.Whiting, M.C., 142, 208,Whitham, G. H., 227, 236.Whittaker, A. G., 86.Whittle, C. W. , 198.Whittle, E., 50.Wiberg, E., 123.Wiberg, K. B., 182, 183,Wiberley, S. E., 116.Wichterle, O., 262.Wickens, J. C., 214.Wickliffe, R. A., 119.Wickson, M. E., 360.182.309, 310.257.216, 249.184, 223.449Widmaier, I., 74.Widom, B., 57.Wiebenga, E. H. , 129.Wiedemann, E., 270.Wieland, T., 251, 279, 304,Wiesner, K., 283, 284.Wigert, H., 299.Wiggins, L. F., 288.Wilcox, W. S., 20.Wild, W., 21.Wildman, W. C., 282.Wilen, S. H., 52.Wiley, R. H., 84.Wilhelmi, K.-A., 150, 151.Wilke, G., 142.Wilkes, G., 248.Wilkins, C. J., 120.Wilkins, D. H., 398.Wilkins, J. E., 329.Wilkinson, D. I., 216, 273.Wilkinson, G., 74, 136-140, 143, 144, 151, 152,306, 311.153, 247-249, 250.Wilkinson, R.G., 242.Will, H., 40.Willard, J. E., 65.Willeford, B. R. , 186.Willemart, R., 392.Willi, A. V., 45, 53, 167.Williams, A. A., 102.Williams, A. I., 417.Williams, D., 85.Williams, D. E., 112.Williams, D. L. H., 175.Williams, G., 50.Williams, G. A., 81, 83.Williams, G. H., 52, 239.Williams, J., 380.Williams, J. K., 210, 219,Williams, N. E., 334.Williams, R. C., 379.Williams, R. E., 84, 85,117.Williams, R. J. P., 88, 89,91, 92, 93, 95, 98, 100,101, 104, 105, 109.Williams, R. L., 116.Williams, R. P., 216.Williams, R. R., 8.Williams, T. F., 21.Williams, W. D., 227.Willis, D., 230.Willis, J. B., 76, 109.Willis, J. L., 226.Willmer, J. S., 342.Willner, D., 237.Wilmarth, W. K., 118.Wilmshurst, J. K., 233.Wilson, A. N., 270.Wilson, A. J. C., 278.Wilson, C. L., 257.Wilson, J. M. , 119.Wilson, R. M., 360.Wilson, S., 318.220, 223450 INDEX OF AUTHORS’ NAMES.Wilson, W., 319.Wilson, W. A., 19.Wilzbach, K. E., 10.Winberg, H. E. , 224.Windgassen, R. J., 265,Winefordner, J. D., 391.Winitz, M., 197, 305, 309,Winkler, C. A., 63.Winkler, G., 112.Winstein, S., 43, 170, 172,173, 174, 199.Winter, R., 178, 219, 257.Winterstein, A. , 337.Wintersteiner, 0. , 276.Wiper, A., 399.Wippel, H. G., 205.Wiss, O., 213.Wissmann, H., 312.Witkop, B., 306, 307, 362.Wittenberg, D. , 120.Wittenburg, E., 302.Wittig, G. , 175, 239, 337.Woessner, D. E. , 133.Wohlauer, G., 112.Wojcicki, A., 153.Wojtowicz, P. J., 32.Wolf, C. F., 216.Wolf, D., 44.Wolf, D. E., 213.Wolfe, J. B. , 287.Wolfe, J. R., jun., 171.Wolfe, S., 199, 230.Wolff, E. C., 370.Wolff, I. A., 214.Wolff, R. , 236.Wolfhard, H. G. , 65.Wolfrom, M. L., 16, 288,290, 297, 298, 299.Wolfsberg, M., 8, 51.Wolfson, M. L., 186.Wolinsky, J., 230.Wolkers, G. J., 28, 29.Wolovsky, R., 207, 222,Wood, J. C., 370.Wood, L. L., jun., 170.Wood, N. V., 323.Woodburn, H. M., 256.Woods, J. W., 295.Woods, R. J., 21.Woodward, L. A., 72, 73,Woodward, R. B., 193,223,Woodworth, R. C., 178.Woolley, D. W., 315.Woolner, M. E., 317.Worker, N. A., 342.Worms, K.-H., 124.Worrall, R., 19.Wotiz, J. H., 136.Wrench, E. , 223.Wright, D., 20, 21.Wright, D. A., 125, 126.277.360.246.120.279.Wright, E. M., 299.Wu, C. Y., 196.Wiinsch, E., 309, 312.Wiirsch, J., 274.Wiist, W., 273.Wunderlich , D. , 259.Wustrow, H. J., 352.Wyckoff, R. W. G., 325.Wyluda, B. J., 38, 87.Wynne- Jones, W. F. K., 44.Yajima, H., 317.Yakovleva, M. K. , 20.Yalman, R. G., 384.Yalow, Rosalyn S., 17.Yamada, S., 155.Yamagata, Y., 87.Yamaguchi, A., 102.Yamakawa, T. , 309.Yamamura, S. S., 392.Yamane, T., 158.Yamazaki, H., 151.Yanaihara, N. , 282.Yang, D. D., H. , 309.Yang, K., 9, 10.Yang, N. C., 20, 184, 206.Yard, A. S., 360.Yasuda, S. K., 416.Yasunga, T. , 36.Yates, K., 50, 55, 170.Yates, L. D., 238.Yates, M. L., 374.Yates, P., 216, 261.Yatsimirskii, K. B., 101,Yeager, E. , 40.Yeager, Y., 40.Yeh, S.- J. , 49.Yemm, E. W., 368.Yerick, R. E., 107.Yntema, J. L., 27.Yoe, J. H. , 403.Yofa, 2. A., 34.Yoffe, A. D., 122.Yonemitsu, O., 274.Yonezawa, T., 160.Yoon, Y. K., 128.Yorke, R. W., 127.Yoshimura, J., 294.Yoshino, T. , 67, 68.Yosim, S. J., 21, 126.Yosizawa, Z., 290.Young, G. T., 310.Young, J. A., 31, 124.Young, J . C., 178.Young, J. P., 405.Young, R. C., 138, 147.Young, R. J., 185.Young, R. W., 312.Young, T. F., 70.Young, W. G., 174.Young, V. O., 202.Yrjana, T., 179.Yu, W., 292, 293.Yuan, E. L., 59.WU, T.-Y., 23.104.Yuan-Lang Chow, 45,179.Yura, T., 363.Yurev, Y. K., 77.Zacharewicz, W., 227.Zachariasen, W. H., 147.Zacharius, R., 370.Zacharius, R. M. , 315.Zachau, H. G., 314, 362.Zackrisson, M., 75, 76.Zach, D., 225.Zalhner, H. , 242.Zahn, U., 144, 249.Zalkin, A., 150, 151.Zalkow, L. H., 228.Zalkow, V., 192.Zander, J., 266.Zander, M., 241.Zanger, M., 206.Zannetti, R., 112.Zansokhova, A. A., 17.Zaoral, M., 306, 365.Zarembo, J. E., 384.Zatsk6, K., 309.Zbiral, E., 250, 251.Zechmeister, L., 331, 333.Zehrung, W. S., 256.Zeilen, A. J., 101.Zeiss, IT, 142, 209, 248.Zeller, P., 211,331,332,335.Zeltman, A. H., 12.Zemplh, G. , 298.Zenewitz, J,, 326.Zervas, L., 293, 296, 309.Zetterqvist, 8., 319.Zetterstrom, R. , 323.Ziegenbein, W. , 262.Ziegler, K., 118, 201.Ziegler, M., 383, 398, 404.Zilliken, F., 270.Zimmerman, E. , 407.Zimmerman, H. E., 177.Zimmerman, H. K., jun.,Zimmermann, J. P., 313.Zingaro, R. A., 130.Zink, J., 29.Zink, T. H., 413.Zinner, H., 296, 299, 302.Zipkin, I., 327.Zittel, H. E. , 395.Zollinger, H., 53, 164, 165,Zook, H. D., 218.Zschocke, A., 265.Zuber, H., 315, 317.Zucker, I. J., 27.Zucker, L., 47.Ziircher, A+, 281.Ziircher, P., 211.Ziist, H., 103.Zviagintseva, E. N. , 45.Zweifel, G., 199, 200, 208,Zwickel, A., 54, 134.Zydowo, M., 357.294.204, 239.221, 257

ISSN:0365-6217    

DOI:10.1039/AR9595600421

出版商:RSC    

年代:1959

数据来源: RSC

摘要:

