Serveur d'exploration sur la musique en Sarre

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Proceedings of the Chemical Society. February 1962

Identifieur interne : 000C75 ( Istex/Corpus ); précédent : 000C74; suivant : 000C76

Proceedings of the Chemical Society. February 1962

Auteurs :

Source :

RBID : ISTEX:79887D401C4DB288114B6AD14EBE6A43FA49D439

English descriptors


Url:
DOI: 10.1039/PS9620000037

Links to Exploration step

ISTEX:79887D401C4DB288114B6AD14EBE6A43FA49D439

Le document en format XML

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<term>Anniversary meeting</term>
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<p> PROCEEDINGS OF THE CHEMICAL SOCIETY FEBRUARY 1962 REPORT OF COUNCIL 1960-61 I. GENERAL during 1961 by 860 to a total of 11,769 (see Table 1). Period of Report.-The financial section of this Although the growth was not as large as in 1960 it report and the record of appointments meetings was higher than in any other year in the history of and other events relate to the twelve months ended the Society. September 30th 1961. 2. Honorary Fellows.-The Council has during Statistical information on Fellowship and Publica- the year elected four new Honorary Fellows of the tions however refers to the calendar year 1961 since Society this corresponds with the subscription period. Sir Howard Florey (United Kingdom); Henry Gilman (U.S.A.); 11. FELLOWS-Alexander Nicolaevich Nesmeyanov (U.S.S.R.); 1. </p>
<p>Statistics.-The number of Fellows increased Vlado Prelog (Switzerland). TABLE 1. Fellowship changes 1956-1961. 1956 1957 1958 1959 1960 1961 No. of Fellows on Jan. 1st 8,936 9,074 9,389 9,539 9,943 10,909 Additions Elections .. .. 656 765 595 802 1,326 1,246 Reinstatements .. 29 24 37 29 27 16 Miscellaneous.. .. 3 -1 --688 -789 -632 -831 -1,354 -1,262 Deductions Deaths .. .. .. 61 52 54 73 67 61 Resignations .. .. 288 293 277 194 194 198 Removals .. .. 199 129 150 159 127 142 Miscellaneous . . .. 2 -1 1 -1 550 -474 -482 -427 -388 -402 Fellowship growth .. 138 315 150 404 966 860 No. of Fellows on Dec. 31st 9,074 9,389 9,539 9,943 10,909 11,769 PROCEEDINGS TABLE 2. </p>
<p>Numbers of scienti9c item in the Journal. 1958 1959 1960 1%1 Papers (General Physical and Inorganic)Papers (Physical Organic) .. .. Papers (Organic) .. .. .. .. Notes .. .. .. .. .. .. .. .. .. .. .. .. .. .. L. .. .. 173 170 476 157 - 182 156 394 108 - 252 197 461 112 - 236 201 498 159* 976 840 1,022 1,094 * General Physical and Inorganic 41 ;Physical Organic 18; Organic 100. TABLE 3. Contributions to the JournaI. 1958 1959 1961 Papers and Notes received . . .. .. .. .. 1,005 1,056 1,127 Less rejected or withdrawn .. .. *. .. .. -57 -51 80 -948 1,005 1,047 Papers and Notes published . . .. .. .. .. 976 840 1,094 No. of pages (Papers and Notes). . .. .. .. .. 4,784 4,141 5,563 Average no. of pages per contribution .. .. .. .. 4.90 4.93 5.08 TABU4. </p>
<p>Papers and Notes from outside the United Kingdom. (Parentheses indicate publicationjointly with a British laboratory.) 1961 Australia .. .. .. .. .. .. .. .. 71 (2) Commonwealth (countries not separately listed) .. .. 15(1) Canada .. .. .. .. .. .. .. .. 6(2) Emt .. .. .. .. .. .. .. .. 14 .I France .. .. .. .. .. .* .. 7(1) Hungary .. .. .. .. .. .. .. .. 5 India Pakistan and Ceylon .. .. .. .. .. 14 Irish Republic . . .. .. .. .. .. .. 5 Israel. . .. .. .. .. .. .. .. .. 36(u .t Italy .. .. .. .. .. .. .. .. 3 New Zealand .. .. .. .. .. .. .. 14 South Africa .. .. .. .. .. .. .. 4 U.S.A. .. .. .. .. .. .. .. .. 29(4) Japan .. .. .. .. .. .. .. .. 8 Belgium .. .. .. .. .. .. .. .. 4 Roumania .. .. .. .. .. .. .. ,. </p>
<p>4 .I Miscellaneous .. .. .. .. .. .. -20(3) 167(20) 212(26) 21 l(8) 25x14) TABLE 5. Percentage distribution in fhe Journal. 1958 1959 1960 1961 A* B* Papers (General Physical and Inorganic) . . ,. 17.7 21.6 24.7 21-6 25.3 Papers (Physical Organic) .. .. .. .. 17.4 18.6 19-2 18.3 20.0 .I Papers (Organic) .. .. .. .. .. 48.8 46.9 45-1 45.5 54.7 -Notes .. .. .. .. .. .. .. 16.1 12.9 11.0 14.6 100-0 100-0 100.0 100.0 100.0 A Notes not classified. B Notes dassified and included with papers. FEBRUARY 1962 39 3. Congratulations.-The congratulations of the Council were conveyed to Fellows mentioned in the New Year Honours list Baron Sir Alexander Fleck Knight Bachelor Alan Heries Wilson C.B.E. Gordon Edward Watts Congratulations were also conveyed to Sir Cyril Hinshelwood as the first recipient of the new Gold Medal offered by the Leverhulme Trust Fund to mark the Tercentenary of the Royal Society and to Professor J. </p>
<p>M. Robertson who was awarded the Davy Medal by the Royal Society. 111. ~BLICATIONS 1. Journal.-The customary statistics given in Tables 2-5 show the usual qualitative features but quantitatively the figures are the highest in the Society’s history. The number of papers and notes submitted during 1961 was 1,127 (Table 3) which exceeds by 4% the previous highest number (1,084) submitted in 1955 and 1960. The number of papers and notes published in 1961 was also a record 1,094 totalling 5,563 pages (plus indexes). Part of this increased size was due to publication of arrears which remained at the end of 1960 and unless the rate of submission of manu- scripts increases still further during the early part of 1962 the Journal for 1962 should be smaller than that for 1961. </p>
<p> Contributions published in 1961 from industrial laboratories and industrial research organisations totalled 123 (including 13jointly with academic insti- tutions); this represents 11.2% of the total (the figures for 1960were 108 and 10.5 %). Published con- tributions from Government sources were 45 (includ-ing 9 jointly with academic or industrial organisa- tions) amounting to 4.1% of the total (1960 28 2.7 %). Published contributions from outside the United Kingdom during 1961 numbered 259 (in-cluding 14 jointly with British laboratories) amount- ing to 23.6% of the total (1960 211 20.6%); features of this distribution are the continued large numbers from Australia and the increasing numbers from Israel and U.S.A.,as shown in Table 4. </p>
<p>It may be noted that the increase (48) in contributions from outside the United Kingdom in the year 1961 com-pared with 1960 is substantially the same as the in- crease (43) in the total number of notes and papers submitted during those periods. 2. Proceedings.-During 1961 ProceedinRs con-tained 216 scientific short Communications the Presidential address and 7 lectures 9 special articles 9 reports of meetings 15 obituary notices the Annual Report of Council and various recurring items. Although the standard required for acceptance of Communications was raised during the year the numbers submitted increased so greatly as to put great pressure on the space available. </p>
<p>Tables 6 and 7 give statistics to illustrate this growth 3. Annual Reports on tbe Progress of Chemistry for 1960 Volume LW.-Thk volume contained 572 pages (476 in Volume LVJ). 4. Quarterly Reviews.-Volume XV contained 17 articles occupying 460 pages. Volume XIV (1960) contained 19 articles occupying 452 pages. 5. Current Chemical Papers.-Tables 8 and 9 give statistics in the form of previous years. There was an increase in size of 19.5 % over the previous year due mainly to a deliberate increase in the number of entries duplicated from one section to another. The increase in the number of different titles was only 2%; a small increase was also caused by the intro- duction during the year of italic subheadings within sections. </p>
<p> 6. Special Publications.-No new Special Publica- tons were issued during the financial year 1960-61. TABLE 6. Pages devoted to Communications in Proceedings. 1957 1958 1959 Whole of Proceedings .. .. .. .. .. 376 371 423 Communications pages .. .. .. .. .. 68 86 138 .I Communications percentage .. .. .. 18 23 33 Other items pages .. .. .. .. .. .. 308 285 285 TABLE 7. Numbers of Commsrnications for Proceedings. 1957 1958 1959 1960 1960 1961 450 500 170 227 38 45 280 273 1961 Total (year) .. .. .. 100 x PubLIRecd. .. .. Annual increase nos. .. Annualincrease percentage . </p>
<p>. Rec. PubI. Rec.Publ. Rec. Publ. Rec.Publ. Rec. Publ. 112 78 128 93 203 148 236 170 326 218 70 -73 -73 -72 -67 -16 15 75 55 33 22 97 48 -13 19 59 59 16 15 41 28 PROCEEDINGS TABLE 8. Current Chemical Papers summary. 1955 1958 1959 1960 1961 Titles of papers Iisted . . .. .. .. ..21,360 26,030 27,440 27,916 28,433 .t Pages of Current Chemical Papers . . .. 706 835 909 913 1,091 Total no. of journals scanned .. .. .. .. 469 519 521 539 537 Issues of journals yielding titles . . .. .. . . 2,277 2,726 2,624 2,369 2,330 Issues not yielding titles .. *. .. .. .. 1,438 1,037 1,392 1,443 1,559 TABLE 9. Languages used in papers included in Current Chemical Papers approximate percentages. 1956 1957 1958 1959 1960 1961 English German . </p>
<p>. .. *. .. .. .. .. *. .. .. 55.1 13.0 55.8 11.8 56.8 13.6 55.4 13.5 53.9 12.0 55.9 12.1 Russian .. .. .. .. .. 12.1 11.5 11.8 14.0 17.1 15.5 Japanese French Czech . .. .. .. .. .. .. ,. .. .. .. .. .. .. .. 6-5 6.1 2.1 6.1 5.6 3.6 4.7 5.6 2.2 4.8 5.2 1-0 5.9 5.1 0.9 5-6 4-8 0.7 Italian . . .. .. .. .. 1.8 1.6 1.8 2.2 1.7 1-7 Polish .. .. .. .. .. 0.5 1.2 1.0 1-6 1.3 1.9 Miscellaneous .. .. .. .. 2.8 2.8 2.5 2.3 2.1 1.8 100.0 IV. OTHERACTIVITIES years-a situation that prohibits readers from 1. Scientific Meetings and Lectures.-Details of browsing through the older material. meetings held in London or under arrangements The number of periodicals taken in the Library is made by the Society’s Local Representatives in other now 671 an increase of 13 during the year. </p>
<p> towns have kn published in Proceedings.These in- Mr. 3. Kennedy was appointed to the post of clude meetings arranged jointly with the local Senior Assistant Librarian in January 1961 filling a sections of other bodies and with local student staff vacancy which had existed for some six months. chemical societies. 4. Liaison Officers.-The Council has agreed that 2. Symposia.-In association with the Anniversary Fellows should be appointed to act as Liaison Meetings held in Liverpool on April ll-l4th Officers at certain academic industrial or other in- Symposia on “Developments in the Chemistry of stitutions where there is no Local Representative. Boron Compounds’’ and on “Some As;?.ects of the Whereas the Local Representative’s responsibilities Chemistry of Natural Products� were arranged. </p>
<p>A usually cover a considerable area those of the well-attended Symposium on “Inorganic Polymers’’ Liaison Officers are confined to their own institu- was held at Nottingham in the period July 18th to tions. The Liaison Officer’s function is to act as a 21st. These meetings have been reported in Pro-link between the Society and Fellows working at the ceedings and the Symposium on “Inorganic Poly- institution and to assist the Local Representative in mers� will be published by the Society as Special such a way as may be necessary. A number of Publication No. 15. appointments have been made and the Council is of the opinion that these have helped considerably to 3. Library.-The main feature of the past year in arouse interest in activities of the Society amongst the Library’s work has been the success of the scheme existing Fellows and potential candidates for Fellow- for Library Subscribers. </p>
<p>Some 157 organisations ship. (A list of Liaison Officers as at December 31st, have joined and borrowed heavily from the Library 1961 is given as an Appendix to this Report.) thereby increasing the number of loans from around 10,OOOto 15,000 per annum. 5. Grants for Research.-Grants from the Re- The stock in the reading room has again been search Fund totalling &957 were made to 28 appli-overhauled and little-used or older material relegated cants. The income at the disposal of the Council for to store. Except for a few standard or classical works this purpose is very limited and the Society cannot the shelf-space in the reading room is now entirely make grants on the same scale as some other grant- taken up by material published within the last ten giving bodfes. </p>
<p>Nevertheless the Council is of the FEBRUARY 1962 opinion that these grants fulfil a most useful purpose in that they often enable those working at smaller or less well-endowed establishments to obtain some special piece of apparatus or scarce chemicals that could not otherwise be made available. 6. Index amicus.-The Council has approved an arrangement whereby the periodical Index Chemicus published by the Institute for Scientific Information Philadelphia U.S.A. is available to Fellows of the Society at a substantial discount. </p>
<p> v. FINANCE AND ADMINISTRATION 1. The Annual Accounts.-The manner of pre- sentation of the Accounts for the year ended September 30th 1961 is similar to that adopted in recent years and it is gratifying that income both from Fellowship Subscriptions and from the Sales of Publications has continued to rise. On the other hand expenditure shown in the General Purposes Library and Publications Accounts was sub-stantially greater in 1960-61 than in the previous year. The size of this increase is exceptional and can be attributed to two main causes. The Council has approved new salary scales for the Society’s staff which took effect on January lst 1961. These recog- nise the substantial rise in the cost of living and remuneration levels since the previous comprehensive review made in 1955. </p>
<p> The increase in the cost of the Journal over the previous year is almost entirely due to circumstances brought about by the printing strike in the summer of 1959. Although provision had been made for printing the resulting accumulation of unpublished papers in the year 1959-60 the arrears were in fact not significantly reduced until 1960-61. In that year an exceptionally large Journal was printed and the full cost is shown in these accounts. Although it is inevitable that costs and especially printing costs will rise in the year 196142 it is not expected that the increase will be as great as that shown in the accounts under review. The growth in the principal items of Income and Expenditure over the past four years are shown in Table 10. </p>
<p> 2. Library Grants.-The Council records its thanks for a grant of €2,382 from the Chemical Council towards maintenance costs of the Library and to those Societies that in return for the use of the Library by their members have continued to contribute towards the expenses of maintenance. The Chemical Society’s contribution towards Library expenses was E7,444 of which E4,868 was for ex- penditure of a capital nature including the purchase of books periodicals etc. and binding. 3. Investments.-There have been few changes of investments during the year and although the economic situation is uncertain the Council’s invest- ment advisers are satisfied that the Society should continue its present investment policy of having a substantial proportion of its capital invested in Ordinary shares. </p>
<p>During the year the yield on cost on the Society’s investments has again improved. The growth of Investment Income shown in Table 10 is of course largely the result of the investment of surplus funds but it also reflects a rising income from the individual stocks held. Copies of the investment schedule are available on application from the General Secretary. TABLE10. Principal items of income and expenditure 1957-1961. Income Fellowship Subscriptions E Sales of Publications E General Purposes Investments E Outside Grants for Publications E 1957-8 .. .. .. 18,443 87,400 3,260 1,913 1958-9 *. .. .. 19,390 101,685 4,500 Nil 1959-60 ,. </p>
<p>.. .. 20,906 1 12,394 6,618 Nil 1960-1 *. .. .. 22,593 1 15,972 8,540 Nil Expenditure Administration E Journal and Proceedings c Other Publications E Library (Total Cost) E 1957-8 .. .. .. 8,200 63,554 17,307 13,668 1958-9 0 . .. .. 9,154 73,146 18,985 14,115 19594 .. .. .. 10,593 68,390 20,605 14,691 1960-1 .. .. .. 12,703 90,298 28,303 17,810 During the year the Society has participated in several sub-underwriting commitments and the total commission received has amounted to €386. 4. Conncil.-The following appointments to Council were announced at the Annual General Meeting heid in Liverpool on April 13th 1961 Vice-Presidents who have not filled the Ofice of President Dr. F.1. Bowen Honorary Treasurer Dr. </p>
<p>J. W. Barrett Elected Ordinary Members of Council Constituency I Dr. L. J. Bellamy Professar D. P. Craig Dr. W. Gerrard Mr. H. M.Powell Constituency 11 Professor D. H. Everett Constituency III Dr. A. K.Holliday Dr. J. Honeyman Constituency v Dr.a.0.Aspinall Constituency VI Professor W.Cocker Professor D. H. Hey was appointed Chairman of the Publication Committee and became ex oficio a member of Council. 5. Local Representatives.-Local Representatives were appointed for the first time at two further centres North Stafford- shire (Keele) .. Dr. I. T. Millar Readin5 . . Dr. J. E. Prue Other changes among Local Representatives have been as follows Aberdeen ,. Dr. D. R. Hogg in place of Dr. P. </p>
<p>Meares Ceylon .. .. Dr. R. 0. B. Wijesekara in placeof Dr. R. P. Wannigama Edinburgh .. Dr. C. T. Greenwood in place of Dr. G. 0. Aspinall Hong Kong .. Dr. H. R. Arthur in place of Professor J. E. Driver Manchester .. Dr. P. C. Crofts in place of Dr. H. Smith Dr. E. H. P.Young in place of Dr. J. Honeyman Oxford .. .. Dr. L. M. Venanzi in place of Dr.Muriel Tomlinson PROCEEDINGS vr. ACKNOWLEDGEMENTS The Council wishes to express its grateful apprecia- tion to those Fellows who have given their services freely to the Society during the year. They would especially mention Local Representatives and Liaison Officers Members of Committee and Referees of papers for the Society’s publications and those who have delivered lectures or taken part in Scientific Meetings. </p>
<p>The Council also deeply appreciates the generosity of those Fellows who have made gifts of the Society’s publications or of books for the Library. APPENDIX Liaison Officersas at December 31st 1961 Admiralty Materials Labors-tory Poole .. .. .. Dr. T. C. Ovenston Aero Research Ltd. (CIBA), Cambridge . . .. .. Dr. G. Winfield Ashburton Chemical Works Manchester .. .. .. Dr. F. R. Basford Battersea College of Tech-nology .. .. .. Dr. J. E. Salmon Bedford College N.W.1 .. Dr. M. M. Harris Belfast College of Technology Dr. D. Hamer Birkbeck College W.C.1 .. Dr. D. J. G. Ives College of Advanced Tech- nology Birmingham .. Dr. A. Holt Bolton Technical College . . Dr. G. W. Wood Boots Pure Drug Co. </p>
<p>Notting- ham .. .. .. . . Dr. J. R. Marshall Borough Polytechnic S.E.l .. Dr. J. R. Powell Bournemouth Municipal Col- lege .. .. .. .. Dr. D. J. Collins Brewing Industry Research Foundation Surrey . . Dr. G. Harris Brighton Technical College .. Dr. E. G. Cowley British Hydrocarbon Chem-icalsLtd. Grangemouth . Dr. M. M. Wirth British Nylon Spinners Ltd. Pontypool .. .. .. Dr. A. C. Davis British Resin Products Glamorgan .. .. . . Mr. R. A. Sutton Brunel College of Technology, w.3 .. .. .. Dr. J. H. Skellon Sir John Cass College E.C.3. . Dr. A. J. Lindsey Chelsea College of Science and Technology. . .. .. Dr. J. F. J. Dippy Chemical Defence Experi-mental Establishment Salis-bury .. .. . Dr. J. M. Wright Chester Beatty Research Imti- tute S.W.3 ,. </p>
<p>.. .. Dr. C.L. Lase )IEBRUARY 1962 Chesterford Park Research Station Fisons Pest Con- trol Ltd. Saffron Walden .. Dr. G. T. Newbold Clayton Aniline Company, Manchester .. . . Dr. E. N. Abrahart University College Cork .. Professor F. L. Scott Derby and District College of Technology. . .. .. Dr. C. M. Atkinson Flin tshire Technical College Chester . . .. .. Dr. C. G. Lyons University College Galway .. Professor P. O’Colla Glamorgan College of Tech-nology .. .. . . Mr. L. H. Thomas Glasgow Royal College of Science and Technology .. Dr. H. C. S. Wood Hatfield Technical College . . Dr. R. F. Robbins Heriot-Watt College Edin-burgh .. .. .. Professor F. Bell I.C.I. Ltd. Alkali Division Northwich .. </p>
<p>.. .. Dr. H. L. Roberts I.C.I. Ltd. Dyestuffs Division Blackley .. .. . . Dr. G. de W. Anderson I.C.I. Ltd. Nobel Division Stevenston .. .. .. Dr. R. C. Anderson I.C.I. Ltd. Pharmaceuticals Division Alderley Edge . . Dr. R. Hull Imperial College S.W.7 .. Dr. J. A. EIvidge King’s College Strand W.C.2 Dr. C.W. Rees Kingston -on -ThamesTech-nical College .. . . Mr. N. Lindop Lanchester College of Tech- nology Coventry .. .. Dr. W. R. McGregor Leicester College of Tech-nology . . .. . . Dr. E. R. Ward Lister Institute of Preventive Medicine S.W.3 .. . . Dr. W. J. Whelan Arthur D. Little Research Institute Edinburgh .. Dr. W. Banks College of Technology Liver- pool .. .. .. Loughborough College .. </p>
<p>Mr. C. B. F. Rice of Technology. . .. . . Mr. G. Oldham Manchester University .. Dr. G. F. Smith Medway College of Tech-nology Chatham .. .. Dr. C. E. Seaman Midland Silicones Ltd. Barry Glamorgan .. .. . . Dr. F. C. Saunders Monsanto Chemicals Ltd. Fawley .. .. .. Mr.K. C. Bryant Monsanto Chemicals Ltd. Newport .. .. .. Dr. T. T. Jones Monsanto Chemicals Ltd. Ruabon .. .. .. Dr. R. A. Baxter National Chemical Labora-tory Teddington . . .. Dr. J. Idris Jones Northampton College of Ad- vanced Technology E.C.l Dr. J. Leicester Northern Polytechnic N.7 .. Dr. W. Gerrard Nottingham and District Tech- nical College .. . Dr. D. Harrison Paint Research Station Teddington .. .. Dr. S. H. Bell Paisley College of Technology Mr. </p>
<p>G. R. Jamieson Petrochemicals Ltd. Urmston Dr. A. V. Mercer The Technical College Plymouth .. .. .. Dr. B. L. Tonge Portsmouth College of Tech-nology .. .. .. Dr. J. W.Grifi School of Pharmacy W.C.l . . Professor W.H. Linnell Queen Elizabeth College W.8 Dr. P. F. G. Praill Queen Mary College E.l .. Dr. R. F. Garwood Robert Gordon’s Technical College Aberdeen . . . . Dr. M.B. Watson Royal Aircraft Establishment Farnborough .. .. Mr. G.A.Earwkker Royal Holloway College Surrey .. .. .. Dr. T. G. Bonner Royal Military College of Science Shrivenham .. Professor J. H. Turnbull St. Andrews University . . Dr. C.Horrex Royal Technical College Salford .. .. . . Dr. H. Suschitzky Slough CoIlege of Further Education .. </p>
<p>.. .. Dr. B. W. V. Hawes South-West Essex Technical College E.17 . . .. Dr. S. Lewin Stockport College for Further Education .. .. . . Mr. H. H. Armstrong U.K.A.E.A. Dounreay Ex-per imen tal Reactor Estab- lishment .. .. .. Mr. P. Lees U.K.A.E.A. Risley Nr. Warrington Lancs. .. Dr. H. C.Dunn Unilever Ltd. Sharnbrook .. Mr. D. Welti University College W.C.l .. Dr. C.A. Bunton Welsh College of Advanced Technology .. . . Dr. V. Askam Westfield College N.W.3 .. Professor W. Klyne West Ham College of Tech- nology E.15 .. .. Dr. F. L.Allen Woolwich Polytechnic S.E.18 Dr. A. I. Vogel Wrexham Technical College.. Dr. E. W. Claydon FEBRUARY 44 PROCEEDINGS 1962 45 THE CHEMICAL SOCIETY INCOME ANI)EXPENDITURE 1961 ACCOUNTS FOR THE YEAR ENDED3hI-I SEPTEMBER 1959160 Expenditure 1960/61 1959/60 Income 1960161 E E General Purposes E E f. </p>
<p>€ General Purposes E € 7,039 820 1,475 1,259 10,593 1,665 1,475 716 $41 5 1,060 Administration Salaries Superannuation etc. .. .. House Expenses etc. .. .. .. Stationery Postages and Office Expenses.. Miscellaneous .. *. .. .. Meetings .. .. .. .. .. Local Representatives . . .. .. .. Travelling .. a . .. .. .. Capital Improvements .. .. Contribution to the Trust Funds .. .. .. .. .. .. .. .. .. .. .. . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 8,844938 1,595 1,326 12,7031,473 1,828 803 1,723- 20,671 235 1,989 22,8956,618 2,783 1,237 Feltows’ Subscriptions For 1960/61 .. .. .. .. .. .. For previous years .. .. </p>
<p>.. .. .. Income Tax recovered on Subscriptions under Covenant Income from Investments . . .. .. .. .. Deposit Interest .. .. .. .. .. .. Miscellaneous .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 22,369 224 - 22,593 8,5402,919 1,648 Transfers Publications Account- 2,698 3,1882,185 950 9,02 1 3,588 Library Account- Books Periodicals etc. .. .. .. .. .. .. .. Maintenance .. .. .. .. .. .. .. .. Staff Pensions Fund .. .. .. .. .. .. .. Balance being Excess of Income over Expenditure carried to Balance Sheet .. .. .. .. .. .. *. .. .. .. Cost of free publications to Fellows under 27 years of age .. .. 3,522 4,868 2,576 1so00 11,966 5,204 €33,533 f35,700 €3 3 33 3 f35’700- E Staff Pensions Fund E E Staff Pensions Fund f 1,05 1 12 26 Pensions * .. .. .. .. .. </p>
<p>.. .. .. Miscellaneous .. .. .. .. .. .. .. .. Balance being Excessof Income over Expenditure carried to Balance Sheet .. *. .. .. .. .. *. .. .. 1,078 16 120 139 950 Income from Investments Transfer from General Puq&& &unt .. .. 1. .. .. .. .. .. .. .. 214 1so00 El ,089- f1,214- El ,089- El ,214- 46 PROCEEDINGSFEBRUARY1962 47 INCOMEAND EXPENDITURE ACCOUNTs FOR THE YEAR ENDED 30TH SEPTEMBER 1961 1959160 Expenditure 1960/6 1 1959160 Income 1960161 Publications Publications € 68,390 6,034 5,890 8,681 15,000 11,465 Journal and Proceedings of the Chemical Society .. .. .. Annual Reports on the Progress of Chemistry .. .. .. .. Quarterly Reviews . . .. .. .. .. .. .. .. Current Chemical Papers .. .. .. .. .. .. .. Transfer to General Reserve .. </p>
<p>.. .. .. .. .. Balance being Excess of Income over Expenditure carried to Balance Sheet. . I. .. .. .. .. .. .. .. .. f E € 90,298 7,463 82,663 7,556 9,355 13,284 8,547 86 1,432 -112,394 368 -11,743 Sales and Revenue from Advertisements Journal and Proceedings of the Chemical Society Annual Reports on the Progress of Chemistry .. Quarterly Reviews .. .. .. .. .. Current Chemical Papers .. .. .. .. Other Publications.. .. .. .. .. Income from Investments .. .. .. .. . . .. .. .. .. .. .. .. .. *. .. .. .. . . .. .. .. .. € 85,693 8,988 8,912 12,337 42 ;E 1 15,972 539 2,698 Transfer from General Purposes Account Cost of free publications to Fellows under 27 years of age .. .. 3.522 El 15,460- f120,033- €1 15,460 - f1 20,033 € Special Publications Fund € E Special Publications Fund & 5,174 27 Cost of Publications .. </p>
<p>Miscellaneous . . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 61 1 36 6,577146 Sales and Royalties . . Income from Investments .. .. .. .. .. .. .. .. .. .. .. .. .. .. 2,766 188 1,910 Balance being Excess of Income over Expenditure carried to Balance Sheet.. .. .. .. .. .. .. .. .. .. 2,790 388 Deposit Interest .. .. .. .. .. .. .. .. 483 €7,111- f3,437- f7.111- $3,437- € 3,346 876 58 7,601452 1,680 403 275 € 4,280 10,411 Library Books and Periodicals . . .. .. Binding .. .. .. .. .. Furniture .. .. .. .. .. Maintenance Salaries Superannuation etc. .. .. Re-binding .. .. .. .. .. House Expenses etc. .. .. Miscellaneous .. .. .. .. Stationery Postages and Office Expenses .. .. .. .. .. .. .. . . .. .. .. .. .. .. .. .. .. </p>
<p>.. .. .. .. .. .. .. .. .. .* .. .. .. .. .. € 3,5921,51161 8,970 405 2,294631 345 f E 186 93 5,164 -2,185 5,00512,645 1,549 564 349 605 1 t 999 93 3,188 10,258 € 4,280 Library Grant :The Chemical Council .. .. Library Subscribers .. .. .. Less Transfer to Maintenance . . .. Transfer from General Purposes Account Maintenance Contributions towards Maintenance Through the Chemical Council- Chemical Society . . .. .. Royal Institute of Chemistry .. Society of Chemical Industry .. Faraday Society . . .. Society for Analytical Chemistry Biochemical Society Chemical Council (Direct Grant)’ . From other sources- .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. E 592 296 -2,576 4,4381,298 495 347 753 2,382 €-296 4,868 12,289 f 5,164 50 10 60 Institute of Brewing .. .. Society of Dyers and Colourists .. </p>
<p>.. .. .. .. 50 10 60 93 10,411 Library Subscribers . . .. .. .. .. 296 12,645 €14,691- f17,809- E14,691- f 17,809- FEBRUARY 48 PROCEEDINGS 1962 49 THE CHEMICAL SOCIETY GENERAL BALANCE SHEET 3OrH SEPTEMBER 1961 1960 1961 1960 1961 Liabilities Assets 2 E € E f 18,090 Sundry Creditors .. .. .. .. .. .. .. .. 27,406 Investments at cost or value when acquired Receipts in Advance 8,378 Publications Fund (Market Value f7,992) .. .. .. 8,378 5,390 Fellows' Subscriptions .. .. .. .. .. .. .. .. 5,863 2,915 Special Publications Fund (Market Value f2,78i) .. .. .. .. 2,915 I. 24,439 Sales of Publications etc. .. .. .. .. .. .. .. 24,671 5,024 Staff Pensions Fund (Market Value €5,913) .. .. .. .. .. .. 5,083 30,534 137,041 General Purposes (Market Value €198,490) -. </p>
<p>.. .. .. .. .. 154,853 55,339 General Reserve .. .. .. .. .. .. .. .. 55,339 I. Life Composition Fees 18,941 Sundry Debtors and payments in advance.. .. .. -. .. 17,771 Balance at 1st October 1960 .. .. .. .. .. .. *. 6,220 Add Receipts during year .. .. '. .. .. .. .. .. 93 4,7 10 Stock of Paper .. .. .. ,. .. .. .. .. .. 5,561 6,220 6,313 8,378 Publications Fund .. .. .. .. .. .. .. .. 8,378 45,225 Balances at Banks (including Deposits) and Cash in Hand .. .. .. 48,789 Special Publications Fund Balance at 1st October 1960 .. .. .. .. .. .. .. 12,714 (Stocks ofpublications are not included) Add Excess of Income over Expenditure for the year . . .. .. .. 2,790 12,714 15,504 Staff Pensions Fund Balance at 1st October 1960 .. </p>
<p>.. .. .. .. 5,259 Add Excess of Income over Expenditure for the ;ear .. .. .. .. 120 5259 5,379 Accumulated Fund Balance at 1st October 1960 .. .. .. .. .. .. 86,405 #. .I Add Net Profit on change of Investments .. .. .. .. 1,456 Excess of Income over Expenditure for the year-I. General Purposes .. .. .. .. .. *. .. 5,204 Publications .. .. .. .. .. .. .. .. 1,432 86,405 94,497 E222,234 E243,350 E222,234 E243,350 -J. W. BARRETT, Honorary Treasurer. We have examined the General Balance Sheet the Trust and Lecture Funds Balance Sheet and accompanying Income and Expenditure Accounts with the Rooks and Vouchers of the Society and certify them to be in accordance therewith and in our opinion correct. </p>
<p>We have also verified the Balances with the Bankers and the Investments. FZNSBURY CIRCUSHOUSE, BLOMFIELD STREET,E.C.2 W. B. KEEN& Co. 1961. 14th DECEMBER Chartered A ccountants. PROCEEDINGS TRUST AND LECTURE FUNDS Income and Expenditure Accounts for the Year ended 30th September 1961 1959/60 1960/61 -____ IT c) 5 2% Trust 2s 4% Funds 2iG U w s" 4 2 E E E --Ethel Behrens Fund . . .. .. 39 2 1,155 968 +187 Centenary Fund .. 1,214 891 468 259 +209 Corday-Morgan Medal and Prize'Fund * 562 403 669 555 3-114 Corday-Morgan Memorial Fund .. 729 565 37 1 + 36 Faraday Lecture Fund . . .. .. 22 3 38 91 -53 Robert John Flintoff Trust .. 35 4 50 8 + 42 Edward Frank Harrison Trust Fund .. 53 128 28 43 -15 Liversidge Lecture Fund . </p>
<p>. .. .. 30 3 28 2 + 26 Pedler Lecture Fund . . .. .. 30 81 983 883 +100 Research Fund .. .. .. .. 1,114 997 67 2 + 65 Simonsen Lecture Fund .. .. .. 24 62 100 92 f8 Tilden Lecture Fund .. .. .. 120 115 -____ ~ Balance Sheet 30th September 1961 1960 1961 t E E E Fund Balances -Ethel Behrens Bequest .. .. .. 1,037 24,741 Centenary Fund-Capital ALount' ' .. .. .. 24.849 1.745 -Income Account .. .. .. 2,068 26,486 26,9 17 12,276 Corday-Morgan Medal and Prize Fund .. .. 12,435 15,847 Corday-Morgan Memorial Fund .. .. .. .. 16,011 531 Faraday Lecture Fund .. .. .. *. *. 55 1 736 Robert John Flintoff Trust .. .. .. 769 1,139 Edward Frank Harrison Trust Fund .. .. .. 1,062 673 Liversidge Lecture Fund .. </p>
<p>.. .. .. .. 700 704 Pedler Lecture Fund. . .. .. .. .. .. 653 23,074 Research Fund .. .. .. .. .. 23,191 567 Simonsen Lecture Fund .. .. .. .. .. 529 2,705 Tilden Lecture Fund .. .. .. .. .. 2,709 E84,738 ;E86,564 Represented by: 79,843 Combined Pool of Trust Investments . . .. .. 81,383 (Market Value f76,037) 3,754 Balances at Banks (including Deposits) . . .. .. 4,638 83,597 86,02 1 1,313 Sundry Debtors .. .. .. .. .. 1,001 172 Less Sundry Crediidrs . . .. .. .. .. 458 1,141 543 E84,738 The fund balances. do not reflect gains or losses on change of investments &86,564 and the comparative figures have been adjusted accordingly. - FEBRUARY 1962 51 SCIENCE AND INDUSTRY IN SHEFFIELD SOME HISTORICAL NOTES* By Professor W. </p>
<p>H. G. ARMYTAGE (DEPARTMENT UNIVERSITY OF SHEFFIELD) OF EDUCATION LYINGon successive strata of coal with a good supply of water power tumbling from the sur- rounding hills Sheffield has a long tradition of wrestling with Nature. Many of the earliest references to iron works or coal mines at nearby Cawthorne Wentworth Canklow Wortley Silkstone and Worsborough show that a diffused expertise in mining grew up before the sixteenth century. During the sixteenth century the Yorkshire mines were in general too shallow to be troubled by fire damp but the presence of black- or choke- damp in areas from which the coal had been extracted troubled miners often fatally. This and other gases in the coal pits exercised the wits of many and in the following century a local Sheffield coal owner Francis Jessop was to com- municate with the Royal Society about it. </p>
<p>But until chemical knowledge had increased super- stition held the field. Thus it was thought that foul gases entered the mines from the surface at the express command of the Devil. When a miner was affected by them his fellows took him to the surface scratched a small hole in the ground and laid the victim’s face in it half bury- ing his head with loose dirt. This technique sur- vived up to the period of railway development when men were overcome in the tunnelling opera- tions. There was a sound empirical reason for it since it made the victim gasp for breath thereby clearing his lungs more quickly. The modern technique is administration of carbon dioxide and oxygen to victims of carbon monoxide poisoning. </p>
<p> Expedients hardened into rituals. In the shallow shafts liable to contain black damp it was the custom first to lower a dog in the know- ledge that if it howled gas was present and descent dangerous. So it is not surprising that two classes of people are first discernible as cultivators of science in the area the coal owners and the doctors. Four coal owners stand out as pioneers of scientific endeavour. The first’ was Francis Jessop (1638-9 1) whose ancestral mansion of Broom-hall seems to have been the first seat of serious scientific experiment and speculation in Sheffield. For brief periods it housed some of the foremost scientists of the seventeenth century. </p>
<p> Jessop was a great friend of the naturalist John Ray F.R.S. whom he met on a journey to Montpellier. Ray then thirty-eight was ob-viously attracted to this intelligent young York- shire squire eleven years his junior accepted his hospitality at Broomhall and introduced him to Francis Willughby F.R.S. another naturalist. Others whom Jessop knew were William Croone F.R.S. the physician (then a professor at Gresham College London) founder of the lec- ture that bears his name and Martin Lister F.R.S. the York physician who later became a noted zoologist. With such friends it was not surprising that Jessop should develop scientific interests. Wil- lughby’s “Ornithologiae� contained a testimony to Jessop for sending “descriptions and cases of many rare birds� and for “discovering and giving notice of many species thereabouts (i.e. </p>
<p>near Broomhall) which he knew not before to be natives of England.� Through his friends Jessop’s own scientific researches were reported and published in Philosophical Transactions of the newly-founded Royal Society. The problem of fire damp in mines with instances of recorded explosions was the subject of one communica- tion made by Jessop in 1671. Another describing experiments he had made together with two Nonconformist physicians on the production of formic acid was published in 1675. The Philo-sophical Transactions also reviewed Jessop’s “Propositiones Hydrostaticae ad illustrandum *Published in connection with the Society’s Anniversary Meeting. </p>
<p> l Before Jessop’s time we can trace three forerunners John Jones M.D. Rector of Treeton from 1581 to 1600 a transIator of Galen; Timothy Bright M.D. of Carbrook author of medical texts and alleged originator of shorthand; and Gilbert Watts the first translator of Francis Bacon’s great work “Of the Advancement and Proficience of Learning,� published in 1640. But Jones was a Welshman who did most of his scientific work before coming to Sheffield. Bright spent most of his time at Methley or Berwick-in-Elmet while Watts exercised his “excellent wit� and “smooth pen� at Oxford and in Essex. Aristarchi Samii Systema destinatae et quaedam Phaenomena Naturae Generalia,� in 1 687.2 An even better known country gentleman of the district was Sir Godfrey Copley F.R.S. </p>
<p> (1653-1 709) of Sprotborough near Doncaster. Copley’s name is perpetuated by his bequest3 of f 100 to the Royal Society in 1709 (‘for improving natural knowledge to be laid out in experiments or otherwise for the benefit thereof as they shall direct and appoint.� He employed an eminent contemporary water engineer George Sorocold to design fountains and canals for him. The third great landowner who utilised scientific knowledge to develop his estates was the Marquis of Rockingham F.R.S. (1730-82) who experimented at his colliery at Elsecar and extracted tar oil from coal. In this he was helped4 by Shefield-born Dr. John Roebuck F.R.S. (1 718-98). Rockingham also made experiments with the different kinds of clay to obtain bricks and tiles partly for his house at Wentworth Woodhouse and partly for draining land. </p>
<p>Arthur Young F.R.S. described his work “I never saw the advantages of a great fortune applied so nobly to the improvement of a country. Every discovery of other countries-every successful experiment in agriculture,-every new improve- ment (and many of his Lordship’s own inven- tions) introduced at great expence.-Draining.- The general management of grassland-and manures among numerous other articles are at Wentworth carried to the utmost perfection. Nor should I forget to observe how much I was in- debted to his Lordship for recommending me to several excellent cultivators.5 “The husbandry of the Marquis,� he con- cluded “is much more worthy of attention than any palace; the effects which have and must con- tinue to result from it are of the noblest and most truly natural kind.� PROCEEDINGS The fourth local landowner in the story is the Earl of Arundel and Surrey who took over the working of his colliery at Arbourthorne in about 1781 because he had seen the success of its lessees Townshend and Furness in exploiting the scientific genius of John Curr. </p>
<p>Curr had about 1775 invented a cast-iron narrow-gauge railroad with L-shaped rails-the first iron railway to be used underground. He promptly entered the Earl’s employment and the results of his labours are described in his “Colliery Viewer� (1797). Curr’s underground railway was used for seventy years and the design of his tubs is still standard.6 Concomitantly the medical profession was providing a great stimulus to industry in Sheffield. </p>
<p>William Lyon helped promote the River Dun Navigation Company in 1730 and six years later was engaged in lead-mining at Bradfield. Dr. Buchan’s “Domestic Medicine� (1 769) which ran to nineteen editions in the author’s lifetime and was translated into all European languages including Russian is said to have been written at the Hartshead in a house behind the present offices of the Shefield Telegraph. The first analytical chemist in Sheffield was Dr. Thomas Short’ (1690-1772) who settled here about 1728. Tea sugar milk wines spirits and tobacco all came under his scrutiny but his speciality was spa water.* Either he or his friends would collect specimens from all over England mixing them in the course of his analysis with blood serum bile and other organic matter till the specimens “began fetid,� whiIst others be-came “past enduring in the house.� He also kept a daily record of the weather at Sheffield from January 1727 to December 1755. </p>
<p>In this now in the Bodleian Library are noted barometric and thermometer readings wind directions and a general description of the weather. Short slept C. Hutton G. Shaw and R. Pearson “ThePhilosophical Transactions of The Royal Society of London from their commencement in 1665 to the year 1800,� Baldwin London 1809 Voi. 5 (1671) pp. 556ff.; Vol. 10 (1675) pp. 244ff.; Vol. 16 (1687) pp. 417-8. </p>
<p> This in 1736 was utilised by the council to award a medal “to the author of the most important scientific discovery or contribution to science by experiment or otherwise.� The Copley Medal of the Royal Society is one of the most highly prized awards for scientific endeavour. “Wentworth Woodhouse MunitnenW (in Sheffield Public Library) and A. and N. Clow,“The Chemical Revolu- tion,� Batchworth London 1952 p. 393. A. Young “A Six Months Tour through the North of England,� W. Strahan London 2nd ed. 1771 pp. i xvi, and 271. F. Bland “John Curr Originatorof Iron Tramroads,� Transactions of the Newcornen Society 1930-1 11 1-10. C.L. Sutherland “Thomas Short M.D.:An Eighteenth Century Medical Practitioner in Sheffield,� British Medical Journal 1934.6. T.Short,“A Rational Discourse on the Inward Uses of Water,� London 1725; “A Dissertation on Tea,�London, 1730; and “A Treatise on the different Sorts of Cold Mineral Waters in England,� London 1766. </p>
<p> FEBRUARY 1962 over the coal-house as he believed it good for his lungs. Short’s statistical zeal is reflected in his “General Chronological History of the Air Weather and Seasons� (based on the results of his weather diary) and “New Observations on City Town and County Bills of Mortality� (the results of much work upon parish registers). Both are in the best tradition of Petty and Graunt. Like Jessop and Copley Dr. Short had numerous correspondents. They included Sir Hans Sloane then President of the Royal Society; Dr. John Rutty (1698-1775) whose “Spiritual Diary� excited Dr. </p>
<p>Johnson’s amuse- ment; Richard Richardson F.R.S. (1 663-1741) of Bradford whose botanical garden at North Brierley contained the best collection in the north of England and who sent him waters from many Yorkshire spas. He was also a friend of Peter Shaw (1694-1 763) a well-known chemist of three apothecaries John Hussey John Ellison and John Fenton and of John Dossie then Vicar of Sheffield. When the Royal Society of Arts was formed in 1754 in London to encourage “Arts Manu-facturers and Commerce,� Dossie’s son Robert was thirty-seven years old. He went to London and joined it with the assistance of Dr. Samuel Johnson six years later. His “Elaboratory Laid Open or The Secrets of Modern Chemistry and Pharmacy Revealed� (1759 “Handmaid to the Arts� (1758) and “Institutes of Experimental Chemistry� (1759) were very well received and the Critical Review described the first as “the best of the kind that ever was published.� Robert Dossie’s work earned the gold medal of the Royal Society of Arts in 1767 “for effectually aiding to establish the Manufacture of Pot Ash in North America.�D The first distinguished specialist in industrial chemistry in Sheffield’s (and the nation’s) history was John Roebuck (1718-94) who like Dossie went from the local grammar school to Dr. </p>
<p> Doddridge’s Academy at Northampton and graduated at the Universities of Edinburgh and Leyden. Setting up in practice in Birmingham in 1743 he fitted up a laboratory in his own house where his “high views� of its usefulness and his intention to “render it subservient to the im-portance of Arts and Manufactures’’ led him to pioneer in the recovery of precious metals. </p>
<p> Setting up in partnership with a Birmingham business man Samuel Garbett he established a chemical works and succeeded in manufacturing sulphuric acid at a quarter of its previous price by using lead chambers six feet square. One of their employees took the secret to Samuel Skey of Bewdley who built lead chambers ten feet square and made his fortune. One of Skey’s apprentices John Read (1744- 1803) came to Sheffield in 1760 with his uncle Samuel Lucas a fellow pupil of Roebuck’s at Northampton. Together they set up a refinery of precious metals (especially silver) to cater for the trade of the town. </p>
<p>They refined silver-copper scrap and probably influenced by the furnaces of the Derbyshire lead mines later built a rever- batory furnace. Beginning operations in Water Lane Read moved in 1770 to Green Lane by the River Don. He kept abreast of current work in chemistry and an extant portrait shows him holding from his ruffed wrist a copy of Watson’s “Chymistry.�lo By 1780 Read was expert in the use of nitric acid for refining in making copper sulphate copper- based paints pot-metal and standard silver. He had also established a still department to supply button makers with metal. When his cousin twenty-three year old Samuel Lucas from Birmingham joined him in 1787 the firm moved to Royds Mill. </p>
<p> Samuel Lucas was an avid experimentalist and brought to Sheffield the sanguine spirit of the Lunar Society. Within three years of arriving in Sheffield he had obtained a patent for making steel. By mixing Cumberland or Lancashire ore with charcoal or bone dust and melting them in air-tight pots he professed to obtain steel which could be subsequently cast into ingots. In 1793 with his brother Edward and John Read he decided to exploit this patent to make spades and shovels at Wath and Cleator but in 1799 they had to abandon their enterprise. Another patent of his was taken up in 1804 by his brother Thomas at Chesterfield. F. W. Gibbs “Robert Dossie (1717-1777) and the Society of Arts,� Annals of Science 1951 7 149-172. </p>
<p> lo Watson Professor of Chemistry at Cambridge from 1764-1771 had toured Derbyshire and written an account of it. (Philosophical Transactions 1768.) Samuel’s researches financed by his firm were important in the silver trade. He found that the escaping oxygen in cooling silver was responsible for the phenomenon of “spitting�-and com-municated this discovery to John Dalton who saw that his letter was readll to the Manchester Literary and Philosophical Society. The first popular expositor of chemistry to appear in Sheffield was the Rev. Thomas Olivers Warwick M.D.,12 who in 1799 advertised a course of thirty lectures “with a particular refer- ence to the Arts and Manufactures of the Town and Neighbourhood.� For two guineas (single lectures half a crown) his auditors could obtain such a knowledge of metals as their instructor had acquired from Dr. </p>
<p>Black. Warwick then twenty-eight years old was like Lucas’ father a pupil of the Dissenting Academy at Northamp- ton and had graduated in medicine from Glasgow University in 1798. His degree was obtained during extensive leaves of absence from his pulpit at the Presbyterian Chapel in Rotherham. Warwick’s lectures on chemistry were given every Wednesday and Friday in Sheffield’s largest inn the Tontine from December 18th 1799 to April 25th 1800. They were followed by another twelve lectures on metals and metallurgy “for the information of those persons not previously acquainted with Chemistry.� In the following winter of 1800-1 Warwick gave another course on theoretical and practical chemistry “at the express solicitation of a Society of Gentlemen.� This Society was either the Chesterfield Philo- sophical Society13 or a monthly dining club in Sheffield. </p>
<p>We are very fortunate in having the notes taken at these last lectures by Joseph Hunter Sheffield’s greatest native historian to- gether with notes of the names of those present at the lectures-at no time more than eleven. From these we can see that a real interest in chemistry and its applications had been aroused. One of the audience the Rev. Benjamin Naylor was a partner in a silver plating firm as well as being a Presbyterian minister; another John Moorhouse was surgeon to the Overseers of the PROCEEDINGS Poor; a third William Staniforth also a surgeon had introduced the practice of inoculation into Sheffield; a fourth Dr. </p>
<p>Hugh Cheyney was the first surgeon of the Sheffield General Infirmary founded in 1797. These four Naylor Moorhouse Staniforth and Cheyney were with Samuel Lucas respons- ible for the creation in 1804 of the first scientific society in Sheffield known as The Sheffield Society for the Promotion of Useful Know- ledge?* This group balloted for subjects to be discussed “embracing every department of human knowledge with the exception of British politics and religion.� The chemist of this group was Richard Sutcliffe a local doctor who read papers on “The reason that (facula) of vegetables in March will not dissolve in cold water until it has been immersed in hot,� “What manner does lime act in promoting vegetation when used as a manure,� and “The sliding rule.� An even more interesting member was Charles Sylvester an enthusiastic investigator of “magnetism and gal- vanism� who read papers on “Galvanic experi- ments on potash.� This society lasted for a year terminating without any recorded reason. </p>
<p> Seventeen years later several of those con- nected with the first society like Thomas Asline Ward formed a Literary and Philosophical Society.15 Its prospectus ended with the words “Since lectures accompanied by experiment may be regarded as bringing all theory to the test of fact and reality such means of improvement will be another most important feature in the intended society. </p>
<p>� From its first meeting on January loth 1823 it took chemistry seriously. Lectures on galvan- ism were given by a local schoolmaster J. H. Abraham founder of the Milk Street Academy and inventor of a process for protecting grinders from dust. Public lectures in the Assembly Rooms were also offered by Mr. John Webster. In 1828 the society approached the newly-founded Medical School with a view to establish- ing a “Philosophical Hall,� but received a dusty answer. In 1841 they also approached the l1 On March 6th 1818. l2 W. Blazeby “Rotherham The Old Meeting House and its Ministers,� Garnett,,,Rotherham 1906 p. 101; M. Brook “Dr. Warwick‘s Chemistry Lectures and the Scientific Audience in Sheffield Annals of Science 1956 11 224-237. </p>
<p> G. Hall “The History of Chesterfield,� Whittaker London 1839 pp. 197-8. l4 Its rules are in the Jackson Collection in the Sheffield Public Library. 1& W. S. Porter “The Sheffield Literary and Philosophical Society,� Northend Sheffield 1922. FEBRUARY Mechanics Institute but again nothing came of it. The “Philosophical Hall� haunted the imagination of the society right up to the found- ing of Firth College in 1879. Its president in 1846 and 1847 James Yates F.R.S. of Norton Hall was a small hospitable man with a biting wit. He had suggested as early as 1827 the establish- ment of universities in the north and west of England and followed this by helping to found and acting as the first secretary of the British Association for the Advancement of Science in I 83I. </p>
<p>Yates was an advocate of the metric system and later took part in the formation of an inter- national association for that purpose. He was aIso a believer in scholarships and competitive examinations and introduced the principle in Dr. Williams’ Trust. The main theatre of operations of the Literary and Philosophical Society was the old Music Hall (where the Central Reference Library now stands). Here they stored their apparatus and books. Publiclectures on chemistry geology and botany were offered and often the society was able to tempt professors of national distinction like Lardner Burnett Carpenter and Lankester to come to Sheffield. On October lst 1847 the society heard a paper on “The recent discoveries of Baron Liebig in Physiological and Organic Chemistry.� The author was Henry Clifton Sorby then a young man of twenty-two whose later versatile exploita- tion of the techniques of microscopic and spec- t roscopic analysis applied to geology metallurgy and crystallography earned him election to the Royal Society in 1857 at the age of thirty-one. </p>
<p> Sorby was four times secretary of the Sheffield Literary and Philosophical Society (1 849-52 1859-70 1886-89 and 1899-1908) and seven times President (1852 1870 1871 1872 1879 1897 and 1898). His work towards the founding of Firth College was fundamental. By the middle of the century science had taken root in the schools. Thus at the Sheffield Col- legiate School (opened in 1836 “to supply a course of instruction with classical learning mathematics science and general literature with moral and religious learning in conformity with the principles of the Church of England�) William Baker taught chemistry. </p>
<p>One of his pupils was Robert Abbott Hadfield who became very interested in the subject and made experi- ments on the melting of steel in the basement of his father’s house.16 On leaving school he spent a few months in the steel firm of Jonas and Colver before entering his father’s works at Tinsley which produced steel castings. In 1875 Hadfield established a laboratory at his father’s works where he studied the alloys of iron with manganese and with silicon. In 1882 (when he was twenty-four years old) he found that though increasing the manganese content beyond the then normal proportion made steel brittle a further increase-up to 12-14 %-gave a soft but extremely durable alloy most useful in applications where resistance to the effects of considerable abrasion or pressure was needed for example in the production of rail and tram- way crossings and crushing machinery. </p>
<p> Hadfield’s silicon steels with their highly electrical resistance were pioneered with William Barrett and played a great part in the manufac- ture of lighter electrical transformers His zest for experimental work increased rather than diminished when he became at the age of thirty Chairman and Managing Director of the firm. Here he introduced an eight-hour day in 1891. </p>
<p> Elected F.R.S. in 1909 (a year after he was knighted) Hadfield published “Metallurgy and its Influence on Modern Progress� in 1925 and in 1931 “Faraday and his Metallurgical Re- searches.� Hadfield was President of the Faraday Society from 1913-1920 and a great supporter of the international organisation of science. By the time he died in 1940 science and industry were married in Sheffield at least. I6 Hadfield was so stimulated by reading Pepper’s “Playbook of Science,� Routledge London 1860 and “Playbook of Metals,� Routledge,. London 1861 that in later life he presented a large number of copies to Sheffield Schools “with the object of encouraging boys to make experiments rather than to acquire knowledge merely by reading of books.� (Obitunri,notices of Fellows of the Royal Society 1941 3 648.) PROCEEDINGS THE UNIVERSITY AND ITS CHEMISTRY DEPARTMENT By Dr. </p>
<p>T. S. STEVEN$ (DEPARTMENT UNIVERSITY OF CHEMISTRY OF SHEFFIELD) THE University of Sheffield arose from the con- fluence of several educational streams during the nineteenth century. The earliest rivulet was the Sheffield School of Medicine whose precarious meanderings can be traced back to 1828. It was conducted in the main by local medical practi- tioners in connection with the current system of medical apprenticeship; with the growing re- quirement for formal teaching its absorption into the organisation of a University became imperative. Chemical instruction in the School which had been taken over by Mr. </p>
<p>A. H. Allen the Public Analyst was latterly provided by the Firth College. The Rev. Samuel Earnshaw son of a file-cutter who rose “the hard way� to be Senior Wrangler promoted successful University Ex-tension Lectures in Sheffield in the 1870s. This pointer led Mark Firth (1819-1880; steel pioneer Master Cutler and Mayor of Sheffield) to found a permanent institution He devoted E20,OOO to the erection of Firth College at the corner of Leopold and West Streets provided a further endowment of E5000 and vested the whole in eighteen Trustees under his own chair- manship. The project quickly took the definite shape perhaps not originally intended of an embryo University. Prince Leopold youngest son of Queen Victoria opened the building in October 1879 and classes opened with 89 day and 313 evening students. </p>
<p>The staff consisted of Mr. A. T. Bentley as Principal and Professor of Mathematics with a Professor of Classics and Ancient History and part-time lecturers in modern history and the theory of music. Attempts to establish a Technical School in the 1860’s came to nothing largely owing to feeble support from industry. In 1886 the Firth College instituted a Technical Department with powerful support from Frederick Thorpe Mappin (Master Cutler Mayor and Member of Parlia- ment). The Technical Education Act of 1889 empowering municipal support rescued the ven- ture financially but the conditions attached to the grants forced the separation of the Technical School from the College. </p>
<p>Chemical instruction for students of the School was provided by the College and more curiously instruction in mining also. Near the end of the century Sheffield aspired to a place in the federal Victoria University and as a first step the Firth College the Technical School and the Medical School were united and received a Royal Charter as the University Col- lege of Sheffield. In the following year (1898) an application to join the by then ramshackle Victoria University elicited a reply in which dis- paragement was more evident than courtesy. The College decided to “go it alone�; the accumula- tion of funds was quickened by a sense of out- raged local pride and a new building was erected at Western Bank. </p>
<p>In May 1905 King Edward VII granted a new charter to an independent University of Sheffield opening the Western Bank buildings in person two months later. The Firth College had met an early reverse in 1880 by the death of its founder Mark Firth. It never had the massive benefactions from a single source enjoyed by some other civic Universities and in its first generation was pitifully ill- endowed. That it survived tenaciously solvent was due partly to the vigorous prudence of Principals J. V. Jones (1880-1883) and W. M. Hicks (1883-1905) to the generosity of such benefactors as Henry Stephenson and H. C. Sorby and to the institution in 1889 of Govern- ment Grants to University Colleges. This last modest but decisive subvention can be traced to the establishment of a pressure group by Prin- cipals Jones and Hicks with William Ramsay on the return voyage from the British Association’s meeting at Montreal in 1884. </p>
<p>H. M. Gibbons Registrar and in effect Bursar from 1902 main-tained until his retirement in 1944 a tradition of strict financial circumspection which older members of the University recall with rueful admiration to this day. In the University College as in Firth College Hicks had served both as Principal add as Pro- fessor of Physics. On the foundation of the in- dependent University he wished to relinquish the former post but to retain the latter; but his col-*Published in connection with the Society’s Anniversary Meeting. FEBRUARY 1962 leagues felt that the leader who had steered the College wisely and resolutely through hard times should have the honour of the Vice-Chancellor- ship. </p>
<p>A fitting compromise was found Hicks became the first Vice-chancellor of the Univer- sity of Sheffield and performed the functions of that officeuntil his planned retirement three days later. It is not necessary to develop the later history of the University as a whole. It remained one of our smaller Universities (some 700 students in 1938-39) and has grown rapidly since the war -now over 3000 students with further expansion planned. This proportionately very large increase accounts for the conspicuous building develop- ment. While the largest group of buildings in- cluding the Department of Chemistry is in the Western Bank area the main applied science group adjoins St. </p>
<p>George’s Square some six hundred yards to the east while the unique Department of Glass Technology stands several hundred yards in the opposite direction. The Department of Chemistry.-One candidate for the Principalship of Firth College in 1879 was a young Manchester chemist Thomas Carnelly who so impressed Mark Firth that he offered to endow a Chair of Chemistry on condition that Carnelly be the first incumbent at a guaranteed stipend of E250. As an afterthought the Firth family contributed &lo00for the equipment of a laboratory. Starting with four part-time day students and 63 evening students and the occa- sional services of the college porter as laboratory technician Carnell y established a well-organised Department with courses leading to the London B.Sc. </p>
<p>His researches on the physical properties of elements and compounds in relation to the periodic system were enthusiastically com-mended by Mendeleev. He left in 1883 for Dundee and died while still in his thirties. Carnelly’s successor W. Carleton Williams a pupil of Roscoe Bunsen and KekulC main- tained the Department devotedly through most difficult times. Though Williams found little leisure for research George Young who had joined as Lecturer contributed some twenty papers on heterocyclic topics and also took an active part in student affairs. Carleton Williams retired in 1904 and was followed by William Palmer Wynne distin- guished formidable and in a sense the second founder of the School of Chemistry. </p>
<p>When Wynne took over the Western Bank premises were under construction George Young had retired owing to ill-health Williams had re-moved most of the available apparatus (his own property) and the only link with the past was the lab. boy! Wynne played a large part in tlie affairs of the young University; he was Dean of the Faculty of Pure Science for twenty years and he gave doughty support to the Students’ Representative Council and the Athletics Committee. Not the least acceptable of the honours which came to him was the award of honorary athletic colours by the student body. These duties together with the claims of teaching and departmental ad- ministration occupied all his time so that his fundamental work on orientation in the naph- thalene series came to a full stop-to be resumed characteristically on his retirement twenty-seven years later. </p>
<p>His extremely fastidious standards of manipulation made it almost impossible for him to conduct research in collaboration but he en- couraged independent workers in the Depart- ment during his long reign. J. F. Thorpe as the first Sorby Fellow worked in Sheffield (1909-1913) on the glutaconic acid problem and on his own “name reaction.� Wynne’s team was reinforced in 1910 by J. Kenner who studied the reactivity of substituents in the benzene nucleus and the chemistry of bi-phenyl; with Christie in 1922he achieved the first optical resolution of a hindered biphenyl deriva- tive and contributed much of the experimental foundation of the “obstacle theory.� W. </p>
<p>E. S. Turner by the necessities of the 1914 war was diverted from his significant work on molecular association to the study of glass which led to the establishment under his direction of the Depart- ment of Glass Technology virtually the first Industrial Research Association. Staffing difficulties in the 1914 war led to the recall of Miss E. G. Turner and Miss D. M. Bennett (Mrs. Leighton) who ruled the inter- mediate classes with an enlightened hess remembered with respect and esteem by genera-tions of students. At the end of the war the staffwas augmented by among others A. W. Chapman and T. </p>
<p>B. Smith. Smith presided over the “temporary� hut that housed advanced inorganic analysis under conditions which developed from the merely un- suitable by way of the impossible to the high fantastical until its unlamented demolition in 1954. The “post-war rush� forced the adoption of desperate expedients; Chapman writes “There were far more students in the Department than . . . cupboards to accommodate their apparatus and the corridor was stacked with small padlocked boxes each containing a set of apparatus. Each student who had no cupboard had one of these boxes which he took to his bench on arriving and took back again on leaving. . . . For several years it was my lot and that of my colleagiles to demonstrate regularly for 30 hours each week during term-time.� In spite of gross under-staffing and other difficulties only slowly overcome Chapman was able to pursue his experiments on the molecular rearrangement of imino-ethers and oxime ethers G. </p>
<p>M. Bennett studied the stereochemistry of sdphoxides and the effect of sulphur-containing substituents on reactivity and S. Glasstone did important work on electrolytic processes. T. B. Smith produced his well-known book “Ana- lytical Processes :A Physico-chemical Interpreta- tion.� In 1931 Wynne retired leaving an efficient highly disciplined polity to his successor G. M. Bennett. The Department continued on the same lines for seven years under Bennett’s attractive and vigorous personality ; R. P. Linstead followed him leaving for Harvard after one year; and in 1939 the present incumbent R. </p>
<p>D. Haworth assumed the Firth Chair. Brynmor Jones con- tinued his elegant researches on substitution reactions while G. C. Hampson drew attention to the phenomenon of steric inhibition of reson-ance and J. M. Robertson applied X-ray crystal- lographic methods to cis-and trans-azobenzene. But the outbreak of war directed work along different channels including studies of the chem- istry of nitramines still vigorously pursued. After the war the small University entered on a period of rapid expansion. The Chemistry De- partment spread urgently and unsystematically taking possession of the main tower some ground-floor territory made available by Botany and a new remote hut. </p>
<p>This wasteful and irk- some situation called for effective action and plans were drafted for a five-storey Y-shaped building some 200 yards away on Brookhill. We PROCEEDINGS have to-day something like this project erected less efficiently and more expensively in two stages. The central block and one wing were opened by the Earl of Scarbrough in 1954; last year the Duke of Edinburgh opened the other wing and a smaller west extension. Detailed plans are in being for a completed west wing (-1963); and in outline for a north block (-1964). Owing to the sloping site the west extension is a three-storey and the new east wing a five-storey construction. Throughout the second floor is devoted to organic chemistry the first to physical the ground floor to inorganic and analytical and the lower ground floor largely to teaching at intermediate level. </p>
<p>The central block provides for stores cloakrooms some ad- ministrative and general services and many research laboratories; it is backed by a stack of three lecture theatres. The small west extension is devoted mainly to research accommodation. Both east wings provide large teaching labora- tories with some provision for research two theatres and the Wynne Library. A 500-curie cobalt source and Metro-Vic nuclear magnetic resonance equipment are housed in the basement of the 1961 wing together with the notable installation of a 21 ft. concave grating spectro- graph. The present building meets the current demand for accommodation reasonably well but with little to spare; before the completion of the planned west and north extensions some diffi- culties can be foreseen. </p>
<p>The past and the pro- jected growth of the Department and its general contribution to the University’s teaching work are outlined in the Table. Since the Department moved to its present site in 1953 we have turned out 286 special honours graduates in chemistry seven M.Sc.s and 107 Ph.D.s. Wynne and the later incumbents of the Firth Chair were organic chemists and until the establishment of a Chair of Physical Chemistry in 1955 the Department’s research work was predominantly but by no means exclusively in the organic field. Wynne’s practice of encourag- ing his junior colleagues to work on individual lines has been followed by his successors so that a wide variety of original work is in progress. </p>
<p> One inorganic group is concerned with com- plexes in which transition elements are co-ordinated with mono-and poly-amines and FEBRUARY 1962 amino-acids. As many of the reactions involved are complete in less than a tenth of a second special methods are used to determine their kinetics. Associations of simple ions into more complex species are studied using measurements of solu- bility and distribution. Heats of formation of such complexes are being measured in a specially- designed micro-calorimeter. Other current inorganic studies relate to the analytical chemistry of niobium tantalum and tungsten and to the chemistry and crystallo- graphy of mixed metallic oxides including com- pounds of protactinium. </p>
<p>Organo-metallic com- pounds of boron gallium and the transition metals including the metallocenes have been the subject of a sequence of investigations. Several different problems are being attacked by the technique of flash photolysis combined with spectrographic analysis in which the grating spectrograph of high resolving power referred to above plays an important part. Thus the 1938-39 Special Honours Chemistry 16 Other Pure Science 67 Medical and Dental 45 Engineering and Metallurgy 50 Post-Graduat e 5 Academic Staff 8 kinetics of the formation of aromatic radicals are examined in detail together with the photolysis of benzaldehyde the rate of recombination of iodine atoms in presence of different third bodies and the photochemical conversion of benzo-phenone into benzopinacol. </p>
<p> The physicochemical study of free radicals is pursued both by these methods and by deter- mination of electron-spin resonance spectra for which apparatus has recently been installed. Other short-lived species whose behaviour is under investigation are atomic nitrogen and oxygen produced photochemically. A relation appears to exist between the fluorescence spectrum and the crystal structure of an aromatic hydrocarbon. Little fundamental work has been published on thermal diffusion in liquid systems. A detailed study is in progress of the relation between the nature of the solution and the sign and magnitude of the separation. </p>
<p> Much attention is being paid to thermo-dynamic properties and the conductance of strong acids (sulphuric disulphuric nitric) con- sidered as dissociating solvents; and to the kinetics and mechanism of reactions in such solvents incIuding reactions of organic solutes. Researches into the chemical constitution of hydrolysable vegetable gallotannins have rigor- ously shown that these substances possess mono- saccharide and not the oligosaccharide cores suggested by some recent investigators. Thus Chinese and Sumach gallotannins are based on /?-penta-0-galloylglucose Turkish gallotannin on incompletely galloylated glucose(s) and Tara gallotannin on a galloylated quinic acid. </p>
<p>Addi- tional galloyl groups are linked in the form of depsides and present work aims at the elucida- tion of the positions of these groups and further towards an evaluation of the homogeneity of the extracts. Work is also in progress on other important plant polyphenols and on biosynthetic routes in the field as a whole. Current work on natural products also includes 1949-50 196142 Late 1960s 90 186 ca. 250 128 202 ca. 400 105 103 ca. 150 71 211 cu. 350 23 60 ca. 80 12 25 ca. 36 studies of carbohydrates of furan derivatives often related to them of synthetic approaches to long-chain hydroxy-acids and of a variety of alkaloids. The study of the steroidal alkaloid conessine has led to a more general examination of the influence of structural and conformational factors on the reactivity of cyclic amines. </p>
<p>Non- alkaloidal steroids are under investigation both in respect of reaction mechanisms and with a view to synthesis. General descriptive and “reaction� organic chemistry are further represented by the work on nitramines already mentioned by studies of a series of electrophilic molecular rearrangements and by an examination of reactions in which an N-sulphonyl group is eliminated as sulphinate ion. New methods have been developed for the production of aromatic and heterocyclic diazon- ium compounds. The behaviour of porphin as an aromatic system is being studied Free radicals are under investigation from the point of view of organic as well as that of physical chemistry. </p>
<p> F’ROCEEDINGS COMMUNICATIONS Electron-spin Resonance Spectra of Some Diazine Radical Anions By C. A. MCDOWELL and J. R. ROWLANDS K. F. PAULUS (DEPARTMENT OF BRITISH OFCHEMISTRY,UNIVERSITY COLUMBZA VANCOUVER 8 B.C. CANADA) AROMATIChydrocarbons are known to react readily with alkali metals in solution to yield radical anions and this has proved a useful means for the prepara- tion of solutions of such anions for electron-spin resonance studies.l We have found that the aromatic diazines in solution in dry degassed solvents such as dime thox ye t hane and te t r ah yd r o furan a1 so easily form the corresponding radical anions. We have measured the electron-spin resonance spectra of a number of these diazine radical anions. </p>
<p> Pyrazine in solution in dimethoxyethane reacts with potassium or sodium (in low concentration) to form a coloured solution which gives an electron- spin resonance spectrum at g = 2.0010 fO.OOO1 resolvable into 25 lines. Fig. 1 shows the spectrum FIG. 1. (a) Electron-spin resonance spectrum at 90 Mc./sec. of pyrazine radical anion (prepared with potassium) in dimethoxyethane. (Note Only half the symmetrical spectrum is shown.) (b) The theoretically predicted spectrum for the pyrazine radical ion. obtained from [pyrazinel-K+ together with the sug- gested interpretation. This analysis is based on the assumption that the pyrazine radical anion is planar with symmetry D2h.The hyperfine splitting constant due to the two equivalent nitrogen atoms is a = 7.15 f0-02 gauss. </p>
<p>That due to the four equivalent protons is a =; 2-61 f0.1 gauss. From the relation- ship a = Q,p, where pz is the electron density on the nitrogen atom or on a carbon atom adjacent to a protcln causing hyperfine splitting and a value of QN = -25 gauss,2 the electron densities on the nitrogen atoms are calculated to be pN = 0-286.For the proton hyperfine splitting we use the value Q = 24.2 gauss to obtain the n-electron densities on the adjacent carbon atoms asp = 0.1078. Values for the electron densities for the pyrazine radical anion were calculated from this simple Hiickel LCAO molecular-orbital theory by using different estimates for the Huckel parameters aN = aC+ hp and PCN= kp,,. Electron densities were calculated for values of h from 0-5 to 2 and for k = 1 or 1-2. </p>
<p>From these results it is apparent that the “experimental� values for the electron spin densities at both the nitrogen and the carbon atoms are in best agreement with the theoretical values calculated with h = 0.6 and k = 1.0 which gave pH = 0.2763 andp = 0-1118. In certain experiments when sodium was used in excess a very complex spectrum was observed for the ion pair [pyrazinerNa+ in solution. Fig. 2 shows I3 gauss FIG. 2. Electron-spin resonance spectrum of the [pyraziiie rNa+ conplex in tetrahydro furan. such a spectrum with tetrahydrofuran as solvent. Though this complex spectrum has not yet been fully resolved it is apparent that there must be electron sharing between the ion pair and that the extra hyperfine splitting observed is caused by the inter- action of an electron with the 23Na nuclear spin of 3/2. </p>
<p>Such effects are known to occur in the electron- spin resonance spectra of ion pairs involving sodium and benzophenone? hexa~nethylacetone,~ nitro- benzene and naphthalene.‘ l Paul Lipkin and Weissman,J. Amer. Chern. SOC.,1956 78 116. McLachlan Mol. Phys. 1958 1 233. McLachlan Mol. Phys. 1960,3 233. Adam and Weissman J. Amer. Chem. SOC.,1958 80 1518. Hirota and Weissman J. Amer. Chem. SOC.,1960,82,4424; Henderson and McDowell unpubfished experiments. Ward J. Amer. Chem. SOC.,1961,83 1296. Atherton and Weissman J. Amer. Chem. Suc. 1961,83 1330. FEBRUARY 1962 The structures of the ion-pair complexesin the case of the ketyls are not known but for nitrobenzene-sodium ion pair it has been suggested6that the alkali ion is located near the nitro-group. </p>
<p>In the present case it is likely that the sodium ion is located at the centre of the pyrazine radical anion somewhat as in the model proposed for the complexes formed between aromatic hydrocarbons and alkali metaka The fact that the spectrum observed for the [pyrazinerNa+ complex is so similar to that ob-served' for [naphthalenerNa+ is in favour of the assumed structure. Pyridazine in either of our solvents yields a coloured solution which gives an electron-spin resonance spectrum at g = 2.0009 f0-0002consist-ing of seven main lines with intensity ratios -I :4 S 10:8:4 1. </p>
<p>Each of these peaks shows evidence of splitting into a further triplet. The hyperfine splitting between the seven main peaks is 6.05 gauss. This spectrum of the pyridazine radical anion is readily interpreted as due to the interaction of the free electron with two equivalentnitrogen atoms and two equivalent protons with accidental degeneracy between the splittings so that there is overlapping. This means we must also have aN = a, - 6-05 gauss. Using the above values for QNand Q we get the experimental electron densities pN = 0.242 and pc = 0.250. The Hiickel LCAO molecular-orbital theory with the parameters a = a + 0.7p and = PcN = 1.2p, yields the values pN = 0-2384 and pCl= 0.2490 which are in good agreement with the experimental estimates and thus substantiate the analysis of the spectra on the assumption that the pyridazine radical anion in planar with symmetry G2v. </p>
<p> We wish to thank the National Research Council of Canada for grants. (Received December 1Sth 196I .) Aten Dieleman and Hoijtink Discuss. Fmu&y SOC.,1961,29 182. The Electronic Spectra of Azabenzene Anions By J. W.DODD,F. J. HOPTON, and N. S.HUSH OF PHYSICAL CHEMISTRY BRISTOL, (DEPARTMENT AND INORGANIC THEUNIVERSITY 8) DURINGa systematic examination of the electronic spectra of aza-aromatic negative ions we have pre-pared the mononegative ions of a number of nitrogen-substituted benzenes. Introduction of a nitrogen atom into the aromatic ring system leads to some experimental difficulties the most important being the lability of several of the anions. </p>
<p>Hydrocarbon anions (e.g. naphthalene negative ions) are some-times slowly attacked by an ether-type solvent lead-ing it is thought to partial ring saturation1 but not usually to dimerisation. Heterocyclic anions appear frequently to dimerise or polymerise irreversibly; indeed organic preparative techniques for linking several such ring systems together have been based on preliminary reduction by an alkali metal. The single-ring systems are probably the most liable to this type of decomposition. We have examined anion formation in tetrahydrofuran solu-tions of pyridine pyrimidine pyridazine and pyra-zine by reaction with a sodium film. Of these substances pyrazine is exceptional in forming a rela-tively stable mononegative ion. </p>
<p>Anions of the other molecules decay moderately quickly. However pro-vided that 1O4-lO4M-solutions are used and further contact with the metal film is avoided reduction by sodium can be used to prepare solutions of the mono-negative ions which are stable long enough for spectroscopic measurement. A simple test for the presence of decomposition products in solution can be carried out. At the conclusion of a run the sample is exposed to oxygen. If the solution contains only anions R-of the original heterocyclic molecule R then the expected reaction by analogy with alkali-metal aromatic solutions is R-+ 0 -+ R + 02- and the spectrum of the original substance is found. Each of the mononegative ions has an absorption spectrum consisting of two principal bands. </p>
<p>The fre quencies and extinction coefficients of these are shown in the Table. McDowell Paulus and Row-Principal absorption frequencies (cm.-l) and extinction coe@cients of sodium salts of azabenzene anions in tetrahydrofuran. Anion of V1 €1 v2 €2 Pyridine Pyridazine Pyrimidine Pyrazine 29,850 28,450 30,260 27,470 2000 1420 2160 3040 40,980 41,390 40,110 40,160 3340 2870 3540 4680 lands2 have measured the electron-spin resonance spectra of dilute solutions prepared in this way. As Hoitiink and Zandstra. Mul. Phvs.. 1960. 3. 371. Rowlands 1961 personal co&mication; & McDowell Paulus and Rowlands Proc. Chem. SOC.,1962 preceding paper. hyperfine splitting due to interaction with the 2aNa nucleus is observed the electronic spectra actually refer to the ion-pairs rather than to free anions. </p>
<p> WardS reported recently that the pyridine anion cannot be prepared in 1,Zdimethoxyethane solution by reduction of pyridine with potassium as under these conditions the first product observed is the mononegative ion of 4,4'-bipyridyl (identified by means of the electron-spin resonance spectrum). A similar dimerisation has been observed in the hydro- carbon series in tetrahydrofuran in which the benzyl Ward J. Amer. Chem. SOC.,1961,83 3623. Hopton and Hush Mu].Phys. 1962 in the press. PROCEEDINGS anion is slowly transformed into the dinegative ion of ~tilbene.~ We have found that the 4,4'-bipyridyl anion (deep royal blue) is fairly stable in tetrahydro- furan in absence of an excess of sodium; the absorp- tion spectrum shows two principal peaks at 17,240 and 26,140 cm.-l. </p>
<p>This is very similar to the spectrum of biphenyl mononegative ion.6 Evidently reduction in tetrahydrofuran by a metal less active than potas- sium provides more favourable conditions for stability of the pyridine anion than Ward's. (Received December 1lth 1961.) Balk de Bruijn and Hoijtink Rec. Trav. chim. 1957,76,907. The Production of CF CCl and CBr through the Decomposition of Energised Halogenomethyl Radicals By A. J. YARWOOD and J. P.SIMONS (THEUNIVERSITY, BIRMINGHAM) TRANSIENT ultraviolet absorption spectra obtained by flash photolysis of gaseous polyhalogenomethanes such as CCI,Br, CHCl,Br CHCIBr, and CHBr, have been assigned to the radicals CCI and CBr? By studying the effect of photon energy input total pressure and flash intensity on the yields produced under isothermal conditions it was established that the diatomic species result from the secondary de- composition of energised radicals produced in the primary step; for example where X = halogen and M = N2or SF, CHX,Br + hv 3 CHXt* + Br _+ CX + HX CHXa* d-+ CHX +M When the parent molecules contained hydrogen hydrogen chloride or bromide was found amongst the final products. </p>
<p> Further work has shown that yields of these acids vary with total pressure in the same proportion as those of the CCl and CBr. This confirms the con- clusion that CX and HX are formed simultaneously rather than through the separate steps CHX,Br + hv 3 CX,* + HBr cx+ x cx,* -r -cx +M These studies have been extended to fluorine- substituted methyl bromides. </p>
<p>We find that flash photolysis of di-and tri-bromofluoromethane under isothermal conditions results in the transient appearance in absorption of the double-headed band system due to the X2n+ A2C transition in CF (previously observed in emission only).2 Both the (0,O) and the (0,l) transition at 2330 and 2240 A are clearly visible the latter being the more intense. By analogy with the other poly-halomethanes we pro- pose that CF arises in sequences such as CHFBr + Itu -f CHFBr* + Br -CF+ HBr CHFBr*d -+ CHFBr +M All these secondary decompositions require the concentration of a very large proportion of the excess photon energy into the halogenomethyl radicals Under these circumstances momentum cannot be conserved unless these radicals are produced initially in an electronically excited state. </p>
<p>On the other hand measurements of the reduction in yields of CX as the total (N and SF,) pressure increases indicate that decomposition occurs as a result of vibrational excitation? It follows that upper vibrational levels in the ground electronic state are populated through internal conversion of the energy in the electronically excited radical. If the same process is responsible for the abnormal excitation in methyl radicals derived from photoIysis of methyl iodide then the explana- tion in terms of the disparity in the masses of methyl radicals and iodine atoms is invalid. </p>
<p>The generality of the phenomenon certainly supports the extrapola- tion to monohalogenomethanes. (Received December 6th 1961.) Simons and Yarwood Trans. Faraday SOC.,1961.57,2167. Andrews and Barrow Proc. Phys. Soc. 1950 A 64,481. FEBRUARY1962 Mechanism of the Reactions of Peresters Catalysed by Copper Salts By A. L. J. BECKWITH and G. W.EVANS (UNIVERSITY Sow AUSTRALIA) OFADELAIDE THERE is conflicting evidence concerning the reaction of t-butyl peresters with olefins catalysed by copper salts and two mechanisms have been proposed one involving a transition complex containing olefin copper ion and peroxide (or t-butoxy radical),14 the other proceeding by a series of oxidation-reduction reactions? RC02*OBU‘ + CU(I) -R.C02Cu(D) + Bu‘O. </p>
<p>***-(I) Ill Il --C;-C-$-H + &‘O. __c. Bu‘OH +[-C-&C-]*l ..-0 p..’‘1 f f?;co2cuQI) -c-c-c-Ill Ill cU(I) + -C.=C-$-O,C*R + RCO -C-C-C-.-*@ 21 We now describe further experiments. Thermal decomposition of di-t-butyl peroxide in the presence of an excess of cupric benzoate benzoic acid and toluene gave benzyl benzoate; benzyl acetate was produced in a similar reaction with cupric acetate and acetic acid. These results indicate that benzyl radicals formed by hydrogen-atom abstraction from toluene may be oxidised by cupric benzoate in a non- polar solvent. Examples of similar oxidations in aqueous solution have been previously de~cribed.~ Formation of methyl benzoate by catalysed decom- position of t-butyl perbenzoate1s6 may occur by the same route. </p>
<p> Decomposition of benzoyl peroxide yielded 22 % of benzoic acid whereas in the presence of an excess of cuprous bromide the same reaction gave 70% of benzoic acid. Apparently reduction of benzoate radicals occurs as follows These results accord with Waters’s suggestion’ that the ease and direction of oxidation-reduction of free radicals in solution may be estimated approxi- mately from the relative stabilities of the ions pro-duced. It is noteworthy that according to this ap- proach the t-butoxy-radical should not be readily oxidised or reduced by copper ions. Our observations agree with the suggestion that catalysed reactions of t-butyl peresters proceed as in (1-3). </p>
<p>However further experiments indicated that under certain conditions free substituted allyl radicals are not intermediates. We have confirmed earlier reports that cuprous bromidecatalysed de- composition of t-butyl perbenzoate in an excess of oct-1-ene yields only 1 -pentylallyl benzoate;l and there was no rearrangement during acetoxylation of oct-1-ene. Also in accord with earlier work is our observation that cuprous bromide-catalysed reaction of t-butyl perbenzoate with allylbenzene in the absence of solvent occurs without rearrangemmt,% but this reaction in benzene yielded mainly l-phenyl- allyl benzoate with a smaller amount of cinnamyl benzoate. </p>
<p> Treatment of cholesteryl benzoate with t-butyl perbenzoate and a catalytic amount of cuprous bromide in benzene gave equal quantities of cholest- 5-ene-3P,7a-and -3P,7j?-diol dibenzoate with a trace of the rearrangement product cholest-4-ene 3/3,6/3-diol dibenzoate. This reaction provides a new route to cholest-5,7-dien-3~-01. In all these reactions and in others involving di-isobutene and oct-2-ene as substrates t-butyl alcohol and acetone were formed in relative amounts com- parable with those obtained from reactions of t-butyl perbenzoate in the absence of copper salts. The inter- mediate formation of free t-butoxy-radicals in the copper-catalysed reactions is thus indicated. Our results support previous suggestions concern- ing a termolecular transition state for copper salt- catalysed reactions of t-butyl peresters with olefins in high concentration. </p>
<p>Having regard to the ability of copper(1) to form n-complexes with olefins* we suggest mechanism (A) (curved arrows indicate movement of single electrons). Alternatively a con- certed mechanism (B) may be drawn but does not account for the formation of acetone. Similar mechanisms involving complex formztion between copper ion and oxygen or sulphur account for the reaction of peresters with ethers and sul- phides. Kharasch and Sosnovsky J. Amer. Chem. SOC.,1958,80,756; Kharasch Sosnovksy and Yang ibid. 1959,81,5819 a Kharasch and Fono J. Org. Chem. 1958 23 324; 1959 24 606; Denney Denney and Feig TetrahedronLetters‘ 19S9 No. </p>
<p>15 19. Story,J. Org. Cltem. 1961,26 287; Lawesson and Bergland Tetrahedron Letters 1960 No. 2 4. ‘ Kochi J. Amer. Chem. SOC.,1961 83 3162. Kumarnoto de la Mare and Rust J. Amer. Chem. Suc. 1960 82 1935; de la Mare Kochi and Rust ibid.,1961, 83 2013. * Lawesson and Berglund Arkiv Kemi 1961 17 485. ’Waters “Vistas in Free Radical Chemistry,� Pergamon Press London 1959 p. 155. a Abel Bennet and Wilkinson J. 1959 3178; Slade and Jonassen J. Amer. Chem. SOC.,1957 79 1277; Keller, Chem. Rev. 1941,28,229. PROCEEDINGS Although cupric complexes of olefins appear not benzoate is much more soluble in olefins than in to have been reported our observation that cupric related alkanes suggests that such complexes do exist. Tt would be expected that under experimental con- ditions unfavourable for copper ion-olefin complex formation the reaction would proceed by the oxidation-reduction sequence (I -3). </p>
<p>Thus experi-ments conducted in dilute solutions of olefins or at high temperatures should yield rearranged products. It appears that in this manner the conflicting experi- mental evidence may be reconciled. We thank Laporte Chemicals (Australia) Pty. Ltd. for gifts of di-t-butyl peroxide and t-butyl per- benzoate. (Received November 3rd 1961 .) The Internuclear Distance in Gaseous Cu By D. N. TRAVISand R. F. BARROW CHEMXSTRY OXFORD (PHYSICAL LABORATORY UNIVERSITY) molecules of the copper-silver-gold group more overlapping than in the B-X bands and no DIATOMIC were first observed through their electronic spectra in analysis of the A-X system has yet been attempted. </p>
<p> high-temperature absorption and emission experi- TABLE 1. Constants for 63Cu2. ments.'S8 More recently they have been studied State AGO, ~e 104~ IOSD re(8i) mass-spectroscopically and values of several dis- B 'c+ 242.14 0.09892 5.9 6.2 2.327 sociation energies are now a~ailable.~ However X 'c+g 264.5 0.10879 6.1 7.2 2.219 nothing is yet known about the spectroscopic charac- ters of the ground or excited states and although The observed internuclear distance in the ground they are of interest in their relation to the inter- state 2.219 A is somewhat shorter than would have nuclear distances in the metals no values of inter- been predicted from the single-bond radius or from nuclear distances in the gaseous molecules have the internuclear distance in the hydride4 (Table 2). </p>
<p> hitherto been published. TABLE 2. We have now completed the rotational analysis of Cu Ag Au the 1-O O-O and 0-1 bands of the B-X system of Cu2 Singlebond radius (A) 1.176 1.342 1.339 (Te = 21,758 cm.-l). The bands were photographed re(M-H) -0.3 1.163 1.317 1.224 in absorption a King furnace being used at about ire (M2) 1.110 (1.26)* (1-17)* 46 38 52 1800°c in a second order of a 6-65-m. concave D" (k~ai./moie)3 * Estimated grating spectrograph with 30,000 lines/inch. The bands of a given isotopic species consist of only two This fact together with the unusual trends in the strong branches so that dA = 0. The transition is values of the dissociation energies suggests that -lZ+ although weak Q branches at hybridisation occurs in these molecules to significant probably lc+u g low values of J would have escaped detection Con- but varying extents so that it is difficult to make any stants obtained in the present work are summarised very reliable predictions for the internuclear in Table 1. </p>
<p>Bands of the A-X system (Te = 20,433 distances in Ag and in Au,. cm.-l) were also photographed but there is even (Received January loth 1962.) l Kleman and Lindqvist Arkiv Fys. 1954,8 333. Ruamps Ann. Phys. (France),1959 4 1111. a Ackerman Stafford and Drowart J. Chem. Phys. 1960 33 1784. Pauling "The Nature of the Chemical Bond," Cornell Univ. Press New York 1960. FEBRUARY 1962 65 The Structure of Diginin and Diginigedn By C. </p>
<p>W. SHOPPEE, RUTHLACK,and A. V. ROBERTSON UNIVERS~ OF SYDNEY N.S.W. AUSTRALIA) DIGININ, the first and simplest of the digitenolides was isolated in 1936 from Digitalis purpurea;l it was shown in 1940 by Shoppee and Reichstein2 to be the D( +)-diginoside of diginigenin C21H2804. Chemical investigation of diginigenin by Shoppee4 disclosed one secondary hydroxyl group and one reactive and one unreactive carboxyl group; the fourth oxygen atom could not be characterised and was considered to be o~idic.~ Successive elimin- ation of the four oxygen atoms furnished the parent hydrocarbon diginane4 (subsequently identified as 5 a 14/? 17a-pregnane by Press and Reichstein6). On the basis of an assumed analogy with the Digitalis saponins and sapogenins Shoppees suggested the 16p,21 -epoxy-structure (I) for diginigenin with one hindered carbonyl group unplaced but possibly located at position 11 or 12. </p>
<p> P&&h &' OHC HO HO Ye P 9 PO-O7C-H Tschesche and Grimmer' suggested that the hindered carbonyl group is present as an angular 10-aldehyde group mainly on account of the ultra- violet maximum at 310 mp (log E 1.95); Tschesche and BuschaueI.8 suggested by analogy with the C,,-cardenols the 14/l,21 -epoxy-structure (II) for diginigenin. We have now supplemented the chemical evidence for the structure of diginin and diginigenin2p3p5 by physical methods. Mass spectrometry confirms the molecular weight for diginigenin C21H2804 (A4= 344). </p>
<p> The nuclear magnetic resonance spectrum of diginin shows the presence of five methyl groups (i) singlet at 7 9-00 for c(l8);(ii) two overlapping doublets at r 8.67 (J 6-5 c./sec.) and 8-72 (J6.5 c./sec.) for the diginose terminal methyl group and C(21); (iii) singlet at T 8.45 for C(lQ); (iv) singlet at T 6.60 for the diginose methoxyl group. The spectrum of diginigenin acetate shows the presence of four methyl groups (i) singlet at r 8-99 for c(18);(ii) doublet at T 8-73 (J6-5 c./sec.) for C(21);(iii) singlet at r 8-46 for C(lQ); (iv) singlet at T 8-02 for the acetoxy- group. A 19-aldehydic proton should appear as a sharp singlet at T 0-1 and this region is completely bare. The skeleton of diginin and diginigenin thus contains two angular methyl groups. </p>
<p>The ether oxygen must be bound to C(20) to account for the chemical shift and splitting pattern of the 21 -methyl group. These facts are expressed in the partial formula (m. The infrared spectra of diginin and diginigenin disclose two carbonyl groups [urnax. (in CHCl,) 1735 1712 cm.-l]; one must be in ring D and the other in a six-membered ring. The maximum at 1735 cm.-l disappears in dihydrodiginigenin [v max. (in CHCl,) 1710 1655 cm.-l (C=C)] obtained by brief treatment with sodium borohydride and in tetrahydrodiginigenin2[urnax.(in CHCl,) 1710 cm.-l no C=C absorption] obtained by hydrogenation with platinum-acetic acid so that in these com- pounds the reactive ring-D carbonyl group has been reduced. </p>
<p> The optical rotatory dispersion curves (in meth- anol) of diginin diginigenin dihydrodiginigenin and tetrahydrodiginigenin show molecular amplitudes of -247" -226" -30" and -34" respectively. The very strong negative Cotton curves for diginin and diginigenin are consistent only with a 16-0x0-14a- system (10-'a -279") or a 15-oxo-14~-system (10-2a -125"); because of the established 14/3-structure of diginane,6 the ring-r carbonyl group is placed at position 15. The small negative Cotton curves given by dihydro- and tetrahydro-diginigenin show that the 15-carbonyl group has been reduced; further the small negative amplitudes observed are compatible with values found for 1 1-oxo-l4~-steroids (lo-% -48" -36") but not with those found for 12-0x0- 14p-steroids (10-2a +130° +135").' The hindered Walter Karrer Festschriftfur Elnil Barell Basle 1936 p. </p>
<p>238. a Shoppee and Reichstein Helv. Chim. Acta. 1940 23 975. a Shoppee and Reichstein Helv. Chim. Acta. 1942 25 161I. Shoppee Helv. Chim. Acta 1944,27 24.6. ti Shoppee Helv. Chim. Acta 1944,27,426. Press and Reichstein Helv. Chim. Acta 1947 30 2127. Tschesche and Grimmer Chem. Ber. 1955,88 1569. Tschesche and Buschauer. Annalen. 1957 603 59. *Djerassi Halpern Halpern Schindler and Tam Helv. Chim. Acfa 1958 41 250. PROCEEDINGS six-membered ring carbonyl group is therefore placed the negative Cotton curves for diginin and di-at position 11. ginigenin which require an axial OR linkage The integrated nuclear magnetic resonance adjacent to the 1 l-carbonyl group. </p>
<p> spectrum of diginigenin acetate shows four protons Diginigenin is 12a,20a-epoxy-3p-hydroxy-l4p,-at low field (i) multiplet 7 4-55 one olefinic proton 17a-pregn-5-ene-l1,15-dione(IV; R = H) dihydro-(6-H); (ii) overlapping multiplets r 5-40,two protons diginigenin is the related 3p,l Sa-diol and tetra-(3a-H 20-H); (iii) r 6.08 a singlet for one proton hydrodiginigenin is the saturated 3p 15a-diol. The on carbon attached to oxidic oxygen so that there structure (IV) readily explains the formation from are no hydrogen atoms on the adjacent carbon atoms diginigenin by Wolff-Kishner reduction and sub- sequent hydrogenation of 5 a,14p 17a-pregnane- [-CO-CH-C+]./c The third observation determines 3/3,20a-diol,* So! 14p 17a-pregnane-3,20-di0ne,4~~ and Sa 14p 17 a-pregnane.4.' Digifologenin is 12a,- b the structure of c diginigenin as (N). </p>
<p>Stereochemical 20a-epoxy- 2/?,3p- dihydroxy- 14p 17 a-pregn-5-ene-factors can account for the signal from the 12-proton 11,15-dione (IV; R = OH). appearing at higher field than that from the 20-Nuclear magnetic resonance spectra were taken on proton. The 12a,20a-orientation of the epoxide ring a Varian DP 60 instrument at 60 Mc./sec. with is preferred to the more strained 12p,20ar-alternative deuteriochloroform as solvent and tetramethylsilane because of the very high A values (335 338 mp) of as reference. (Received November 20th 1961 .) The Crystal Structureof the n-Allylic Complex DpdCi(C,H,)] By J. M. Row (AKERS LABORATORIES INDUSTRIES LIMITED, RESEARCH IMPERIALCHEMICAL HEAVY ORGANIC CHEMICALS DIVISION WELWYN, THEFRYTHE HERTS.) REPORTSof allyl complexes of palladium1 have system and the group itself is symmetrical about a caused speculation about their molecular structure. </p>
<p>mirror plane which passes through the palladium An X-ray structure determination of di-p-chloro- atoms and is perpendicular to the (PdCl) and allyl diallyldipal ladium now being carried out confirms group planes. The symmetry of the molecule there- the structure suggested by Diehm and Chien on the fore approximates closely to 2/m (C2J. The inde- basis of nuclear magnetic resonance and infrared pendent palladium-chlorine bond lengths are both spectra in which the double bond of the allyl group 2.39 A and the ClPdCl bond angle is 87"; the is delocalised and the group is bonded to the metal palladium-carbon distances are all 2.1 f0.05 A atom by a n-type bond similar to that between a and the carbon-carben bond lengths are both 1.3 f cyclopentadienyl ring and a metal atom. </p>
<p>0.1 A. The central carbon atom of the allyl group is The crystal data for this compound are pdCl(C,H,)],. A4 = 365.86. Monoclinic. a = 7-44 f0.02 b = 7.40 f0-02,c = 11.03 f0.03 A p = 128.33" U=476.2 A3 Dm M 2*4,Z= 2 D =2-55. Space group P2Jc (C5h,no. 14). The binuclear mole- cule [PdCI(C,H,)] must have a centre of symmetry. The structure was determined from a-and b-axis about 0-4 8 above and the terminal carbons about projections; refinement has been carried out by 0.1 A below the (PdCl) plane. The angle subtended difference Fourier methods anisotropic temperature by the two terminal carbon atoms at the central factors being applied to the palladium and chlorine carbon is 123" and at the palladium is 66". </p>
<p> atoms only. The reliability factors are now 0-095 and 0.103 for The configuration of the molecule is shown in the a-and b-axis projections; further refinement is in progress. Figure the plane of the allyl group is approximately perpendicular to the plane of the (PdCI) bridge (Received December 22nd 1961.) Smidt and Hafner Angew. Chem. 1959 71 284; Moiseev Fedorovskaya and Syrkin J. Jnorg. Cbem. (U.S.S.R.), 1959 4 2641 ; Shaw Proc. Chem. Sac. 1960 247; McLellan Hoehn Cripps Muetterties and Howk J. Amer. Chem. Soc. 1961 83 1601. Diehm and Chien,J. Amr. </p>
<p>Chem. Sac. 1960,82,4429. Professor John Monteath Robertson M.A. D.Sc. F.R.I.C. F.R.S. President Elect of the Society for the period 1962-1964 Town Hall and St. Paul's Gardens (By coui'tesy Civic Informotion Service Sheffickl) Sheffield University Library (By courtesy Henk Si?oc)k,London) Model of projected University building scheme in the Western Bank area. (Some of the buildings are already completed. The proposed Arts Tower stands to the right of the Library) (By corrr-tesy The Univrrsity) Department of Chemistry Sheffield University (Bv coi4rtesy The University) Typical Derbyshire scene at Derwent about five miles outside the city (By courtesy The Shefield “Telegraph� and “Star�) FEBRUARY 1962 67 ~~~~ ~ The Kinetics and Mechanism of Homogeneous Aldehyde Hydrogenation with Cobalt Carbonyl as Catalyst By L. </p>
<p>MARK^ (HUNGARIAN INSTITUTE, OILAND GAS RESEARCH “MAFKT,� WARTHA VINCEGTCA 4-6,VESZPRh HUNGARY) WEhave carried out batch experiments to determine of cobalt added but by the equilibrium of carbony1 the kinetics of hydrogenation of propionaldehyde to formation.2 This explains the ascending part of the propyl alcohol in toluene at 150� in presence of di-curve shown. cobalt octacarbonyl. The rate of alcohol formation Since activation of molecular hydrogen apparently was approximately of the first order with respect to does not require the simultaneous action of two aldehyde cobalt and hydrogen; its variation with metal atoms,3 we propose the annexed mechanism the partial pressure of carbon monoxide is shown in for the hydrogenation analogous to Breslow and the Figure. </p>
<p>Heck‘s mechanism of hydroformylation? -to -co ~~ OHCCofCO) HCo(CO) +HCo(CO), +co +co R.CH=O RCHO +-HCo(CO) + J c+ R.CH,-OCo(CO), HCo(CO) A-HI (slow) ,-R-CH,.O*CoH,(CO) (Ill) -+ R.CH,-OH + HCo(CO) (11) \ +co -t R-CH,.O.CO(CO)~(IV) F1 R-CH,.O-CO*Co(CO) (V) -co +co (V) F=* R.CH,*O*CO*CO(CO)~ (VI) -co The results indicate that carbon monoxide has an We assume that hydrogen is activated by a effect on aldehyde hydrogenation similar to that on co-ordinately unsaturated complex such as (IT) hydroformylationl in that the reaction is in both cases while co-ordinately saturated derivatives such as (IV) fastest at relatively low partial pressures of carbon and (VI) are inactive. </p>
<p>Complex (11) contains two monoxide (-10 atm. at 110� for hydroformylation fewer molecules of carbon monoxide than and 20 atm. at 150�for hydrogenation) above which HCOCo(CO) and complex (VI) and if cobalt is the reaction is retarded by inoleasing concentrations considered to be present principally in the form of of carbon monoxide. The “effectiveness� of carbon the latter two complexes it would account for the monoxide in diminishing the reaction rate is how- (pc0)- term of the kinetic equation. The active com- ever much greater for hydrogenation the rate of plex RCH,CH,-COCo(CO) proposed as an inter- has only one fewer alcohol formation between 32 and 210 atm. </p>
<p>being mediate in hydroformylati~n~ inversely proportional to the square of the partial molecule of carbon monoxide than its inactive pressure of carbon monoxide. The full kinetic ex- counterpart R-CH,CH,.COCo(CO), in accordance pression of aIcohol formation above 32 atm. carbon with the first-order inverse effect of carbon monoxide monoxide partial pressure is therefore in this reaction. Postulation of an intermediate step (111) in the splitting of the hydrogen molecule is justified by the existence of several hydrides of transi-tion metals that have two hydrogen atoms associated Ifp = < 32 atm. cobalt is already partly precipi- with the central metal atom.5 Fission of the cobalt- tated as metal and the concentration of cobalt carbon bond is therefore accomplished by the carbonyls is no longer determined by the quantity hydrogen already in the co-ordination shell of the Natta Ercoli and Castellano Chimica e Jndustria 1955 37 6; Martin Chem. </p>
<p>and Jnd. 1954 1536. Berty Oltay and Mark6 Chem. Tech. (Berlin) 1957,9 283; Mark6 and Budavari Magyar Tud. Akad. Kkm.Tud. Oszt. KOzl. 1960 13 153. a Halpern “Advances in Catalysis,� Vol. XI Academic Press New York,1959 p. 318. Breslow and Heck Chem. and Ind. 1960,467. Green Angew. Chem. 1960,72,719. 68 PROCEEDINGS metal a mechanism similar to the insertion of carbon Complex (V)is also a co-ordinately unsaturated monoxide.6 molecule which could react with molecular hydrogen and this reaction explains the formation always 4 observed of fonnates from aldehydes carbon monoxide and hydrogen:’ 3 Slow (V) + H +RCH2*OCO*C~H,(CO) -+ R.CHZ.O.CHO + HCo(CO) n -?2 The general conclusion seems to be justified that molecular hydrogen is homogeneously activated by 4. </p>
<p>co-ordinately unsaturated cobalt-carbon monoxide ,tf complexes that contain unfilled d-electron shells. -c I While a minimum pressure of carbon monoxide is essential for formation and stability of cobalt car- bony1 complexes higher pressures diminish the con- centration of the active species. The effect of carbon monoxide at high pressures in these reactions further supports the analogy between homogeneous and heterogeneous hydrogenation the well-known Efect of partial pressure of carbon monoxide (pco) “poisoning� of solid metallic hydrogenation catalysts on the rate of hydrogenation (pH = 95 atm.) of by carbon monoxide,8 and the inhibiting action of propionaldehyde in presence of dicobalt octacarbonyl carbon monoxide in hydroformylation and in hydro- genation of aldehyde are both caused by filling of the (0.2 mole % of Co). </p>
<p> a = initial aldehyde concentration; x = concentra-d-shells of the metal atom. tion of alcohol formed. (Received October 2nd 1961.) 6 Coffield Kozikowski and Closson Chem. SOC. Special Publ. No. 13 1959 p. 126; Booth and Chatt Proc. Chem. SOC.,1961 67. 7 Sternberg and Wender Chem. SOC. Special Publ. No. 13 1959 p. 35; Mark6 and Szab6 Chem. Techn. (Berlin) 1961 13 482. * Maxted “Advances in Catalysis,� Vol. 111 Academic Press New York 1951 p. 156. The Action of Fenton’s Reagent on Acidic Polysaccharides By P. </p>
<p>S. O’COLLA,J. J. O’DONNELL, and T. M. D. FEELEY (DEPARTMENT IRELAND) OF CHEMISTRY UNIVERSITY COLLEGE GALWAY IN a search for selective methods of cleaving poly- containing 1% of hydrogen peroxide and 1% of ferric saccharides we have found that Fenton’s reagent acetate was completely degraded after 15 minutes cleaves uronic acid units. The action of Fenton’s yielding acids two substances which give the colour reagent is due to hydroxyl radicals,l hence the re- reactions of pentoses and galactose in 50% of the action may not be completely selective; e.g. the theoretical yield. In similar experiments with maltose reagent has been used to demethylate sugar deriva- starch and esters of the aldobiouronic acid there was tives? However we have used the less active Ruff no effervescence and the compounds were recovered modification3 of the reagent at 15� and at pH 3-6. </p>
<p>unchanged. Sodium alginate was degraded rapidly to Under these conditions tetra-0-methylglucose was low-molecular dialysable materials whereas the not demethylated and polysaccharides are not hydroxypropyl ester did not react. The action of the attacked by hydrogen peroxide in the absence of reagent on pectin has been described.6 cat a1 ysts? One degradation of gum arabic yielded 10%of A 6 % solution of 6-~-glucuronosy~-~-galactose~dialysable materials which after deionisation con- 1 Fenton J. 1894 899; 1899 1; Weiss Adv. Catalysis 1952 4 343. 2 Jones Fraser-Reid and Perry Canad. J. Chem. 1961,39 555. </p>
<p> Ruff Ber. 1898 31 1573. 4 Whistler and Schweiger J. Amer. Chem. SOC. 1959 81 3136. Challinor Haworth and Hint J. 1931 258. 6 von Euler Hasselquist and Eriksson Makromol. Chem. 1956 18/19 375. FEBRUARY 1962 sisted of galactose arabinose rhamnose and a disaccharide. The non-dialysable material still con- tained uronic acid and was again partially degraded to yield the same sugars and traces of oligosac-charides. This indicates that these sugars are the labile moieties actually linked to glucuronic acid units. The acidic polysaccharide obtained by auto-hydrolysis of arabic acid7 yields galactose glucuronic acid and traces of arabinose on hydrolysis and Smith' has concluded from methylation data that the uronic acid units are end-groups. </p>
<p>One degradation with Fenton's reagent converted the degraded arabic acid into three low-molecular neutral galactans. The esters of arabic acid and autohydrolysed arabic acid do not react with the reagent hence the above results indicate that the reaction may prove of value in solving two difficult problems in the struc- tural determination of acidic polysaccharides (1) the nature of the labile residues attached to uronic acid; and (2) the detailed structure of the backbone. Pre- liminary experimepts indicate that the reaction may be of greater value in the investigation of polysac- Smith J. 1939 1724. O'Colla O'Donnell and Mulloy Proc. 1961 300. charides such as flax-seed mucilage and gum tragacanth which contain uronic acid units in the core of the molecule than in that of gum arabic which has most of the acidic units near the periphery. </p>
<p> Although the mechanism of the reaction is not known there are apparently two distinct conse-quences:(a)cleavage of glycosiduronic acid linkages and (2) cleavage of the glycosidic linkages by which substituents are attached to uronic acid. The latter cleavage may be peculiar to the C(,$inkage as in gum arabic. We have described already the application of the Weermann reaction to the elimination of oxidised fragments in periodate-oxidised polysaccharides.8 Fenton's reagent has proved of value for the same purpose. Oxystarch was further oxidised with bro- mine water and the acidic polymer was readily cleaved whereas its esters did not react. </p>
<p> We thank an Foras Taluntais for the award of a scholarship to one of us (T.M.D.F.) and the Chemical Society for a grant from the Research Fund. (Received,Deceniber 6th,1961.) Tetrameric Borazynes A New Boron-Nitrogen Ring System By H. S. TURNER and R. J. WARNE (NATIONAL LABORATORY, CHEMICAL D.S.I.R. TEDDINGTON) TRIMERIC borazynes the borazoles are well known1 but there are no accounts of other well-defined oligo- mers either cyclic or linear. We now report the preparation of a series of tetrameric borazynes (RNBX) and their tentative characterisation as eight-membered ring compounds (I).* The parent compound of this series has structure (11) systemati-cally named 1,3,5,7-tetra-aza-2,4,6,8-tetraborocine and our compounds are to be regarded as substitu- tion products of the octahydro-compound for which the trivial name borazocine has been suggested. </p>
<p> Primary amines generally form 1 :1 adducts with boron halides. Under suitable conditions the adducts with boron trichloride or tribromide will lose hydro- gen halide and the course of the reaction depends on the degree of substitution of the a-carbon atom of the primary amine. Thus while 1,2-dimethyl- propylamine and other less hindered amines give good yields of sym-N-alkyl-B-halogenoborazoles 1-isopropyl-2-methylpropylamineand other more hindered secondary alkyl primary amines give mix- tures from which the borazole may be absent. When the a-carbon atom is fully substituted the reaction normally takes a simpler course and the tetrameric borazynes (RNBX) are formed; of these the pro- duct (A) from t-butylamine and boron trichloride (ButNBCI) has been most thoroughly examined. </p>
<p> This substance is a white solid m.p. 248" (in vacuo) easily soluble in non-polar slightly polar and less so in polar organic solvents. Its composition has been established by direct elementary analysis and by hydrolysis which gives t-butylamine boric acid and hydrogen chloride in equimolar amounts. The mole- cular weight was determined crysoscopically and ebullioscopically and was confirmed by the presence of peaks in the 560 m/e region of the mass spectrum of the tetraisothiocyanate derived from (A). The compound sublimes very readily and the molecular depression constant falls within the limits of 53 and 95 (camphor 40). </p>
<p>Even after allowance for the higher Sheldon and Smith. Quart. Rev.. 1960. 14.200. * A preliminary accobnt ofthis work w& read at the symposium on Recent Advances in Boron Chemistry Anniver- sary Meeting April 1961. PROCEEDINGS ~~~ ~~ melting point the latent heat of fusion of compound (A) must be below that of camphor. Compound (A) and related substances have characteristic infrared absorption spectra.+ The reactivity of the tetrameric borazynes is in striking contrast to that of the B-chloroborazoles they are relatively stable to hydrolysis and react only slowly or not at all with reagents (Grignard and lithium reagents lithium borohydride etc.) towards which the chloroborazoles are very reactive. </p>
<p>Indeed the only replacement reaction so far encountered that takes place readily under mild conditions is the formation of the tetra-B-isothiocyanate with potas- sium thiocyanate in organic solvents. YR Three possible structures (I) (III) and (1V) have been considered. Planar forms of (I) are sterically impossible but molecular models of the boat chair and crown forms can be made. The boat form is apparently strain-free; within the ring sterically favoured n-bonding is possible between boron and nitrogen atoms of the separate B-N pairs but not between those of adjacent pairs. The chair and the crown form are progressively more overcrowded and opportunities for p-orbital overlap in the ring atoms show a concurrent decrease. </p>
<p>The energy barriers be- tween the conformations should be quite large. A molecular model of structure (111) can be made but not of (IV). In all cases the molecule is almost spherical with highly inaccessible boron atoms; all of these structures are generally compatible with the low reactivity high volatility and solubility of the tetramers. The llB nuclear magnetic resonance spectra of compound (A) and the corresponding bromo-compound contain only a single boron resonance and a comparison of the chemical shifts with those of reference compounds (see the Table) strongly sug-gests that the tetrarners contain only 3-co-ordinate boron atoms. Structure (111) with both three- and four-co-ordinate boron atoms is thus ruled out and (IV) is improbable. </p>
<p> Preliminary measurements have shown that corn-pound (A) has no significant dielectric absorption in solution over a wide range of frequencies:the dipole moment is thus probably zero. This is compatible with the boat form of structure (I) and with (IV) but probably not with (111). With zero dipole moment the difference (12 c.c.) between the total electric polarisation (1 32 c.c.) and the electron polarisation (120 c.c.) is attributable only to the atom polarisa- tion and this is considerably less than the value (17-5 c.c.) found for the dimer of aminodiphenyl- borane.2 Structure (IV) with a more extensive system of balanced dipoles than the aminoborane dimer and to a smaller extent structure (111) might be expected to have larger or at least comparable atom polarisations. </p>
<p>Even if the dipole moment were not zero the maximum possible value (on the highly improbable assumption of zero atom polarisatton) would be only 0-75 D and with the possibility of molecular distortion through overcrowding even this value would probably not be inconsistent with our conclusions. Substance Chemical shift (BCI = 0) (P.P.rn.1 (But NBCI) + 17-4 (But NBBr) + 17.2 (HNBCI) + 11 (CH ,NBCl ) + 14 B(N Et213 + 16*33 B(NC,H,),-+ 46 B(0Me),-+ 44.48 (ButNHBCl,) + 43.3 (Me,N.BCl,) + 37-2 aNC4H4 = 1-pyrrOlyl We therefore consider that the tetrarneric bora- zynes are borazocines probably normally existing in the boat conformation. The ring itself may have highly localised alternating n-bonds the low reac- tivity is steric in origin. </p>
<p>Some approximate measure- rients of the rate of hydrolysis of compound (A) have shown that within the experimental error the rate is independent of pH over a wide range. This suggests an S,l reaction as would be expected if our views on the structure are correct. We thank Dr. B. N. Figgis (University College) for the nuclear magnetic resonance spectra and for discussion of the results and Mr. E. Rushton (Standards Division National Physical Laboratory) for the electrical measurements. (Received December 6th 1961.) t The infrared spectra of (A) and some related compounds will appear in the DMS Index (Buttenvorths) on spectral cards numbered 9510 onwards. </p>
<p> Coates and Livingstone J. 1961 1OOO. a Phillips Miller and Muetterties J. Arner. Chem. Soc. 1959 81,4496. FEBRUARY 1962 71 Calculation of Photoelectric Thresholds and Electron Amties of Molecular Crystah By L. E. LYONSand J. C,MACKE (DEPARTMENT CHEMISTRY OF SYDNEY) OF PHYSICAL UNIVERSITY WEreport values calculated for the photoelectric charged kth molecule; Nis the number of molecules threshold I, and the electron affinity A, of in the crystal; ’ indicates that the summation omits molecular crystals. the charged molecule. A knowledgeof both I and A is important for an We have evaluated expression (1) for the entire understanding of ionised states in molecular crystals crystal by a convergence methodlo and have allowed I and A for Some Molecular Crystals (ev). </p>
<p> Subs tan= 43 P (calc.) 1 (calc.) I (exp.) A (talc.)* Naphthalene 8.1214 -1.28 6-84 6-7Y 2.1 Ant hracene 7.3815 -1.74 5-64 5~65~ 3.1 Naph thacene 6.881b -1.58 5-30 5*2S6 3-3* 9,lO-Dibromoanthracene 7-0t -2.37 4.6 p-Dichlorobenzene 8~93’~ -1.71 7.22 n-Hexane 10-1714 -1.7 8.5 Iodine 9*2814 {-3.0) (6.3)f 5*255 * Values quoted in ref. 16 for & are assumed. t Estimated. # Doesnot include dipole-dipole interaction. such as occur in semi- and photo-conduction,l and for the interaction of induced dipoles in the expres- photovoltaic2 and thermoelectric effect^,^ as well as sion (2) where rkl is the magnitude of the distance in electrets4 and crystals which have emitted or between molecules k and 1. gained electrons. None the less although there has Values so calculated are listed in the Table been considerable recent activity in the measurement together with values of I and A deduced from the of such photoelectric threshold^^^ and a little in that ionisation potcntial I, and the electron affinity. </p>
<p> only very approximate cal- A, of individual molecules. of electron affinities,’~~ culatians have been made previously. The agreement between theory and experiment in Nf . . (2) == 2 or2e2r.k-+z~ rklA{Fk*Fl-3r; 3 ~k*~kl)(~z*~kz) . k</p>
<p>. . (1) validity of the model is established. It also follows k= 1 that less energy is needed to ionize a molecule in the where GC is the mean polarisability of a molecule and bulk of the than on the surface- rL is the separation between a charged and the un-(Received November 7th 1961 .) Lyons J. 1957 5001. * Kallmann and Pope J. Chem. Phys. 1959,30 585; Nature 1960,188,935. * Fielding and Gutman J. Chem. Phys. 1957,26,411. Baldus 2. angew. Phys. 1954,6,481; Beliaev Belikova Fridkin and Zheludev Sov. </p>
<p>Phys. Cryst. 1958,3,772. West Canad.J. Phys. 1953 31 691. Lyons and Morris J. 1960 S192. Kearnsand Calvin J. Chem. Phys. 1961,34 2026. Kearns and Calvin J. Amer. Chem. Soc. 1961,83 2110. Fox J. Phys. and Chem. Solids,1959 8,439. lo Nijboer and de Wette Physica 1957 23 209. l1 Bardeen fhys. Rev. 1935,48 84. Is Wright Proc. Phys. Soc. 1948 60,13. la Mott and Gurney “Electronic Processes in Ionic Crystals,� Oxford 1940. l4 Watanabe “Preliminary Table of Ionization Potentials,� Univ. Hawaii 1957. l6 Vilesov Doklady Akad. Nauk S.S.S.R. 1960 132 632. Lyons Nature 1950,166 1936. PROCEEDINGS The Structure of Hunterburnine By J. D. M. ASHER ROBERTSON, J. MONTEATH G. A. S~M DEPARTMENT GLASGOW, (CHEMISTRY THEUNIVERSITY W.2) M. </p>
<p>F. BARTLETT and W. I. TAYLOR R. SKLAR (RESEARCH CIBA PHARMACEUTICAL DIVISION DEPARTMENT COMPANY OF CIBA CORPORATION SUMMIT, N.J. U.S.A.) THEalkaloids of Hunteria ebcrrnen Pichon comprise both tertiary1 and quaternary2 bases. By degradative methods and partial syntheses three of the quater- nary alkaloids were shown to be akuammicine methochloride yohimbol methochloride and di-hydrocorynantheol methochloride (I). Also among the quaternary bases is a group of isomeric com- pounds C2,H2,0,C1N2 all of which contain a 5-hydroxyindole chromophore an isolated double bond and an aliphatic hydroxyl group which is readily acetylated ; paucity of material precluded any detailed degradative study. One of these com- pounds hunterburnine methiodide m.p. </p>
<p>277-280" (methochloride m.p. 307-308 O ; dihydrometho-chloride C,,H ,02C1N2 m.p. 290-292") has now been subjected to X-ray analysis by the Glasgow group and the results obtained define its constitution and stereochemistry (apart from absolute configura- tion) to be as in (II).(It is expected that the tertiary base hunterburnine will be found to occur naturally.) Hunterburnine is the first recognised representative of a new class of indole alkaloid. The biogenetic relationship to other indole alkaloids becomes clear when it is realised that the skeleton of (11) can be derived from (I) by an appropriate scission and re- cyclisation as indicated by the numbering in the formulz. The absolute stereochemistry indicated in (11) is based on the assumption that the rule3 of uni- form absolute stereochemistry of the C(151equivalent of yohinibine [C(,,) in (I) and (II)] is valid in this case also. </p>
<p> Hunterburnine methiodide crystallises in the orthorhombic system space group P2,2,2, with four molecules of C,,H,,021N2 in a unit cell of dimen- sions CI = 10.96 b = 18-83 c = 9-20 A. Three-dimensional X-ray intensity data were recorded on equi-inclination Weissenberg photographs and esti- mated visually; in all 1784 independent structure amplitudes were evaluated. The co-ordinates of the iodine atom were obtained initially from Patterson syntheses. Successive three dimensional Fourier syntheses were then carried out with the inclusion of further atoms in the phasing calculations as they became clearly defined. </p>
<p>After five rounds of structure-factor and Fourier calcula- tions structure (ti) was clearly established. Two further rounds of structure-factor and Fourier cal- culations were followed by least-squares adjustment of the positional and thermal atomic parameters. The value of R is now 15.8 % and the co-ordinates yield satisfactory bond lengths and valency angles. Superimposed contour ssctions illustrating the sixth three-dimensional elect ro n-densi ty distribution over one molecule are shown in the Figure. xt Y The sixth three-dimensional electron-density distri- bution over one molecule of hunterburnine methiodide shown by means of superimposed contour sections drawn parallel to (001). </p>
<p> The assignment of the double bond between qls) and C(19!was based on an examination of the bond lengths in the molecule and on nuclear magnetic resonance studies by the CIBA group. Bartlett and Taylor J. Amer. Chem. SOC.,1960 82 5941. Bartlett Sklar Smith and Taylor unpublished work. a Wenkert and Bringi J. Amer. Chem. SOC.,1959. 81 1474 6535. FEBRUARY 1962 73 For the extensive calculations on the Glasgow by Dr. J. S. Rollett4 and Dr. J. G. She5 were University DEUCE computer programmes devised employed. (Received December 22nd 1961 .) * Rollett in “Computing Methods and the Phase Problem in X-Ray Crystal Analysis� ed. Pepinsky Robertson and Speakman Pergamon Press Oxford 1961 p. 87. ‘ Sime in “Computing Methods and the Phase Problem in X-Ray Crystal Analysis�,ed. </p>
<p>Pepinsky Robertson and Speakman Pergamon Press Oxford 1961 p. 301. The Oxidation of Anthranilic Acid by Manganese Dioxide By L. R. MORGAN, JUN. and C. C. AUBERT (DEPARTMENT LOUISIANA OF PHARMACOLOGY STATEUNIVERSITY SCHOOL NEWORLEANS U.S.A.) OF MEDICJNE 12 LOUISIANA ANTHRANILIC ACID an intermediate in the biosyn- thesis of tryptophan in micro-organisms,l has been shown to be incorporated into the phenazine pig- rnent chlororaphin [a 3 :1 molecular compound of phenazine-1-carboxamide (I) and its 9,lO-dihydro- derivative] in Pseudomonas chlororaphis.2 Although chemical synthesis of phenazine deriva- tives has been extensively in~estigated,~ the scheme based on the chemical oxidative dimerisation of anthranilic acid and other aromatic amino-precur- sors has remained untested. </p>
<p>Oxidative coupling (C -+ 0 and/or C -+ N) of phenolic compounds by one- electron-transfer oxidising agents has been incor- porated in several proposals concerning biogenesis of certain plant phenols and Amaryllidaceae alkaloid^.^ A plausible biogenesis of the amide (1) and its dihydro-derivative may involve pairing of the radical (VI or VIII) formed through the precursor (I1 or 111) on enzymic oxidation of anthranilic acid. The initial product would be a dihydrophenazine (VII or IX) capable of undergoing decarboxylation amination and dehydrogenation to give the amide (I). Treatment of anthranilic acid with manganese dioxide5 in benzene or chloroform at 40�followed by rapid chromatography over alumina (grade 111) and elution with acetic acid and methanol afforded a 5 % yield of phenazine-l,6-dicarboxylic acid (X) that gave the known diethyl ester,6 m.p. </p>
<p>143�.During the process the postulated dihydro-intermediate (VII or IX) is entirely oxidised. The acid (X) had the same infrared and ultraviolet spectra as an authentic sample.6 Heating the dibasic acid (X) at 270� in diphenyl ether with copper for 2 hours afforded a mixture of phenazine- 1 -carboxylic acid and phenazine which were separated on alumina. The amide (I) was pre- pared from phenazine-1 -carboxylic acid by using thionyl chloride and ammonia.’ This synthesis supports the postulated biogenesis of phenazine derivatives. </p>
<p>That a biogenetically Plausible Process of ~ino-co~Pling can be written does not however exclude other mechanisms and a final decision awaits tracer studies. The authors thank Professor D. H. R. Barton for his interest. (Received November 28rh 1961.) Yanofsky in “Amino Acid Metabolism,� ed. McElroy and Glass The Johns Hopkins Press Baltimore Md. 1955 pp. 930-939; Yanofsky J. Biol. Chem. 1957 224 783. Carter and Richards J. Amer. Chem. SOC.,1961 83 495. Swan and Felton “Phenazines,� Interscience Publ. Co. New York N.Y. 1957. * Barton and Cohen “Festchrift Arthur Stoll,� Birkhauser Basle 1957 p. 117; Barton and Kirby Proc. Chem. Soc., 1960 392. For previous uses of manganese dioxide see ref. 4; Davidson and Scott J. 1961 4075 and preceeding papers; Brown Clark Ollis and Veal Proc. </p>
<p>Chem. SOC.,1960 393. Birkofer and Wildman Eer. 1953 86 1297. ’ Kogl and Tonnis Annalen 1932 486 497 PROCEEDINGS A Novel Reaction Abstraction of a Hydride Ion from Some a-Bonded Iron-Akyl Complexes By M. L. H. GREEN and P. L. I. NAGY (UNIVERSITY LABORATORIES, CHEMICAL CAMBRIDGE) TRJZATING pure dry tetrahydrofuran solutions of the complex. Treatment of the methyl compound complexes ~-C,H,Fe(C0)&lkyl~~~ (I) where Alkyl n-C5H,Fe(CO)2Me with triphenylmethyl perchlorate = Et Prn or Pri with stoicheiometric amounts of caused no immediate reaction and after 10 hours only triphenylmethyl perchlorate in tetrahydrofuran small yields of the cation [n-C5H5Fe(CO)2HzOJ+ affords organometallic cations whose aqueous solu-could be isolated.2 tions are moderately stable in air and give precipi- This abstraction of a hydride ion by triphenyl-tates with the usual large anions. </p>
<p>The infrared spectra methyl perchlorate indicates novel properties of what of the hexafluorophosphate perchlorate and silico- have hitherto been regarded as conventional alkyt tungstate prepared from the ethyl complex were groups. The unusual reactivity may be associated identical with those of the salts of the previously with the nature of the iron-carbon bond with some reported n-ethylene cation (II)where R = R’ = H.3 interaction of the 2-carbon atom or its protons or Similarly the cation salts prepared from the n-propyl both with the metal. Unusual chemical and spectro- and the isopropyl complex had spectra identical with scopic properties have been reported for the CH,H those of the n-propene cation salts (It;R = Me group of the cyclopentadiene complexes of cobak R’ = H or vice versa)? Analytical and chemical and rh~diurn.~ This group may be regarded as being data also confirm that the cations formed are those in a similar position with respect to the metal as the formulated as (XI). </p>
<p>group in position 2 of the alkyl compounds. Some interaction of the 2-protons with the non-bonding ,+ d-orbitals of the metal seems possible. Recently it -H‘ was suggested6 that these orbitals take part in the ___c bonding of the proton to iron in the ferrocens hydride cation.’ The r61e of the iron therefore may be to facilitate removal of the hydride ion and then stablise the intermediate by formation of an ethylenic complex. </p>
<p> The reaction of the alkyl complexes with triphenyl- methyl perchlorate is fast and in all cases gives very We thank the International Nickel Company good yields. The propene cation (IT) is therefore (Mond) Ltd. for a gift of iron carbonyl and the formed either by proton addition to the a-ally1 com- Hungarian Relief Fund for hancial support (to plex n-C5H5Fe(CO),a-CH2CH=CH2,4 or by P.L.I.N.). hydride abstraction from the n-or iso-propyl (Received November 8th 1961.) Piper and Wilkinson J. Inorg. Nuclear Chem. 1956 3 104. Ariyaratne Green and Nagy unpublished work. Fischer and Fichtel Chem. Ber. 1961,94 1200. Green and Nagy Proc. Chem. SOC. 1961 378. Green Pratt and Wilkinson J. </p>
<p>1959 3753. Gillespie and Kirschner Proc. the Sixth Internat. Conference on Co-ordination Chemistry 1961 MacmilIan New York 1961 p. 34. Curphy Sauter Rosenblum and Richards J. Amer. Chem. Soc. 1960 82 5249. Steric Control in Addition to 4-Methylcyclopentene By H. B. HENBEST and J. J. MCCULLOUGH (THE QUEEN’S UNIVERSITY OF BELFAST) THEdirection of attack of certain reagents (perlauric fluences the preferred direction of attack of the above acid acetyl hypobromite) on endocyclic double named reagents in opposite ways in the two series bonds can be influenced by dipolar substituents even the methy1 group in the bicyclic compound (I) causes when these are located at a distance across two or the formation of more cis-epoxy-nitrile (peracid re-three rings.l RepIacement of hydrogen by methyl (at action) or more trans-epoxy-nitrile (acetyl hypo- R) in bicyclic (I) and monocyclic compounds (U)in-bromite addition followed by ring closure with Crossley Darby Henbest McCullough Nicholls and Steward Tetrahedron Letters 1961 398. </p>
<p> FEBRUARY 1962 alkali) whereas the methyl group in the monocyclic compound (11) gives the converse directing effects. The suggestion1 that the alkyl group in the latter series is exerting a steric effect (whereas the effect of the methyl group in the bicyclic series is probably polar and conformational in origin) is now supported by a study of addition to the parent alkyl compound 4-methylcyclopentene(111). U With acetyl hypobromite in carbon tetrachloride solution this gave an adduct which was evidently (IV) as cyclisation with alkali yielded the cis-epoxide (V) (70% from HI). </p>
<p>The selective formation of the adduct (1V) in which bromine is trans to the methyl group may be ascribed to the larger size of bromine than of oxygen (respective van der Waals atomic radii 1-95 and 1a4 A). Reduction of the cis-compound (V) with lithium aluminium hydride gave the cis-alcohol (VII) also obtained from the cis-hydroxy- ester2 (IX)by successive reactions with a hydride. toluene-p-sulphonyl chloride and a hydride. The alcohols obtained by the two routes gave the same p-nitrobenzoate m.p. 69-70" (lit.,3 71 "). Reactions of 4-methylcyclopentene with perlauric acid in cyclopentane and in acetonitrile gave mix- tures (85% yields) of the cis-and the trans-epoxy- compounds (V and VI) in the ratios 27 :73 and 26 74 respectively. </p>
<p>Reduction of the former mixture gave a product from which the trans-alcohol (VIII) was isolated as its p-nitrobenzoate m.p. 42.5-43.5 O (lit.,3 44").Selectivity by steric control is therefore not as great in the peracid reaction as in the addition of acetyl hypobromite. The absence of a marked solvent effect in the peracid reaction is consistent with the proposal that the effect of the methyl group is steric and not polar in origin. 4-Methylcyclopentene b.p. 62O was synthesised from cyclopent-3-enecarboxylicacid by a sequence of reactions similar to those used for the conversion of ester (IX) into the methyl compound (VII). </p>
<p> This work was carried out during the tenure (by J. J. Mc.) of a Senior Studentship of Queen's University. (Received November Bth 1961.) Novce and Fessenden. J. Om. Chem. 1959 24 715. Godchot Cauquil and Cal&. Bull. Sue. chim. France 1939 6 1353 1355. The Kinetics of the Reaction Between Nitric Oxide and Hydrogen Iodide and the Dissociation Energy D(H-NO) By J. L. HOLMES (DEPARTMENT OF CHEMISTRY UNlVERSITV OF EDINBURGH) THEreaction between nitric oxide and hydrogen iodide has been investigated over the temperature range 90-300". Its stoicheiometry is represented by NO + 6HI -+ NHJ + H,O + $1,. Other products were observed only at the higher temperatures where traces of nitrous oxide and nitrogen were found. </p>
<p> The kinetics of the reaction have been studied from 95" to 250" at pressures of nitric oxide from 40 to 500mm. and of hydrogen iodide from 120 to 750 mm. The rate of reaction was determined by analyses for nitric oxide and iodine at various times and in some experiments also of ammonium iodide and hydrogen iodide. The results fit the bimolecular expression -d(NO)/dt = kl [NO][HI]. In clean Pyrex vessels the rate constants were poorly reproducible. In "seasoned" vessels (coated with a carbonaceous deposit) results were reproduc- ible and the homogeneity of the reaction was estab- lished when a ten-fold increase in surface:volume ratio was found to have no effect on the rate. The results were fitted to the Arrhenius equation k = *Oaol5 exp( -22,000 f 400/RT) C.C. </p>
<p>mole-l set.-' (the error shown is the standard deviation). It is proposed that these are the Arrhenius parameters for the reaction NO + HI -+ HNO + I-... (1) After -40% reaction the rate constants k decreased. This decrease could be reproduced by addition of iodine to the system before reaction and was attributed to the back reaction I. + HNO + HI + NO ... (-1) The emission spectrum of HNO has been observed by Clement and Ramsayl who gave an upper limit of 48.6 kcal./mole for the dissociation energy of HNO. CIyne and Thrushz have shown that Ramsay's limit is close to the actual value of D(H-NO) and use a value of 48 kcal./mole in their calculations. The dissociation energy of HNO is of current interest for organic pyrolyses inhibited by nitric oxide. </p>
<p>Laidler et al? assumed a value of 48 kcal./mole in their investigation of the inhibited pyrolysis of ethane. If D(H1) = 71 kcal./mole is used the present work yields a value of 49 kcal./mole for D(H-NO) in good agreement; the back-reaction (-1) has zero activa- tion energy. HNO $-HI + NH,IO . . . (2) NH,IO + HI NHI + H,O . . . (3a) NHJO + HI 3 NH,*OH + I ... (3b) NHI + HI -f NH,I + I . . . (4a) NH,.OH + HI+ NH,I + H,O . . . (4b) NH,I + HI+NH 4-I ... (5) NH + HI -+ NHJ ... (6) PROCEEDINGS The rapid reduction of HNO by hydrogen iodide may be represented by two reaction schemes one proceeding by way of hydroxylamine the other by way of iodine-substituted ammonia. An attempt to obtain evidence for scheme (a) was made by adding a large excess of hydrogen chloride to the system at 120" and at 180". </p>
<p>At the lower temperature hydroxylamine might be stabilised as the hydrochloride and at the higher temperature hydroxylamine hydrochloride decomposes to yield nitrogen. Neither hydroxylamine nor nitrogen could be detected in the products. The addition of the large excess of hydrogen chloride had no effect either on the rate of disappearance of nitric oxide or on the yield of iodine. The author is indebted to the University of Edinburgh for an I.C.J. Fellowship. (Received October 24th 1961.) I Clement and Ramsay. Canad. J. Phvs.. 1961.39. 205. Clyne and Thrush 7kms. Furuduy Soc. 1961,57 1305. Laidler and Wojciechowski,Pruc. </p>
<p>Roy. Suc. 1961 A 260 103. Tetranitratozirconium(w)-A New Volatile Complex By B. 0. FIELD and C. J. HARDY (ATOMLC HARWELL, ENERGYRESEARCH ESTABLISHMENT BERKS.) WE report the first isolation of anhydrous tetra- nitratozirconium(rv) which was prepared by the reaction of anhydrous zirconium tetrachloride with dinitrogen pentoxide at 30" ZrCl + 4N,O -+ Zr(NO& + 4N0,Cl. An excess of dinitrogen pent- oxide prepared by dehydrating fuming nitric acid with phosphorus pentoxide was distilled on to fresh- ly prepared anhydrous zirconium tetrachloride at about -200". The mixture was allowed to warm to room temperature and was heated on a water-bath to 30"to melt the dinitrogen pentoxide which was allowed to reflux for 15 minutes during which time nitryl chloride was evolved. </p>
<p>The excess of pent-oxide was then pumped off and the yellow solid remaining was evacuated for 1 hour at 21 "/0.1mm. A product Zr(N0 3)4,0.4N205 ,0-6N204,was then obtained which was free from chloride. This salt lost its co-ordinated nitrogen oxides when heated on a water-bath for 4 hours at 100"/0~01 mm. and the anhydrous tetranitrato-complex slowly sublimed on to a water-cooled cold finger as colourless crystals. Analyses of 0.5-g. samples of the sublimate gave 262% of Zr by ignition to ZrO and 73.2% of nitrate as nitron nitrate [Zr(NO,) requires Zr 26.9; NO3 73-1%I. Gutmann and Tannenberger Monntsh. 1956 87,421 Infrared spectra of anhydrous tetranitratozircon- ium(xv) in a Nujol mull prepared in a dry-box gave strong peaks at the following frequencies (cm.-l) characteristic of co-ordinated nitrato-groups (assign- ments v,-v,; more than one frequency indicates splitting) and no peaks at frequencies characteristic of the nitrate ion v1 v2 v4 v3 and v6 1224 983 1576 764 772 1253 1002 1611 778 783 1284 1015 1631 792 X-Ray powder diffraction spectra have also been obtained. </p>
<p>Anhydrous te trani t ra t ozirconium(Iv) is very hygroscopic and is extremely soluble to give clear solutions in water ethanol acetone ether and tri-n-butyl phosphate. It is insoluble in toluene with which it rapidly reacts at room temperature to produce nitro-compounds. Gutmann and Tannenbergerl prepared anhydrous zirconium oxynitrate by the reaction of dinitrogen tetroxide with anhydrous zirconium tetraiodide sus- pended in carbon tetrachloride but they were unable FEBRUARY 1962 to isolate the anhydrous tetranitrate which they con- sidered to be the initial product of the reaction and appeared to decompose at room temperature. </p>
<p>We have examined a number of reactions of dinitrogen tetroxide with various zirconium compounds for the preparation of the tetranitrate but without marked success. The authors thank Mr. D. Scargill for obtaining the infrared spectra and Mr. F.Moore for the X-ray diffraction spectra. (Received January 2nd 1962.) The Formation of Indenes Dimetbyienecyclobutaaes and Rubrenes from Aromatic Tertiary Acetylenic Alcohols By PHnus D. LANDOR and S. R. </p>
<p>LANDOR (WOOLWICH LONDON S.E.18) POLYTEC~IC THEreaction of thionyl chloride with aliphatic 2-plysubstituted tertiary acetylenic alcohols gives chloroal1enes.l It is well known that 1,1,3-triphenyl- prop-2-yn-1-01 (I; X = H Y = Ph) and thionyl chloride give an intermediate chloride of hitherto uncertain structure which can be dehydrohalogenated to rubrene.a We have now shown by immediate infra-red examination of the reaction mixture (which gives band at 1920 crn.-' considerably stronger than the normal aromatic bands in this region) that the allenic chloride (11)is the first product although it could not be isolated. Instead 5-chloro-5,12-dihydro-5,6,11,12-tetraphenylnaphthacene (III) hmtix. (CHCla 248 312 mp (E 64,OOO and 12,800) and 1,3,3-triphenyl- ~ro~-2-en-1 -one3 were obtained. </p>
<p> From the reaction of 3,3-diphenylprop-l-yn-3-01 (I;X = Y = H)with thionyl chloride two main pro- ducts l-chloro-3-phenylindene,m.p. 70" hmax. 322 mp (e 6800) and the-dimeric 3,4-c&-dichloro-l,2- * Bhatia Landor and Landor J. 1959 24. Dufraise Bull. SOC. chim. France 1936 1847. Meyer and Schuster Ber. 1922 55 819. Cf. also Nagase Bull. Chern. SOC. Japan 1961,34 139. Cf. Roedig and Niedenbruck Chem. Ber. 1957,90 673 bisdiphenylmethylenecyclobutane(IV;X =Y =H) m.p. 191" h,,,. 267 380 mp (E 31,700 and 22,700) were isolated. The pp'-dichloro-substituted alcohol (I; X = C1 Y =H) also yielded the dimeric cycIobutane (IV;X = CI Y = H)? All these reactions can be explained by a general scheme the allenic chloride intermediate can rearrange or dimerise by an acidcatalysed mechanism (pyridine hydrochloride or ether-hydro- chloric acid could act as catalysts) leading via pro-tonation at the central carbon atom to the de- localised carbonium ion (V) and to different products depending on the nature of Y. </p>
<p> We thank the Chemical Society for a grant for chemicals. (Received September 26th 1961. ) 78 NGS FROCEEDI Deoxygenation of Aromatic C-Nitroso Compounds :A New Cyclisation Reaction By P. J. BUNYAN and J. I. G. CADOGAN OF LONDON,KING'SCOLLEGE LONDON, (UNIVERSITY STRAND W.C.2) EARLYwork1 on the thermally or photochemically induced decomposition of aryl azides involving intra- molecular cyclisation with an adjacent aromatic ring has recently acquired further significance through the work of Smoiinsky2 on the decomposition of a series of 2-azidobiphen yls and o-alkyl- and o-cyclo- alkyl-substituted azidobenzenes. </p>
<p>These have led to a variety of products e.g. carbazoles from 2-azidobi- phenyls which suggest the participation of a discrete azene (electron-deficient nitrogen) intermediate which is assumed to act as a diradical rather than as an electropkile having paired electrons. Smith and his co-workers3 have provided kinetic evidence to support this postulate and the preparative sig- nificance of reactions involving azenes has recently been enhanced as a result of the work of Barton and Morgan.* In view of the ease with which organic tervalent- phosphorus compounds enter into deoxygenation reactions it seemed reasonable to expect that such reduction of C-nitroso-compounds might lead to the corresponding azene. </p>
<p>This can be inferred from the novel reaction which occurred on the addition of a benzene solution (0.8~) of triethyl phosphite (0.01 rnol.) to a similar solution (0.4~) of hitrosobi-pheny15(0.01 mol.) under nitrogen at 0-5". Within a few minutes carbazole (m.p. and mixed m.p. 245-247") crystallised from the solution and it was finally recovered in 76% yield together with triethyl phosphate (84 %). Preliminary publication of our results is prompted by Boyer and Ellzey's recent report6 that reaction of o-dinitrosobenzene and triethyl phosphite affords benzofurazan. The only previous reference to a reaction between these classes of compound is that due to Horner and Hoffmann who state,' in a reference to unpublished work that substituted nitrosobenzenes but not nitrosobenzene itself react with triphenylphosphine to yield the corresponding azoxybenzenes. </p>
<p>We find however that azoxybenzene is obtained in low yield from the reaction of nitroso- benzene with triphenylphosphine better yields being obtained with triethyl phosphite. It is reasonable to suppose that the latter reaction and that reported by Boyer and Ellzey may also pro- ceed by reaction of an azene intermediate with an unchanged nitroso-group although the possibility of participation of other intermediates cannot at this stage be discounted. (Received January 9th 1962.) Smith and Brown J. </p>
<p>Amer. Chem. SOC.,1951 73 2435; Smith and Boyer ibid. p. 2626; Smith Brown Putney, and Reinisch ibid. 1953 75 6335; Smith Clegg and Hall J. Org. Chern. 1958,23 524. Smolinsky,J. Amer. Chem. SOC.,1960,82,4717; 1961,83,2489; J. Org. Chem. 1961,26,4108. Smith Hall and Carter Amer. Chem. SOC. 139th Meeting 1961 Abs. p. 42-0. Barton and Morgan Proc. Chem. SOC.,1961 206. Mijs Hoekstra Ulmann and Havinga Rec. Trav. chim. 1958 77 746. Boyer and Ellzey J. Org. Chem. 1961,26 4684. 'Horner and Hoffmann Angew. Chem. 1956 68 473. The Effect of Solvent on the Electronic Absorption Spectrum of p-Nitroaniline By B. D. PEARSON (AVERY UNIVERSITY OF NEBRASKA NEBRASKA, LABORATORY LINCOLN U.S.A.) IT has been shown1$2 that the long-wavelength absorption band of p-nitroaniline is very solvent- dependent undergoing a bathochromic shift with increasing solvent polarity. </p>
<p>The electronic transition involved probably corresponds to the n-and 7-charge transfer band of the amino- and nitro- groups and hence is related to the mesomeric inter- action of these groups with the aromatic nu~leus.~ The ultraviolet absorption spectrum of p-nitro-aniline in thirty-one solvents has now been measured. The long-wavelength maximum varies from 380 mp in NN-dimethylformamide to 320 mp in n-hexane. The solvent-induced shifts relative to n-hexane (AX) are shown plotted against the dielectric con-stant of the solvent (Fig. 1). Initially the solvent- induced bathochromic shift is directly proportional to the dielectric constant (branch A). </p>
<p>This region probably represents the increasing electrostatic inter- action of solvent with the solute until the force field of the latter is saturated. Then above a dielectric Dede and Rosenberg Ber. 1934 67 147. Kumler and Strait J. Amer. Chem. SOC.,1943 65 2349. Lutskii and Konel'skaya J. Gen. Chem. (U.S.S.R.), 1960 30 3735. FEBRUARY 1962 constant of 3-5 the solvent shift Ah becomes pro- portional to (E -1)/(2~+ 1) (Fig. 2). This region probably represents the changing molecular polarisa- bility of the solute and the formation of intermole- cular hydrogen bonds with the solvent as the polarity of the latter increases. The formation of three branches (Fig. l) related to the nature of the solvent ‘OH OLA’ I I I I I --....I 0 20 40 80 Dielectric constant (&) FIG. </p>
<p>1. Increase in solvent shift (Ah) relative to n-hexane with increasing polarity of the solvent. indicates that solvation effects are dependent on the functional groups in the solvent molecules aliphatic alcohols (except methanol) esters NN-dimethyl- formamide and water form branch B; aldehydes ketones and methanol form branch C; nitriles form branch D. The anomalous behaviour of methanol may be due to the higher proportion of polymeric molecules found in methanol than in other aliphatic alcohol^.^ The small differences in dh at a particular di- electric constant between branches B C and D are probably related to differences in intermolecular hydrogen bonding in the different types of solvent. </p>
<p> I 1 I I 20 30 40 50 60 Solvent shift (AA) FIG.2. Relation of solvent shift (Ah) to dielectric constant (E) at higher values of the latter. The energy difference between transitions in aceto- nitrile (E 37.5; Amax. 364 mp; branch D) and ethylene glycol (E 38.7; Am,,. 379 mp; branch B) is 3.10 kcal./mole. Similar values have previously been observed for hydrogen bonding to amine~.~ The long-wavelength absorption band of o-nitro- aniline is less solvent-dependent (Amax. in EtOH 403 in n-hexane 375 mp) than that of the para-isomer but gives a three-branched plot similar in general to Fig. 1. The 2 values used by Kosower6 to relate solvent effects with transition energies in carbonyl com- pounds were not correlated with the solvent effects observed for p-nitroaniline. </p>
<p> (Received December 5th 1961.) Ens and Murray Canad. J. Chem. 1957 35 170; Connor and Reid J. Mol. Spectroscopy 1961 7 32. Pimentel and McClellan “The Hydrogen Bond,� Freeman and Co. London 1960 p. 360. Kosower J. Amer. Chem. SOC. 1958 80 3261. The Formation of Methylene by the Photolysis of Diazirine (Cyclodiazomethane) By H. M. FREYand I. D. R. STEVENS (DEPARTMENT OF CHEMISTRY THEUNIVERSITY SOUTHAMPTON) METHYLENEis formed by photolysis of keten or phase also affords methylene. When it is photolysed diazomethane. It is somewhat more reactive when alone the major products are ethylene and nitrogen produced from diazomethane as shown for example by its less selective insertion in primary and second- ary carbon-hydrogen bonds1 These and other differences have been explained by assuming that the rnethylene may be formed with an excess of both translational and vibrational energy. </p>
<p> H2C/N[I + hV -CH2 + N ....(I) ‘N /N + H2C,A -C,H + N . ..@I CH We fmd that photolysis of diazirine2 in the gas Frey J. Amer. Chem. SOC. 1958 80 5005 and refs. cited therein. Schmitz and Ohme Chem. Ber. 1961,94,2166; Schmitz and Ohme Tetrahedron Letters 1961,612. (By using Pyrex vessels and a medium-pressure mercury arc the photolysis is almost entirely due to the band at 3130 A.) In the presence of a large excess oftrans-but-2-ene at a total pressure of -500 mm. it yields trans-l,2-dimethylcyclopropane,trans-pent-2ene and 2-methylbut-2-ene with only a trace of cis-l,2-dimethylcyclopropane.Addition to the double bond is stereospecific so the methylene from di- azirine is presumably in the singlet state. </p>
<p> When photolysed in the presence of a SO-fold excess of propane the major products were n- and iso-butane in the ratio 1.99 1 (under similar condi- tions keten gave 2.05 :1 and diazomethane 2.65 1). Minor products were ethane propene ethylene and traces of C alkanes. Other than ethylene which is formed by reaction (2) the products result from the abstraction reactions of methylene? Photolysis in the presence of n-butane gave n- and iso-pentane in the ratio 1:1.09 (diazomethanel gives 1.25 1) minor products being ethane propene but- 1-ene iso-butene and ethylene. </p>
<p>These results indicate that methylene from diazirine is considerably more selec- tive than that from diazomethane and is in this respect very similar to methylene from keten. Photolysis of diazirine with cyclobutane yields an a Frey Proc. Chm SOC.,1959 318. Frey Trans. Faraday SOC.,1960,56 1201. PROCEEMNGS excited molecule of methylcyclobutane. From the yields of methylcyclobutane and propene (formed by decomposition of the excited molecule) at various pressures the rate constants for the decomposition of methylcy~lobutane~ have been calculated to be at 134 mm. 27 x lo8sec.-’; at 250 mm. 30 x 108 sec.-l. These values are almost identical with those obtained by using diazomethane and 3660 A radiation and are considerably greater than the values obtained by using keten. </p>
<p>This suggests that rnethylene from di- azirine contains approximately the same total energy as methylene from diazomethane. Since it is some what more selective to C-H bonds it probablycon- tains less translational energy and correspondingly more vibration energy than methylene from diazo-methane. In comparison with methylene from keten it contains approximately the same translational energy excess but is vibrationally excited to a con-siderably greater extent. These findings are reason- able in the light of the cyclic structure of diazirine compared with the linear structure of diazomethane. One of us (H.M.F.) thanks the Royal Society for a grant for equipment. (Received December 14th 1961.) The Alkaloids of the Amaryllidaceae. </p>
<p>Part X.* Biosynthesis of Haemanthamine By P.W. JEWS (C.S.1.R. NATURAL OF CHEMISTRY, PRODUCTSRESEARCH UNIT,DEPARTMENT UNIVERSITY OF NATAL, PETERMARITZBURG NATAL) IN connexion with the biosynthesis of Amaryl-lidaceae alkaloidsf we report the incorporation of [3-14C]tyrosine (I) into haemanthamine (11; R’ = OMe R’ = R�’ = H) haemanthidine (XI; R’ = OMe R� = H R�’ = OH) and 6-hydroxy- crhaniinet (II; R’ = H R� = OMe R�’ = OH). The labelled tyrosine was injected into Hamanthus natalemis B. bulbs which were harvested after 10 days. The total crude alkaloid obtained by standard procedures2 was radioactive (incorporation 4.65 %). Isolation of the pure alkaloids showed them to be radioactive (see Table). </p>
<p> Radioactive hamanthamine was oxidised to oxo-hamanthamine (111) and this was cleaved to the glycine derivative (IV) by potassium t-butoxide de-carboxylation of which with ninhydrin gave carbon dioxide (collected as barium carbonate). The ex- pected amide (V) was not isolable but the acid (IV) with N-chlorotoluene-p-sulphonamide at 100� afforded carbon dioxide and 6-phenylpiperonal(VI). * Part IX J. 1961,4038. t The alternative name 3-epihzemanthidineP was used in an earlier publication from these laboratories but with the structure of crinamine now establishedg the name 6-hydroxycrinamine is preferable and has been used.s (a)Barton and Kirby Proc. Chem. SOC.,l960,392;.(b) Battersby Binks and Wildman ibid. p. 410; (c) Battersby, Bhks Fales and Wildman ibid. </p>
<p>1961 243; Barton,Kirby Taylor and Thomas,ibid. p. 254. Goosen Jeffs Graham Warren and Wright J. 1960 1088. Fales and Wildman J. Amer. Chem. Soc.,1950,82,197. ‘Leete Tetraheriron 1961.14 35. FEBRUARY 1962 81 Yield* Incorpn. Diln? Activity (%) (%j (x in 104) (10a c.p.m./imole) Hamanthamine 1-00 0.97 1-16 1-39 Haemanthidine 0.4 1 0.19 2.52 0.64 6-Hydroxycrinamine 0.91 1-08 91.0 1-77 * Based on dry wt. ofplant material. The results shown in the chart8 indicate that all the radioactivity in bmanthamine is located at the posi-tion marked with an asterisk. The reaction (1V) -+ (VI) afforded barium carbonate having half the activity of that obtained by use of ninhydrin; in con-junction with the isolation of 6-phenylpiperonal this shows that N-chl or0 t oluene-p-sulp honamide oxidises both carbon atoms in the glycine residue of the acid (1V) to carbon dioxide. </p>
<p> These results are in keeping with the fact that tyrosine is incorporated into the alkaloid as a com- plete unit and indicate that phenol-oxidative coupling6 is an important step in the biosynthesis of /(IV) (0*96*C) \ haman t hamine. The author thanks Professor F. L. Warren for his interest Mr. C. Hughes for the radiochemical measurements and African Explosives and Chemical Industries for grants. (Received December 3rd 1961.) $ For expression of the results see ref. 1 (b). Barton and Cohen “Festschrift Arthur Stoll,� Birkhauser Verlag Bade 1957 p. 117. A Kinetic Study of the Addition of the Ethyl Radical to Conjugated Dienes By A. </p>
<p>C. R. BROWN and D. G. L. JAMES (DEPARTMENT OF CHEMISTRY UNIVERSITYOF BRITISHCOLUMBIA 8 B.C. CANADA) VANCOUVER To place the reactivity of conjugated dienes upon a where R is the rate of formation of the product Y quantitative basis we are measuring the energy of and p] is the concentration of the diene. The activation for the addition of ethyl radicals (gen- apparatus and method are as described in previous erated by photolysis of diethyl ketone) in the gas papers supplemented by gas chromatography. phase to representative dienes starting with 2,3-di- The abstraction of hydrogen atoms from the methylbuta-l,3-diene and cyclohexa-l,3-diene. methyl groups of 2,3-dimethylbuta-l,3-dieneby the The method is essentially a comparison of the ethyl radical is too slow to be detected under our rates of two competing reactions at a series of experimental conditions. </p>
<p>In contrast the metathetical temperatures; for 2,3-dimethylbuta- 1,3-diene these and addition reactions of cyclohexa-1,3-diene pro- are ceed at comparable rates CH,-CH,. + CH,= CMeCMe= CH 3 0-CH,*CH 0 (11 CH;CH29 3. CHBCH,.CH,.CMe-CMe = CH ..... (1‘) ZCH,.CHB. 3 CaH, (2) At higher light intensities and below 160� it may be shown that kdk,,= (R,-((R,,,,fR,,,S)/IBl(R,,,)b 9 0 .-. ...-..(3) li James and Steacie Proc. Roy. Soc.,1958 A 244,289,297. PROCEEDINGS Now equation (I) is rigorous only if the removal of mono-olefin; the difference in reactivity between the each of the radicals formed by reactions (1') and (3) cyclic and non-cyclic dienes is due to a difference in involves the consumption of one ethyl radical and El rather than in A'. </p>
<p> yields no ethane. In this system a trace of benzene Allylic reactivity in metathesis is expected and was found in the products and accordingly R,,, observed in cyc€ohexa-l,3-diene and again arises was corrected for the ethane formed in the dispropor- from a low energy of activation. A comparison of the tionation CH3CH,. + (A) + CH,CH + C&,. relative magnitudes of our rate constants at 65" with Reactions of the ethyl radical with conjugated dienes Substrate Nature of reaction No. of runs 13 + log (A,/A,+) Er-3E2 (kcal./mole) 1013kr/k2+ at 65" Methyl affinity2 2,3-Dimethylbuta-l,3-dieneAddition Cyclohexa-l,3-diene Addition Hept-1-ene Addition Cyclohexa- 1,3-diene Metathesis Heyt-1 -ene Metathesis 27 14 34 17 22 5.64f-0.15 5.55&0*17 5*2&-0*1 5-010.3 5-6f0.3 (cm.3 mol.-+sec.-t)4-5f0.2 515 5.2f0.3 147 7*0*0*2 4.3 5.4f0.5 31 8.3 f0.5 1.6 at 65" 2230 665 26 204* 13* * The corresponding rate constant for the metathetical reaction. </p>
<p> The results obtained with the conjugated dienes those for the corresponding reactions of the methyl are compared with those for hept-1-ene in the Table. radical in solution2 reveals a common pattern of The limits of error are calculated at the 5 % reactivity in the two systems. probability level. Three conclusions may be drawn the conjugated We thank the National Research Council of dienes owe their high reactivity to a low value of El; Canada for the financial support and for a student- their bifunctional nature is paralleled by a value of ship (to A.C.R.B.). </p>
<p> A approximately twice the magnitude of A for a (Received December 18th 1961.) Szwarc et al. Proc. Roj,. Soc. 1957 A 240 396; J. Amer. Chem. SOC.,1957 '79 6343; 1961 83 3005. Nonacarbonyl(vinylsilicon) tricobalt By S. F. A. KETTLE and JRSHAD A. KHAN OF CHEMISTRY SHEFFIELD, (DEPARTMENT THE UNIVERSITY 10) THE evidence available appears to favour the structure shown in Fig. 1 for the cobalt carbonyl complexes Co,(CO),CR. Thus although this struc- ture is incompatibIe with the reported proton mag- netic resonance spectrum of the compound with R = Me,' it is strongly supported by synthetic2 and de- gradztive3 work. </p>
<p>t HC 'FH We have prepared nonacarbonyl(vinylsi1icon)tri-cobalt to which we tentatively assign a similar struc- FIG.1. FIG.2. ture shown in Fig. 2. Reflixing octacsrbonyl dicobalt Markby Wender Friedel Cotton and Sternberg J. Amer. Chem. SOC.,1958 86 6529. Dent Duncanson Guy Reed,and Shaw Proc. Chem. SOC.,1961 169. Kriierke and Hubel Chem. and Ind. 1960 1264. t An X-ray structure determination is in progress (Dahl Corey de Gil and Sutton 140th Meeting Amer. Chem. Soc., Chicago Sept. 1961 Abs. p. 48 N. FEBRUARY 1962 with tetravinylsilane in light petroleum ether under nitrogen gave a dark brawn solution which was centrifuged and placed on alumina. Elution with light petroleum ether gave two bands. The first fast- moving contained a cobalt carbonyl derivative having infrared peaks at ca. </p>
<p>2015 2050 and 2080 crn.-l (Infracord spectrometer). This compound was obtained in less than 0.1%yield and has yet to be characterised. Continued elution gave a dark purple band from which purple-black crystals of nonacar- bonyl(vinylsi1icon)tricobalt were obtained. This is stable in air if refrigerated (Found C 27.2; H 1.0; Si 6.3; Co 36.5; CO 49.2. Cl1H,Co,O9Si requires C 27.3; H 0.6; Si 5.8; Co 36.5;CO 52.1%)and has vmax. 2130m 2080~,2055s and 2037w cm.-l. The 2130 cm.-l peak could indicate a Si-H bond (which would be required for the structures proposed by Markby et a1.l) but we consider that it is more likely to correspond to that reported at 21 10-21 16 cm-l in the carbon series.lS2 It is significant that a peak which has an almost constant position for a wide range of substituents R in the carbon series should move when silicon is substituted for carbon. </p>
<p> This shift is probably an indication of d+ d bonding (Co+ Si) since this would reduce the electron density in the carbon monoxide r*orbitals with consequent increase of the C f0 stretching frequency? The mechanism of this bonding is exemplified in Fig. 3 which shows the interaction of the silicon 3d, orbital with the combination 2dzz(Co1)-dzz(Co2)-d,~(Co3). Although it is known that vinylstannanes lose vinyl groups when treated with transition-metal carbonyls a comparable reaction has not been reported for vinyl-silanes. Co-ordination through vinyl groups has been suggested for the compounds M(CO),(C2H,),SiMe2 where M = W or Mo.~ We are indebted to the Mond International Co. </p>
<p> Ltd. for a gift of cobalt carbonyl and to the Asia Foundation for a grant (to I.A.K.). (Received December 6th 1961.) Cf. Seyferth and Kahlen J. Arner. Chem. Soc. 1960 82 1080; Cotton and Parish J. 1960 1440. Manuel and Stone Chem. and Znd. 1960 231. NEWS AND ANNOUNCEMENTS New Year Honours List.-Included in the New Year Honours List were Sir Harry Jephcott lately Chairman Council for Scientific and Industrial Research (Baronet) E. A. Pevren lately Director Chemical Defence Experimental Establishment War Office (C.B.) F. H. Banfield lately Director of Research British Food Manufacturing Industries Research Association (O.B.E.) H. </p>
<p>J. T.Ellingham Secretary and Registrar Royal Institute of Chem- istry (O.B.E.) and J. A. Lovern Senior Principal Scientific Officer Torry Research Station D.S.I.R. (O.B.E.). D.S.I.R. and N.A.T.O. Awards.-The names of the undermentioned Fellows appear among those awarded D.S.I.R. Research Fellowships or N.A.T.O. Science Fellowships or Scholarships administered by D.S.I.R. D.S.I.R. Research Fellowships have been awarded to Mr. A. J. Edwards at Birmingham University and Mr. G. V. Baddeley at Cambridge University. N.A.T.O. Science Fellowships have been awarded to Mr. A. Deavin at Heidelberg University Mr. M. F. A. Dove at Munich University Mr. J. H. P. Utley at Munich University and University College London Mr. N. J. </p>
<p>McLean at Stockholm University Miss M. G. Combe at Basle University Dr. L. Batt at Cambridge University Dr. A. G. Davies at Imperial College London Dr. T. M. Moynehan at King’s College London Dr. P. N. Edwards at Manchester University Mr.J. C. Barnes Mr. J. M. Locke Dr. H. J. Rogers and Dr. R. Taylor at Oxford University. A N.A.T.O. Science Studentship has been awarded to Miss A. K. Kerigan at the University of British Columbia. Professor H. T. S. Britton.-To commemorate the life and work of the late Professor H. T. S. Britton Emeritus Professor of Chemistry of the University of Exeter an ad hoc Committee representing the Local Sections of the Chemical Society the Royal Institute of Chemistry and the Society of Chemical Industry has decided to establish a “Britton Memorial Lecture.� Having due regard to Professor Britton’s interest in young people and in physical chemistry and forensic science the Committee aims to select from people working in or who have worked in the South- Western Area and at such intervals as funds permit a lecturer under 30 years of age primarily interested in these branches of chemistry. </p>
<p> A personal “appeal for funds� will be addressed shortly to members of the Local Sections but it is felt that many chemists formerly resident in the South-West and others who were his friends may wish to be associated with the proposal. All donations should be made payable to the “Britton Memorial Fund� and sent to the Honorary Treasurer Dr. S. J. Gregg Chemistry Department Washington Singer Laboratories University of Exeter Prince of Wales Road Exeter. </p>
<p> Publications Supplied to Younyer Fellows.-Fellows under twenty-seven years of age on January 1st in any year are at present entitled to receive the Annual Reports and Quarterly Reviews for that year on payment of the basic annual subscription of two guineas. Formerly free publications (or a reduced subscription) were allowed to Fellows under twenty- five years of age but the age limit was raised by two years to take account of National Service which it was argued imposed a two-year delay in the training of young chemists. Now that the reason for this concession no longer applies and owing to the considerable increases in the cost of publications the Council has decided that it would be in the general interest of Fellows to revert to the lower age limit of twenty-five years. </p>
<p>In order that recently elected Fellows should not feel that they have been victimised the change will not become effective until January 1964. Election of New Fellows.-1 71 Candidates whose names were published in Proceedings for December have been elected to the Fellowship. Deaths of Fellows.-We regret to announce the death of Miss J. M. Landun (21.11.61) of Scar- borough a Fellow for 37 years. Salters’ Institute of Industrial Chemistry.-Appli- cations are invited for Salters’ Scholarships value f450-&550 p.a. (plus fees) for a resident in the United Kingdom with an Honours degree or equi- valent qualification in Chemistry Biochemistry Physics or Engineering for the purpose of receiving either full-time instruction in the principles of Ckem- ical Engineering or further experience by research in Chemistry or Chemical Engineering. </p>
<p>Applications may be made before graduation. The Scholarships will be tenable for one year and may be renewed year by year for two further years. Tenure abroad may be permitted in the third year. Applications are also invited for Salters’ Fellow- ships of value in the range &800-&1,000 p.a. (plus fees and 10% contribution to F.S.S.U.). These Fellowships may be held by Honours graduates or holders of equivaknt qualifications in Chemistry Biochemistry Physics or Engineering who desire to obtain further training in research in Chemistry Bio- chemistry or Chemical Engineering. </p>
<p>Candidates should have obtained a doctor’s degree or have had not less than three years’ postgraduate experience by the time of their taking up the Fellowship. Fellow- ships will be tenable in the United Kingdom or abroad for one year from September lst 1962 and may be renewed for one further year. Applications for both these awards must be received by the Clerk of the Salters’ Company 36 PROCEEDINGS Portland Place London W.1 by March 28th 1962 on forms which he will supply on application. International Symposia etc.-A Conference on the Corrosion of Reactor Materials will be held in Salz- burg from June 4-9th 1962. Further enquiries should be addressed to the International Atomic Energy Agency 1 1 Kartner Ring Vienna 1 Austria. </p>
<p> An International Conference in Chemical Physics in the Onsager Reciprocal Relations will be held in Providence Rhode Island U.S.A. from June 12-14th 1962. Further enquiries should be ad- dressed to John Ross Associate Professor Chem- istry Department Brown University Providence 12 R.I. U.S.A. An International Symposium on Humidity and Moisture-Measurement and Control in Science and Industry will be held on May 20-23rd 1963 in Washington D.C. U.S.A. Those interested in pre- senting papers are invited to submit two copies of an abstract to ArnoId Wexler Chairman of the Fro- gramme Committee National Bureau of Standards Washington 25 D.C. U.S.A. Symposium-A Symposium on “Enzyme Chem- istry of Phenolic Compounds,� under the auspices of the Plant Phenolics Group will be held at Rathbone Hall University of Liverpool from April 10-1 2th 1962. </p>
<p>Enquries should be addressed to Dr. H. M. Hurst Department of Botany University of Liverpool. Personal.-Professor S. J. Angyal on sabbatical leave from the University of New South Wales will be visiting the Imperial College of Science and Tech- nology London during the period May-August 1962. The Praesidium of the Academy of Sciences U.S.S.R. have invited Dr. S. A. Barker Lecturer in Chemistry University of Birmingham to be their official guest for two weeks and give lectures in Moscow and Kiev. Professor W. F. Barker who has retired as Professor and Head of the Department of Chemistry at Rhodes University has had conferred upon him the title of Professor Emeritus of the University. </p>
<p> Dr. J. R. Nunn and Dr. J. G. Prunty have been appointed Professor of Organic Chemistry and Pro- fessor of Inorganic and Physical Chemistry respectively. Mr. L. W.BlundelZ has been elected Honorary Treasurer of the British Tar Federation for 1961- 1962. Mr. Kenneth Bolsover has taken up the position of Principal Technologist with Forte’s & Company. Dr. B. M. Boyns Chief Technical Adviser to Adam Lythgoe Ltd. has been appointed Agricultural Adviser to the Soil Fertility Group of Companies Hartham Park Corsham Wilts. FEBRUARY 1962 85 Dr. E. G. Cowley at present Head of the Chemistry Department of Brighton Technical College has been appointed Principal of Swansea College of Tech- nology from April 1st next. </p>
<p> Dr. N. R. Dhar a Foreign Associate of the French Academy of Agriculture has been elected Corres- ponding Member in the Chemistry Section of the French Academy of Sciences. Dr. F. P. Doyle has been appointed Deputy Director of Research of the Beecham Research Laboratories Limited Betchworth. The degree of D.Sc. has been conferred on Dr. F. S. H. Head by the Senate of London University for his work in the field of Organic Chemistry; Chemistry of Cellulose. Dr. A. D. Kemp has been appointed Lecturer in Organic Chemistry at the University College of Rhodesia and Nyasaland. Dr. John A. King has been appointed Manager of Research Development of American Cyanamid Company’s Agricultural Division. </p>
<p> Dr. Mortimer M. Labes has been appointed Manager of the Chemistry Laboratory of The Franklin Institute’s Laboratories in Philadelphia U.S.A. Dr. J. Lewis of University College London has been appointed Professor of Inorganic Chemistry at Manchester University to succeed Professor F. Fairbrother who will retire in September. Dr. Frank W. Mitchell formerly with the Univer- sity of Saskatchewan is now a Research Chemist with the Dominion Rubber Company Guelph Ontario Canada. Mr. A. R. Penfold has been appointed Technical Secretary Plastics Institute of Australia. Dr. C. A. Redjarn has been nominated as a United Kingdom representative to attend the internationaf seminar on accelerated vocational training in the manufacture of plastics goods to be held in Paris on March 12-14th 1962 and which is being organised by the European Productivity Agency. </p>
<p> Dr. P. A. Robins at present Lecturer in Organic Chemistry at the University College of Rhodesia and Nyasaland has been appointed to the Chair of Chemistry at the Royal College Nairobi. Dr. Vivian T. Stannett has been appointed Associate Director of the Camille Dreyfus Labora- tory of the Research Triangle Institute. Professor Arne Tiselius of Uppsala Sweden has been awarded the Messel Medal of the Society of Chemical Industry for 1962. Dr. J. H. Wilkinson has been awarded the degree of Doctor of Science by the University of London for his work in biochemistry. </p>
<p> FORTHCOMING SCIENTIFIC MEETINGS London Thursday March 22nd at 7.30 p.m. Faraday Lecture “Mechanism of Olefin-forming Eliminations,� by Sir Christopher Ingold D.Sc. F.R.S. To be held in the Lecture Theatre The Royal Institution Albemarle Street W. I. Aberdeen Wednesday March 14th at 8 p.m. Lecture “Some Aspects of Radiation Chemistry,� by Professor F. S. Dainton Sc.D. 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. Birmingham Friday March 2nd at 4.30 p.m. Lecture “Phytol-the Cinderella of Natural Pro- ducts,� by Professor B. C. L. Weedon D.Sc. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University. </p>
<p> Bristol (Joint Meetings with the Society of Chemical Industry and the Royal Institute of Chemistry.) Thursday March Ist at 6.30 p.m. Lecture “Fuel Technology in the U.S.S.R.,�by Dr. Idris Jones C.B.E. Joint Meeting with the Institute of Fuel to be held in the Department of Chemistry The University. Thursday March 8th at 6.30 p.m. Lecture “Adhesion to Cellulose,� by Dr. A. G. White F.R.I.C. To be given at the British Cellophane Co. Bridgewater. Thursday March 22nd at 7 p.m. Ladies’ Night arranged by British Celanese. To be held at the College of Science and Technology Ashley Down. Cambridge (Meetings will be held in the University Chemical Laboratory Lensfield Road.) Friday March 2nd at 8.30 p.m. </p>
<p> Lecture “Molecular Shapes and Sizes,� by Dr. L. E. Sutton M.A. F.R.S. Joint Meeting with the Univer- sity Chemical Society. Monday March 5th at 5 p.m. Lecture “Chains and Rings in Solution,� by Dr. F. J. C. Rossotti M.A. Tuesday March 6th at 4.30 p.m. Lecture “The Mass Spectrometer in Chemical Physics,� by Dr. J. Cuthbert. Cardiff Monday March 12th at 5 p.m. Lecture “n-Complexes of Iron,� by Professor P. L. P;,uson Ph.D. F.R.L.C.To be given in the Depart- ment of Chemistry The University Cathays Park. Dublin Wednesday March 21st at 5.30 p.m. Lecture “Some Stereochemical Problems in Eudes- mane Chemistry,� by Professor Wesley Cocker D.Sc. M.R.I.A. To be given in the Department of Chemistry University College. </p>
<p> Durham Monday March 12th at 5 p.m. Lecture “Recent Advances in the Organic Chemistry of Boron,� by Dr. W. Gerrard F.R.I.C. Joint Meet- ing with the Durham Colleges Chemical Society to be held in the Science Laboratories The University. Edinburgh Thursday March 22nd at 7.30 p.m. Three short papers on Local Chemical Engineering Topics. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Exeter Friday March 2nd at 5.15 p.m. Liversidge Lecture “Stereospecific Polymerisat ion,� by Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. To be given in the Washington Singer Laboratories Prince of Wales Road. Glasgow Friday March 16th at 4 p.m. </p>
<p> Meeting for the reading of original papers and Annual General Meeting of the local section of the Chemical Society. To be held in the Royal College of Science and Technology. Hull Friday March 9th at 5 p.m. Lecture “What is a Dipole Moment?� by Professor C. A. Coulson D.Sc. F.R.S. To be given in the Chemistry Department The University. PROCEEDINGS Keele Thursday March lst at 5.15 p.m. Lecture “Some New Reactions of Alkoxyacetyl- enes,� by Dr. D. Cohen M.A. Joint Meeting with the University College Science Society to be held in the Department of Chemistry University College of North Staffs. Leeds (Meetings will be held in the Chemistry Lecture Theatre The University.) Thursday March lst 1962 at 6.30 p.m. Liversidge Lecture “Stereospecific Polymerisation,� by Professor C. </p>
<p>E. H. Bawn C.B.E. Ph.D. F.R.S. Thursday March 8th 1962 at 6.30 p.m. Lecture “Some New Natural Phenolic Compounds -Structural and Biosynthetic Studies,� by Dr. W. D. Ollis. Joint Meeting with the University Union Chemical Society. Leicester Thursday March 8th at 7.30 p.m. Tilden Lecture “Hydrido- and Related Organo-complexes of Transition Metals,� by Dr. J. Chatt M.A. F.R.S. To be given in the University. Note.-The time of this meeting has been brought forward. Newcastle upon Tyne Friday March 16th 1962 at 5.30 p.m. Bedson Club Lecture “The Mode of Action of Lead Tetraethyl as an Anti-knock,� by Professor A. D. Walsh M.A. Ph.D. To be given in the Chemistry Department King’s College. </p>
<p> North Wales (Joint Meetings of the University College of North Wales Chemical Society to be held in the Chemistry Department University College Bangor.) Thursday March 8th at 5.45 p.m. Lecture “Some Chemical Aspects of Tropical Agri- culture,� by Professor R. L. Wain D.Sc. F.R.S. Joint Meeting with the Society of Chemical Industry. Thursday March 15th at 5.45 p.m. Lecture “Stereochemical Correlations,� by Profes-sor W. Klyne M.A. D.Sc. Ph.D. Nottingham Tuesday March 6th at 5 p.m. Lecture “Chemical Reprocessing of Plutonium-containing Fuels,� by Dr. D. M. Donaldson A.R.I.C. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University. FEBRUARY 1962 Oxford Monday March 5th at 8.30 p.m. </p>
<p> Lecture “Surface of Metals,� by Professor A. W. Adamson. Joint Meeting with the Alembic Club and the Royal Institute of Chemistry to be held in the Lnorganic Chemistry Laboratory. St. Andrews and Dundee Tuesday March 13th at 5 p.m. Lecture “The Triplet Stage in Chemistry,� by Professor G. Porter Ph.D. F.R.S. To be given in the Chemistry Department Queen’s College Dundee. Sheffield Thursday March 15th at 4.30 p.m. Lecture “Carotenoids and Related Terpenes,� by Professor B. C. L. Weedon D.Sc. F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the University Chemical Society to be held in the Chemistry Department The University. Sout hampton Friday March 9th at 5 p.m. Lecture “The Adsorption of Vapours on Solids,� by Professor A. </p>
<p>W. Adamson. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry to be held in the Chemistry Depart- ment The University. Thursday April 5th at 7p.m. Lecture “Analytical Research,� by Dr. J. Haslam. Joint Meeting with the University Chemical Society to be held in the College of Technology Portsmouth. Swansea (Joint Meetings with the University College Chem- ical Society to be held in the Department of Chem- istry University College.) Monday March 5th at 4.30 p.m. Lecture “The Active Centres of Enzymes,� by Professor H. N. Rydon D.Sc. D.Phil. F.R.I.C. Monday March 19th at 4.30 p.m. Tilden Lecture “Hydrido- and Related Organo- complexes of Transition Metals,� by Dr. </p>
<p>J. Chatt M.A. F.R.S. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicPte 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.) Allan Leslie Thomas M.Sc. 9 Woodhead Road, Walkergate Newcastle-upon-Tyne 6. Allara David Lawrence B.S. Chemistry Department University of California Los Angeles 24 Calif. U.S.A. Anirudhan Chulliparambil Achuthan M.Sc. The School of Pharmacy 29/39 Brunswick Square London W.C.l. Anselmi. Robert T.. B.Sc. Department of Chemistry University of Rochester River Campus Rochester 20 New York U.S.A. </p>
<p> Ashcroft Stanley John B.Sc. Department of Physical Chemistry The University Leeds 2. Asher John David Mitchell B.Sc. 8 Caledonian Man- sions Glasgow W.2. Banks David Franklin. Chemistry Department Reed College Portland 2 Oregon U.S.A. Barton Lawrence B.Sc. Department of Inorganic, Physical and Industrial Chemistry University of Liverpool Vine Street Liverpool 7. Beagley Brian B.Sc. 38 Sandford Road Moseley, Birmingham 13. Beak Peter B.A. Ph.D. Chemistry Department, University of Illinois Urbana Illinois U.S.A. Beebe George Warren B.S. Kedzie Chemical Labora- toy Michigan State University East Lansing, Michigan U.S.A. Ben-Dor. Lina Ph.D. Department of Chemistry, Imperial College of Science and Technology S.W.7. </p>
<p> Berchtold Glenn Allen B.S. Ph.D. Massachusetts Insti- tute of Technology 77 Massachusetts Avenue, Cambridge 39 Mass. U.S.A. Berger Jack Solomon. 606 West Ohio Street Urbana Illinois U.S.A. Bick Susan Margaret. “Wychwood,� 131 Bryanston Road Solihull Warwickshire. Black Dennis B.Sc. 13 Holmside Place Heaton, Newcastle-upon-Tyne 6. Boddington Terry B.A. Laboratory for the Physics and Chemistry of Solids Cavendish Laboratory Free School Lane Cambridge. Bowie Raymond Alexander B.Sc. 4 Park Road Aber- deen Scotland. Bridges Paul Richard. c/o 41 Rock Hill Road Ponty- moile Pontypool Monmouthshire. Brimacombe Richard Louis Carter B.A. University Chemical Laboratory Lensfield Road Cambridge. Brooker Edgar George M.Sc. Ph.D. </p>
<p>A.N.Z.I.C. 630 South Road New Plymouth New Zealand. Brown Colin Campbell. 26 Greenway Greasby Upton Wirral Cheshire. Brown Derek B.A. 8 Wilkins Road Cowley Oxford. Brown David. Ph.D. A.E.R.E. Harwell Didcot Berks. Brown Graham Cardy B.Sc. 11 Erlesmere Gardens London W. 13. Brown James Howard Ph.D. Hooker Chemical Cor- poration Research Centre P.O. Box 344 Niagara Falls New York U.S.A. Brown Philip Edgar B.A. Oriel College Oxford. Brown William Alexander Crawford B.Sc. Room 269 Chemistry Department The University Glasgow W.2. Bryce Douglas James B.Sc. 109 Whinton Mains Road Edinburgh 13. Burgess John B.A. University Chemical Laboratory Lensfield Road Cambridge. Burke Patrick Michael B.Sc. 11Spadina Road Toronto 4 Ontario Canada. </p>
<p> Caddy Brian B.Sc. The Chemistry Department The University of Sheffield ShefField Yorks. Caldwell Richard Averill S.B. Department of Chem- istry University of California Berkeley 4 Cald, U.S.A. Capon Noel B.Sc. 11 Rotherwick Road Golders Green N.W.ll. Carson Mary Silvey. 11 Booterstwon Park Blackrock Co. Dublin Eire. Casey Allan Terence M.Sc. Ph.D. Chemistry Depart- ment University of Melbourne Parkville N.2, Victoria Australia. Chalfen Stuart Philip B.Sc. Chemistry Department University College Gower Street W.C.l. Chambers Colin B.Sc. 8 Aigberth Hall Road Grossen- dale Liverpool 19. Chinnick Christopher Charles Thomas. 69 Lansdowne Road London W. 1 1. Churchill Melvyn Rowen B.Sc. A.R.C.S. Chemisty Department Royal College of Science Imperial Institute Road S.W.7. </p>
<p> Clark David Thomas B.Sc. 58 Harcourt Road Sheffield 10. Clarke John Joseph M.Sc. 73 Gt. King Street, Edinburgh 3. Cole William John B.Sc. Department of Chemical Pathology Kings College Hospital Medical School Denmark Hill S.E.5. Constantinides Erricos B.Sc. 24 Conway Street London w.l. Cook Brian R.Sc. A.R.I.C. 103 Animal Genetics Building University of Illinois Urbana Illinois, U.S.A. Coutts Ronald Thomson Ph.D. A.R.C.S.T. M.P.S. 4 Ringmore Court Tunstall Road Sunderland Co. Durham. Covell Albert Nelson B.Sc. 108 Widecombe Road Mottingham. S.E.9. Dailly Bryce Nelson. 14 Langdon Crescent East Ham E.6. Dakin Howard Granville. 41 Coombe Lane W. Wimbledon S.W.20. Davidson Hugh B.A. </p>
<p>43 Highfield Road Pontefract Yorkshire. Davidson Theodore B.A. Department of Chemistry University of Chicago 5747 S. Ellis Avenue Chicago 37 Ill. U.S.A. Demetriou Basil B.Sc. Chemistry Department Wool-wich Polytechnic London S.E. 18. Deuters Barrie Eugene M.Sc. A.R.I.C. Golden Elm Sewardstone Road Chingford E.4. Dhami Kewal Singh M.Sc. Department of Chemistry University of Western Ontario London Ontario Canada. Dorchai Rafael O. B.Sc. 84 Lindsay Road Glasnevin Dublin 9. Durst Tony B.Sc. 184 Huron Street London Ontario Canada. Elenius Eero Pietari Johannes. Turun Yliopiston Kemian Laitos Vesilinnantie 5 Turku 2 Finland. Engelhardt Edward L. B.S. Ph.D. Plymouth Road Gwynedd Valley Pennsylvania U.S.A. Fawcett Richard Fennelly B.A. </p>
<p>D.Phi1. “Hillcrest,� Egham Hill Englefield Green Surrey. Fawcett. William Ronald B.A. 866 Windermere Avenue Toronto 9 Ontario Canada. PROCEEDINGS Feast William James BSc. 14 Chase Road Burntwood Lichfield Staffordshire. Ferguson George Ph.D. Chemistry Department The IJniversity Glasgow W.2. Ferrari Corrado D.Chem. Division of Pure Chemistry Room 2099. National Research Council. Ottawa 2. Canada. Finnev. Graham. B.Sc. 37 Clarendon Road Whalley RaGge Manchester 16. Fisher Keith John. 2 The Elms Marroway Street Rotton Park Birmingham 16. FIowers William Thain B.A. Room E.38 Department of Chemistry Manchester College of Science and Technology Manchester 1. Frith Brian Chapman. c/o J. M. Collett & Co. Ltd., Chemical Works Bristol Road Gloucester. </p>
<p> Furkert Roderick John B.Sc. 58 Matai Road Hataitai Wellington E.2 New Zealand. Ghosh Peter Bhoson. 20 Newall House Harper Road S.E.1. Gibbard Brian. 4 Downside Avenue Bitterne South- ampton. Gilbert Richard Frank B.A. West Cheynes Corbridge Nort humberland. Glen Alasdair Thomas B.Sc. Chemistry Department Royal College of Science and Technology George Street Glasgow. Grant Eric McPherson B.Sc. Room 264 The Chemistry Department The University Glasgow W.2. Green David Edward B.Sc. 54-A Aldermaston Park Estate Aldermaston Berkshire. Green Dallas Maxwell. 18 Carr Road Greenford Middlesex. Greene Arthur F. Jr. M.Sc. 1486 Cohassett Avenue Cleveland 7 Ohio U.S.A. Grochowski Andrzej B.Sc. 99 Longthornton Road London S.W. </p>
<p>16. Hall Michael Edgar M.Sc. Ph.D. Development Unit Glaxo Laboratories Ltd. Greenford Middlesex. Harper Edwin T. Ph.D. 56 Wells Avenue Dayton 31, Ohio U.S.A. Harris David Clayton B.A. Jesus College Oxford. Hayon Elie Ph.D. A.R.C.S.T. Department of Physical Chemistry Cambridge University Cambridge. Heitzman Raymond John Ph.D. Chemistry Depart- ment Birmingham University Edgbaston Birmingham 15. Hewitson Keith B.Pharm. M.P.S. 3A Montpelier Crescent Brighton Sussex. Hewitt Graham. 79 Islip Manor Road Northolt, Middlesex. Hinchcliffe Harry A.R.T.C. 265 Pontefract Road, Burton Grange Barnsley Yorks. Hirst Joseph Clement. 34 Lee Road Lewes Susscx. Holland Frank Stanley. Chemistry Department The University Sheffield 10. </p>
<p> Hollands T. Ralph B.Sc. Apt. 306 1201 Richmond Street London Ontario Canada. Homburg Friedhelm. Braunschweig Jacob-Hofmann- Weg 1 Germany. Homer Roger Beale B.Sc. The Washington Singer Laboratories Perry Road Prince of Wales Road, Exeter. Hurst Jim B.Pharm. 53 Cromwell Avenue Winlaton Blaydon-on-Tyne Co. Durham. Irwin William Derek English B.Sc. 59 Dunlambert Park Belfast 15 Northern Ireland. Johnson Peter. 8 Goodwood Grove Great Sutton W irral Cheshire. Jolly Peter Walter B.Sc. A.RC.S. 897 William Street, London Ontario Canada. FEBRUARY 1962 Keane Francis Martin M.Sc. Ulvemosevej 6 Rungsted, Denmark. Keen Peter Clive B.Sc. Department of Chemistry The University Brookhill Sheffield 3 Yorks. Kenworthy John Grahame B.A. </p>
<p>Lincoln College, Oxford. Khan Trshad Admed M.Sc. Chemistry Department The University Sheffield 3. Khan Misbahulain M.Sc. 56 Portugal Cove Road St. Johns Newfoundland Canada. Khan Obaidur Rehman M.Sc. Department of Chem-istry University Ccllege Gower Street W.C. 1. box Graham Ramsay Ph.D. Department of Chem- istry The Royal College of Science and Technology Glasgow C. 1. Knox Kerro Ph.D. Bell Telephone Laboratories, Murray Hill New Jersey U.S.A. Krabbendam Hendrik. Chemistry Department Univer- sity of Fdinburgh West Mains Road Edinburgh. Ktay William Christian Jr. B.S. 2105 Heliotrope Drive Santa Ana California U.S.A. Labana Santokh Singh M.Sc. Baker Laboratory, Cornell University Ithaca N.Y. U.S.A. Lemieux Raymond LJ.,Ph.D. </p>
<p>Department of Chemistry University of Alberta Edmonton Alberta Canada. L’Enfant Raymond John. 72 Parkfield Avenue North Harrow Middlesex. Levi Michael Phillip B.Sc. Biophysics Sub-Department Department of Botany The University Leeds 2, Yorks. Lumme Paavo Olavi Ph.D. Ph.M. Institute of Chem- istry University of Helsinki Hallitusk 5 Helsinki, Finland. Lynch Thomas Robert B.Sc. Chemistry Department University of Toronto Toronto Canada. McClare Colin William Fraser B.A. 9 Balsham Road Fulbourn Cambridge. MacGregor Alexander William B.Sc. c/o MacAlpine 43 Braid Avenue Edinburgh 10. MacKenzie Samuel Leonard B.Sc. 5 Hartington Gardens Edinburgh 10. McKinnon David Mackie B.Sc. 1 Society Place West Calder Midlothian Scotland. </p>
<p> Majer John Raymond Ph.D. D.T.C. A.R.I.C. Chem- istry Department University of Birmingham Edg- baston Birmingham 15. blander David Charles. Hertford College Oxford. Melson Gordon Anthony B.Sc. 197 Westwick Road Sheffield 8 Yorks. Meyerstein Dan M.Sc. Arlosorov Street 16 Jerusalem, Israel. Miles David Trevor. 64 Newlands Avenue Shirley Sou thamp ton. Miller Jack Martin B.Sc. Room C-502 Chemistry Department McGill University Montreal Quebec Canada. Mittag Thomas Waldemar B.Sc. Chemistry Depart- ment University of Capetown Private Bag Ronde- bosch C.P. Republic of South Africa. Moorcroft David. 6 Tatton Road South Heaton Moor Stockport Cheshire. Moore Peter B.Sc. 45 Sunny Bank Sheffield 10 Yorks. Moritz Alan Gilbert Ph.D. University Chemical Laboratories Lensfield Road Cambridge. </p>
<p> Morris David Gerald B.Sc. Department of Chemistry University College of London Gower Street W.C.l. Mutter Gordon Peter Bouverie B.Sc. Department of Chemistry University of Leicester Leicester. Nadkami Shalini B.Sc. 2/13 Endsleigh Court Upper Woburn Place London W.C. 1. Nelson Peter Harold M.Sc. Department of Chemistry The University Manchester 13. Neta Pedatsur M.Sc. Ramat-Aviv 138 Tel-Aviv Israel. Noack Klans Dr.rer.nat. Cyanamid European Research Jnstitute. 91 Route de la Capite Cologny (Geneve) Switzerland. Norman Laurence Arthur. 14 Barleyhill Road Garforth Nr. Leeds Yorks. Ntamila Maulidi Suwedi B.A. University Chemical Laboratories Trinity College Dublin 2 Eire. Nunn Derek Ormond. </p>
<p>15 Twickenham Gardens, Green ford M iddlesex. Nye Martin John B.Sc. Chemistry Department The University Southampton Hants. Ogle Christopher John B.Sc. Department of Physical Chemistry The University Leeds 2 Yorks. Orzech Chester Eugene Jr. B.S. Kedzie Chemical Laboratory Michigan State University East Lansing Michigan U.S.A. Oughton Raymond Edward Oliver. 154 Prestwick Road South Oxney Herts. Owen Noel Lewis B.Sc. Department of Organic Chemistry University Chemical Laboratory Cam-bridge. Palmer Gordon B.Sc. 8 Coniston Road Coventry Warwicks. Palmer William Pitt B.Sc. Manwood Grange Sandwich Kent. Park Anthony John. 7 Cypress Road South Notwood S.E.25. Patterson David Alan B.Pharm. Pharmacy Department Sunderland Technical College Sunderland Co. </p>
<p> Durham. Payne Kenneth Richard Ph.D. A.R.T.C. 65 Moorlands Welwyn Garden City. Herts. Pemer. Edward Sandon. B.Sc. 122 Woodc;ide Road Sidcup Kent. Pillar Anthony Rowland B.A. St. Catherine’s Society Oxford. Pinnegar Michael Alan. Miles Laboratories Ltd. