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Proceedings of the Chemical Society. January 1957 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue January,
1957,
Page 1-32
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PROCEEDINGS OF THE CHEMICAL SOCIETY JANUARY 1957 THEProceedings of the Chemical Society at one time occupied a much more important place amongst the Society’s publications than has been the case in recent years. Nevertheless the fact remains that the Proceedings now form the only regular link which the Society maintains with the majority of its Fellows. It has long been the wish of Council to strengthen these links and a step in this direction is now being taken by revision of the scope and format of Proceedings. It is my privilege to commend this change to Fellows of the Society and to outline the plans made for the revised and enlarged Proceedings. As in the past the Proceedings will contain an official record of the Society’s business including notices of forthcoming meetings and records of the election of Fellows Officers Local Repre- sentatives and Committees.There will be how- ever many changes and additions designed to keep Fellows in touch with the work of the Society and with the general progress of chemical science. For instance it is proposed to publish abstracts of papers read at meetings of the Society together with an account of the discussions which followed. This will apply also to Symposia spon- sored by the Society if the papers presented are not to be published in full in the form of Special Publications The new Proceedings will contain the Report of the Anniversary General Meeting and the Special Lectures and Obituary Notices which have hitherto appeared in the Journal.It is pro- posed also to establish an entirely new feature by I the publication in the Proceedings of short Com- munications dealing with work which merits publicity before a full report can be prepared and published. These Communications will be refereed and edited. They are to be confined to scientific matters which can be regarded as of immediate importance to a substantial body of chemists. Details of the mode of operation of the new scheme will be found on page 18 of this issue. In addition Letters to the Editor on matters of general interest to chemists will be accepted sub-ject to Editorial discretion and from time to time it is hoped to include longer articles on subjects of special interest to Fellows.It is hoped that the new Proceedings will provide something of interest and value to each Fellow and with this end in view it has been decided to include items of topical interest such as new appointments of Fellows honours and awards made to Fellows the expected arrival in this country of scientists from overseas notices of awards open to competition announcements concerning kindred organisations accessions to the Library and so on. The Publication Committee has accepted responsibility for the new Proceedings and an Advisory Panel has been appointed to deal with its development. Suggestions comments and criticisms will be welcomed by the Editor and I appeal to all Fellows to assist in any way they can to make the new venture play its full part in maintaining the continued progress of the Chemical Society’s activities.E. L. HIRST PROCEEDINGS THE SOCIETY’S ANNIVERSARY MEETINGS AT CAMBRIDGE 1957 THISyear the Chemical Society’s Anniversary Meetings will be at Cambridge during four days April 9th to 12th 1957. The usual meetings and social events will be supplemented by three symposia with concurrent sessions extending over the whole period of the meeting. Fellows will be able to stay in Queens’ Sidney Sussex or Trinity College so social contacts should be easy; and the Small Examination Hall which is near the lecture theatres where meetings will be held will be fitted as a social room where Fellows and their guests may meet have coffee afternoon tea and refreshments and collect mail and tickets.Fellows may attend scientific meetings and symposia free of charge and without written application. Those who want abstracts of the papers read at symposia or to take part in the visits or social events or to stay in a College, pay a registration fee of lo/-. Non-Fellows pay a registration fee of 62 2s. Od. Accommodation in a College will be charged at a rate of 33/- per person per day all meals and gratuities in- cluded. Dinner Receptions Dances etc.-The Anni-versary Dinner will be in the evening of ApriI 10th. Limitations of space have made it neces- sary to divide this into two parts one in Trinity College and one in Queens’ College. The two dinners will however be equal in status (and price El 8s.Od.) and the toast list will be the same at each. The Society is most grateful that the follow- ing invitations have been extended By the Mayor of Cambridge to a reception and dance at the Guildhall on Tuesday April 9th 8.30 p.m.-12.30 a.m. By the Vice-Chancellor to a reception in the University Combination Room on April loth 6.00-7.15 p.m. By Aero Research Limited (a CIBA company) to a luncheon to be given in two parts at St. John’s College and the University Arms Hotel respectively on April 1 lth at 1 p.m. By Fisons (Pest Control) Limited to a reception and dance in the Dorothy Ballroom on April llth at 8.30 p.m.-12.30 a.m. There will be an organ recital in King’s College Chapel on April 1lth at 5.30-6.30 p.m.And Corpus Christi and Trinity Hall invite visitors to view their College silver. Visits and Tours.-There will be conducted tours of the Cambridge Colleges for those who do not already know their way round; and guides for the new Chemical Laboratory in Lensfield Road a large part of which is now complete and occupied. Visits have been arranged to Aero Research Limited W. G. Pye and Company Unicam Limited Fisons Limited Cambridge Instrument Company Limited Kayser Bondor Limited Chivers Limited and Tube Tnvestment Limited. There will also be opportunities for a visit to Sawston Hall and for a day tour of Wool Towns. Lectures.-There will be three lectures. The first will be given by Alderman G. F. Hickson on “Cambridge” after tea on Tuesday April 9th.Then on the following morning Professor H. Brockmann of Gottingen will deliver the Centenary Lecture “Photodynamically Active Natural Pigments”. On the morning of Thursday April llth the Annual General Meeting will be followed by the Presidential Address ‘‘Some Aspects of Chemistry of Fructosans” (Professor E. L. Hirst). Symposia.-An Organic Symposium on “Phosphoric Esters and Related Compounds” will occupy four half-day sessions. Those ex- pected to read papers include B. A. Arbuzov (Kazan) E. Baer (Toronto) F. H. Westheimer (Harvard) E. V. Spencer (London Ontario) F. R. Atherton J. Baddiley G. S. Hartley A. R. Peacocke H. N. Rydon M. Stacey and A. S. Jones Sir Alexander Todd. A Physicochemical Symposium on “Reactions of Free Radicals in the Gas Phase,” will occupy four half-day sessions.Among those reading papers the following are expected W. Jost (Gottingen) Dr. Wagner (Gottingen) P. G. Ashmore C. E. H. Bawn F. S. Dainton W. H. T. Davison P. Gray Sir Cyril Hinshelwood K. J. Ivin and F. Wilkinson H. C. Longuet- Higgins R. G. W. Norrish J. C. Robb and R. Burgess T. M. Sugden and E. M. Bulewicz B. A. Thrush A. F. Trotman-Dickenson A. D. Walsh. JANUARY 1957 An Inorganic Symposium on “Recent Aspects of the Inorganic Chemistry of Nitrogen” will occupy three half-day sessions. Those expected to read papers include M. Goehring (Heidelberg) J. Jander (Freiburg) F. See1 (Wiirzburg) C. C. Addison C. A. Bunton B. G. Gowenlock W.C. E. Higginson J. Lewis R. E. Richards P. L. Robinson D. A. Spratt. Abstracts of the papers to be read will be available for those registering. Later the papers will be published in full together with reports of the discussions. in the series of Chemical Society Special Publications. Details.-The full programme and an applica- tion form are circulated with this issue of Proceedings. Details of times and prices and of the Symposia are given there. Numbers are limited for some of the social events and for the visits; so early application is urged and in any case not later than Monday March 1 lth 1957. NEWS AND ANNOUNCEMENTS I.U.P.A.C. Meetings in Paris.-Forthcoming meetings of the International Union of Pure and Applied Chemistry include an International Sym- posium on Purity Control by Thermal Analysis to be held in Amsterdam April 24-26th.Further particulars may be obtained from the Secretary Dr. W. M. Smit Centraal Institut voor Physisch- Chemische Constanten-Biltstraat 172 Utrecht Netherlands. As has been announced in Proceedings and else- where the XVIth International Congress of Pure and Applied Chemistry will be held in Paris on July 18-24th. Fellows wishing to attend who have not received a copy of the preliminary circular are urged to communicate without delay with M. le SecrCtaire GCnCral du XVIe Congrks International de Chimie Pure et Appliquk 28 Rue Saint-Dominique Paris 7e. In addition to the Congress and to the XIXth Conference of the Union to be held from July 16th to 25th symposia are being organised under the auspices of various sections of the Union to take place in Paris during July.The Physical Chemistry Section is arranging a symposium on Structure Properties Relationships of Polymers (Secretary Dr. P. Dubois Centre d’Etudes des Matibres plastiques 28 Rue Saint- Dominique Paris 79. The Section of Biological Chemistry is arranging a symposium on Protein Chemistry. Particulars may be obtained from Professor E. J. King London Post-Graduate Medical School Duane Road London W.12. A symposium on Geochemistry will be held on July 1619th under the auspices of the Commission of Geochemistry as part of the meeting of the Section of Inorganic Chemistry. Details are available from the Chairman of the Commission Dr.Michael Fleischer U.S. Geological Survey Washington 25 D.C. U.S.A. International Symposium on Macromolecular Chemistry.-A meeting organised under the auspices of I.U.P.A.C. will be held in Prague Czechoslovakia September 9-15th 1957. The Symposium will be devoted to two main topics (a) Physics and Physical Chemistry of Macromolecular Substances; (b) Polyreactions. Further subdivision will be considered according to the nature of the papers received. Each topic will be introduced by a main lecture. Provisional applications are requested before the end of February 1957 and final application forms will be sent out in March. Full particulars can be obtained from the Organising Committee inter- national Symposium on Macromolecular Chemistry Prague 1957,5 Technicka Prague 6 Czechoslovakia or from Mr.J. C. Bevington Chemistry Depart- ment The University Birmingham. International Symposium on Hydrogen Bonding.-A meeting under the auspices of I.U.P.A.C. and the Union of the Chemical Societies of Yugoslavia will be held at Ljubljana (Yugoslavia) between July 30th and August 3rd 1957. Papers on all aspects of hydrogen bonding (spectroscopy crystallography dielectric properties theoretical interpretations influence upon various physicochemical processes) are invited. Additional information may be obtained from Slovensko kemijsko drugtvo Hajdrihova 19 Ljubljana Yugoslavia. International Union of Crystallography.-The International Union of Crystallography has accepted the invitation of the National Research Council of Canada to hold its Fourth General Assembly and International Congress in Canada from July 10th to 17th 1957 followed by two symposia on the 18th and 19th.At the Congress papers will be presented on all aspects of crystallographic re- search; the subjects of the symposia will be “Physical Techniques of Crystallographic Interest” and “Electron Diffraction.” Through the co-operation of McGill University and the Universitv of Montreal the meetings are being held in the City of Montreal. Technical excursions to other parts of the Province of Quebec and to sections of the Province of Ontario are being arranged. The Canadian National Committee on Crystallo- graphy is acting as the Local Committee of the Congress and has prepared a brochure giving details of the technical programme topics and of accom- modation for the Congress.Copies of this have been forwarded to the Secretaries of the National Com- mittees of the Member Countries of the Union. Copies may be obtained from them; from the General Secretary of the Union Dr. D. W. Smits Labora- torium voor Anorganische en Fysische Chemie Bloemsingel 10 Groningen The Netherlands ; or from the Secretary of the Canadian Committee Dr. W. H. Barnes Division of Physics National Re- search Council Ottawa 2 Ontario Canada (envelope to be marked “Personal”); or from the Chairman of the Programme Committee Dr. W. N. Lipscomb School of Chemistry University of Minnesota Minneapolis U.S.A.Symposium on Solvent Effects and Reaction Mechanism.-This Symposium is being arranged by the Chemistry Department of Queen Mary College with the support of the Chemical Society. It will be held in the Queen’s Building Queen Mary College London E.l on the afternoon of July 8th and in the morning and afternoon of July 9th 1957. The following have expressed their willingness to participate Professor E. A. Amis Professor P. D. Bartlett Mr. R. P. Bell Professor M. L. Bender Dr. C. A. Bunton Professor M. J. S. Dewar Professor W. Doering Professor A. G. Evans Dr. R. J. Gillespie Dr. V. Gold Dr. R. F. Hudson Professor C. K. Ingold Professor J. E. Leffler Dr. F. A. Long Dr. V. J. Shiner Dr.C. Wilson. A further announcement giving full details will be made in April. Symposium on Terpenoid Compounds.-The Society has arranged to hold a meeting in Glasgow on “Recent Advances in the Chemistry of Terpenoid Compounds” on July 11-12th 1957. The President will open the proceedings and the ensuing sessions will be under the chairmanship of Sir John Simonsen Professor John Read Professor E. R. H. Jones and Professor A. J. Birch. Professor Sir Ian Heilbron has agreed to attend and to take the chair at the Dinner which is to be arranged during the meeting. The following have agreed provisionally to make contributions to the Symposium :Professor D. H. R. Barton Professor A. J. Birch Professor G. Biichi Professor W. Cocker Dr. R.C. Cookson Dr. T. G. Halsall Professor 0. Jeger Professor E. R. H. Jones Dr. R. N. Jones Dr. F. J. McQuillin PROCEEDINGS Professor G. Ourisson Professor R. A. Raphael Professor F. Sorm Professor F. S. Spring Professor F. S. Wenkert Dr. W. B. Whalley Professor K. Wiesner. Further details and registration forms will be circulated in due course. The Perkin Centenary Trust.-The following awards for educational purposes relating to the manufacture or the application of colouring matters have been announced by the Perkin Centenary Trust. The Perkin Centenary Fellowship is to be offered for one or two years to a graduate for the purpose of higher study. It will have a value of f600per annum and will be tenable at any university or technical college approved by the Trustees.Two Perkin Centenary Scholarships will be offered each for two years renewable at the discretion of the Trustees for one further year to enable candidates employed in the appropriate industries to receive an education at a university or technical college. Each award will have a value of f300 per annum. There will be no means test for the award and a successful candidate shall not be debarred from receiving the whole or a part of his normal salary from his employers during his tenure of the Scholar- ship. Two Perkin Exchange Lectureships are also created. The first of short term is intended to enable a senior teacher at any appropriate university technical college or other institution to visit scme similar establishment overseas in order to deliver a short course of lectures.In return a similar visit to a British institution by some overseas scientist will be arranged. A second appointment contemplated will permit the exchange of lecturers for a period of up to one year between some British university technical college or other institution and a similar institution overseas. The Perkin Centenary Trust was established in January 1956 to administer the funds subscribed to commemorate the discovery of the first synthetic dyestuff by Sir William Perkin in 1856. The Trustees are Mr. H. Jackson (Chairman) Dr. D. W. Hill Dr. L. H. Lampitt Mr. W. Mathers Mr. M. W. Perrin and Sir Robert Robinson. The Secretary to the Trustees is Mr.J. R. Ruck Keene to whom enquiries relating to the above awards should be addressed c/o The Chemical Society Burlington House London W.l. The History of Chemistry.-Nominations are invited from individuals for the 1957 Dexter Award in the history of chemistry which is administered by the Division of History of Chemistry of the American JANUARY 1957 Chemical Society. This award is made on the basis of services which have advanced the history of chemistry in any of the following ways by publica- tion of an important book or article; by the further- ance of the teaching of the history of chemistry; by significant contributions to the bibliography of the history of chemistry; or by meritorious services over a long period of time which have resulted in the advancement of the history of chemistry.All pertinent information concerning nominees should be sent by March 10th to Dr. Sidney M. Edelstein Secretary Division of History of Chemistry American Chemical Society 819 Edge- water Road New York 59 N.Y. U.S.A. Special Publications.-The report of the Sym- posium first published in November 1954 under the title “The Kinetics and Mechanism of Inorganic Reactions in Solution. A Survey of Recent Work” (Special Publication No. l) which has been out of print for several months is now once more available and can be obtained from The General Secretary. Price 151- per copy. Special Publication No. 5 “Antibiotics and Mould Metabolites” the report of a Symposium held during the 1956 Anniversary Meetings in Notting- ham has also now been issued.Price 151-. Fellows who have ordered copies can expect to receive them in the near future. The next two volumes in the series to be published by the Society during 1957 under the auspices of I.U.P.A.C. are Tables giving Stability Constants of Metal-ion Complexes with Stability Products of Inorganic Substances. Complex compounds have assumed increased importance in many branches of chemistry not merely for co-ordination chemistry but also for analysis catalysis biochemistry and even biology particularly where trace concentrations of metal ions are concerned. Their stability constants have been widely scattered. So under the auspices of the Commission of Equilibrium Data of the Section of Analytical Chemistry of the Union of Pure and Applied Chemistry a compilation of these stability constants already begun by Professor Jannik Bjerrum was extended and brought up to date by him and by Professors Gerold Schwarzenbach and Lars Gunnar Sillkn and their collaborators.These Tables will be in two Parts dealing respec- tively with organic and inorganic ligands and forming Nos. 6 and 7 in the Society’s series of Special Publications. The price will be f3 and f2 respectively but both Parts will be available at the special combined price of f4 for prepaid orders received by the Society before June lst 1957. Full details and specimen entries will be circulated to Fellows. New Year Honours List.-Awards to Fellows announced in the New Year Honours List include Sir Harold Hartley (G.C.V.O.); Dr.B. K. Blount Deputy Secretary D.S.I.R. (C.B.); and Dr. H. Phillips Director of Research and Secretary British Leather Manufacturers Research Association (0.B.E.). Deaths.-The death is announced on December 16th 1956 of Professor F. G. Donnan C.B.E. F.R.S. formerly Professor of General Chemistry at University College London and President of the Society 1937-1939. A full obituary notice will be published in due course. The death is also reported of Mr. David Avery (27.10.56) of Berwick Victoria Australia a Fellow since 1892; of Mr. S. R. Best (19.10.56) of Cheadle Hulme Cheshire formerly a consulting chemist ; of Mr. J. S. Buck (9.8.56) of Albany New York; and of Dr.T. R. Burnett (28.8.56) of Kirkton Dumfries who was elected in 1900. We also record with regret the death of Dr. R. E. De Lury (29.9.56) who was until his retirement in 1946 Acting Director of the Dominion Observatory Ottawa; of Mr. G. Fearnley (Nov. 1955) of Inter- national Paints (Canada) Limited; of Dr. Thomas Thomson (21.1 1.56) an Assistant Manager at Imperial Chemical Industries Limited Nobel Division and of Mr. Leo Wallerstein of Wallerstein Co. Inc. New York. Retirement.-Professor Alexander Robertson F.R.S. is to retire from the Heath Harrison Chair of Organic Chemistry in the University of Liverpool as from the end of the present session. Appointments.-Dr. Ronald Holroyd Director in charge of research had been elected a deputy-chairman of Imperial Chemical Industries Limited with effect from January lst in place of Mr.A. J. Quig who is retiring after nearly 50 years’ service with the company and its predecessors. There are two other I.C.1 deputy-chairmen Mr. S. P. Chambers and Sir Ewart Smith. Dr. Holroyd who is 52 joined I.C.I. in 1928. He went to Billingham Division in 1930 and rose to be joint managing director of the Division in 1951. In 1952 he joined the I.C.I. main Board. Professor D. H. R. Barton D.Sc. F.R.S. Regius Professor of Chemistry in the University of Glasgow has been appointed to the University Chair of Organic Chemistry tenable at the Imperial College of Science and Technology London. Professor Barton is to visit the United States in April to receive the Fritzche Medal of the American Chemical Society.Mr. George Brearley a partner in Messrs. Cremer & Brearley consulting chemical engineers has been appointed as Director of the Association of British Chemical Manufacturers in succession to Mr. J. Davidson Pratt who is to retire in June next. In order to allow for a period of overlap Mr. Brearley will take up his appointment on April lst 1957. The title of “Reader in Chemistry in the University of London” has been conferred on Dr. P. B. D. de la Mare M.Sc. (New Zealand) Ph.D. D.Sc. in respect of his post at University College London. Dr. J. Honeyman has resigned from his Lecture ship at King’s College London in order to take up an appointment on January lst 1957 as Head of the Chemistry Department at the British Cotton Industry Research Association (Shirley Institute).Dr. C. W. Rees Lecturer in Chemistry at Birkbeck College has been appointed Lecturer in Chemistry at King’s College London from October lst 1957. The Court of the University of Durham has approved the establishment of a Professorship of Inorganic Chemistry in the Newcastle Division for October Ist 1957. Visitors.-The title of Visiting Professor in the University of Leeds has been conferred on Professor P. R. O’Connor Chief and Associate Professor of the Inorganic Division of the School of Chemistry of Minnesota University who will be working in the Department of Chemistry at Leeds during the period April 1st to August lst 1957.Dr. Frank A. Long Professor of Chemistry of Cornell University since 1946 and Chairman of the Department of Chemistry since 1950 will be staying at University College as Honorary Research Associate for the Session 1956-57. Professor Long is to lecture to the Society in London on February 28th on “Application of Acidity Functions to the Mechanisms of Acid-catalyzed Reactions”. Professor H. C. Urey (Honorary Fellow) is spending the current academic year at Oxford as Eastman Professor. He is to lecture to the Society in London on March 14th on “Chemical Problems relating to the Origin of the Earth”. Awards and Congratulations.-Professor A. W. K. Tiselius Honorary Fellow has been elected as President of the Royal Swedish Academy of Sciences and Professor W.T. Astbury Professor of Bio-molecular Structure in the University of Leeds has been elected an Honorary Foreign Member of the Academy. The Honorary degree of Doctor of Science was conferred on Sir Henry Tizard by H.M. Queen Elizabeth the Queen Mother Chancellor of the PROCEEDINGS University of London at a ceremony held in the Senate House on November 23rd. The President has congratulated Mr. William Stone (London) on reaching his hundredth birthday; Mr. Stone has been a Fellow of the Society since 1879. Mr. S. J. Pentecost of Nottingham completed seventy years as a Fellow of the Society on December 16th and has been congratulated by the President. On leaving school Mr. Pentecost studied at the Technical College Nottingham where he was associated with F.S. Kipping and continued his association with the College later in life when he gave lectures on bleaching and dyeing. Mr. Pentecost who is now aged 93 still goes to work every day with his firm Messrs. Hicking Pentecost & Co. Ltd. bleachers and dyers of Nottingham. The President also congratulated the following who have completed 50 years of Fellowship Oscar Walter Bethea (New Orleans) Percy Henry Carpenter (Sussex) Hubert Frank Coward (Sheffield) Archibald Prideaux Davson (London S.E.1) John Hamer (Bolton) H. Norman Hanson (Scarborough) Robert Le Rossignol (Beaconsfield) Sir John Simonsen (Putney Heath) Election of New Fellows.41 Candidates whose names were published in the Proceedings for November were elected to the Fellowship on December 13th 1956.Research Fund.-Grants for research have been awarded by Council to the following f. s. a. Battersby A. R. (Bristol) .. .. .. 35 0 0 Brown M. G. (Winchester) .. .. .. 35 15 6 Buchwald H. (Whitehaven) . . .. .. 13 10 0 Cadogan J. I. G. (London) . . .. .. 26 7 3 Cavell E. A. S. (Southampton) .. .. 15 0 0 Cort L. A. (London) . . .. .. .. 18 15 0 Evans A. G. (Cardiff) .. .. 50 0 0 Graham S. H. (Aberystwyth) ‘ .. .. 30 0 0 Gray G. W. (Hull) .. .. .. 35 0 0 Guthrie R. D. (London) .. .. .. 21 0 0 Hadzi D. (Yugoslavia) . . .. .. 30 0 0 Hoare D. E. (Dundee) .. .. .. 25 1 6 Kurzer F. (London) .. .. .. .. 15 0 0 Landor S. R. (London) .... .. 30 0 0 Leicester J. (London) .. .. .. 17 0 0 Lewis J. (London) . . .. .. .. 30 0 0 Mason S. F. (Exeter) .. .. .. 33 18 3 Monks E. R. (London) .. .. .. 30 0 0 0 Colla P. S. (Galway) .. .. ,. 50 0 0 Peacock R. D. (London) .. .. .. 30 0 0 Pinder A. R. (Cardiff) .. .. .. 25 0 0 Raphael R. A. (Belfast) . . .. .. 30 0 0 Schofield K. (Exeter) .. ,. .. .. 40 0 0 Whelan W. J. (London) .. .. .. 15 0 0 JANUARY 1957 SCIENTIFIC MEETING OF THE SOCIETY THE President was in the Chair at a Scientific Meeting of the Society at Burlington House on Thursday November 15th 1956. In his introductory remarks he stated that the meeting was coupled with a tribute to Sir Ian Heilbron on his seventieth birth- day and referred particularly to the affectionate regard in which Sir Ian was held by his colleagues; he offered him the Society’s congratulations on his “scientific” though not his calendar birthday.The papers to be read were from a group which had been submitted by past and present collaborators for publication in honour of the occasion in the November Journal. The Aporphine Series. Part II. Application of the Bischler-Napieralski Reaction to 2-Nitrophenyl- N-phenethylacetamides. By D. H. HEYand A. L. PALLUEL. The application of the Bischler-Napieralski reaction to 2-nitrophenyl-N-phenethylacetamides to convert them into 3 :4-dihydro-1-2’-nitrobenzyliso-quinolines is of special interest for three reasons. In the first place this reaction constitutes an essential stage in Spath and Hromatka’s synthesis1 of apo-morphine dimethyl ether although the method had failed at the hands of Kay and Pictet of Kondo and of Gulland and Haworth and their co-workers.Secondly Spath and Hromatka’s reaction provides the only known example of the ring closure of an o-nitrophenyl-N-phenethylacetamide into a 3:4-dihydroisoquinoline in which the nucleus involved in the ring closure is not activated by the presence of a suitable substituent atom or group. Thirdly when- ever a 3 :4-dimethoxy-2-nitrophenyl-N-phenethyl-acetamide is subjected to the experimental condi- tions required for the Bischler-Napieralski reaction there is invariably formed sometimes as the sole product a neutral compound which is isomeric with the desired dihydroisoquinoline.Such neutral com- pounds have been represented as either (a) keten imines or (b)acetylenic compounds but experimental evidence for such structures has never been obtained. Spath and Hromatka’s preparation of 1-(3:4-dimethoxy-2-nitrobenzyl)-3:4-dihydroisoquinoline (11) from 3 :4-dimethoxy-2-nitrophenyl-N-phenethyl-acetamide (I) has now been repeated (for the first time) and the neutral isomeric by-product is shown to be neither the keten imine (111) nor the acetylenic derivative (IV) but a derivative (V)of anthranil-3- carboxylic acid. The evidence for the anthranil structure is based on the fact that hydrolysis of the neutral compound with alcoholic potassium hydroxide gave phenethyl- ~_ Spath and Hromatka Ber.1929,62 326. amine and 6 :7-dimethoxyanthranil-3-carboxylicacid. If the neutral compound had either a keten imine or an acetylenic structure hydrolysis should have led to some 3 :4-dimethoxy-2-nitrophenylacetic acid which was never found. The 6:7-dirnethoxyanthranil-3-carboxylic acid was identical with an authentic specimen prepared from either 3 :4-dimethoxy-2-nitrophenylacetic acid or 3:4-dimethoxy-2-nitro-mandelic acid by known methods. The synthetic acid was also converted into its phenethylamide which was shown to be identical with the neutral product from the Bischler-Napieralski reaction. The identity of these compounds was confirmed by ultraviolet and infrared spectroscopy. Me 0 N-0 MeouCO*NH*CH2CHPh Me0 (Y) The identity of the 1-(3:4-dimethoxy-2-nitro-benzyl)-3:4-dihydroisoquinoline (11) was confirmed by its conversion into the hydrochloride of (f)-apo-morphine dimethyl ether (VI) the ultraviolet absorp- tion spectrum of which was identical with that of (-)-apomorphine dimethyl ether hydrochloride pre- pared from (-)-apomorphine hydrochloride.Discussion. Dr. R. A. ABRAMOVITCH made the following contribution In an attempt to decide which struc- ture ortho-quinonoid or benzenoid was to be applied to anthranil and its derivatives some of these com- pounds were studied by means of infrared spectro- scopy. Of particular interest were the positions of the carboxyl bands in anthranilcarboxylic acid. The two possible extreme forms can be exemplified by the o-quinonoid (I) and the dipolar benzenoid form (11).In (I) the carboxyl group would be expected to behave like a strongly ap-conjugated acid and should therefore absorb at 169&1710 cm.-l. On the other hand if the structure is correctly repre- sented by (11) the carboxyl group would be similar to one having a strongly electron-attractive sub-stituent in the cc-position and would therefore be expected to absorb in the 1730-1740 cm.-l region. In fact anthranil-3-carboxylic acid itself had the carboxyl band at 1733 cm.-l indicating that it exists mainly as (11). This was confirmed by the presence of a strong band at 752 cm.-l attributed to an ortho- disubstituted benzene band as well as a band at 1520 (phenyl) though the band at 1637 cm.-l was at a higher frequency than was expected and might be considered as being due to a contribution from the C= N.In the case of 6:7-dimethoxyanthranil-3-carboxylic acid however the carboxyl band was present at 1695 cm.-l indicating that it probably existed mainly in the form (I). This was in accord with the colour of the acids the unsubstituted acid is colourless the dimethoxy-acid deep yellow (quino- noid?). The dimethoxy-acid had no band at ca. 750 cm.-l but had bands at 1645,1575,1536 and 803 cm.-l. Anthranil itself had a strong band at 75 1 cm.-l (ortho-disubstituted benzene) as well as strong bands at 1527 and 11 15 cm.-l indicative of a benzenoid structure though again the band at 1650 cm.-l was at a higher frequency than is usually found.These results confirm those of Jensen and Friediger2 who from the dipole moment of anthranil (3-06 D) concluded that it could be represented as a 3 :4-benzisooxazole with two mesomeric condi- tions (111)-(V). It seems therefore that according to the type of substituent present in the molecule either form (I) or form (TI) contributes more to the Jensen and Friediger Clzern. Zentr. 1944 I 416. PROCEEDINGS actual structure so that the anthranil molecule falls within the scope of Professor Wi!son Baker’s defini- tion of a mesoionic compound since it cannot be represented satisfactorily by any one covalent or polar structure and fulfils all the other conditions required of such compounds. Professor Wilson Baker has suggested to the authors that the anthranil molecule might best be represented by structure (VI).tJ((0 (m H Professor HEY pointed out that although the ultraviolet and infrared spectra of the neutral com- pound from the Bischler-Napieralski reaction were somewhat difficult to interpret they did serve to rule out the alternative keten imine and acetylenic struc- tures. In answer to further questions he stated (a) that if phosphorus pentachloride is used in place of phosphoric oxide in the Bischler-Napieralski reac-tion with 3 :4-dimethoxy-2-nitrophenyl-N-phenethyl-acetamide the sole product is the neutral compound and (6) that the probable reason why previous workers had failed to repeat Spath and Hromatka’s synthesis of apomorphine dimethyl ether was because they had failed to appreciate that the hydrochloride of the dihydroisoquinoline is soluble in chloroforni their products were most probably inadvertently consigned to the sink! Chemistry of the Higher Fungi.Part VI.Isomerisation Reactions of Naturally Occurring Allenes. By J D. BU’LOCK,E. R. H. JONES,P. R. LEEMING, and J. M. THOMPSON. Cultures of the Basidiomycete “B.841” produce nemotinic acid (I) and the corresponding lactone nemotin (11). They were separated from one another and from a related pair of compounds odyssic acid and odyssin by counter-current distribution of ethyl acetate extracts of the culture medium. In spite of their instability conclusive evidence for the structures (I) and (11) was ~btained.~ (I) HC C C C CH C CH CH(OH) CH CH CO,H (a) HC C C C CH C CH CH CH CH CO I.3 One of the most striking properties of nemotinic acid and nemotin is their instability towards dilute aqueous alkalis nemotin being changed at pH 10 into nemotin A and nemotinic acid being converted by 0.1 N-sodium hydroxide into isonemotinic acid.Both of these changes are accompanied by profound alterations in the ultraviolet absorption spectra; nemotin has the ultraviolet absorption of an ene- triyne and is optically inactive whilst isonemotinic Bu’Lock Jones and Leeming J. 1955 4270. JANUARY 1957 -acid shows the characteristic low-intensity triyne absorption but retains weak optical activity. In both cases the sharp allene peak at 1960cm.-l in the infra- red spectrum disappears.isoNenaotinic acid has been shown to have structure (HI) since it contains an acetylenic hydro- gen atom and on hydrogenation and distillation of the product (+)-y-undecanolactone is produced. Nernotin A (C1,H,CO,H) also contains an acetyl- enic hydrogen atom; on hydrogenation it is con- verted into undecanoic acid and hence it must be represented by structure (1V). HC! c-c:C.C:C.CH,.CH (OH) CH2.CH2.C0,H HCiC*CrC.CiC.CH CH*CH,.CH,*CO,H Rearrangements of allenic compounds under alkaline conditions are well known and one of the most striking examples is that of mycomycin into isomy~omycin.~ The behaviour of nemotinic acid and nemotin is discussed in relation to that of mycomycin and other allenic systems.Pulcherrimin A Synthesis of 1:4-Dihydroxy-2:5-dioxopiperazines. By A. H. COOKand C.A. SLATER. Pulchcrrimin a pigment produced under certain conditions by the yeast Candida pulcherrima was formulated by Kluyver et aL5 on limited evidence as the ferric complex of 2 :5-diisobutyl-l :4-dihydroxy-3 :6-dioxopiperazine (1). This formulation was for a time supported by further degradation studies,6 par- OH I BU~CHB~5B~ICH (11) ' /NH -+ wI I HO,C ?H QH ticularly on the parent pulcherriminic acid supposed to be represented by (I) and the synthesis of this compound was accordingly undertaken. After pre- liminary work on the preparation and behaviour of representative 2-hydroxyamino-acids the synthesis of the compound (I) was accomplished by the route .-_______I shown.Certain analogues and by substituting ammonia for hydroxylamine corresponding 2 :5-di-isobutyl-monohydroxy-3:6-dioxopiperazines were also obtained. None of the synthetic compounds however in any way resembled pulcherriminic acid. In particular the synthetic compound (I) had quite different physical characteristics and gave with ethanolic ferric chloride only a red colour and not a highly insoluble pigment as does pulcherriminic acid. The original formulation for the pigment was therefore abandoned. OH OH 1 I Pulckrrirninic acid AqzrgiIIic acid BXE30 x",p H H Bu' BU' H 0 (a) Re-investigation suggests that the structures of the acid of natural origin and of all its derivatives con- tain two fewer hydrogen atoms than were previously supposed.On this basis pulcherriminic acid may be formulated as 01). This pyrazine formulation is compatible with the infrared absorption charac- teristics especially as compared with those of aspergillic acid (111). Moreover its ferric complex would exhibit an Fe:N ratio in agreement with that actually found in pulcherrimin. Finally it explains how pulcherriminic acid gives on reduction a dideoxy-compound (IV) which only on further reduction passes into leucine anhydride (V). Discussion. Dr. J. A. ELVIDGE asked two questions (1) Has the leucine anhydride degradation product been identified with certainty? In degrading aspergillic acid Dutcher and Wintersteiner obtained a dioxo- piperazine indistinguishable from isoleucine an-hydride.Their structure for aspergillic acid based on this was incorrect however. Dunn Newbold and Spring subsequently showed that the dioxopipera- zine product appeared identical also with leucine isoleucine anhydride. Not until they had hydrolysed the dioxopiperazine effected a separation of the amino-acids through copper salts and obtained aldehydes via reaction with ninhydrin did it become clear that the aspergillic acid degradation product Celiner and Solomons J. Amer. Chem. Soc. 1952 74 1870 and later papers. ___ Kluyver van der Walt and van Triet Proc. Nat. Acad. Sci. U.S.A. 1953,39 583. * Cook and Slater J. Inst. Brewing,1954,60 213. was leucine isoleucine anhydride.(Paper chromato- graphy of the amino-acids given on hydrolysis was incapable of demonstrating this.) Have the side chains in pulcherriminic acid therefore been com- pletely established ? (2) The formation of a precipitate with ferric salts by pulcherriminic acid contrasts with the mere production of a red colour by aspergillic acid. The latter however gives a precipitate with copper salts. Does pulcherriminic acid do so-is it a potential gravimetric reagent for cupric (and other) ions? In reply Dr. COOKsaid that the nature of the dioxopiperazine degradation product of pulcher-rimin had been unequivocally established by hydro- lysis followed by chromatographic analysis. Only leucine uncontaminated by any other amino-acid was detected.Pulcherriminic acid did not yield a highly insoluble precipitate with copper ions and indeed extensive PROCEED~NGS search had failed to reveal any other metal ions which gave complex salts comparable with pulcher- rimin itself. In reply to a question by Dr. V. PETROW, Dr. C. A. SLATERquoted a statement by Van der Walt’ that when Candida pulcherrima was grown in the absence of iron the resulting colourless yeast was not reddened on treatment with ferric chloride solution. He concluded therefore that iron is essential for the production of pulcherrimin by the yeast. However it was found in one experiment that when C.pulcher-rinm was grown in the absence of iron and then extracted with methanolic potassium hydroxide the solution so obtained gave on acidification and sub- sequent treatment with ferric chloride solution a red precipitate which was apparently identical with pulcherrimin.Van der Walt Proefsch. Tech. Hoges. Dewt 1952 NEWER INTERPRETATIONS OF REACTIONS AND STRUCTURE IN CARBOHYDRATE CHEMISTRY (REPORT 1ST 1956, OF A CHEMICAL SOCIETY SYMPOSIUM,HELD ON NOVEMBER AND ORGANISED BY DR.G. R. BARKER) THISSymposium which took place in the Depart- ment of Chemistry of University College London was attended by upwards of two hundred Fellows of the Society. Afternoon and evening sessions were held and papers were delivered by five principal speakers. Between the two sessions there was an informal dinner in the dining room of the University College Club at which approximately seventy Fellows and guests were present.The President expressed the indebtedness of the Society to University College and welcomed Dr. R. U. Lemieux of Ottawa the principal guest. With Dr. G. R. Barker in the Chair the afternoon session of the Symposium was opened by Professor E. J. Bourne of Royal Holloway College London who spoke on “Some physical methods used in the determination of carbohydrate structures.” Professor Bourne outlined various techniques for the determination of infrared spectra of carbo-hydrates. The use of discs of potassium bromide containing approximately 1% of the compound under test was particularly convenient since samples could be kept in this form for future reference. How- ever unless special precautions were taken the spectra sometimes changed on storage of the discs and this was shown to be due to hydration of the sample.As little as 0.1 % of moisture in the potassium bromide is sufficient to cause these changes and it was recommended that the potassium bromide should be dried at 650”for 4 hours before use. Under these conditions a-and /%glucose exhibited distinct and stable spectra. Professor Bourne emphasised the usefulness of infrared spectroscopy for comparison of supposedly identical materials and for the analysis of mixtures. He also illustrated its application to the detection of polar groups for example in the assessment of the completeness of methylation of a polysaccharide. Certain information could also be obtained about the ring size conformation and anomeric character of a carbohydrate.The application of infrared and Raman spectroscopy to acetal ring systems was also described. Professor Bourne then outlined a method developed by Dr. D. H. Whiffen for calculating molecular rotations from certain parameters which are functions of structure. The method was based on the assumption that the molecular rotation of a cyclic carbohydrate depends largely on contributions from bonds rather than asymmetric centres and very close agreement was obtained between calcu- lated and experimental values for a variety of sugars and their derivatives. In the discussion that followed Professor Bourne’s paper Dr. Whiffen described some preliminary work on the application of electron spin resonance spectro- scopy to the study of radicals produced by the action of ionising radiations on carbohydrates.Dr. Lemieux made the observation that for certain purposes potassium bromide plates could be made con- JANUARY 1957 veniently by lyophilising a solution containing potassium bromide and the material under test. In the second paper of the afternoon on “Toluene- p-sulphonic esters and three-membered oxide rings,’’ Dr. J. C. P. Schwarz of Edinburgh outlined the steric factors influencing the formation and the reactions of these compounds. He pointed out that in the absence of kinetic studies on toluene-p-sulphonic esters precise interpretations were impossible but it seemed clear that steric effects were responsible for the preferential toluene-p-sulphonylation of primary hydroxyl groups and the more rapid esterification of equatorial secondary hydroxyl groups than of axial groups.Similar considerations explained variations in the behaviour of different toluene-p-sulphonic esters towards such reagents as sodium iodide sodium methoxide sodium hydroxide sodium methyl sulphide and lithium aluminium hydride. Examples were chosen to illustrate how hindrance encountered by the incoming group may determine the relative reactivities of the sulphonic esters. Participation of a neighbouring group materially affected the behaviour of sulphonic esters and it was shown how cyclisation and elimination necessitated a biaxial distribution of the adjacent residues so that the four centres involved lay in one plane.The rate of these reactions therefore depends on the ease with which the biaxial arrangement can be attained. In the subsequent discussion Dr. G. N. Richards and Dr. Schwarz indicated that coplanarity of four centres was necessary for eliminations of the type whereby 3-0-methanesulphonyl- or 3-0-toluene-p-sulphonyl-D-glucose is converted into 2-deoxy-~- ribose. Dr. H. B. Henbest drew attention to a case in which the fission of a three-membered oxide ring gave the unexpected diequatorial product and Dr. Schwarz mentioned that a high proportion of the diequatorial product had been obtained in the fission of methyl 2 :3-anhydro-4 :6-0-benzylidene-a-~-alloside with methylmagnesium iodide.The final paper of the afternoon session was given by Dr. A. B. Foster of Birmingham on “Conforma- tional aspects of the formation and reactions of certain cyclic derivatives of carbohydrates.” Dr. Foster first showed that the preferred reactions of acyclic polyalcohols with aldehydes to yield cyclic acetals could be correlated with (a)the conformation of the polyol and (b)the thermodynamic stability of the cyclic acetals formed under equilibration con- ditions which establish equilibrium. The different affinities of aldehydes and ketones for certain diols could be rationalised similarly. The formation of acetals by cyclic polyols was governed partly by the distribution of the substituents attached to the result- ing bicyclic system.Thus condensation of acetone with the hydroxyl groups at positions 1 and 2 of ribose would produce a system possessing an endo- hydroxylmethyl and one endo-methyl group whereas in fact condensation takes place with hydroxyl groups at positions 2 and 3 and results in only one endo-group. Dr. Foster described how the ease with which diols yield cyclic complexes with the borate ion could be assessed readily by measurement of the electro- phoretic mobility of the diol in presence of borate. Thus the lower mobility of methyl cc-D-glucopyrano- side under these conditions compared with that of j3-anomer is due to repulsive non-bonded interactions which reduce the stability of the borate complex of the former substance.In an analogous manner reduction of the non-bonded interactions in a diol- borate complex increases its stability and engenders a higher electrophoretic mobility. This effect was observed when a methylene group in cycfohexane- cis-1 :2-diol was replaced by oxygen to yield the corresponding pyrandiol. Steric factors (non-bonded interactions resulting from axially disposed hydroxyl groups) were also shown to determine the facilities of various hexoses in forming 1 :6-anhydro-com-pounds in acid solution and to control the ease of formation of “tridentate” borate complexes of certain inositols. In the evening session under the chairmanship of Professor Stacey Dr. W. G. Overend of Birkbeck College discussed the “Hydrolysis of glycosides.” It was pointed out that pentosides methylpentosides hexosides and heptosides exhibited increasing stability towards hydrolysis in the order given and analogies for these differences were drawn.In the case of a five-membered ring compound a closer approach was possible to the structure required for the transition state of an SN2 reaction. The hydrolysis of hexopyranosides was considered as the decom- position of the conjugate acid produced in the initial protonation. This decomposition as was to be ex- pected followed the unimolecular law and it rather than the protonation is the rate-determining step. In the transition state the ring was believed to be in a half-chair conformation and on the basis of this interpretation of the reaction it was possible correctly to predict the relative rates of hydrolysis of a number of glycosides.The final paper of the Symposium was given by Dr. R. U. Lemieux of Ottawa on “Reactions at the anomeric centre of acetylated glycopyranosyl acetates and halides.” Dr. Lemieux outlined the older views concerning reactions at the anomeric position whereby reactions involving inversion were held to follow an SN2 mechanism; S,l reactions were believed to lead to racemisation due to the trigonal structure at C(q in the transition state. However in 1955 Dr. Lemieux had shown that inversion of configuration occurred in reactions involving an S,l mechanism and this led to a reconsideration of the course of certain reactions. Inversion of configuration at the anomeric position during replacement reactions of acetylated a-glucosyl bromides could not be attributed to shielding by the 2-acetoxy-group.It was rather to be regarded as arising from a steric hindrance by the withdrawing halogen ion which is believed to be expelled by an attack of the lone pair of the ring-oxygen atom to give a positive ion possessing a half-chair conforma- tion. Further it was postulated that ionisation in this way is related to an elimination and would there- fore be expected to take place more readily with the halogen occupying an axial position. This last con- sideration applied equally to replacements in which a 2-acetoxy-residue participated. Examples of this type of reaction were the formation of orthoesters from acetylated /3-glucosyl halides and the replace- ment of a 1-8-acetoxy-group by a halogen methoxyl or ethylthio-residue.In these reactions it was assumed that a change first takes place to produce PROCEEDINGS the unfavoured conformation in which the group to be replaced is in an axial position. A similar mechan- ism was believed to account for the introduction of an isotopically labelled acetoxy-group without inver- sion by means of acetoxytin trichloride and for the formation of 1 :6-anhydrohexoses. The ease with which reactions of this type could be brought about was materially affected by structural modifications which alter the relative stability of the conformation having an axial anomeric group and amongst these the eclipsing of the oxygen atoms of the ring and at was the most important.Finally a brief summary was given of the applica- tion of proton magnetic resonance spectroscopy to the study to carbohydrate structure. Peaks due to the various hydrogen atoms of acetylated sugars could be distinguished and it was possible on the basis of these results to determine the conformation adopted by certain compounds. In concluding the meeting Professor Stacey thanked the organisers of the Symposium as well as those who had contributed. G.R.BARKER. SOME IMPRESSIONS OF RUSSIAN CHEMISTRY AND BIOCHEMISTRY* By M. STACEY,F.R.S. LATEin 1955 some members of the U.S.S.R. Academy of Sciences were the guests of the Royal Society and in May 1956 a “return match” was played in the U.S.S.R.by a delega- tion of the Council of the Royal Society. This delegation which was supported by the Soviet Relations Committee of the British Council was led by Lord Adrian the other members being Lady Adrian Dr. H. G. Thornton (Foreign Secretary of the Royal Society; microbiologist) Dr. Mary L. Cartwright (Girton; mathemati- cian) Professor J. H. Gaddum (pharmacologist) Professor J. M. Robertson (physical chemist and crystallographer) Dr. D. C. Martin (Assistant Secretary of the Royal Society) and myself (organic chemist). The main objective of the visit was to establish contacts with scientists in various fields and to explore with representatives of the Academy the possibility of improved co-operation between Russian and British scientists.It was hoped to arrange some further exchange of visits by both senior scientists and research workers.? Moscow We flew by Vickers-Viscount to Copenhagen by Finnair (Douglas) to Helsinki and thence in a small Russian 12-seater to Moscow. There was a slight hitch at Helsinki for it was discovered that Messrs. Martin and Stacey were seated side by side at the rear of the plane and it could not rise until the “two large gentlemen” had moved to take up D- and L- positions nearer the front! On arrival at 2 a.m. at Moscow Airport there was a filmstar-like reception with beautiful bouquets of flowers for the two ladies by the President of the Academy (Professor A. N. Nesmeyanov) and many other members of the Academy.Members of the British Atomic Scientists team were also there with Professor P. Kapitza. After Lord Adrian had broadcast we were driven in a fleet of enormous Russian cars * This is the first of a number of articles which it is proposed to print on-subjects of topical or historical interest including articles in which the writer’s personal view is presented. t An agreement for an exchange of scientists has recently been made. JANUARY 1957 to the Sovietskya Hotel where we were intro- duced to the first of the many wonderful banquets provided for our sustenance. The day-to-day organisation of our tour was in the hands of the very capable and hard-working Peter I. Pizikov who was most ably supported by our interpreters Mrs.Ileana Dimitreva Stanislav I. Chetinin and Bogdan Delazary. We had as British inter- preter Mr. Paton-Smith of the Foreign Office though we found that most of the older scientists had excellent French while almost all the younger ones understood English and many could speak it well. In general we visited Universities and labora- tories gave lectures etc. in the mornings and “did” the museums art galleries and sight-seeing etc. in the afternoons during which Lord Adrian was probably the most photographed man in the world. The evenings were devoted to the ballet the banquet the opera the choir the reception and the circus! We were introduced to the Academy of Sciences by Professor Nesmeyanov a great and dynamic personality who with Mrs.Nesmeya- nov devoted a great deal of time to our enter- tainment and education! The Academy was founded in 1725 in Leningrad by Peter the Great. In 1934 it was “revitalised” and moved to Moscow. The Praesidium is now housed in a fine building formerly a Royal Palace near the centre of Moscow. The Academy has responsi- bilities beyond the Natural Sciences and has eight divisions as follows (1) Physics and Mathematics (2) Chemistry (3) Biology and Biochemistry (4) Geography and Geology (5) Technical Sciences (6) History (7) Language and Literature (8) Philosophy Economics and Law. However all persons professionally connected in any way with the Academy e.g. the inter- preters appeared to be classed as scientists and what is important to them paid as such! A member of the Praesidium acts as Chief of a Division;thus Academician Dubinin is in charge of Chemistry and Academician Engelhardt of Biology.Medical Science is the concern of a separate Academy while Technology is mainly looked after by the Technology Institutes of in- dustry. Thus the rubber industry has its own Institute of Rubber Technology where both short-term and long-range research on rubber is carried out. The Academy of Sciences has two classes of membership Actual (full) and Corresponding and at present there are 150 full members and 475 corresponding members. Elections take place when vacancies are declared. Full membership appears to carry a stipend in most cases. The Academy governs particularly in regard to the budget the activities of 126 Research Institutes most of which are in Moscow and Leningrad with a few scattered over the vast Union in places such as Omsk Sverdlovsk and Vladi- vostok.The Academy has advisory powers in relation to 13 other Academies in the Soviet Union though some such as the Ukrainian Academy of Sciences in Kiev are quite inde- pendent. Almost all the fundamental scientific research in the U.S.S.R. is done by full-time research workers in the Academy Research Institutes though some is carried out in the Universities mainly for training the post-graduates or “aspirants” (i.e. aspirants to doctorates etc.). Most of the senior Academicians are the holders of Chairs in the University.Thus Professor Nesmeyanov is the President of the Academy he holds the Senior Chair of Chemistry in Moscow University and he is Director of the Zelinsky Institute of “Element” Organic Compounds. This Institute was the first we visited. It was housed in a very old building in a poor quarter of the city and the laboratories were in an over- crowded condition. A large new building how- ever will shortly be provided to rehouse and expand the activities of the Institute. All the laboratories were well planned with fine benches fume chambers etc. and they were superbly equipped with up-to-date apparatus mostly made in U.S.S.R. but generally very similar in type and equal in quality to the best American British or German analogue.The number of research workers was 350 with about 200 trained technicians and 150 lower-grade technicians and labourers. The theme of the research was the study of compounds of carbon with other ele- ments such as S N F and P etc. We visited about 12 different Departments including that of Corresponding Member Kabachnik who has 12 graduates working in six laboratories on a variety of topics including organophosphorus com-pounds and “tautomerism”. Academician Knun- yants had a group of similar size engaged mainly on the synthesis of organic fluorine compounds. I found it most difficult to remember names of Russian scientists but other senior people I met were Professors Andianov and Obraincov and Professor Mrs. Freidlina. Professor Freidlina described some quite exciting new work on the reactions between carbon tetrachloride and alk- anes which had given rise by further steps to a series of unusual amino-acids and polyamides.We were told that ideas for research came from three directions “from above from below and from themiddle” i.e. from the State from the research workers themselves and from the research directors. The approach to the problems was fundamental though one got the impression that all the senior workers were alive to possible industrial applications of their results. The next Institute visited was the Institute of Higher Organic Compounds of which the Director is Professor Kasansky. This is a fine new building with a particularly good library and excellent well-equipped laboratories with all types of spectroscopic equipment.I had the honour of being the first foreigner to lecture in what must be one of the finest Chemistry lecture theatres in the world. In this Institute I noted that the microanalytical department possessed no less than 16 brand new modern-type micro- balances which was two more than I counted at Professor Nesmeyanov’s Institute. We were told that there were about 300 full-time graduate research workers in the Institute and an equal number of technical assistants. Although new it appeared to be already over-crowded. Everyone in the laboratories was delighted to show us their equipment and compounds. A great variety of basic work was being conducted with particu- lar attention to the search for new drugs.In both organic chemistry Institutes one found a strong interest in mechanisms and rates of reaction. There are two large Academy Institutes for Biochemistry. The Medical and Biochemical Institute under the Directorship of Orekhovitch and the Biochemistry Institute directed by A. I. Oparin. The Medical Institute housed over 200 graduate research workers in a large and over- crowded building which was due shortly to move to new premises. There were six Biochemical Departments two for Organic Chemistry and one for Biophysics. The subjects we saw being studied were amino-acid assimulation nitrogen PROCEEDINGS exchange transamination oxidation and reduc- tion of keto-acids steroid hormones and metabolism collagen serum proteins new anti- biotics antitumour agents etc.A very large Svedberg-type ultracentrifuge was much in evidence. The Biochemistry Institute housed 170 gradu-ate workers in 14 departments and was a veritable hive of activity with work proceeding on the chemistry of evolution (Oparin) proteins vita- mins plant and grain biochemistry micro-organisms tea biochemistry radiobiology photosynthesis plant and insect pigments and technical biochemistry. We saw a good deal of Professor Engelhardt’s interesting studies of adenosine-triphosphatase in plants. As in all the Institutes women scientists constituted almost half of the staff. The equipment and facilities were excellent and in both Institutes resin-exchange and chromatography (techniques en- tirely absent from the Organic Institutes) were much in evidence.Further biochemical studies were carried out at a very large new Institute for Blood Studies in Moscow where every aspect of blood in health and disease was studied. There was a keen interest in blood substitutes. I was informed that the specification of British dextran-indeed our own “1ntradex”-had been adopted as being as near the ideal substitute as possible. It was excel- lent for the scattered population of the U.S.S.R. and they already had two factories in production. I was cross-questioned very closely about differences between British Swedish and American dextrans and I was able to score a paint which was well taken when I ventured that British dextran would always have to be very special since there was still so much “blue blood” in Britain! A forthright practical attitude was very much in evidence here and indeed among the scientists in all the Institutes the view was certainly taken that anything published or any instrument sold henceforth belonged to “humanity” and they were entitled to use or copy it! The whole-day visit to the University of Moscow Science Faculty was indeed a “red” letter day.The Deputy Director showed us over the University and he had all the statistics at his finger tips. This University one of 33 in the Union is now 200 years old and is being completely JANUARY 1957 rebuilt on the Lenin Hills south-west of Moscow.The completed parts of this fabulous building provides a 5-year course for 22,000 full-time students of whom some 8,000 have hostel accom- modation in a block near the main administration building the latter being 32 storeys high. An additional 6,000 students take correspondence courses and there are 2,650 members of staff; 33 of the Professors are full members of the Academy and 57 are corresponding members. There are six Faculties of Natural Science and six of the Humanities (still located in central Moscow). The Science Faculties were Mechanical Mathematics Physics Chemistry Biology Geo- logy and Geography. The humanities were History Philosophy Law Philology Eco-nomics and Journalism. About 60% of the students-composed of equal numbers of men and women-are science students.Attendance at lectures and laboratories was compulsory and the marks were awarded mainly on record and on viva examinations. We were able to see many of the chemistry students at work in the labora- tories or in the libraries and they appeared to be taking life very seriously. A good deal of time in the first 3 years was spent on political studies and on languages English being compulsory. Chem- ists study mathematics and physics but not biology. A large new sports town was being built with fine athletic tracks and football pitches and a huge stadium. Television gramophone records and debates occupied a good deal of the student’s leisure time. Professor Nesmeyanov showed us over the splendidly equipped and furnished Chemistry Department which has over 1,000 students.We met all the Professors of Chemistry and mem- bers of his research school who were delighted to show us their compounds including a wide variety of ferrocene-type substances. Professor Engelhardt showed us over the equally fine Biology and Biochemistry Depart- ments in which microbiology teaching was much in evidence. It appeared that during the next few years over 90 % of the University students are being directed into school teaching. Medical students are taught in a separate Medical Academy while Engineer- ing students are taught in the Institutions of Higher Technology. One criticised this segrega- tion and it was admitted to be a mistake which would be corrected in the future! The fine lay-out of the University grounds with some 84 acres of botanical gardens was very impressive.LENINGRAD From Moscow we travelled overnight by the Red Arrow train to Leningrad. An impressive delegation from the Leningrad Scientific Insti- tute led by General Orbelli greeted us at the station. We stayed at the interesting Astoria Hotel which was bustling with a great variety of tourists. Leningrad in the Spring sunshine ap- peared to us to be a much gayer city than MOSCOW, and as a great port it was in much closer touch with the outside world. My first visit with the wise and charming Professor Nikitin as interpreter (he had studied cellulose chemistry in England many years ago) was to the Institute of Forestry from which 1,000 gradu-ates are sent out every year.Here chemists physicists and engineers are studying every aspect of the timber industry of which Russia has the greatest reserves in the world. The cellulose chemistry division was small but handsomely equipped and research workers were particularly pleased to try out their English. The parks of Leningrad University which was situated on the banks of the Gnever River were very extensive and here one had the opportunity of meeting a variety of students among whom were many engineers (both men and women). One dis- covered that when students progressed well with their studies the amounts of their scholarships and allowances substantially increased. Most of the geology and engineering students apparently had “volunteered” to go out after graduation for three-year periods to the vast new road- and dam-building projects in Siberia.One found the Institute of High Polymers in Leningrad a busy and interesting place. It was housed in a former warehouse but laboratory accommodation was adequate and equipment excellent. A fine new building was planned because with 300 research workers over-crowding was acute. The main theme of the research work of the Institute was to provide new materials of construction with increased thermal stability and this meant studying a wide range of synthetic and natural polymers. The researches especially on vulcanisation of rubber appeared to be of sound quality and reasonable originality.The great respect indeed homage paid to scientists in the U.S.S.R. was particularly apparent in Leningrad. The House of Scientists (House of Gorky) was a former Palace with beautiful views across the river. It was essentially a Club for some 1,500 Leningrad scientists and engineers and their families with four main activities scientific cultural sporting and social. Our hosts were proud indeed because some 300 scientific papers on different branches of science were read there in 1955. They were equally proud of a system of child-care which enabled mothers to follow a profession and both parents to enjoy social and cultural activities together ! We spent a memorable day in the fabulous Hermitage Museum where there are some 16 acres of rooms containing priceless art treasures including collections of the Italian masters equal to anything in Rome.Four museum rooms con- tained objects made entirely of solid gold to be viewed only by V.1.P.s such as the Royal Society party. After our visit to the ballet choir banquet etc. it was with the greatest reluctance that we parted from newly found friends to fly 1,OOO miles south to Kiev. In order to give us an im- pression of the vast expanse of country our pilot “hedge-hopped” almost the whole journey. We had a one-hour pause for a meal at Minsk and then on to Kiev. KIEV Kiev was a fair city in full midsummer with heavy bundle-laden peasants rubbing shoulders with elegant “summer clad” young women and men dressed in white tropical drill.After the German devastation Kiev is a completely re- built city with fine new buildings and wide tree- lined streets. Only on the outer ring and nearby villages are the poor slum-dwellings in evidence. The firm independence of the Ukraine is much to the fore and we were slightly amused at our Russian interpreter’s occasional struggles with the language. The Ukrainian Academy of Sciences was founded in 1918. It has 100full members and 100 corresponding members and a Praesidium of 15 members. It governs the activities of numerous research establishments throughout the Republic of the Ukraine. The Kiev Praesidium was housed in a very beautiful building. The Academy had PROCEEDINGS four main departments Mathematics and Physics Chemical and Geological Sciences Biological Sciences and Technical Sciences.In the Chemistry Department where the laboratories were on a much more moderate scale one got the impression that chemical activities were a recent innovation. Nevertheless there were in all some 90 graduate research workers. On the organic side the interests were in synthesis mechanism of reactions vitamin chemistry and carbohydrates. In synthesis cyanine dyes phenazines and thiazoles received particular attention ; fluorine compounds were much to the fore in the study of reactions and in the search for insecticides for particular applica- tion against insects which attack sugar-beet seedlings. The vitamin work was very “old-fashioned” while the carbohydrate studies mainly concerned fructose derivatives and problems of canning.There was a great spirit of keenness among the research people young and old ;my seminar went well and our visit appeared to be a great stimulus for them. Many of the senior people taught at the University but only the beginnings of research training were evident there. Library facilities appeared to be inadequate. While in Kiev we had a memorable day at a collective farm and saw something of Ukrainian village life. This farm was some 5,000 acres in extent and the work was shared by 180 men and women. The living standards of the community appeared rather poor but the workers were happy enough. Many contrasting things attracted our attention we found an enormous television set in the centre of a wooden-benched rest-room for women workers tractors were not in evidence we discovered that sanitary engineering had by no means reached the village we were served with a three-hour banquet which no hotel in Moscow could match and the farm possessed a champion milkmaid worthy of the name.On our departure we were touched by the fact that some 40 village children had lined up to present us all with bouquets of lilac. We flew back to Moscow and after a pleasant visit to the fine country home of Professor and Mrs. Nesmeyanov spent an intensive few days giving lectures visiting further laboratories and discussing many matters with Academy col- leagues. We were vastly entertained by a visit of PLATE 1.The President of the U.S.S.R. Academy of Sciences (Pro- fessor A. N. Nesmeyanov) welcomes Lord Adrian ; with (left to right) Dr. Mary Cartwright Mrs. I. Dimitreva, and Lady Adrian. PLATE2. Lord Adrian is formally elected a member of Moscow University by Pro-Rector Vovchenkov. PLATE 3. Moscow University. PLATE4. A third-year student at Moscow University carrying out a Grignard reaction. PLATE 5. (Left to right) Professor J. H. Gaddum Professor M. Stacey and Lord Adrian admire a golden coach among other treasures at the Kremlin Museums. PLATE6. Forestry Institute of the Academy Leningrad. PLATE7. Students of civil engineering in the park of Leningrad University.PLATE8. The rebuilt city of Kiev. PLATE 9. Children on a collective farm in the Ukraine. PLATE10. Home and car of the Chairman of a collec-tive farm near Kiev. JANUARY 1957 the whole of the Soviet leaders at a very elegant and very English garden party at the British Embassy and some of us were shaken by the hand by Mr. Bulganin. My colleagues had many stories to tell of their personal visits to various other laboratories. At the Institute of Crystallography (600 research workers !) Professor Robertson had set before him reprints of all his own papers published since 1933 and he was expected to answer detailed questions concerning many of them. Dr. Martin had strenuous days at the Institute of Scientific Information which was set up in 1953 with the object of providing abstracts in twelve series covering all aspects of natural science.Eleven thousand publications (9,000 translated) are abstracted annually. An extensive photocopying service is available with the result that although the Russians buy only very few copies of each issue of the J.C.S. almost every library in the U.S.S.R. has a c0py.l Experiments are well advanced for the development of an electronic translating machine. Drs. Cartwright and Thornton were usually subjected to fierce cross-questioning about their own researches before being shown Russian work. Lord Adrian and Professor Gaddum saw many interesting physiological demonstrations 17 and Lady Adrian visited fine new housing estates and studied care of children.CONCLUSION We all felt that our visit was well worthwhile. One was convinced that Russian colleagues are anxious to know more about scientists and work in other lands and that they will welcome foreign research workers among them. There are more than the beginnings of a great scientific revolu- tion in Russia today and there is a great appreciation of the fact that science and tech- nology can exploit the vast natural resources of the Soviet Union and bring a better standard of living to their people. There is much that they can eventually share to mutual advantage with other peoples of the world and one feels that despite the recent shocking events in Hungary despite the singular unattractiveness of their political system to most of us we must get to know the scientists and the people much better than we do now.Their great shortage of consumer and luxury goods must some day give us great opportunities for increased trade. As a Birmingham citizen I could see a wide market for the many fine manu- factured goods from my city and as an academic chemist perhaps more than a little in close touch with Industry I noted a vast potential market for plastics textiles and chemicals of all kinds. 1154copies of J.C.S. were sold to U.S.S.R. in 1955 but only 17 copies in 1956; the figures for China were 100 in 1955 and 3 in 1956. Similar figures have been quoted for Nature (Nature 1956,78 1199). Communist countries do not recognise copyright no fees are paid for photocopying and no permission is sought.EDITOR]. PROCEEDINGS COMMUNICATIONS “Communications” are required to satisfy each of the three following requirements urgency importance and wide interest. The primary consideration will be that chemists in general shall benefit from information in advance of full publication. The object shall be to share knowledge not claim priority or reserve a field. Polemics including prolonged argument about known experimental facts would not be acceptable. Details of experimental methods will not be published unless they are an essential part of the “Communications,” nor will the physical or chemical properties of intermediates in syntheses OF degradations.“Communications” will be considered for publication whether or not the author is a Fellow of The Chemical Society. They will be subject to refereeing and if accepted to editing. Authors are advised to submit with the manuscript a statement for the benefit of the referees setting out briefly the reasons why publication in advance of full presentation is requested. Authors whose “Communications” are accepted should consider themselves under obligation to publish adequate details as soon as possible or to withdraw the claims made but not necessarily in a publication of The Chemical Society. Manuscripts must be marked “Communication for Proceedings” and sent in duplicate to the Honorary Secretaries The Chemical Society Burlington House Piccadilly London W.1. They should not normally exceed 600 words in length i.e. three quarto pages of typescript in double-line spacing including formuk or diagrams which should be kept to a minimum and may dclay pub-lication. Authors should observe the Society’s conventions for nomenclature symbolism etc. outlined in the brochure “The Presentation of Papers for the Journal of The Chemical Society,” but references should be given as footnotes (see Proceedings qf The CIzemicaI Society July 1955 pp. 79-81). Dissociation in solid solution in potassium bromide. The monomeric hyponitrite ion NO-By D. J. MILLEN,C. POLYDOROPOULOS, and D. WATSON RAMSAY LABORATORIES COLLEGE ST. LONDON, (WILLIAM AND RALPHFORSTER UNIVERSITY GOWER W.C.1) THEexistence of the series NO2+,NO2,NO,-suggests plex infrared spectrum had disappeared and had the possibility of completing the series NO+ NO become replaced by a single new frequency NO-by discovery of the “monomeric hyponitrite” (1445 cm.-l).This we suggest is the spectrum of ion NO- and it was with this thought that a Raman the originally sought NO- the hyponitrite ion having and infrared spectroscopic study of metal hyponi- undergone dissociation to two NO-ions which take trites in solution and in solid form was begun. the place of Br ions in solid solution in the potas- sium bromide. The significance of this result for The first result was the observation of a two-line infrared spectroscopy is that the interpretation of Raman spectrum (frequencies 1383 and 1 115 cm.-’) spectra observed when discs of potassium bromide and a moderately rich infrared spectrum (frequencies are used needs to take into account the possibilities 504 863 1020 1129 and 2207 cm.-l) which ob- of the presence of the sample as suspended micro- viously could not belong to NO-.An analysis of crystals,2 as a solid s~lution,~ and also as a solid these spectra has led us to conclude that as has been solution of dissociation products. Since the investiga- suggested before,’ the hyponitrite ion is N20,2-with tion of dissociation in solid solution is bound to be a planar centrosymmetric trans-bent configuration. protracted we are reporting this initial result to It was in the course of this work that we changed draw attention to such dissociation and its implica- our practice of preparing solids for infrared examina- tions for infrared spectroscopy.As far as concerns tion from the older mull method to the newer device NO-itself we hope to study it magnetically and in of compression with potassium bromide into a clear other physical ways. disc. We found that in such preparations the com- [Received November 26th 1956.1 ~~ Kuhn and Lippincott J. Amer. Chem. Soc. 1956 78 1820. Ford Wilkinson and Price “Molecular Spectroscopy,” Ed. George Sell Inst. Petroleum 1955 p. 89. Pliskin and Eixhens J. Phys. Chem. 1955,59 1156. Ketelaar Haas and van der Elsken J. Chem. Phys. 1956,24 624; Jones and Chamberlain J. Chem. Phys. 1956 25 365. JANUARY1957 Gaseous Copper Nitrate By C. C. ADDISON and B. J. HATHAWAY (THE UNIVERSITY NOTTINGHAM) ANHYDROUS nitrates of many of the transition metals are unknown heating of the hydrate frequently resulting in formation of basic salts.Anhydrous cupric nitrate is stated to be unknown,l although white to pale blue amorphous powders of this com- position have been described. We find that copper metal reacts vigorously with a dinitrogen tetroxide- ethyl acetate mixture and that the compound Cu(NO,),,N,O crystallises from the solution. This compound has a dissociation pressure of 1 atm. at 85" and dissociation Cu(NOa,,N,O -+ Cu(NO,), + N,O, gives the pure anhydrous nitrate. When heated in a vacuum at I 50-200' theanhydrous nitrate rapidly sublimes and can be condensed in the form of deep blue-gram crystals in almost 100% yield on a cool surface.The vapour pressure of the anhydrous nitrate (m.p. 255-256') rises from 0.25 mm. Hg. at 150" to 3-0mm. Hg. at 214" with a heat of sublima- tion of 15 kcal./mole and the vapour appears to be monomeric. Copper nitrate is soluble in a number of oxygen-containing solvents (dioxan ethyl acetate nitrobenzene) and is also monomeric in solution. Thermal decomposition of the solid (to copper oxide) is detectable at I 50° but no decomposition of the vapour occurs below about 225" so that the copper nitrate molecule is more stable in the vapour than in the solid state. These surprising properties indicate a high degree of covalency in a simple molecule which would normally be regarded as fully ionic. The nitrate group in co-ordination complexes is regarded as a weak ligand readily replaceable by the water mole- cule but when the hydrate Cu(N0,),,3H20 is heated in a vacuum some sublimation also occurs so that Cu(NO,) and H,O molecules can exist together in the vapour phase without reaction.These pro- perties indicate that the nitrate group is capable of a type of bonding not hitherto realised. The copper nitrate molecule must be considered as a co-ordination complex; as such strong covalent bond- ing of the copper atom to one oxygen atom in each nitrate group (or to two as the colour of the com- pound might imply) seems unlikely in view of the equivalence of the three oxygen atoms in the nitrate group. Covalency may result however from overlap of a 7r-orbital of the NO3-group with metal d-orbitals and since the former will be centrosym- metrical the gaseous molecule may have a ferrocene- shaped structure.Other anhydrous metal nitrates are being examined. [Received December 13rh 1956. * Sidgwick "Chemical Elements and their Compounds," Oxford Univ. Press 1950 p. 155. Guntz and Martin Bid. Soc. chim. France 1909 5 1004; Chretien and Boh Compt. rend. 1945 220 822; Boh, Ann. Chim.(France) 1945 20,421 ;Ferraro and Gibson J. Amer. Chern. SOC.,1953,75 5747. A Boron Trichloride-catalysed ortho-Claisen Rearrangement By W. GERRARD and H. B. SILVER M. F. LAPPERT POLYTECHNIC LONDON, (NORTHERN HOLLOWAY N.7) THEClaisen rearrangement is a reaction of consider- able application in organic chemistry.l In one of its modifications it comprises the transformation of an aryl allylic ether into a C-allylic phenol in the simplest instance allyl phenyl ether into o-allylphenol.The rearrangement is generally effected by prolonged heating; for instance for the preparation of o-allyl- phenol Tarbell' recommends that allyl phenyl ether (b.p. 192") be heated for 5-45 hours under reflux. For higher-boiling ethers solvents such as dimethyl- aniline (b.p. 193") are frequently employed but these do not act as catalysts. The orrho-Claisen rearrangement has been considered to differ from the rearrangements of alkyl aryl ethers (to give o-and p-alkylphenols) by not being susceptible to acid catalysis as is evident from the only previous report in which it is stated that allyl a-methoxy- phenyl ether in the presence of the boron trifluoride- acetic acid complex at 78' afforded a mixture con- taining eugenol (38 %) (a para-Claisen product) as the main constituent.It is now found that allyl phenyl ether reacts with boron trichloride at low temperature (-80") to give a product which on hydrolysis or methanolysis gives exclusively o-allylphenol. The fact that this rear- rangement is shown to take place at a low tempera- ture is likely to be of preparative advantage particu- larly with compounds not having exceptional thermal stability. The mechanism of the orlho-Claisen re- arrangement has been proved to be of SJ' type (see ref. 4,p. 757) and it is interesting that boron trichloride (a Lewis acid) is capable of catalysing such an intramolecular reaction.When the ether (3 mols.) was treated with the trichloride (1 mol.) at -80",some unchanged ether PROCEEDINGS and tri-o-allylphenyl borate (73 %; b.p. I 88"/0-05 ethers gave alkyloxy(or a1lyoxy)-boron compounds mm. n 1.5600) were obtained beforemethanolysis. and alkyl (or allyl) chlorides (the chlorides from the This reaction is a novel type of ether-boron tri-more electron-releasing of the two groups) and chloride reaction; previously it had been found that alkyl I-chloroalkyl ethers gave alkyl chlorides and diary15 and bis-1 -chloroalky16 ethers did not react the bis-1 -chloroalkyl ethers.6 alkyl aryl ethers gave alkyl chlorides and aryloxy- [Received December 6rh 1956.1 boron compounds,' mixed dialkyls (or alkyl ally19) -___ --~ ---___ -__ --___ Tarbell "Organic Reactions," Vol.11 J. Wiley & Sons N.Y.. 1944 p. 1. Kincaid and Tarbell J. Amer. Chem. SOC., 1939 61 3085. Bryosova and Joffe J. Gen. Chem. (U.S.S.R.),1941 11 722. DeWolfe and Young Chem. Rev. 1956,56 753. Colclough Gerrard and Lappert,J. 1955 907. fi Edwards Gerrard and Lappert J. 1957 377. Gerrard and Lappert J. 1951 1020. Idem. J. 1952 1486. @ Gerrard Lappert and Silver J. 1956 4987. A New Synthesis of Carboxylic Acid Anhydrides By D. BRYCE-SMITH (CHEMISTRY DEPARTMENT BERKS.) THE UNIVERSITY READING REACTIONS between silver carboxylates and carbon disulphide (8 rnl.) in a sealed tube at 100" for 8 hr. disulphide appear not to have been described in the After cooling in solid carbon dioxide-alcohol the literature.Very little reaction occurs when a silver tube was opened. On warming carbon dioxide carboxylate e.g. silver benzoate is heated under (0.18 g.) was evolved. The tube was washed out with prolonged reflux (46") with carbon disulphide ; but dry ether and the washings were evaporated to give it has been found that at 100-150" reaction is com- pure benzoic anhydride (1.40 g. 98%) m.p. and plete within 6-20 hours. The acid anhydride is pro- mixed m.p. 42-43' without recrystallisation. duced. The overall equation may be written as follows It is suggested that the reaction steps in the 2R*C02Ag+ CS2 -+ (R.CO),O + CO 4 AgZS. annexed scheme are involved. This is supported by The pure anhydride has been obtained in yields of 98.0,98.5,100 and 45 % with R = Ph m-N02C 6H4 4R-CqAg + CS2 -(R.C02)4C + 2AgzS p-BrC ,H and Me respectively.These reactions are very clean and the only other organic product [possibly via (RCO 2) SCS] in each case has been the free carboxylic acid prob- (RaC02)4C -(R*Cq)3C-R + CO, ably produced by fortuitous hydrolysis. Since silver carboxylates can be made almost quantitatively from RC02 ' x' c ,R -2(R.C0),0 the free acids the method makes possible a virtually R-C$' 0 C.R quantitative conversion of acids into anhydrides under neutral conditions. Sodium salts appear to be the observation that carbon tetrahalides also react unsuitable for this reaction. with silver benzoate to give benzoic anhydride. The following preparation illustrates the method.Silver benzoate (2.90 g.) was heated with dry carbon [Received October 30th 1956.) Mechanism for the Decarboxylation of Aconitic Acid By RONALD BENTLEY (DEPARTMENT AND NUTRITION SCHOOL UNIVERSITY OF BIOCHEMISTRY GRADUATE OF PUBLICHEALTH OF Frr~ssu~an, PITTSBURGH13 PA.) ACONITIC ACID is decarboxylated to itaconic acid Aspergillus terreus which specifically decarboxylates (a) when heated above the m.p. at ordinary pres- cis-aconitic acid.5 Since preparations of this enzyme sure,l or (b) when heated with water at 180°,2 or at also contain aconitase,14C-labelled citric and (+)-I&-150" in the presence of calcium a~onitate;~ and (c) citric acid were used to supply 14C-labelled cis-when heated in vacuu at 140" it affords cis-aconitic aconitic acid for studies of the reaction mechanism.anhydride and subsequently (at 175-190") itaconic anhydride.* More recently an enzyme cis-aconitic From asymmetrically labelled citric acid decarboxylase (CAD) has been obtained from (I;R = OH R' = H)where the 14C-carboxyl groups JANUARY 1957 are those derived from oxaloacetic acid aconitase removes water to yield cis-aconitic acid 01; R = 14C01H R’ = COzH).6 From this material cis-aconitic carboxylase formed carbon dioxide con- taining only 3% of the 14C present in citric acid. From 14C-labelled (+)-isocitric acid {(I; R = H R’ = OH) synthesised from glyoxylic acid and [a-14C]succinic acid by action of isocitritase) which with aconitase yielded the acid (I1 ;R =CO 2H; R’= l4COZH),the carbon dioxide contained more than 80% of the 14C present in one of the labelled carboxyl groups.It was therefore apparent that this enzyme removes the primary carboxyl group of cis-CH2j4C02H C H R C H D-CO H I II CR. I4CQH C -I4CO,H I I CHR‘C0,H CH,R’ (r) (II) (mi 0 CH.CO,H CHR*C02H II I C.C02H C-CO,H I It CR;CO,H CR; (IV) w aconitic acid; this accounts for the unexpected results obtained in tracer studies of itaconic acid synthesis in moulds. This reaction mechanism agrees with the known greater lability of y-than a ,!I-unsaturated acids 8y @ and was confirmed by decarboxylation of cis-aconitic acid with cis-aconitic decarboxylase in deuterium oxide. The isolated itaconic acid con-tained a little more than one atom of deuterium per molecule (1-19); hydrogenation and Kuhn-Roth oxidation to acetic acid indicated that only 11*3% of the deuterium in itaconic acid was associated with the methylene group thus eliminating citraconic acid as a possible intermediate.A detailed mechan- ism for the enzymic decarboxylation accounting for all the known facts and particularly for the low pH optimum (5-6-5.9) for cis-aconitic decarboxylase Crasso Annnlen 1840 34 53. a Pebal ibid. 1856 98 67 is that considered but rejected for the thermal decarboxylation of morolic acid.l0 In deuterium oxide addition of a deuteron yields the carbonium ion (111) and the indicated electron shifts lead to itaconic acid (V; R = D R’ = H). The chemical decarboxylation of aconitic acids in water is prob- ably a similar process involving the 7-unsaturated acid structure.This is confirmed by the formation of yy-dimethylitaconic acid (V; R = H R’ = Me) from a a-dimethylaconitic acid whose structure (IV; R = Me) is proved by oxidation to dimethyl- malonic and oxalic acid with alkaline permanganate.’l The thermal decarboxylation of cis-aconitic anhydride is frequently written as (VI; R = H) -+ (VIII; R = H)4e12 even though the structure of the cis-anhydride (m.p. 78-78.5”) is known to be (VII; R = H).13 There seems little doubt that this CH-CO,H CHiC0,H II I FH2 c -co c-CQ c -CQ I ,o II ,o I ,o R -CH-CO R-C-CO RCH-CO is a further example of the more ready decarboxyla- tion of a 16punsaturated acid correctly represented as (VII; R = H) -+ (VTII; R = H).The anhydride of a( 7)-methylaconitic acid also has a low m.p. (5 1”) and is probably (VII; R = Me) rather than (VI; R = Me). It is known to yield a cis-acid under the proper conditions and decomposes when heated to a-methylitaconic anhydride (VIII; R = Me).14 Thermal decarboxylations of aconitic acid and its derivatives probably involve a cyclic intramolecular transition state rather than the initial formation of a carbonium ion.8.10 The author thanks Dr. S. F. Carson for the labelled citric acid and Dr. I. C. Gunsalus for isocitritase. [Received August 27th 1956.J Ambler and Curl U.S.P. 2,448,506/1948; Henry and Clifcorn Ind. Eng. Chem. 1949 41 1427. Anschutz Ber. 1880 13 1541 ;Anschutz and Bertram Ber.1904 37 3967. Bentley and Thiessen Science 1955 122 330. For a review see Arnstein and Bentley Quart. Rev.,1950 4 172. Corzo and Tatuni Fed. Proc. 1953 12 470; Bentley ibid. 1954 13 182; Bentley and Thiessen 3rd Internat. Congr. Biochemistry RCsumCs des Communications 1955 5 41. Arnold Elmer and Dodson J. Arner. Chem. Soc. 1950,72 4359. Curtis Heilbron Jones and Woods J. 1953,457; Jones and Woods J. 1953 464. Barton and Brooks J. 1951 257. Farmer Ingold and Thorpe J. 1922 121 128. For a recent example see Rodd “Chemistry of the Carbon Compounds” Elsevier Publ. Co. Amsterdam 1952 1 B 1187. lS Malachowski GiedroyC and Jerzmanowska Ber. 1928 61 2525. l4 Rogerson and Thorpe,J. 1906 631 ;Desai J. 1932 1088. PROCEEDINGS cycluAlkatetra ynes By Y.AMIEL,F.SONDHEIMER, and R. WOLOVSKY (DANIEL SIEFF RESEARCH THE WEIZMANN INSTITUTE INSTITUTE REHOVOTH, OF SCIENCE ISRAEL) A NEW cyclization reaction involving the oxidation are very close to each other and considerable inter- of a terminal diacetylene has recently been reported action would be expected. That this is actually the by US,~octa-l:7-diyne (I; n = 4) yielding cyclu-case is shown by the fact that the substance on being hexadeca-1 3 :9 1 l-tetrayne (11; n = 4). Independ-heated decomposes explosively at ca. 1 15-1 20' and ently Eglinton and Galbraith2 described a similar by the anomalous position of the ultraviolet band method of cyclization but used different experi- highest wavelength (Amax.226 238 and 263 mp; mental conditions. Diacetylenes in which the terminal E 550 610 and 390). The other cyclic compounds acetylenic groupings were separated by at least ten (11; n =4 and 5) have ordinary melting points above methylene groups were studied and with these the 150" and show normal3 ultraviolet spectra (Amax. conventional method of oxidation used by ourselves 227 239 and 254 mp; E 580 600 and 360). The failed to give cyclic products. cyclic tetrayne (11; n = 3) is the first aliphatic -1 28% m.p. 99-100" 1 20% m.p. 167-168" 3 I 12% explodes 115-120" I 26% b.p. 110-111"/0~7 mm. m.p. ca. -5" I IS% m.p. 60-61' 4 1 8% m.p. 158-160' I 45% b.p. 119-120"/0~1 mm. m.p. 21-22' 1 19% m.p. 92-93' 5 I 2 % m.p. 205-206" I 58 % m.p. 75-77' j 0% -6 10% -1 60% m.p.30-31" 1 3% m.p. 59-61" We have investigated the scope of our method and substance in which this type of proximity effect is found that the yield of cyclic tetrayne (11) increases observed. Compounds of type (11) in which the as n decreases as far as n = 3. This is fortunate since a-diyne functions are replaced by para-disubstituted the compounds (11) become more interesting (because benzene groups have been shown to exhibit similar of intramolecular proximity effects) as n becomes effect^.^ * smaller. The results are summarised in the Table. All It is not surprising that the oxidation of hexa-1 :5-oxidations were performed by bubbling oxygen diyne (I; n =2) yielded some polymeric material and through the diyne (I) dissolved in aqueous ethanol no cycludodeca-1 :3:7 :9-tetrayne (11; n = 2) for the containing ammonium chloride cuprous chloride latter would require the cc-diyne rods to be "bent" and hydrochloric acid at 55".The structures of the and no model can be constructed. products which were separated by chromatography on alumina were determined by analysis infrared In addition to the hydrocarbons described the spectroscopy titration against silver nitrate and full coupling reaction gave rise to chlorine-containing hydrogenation to known hydrocarbons. compounds. The properties of these as well as The smallest cyclic compound of type (11) for reactions carried out with the cyclic acetylenes (11) which a model can be constructed from "Catalin" will be reported later. modelsiscyclutetradeca-1:3 8 lO-tetrayne(II;n=3) We are indebted to Professor V.Prelog for a the one obtained in highest yield. In the model sample of cyclotetradecane. (which is quite strainless) the two ol-diacetylene rods [Received December 1 1 th 1956.1 Sondheimer and Amiel J. Amer. Chem. SOC.,1956 78,4178. Eglinton and Galbraith Clzem. and hid. 1956 737. Armitage Cook Entwistle Jones and Whiting J. 1952 1998. Brown and Farthing Nature 1949 164,915; Cram et al. J,Amer. Chem. SOC., 1351,73 5491 ; 1954,76 4132; 1955 77 6289. JANUARY 1957 Paper Electrophoresis in a Centrifugal Field By H. J. MCDONALD jun. and H. G. SHEPHERD, E. W. BERMES jun. OF BIOCHEMISTRY UNIVERSITY 12 ILLINOIS) (DEPARTMENT LOYOLA CHICAGO THIS Communication deals with a simple but effective apparatus for rapid continuous electrophoresis.In the usual method the solution is applied to the top of a vertical sheet of paper the edges of which are fitted with electrodes. In the new method the paper is horizontal and is rotated so that the solution moves across the paper under both electrical and centrifugal instead of gravitational force. With a simple change from the rectangular head to a circular planar one and without the application of an electrical potential centrifugally accelerated chromatographic separa- tions have been carried 0ut.l A B C Apparatus for conducting centrifugally accelerated electro- chromatographic separations. A Top view. B View of under-side of rotating paper holder C Side view of apparatus, showing drive motor and spring-loaded carbon brushes which are connected electrically to high-voltage direct-current source.The arrows in section A indicate the paths of two negatively changed components of a solution in the combined electrical and centrifugal field. As shown in the Figure the rotating head for electrochromatographic separations consists of a lower and an upper shallow tray (in the experimental model made of linen-based Bakelite sheet each measuring 56 x 23 cm. and a depth of 0.5 cm.) which can be clamped together in such a way as to hold a rectangular sheet of filter paper or similar material between them. Electrodes connected to a high-voltage direct-current source through two brass col- lector-rings and spring-loaded carbon brushes on the bottom of the lower trays form the side walls of the -rectangular trays thus insuring good contact with the moist paper sheet.To the ends of the bottom tray to which the upper tray was clamped collection troughs divided into several individual compart- ments were attached at each end by a hinge arrange- ment. In the centre attached to the drive shaft of the motor was a circular cup-like container for the buffer solution. A ring of pin-holes was provided around the bottom circumference of the cup to per- mit the solution to leak into the paper sheet at points away from the central point of the rectangular sheet of paper. In later models the circular cup was re- placed by an elliptical cup with a pin hole at either end of its major axis.The mixture to be separated was placed in the cup and leaked away into the paper sheet as the latter was rotated. When this apparatus was used for continuous electrophoresis the buffer solution was added to the paper as a thin continuous jet of liquid from a micropipette regulated by controlled gas pressure. For the electrochromatographic separations the paper sheet (Whatman No. 1) was cut to fit between the two halves of the rectangular head and V-shaped drip-points were cut into the ends to correspond with the number of drip-collector compartments in the collector troughs. It was then wetted with a suit- able buffer solution in a manner similar to that used in ionographic separations? The paper sheet was pulled taut and in the earlier experiments which were of a batch or discontinuous type the migrant solution was spotted on to the paper at selected points near the central part of the paper sheet by means of a micropipette.In later experiments of a continuous type the migrant sorution was fed into the paper continuously from the elliptical feeder cup. A direct-current potential was applied to the strip electrodes so as to yield a gradient of 8-40 v/cm. across the sheet and the head was rotated in a horizontal plane at about 250 r.p.m. by adjusting the speed of the motor with a voltage-regulator. Under these conditions the migrant solution because of the centrifugal force began to move out radially from its point of introduction to the paper sheet; if however positively or negatively charged com-ponents were present they separated in the electrical field and distinct paths of migration were soon assumed.The ionic strength of the buffer solution saturating the paper can be adjusted so as to main- tain the current carried by the sheet within the rated capacity of the line-operated electronic power supply. 5 McDonald Bermes and Shepherd Naturwiss. in the press. -McDonald “Ionography ; Electrophoresis in Stabilized Media,” Year Book Publishers Inc. Chicago IU. 1955. By introducing sufficient buffer solution to the paper sheet it is possible to wash the separated migrant components completely through the sheet and into the appropriate collector vessel. Solutions of plasma proteins mixtures of dyes such as bromophenol- blue and methyl-orange amino-acids and their dinitrophenyl derivatives have been separated into their component fractions in the manner described above.In the traditional hanging-curtain type of paper hOCEEDiNGS electrophoresis the factor responsible for the long times (24-72 hours) required for separations by the continuous technique was the chromatographic element. By using a centrifugal field of the proper magnitude. the chromatographic factor can be speeded up 50-fold and consequently the time required for the over-all electrochromatographic separation can be reduced markedly. Complete details of the apparatus and technique will be published later. [Received Nowruber 23rd 1956.1 The Stereochemistry of Acid-catalysed Opening of Styrene Oxides By R.C. COOKSON and J. HUDEC (BIRKBECK MALETST. LONDON, COLLEGE W.C. 1) As part of a study of conformational effects in the formation and reactions of tertiary benzyl carbonium ions we have investigated the nucleophilic and electrophilic opening of 2a :3 a-epoxy-3P-phenyl- cholestane (I). Nucleophilic reagents opened the oxide (I) normally to form diaxial products thus lithium aluminium hydride reduced it to 3/%phenylcholestan- 3a-01. But treatment with very dilute perchloric acid in aqueous acetone led mainly to 3p-phenyl-cholestane-2x :3 a-diol (11) identical with a sample made by oxidation of 3-phenylcholest-2-ene with osmium tetroxide together with a small amount of the diequatorial 2a:3P-diol.The two diols were stable to the conditions of ring-opening. The oxide (I) isornerised to 3 a-phenylcholestan- 2-one (111) under the influence of dry hydrogen bromide or better boron trifluoride in non-basic solvents such as chloroform or carbon tetrachloride. The structure of the ketone (111) was proved by preparing it by oxidation of the alcohol (IV) pro-duced by treatment of 218:3/3-epoxycholestane with phenyl-lithium. The axial phenyl-ketone (111) rapidly changed into the equatorial isomer (V) on treatment with acid in more basic solvents. Nucleophilic opening of the oxide is a concerted process governed by well-known stereoelectronic forces,l whereas electrophilic opening may not be ~ concerted. In polar solvents the protonated oxide opens to give the (strongly solvated) carbonium ion (VI; X =-H) which like the 3-methylcholestan-3-yl carbonium ion,2 is attacked by the solvent pre- dominantly from the less hindered side to form the more stable product W).* In non-polar non-basic solvents the poorly solvated carbonium ion-pair or zwitterion (VI ; X =H or BF,-) cannot become stabilised by attack- ing the solvent as in water or by loss of the proton from C, to the solvent so that intramolecular migration of hydrogen from C(p,to C(3)supervenes.The axial 2p-hydrogen atom is well disposed for hyperconjugation and migration since the C-H bond is almost parallel with the axis of the partially vacant p-orbital of C(3). [Received December 17th 1956.1 ___I____-* While this simple scheme suffices to explain our results the apparent generality of cis-opening of styrene oxides may demand a mechanism of the SNi type3 that necessarily leads to ~is-glycols.~ Barton and Cookson Quart.Rev. 1956 10 67. * Barton Campos-Neves and Cookson J. 1956 3500. a Cowdrey Hughes Tngold Masterman and Scott J. 1937 1269. 'See Wasserman and Aubrey J. Amer. Chem. Soc. 1956 78 1726; Brewster ibid. p. 4061 ;Curtin Bradley and Hendrickson ibid. p. 4064. JANUARY 1957 ~~ The Structure of Ophthalmic Acid By S. G. WALEY LABORATORY UNIVERSITY (NUFFIELD OF OPHTHALMOLOGY OF OXFORD) OPHTHALMIC ACID is a tripeptide isolated from calf 1ens.l Acid hydrolysis afforded a-amino-n-butyric acid glutamic acid and glycine; the amino-acid residue bearing a free amino-group was found to be glutamic acid.l Selective cleavage in the presence of carboxypeptidase has now shown that the amino- acid residue bearing a free carboxyl group is glycine.This establishes the sequence of the amino-acid residues and the main remaining question is whether the glutamic acid residue is a-linked or y-linked. When simple model substances were examined by paper electrophoresis at pH 4 y-glutamyl-peptides were found to move over twice as fast as or-glutamyl- peptides (as is to be expected on the basis of the relative net charges) and from its mobility ophthal- mic acid has the glutamic acid residue y-linked. This evidence leads to the structure (I) for ophthalmic acid. hydrogenation removed the protective groups and H2NCH*CO*NHCH2C02H I CH2*CH3 afforded L-a-amino-n-butyrylglycine (IT).N-Benzyl-oxycarbonyl-y-L-glutamyl azide2 was condensed with the dipeptide (11) to give N-(benzyloxy-carbonyl-y-~-glutamyl)-L-a-amino-n- butyric acid which on hydrogenation afforded the tripeptide (I). Comparison of this synthetic tripeptide with ophthalmic acid by paper chromotography paper electrophoresis and X-ray powder diagrams left little doubt that ophthalmic acid had the structure (I). The striking feature about the structure of ophthalmic acid is that it is a homomorph3 of glutathione. Biological antagonism between two H2NCHCH2*CH2*C0.NHCH*CO*NHCH2C02H such similar compounds may be expected and this I I is being investigated.CO,H CH2CH3 I thank Mrs. D. M. Hodgkin F.R.S. for the The synthesis of this tripeptide was accomplished X-ray powder diagrams Dr. G. T. Young for the by the following route. N-Benzyloxylcarbonyl-L-a-model substances and the National Council to amino-n-butyric acid was treated with ethyl chloro- Combat Blindness Inc. N.Y. for a grant to this formate and the mixed anhydride condensed with Laboratory. glycine ethyl ester ; saponification followed by [Received December 17th 1956.1 ’Waley Biochern. J. 1956,64,715. Le Quesne and Young J. 1950 1959. Brown J. 1956 1248. Synthesis of N-Acetylneuraminic Acid (Lactaminic Acid 0-Sialic Acid) By J. W. CORNFORTH and M. E. DAINES (NATIONAL FOR MEDICAL LONDON, INSTITUTE RESEARCH N.W.7) and A.GOTTSCHALK AND ELIZA HALL INSTITUTE RESEARCH AUSTRALIA) (WALTER OF MEDICAL MELBOURNE N-ACETYLNEURAMINIC ACID Cl1H1,O,N and ON-diacetylneuraminic acid (B-sialic acid) C13H2P010N are recognised as integral components of the carbo- hydrate moiety of many mucoproteins of animal 0rigin.l Consideration of the relevant chemical data especially the formation of pyrrole-Zcarboxylic acid by of the acetyl-very mild alkaline treatment neuraminic acid released from mucoprotein by oxidation314 of N-acetylneuraminic acid and of the related methylneuraminide (11) by the formation5 of pyrrole-Zcarboxylic acid in 20 % yield by condensa- CH-OH CHaOH H,C’ ‘~H-NHA~ y/\cH.NH MeOXC I Ho\L CH ‘0’1 \o/YH HO&’ H02C’ enzymic action,2 led us to suggest the structure (I)-H-$*OH H-YOH at that time without indication of the stereochemistry H$-OH H*$*OH -for N-acetylneuraminic acid.This structure was (1) CHiOH (n) CHiOH subsequently supported by the results of periodate -__ For review see Gottschalk Yale J. Biol. Med. 1956 28 525. Gottschalk Nature 1954 174 652; Biochern. J. 1955 61 298. Blix Lindberg Oh and Werner Acta SOC.Med. Upsaliensis 1956 61 1. Klenk Faillard Weygand and Schone 2.Physiol. Chem. 1956 304 35. Gottschalk Nature 1955 176 881 ;Arch. Biochern. Biophys. in the press. tion of D-glucosamine and pyruvic acid at 100"and pH 11.0 and recently6 by the isolation of N-acetyl-D-glucosamine along with carbon dioxide and an unidentified two-carbon fragment when N-acetyl- neuraminic acid was heated with pyridine and nickel acetate.When N-acetyl-D-glucosamine and oxaloacetic acid in aqueous solution at room temperature were maintained for 2-3 days at pH 10-1 1 by occasional addition of sodium hydroxide carbonate ion was liberated and a solution was obtained which with Bial's orcinol reagent Dische's diphenylamine re- agent and Ehrlich's p-dimethylaminobenzaldehyde reagent gave coloured solutions absorbing maximally at the same wavelengths as corresponding solutions prepared from N-acetylneuraminic acid. Ion-exchange resins were used to prepare from the solution an acidic product giving about 20% of the colour intensity given by N-acetylneuraminic acid in the quantitative Bial test.' On paper chromatograms in two different solvent systems the material produced a spot coinciding in R value with authentic N- acetylneuraminic acid when sprayed with Ehrlich's reagent or with orcinol-trichloroacetic acid but another Ehrlich-positive spot was also present.The material had the property shared by N-acetylneuraminic acid of forming a neutral PROCEEDINGS methyl ester when kept at 20" in dry methanol. Chromatography of the acidic material on acti- vated carbon gave a fraction which crystallized from methanol-water-ether-light petr~leum.~ The crystal- line material was identical in decomposition tempera- ture R on a paper chromatogram X-ray diffraction pattern and infrared spectrum with authentic N-acetylneuraminic acid (generously supplied by Professor Blix).Production of N-acetylneuraminic acid under these mild conditions affords the final proof that structure (I) is correct; the synthesis essentially an aldol condensation accompanied by decarboxylation of a /3-oxo-acid may well have followed the path of bio-synthesis. Two structural details remain ambiguous the configurations of the two hydroxyl groups in the heterocyclic ring. The apparent failure of N-acetyl-neuraminic acid to form lactones taken together with the known stereochemistry of D-glucosamine suggests that in this ring the secondary hydroxyl group the acetamido-group and the trihydroxy- propyl group may be cis to each other. We thank Mrs. 0. Kennard for the X-ray photo- graphs and Dr. R. K. Callow for the infrared spectra.[Received December 14th 1956.1 Kuhn and Brossmer Chem. Ber. 1956 89 2471. Werner and Odin Acta SOC.Med. Upsaliensis 1952 57 230. The Alkali-stability and Molecular Size of Glycogens By C. T. GREENWOOD and D. J. MANNERS (DEPARTMENT UNIVERSITY OF CHEMISTRY OF EDINBURGH) INview of present interest in the alkaline degradation of polysaccharides and in particular of starch1 and its component amylose2 and amyl~pectin,~ we now report the effect of alkali on the molecular size of glycogen. The classical Pfliiger method for the preparation of glycogen involves digestion of the tissues with 20-60 % aqueous potassium hydroxide at loo" followed by precipitation of the glycogen with alcohol. The method has been criticised by Meyer and Jeanloz who suggested that degradation of the glycogen occurred during the alkaline extraction.However Bridgman reported that glycogen ex- tracted by the Pfliiger method or with trichloroacetic acid from two halves of a rabbit liver had a similar molecular weight. We have determined the sedimentation constants of four samples of glycogen isolated from the halves of two rabbit livers as shown in the Table Sedimentation Sample Method of const. x 1018 Liver A 1 Hot water extraction 85(c.g.s. units) Liver B 2 3 Huger Hot water 86 76 4 Huger 83 It is concluded that in the presence of air the extent of degradation of glycogen by 30 % aqueous potassium hydroxide at 100"is no greater than that which might be caused by the action of boiling water.Baum and Gilbert Chem. and Ind. 1954,489. Bottle Gilbert Greenwood and Saad ibid. 1953 541. Stacy Foster and Erlander Makromol. Chem. 1955 17 181. 4 Meyer and Jeanloz Helv. Chim. Acta 1943 26 1784. 5 Bridgman J. Amer. Chem. SOC.,1942 64 2349. JANUARY 1957 These results are in agreement with those of StaudingeP who showed that the molecular weights of guinea-pig liver and muscle glycogens were unaffected by digestion with 15-30 % potassium hydroxide at 100” for 1 hour. By contrast hot dilute alkali appears to degrade glycogen. Digestion of another sample of rabbit-liver glycogen in 8% sodium hydroxide solution at 100” for 1.5 hours caused a reduction in the sedi- mentation constant from 86 to 57 x c.g.s.units and an increase in p~lymolecularity~ of the poly- saccharide as shown by a broadening of the peak of the schlieren pattern. In continuation of physicochemical studies on starch-type polysaccharides the sedimentation con- stants of 17 other samples of glycogen have been determined. The majority of the samples from verte- brate and invertebrate tissues were isolated by the Pfliiger method and the sedimentation constants were found to vary between 39 and 130 x c.g.s. units. A mean value of 1.5 x being assumed for the diffusion constant of glycogen * these results correspond to molecular weights of 2-6 x loG. All the samples were polymolecular. In addition six of the glycogens were polydisperse and showed the presence of a second component in some instances heavier and in others lighter than the bulk.These glycogens are unusual although the polydispersity of samples of human-liver glycogen has previously been reported. It has been suggestedlO that purification of glycogen by precipitation with glacial acetic acid may render it unsuitable for ultracentrifugal analysis. The sedimentation constant and schlieren pattern of rabbit-liver glycogen (sample 4) is however un- altered after four precipitations of the glycogen with 80% acetic acid. The authors thank Professor E. L. Hirst F.R.S. for his interest in this work and the Rockefeller Foundation for a grant. [Received November 7th 1956.1 Staudmger Makromol. Chem. 1948 2 88. ’The term “polymolecular” is used to describe a chemically homogeneous polymer having a variation in molecular weight whilst “polydisperse” denotes a polymer system containing more than one component.Bell Gutfreund Cecil and Ogston Biochen~J. 1948 42 405. Polglase Brown and Smith J. Biol. Chem. 1952 199 105. loIllingworth Larner and Cori ibid. p. 636. FORTHCOMING SCIENTIFIC MEETINGS London Thursday Feb. 14th 1957 at 7.30 p.m. Pedler Lecture “The Course of Polar Reactions in Non-polar Conditions,” by Professor C. K. Ingold D.Sc. F.R.I.C. F.R.S. To be given in the Lecture Theatre The Royal Institution Albemarle Street w.l. Thursday Feb. 28th 1957 at 7.30 p.m. Lecture “Application of Acidity Functions to the Mechanisms of Acid-catalyzed Reactions,” by Professor F.A. Long M.A. Ph.D. To be given in the Rooms of the Society Burlington House W.1. Aberdeen Thursday Feb. 21st 1957 at 7.30 p.m. Lecture “The Use of Photography in Scientific Investigations,” by Dr. J. F. Padday B.Sc. D.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. To be held at Marischal College. Thursday March 7th 1957 at 7.30 p.m. Lecture “Intermolecular Compounds,” by Mr. l1. M. Powell B.Sc. M.A. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. To be held at Marischal College. Birmingham Friday Feb. 8th 1957 at 4.30 p.m. Lecture “Some Current Problems in Phase Transi- tions,” by Professor A. R. Ubbelohde M.A. D.Sc. F.R.S.Joint Meeting with Birmingham University Chemical Society. To be held in the Chemistry Department The University. Bristol Thursday Feb. 7th 1957 at 5.1 5 p.m. Lecture “From Wallpaper to Crystals,” by Mr. F. Coles Phillips M.A. Joint Meeting with the Student Chemical Society. To be held in the Chemistry Department The University. Thursday Feb. 14th 1957 at 7 p.m. Lecture “Free-radical Chemistry-A Survey,” by Professor D. H. Hey D.Sc. Ph.D. F.R.I.C. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. To be held in the Chemistry Department The University. Thursday Feb. 21st 1957 at 5.15 p.m. Lecture “The Chemistry of Actinomycin,” by Professor A. W. Johnson Ph.D. A.R.C.S. Joint Meeting with the Student Chemical Society.To be held in the Chemistry Department The University. Bristol (contd.) Thursday Feb. 28th 1957 at 5.15 p.m. Lecture “Living Molecules,” by Professor J. D. Bernal M.A. F.R.S. Joint Meeting with the Student Chemical Society. To be held in the Chemistry Department The University. Thursday March 7th 1957 at 7 p.m. Society of Chemical Industry Jubilee Memorial Lecture “The Combustion of Coal,” by Dr. A. C. Monkhouse F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. To be held in the Chemistry Department The University. Cambridge Friday Feb. lst 1957 at 8.30p.m. Lecture “The Control of Chemical Reactions in Living Cells,” by Professor H. A.Krebs M.A. M.D. F.R.S. Joint Meeting with the University Chemical Society. To be held in the University Chemical Laboratory Pembroke Street. Monday Feb. 11 th 1957 at 8.30 p.m. Lecture “Reaction Kinetics in Acidic Media,” by Dr. V. Gold B.Sc. To be given in the University Chemical Laboratory Lensfield Road. Friday Feb. 15th 1957 at 8.30 p.m. Lecture “Some Recent Developments in the Chemistry of Metallic Surfaces,” by Professor K. W. Sykes B.Sc. M.A. D.Phi1. Joint Meeting with the University Chemical Society. To be held in the University Chemical Laboratory Pembroke Street. Friday Feb. 22nd 1957 at 8.30 p.m. Lecture “Some Recent Studies in Relation to Bio- synthesis,’’ by Professor A. J. Birch D.Sc. D.Phi1. Joint Meeting with the University Chemical Society.To be held in the University Chemical Laboratory Pembroke Street. Edinburgh Tuesday Feb. 5th 1957 at 7.30 p.m. Lecture “Nucleotide Structure and Function,” by Professor J. Baddiley D.Sc. Ph.D. Joint Meeting with the Royal Institute of Chemistry Society of Chemical Industry and Edinburgh University Chemical Society. To be held in the Biochemistry Lecture Theatre Teviot Place. Thursday Feb. 14th 1957 at 7.30 p.m. Lecture “Tetraethyl-lead as an Engine Anti-knock,” by Professor A. D. Walsh M.A. Ph.D. Joint Meet- ing with the Royal Institute of Chemistry and the Society of Chemical Industry. To be held in the Pharmaceutical Society Rooms York Place. Thursday March 7th 1957 at 7.30 p.m. Visit to Research Laboratories and Pilot Plant of Scottish Agricultural Industries Ltd.Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. PROCEEDINGS Exeter Friday Feb. 8th 1957 at 5 pm. Lecture “Some Developments in Inorganic Stereo- chemistry,” by Professor R. s.Nyholm D.Sc. Ph.D. F.R.I.C. To be given at the Washington Singer Laboratories Prince of Wales Road. Glasgow Friday Feb. 15th 1957 at 7 p.m. Annual General Meeting of Local Fellows followed at 7.15 p.m. by a Meeting for the Reading of Original Papers. To be held in Room 24 Royal College of Science and Technology. Null Thursday Feb. 21st 1957 at 6 p.m. Lecture “Polyesters and their Uses,” by Dr. M. Gudgeon B.Sc. A.R.I.C. To be given in the Organic Lecture Theatre The University.Thursday March 7th 1957 at 6 p.m. Lecture “The Shapes of Simple Molecules,” by Professor A. D. Walsh M.A. Ph.D. To be given in the Organic Lecture Theatre The University. Irish Republic Wednesday Feb. 6th 1957 at 7.45 p.m. Lecture “Co-catalysis in Friedel-Crafts Reactions,” by Dr. D. C. Pepper M.A. F.I.C.I. M.R.I.A. Ta be given in the Chemistry Department University College Dublin. Friday March 8th 1957 at 7.45 p.m. Lecture “Some Recent Studies in Relation to the Biosynthesis of Aromatic Rings,” by Professor A. J. Birch D.Sc. D.Phi1. Joint Meeting with the Werner Society. To be held in the University Chemical Laboratory Trinity College Dublin. Leeds Thursday Feb. 7th 1957 at 7 p.m. Lecture “Chocolates and Confectionery,” by Dr.F. H. Banfield M.Sc. F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. To be held in the Chemistry Lecture Theatre The University. Monday Feb. 11 th 1957 at 7 pm. Society of Chemical Industry Lecture “Organo- phosphorus Insecticides,” by Dr. B. A. Kilby M.A. Ph.D. F.R.I.C. To be given in the Chemistry Lecture Theatre The University. (All Fellows are invited.) Monday Feb. 18th 1957 at 6.30 pm. Royal Institute of Chemistry Lecture “Silicones and their Industrial Applications,” by Mr. R. Nattrass B.Sc. To be given in the Chemistry Lecture Theatre The University. (All Fellows are invited.) JANUARY 1957 Leeds (contd.) Monday Feb. 25th 1957 at 6.30 p.m.Lecture “Steric Hindrance and Analytical Chem- istry,” by Dr. H. M. N. H. Irving M.A. F.R.I.C. Joint Meeting with Leeds University Union Chemical Society. To be held in the Chemistry Lecture Theatre The University. Liverpool Thursday Feb. 14th 1957 at 5 p.m. Lecture “Metal Derivatives of cycZoPentadiene,” by Professor G. Wilkinson Ph.D. A.R.C.S. Joint Meeting with the University Chemical Society. To be held in the Chemistry Lecture Theatre The Univer- sity. Wednesday Feb. 27th 1957 at 5 p.m. Official Meeting and Pedler Lecture “The Course of Polar Reactions in Non-polar Conditions,” by Professor C. K. Ingold D.Sc. F.R.I.C. F.R.S. To be held in the Chemistry Lecture Theatre The University. Manchester Friday Feb.15th 1957 at 6.30 p.m. Lecture “The Biosynthesis of Cholesterol,” by Dr. J. W. Cornforth M.Sc. F.R.S. To be given in the Chemistry Lecture Theatre The University. Newcastle and Durham Monday Feb. 4th 1957 at 5.15 p.m. Lecture “Electron-diffraction by Gases and its Chemical Application,” by Dr. L. E. Sutton F.R.S. Joint Meeting with the Durham Colleges Chemical Society. To be held in Lecture Room 239 University Science Laboratories South Road Durham. Monday Feb. lSth 1957 at 5.15 p.m. Lecture “The Study of Fast Reactions,” by Mr. R. P. Bell F.R.S. Joint Meeting with the Durham Colleges Chemical Society. To be held in Lecture Room 239 University Science Laboratories South Road Durham. Friday Feb. 22nd 1957 at 5.30 p.m. Official Meeting and Lecture “The Biological Synthesis of Oligosaccharides,” by Professor M.Stacey Ph.D. F.R.I.C. F.R.S. To be held in the Chemistry Building King’s College Newcastle upon Tyne. Northern Ireland Thursday Feb. 21st 1957 at 7.15 p.m. Lecture “The Study of Very Rapid Reactions by the Methods of Flash-photolysis,” by Professor R. G.W. Norrish Sc.D. F.R.I.C. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. To be held at the Queen’s University Belfast. North Wales Thursday Feb. 21st 1957 at 5.45 p.m. Lecture “Some Aspects of the Structural Chemistry of Proteins and Nucleic Acids,” by Professor H. D. Springall M.A. D.Phil. F.R.I.C. Joint Meeting with the University College of North Wales Chemical Society.To be held in the Department of Chemistry University College of North Wales Bangor. Nottingham and Leicester Monday Feb. lSth 1957 at 4.30 p.m. Lecture “Metal Atoms as Aromatic Systems,” by Dr. J. Chatt M.A. Sc.D. F.R.I.C. Joint Meeting with the Chemical Society of the University College of Leicester. To be held at University College Leices ter . Tuesday Feb. 19th 1957 at 4.45 p.m. Lecture “Organometallic Co-ordination Com-pounds,” by Professor G. E. Coates D.Sc. Joint Meeting with Nottingham University Chemical Society. To be held in the Chemistry Department The University Nottingham. Oxford Monday Feb. 4th 1957 at 8.15 p.m. Lecture “Chemical and Physical Properties of Metal-Ammonia Solutions,” by Professor A.J. Birch D.Sc. D.Phi1. Joint Meeting with Oxford University Alembic Club. To be held in the Physical Chemistry Laboratory. Monday Feb. 25th 1957 at 8.15 p.m. Lecture “Polonium,” by Professor W. Fernelius. Joint Meeting with Oxford University Alembic Club and the Royal Institute of Chemistry. To be held in the Physical Chemistry Laboratory. St. Andrew’s and Dundee Tuesday Feb. 5th 1957 at 5 p.m. Lecture “Some Recent Developments in the Chemistry of Metallic Surfaces,” by Professor K. W. Sykes M.A. D.Phi1. To be given in the Chemistry Department Queen’s College Dundee. Friday Feb. Sth 1957 at 5.15 p.m. Lecture “Liquid-phase Oxidation of Hydro-carbons,” by Dr. G. Twigg Joint Meeting with the University Chemical Society. To be held in the Chemistry Department St.Salvator’s College St. Andrew’s. Friday Feb. 15th 1957 at 5.15 p.m. Lecture “Reduction by Metal-Ammonia Systems,” by Professor A. J. Birch D.Sc. D.Phi1. Joint Meet- ing with the Royal Institute of Chemistry and the University Chemical Society. To be held in the Chemistry Department St. Salvator’s College St. Andrew’s. St. Andrew’s and Dundee (contd.) Monday Feb. lSth 1957 at 5 p.m. Lecture “The Photochemical Primary Process,” by Professor W. A. Noyes. To be given in the Chemistry Department Queen’s College Dundee. Friday March lst 1957 at 5.15 p.m. Lecture “Phosphorus Chemistry-Past Present and Future,” by Dr. D. S. Payne B.Sc. A.R.I.C. Joint Meeting with the University Chemical Society.To be held in the Chemistry Department St. Salvator’s College St. Andrew’s. Sheffield Thursday Feb. 14th 1957 at 7.30 p.m. Lecture “Adsorption Hysteresis,” by Professor D. H. Everett M.B.E. M.A. D.Phi1. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry. To be held in the Chemistry Lecture Theatre The University. Thursday Feb. 28th 1957 at 7.30 p.m. Lecture “Reduction by Metal-Ammonia Solu-tions,” by Professor A. J. Birch D.Sc. D.Phi1. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry. To be held in the Chemistry Lecture Theatre The University. Southampton Friday Feb. lst 1957 at 5 p.m. Lecture “Nuclear Magnetic Resonance Tech-niques,” by Dr. R. Richards M.A.Joint Meeting with the University Chemical Society and the Royal PROCEEDINGS Institute of Chemistry. To be held in the Chemistry Department The University. Friday March Sth 1957 at 5 p.m. Lecture “Chemistry of Vitamin BIZ,’’ by Professor A. W. Johnson Ph.D. A.R.C.S. Joint Meeting with the University Chemical Society. To be held in the Chemistry Department The University. South Wales Monday Feb. 18th 1957 at 5.30 p.m. Lecture “Recent Advances in Acetylene Chemistry,” by Professor R. A. Raphael D.Sc. F.R.I.C. To be given in the Chemistry Department University College Cardiff. Tuesday Feb. 19th 1957 at 6 p.m. Lecture “Recent Advances in Acetylene Chemistry,” by Professor R. A. Raphael D.Sc. F.R.I.C. Joint Meeting with the University College of Swansea Chemical Society.To be held in the Chemistry Department University College Swansea. Monday March 4th 1957 at 5.30 p.m. Lecture “The Chemical Significance of Vibrational Band Intensities,” by Dr. H. W. Thompson M.A. F.R.S. To be given in the Department of Chemistry University College Cardiff. Monday March 4th 1957 at 6 p.m. Lecture “Aromatic Compounds with a Nitrogen Atom Common to Two Rings,” by Dr. B. R. Brown M.A. Joint Meeting with the University College of Swansea Chemical Society. To be held in the Chemistry Department University College Swansea. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings.Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Alwan Abdul Sahib B.Sc. (Wales). 31 Elvaston Place London S.W.7. Armstrong Valerie Sylvia. 95 Farnaby Road Bromley Kent. Ashworth John Michael. 28 Trewsbury Road Sydenham S.E.26. Bachelor Frank William S.B. (Calif.). 57 Berkeley Street Somerville 43 Mass. U.S.A. Bayley Colin Raymond B.Sc.. (Lond.),. A.R.C.S. Chemistry Department The University Birmingham 15. Beck David Ph.C. (Lond.) M.P.S. 17 Exeter Road London N.W.2. Beynon Kenneth Ivor B.Sc. Ph.D. (Wales). 2 Granville Street Abertillery Monmouthshire. Bibby Norman William. 245 Darlington Street East, Wigan Lancs.Birnbaum Henry B.Sc. (Lond.). 977 Finchley Road London N. W.1 1. Blair Alan John Frederick B.Sc. Ph.D. (Lond.), A.R.C.S. Greengarth Hall Holmrook Cumberland. Blythe Anthony Reginald. 28 Robin Down Lane, Mansfield Notts. Boyce Clive Beresford Challis B.Sc. (Lond.). Chemistry Department Washington Singer Laboratories Perry Road Exeter. Brantley Lee Reed A.B. (Calif.) M.S. Ph.D. (Calif. T.T.). Occidental College Department of Chemistry 1600 Campus Road Los Angeles 41 California USA. Bull John Leonard. 60 Elm Road Leytonstone London E.ll. Campbell Kenneth Caisley B.Sc. (Dunelm) A.R.I.C. 16 Western Hill Durham City. Chandross Edwin B.S. (M.I.T.). Department of Chemistry Converse Laboratories Harvard University Cambridge 38 Massachusetts U.S.A.Cherry Roger. 12 The Crest Widley Nr. Portsmouth Hants. Chivers Kenneth John. 77 Rushes Road Petersfield Hants. Claridge Peter Gordon B.Sc.(Lond.). Chemistry Depart-ment University College Gower Street London W.C. 1. Claridge Rodney Francis Carre B.Sc. (New Zealand). c/o Chemistry Department Auckland University College Auckland New Zealand. JANUARY 1957 Colbourne Neville. 12 Darnall Drive Sheffield 9. Cowie John McKenzie Grant 3.Sc. (Edin.). c/o Chemistry Department University of Edinburgh West Mains Road Edinburgh 9. Cowling Ronald B.Sc. (Dunelm). Department of Chemistry King’s College Newcastle upon Tyne. Crabb Trevor Arthur B.Sc. (Lond.). Washington Singer Laboratories Perry Road Exeter.Creak George Alan. Emmanuel College Cambridge. Cubbon. Robert Charles Patrick. 45 Woodlands Road. Liverpool 17. Curtis. Edgar John Colin. B.Sc. (Bris.). 293 Alfred Street. ..I Kingsto Ontario Canada. Das Gupta Paresh Chandra M.Sc. D.Phi1. (Calcutta). 2B Parasar Road Calcutta 29 India. Day Allan R. Ph.D. (Penna.). Department of Chemistry, University of Pennsylvania Philadelphia 4 Penna., U.S.A. De Gouveia Antbnio Jorge Andrade B.Sc. (Coimbra) Ph.D. (Liv.). Laboratbrio Quimico da Universidade Coimbra Portugal. Derwish Ghazi Abdul Wahhab B.Sc. (Lond.). 1 Neville Street London S.W.7. Duggan Ann Charles B.S. (Siena Heights Coll.) Ph.D. (Catholic University of America). Siena Heights College Adrian Michigan U.S.A. Elliott James John B.Sc.(Lond.). 37 Irvine House Uamvar Street London E.14. Evans Delme. 81 Heol Bryngwili Cross Hands nr. Llanelly Carms. Fanta Paul E. B.S. (Illinois) Ph.D. (Rochester). Department of Chemistry Illinois Institute of Tech-nology Chicago 16 Illinois USA. Farren John. 64 Dudley Street Bell Green Coventry Warwickshire. Fawcett Colvin Peter B.Sc. (Dunelm). Department of Chemistry King’s College Newcastle upon Tyne. Ferris James P. B.S. (Penna.). Chemistry Department Indiana University Bloomington Indiana U.S.A. Fluendy Malcolm Anthony Davis. Balliol College, Oxford. Fonor Henry Albert. 99 Vivian Road Sketty Swansea Glam. French James C. Ph.D. (Wayne). Research Department Parke Davis &Co. Detroit 32 Michigan U.S.A.Ganellin Charon Robin B.Sc. (Lond.) A.R.I.C. 40 Culver Grove Stanmore Middlesex. Gay Terence Bernard B.Sc. (Bris.). 36 New Queen Street Kingswood Bristol 5. George William Owen. 14 Victoria Terrace Brynmill Swansea Glam. Ghosh Rames Chandra M.Sc. (Calcutta). I.G.S. Labora- tories Ahmedabad House Ballard Estate Bombay 1, India. Gilbert Anne Frances B.Sc. (Nott.). 39 Manningtree Road Ruislip Middlesex. Gillard Robert David. 74 Spencer Road Commonside East Mitcham Surrey. Gladych Jan Mieczyslaw Zygmunt BSc. (Lond.). 11 3 Church Lane Cheshunt Herts. Goodson Leslie Alan. 239 Upland Road E. Dulwich London S.E.22. Gottfried Herbert A.R.I.C. 20 The Vale London, N.W.11. -. .-~-Green David Beeching. Southlands High Street, Cranbrook Kent.Gregory Michael John. South Stoneham House Wessex Lane Swaythling Southampton. Hammersley Peter Alan Gibbs. Waterloo House, Wickham Market Suffolk. Hay James Neilson. 23 Forth Place Stirling. Higgs Frank Roe. 18 Lichfield Road Walsall Wood nr. Walsall Staffs. Hope Derek Birtley M.A. D.Phil. B.Sc. (Oxon.). 9 Norreys Avenue Oxford. Ito Sho D.Sc. (Tohoku). Chemistry .Laboratory University of New Brunswick Fredericton N.B., Canada. Jones Peris Pritchard B.Sc. (Birm.). 10 Oxford Road Moseley Birmingham 13. Latham Michael. 172 St. Helens Road Bolton Lancs. Lees; Edward Brian. Kitchener Hall Royal Military College of Science Shrivenham nr. Swindon Wilts. Lindberg Bengt Ph.D (Stockholm). Svenska Traforsk- nings Institutet Drottning Kristinas Vag 61 Stockholm 0 Sweden.Long Anthony Alfred Walter B.Sc. (Lond.). 8 Court Road Oldland Common nr. Bristol Glos. Long Franklin A. M.A. (Montana) Ph.D. (Calif.) Department of Chemistry University College Gower Street London W.C.l. Luft Charles Frederick. 89 Seymour Drive Overpool Ellesmere Port Wirral Cheshire. McDougall Angus Oliphant B.A. (Oxon.). 27 St. Helen5 Road West Bridgford Nottingham. McGee Michael Anthony B.Sc. (Glas.). 31 7 Cumberland Street Glasgow C.5. Madan Ramesh Chander B.Sc. (Panjab). Firestone Tyre and Rubber Co. Ltd. Great West Road Brentford Middlesex. Martin Brian. 9 Redcliffe Gardens Ilford Essex. Mauger Anthony Brian B.Sc. (Nott.). 34 Russell Avenue Wollaton Nottingham. Miller Johannes Evangelist Dip.Chem.(Munich). P.O. Box 344 McAllen Texas U.S.A. Modena Giorgio. Instituto Chimica Industriale Viale Risorgimento 4 Bologna Italy. Morin Robert Bennett B.A. (Swarthmore College). Department of Chemistry The Rice Institute Houston Texas U.S.A. Morris Alan. 1 Ventnor Avenue Astley Bridge Bolton Lancs. Ogawa Tetsuo Dr.Ing. (Osaka). c/o Ajinomot Co. Inc. Suzukicho Kawasakishi Japan. O’Mant Derrick Michael B.Sc. Ph.D. (Birm.). 40 Beech Avenue Quinton Birmingham 32 Parker Derek. 4 Hawthorne Place Clitheroe Lancs. Patel Chunibhai K. B.Pharm. (Gujarat). P.O. Box 242, Jinja Uganda B.E. Africa. Patterson Alexander Winter F.P.S. 25 Montpelier, Edinburgh 10. Pearson Charles Harold B.Sc. (Leeds). Department of Leather Industries The University Leeds 2.Place John. The Queen’s College Oxford. Preston John. 29 Rydal Grove Old Basford Nottingham. Rees,Peter Sherred M.A. B.Sc. (Oxon.). 105 Gipsy Hill London S.E.19. Reinecke Manfred G. B.Sc. (Wisconsin). Department of Chemistry University of California Berkeley 4, California U.S.A. Rossmann Michael George M.Sc. (Lond.) Ph.D. (Glas.). c/o School of Chemistry University of Minnesota, Minneapolis 14 Minnesota U.S.A. Sandegren Knut Evald Ph.D. (Uppsala). AB Stockholms Bryggerier The Library Ludvigsbergsgatan 5,Stock-holm So Sweden. Sanderson William Anthony B.Sc. (Lond.). c/o 2 Wide Way Mitcham Surrey. Scott John Michael M.Sc. (Leeds). Flat E 2 Park Villas Leeds 8. Shamma Maurice Ph.D. (Wisconsin). Department of Chemistry Pennsylvania State University University Park Pennsylvania U.S.A.Sharman Samuel Henry B.A. (Pomona College), 11314 Homedale Street Los Angeles 49 California. U.S.A. Sloan Alexander David Bankier B.Sc. (Glasgow). A.R.I.C. Allandene Broughton Road Biggar Lanark- shire. Solo Alan Jere B.S. (MLT,) M.A. (Columbia). Depart- ment of Chemistry Columbia University New York 27 New York U.S.A. Somerfield Gordon Alan B.A. (Oxon.). 61 Salisbury Street Beeston Nottingham. Sonnenberg Joseph B.S. (Calif.). University of California, Department of Chemistry Los Angeles 24 California U.S.A. Southern Peter Fulton B.A. (Oxon.). 50 Carrwood Road Wilmslow Cheshire. Stead Barrington John. 8 Meadow Way Farnborough Park Farnborough Kent.Swallow Arnold Graham. 94 Weston Road Gloucester. Swan Alan James. Kitchener Hall Royal Military College of Science Shrivenham nr. Swindon Wilts. Takahashi Nobutaka. Department of Agricultural Chemistry University of Tokyo Bunkyo-ku Tokyo Japan. Taylor Harold John M.Sc. (Cantab.) Ph.D. (Sheffield). 3 Cornwallis Square Calcutta 6 India. PROCEEDINGS Thakor Vidyadhar Manjulal M.Sc. Ph.D. (Bombay). M.R. Science Institute Gujarat College Ahmedebad 6 India. Thomson Kenneth William Barr. Cranwells Regents Road St. Helens Lancs. Thompson Phillip G. B.A. (St. Olaf College). 900 Dryden Road Ithaca New York U.S.A. Topsom Roland David M.Sc. (New Zealand). London House Guilford Street London W.C. 1. Tuite Geoffrey B.Sc. (Lond.). 83 Queens Road Banbury Oxfordshire.Turowski Heinz Gunter. Asbergerstrasse 57 Moers am Rhein Germany. Waddington Thomas Cudworth M.A. Ph.D. (Cantab.). Gonville and Caius College Cambridge. Wang Dennis Y’ling. St. Margaret’s House 21 Old Ford Road Bethnal Green London E.2. Wang Hasting B.Sc. Ph.D. (Edin.). 43 Parkside Gardens North Beeston Nottingham. Washburn Robert M. M.S. (Arizona). 11203 Colima Road Whittier California U.S.A. Weaver Victor Charles 203 Lynmouth Avenue Morden Surrey. Webster David Edward B.Sc. (Lond.). A.R.I.C. 44 Loughborough Road Mountsorrel Loughborough Leics. Winstanley Barbara Kathleen B.Sc. (Lond.). 1 Tanpits, Winstanley nr. Wigan Lancs. Yeowell David Arthur. 38 Beech Grove Hainault Ilford,. Essex. Yuntsen HSU.Department of Agricultural Chemistry University of Tokyo Bunkyo-ku Tokyo Japan. ADDITIONS TO THE LIBRARY during December 1956 Experimental physical chemistry F. Daniels J. H. Mathews J. W. Williams P. Bender and R. A. Alberty. 5th Edn. Pp. 482. McGraw-Hill Book Co. Inc. New York. 1956. Light-scattering in physical chemistry. K. A. Stacey. Pp. 230. Butterworths Scientific Publns. London. 1956. Magnetochemistry. P. W. Selwood. Pp. 435. 2nd Edn. Interscience Publ. Inc. New York. 1956. Polymer solutions. H. Tompa. Pp. 325. Butter- worths Scientific Publns. London. 1956. Introduction to structure in organic chemistry. C. K. Ingold. Pp. 200. G. Bell & Sons Ltd. London. 1956. The chemistry and technology of waxes. A. H. Warth.2nd Edn. Pp. 940. Reinhold Publ. Corp. New York. 1956. Wool wax chemistry and technology. E. V. Truter. Pp. 368. Cleaver-Hume Press Ltd. London. 1956. Neurochemistry. Edited by S. R. Korey and J. I. Nurnberger. 23 Contributors. Pp. 244. Cassell & Co. Ltd. London. 1956. Molybdenum. (Metallurgy of the rarer metals. No. 5.) L. Northcott. Pp. 222. Butterworths Scientific Publns. London. 1956. Principles of flotation. K. L. Sutherland and I. W. Wark. Pp. 489. Australasian Institute of Mining and Metallurgy (Inc.). Melbourne. 1955. The examination of new organic compounds macro and semimicro analytical methods. A laboratory manual. W. T. Smith jun. and R. L. Shriner. Pp. 136. John Wiley & Sons Inc. New York. 1956. Die Trennung von Racematen auf chromato-graphischem Wege.(Forschungsber. Wirtschafts-u. Verkehrsministeriums Nordrhein-Westfalen. Nr 270.) H. Krebs J. Diewald R. Rasche and J. A. Wagner. Pp. 49. Westdeutscher Verlag. Cologne. 1956. (Presented by the Publishers.) The physics of nuclear reactors. A conference arranged by The Institute of Physics in London 1956. (Brit. J. Appl. Phys. 1956 Suppl. No. 5.) Pp. 112. The Institute of Physics. London. 1956. Proceedings of the first and second conferences on carbon held at the University of Buffalo New York 1953 and 1955. Pp. 224. University of Buffalo. Buffalo N.Y. 1956. CIBA Foundation symposium on paper electro- phoresis. Edited by G. E. W. Wolstenholme and E. C. P. Millar. Pp. 224. J. & A. Churchill LtQ.London. 1956.
ISSN:0369-8718
DOI:10.1039/PS9570000001
出版商:RSC
年代:1957
数据来源: RSC
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