INDEX OF SUBJECTS.(dtmn. = determination)ATP, role of, in muscle contraction, 353.Abietadiene diterpenes, biogenesis of, 232.Absorption spectroscopy, 403.Acetamide, vibrational spectrum of, 77.Acetyl groups, dtmn. of, 378, 387.in presence of formyl groups, 402.Acetylacetone, dtmn. of, 409.Acetylene, irradiation of, 9.Acetylenes, 207.complexes of, 140.naturally occurring, 209.Acetylsalicylic acid, assay of, in tablets,Acids, fatty, 214.free, dtmn. of, in metal solutions, 379.saturated, dtmn. of, 392.organic, tests for certain types of, 382.388.Acid-base catalysis, 43.Acidity functions, 46.Aconitine, structure of, 283.Acrylonitrile, dtmn. of, in polymers, 378.Actin, 347.Actinides, 147.Actinidine, structure of, 286.Actiphenol, structure of, 261.Actomyosin, 348.Acylation, 165.Adenosine triphosphatase, 349.Agarol, configuration of, 228.Agropyrene, structure of, 209.Alanine, acids derived from, 366.Albigenic acid, structure of, 236.Albizziine, 365.Aldol condensation, 176.Alicyclic compounds, 2 18.conformation of, 194.Aliphatic compounds, 207.conformation of, 197.Alkali-metal amides, ammoniates of, 113.Alkaloids, 272.Alkanethiols, dtmn.of, in presence ofAlkoxyl groups, dtmn. of, 401.n-Alkyl groups, as side chains, test for, 381.Alkyl sulphides and disulphides, dtmn. of,in presence of alkanethiols, 388.Alkylation. 165.Alkylbenzene sulphates, dtmn. of, 377.Allenes, 210.Alloheterobetulin, formation of, 236.L-a-Allokainic acid, 361.(-)-Allosedamine, configuration of, 273." Alodan," dtmn.of, 411.Alternaric acid, structure of, 218.Aluminium, dtmn. of, 383, 409.Amaryllidinc, structure of, 282.Amine, difluoro-, 'I 22.biosynthesis of, 272.alkyl sulphides, 388.Amino-acids, 304.properties of, 306.new, from plants, 359.properties of, 371.hydroxy-, new, from plants, 367.Aminobutyric acids, 368.y-Amino-a-hydroxybutyric acid, synthesisu- and 8-Aminoisobutyric acid, 370.o-, m-, and p-Aminophenyl 4-pyridylAmino-sugars, 286.synthesis of, 291.Ammonia, collection of, in Kjeldahl dis-tillation, 377.hydrate of, 121.solid, structure of, 121.Ammonia-hydrogen peroxide system, 121.Analysis, qualitative, 381.Analytical chemistry, 373.Andrographolide, structure of, 234.1, 5-Anhydro-~-allitol, preparation of, 298.Anhydro-sugars, 297.Anilines, dialkyl-, spot test for, 382.Anionotropy, 174.Anthracene, radical-scavenging action of,Antimony, 126.Antimony pentachloride, structure of,Aplotaxene, structure of, 210.8-Apocarotenals, preparation of, 213, 334./3-Apocarotenoids, provitamin-A activityApparatus, analytical, 418.Argon, thermodynamic functions of, 28.Aristolactone, 227.Aromadendrene, structure of, 229.Aromatic compounds, 238.Aromatic systems, complexes of, 143.Arsenic, 125.125.of, 370.ethers, rearrangement of, 260.18.dtmn.of, 375.126.Stibines, 126.of, 338.Potassium meta-arsenate, forms of,Tetraphenylarsonium tri-iodide, 129.Aspidospermine, structure of, 278.Asymmetric induction, 188.y-Azatropolone, synthesis of, 263.Azetidine-2-carboxylic acid, biosynthesisof, 253.Azide-nitrite reaction, mechanism of, 122.Aziridines, 253.Azoles, 258.Azulenes, 244.Bacitracin A, 313.Baddeleyite, structure of, 148.45 462 INDEX OF SUBJECTS.Baikaiin, synthesis of, 362,Balfourodine, structure of, 274.Barbituric acids, preparation of, 263.Barium, amperometric titration of,395.dtmn.of, 408.dimethyl-, formation of, 207.Barium peroxide hydroperoxide, struc-ture of, 113.hexaphenyl-, 219.structure of, 144.Bauerol, structure of, 236.Benzene, hexafluoro (perfluoro-), 240.‘‘ Benzene glycol,” preparation of, 221.Benzenechromium tricarbonyl, 144, 249.Benzocyclobutadiene, 245.Benzo-1,3,2-diazaborolines.2-phenyl-,272.Benzo@pyrido[2, l-b]-1,3-oxazepiniumion, derivatives of, 264.Bicarbonate, dtmn. of, 386.Bicycloll, 1,Olbutane-l-carboxylic ester,formation of, 223.Bicyclo[3,3,l]nonenones, formation of,224.Biological chemistry, 322.Bis(hexamethy1benzene) chromium, syn-Biuret, dtmn. of, in urea, 410.Bone minerals, 322.2,l-Borazaronaphthalene, 271.Borazoles, 117.Borneo], 4-acetyl-, formation of, 227.Boron, new form of, 114.preparation of, 114.Boron hydrides, 114.magnetic resonance spectra of, 84.trifluoride, non-reaction of, with sul-phuric acid, 118.Borane (borine), adducts of, 115.aminodimethyl-, polymers of, 115.reactions of, 115.Decaborane, reactions of, 116.Diborane, diammoniate of, 115.Diboron tetrachloride, 117.Hexaborane, 1 16.Polyborane carbonyl, 116.Tetraborane, dipole moment of, 116.Triborane, dipole moment of, 116.10,9-Boroxaphenanthrene, 1 O-chloro-, for-mation of, 271.Branched-chain sugars, 299.Brine, analysis of, 407.Bromination, 164.Bromine, 129.thesis of, 248.reactions of, 114.cations, stabilised, 129.oxides of, 129.trinitrate, 129.Bromate, dtmn.of, in presence ofoxidation by, in volumetric analysis,Butane, decomposition of, in electricperiodate, 386.387.Bromides, complex, 129.discharge, 10.Butyric acid, y-amino-a-hydroxy-, syn-thesis of, 370.Cadinol, structure of, 228.Cadmium, dtmn. of, 408.Casium chloride, structure of, 113.Cafestol, structure of, 233.Calcium, dtmn. of, 384, 403, 408.in dolomites, etc., 379.dimethyl-, formation of, 207.Calcium carbide, acetylide ion in, 113.phosphates, structure of, 125.Gypsum, structure of, 113.Calycotomine, structure of, 274.Camphor, irradiation of, 227.oxidation of, 227.Canavanine, 366.“ Capillen,” identity of, with agropyrene,Capillin, structure of, 210.Capsaicin, dtmn.of, 410.Carbanions, 175.Carbazole, l-ethyl-, formation of, 265.1,2,3,4-tetrahydr0-6,7,8-trimethyl-, 266.Carbene, dichloro-, formation of, 2 17.Carbenes, 177.reactions of, 217.Carbohydrates, 286.anhydrides of, 297.irradiation of aqueous solutions of, 16.oxidation of, by periodate, 302.Carbon monoxide, dtmn. of, 384.Carbonate in bone mineral, 324.Carbonates, dtmn. of, 376.Carbonium ions, 168.non-classical, 172.Carbonyl compounds, dtmn.of, 392.reactions of, 203.Carbonyls, 135.Carboxylic acids, preparation and re-actions of, 204.Car-3-en-7-01, 227.8-Carotenes, metabolism of, 331, 341, 342.Carotenoids, 211.Carotol, amended structure of, 229.Carquhjol, 226.Cassaic acid, structure of, 234.Cerium(Iv), mechanism of oxidation by,183.Chlorination, electrophilic, 164.Chlorine, 128.209.esters, hydrolysis of, 179.dtmn. of, in chlorofluoro-compounds, 399.Chloride, dtmn. of, 375.Hydrogen chloride monohydrate, struc-Chloride-ion analyses, continuous, 380.Perchloric acid, use of, 376.pChlorobenzoy1 isothiocyanate, as re-agent for amines, 382.Chloroform, dtmn. of, 402.Chromatography, 395.small amounts of, 391.ture of, 128.column, 397.gas-liquid, 400.paper, 396INDEX OF SUBJECTS.463Chromium, high-purity, assay of, 395,Chromium compounds, 150.413.organometallic compounds of, 145.hexacarbonyls, preparation of, 135.Chromate ion, force constants of, 74.Chromic acid, mechanism of oxidationby, 182.Chromium(I1) oxide, preparation of,150.Benzenechromium tricarbonyl, 144, 249.Bis( hexamethylbenzene)chromium, 248.Chrysanthenone, formation of, 227.Cinchonamine, synthesis of, 276.Cineole, biosynthetic, 226.Cinerubin, 242.Citrate, role of, in bones and teeth, 327.Cnicin, structure of, 237.Cobalt, dtmn. of, 403.Cobalt compounds, 154.Coenzyme A, formation of, 268.( -)-Colchicine, syntheses of, 286.Colorimetric titrimeter, automatic, 379.Complexes, inorganic, mechanism of re-Complexes of transition elements, 131.Complex ions, absorption of, 87.Configuration, absolute, 188.Conformational analysis, 194.Conopharyngine, structure of, 277.Co-ordination of organic ligands, 103.Copper, dtmn.of, 375, 386, 390, 403.Copper compounds, 156.Coronaridine, structure of, 278.Costunolide, structure of, 227.Coumarins, 269.p-Cresol, 2,6-di-t-butyl-, dtmn. of, 403.Crinamine, structure of, 282.6-hydroxy-, 282.Cryptopimaric acid, 232.Cucurbitacins, 237.Cuparene, 228.Cuparenic acid, 228.Curare alkaloids, 279.Cyanogen fluoride , existence of, 1 19.Cyanides, complex, 137.vibrational spectra of, 74.Hydrogen cyanide, polymer of, 119.Cyclazines, aromatic, behaviour of, 265.Cycloalkanes, methylene-, formation of,Cycloalkene-l.Z-diones, enolic, 222.Cycloalliin, 305.synthesis of, 370.Cyclobutane, unsaturated derivatives of,Cycloeucalenol, 235.Cycloheptane, configuration of, 225.Cyc1ohexa-lJ4-diene, configuration of,Cyclohexa-3,5-diene-l ,Z-diol, formation of,in presence of nickel, 398.Dicobalt octacarbonyl, structure of,135.actions of, 133.stability of, 87.221.219.225.221.Cyclohexane, radiolysis of, 18.chloro-, Raman and infrared spectra of,1 ,kdimethyl-, cis- and trans-, absoluteCyclohexane-1,2-diol sulphates, cis- andCyclohexanones, 2-substituted, formationCyclohexenes, l-alkyl- and 1-phenyl-,Cyclo-octadeca- 1 , 3,7 , 9,13,15-hexaene-Cyclo-octadecanonaene, 246.Cyclo-octane, configuration of, 225.Cyclo-octatetraene, complexes of, 140.Cyclopentadienyl anion, 243.Cyclopentadienylides, 143.7r-Cyclopentadienyl-7r-cycloheptatrienyl-Cyclopentene, 4,4-dimethyl-, frequenciesCyclopent-2-enonesJ preparation of, 220.Cyclopeptides, 3 13.Cyclopropanes, 218.Cyclopropyl methyl ketone, use of, 212.Cysteine, acids derived from, 370.“ D-effect,” the, 238.Dammarenolic acid, structure of, 236.Darutigenol, structure of, 234.Deamination, formation of carbonium( -+) -Dehydroabietane, 230.Delpheline, structure of, 284.Delphenine, structure of, 284.Deltaline, structure of, 284.( +)-Demethanolaconinone, absolute con-figuration of, 283.Dem e t h ylhom ol ycorin e , structure of , 2 8 2.l-Deoxy-D-fructose, 1-(carboxymethyl-amino)-, formation of, 295.2-Deoxy-a-~-glucose, Z-benzamido- 1 , 3,4,6-tetra-O-benzoyl-, nature of, 294.2-Deoxykojic acid, reaction of, withacrylonitrile, 262.Deoxy-sugars, 299.Deuterium isotope effects, secondary, 170.Diamino-acids, 365.Diazo-coupling, kinetic isotope effect in,a-Diazo-ketones, preparation of, 216.3,4 : 5,6-Dibenzazocine- 1-spiro-1’-piper-idinium ion, lJ2,7,8-tetrahydro-, op-tical resolution of, 263.Dibenzenechromium, heat of dissociationof, 248.Dibenzocyclo-octatetraene, 245.2,6-Di-t-bu tyl-p-cresol, dtmn.of, 403.Dichloroacetyl chloride, two forms of, 78.Diet, influence of, on composition ofDifluoroamine, 122.Difluorodi-imine, 122.( f )-Dihydrocorynantheine, total syn-thesis of, 276.77.configurations of, 225.trans- , hydrolysis of, 181.of, 221.oxidation of, 221.5,11,17-triyne, preparation of, 222.vanadium, 145.of, 77.ion in, 173.165.bones and teeth, 325454 INDEX OF SUBJECTS.Dihydrosarcostin, structure of, 235.Dihydrotoxiferine, structure of, 280.Di-imine, trifluoro-, 121.4,4-Dimethylcyclopentene, frequencies of,Dinorocerane, synthesis of, 231.1,3-DioxalanJ Raman spectrum of, 77.1,4-Dioxen, 2,3-diphenyl-, formation of,m-Diphenols, test for, 382.Dipyrrolo[a,flpyridine system, 265.Di-2-quinolylmethane, two forms of,Disulphide bonds, determination of, inDiterpene alkaloids, 283.Diterpenes, 230.1,4-DithiinsJ removal of sulphur from,263.Domoic acid, 362.Dosimetry, 21.Drimenol, structure of, 228.Dyes, radiolysis of, 17.Eburnamine, structure of, 279.Echinomycin, 314.Elastomers containing acrylonitrile, dtmn.Electrical methods of analysis, 390.EIectrochemistry, 32.Electrodeposition and dissolution of solidmetals, 39.Electrodes sensitive to specific elements,374.Electrolytes, nuclear magnetic resonancespectra of, 86.Electrophilic aromatic substitution, 160.Electrophilic substitution, 238.Elleryone, identity of, with zierone, 229.Ellipticine, structure of, 279.Emetine, configuration of, 274.Emission spectroscopy, 412.Endrin, ketone from, correction of struc-13-Episcalerol, synthesis of, 230.Eremophilone, absolute configuration of,Etamycin, 314.Ethoxyl, dtmn.of, inpresence of methoxyl,Ethyl furfuryl sulphide, 257.Ethylene, radiolysis of, 9.Ethylenediaminetetra-acetic acid com-Evodone, structure of, 270.Fat, dtmn. of, in milk, 377.Ferrocene, 247.Fischer’s reagent (for water) , simple prep.of, 378.Fluids, physical properties of, 22.Fluoranil, preparation of, 251.Fluorenone, perhydro-, formation of, 221.Fluoride, amperometric titration of, 395.77.262.267.proteins, 308.of, 377.ture of, 224.228.415.plexes, 132.dtmn.of, in blood serum, 407.test for, 381.Fluorides, addition compounds of, 128.Fluorine, 128.399.in bones and teeth, 330.dtmn. of, in chlorofluoro-compounds,in organic compounds, 399.Formaldehyde, dtmn. of, in air, 376.Formamide, monomeric and trimeric, 76.Formic acid, y-radiolysis of, 16.Formyl groups, dtmn. of, in presence ofacetyl groups, 402.Furans, 256.Gallium, dtmn.of, 409.triffuoride, 119.Gases, compressed , thermodynamicmeasurements of, 28.radiation chemistry of, 8.Geigerinin, structure of, 237.Geissoschizine, structure of, 277.Gelsemine, structure of, 278.General and physical chemistry, 7.Germacrone, structure of, 228.Germanium as semiconductor, 38.Digermane, hexachloro-, 120.Germanes, higher, 120.Geobueol, 229.Glutamic acid, y-hydroxy-, 360.metabolism of derivatives of, 360.Glutaramidines, 260.Glycerol, dtmn. of, 388.Gold, 157.dtmn. of, 404.“ spot ” test for, 416.Guatambuinine, structure of, 279.Gypsum, structure of, 113.Hacmoglobins, 318.Hafnium compounds, 148.Halides, colorimetric dtmn. qf, 406.dtmn.of, in organic substances, 415.Halogens, dtmn. of, 391.free, dtmn. of, 386.Halogenoplatinates, bond energies in , 13 1.Heliotrine, synthesis of, 281.Heptalene derivative, 247.Heterocyclic compounds, 252.conformation of, 195.electrophilic substitution in, 167.High-pressure effects on acidity functions,Himbaccol (viridiflorol), 229.Homolytic substitution, 240.(-)-Homostachydrine, synthesis of, 273.Hopenone, hydroxy-, structure of, 235.Hormones, melanocyte-stimulating, 31 7.Humulene, structure of, 227.Hydration energies in complexes of in-organic ligands, 98.Hydrazine, dtmn. of, 388.tetrafluoro-, 121.Hydroboronation, 198.Hydrocarbons, brorno- and chloro-, radio-Hydrochlorides, dtmn. of, 386.48.lysis of, 20.unsaturated, irradiation of, 17INDEX OF SUBJECTS.465Hydrogen, 112.acetylenic, dtmn. of, 389.active, dtmn. of, 390.catalytic activation of, 11 2.Hydrogen bonds, very strong, 112.Hydrogenation, catalytic, 198.Hydrogen-isotope effects on kinetics inHydroxy-compounds, acetylation of, 388.2-Hydroxyethylamines, secondary, dtmn.Hydroxylamine, dtmn. of, 388.Hypertensins, 315.Hypoglycin A and B, 304.Hypohalogenites, etc., dtmn. of, 386.Hypoxanthine, one-step synthesis of, 268.Ichthyopterin, structure of, 269.Imidazoles, l-triphenylmethyl-, 258.Imino-acids, new, from plants, 361.solution , 50.exchange, 162.of, 395.properties of, 371.hydroxy-, 362.biogenesis of, 364.Indium, dtmn. of, 409.use of, as internal standard in spectro-graphy, 413.Indole alkaloids, 276.Indoles, 265.Induction, asymmetric, 188.Infrared analysis of solids, 408.Inorganic chemistry, 11 1.species, Raman spectroscopy of, 72.Intensities of Raman spectra, 68.Inuline, 284.Iodination, kinetic isotope effect, 165.Iodine, 129.cations, stabilised, 129.cyanide, complexes of, 130.Iodine-lefin complexes, 130.Iodic acid, dissociation of, 70.Iodides, complex, 129.Periodate, dtmn. of, in presence ofbromate, 386.mechanism of oxidation by, 185.oxidation of carbohydrates by, 302.Periodic acid, dehydration of, 130.Ion-exchange resins, analytical uses of,398.Ions, complex, absorption spectra andstability of, 87.hydration of, 33.Iron, oxides of, 153.Iron(rI), specific dtmn.of, 381.Iron(m), dtmn.of, 385, 404.Iron pentacarbonyl , Raman spectrumIron(r1) sulphate, induced oxidation of,Isobutene, radiation-induced polymeris-Isobutyric acid, a- and p-amino-, 370.Isocoenzyme A, formation of, 268.Isocyanates, dtmn. of, 415.Isocyanides, complex, 137.of, 74.16.ation of, 19.structure of, 135.Isoeburnamine, structure of, 279.(+)- and (-)-Isoiridomyrmecin, synthesisIsomerism, rotational, 78.Isopelletierine, synthesis of, 273.Isophyllocladene, 233.Isopimaric acid, 232.Isoquinolines, 267.Isothiazole (1,2-thiazole), 4-amino-, 259.Isothiocyanates, dtmn. of, 415.Isotope effects in solvents, 53.secondary, in solutions, 55.Jacobine, structure of, 281.Jacoline, structure of, 281.Jaconine, structure of, 281,Junipal, 257.Kahweol, structure of, 233.L-a-Kainic acid, 361.Ketones, colorimetric test for, 382.Kinetics of reactions in solution, 41.Kojic acid, reaction of, with acrylonitrile,of, 265.of small radicals and molecules, 55.262.Lanthanides, 146.Lead, separation of, from silver, 383.Lead(11) chloride, bisthiourea-, 121.Ledol, 229.Ligand properties in complex ions, 91.Ligand-cation fields, 91.Linear energy transfer, 13.Liquids, thermodynamic measurementsLithium aluminium hydride, uses of, 200.Lombricine, structure of, 319.Lophocerine, structure of, 274.(-)-Lunacrine, probable structure of,Lunine, structure of, 274.Lycoctonine, identify of, with royline, 284.DL-Lysine, synthesis of, 306.Macrocyclic rings, synthesis of, 222.Macrolides, 216.Magnesium, dtmn.of, 404, 408.in dolomites, etc., 379.iodide, pure, preparation of, 113.peroxide, structure of, 113.tetra-acetate, mechanism of oxidationPlumbanes, 121.by, 187.of, 28.borohydride, ammoniates of, 113.selenide, 113.273.hydroxy-, structure of, 284.Mammein, structure of, 270.Manganese carbonyl, preparation of, 135.compounds, 152.organometallic compounds of, 145.Cyclopentadienylmanganese tricarb-onyl, 249.Permanganate, mechanism of oxidationby, 113.Marasin, structure of, 209.Marmin, 270456 INDEX OFMercury(rr), dtmn. of, 385.Mercury(I1) chloride, symmetrical stretch-Metal carbonyl-acetylene complexes, 208.Metallocenes, 247.Methane, compressibility of, 24.Methoxyl, dtmn. of, in presence of ethoxyl,8-Meth y lasp artic acid, 3 5 9.3-Methylcyclohexanone, optical resolu-Methylenecyclopropane, C =C stretchingMicro-analysis, 414.Micro-organisms, stereospecific action of,Mixtures, liquid, of inert gases, 29.Moisture content of bone and toothMolecular interactions, 75.Molisch test, improvement in, 382.Molybdenum(vI), dtmn.of, 385.Molybdenum carbonyl, preparation of, 135.compounds, 151.dichloride, reactions of, 151.Molybdate, separation of, from vanad-ate, 383, 404.Monocrotaline, absolute configuration of,Monoterpenes, 226.Multiflorine, constitution of, 273.Muscle contraction, chemistry of, 343.relaxation, chemistry of, 355.Myosin, 346.Naphthalene, dtmn. of, 402.Nephelauxetic series, 94.Neptunium hexafluoride, 147.Neutralisation, carbanions in, 170.Nickel, dtmn.of, 403, 405.in gold-nickel alloys, 398.in presence of cobalt, 398.Nickel complex of dichlorotetramethyl-compounds, 154.Dicyclopentadienylnickel(0) , 249.Tetramethylcyclobu tenedichloronickel,compounds, 157.ing frequency of, 75.415.tion of, 204.frequency of, 77.225.minerals, 326.281.cyclobutene, 245.245.Nicotinaldehyde, synthesis of, 260.Nimbiol, structure of, 234.Niobidm compounds, 150.Nitidine, structure of, 284.Nitration, 163.Nitrogen bases, titration of, in non-Dinitrogen trioxide, structure of, 122.Nitrate, dtmn. of, in meat and brines,Nitrite, dtmn. of, in presence of nitrate,Nitrite-azide reaction, mechanism of,Nitrous acid, mechanism of oxidationaqueous media, 393.394.in presence of nitrite, 407.407.122.by, 186.;US JECTS.Nitro-compounds, organic, dtmn.of,Nitrosyls, complex, 138.Nona-trans-2, cis-6-diena1, synthesis of,Norbornadiene, complexes of, 139.Norbornane, halogenation of, 224.Norbornane-endo-2-carboxylic acid, stereo-Norpluviine, structure of, 282.Nuclear magnetic resonance, 78.Nucleophilic substitution, 239.Nupharamine, structure of, 286.Nyctanthic acid, synthesis of, 236.Obamegine, structure of, 276.Obtusifoldienol, 235.Occidentalol, 228.Octamethylcyclo-octatetraene, 245.Octa-lJ3,5,7-tetraene, structure of, 76.Oleana-1 1,13 ( 1 8)-diene , 232.Olefinic compounds, 210.Olefins, complexes of, 138.Olivacine, structure of, 279.2- and 8-Onoceradiene, 231.a-Onocerin diacetate, synthesis of, 231.Optical activity, 197.resolution, 197.389.211.chemistry of, 225.formation and reactions of, 205.by vapour-phase chromatography,rotatory dispersion, application of, 224.Organic chemistry, 159.theoretical, 169.Organic compounds, Raman spectra of,ligands, co-ordination of, 103.Osmium compounds, 153.Osmocene, 248.structure of, 143.Oxalic acid, oxidation of, 181.2-Oxazolidones, formation of, 258.Oxepin, 2-arnin0-3-carbamoyl-4~7-di-methyl-, synthesis of, 264.Oxetans (trimethylene oxides), synthesisof, 254.Oxidation (in organic chemistry), 181,201." 0x0 I' reaction, the, 139.2-Oxoazetidines, 3,3-disubstitutedJ syn-Oxomanoyl oxide, structure of, 234.Oxygen, 126.206.76.thesis of, 253.dtmn.of, in beryllium, 417.dissolved, dtmn. of, 394.Trioxygen trifluoride, 126.Oxytetracyclin, dtmn. of, 394.Oxytocin, 316.Ozone, 126.dtmn. of, in air, 376.Ozonides, 126.Palladium, dtmn. of, 383.Palladium compounds, 155.Palosine, structure of, 278.Palustric acid, 233INDEX OF SUBJECTS, 457Palustrol, 229.Paper, dtmn. of chloride in, 392.Paracyclophanes, 246.Paraffins, radiolysis of, 17.Parkamine, structure of, 282.Paromamine, structure of, 286.Parthenolide, 227.Pentacyclosqualene, formation of, 231.Pentalene derivative, 246.Pentane , a-radiolysis of , 10.Peptides, new, 315.structure of, 306.synthesis of, 309.Perfluoro-olefins, complexes of, 138.Perhalogenoarenes, 240.Periodate oxidation of carbohydrates, etc. ,Peroxides, automatic titration of, 380.302.dtmn.of, 409.oxidation by, 201.ation by, 184.Peroxy-compounds, mechanism of oxid-Petasin, absolute configuration of, 228.Phaeantharine, structure of, 276.Phenols, dtmn. of, 409, 410.Phenyl iodosodiacetate, mechanism ofPhenylglycine, m-carboxy-, 359.Phosphole, pentaphenyl-, formation of,Phosphopeptides, 319.Phosphoproteins, 3 19.Phosphorus, acids derived from, 124.compounds of, 123.optically active compounds of, 206.Phosphorus monoxide, polymeric, 124.trisulphide, non-resistance of, 125.Diphosphorus tetrachloride, 123.Hypophosphates, 124.Phosphate, dtmn. of, 386, 404.in presence of sulphate, 387.Phosphonitrilic chloride, trimeric, 123.Phosphorylation, oxidative, mechanismof, 251.Phthalocyanine complexes, 131.Phthiocerol, nature of, 214.Phyllocladene, 233.or-Picoline, dtmn.of, in pyridine, 377.Picolines, alkylation of, 259.Pimaric acid, 232.Pimaricin, structure of, 216.Pinacolic rearrangements, 173.Pipecolic acid, formation of, 363.Pipecolic acids, hydroxy-, 362.Piperidine, BJ6-dicyano-, formation of,Plastics, dtmn. of, 412.Platinum compounds, 155.( f ) -Podocarpa-5,7,13 (14) -triene , 6-meth-Polarography, 394.Polycyclic aromatic compounds, 241.Polyenes, cyclic, 244.Polymers, separation of mixtures of, 397.separation of, 403.spot test for, 382.oxidation by, 187.142.260.OXY-, 230.Polypyrroles, 270.Polyurethane rubbers, test for, and dtmn.of, 412.Potassium, direct titration of, 395.dtmn. of, in coal ash, 413.Potassium chloride, dtmn.of, in presenceof sodium chloride, 398.Potentials, intermolecular, parameters of,26.Potentiometric titration curves, recordingof, 379.Propan-2-01, dtmn. of, 389.Proteins, 304.Provitamins A, metabolism of, 331.Pseudolycorine, structure of, 282.Pteridines, 268.Purines, 268.Pyrans, 2- and 4-, preparation of, 262.Pyrazolines, 258. p- 1-Pyrazolylalanine, 304.Pyridine alkaloids, 273.Pyridines, 259.2-cyano-, trimerisation of, 263.Pyrimidines, formation of, 262.2-cyano-, trimerisation of, 263.4-Pyrone, 2,6-dimethyl-, photo-dimer of,Pyrrocoline, preparation of, 265.Pyrrole, laboratory preparation of, 255.Pyrrole-2-aldehyde , l-methyl- , structureof, 254.Pyrroles, 254.Pyrrolidines, 256.Pyrrolines, 255.Pyrromycin, 243.Pyrromycinones, 242." Quinol " acetates, 250.Quinoline alkaloids, 273.Quinolines, 266.Quinones, 250.Radiation chemistry, 7.Radical scavengers, 19.Radiochemical methods of analysis, 417.Raman spectroscopy, 67.Resonance Raman effect, 71.[U-14C]Retinene, metabolism of, 342.(-) -Retronecanone, absolute configur-ation of, 281.Rhenium carbonyl, derivatives of, 136.compounds, 163.Rhodium.Cyclopentadienecyclopentadienyl-rhodium, 249.Rhodoxanthin, synthesis of, 212.Ribonuclease, 320.Rimuene, structure of, 233.Ring-oven procedure, applications of,Rosenolactone, absolute configuration of,Rotation, molecular, 188.Royline, identity of, with lycoctonine,261.analytical applications of, 71.381.233.284458 INDEX OF SUBJECTS.Rubbers containing acrylonitrile, dtmn.Ruthenium compounds, 153.Ruthenocene, structure of, 143.Rutilantinone, structure of, 243.of, 377.tetroxide, no oxidising agent, 203.Salt effects on kinetics, 41.Sandarcopimaric acid, 232.Scalerol, configuration of, 234.Scandium-group elements, 146.(-)-Sedamine, configuration of, 273.Selenium, pure, preparation of, 128.synthesis of, 230.dioxide, solution of, in sulphuric acid,halides, complex, 128.128.Semiconductor electrodes, 38.Sesquiterpenes, 227.Shikimic acid , stereospecific synthesis of,Silicon, dtmn.of traces of, 405.optically active compounds of, 206.pure, preparation of, 119.Silicon carbide, wurtzite form of, 120.222.compounds, Raman spectra of, 73,74.hydrides, 120.imide, preparation of, 120.“ monoxide,” nature of, 120.phosphide, 120.Silica, dtmn.of, 375.vitreous, Raman spectrum of, 75.Silicate ion, structure of, 74.Silver, dtmn. of, 391, 417.separation of, from lead, 383.Silver compounds, 157.‘‘ Siloxen,” uses of, 384.Sodium, dtmn. of, in waters, 374.Sodium chloride, dtmn. of, in presence ofpotassium chloride, 398.fluoride, acid fluorides of, 113.hydrogen diglycollate as referencebuffer, 390.nitrite, Raman spectrum of, 75.Solanesol, structure of, 213.Solutions, aqueous, irradiation of, 10.Solvent effects on kinetics, 41.Spectra, rotation and vibration-rotation,Spiropentane, formation of, 223.Squalene, biosynthetic precursors of, 226.Stereochemistry, 171, 187.68.new route to, 213.carbanion intermediates in, 177.entropy of reaction or of activation in,191.Stizolobic acid, 304, 366.Strepogenins, 315.Streptimidone, structure of, 218.Strontium, dtmn.of, 408.dimethyl-, formation of, 207.Strontium peroxide, structure of, 113.SOStrontium in bone and tooth minerals,Styrene, dtmn. of, in copolymers, 411.Succinic acid, (+)-=a’-diamino-, 360.328.Sulphamic acid as primary standard,389.Sulphanes, dtmn. of, 377.Sulphur, 126.Sulphur tetrafluoride, 126.structure’of, 85.oxide ”), 127.ture of, 127.127.dtmn. of, in pyrites concentrates, 399.organically bound, dtmn. of, 375.Disulphur monoxide (“ sulphur mon-Pentafluorosulphur hypofluorite, struc-“ Permonosulphuric amide,” nature of,Sulphate, dtmn.of, 404.in aluminium sulphate solution, 387.in presence of phosphate, 387.Sulphides, dtmn. of, 375.alkyl, dtmn. of, 415.presence of thiols, 392.other acids, 392.Disulphides, organic, dtmn. of, inSulphuric acid, dtmn. of, in presence ofThionyl cyanide, formation of, 127.Thiosulphuric acid, anhydrous, 127.Supinine, synthesis of, 283.Surface-active agents, analysis of, 383.mixtures, analysis of, 400.Tantalum compounds, 150.Technetium compounds, 152.Tetrabenzanthracene, 242.Tetrabenzyl pyrophosphate, solvolysis of,in propan-1-01, 180.Tetracyclines, 242.Tetrazines, 253.Tetrazole ring system, infrared bands of,Thallium(m) chloride, 119.Thelephoric acid, structure of, 270.l-Thiacyclo-octan-5-one, 264.lJ3,4-Thiadiazolidine system, 259.1,2-Thiazole (isothiazole) system, 259.Thioacetals, alkylation of, 217.Thiols, dtmn.of, 409, 415.258.in presence of disulphides, 392.test for, 383.Thiophen, tetrachloro-, 257.Thiourea, vibrational spectrum of, 77.Thorium, dtmn. of, 405, 406.Tin, dtmn. of, 404, 405.in ion, etc., 417.Stannanes, 121.organometallic compounds of, 145.Biscyclopentadienyltitanium dicar-Titanium, dtmn. of, 385, 405, 408.Titanium compounds, 148.Titrimetric procedures, 374.Titrimetry, non-aqueous, 389.Tocopherols, 269.dtmn. of, 397, 410.Tooth minerals, 325.Transition elements, 130.Trichloroethylene vapour, dtmn. of, in air,bonyl, 136.376Tropaiie alkaloids, 272.Tropylium ion, 243.Tropyliumchromium tricarbonyl, 260.Tungsten, dtmn. of, 384.Tungsten carbonyl, preparation of, 135.compounds, 152.Turbidimetry, 374.salts, 243.Uleine, structure of, 279.Uranium, automatic dtmn. of, 380.dtmn. of, 406.147.Sodium uranyl acetate, structure of,Urea, vibrational spectrum of, 77.Vanadium (v), mechanism of oxidation by,Vanadium compounds, 149.183.7-Cycloheptatrienyl-v-cyclopenta-Trivanadium pentoxide, structurc of,Vanadate, separation of, from molyb-Vapour-phase chromatography, use of, indienylvanadium, 145, 348.149.date, 383, 404.optical resolution, 206.5 U lj J BL 1 S. 459Vasopressin, 316.Vinyl ethers, dtnm. of, 389.Viridiflorol (himbaccol), 229.Vitamin A, formation of, from /3-carotene,Volucrisporin, structure of, 251.333.Water, dtmn. of, by Karl Fischer method,in acetone, 378.dtmn. of nitrate, sulphate, and clilorideirradiation of, 10.380.in, 399.Water content of bone and tooth minerals,Willardiine, 306.326.structure of, 367.Ximenynic acid, 8-hydroxy-, synthesis of,Xylenes, isomerisation of, 238.215.Zeisel method, improvements in, 415.Zierone, identity of, with elleryone, 229.Zinc, dtmn. of, 406, 408.Zinc dithiol, uses of, 381.Zirconium, dtmn. of, 384, 406.Zirconium compounds, 148

ISSN:0365-6217    

DOI:10.1039/AR9595600451

出版商:RSC    

年代:1959

数据来源: RSC

摘要:

PRINCIPAL REFERENCES USED IN CHEMICAL SOCIETYPUBLICATIONS AS FROM JANUARY, 1960REFERENCE.Act. sci. ind. .Acta Acad. Aboensis, Math.Acta Biochim. Yolon. .Acta Biochim. Sinica .Acta Biol. Acad. Sci. Hung.Acta Brev. Near. Ph-ysiol. .Acta Chem. Phys. .Acta Chem. Scand. .Acta Chim. Acad. Sci. Hung.Acta Chim. Belg. .Acta Chim. Sinica .Acta Cryst.Acta Med. Scand:Acta Metallurgica .Acta Path. Microbiol. Scand.Acta Phys. Acad. Sci. Hung.A d a Phys. et Chem. Szeged.Acta Physicochim. U.R.S.S.Acta Physiol. Acad. Sci. Hung.Acta Phytochim., Tokyo .Acta Vitawtinol. .Adv. BioE. Med. Phys.Adv. Carbohydrate Chem. .Adv. Catalysis .Adv. Chem. Eng. .Adv. Chem. Phys. .Adv. Clin. Chem.Adv. Colloid Sci.A&J. Enzymol.Adv. Food Res. .Adv.Inorg. Chem. Radiochem.Adv. Pest Control Res.Adv. Phys.Adv. Protein Chem. .Advancement Sci. .Afinidad .Agra Univ,. J . Res. (Sci.)Agric. Chem. .Agrokbm. ks Talajtan .Ambix .Phys. ..Amer. Ceram. SOC. Bull. .Amer. Chem. J . .Amer. Dyestuff Refiorter .Amer. Inst. Chem. EngineersAmer. Inst. Min. Met. Engin-Amer. J . Bot. .Amer. J . Digest. Dis. .Amer. J . Med. Sci. .Amer. J . Pharm. ,Amer. J . Physiol. .Amer. J . Publ. Health .J . -eersFULL TITLE.Actualit& scientifiques et industrielles.Acta Academiae Aboensis, Mathematica et Physica.Acta Biochimica Polonica.Acta Biochimica Sinica.Acta Biologica Academiae Scientiarum Hungaricae.Acta Brevia Neerlandica de Physiologia, Pharmacologia,Microbiologia, e.a .Acta Chemica et Physica.Acta Chemica Scandinavica.Acta Chimica Academiae Scientiarum Hungaricae.Acta Chimica Belgica.Acta Chimica Sinica.Acta Crystallographica.Acta Medica Scandinavica.Ac ta Metallu rgica .Acta Pathologica et Microbiologica Scandinavica.Acta Physica Academiae Scientiarum Hungaricae.Acta Physica et Chemica.Acta Universitatis Szege-Acta Ph ysicochimica U.R.S. 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Matematic& Fizic5, Chimie.Universidad nacional mayor de San Marcos.Anales de la real Sociedad espaiiola de Fisica y Quimica.Analyst.Analytical Chemistry.Analytica Chimica Acts.Anatomical Record.Angewandte Chemie.Annales Academiae Scientiarium Fennicae (SuomalaisenAnnals of Biochemistry and ExperimentaI Medicine.Annals of Botany.Annales de Chimie.Annali di Chimica.Annales de Chimie analytique et de Chimie appliquCe.Annali di Chimica applicata.Annales de Chimie et de Physique (now divided: seeAnnales d’Endocrinologie.Annales des Falsifications et des Fraudes.Annales des Fermentations.Annales de 1’Institut Pasteur.Annals of Internal Medicine.Annales de la Nutrition et de l’hlimentation.Annales pharmaceutiques franGaises.Annalen der Physik.Annales de Physique.Annual Report of the Faculty of Pharmacy.Annual Report of the ITSUU Laboratory.Annual Report of the Takamine Laboratory.Annual Reports on the Progress of Chemistry.Annual Review of Biochemistry.Annual Review of Microbiology.Annual Review of Nuclear Science.Annual Review of Physical Chemistry.Annual Review of Plant Physiology.Annals of Science.Annales du Secteur d’ Analyse physicochimique, Institu tde Chimie gCnCrale (U.R.S.S.).Annales de la Soci6ttC scientifique de Bruxelles.Annali della Sperimentazione agraria.AnnaIi della Stazione chimica-agraria sperimentale,Annales Universitatis Mariae Curie-Sklodowska (severalAnnales Universitatis Turkuensis.Series A. Astrono-Annalen der Chemie (Liebig’s).Annuaire AcadCmie royale de Belgique.Tiedeskatemian Toimit uksia) .Ann. Chinz. and Ann. Phys.).KanazawaUniversity.Roma.sections).mica, Chemica, Physica, MathematicaPRINCIPAL REFERENCES USED.REFERENCE.Antibiotics and ChemotherapyAppita .Appl. Spectroscopy .Arch. Biochem. .Avch. Biochem.Biophys. .Arch. Eisenhutten.w. .Arch. exp. Path. Pharmak. .Arch. klin. Chir.Arch. MikrobioC.Arch. Pharm. .Arch. Sci. .Arch. Sci. biol. (U.R.S.S.) .Arch. Sci. phys. nat. .Arch. 2001.Arhiu Kem. .Arkiu Fys.Arkiv Kemi .Avkiu Kemi, Min., Geol. .Atomic World .Atomics .Atti Accad. naz. Lincei, Rend.Classe Sci. j i s . mat. nat.Atti R. Accad. Sca. Torino .A ustral. J . - Agvic. Res.Austral. J . Appl. Sci. .Ausiral. J . Biol. Sci. .Austral. .J. Chem. .Austral. J . Exp. Biol. Ned.Austral. J . Phys. .Avh. norske Vidensk.-Akad.Oslo, Mat.-nat. Kl.Afioth.-Ztg. . . .sci.FULL TITLE.463Battele Tech. Rev. .Ber. .Ber. deut. bot. Ges. .Rer. deut. keratn. Ges. .Berg- ec. huttewndnn. 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U.S. translationBiochemical and Biophysical Research Communications.Biochemical Journal.Biochemical Pharmacology.Biochemical Society Symposia.Biochemische Zeitschrift.Biochimica.Biochimica applicata.Biochimica et Biophysica Acta.Biofizika.Biokhimiya.Biological Reviews of the Cambridge PhilosophicalBiologisches Zentralblatt.Boletim do Instituto de Quimica Agricola.Boletin del Instituto de Qufmica de la WniversidadBoletin de la Sociedad chilena de Qufmica.Boletin de la Sociedad quimica del Peru.Bolletino chimico farmaceutico.(Changed to Chem. Ber.in 1946.)istichen Hochschule in Leoben.of Biokhimiya. Different pagination.[See also Biochemistry (U.S.S.R.) .]Society.nacional autonoma de Mexico464 PRINCIPAL REFERENCES USED.REFERENCE.Boll. sci. Fac. Chim. ind.BolognaBoll. Soc. ital. Biol. sper. .Bot. Gaz. .Botyu-Kagaku .Brennstoff-Chem. .Brit. Abs. .Brit. Bull. Spectrosco9y .Brit. Chem. Eng. .Brit. Chemist .Brit. Dental J . .Brit. J . Appl. Phys. .Brit. J . Exp. Path. .Brit. J . 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Warsaw.Chemist Analyst.Chemistry and Industry.Chemische Berich t e .Chemical Engineering.Chemical Engineering.Japan.Chemical and Engineering News.Chemical Engineering Progress.Chemical Engineering Progress, Monographs.Chemical Engineering Progress, Symposia.Chemical Engineering Science.Chemie der Erde.Chemische Fabrik.Chemistry of High Polymers (Japan).Chemistry in Canada.Chemische Industrie.Chemie-Ingenieur-Technik.ChemickC Listy.Chemicky Obzor.Chemical and Process Engineering.Chemical Products and the Chemical News.Chemicky prumysl.Chemical Reviews.Chemical Society Special Publications.Chemia StosowanaChemische Technik.Chemical Trade Journal.Chemical Week.Chemisch Weekblad.Chemisches Zentralblatt.Chemiker-Zeitung.ChemickC Zvesti, SlovenskO Acadbmia, Vied, Bratislava.Chemie.Chemist and Druggist.Chemist-Analyst .Chemistry.(Published quarterly by the ChineseChemical Society, Formosa.)Chimie analytique.Chimia .Chimica e I’Industria. 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Enzymforsch. .Ergebn. exakt. Naturwiss. .Ergebn. Physiol. .Ergebn. Vitamin- u. Hormon-Ernahrungsforschung . .Euclides . . .Experientia .forsch. .FULL TITLE.Cold Spring Harbor Symposium on QuantitativeCollection of Czechoslovak Chemical Communications.Colloid Journal (U.S.S.R.). New York.U.S. translu-Colonial Geology and Mineral Resources.Colonial Plant and Animal Products.Combustion and Flame. (Quarterly Journal of theCommunications de la Facult6 des Sciences de 1’Uni-Comptes rendus hebdomadaires des SCances deComptes rendus de 1’AcadCmie bulgare des Sciences.ComDtes rendus de I’Acadbmie des Sciences deBiology.tion of Kolloidnyi Zhurnal. Different pagination.Combustion Institute.)versit6 d’Ankara. B.1’Academie des Sciences.u .R . s . s .ComDtes rendus hebdomadaires des Seances de laSo&& de Biologie et des Filiales.berg.Serie C, Quimica.Comptes rendus des Travaux du Laboratoire de Carls-Contributions from the Boyce Thompson Institute.Contributions Cientificas, Universidad de Buenos Aires,Corrosion.Croatica Chemica Acta.Current Science.Dansk Tidsskrift for Farmaci.Dechema Monographien.Deutsche Lebensmittel-Rundschau.Deutsche medizinische Wochenschrift.Discussions of the Faraday Society.Dissertation Abstracts. Ann Arbor, Mich.(AbstractsDoklady Akademii Nauk S.S.S.R. (See also ProceedingsDopovidi Akademii Nauk, Ukraiiis’koi Radians’koiD . S . I. R . Publications ,of some U.S. theses, issued contmercially.)of the Academy of Sciences of the U.S.S.R.)Sotsialistichnoi Respu’liki.East African Medical Journal.Edinburgh Medical Journal.Egyptian Journal of Chemistry.Electrochimica Acta.Elektrotechnische Zeitschrift.Endeavour.Engenharia e Quimica.Enzymologia.Engineering and Mining Journal.Erdol und Kohle.Ergebnisse der Enzymforschung.Ergebnisse der exakte Naturwissenschaften.Ergebnisse der Physiologie.Ergebnisse der Vitamin- and Hormonforschung.Ernahrungsforschung.Eu cl id es .Experientia.Fed.Proc. . Federation Proceedings.Fette u. Seifen . . Fette und Seifen einschliesslich der Anstrichmittel.Finska Kemistsamfundets Finska Kemistsamfundets Meddelanden (Suomen Kemi-Medd. stiseuran Tiedonantoja) PRI NCIPAL REFERENCES USED. 467REFERENCE.Fiz. Metall. i Metallov. .FoodFood Manuf. :Food Res. .Food Technol. .Forschungsber. Wirtschafls- u.VerkehrsministeriumsNordrhein- WestfalenForlschr. chem. Forsch.Fortschr. Chem. org. NaturstofleFortschr. Hoclapolym .-Forsc I t .FW?lGazzetta .Geneesk.Tijdschr. Neder1.-Indie .General Cytoclcem. Methods .Gtnie chim. .Geochemistry (U.S.S.l?.i :Geochim. Cosmochim. Acta .Geokhimiya .Geol. Mag.Gidrokhim. Mat.Giorn. Biochim. .Grasas y Aceites .Helv. Chim. Acta .Helv. Phys. Acta .Helv. Physiol. Pliarmacol. ActaI n d . Chemist Chem. Manuf.I n d . Chemist .Ind. chim. .lnd. china. belgeTnd. Eng. Chem.Ifld. Eng. Chertz., Analyt. .I n d . Eng. Chem., Chem. Eng.I n d . Finishing .I n d . ParfurnerieIndian J . Appl. Chepn. .Indian J . Men. Res. .Indian J . Pharm. .Indian J . Phys.Indian Pharmacist .Industria y Quinzica .Ing.-chim. .Inorg. Synth. .Inst. Hierro Acero -Inst. internat. Chim. SolvayInst. Pefroleum Rev..Internat. J . Appl. RadiationInternat. J . Radiation Biol.Internat. 2. Vitaminforsch. .Iowa State Coll. J . Sci. .Izvest. Akad. Nnuk Armian.S.S.R. khini. Nuuk.Izvest. Akad. Nauk S.S.S.R.,Otdel. khim. NaukDuta Ser.Conseil Chim.IsotopesFULL TITLE.Fizika Metallov i Metallovdenie.Food.Food Manufacture.Food Research,Food Technology.Forschungsberichte des Wirtschafts- und Verkehrsmini-steriums Nordrhein-Westfalen.Fortschritte der chemischen Forschung.Fortschritte der Chemie organischer Naturstoffe.Fortschritte der Hochpolymeren-Forschung.Fuel.Gazzetta chimica italiana.Geneeskundig Tijdschrift voor Nederlandsch-Indie.General Cytochemical Methods.Genie chimique (suppl. to Chimie et Industrie).Geochemistry (U.S.S.R.).New York.Geochimica et Cosmochimica Acta.Geokhimiya. [See also Geochemistry (U.S.S.R.).]Geological Magazine.Gidrokhimicheskie Materialy.Giornale di Biochimica.Glasnik Khemiskog Drushtra Beograd.chim. Beograd.)Grasas y Aceites.Ilelvetica Chjmica Acta.Helvetica Physica Acta.Helvetica Physiologica et Pharmacologica Acta.Industrial Chemist and Chemical Manufacturer.Industrial Chemist.Industrie chimique et le phosphate r6unis.Industrie chimique belge.Industrial and Engineering Chemistry.Industrial and Engineering Chemistry : AnalyticalEdition.Industrial and Engineering Chemistry, Chemical andEngineering Data Series.Industrial Finishing.Industries de la Parfumerie.Indian Journal of Applied Chemistry.Indian Journal of Medical Research.Indian Journal of Pharmacy.Indian Journal of Physics.Indian Pharmacist.Industria y Quimica.Ingknieur-chimiste.Inorganic Syntheses.Instituto de Hierro y del Acero.Institut international de Chimie Solvay Conseil deInstitute of Petroleum Review.(Quarterly Journal of Fuel Science.)U S .translationof Geokhimiya. Dijferent pagination.(See Bull, SOC.Chimie.International Journal of Applied Radiation and Isotopes.International Journal of Radiation Biology.Internationale Zeitschrift fur Vitaminforschung.Iowa State College Journal of Science.Izvestiya Akademii Nauk Armianskoi S.S.R. khimi-cheskie Nauki.Izvestiya Alrademii Nauk S.S.S.R.. Otdelenie khimiche-skikh Nauk. Moscow. (See also Bulletin of theAcademy of Sciences of the U.S.S.R.468 PRINCIPAL REFERENCES USED.REFERENCE.FULL TITLE.Imrest. Sekt. fiz.-khim. And., Izvestiya Sektora fiziko-khimicheskogo Analiza, InstitutInst. obshchei neorg. Khim. obshchei i neorganicheskoi Khimii, Akademii NaukS.S.S.R.Izvest. Sekt. Platiny drug. bla- Izvestiya Sektora Platiny i drugikh blagorodnykhgorod. Metal., Inst. obshchei Metallov, Institut obshchei i neorganicheskoi Khimii,neotg. Khim. Akademii Nauk S.S.S.R.J . * J . Agric. Chem. Soc. Japan .J . Agric. Food Chem. .J . Agric. Res. .J . Agric. Sci. .J . Amer. Ceram. SOG. .J . Amer. Chem. SOC. .J . Amer. Leather Chemists’J . Amer. Med. Assoc. .J . Amer. Oil Chemists’ SOG. .1. Amer. Pharmaceut. ASSOG.Assoc. ..s (Sci. Edn.)J . Analyt. Chem.(U.S.S.R.) .J . Appl. Chem. .J . Appl. Chem. (U.S.S:R.)J . A$#]. Phys.J . A+pl. Phys. (U.S.S.R.)J . AppE. Polymer Sci.J . Assoc. O@c. Agric. ChemistsJ . Bad. .J. Biochem. f Japan)J . Biochem. Microbiol. Tech-nol. Eng. . .J. Biol. Chem. .J . Biol. Chem. Sci., Proc. .J . Cell. Come. Physiol. .J . Chem. Educ. .J . Chem., Met., Mining SOC.J . Chem. Phys. .J . Chem. SOC. Japan .J . Chem. SOC. Japan, Ind.J . Chim. phys. .J . Chinese Chem. SOC. (For-J . Chromatog. .J . C h . Invest. .J . Colloid Sci. .J . Council Sci. Ind. Res.,3. Econ. Entomol. .J . Electrochem. SOC. .J . Electrochem. Soc. Japan .J. Endocrinol. .J . Exp. Biol. .J . Exp. Med. .J . Fac. Sci. Univ., TokyoJ . Franklin Inst. .S. AfricaChem.Sect.mosa)Australia.Journal of the Chemical Society.Journal of the Agricultural Chemical Society ofJournal of Agricultural and Food Chemistry.Journal of Agricultural Research.Journal of Agricultural Science.Journal of the American Ceramic Society.Journal of the American Chemical Society.Journal of the American Leather Chemists’ Association.Journal of the American Medical Association.Journal of the American Oil Chemists’ Society.Journal of the American Pharmaceutical Association(Sci. Edn.).Journal of Analytical Chemistry (U.S.S.R.). New York.U.S. translation of Zhurnal analiticheskoi Khimii.Diflerent eagination.Journal of Applied Chemistry (London).Journal of Applied Chemistry (U.S.S.R.). New York.U.S. translation of Zhurnal prikladnoi Khimii.Dif-ferent pagination.Journal of Applied Physics.Journal of Applied Physics (U.S.S.R.).Journal of Applied Polymer Science.Journal of the Association of Official AgriculturalJournal of Bacteriology.Journal of Biochemistry (Japan).Journal of Biochemical and Microbiological TechnologyJournal of Biological Chemistry.Scientific Proceedings of the American Society ofJournal of Cellular and Comparative Physiology.Journal of Chemical Education.Journal of the Chemical, Metallurgical and MiningSociety of South Africa.Journal of Chemical Physics.Journal of the Chemical Society of Japan.Journal of the Chemical Society of Japan, IndustrialJournal de Chimie physique.Journal of the Chinese Chemical Society (Formosa).Journal of Chromatography.Journal of Clinical Investigation.Journal of Colloid Science.Journal of the Council for Scientific and IndustrialJournal of Economic Entomology.Journal of the Electrochemical Society.Journal of the Electrochemical Society of Japan.Journal of Endocrinology.Journal of Experimental Biology.Tournal of Emerimental Medicine.Japan.Chemists.and Engineering.Biological Chemists (bound with J .Biol. 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Osaka Inst.Sci. Tkchnoi.(Kinki Univ.)J . Pediat. .J . Pharm. Belg. .J . Pharm. Chim.J . Pharm. Pharmacol.J . Pharm. SOC. Japan .J . Pharmacol. .J . Phot. Sci. .J . Phys. and Chem. SolidsJ . Phys. Chem.J . Phys. Colloid Chem.’J . Phys. Radium .J . Phys. SOC. Japan .J . Phys. (U.S.S.R.j .J . Physiol.J . Polarog. SOC. .J . Polymer Sci. .J . prakt. Chem. .J* HYg. *News Edn.City Univ.Chemists.FULL TITLE.Journal of General Chemistry (U.S.S.R.). New York.U.S. translation of Zhurnal obshchei Khimii. 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[See atso Colloid Journal (U.S.S.R.) .]Kristallografiya.[See also Soviet Physics Crysta-Kumamoto Pharmaceutical Bulletin.Laboratory Practice.Lancet.Liebig’s Annalen der Chemie.kaido University.Metallurgy.graphy.1See AnnalenPRINCIPAL REFERENCES USED. 471REFERENCE.Mag. Concrete Res. . .Magyar Kkm. Folydirat .Magyar Kkm. Lapja .Makromol. Chem. .Manuf. Chemist . .Mededel. vlaam. chem. Ver. .Melliand Textilber. .Mem. Con. Sci., Kyoto Univ.Mem., Fac. Ind. Arts, KyotoTech. Univ., Sci. and Tech.Mem. Fac. Sci., Kyushu Univ.Mem. Inst. Chew., Ukrain.Acad. Sci.Mem. Inst. Protein Res.,Osaka Univ.Mem.Inst. Sci. Ind. Res.,Osaka Univ.M8m. Poudres . . .Mem. Proc. Manchesteev Lit.Mkm. Services chim. Etat .Metal Ind.Metallforsch. .Metallurgia .Methods Biochem. Analysis .Microchem. J . .Mie Med. J . .Melallw. .Mikrochem. .Mikvochem. Mikrochim. ActaMikrochim. Acta .Mineralog. Mag. .Mitt. deut. pharm. Ges. .Mol. Phys. .Monatsh. .Phil. Soc.FULL TITLE.Magazine of Concrete Research.Magyar KCmiai Foly6irat.Magyar Kdmikusok Lapja.Makromolekulare Chemie.Manufacturing Chemist.Mededelingen van de vlaamse chemische Vereniging.Melliand Textilberichte.Memoirs of the College of Science, Kyoto University.Memoirs. Faculty of Industrial Arts, Kyoto TechnicalMemoirs of the Faculty of Science, Kyushu University.Memoirs of the Institute of Chemistry, UkrainianMemoirs of the Institute for Protein Research, OsakaMemoirs of the Institute of Scientific and IndustrialMkmorial des Poudres.Memoirs and Proceedings of the Manchester Literary andMBmorial des Services chimiques de I’ztat.Metal Industry.Metallforschung.Metallurgia. British Journal of Metals.Methods of Biochemical Analysis.Microchemical Journal.Mie Medical Journal.Met allwirt schaf t , Metallwissenscha f t , Me tall t echnik .Mikrochemie.Mikrochemie vereinigt mit Mikrochimica Acta.Mikrochimica Acta.Mineralogical Magazine and Journal of the MineralogicalMitteilungen der deutschen pharmazeutischen Gesell-Molecular Physics.Monatshefte fur Chemie und verwandte Teile andererWissenschaften.University, Science and Technology.Academy of Sciences.University.Research, Osaka University.Philosophical Society.Society.schaft.(Bound with Archiv der Pharmazie.)Nachr. Akad. Wiss. Gottingen,Nature .Naturwiss.Nederl. Tijds. Na’tuurk:Neues Jahrb. Min. .New England J . Med.New Phytol.New Zealand J . kci. TichnoiNord. med. Tidsskr. .NucleonicsNuovo cim.Nutrit. Abs. Rev.~ Math.-+hys. Kl.&err. Chem.-Ztg. .Optics and Spectroscopy .Org. Reactiom .Org. Synth. .Paint Manuf. .Paint Oil Chem. Rev. .Paint Technol. .Pakistan J . Sci. Ind. 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Japan.Pharmaceutical Journal.Pharmaceutisch Weekblad.Pharmazeutische Zentralhalle fur Deutschland.Pharmazeutische Zeitung.Pharmazie.Philosophical Magazine.Philosophical Transactions of the Royal Society.Physics and Chemistry of the Earth.Physics of Fluids.Physical Review.Physikalische Zeitschrift .Physikalische Zeitschrift der Sowjetunion.Physica.Physiological Reviews.Plant Physiology.Poggendorf’s Annalen.Polarographische Berichte.Post Graduate Medical Journal.Poultry Science.PrAce, Acta, Academiae Scientarum CechoslovenicaePraktische Chemie.Vienna.Proceedings of the Academy of Natural Sciences ofProceedings of the Academy of Sciences of the U.S.S.R.U.S. translation of Doklady AkademiiProceedings of the American Academy of Arts andProceedings of the American Society of BrewingProceedings of the Cambridge Philosophical Society.Proceedings of the Chemical Society.Proceedings of the Geologists’ Association.Proceedings of the Im erial Academy (Tokyo).Proceedings of the I n J a n Academy of Sciences.Proceedings of the Indiana Academy of Science.Proceedings of the Japan Academy.Proceedings, koninklij ke nederlandsche Akademie vanProceedings of the London Mathematical Society.Proceedings of the Staff Meetings of the Mayo Clinic.Proceedings of the National Academy of Sciences India.Proceedings of the National Academy of Sciences of theProceedings of the National Institute of Science ofProceedings of the Physical Society of London.Proceedings of the Piastics and Polymer Group, SocietyProceedings of the Royal Irish Academy.Proceedings of the Royal Society.Proceedings of the Royal Society of Edinburgh.Proceedings of the Roval Societv of Medicine.Menschen und der Tiere.Basis Brunensis.Philadelphia.New York.Nauk S.S.S.R.Dinerent pagination.Sciences.Chemists .Wet enschappen.United States of America.India.of Chemical Industry.Proceedin& of the Society for Eiperimental Biology andProceedings of the Soil Science Society of America.Medicine.Proc. 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Aromen .Progress in Biophysics and Biophysical Chemistry.Progress in the Chemistry of Fats and Other Lipids.Progress in Organic Chemistry.Progress in Stereochemistry.Przemysl Chemiczny.Publications of the American Association for theAdvancement of Science.Publications CERCHAR (Centre d’Etudes et Recherchesdes Charbonnages de France).Publicaciones del Instituto de Quimica “ Alonso Barba.”Quarterly Journal of Experimental Physiology.Quarterly Journal of the Geological Society of London.Quarterly Journal of Pharmacy and Pharmacology.Quarterly Reviews.Quimica e Industria.Radiation Research.Radiology.Recueil des Travaux chimiques des Pays-Bas et de laBelgique.Recent Progress in Hormone Research.Recherches .Report of the British Association for the AdvancementReport of the Scientific Research Institute (Japan).Reports of the Government Chemical Industrial Re-Reports of the Instituteof Physicaland Chemical ResearchReports J.Stefan ” Institute.Reports on Progress in Physics.Research.Revista de la Asociaci6n bioquimica argentina.Revista brasileira de Chimica.Revue de Chimie (AcadCmie de la Rdpublique Popula‘ireRevista de Chimie (Roumania).Revista de Ciencia aplicada.Revista de la Facultad de Ciencias quimicas (Quimica yRevista de la Facultad de Farmacia y Bioqufmica,Revista de la Facultad de Qufmica, Universidad nacionalRevue de la FacultC des Sciences de 1’UniversitC d’Istan-Revue d ’ I mmu no logie.Revue de 1’Industrie minerale.Revue de 1’Institut franGais du PBtrole et Annales desCombustibles liquides.Reviews of Modern Physics.Review of Physical Chemistry, Japan.Revue des Produits chimiques.Reviews of Pure and Applied Chemistry (Royal Aus-tralian Chemical Institute).Revista de Quimica industrial.Revista de Quimica pura C aplicada.Revue scientifique, Paris.Review of Scientific Instruments.Ricerca scientifica.Riechstoffe und Aromen.of Science.search Institute, Tokyo.(Japan),*Rou maine.)Farmacia).Universidad nacional mayor de San Marcos.mayor de San Marcos.bul.Universidad nacional de La Plata474 PRINCIPAL REFERENCES USED.REFERENCE.Roczniki Chem. .Roy.Inst. Chem. Lectures,Rubber Chem. Technol.Russ. Chem. Rev. . .Monographs, RefiortsRuss. J . Inorg. Chem. .Russ. J. Phys. Chem. . .S. African Ind. Chemist .S. African J . Sci. .Schweiz. Apoth.-Ztg. .Schweiz. med. Woch. .Sci. J . Roy. Coll. Sci. .Sci. Light .Sci. Papers Coll. Gen. Educ.,Sci. Papers Inst. Phys. Chem.Sci. Proc. Royal Dublin SOC.Sci. Reports Res. Inst., TShokuSci. Reports Saitama Univ. .Sci. Reports Soc. Res. Theor.Sci. Reports TShoku Univ. .Sci. Sinica .Sci. Tools .Science .Science and Culture .Sitzungsber. Akad. Wiss.WienSitzungsber . Ges . Be f ord.ges. Naturwiss. MarburgSitzungsber. iisterr. A kad.Wiss., Abt.I I BSkand. Arch. Physiol.Smithson. Misc. Coll. .Smokeless A i r .Soap .Soc. Sci. Fennica, Commenta-Soil sci. .Soviet Phys. Crystallog. .Sfiectrochim. Acta .Sperimentale, Sez. Chim. biol.Stirke .Stain Technol. .Sth. Med. J. .Studii si Cercetari Chim.(Acad. R.P.R.)Studii si Cercetari Chim. (Fil.Cluj)Studii si Cercetari Sti., Chim.(Baza Cercetari Sti.. Timi-soara)Univ. TokyoRes. Tokyosci. Progv. . .Univ.Chern.tiones Phys.-Math.Sperimentale - . .FULL TITLE.Roczniki Chemji.Royal Institute of Chemistry, Lectures, Monographs, andReports.Rubber Chemistry and Technology.Russian Chemical Reviews (British translatioa ofUspakhi Khimii. Different pagination.)Russian Journal of Inorganic Chemistry. (British trans-lation of Zhurnal neorganicheskoi Khimii.Differentpagination.)Russian Journal of Physical Chemistry. (British trans-lation of Zhurnal- fizcheskoi Kimii. Diflerent pagin-ation.)South African Industrial Chemist.South African Journal of Science.Schweizerische Apotheker-Zeitung.Schweizerische medizinische Wochenschrift.Scientific Journal of the Royal College of Science.Science of Light. (Institute of Optical Research.Scientific Papers of the College of General Education,Scientific Papers of the Institute of Physical andScientific Proceedings of the Royal Dublin Society.Science Progress.Science Reports of the Research Institute, TBhokuUniversity.Science Reports of the Saitama University.Science Reports of the Society for the Research ofTheoretical Chemistry.Science Reports of the T6hoku University.Scientia Sinica.Science Tools.Science.Science and Culture.Sitzungsberichte der Akademie der Wissenschaften inSitzungsberichte der Gesellschaft zur BeforderungSitzungsberichte der dsterreichische Akademie derSkandinavisches Archiv fur Physiologie.Smithsonian Miscellaneous Collection.Smokeless Air.Soap and Chemical Specialties.Societas Scientiorum Fennica, Commentationes Physico-Soil Science.Soviet Physics.Crystallography. U.S. translation ofSpectrochimica Ac ta .Sperimentale, Archivo di Biologica normale et Patologica.Sperimentale, Archivo di Biologica normale et Patologica,St arke.Stain Technology.Southern Medical Journal.Studii si Cercetari de Chimie.(Academie RepubliciiStudii si Cercetari de Chimie. (Academia RepubliciiStudii si Cercetari Stiintifice Chimie. (Baza de CercetariTokyo. )University of Tokyo.Chemical Research8 Tokyo.Wien.der gesamten Naturwissenschaften zu Marburg.Wissenschaften, Abteilung IIB.Mathematicae.Kristallografiya. Different pagination.Sezione di Chimica biologica.Populare Romine.)Populare Romine.Stiintifice, Timisoara.)Filiala Clu j .PRINCIPAL REFERENCES USED. 475FULL TITLE. REFERENCE.Studii si Cercetari Sti. Chim.Studii si Cercetari Sti., Ser. I(Fil.) IasiSiiddeut. Apoth.-Zfg. .Suomen Kem. .Svensk kern. Tidskr. .Svensk Papperstidn. .Symp. SOC. Exp. Biol.Talanta . .Technol. Reports TBhoku U*Z~V.Technol. Reports Osaka Univ.Tetrahedron .Tetrahedron Letters .Textile Res.J . .Tidsskr. Kjemi Bergvesen Met.Trans. Amer. SOC. Metals .Trans. Brit. Ceram. Soc. .Trans. Chalmers Univ. Tech-Trans. Electrochem. SOC. .Trans. Faraday SOC. .Trans. Illinois Acad. Sci. .Trans. Inst. Chem. EngineersTrans. Inst. Metal FinishingTrans. N . Y . Acad. Sci. .Trans. J . Plastics Inst. .Trans. Proc. Inst. Rubber Ind.nol., GothenbuygTrans. Roy. SOC. Canada .Trans. Roy. Soc. EdinburghTrans. Roy. SOC. Trop. Med.Trans. Wisconsin Acad. Sci.Trudy Inst. Krist., Akad.Trudy Kom. analit. Khim.,HYg-Nauk S.S.S.R.Akad. Nauk S.S.S.R.Ukrain. biokhim. Zhur. .Ukrain. khim. Zhur. .Unicam SpectrovisionUS. Bur. Min.lispekhi Khim. .Verhandel. k. ned. Akad. We-tenschap., A f d .Natuurk.Vestnik Slovensk. Kern.DrustvaVitamins and Hormones .Voprosy Med. Khim. .Wallerstein Lab. Comm. .Wied. Ann. .2. analyt. Chent.Z. angew. Chem,2. angew. Min. .Z. angew. Phys. .2. anorg. Chem. .2. Biol. .Studii si Cercetari Stiintifice. Chimie. (Academia Re-Studii si Cercetari Stiintifice. Seria I. Stiinte Mate-Suddeutsche Apotheker-Zeitung.Suo men Kemist ileh ti.Svensk kemisk Tidskrift.Svensk Pappers t id ning .Symposia of the Society of Experimental Biology.publicii Populare Romine. Filiala Iasi.)matice, Fizice, Chimice si Technice.Talanta.Technology Reports of T6hoku University.Technology Reports of the Osaka University.Tetrahedron.Tetrahedron Letters.Textile Research Journal.Tidsskrift for Kjemi Bergvesen og Metallurgi.Transactions of the American Society of Metals.Transactions of the British Ceramic Society.Transactions of Chalmers University of Technology,Transactions of the Electrochemical Society.Transactions of the Faraday Society.Transactions of the Illinois Academy of Science.Transactions of the Institution of Chemical Engineers.Transactions of the Institute of Metal Finishing.Transactions of the New York Academy ofTransactions and Journal of the Plastics Institute.Transactions and Proceedings of the Institution of theTransactions of the Royal Society of Canada.Transactions of the Royal Society of Edinburgh.Transactions of the Royal Society of Tropical MedicineTransactions of the Wisconsin Academy of Sciences,Trudy Instituta Kristallografii, Akademii Nauk S.S.S.R.Trudy Komissii PO analiticheskoi Khimii, AkademhGothenburg.Sciences.Rubber Industry.and Hygiene.Arts and Letters.Nauk S.S.S.R.Ukrainskii biokhimicheskii Zhurnal.Ukrainskii khimicheskii Zhurnal.Unicam Spectrovision.United States Bureau of Mines (Bulletins, TechnicalUspekhi Khimii.Papers and Reports of Investigation).See also Russian Chemical Reviews.Verhandelingen der koninklij ke nederlandse AkademieVestnik Slovenskega Kemijskega Drustva.Vitamins and Hormones.Voprosy Meditsinskoi Khimii.van Wetenschappen, Afdeling Natuurkunde.Wallerstein Laboratories Communications.Wiedemann’s Annalen der Physik.Zeitschrift fur analytische Chemie.Zeitschrift fur angewandte Chemie.Zeitschrift fur angewandte biineralogie.Zeitschrift fur angewandte Physik.Zeitschrift fur anorganische und allgemeine Chemie.Zeitschrift fur Biologie476 PRINCIPAL REFERENCES USED.REFERENCE.2.Elektrochem. .2. 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Leiyzig.Zeitschrift fur Physik.Zeitschrift fur den physikalischen and chemischenHoppe-Seyler’s Zeitschrift fur physiologische Chemie.Zeitschrift fur technischen Physik.Zeitschrift fur Untersuchung der Lebensmittel.Zeitschrift fur Vitaminforschung.Zeitschrift fur Vitamin-, Hormon-, und Ferment-forschung.Zeitschrift der Wirtschaftsgruppe Zuckerindustrie(Verein der Deutschen Zucker Industrie).Zeitschrift fur wissenschaftliche Photographie, Photo-physik und Photochemie.Zavodskaya Laboratoria.Zentralblatt fur Bakteriologie, Parasitenkunde undInfektionskrankheiten.Zentralblatt fur Mineralogie, Geologie and Palaontologie.Zeszyty Naukowe Politechniki lodzkiej.Zhurnal analiticheskoi Khimii. [See also Journal ofZhurnal eksperimental’noi i teoreticheskoi Fiziki.Zhurnal fizicheskoi Khimii. [See also Journal ofZhurnal nauknoi i prikladnoi Fotografii i Kinematografii.Zhurnal neorganicheskoi Khimii. See also RussianJournal of Inorganic ChemistryZhurnal obshchei Khimii. [See also Journal of GeneralChemistry (U.S.S.R.).]Zhurnal prikladnoi Khimii. [See also Journal of AppliedChemistry (U.S.S.R.).]Zhurnal tekhnicheskoi Fiziki.(Berichte der Bunsen-gellschaft fiir physikalische Chemie.)-Forschung.Ausgabe) .Unterricht.Analytical Chemistry (U.S.S.R.)].Physical Chemistry(U.S.S.R.) .]PRINTED IN GREAT BRITAIN BY RICHARD CLAY AND COMPANY, LTD.BUNGAY SUF-FOLK

ISSN:0365-6217    

DOI:10.1039/AR9595600461

出版商:RSC    

年代:1959

数据来源: RSC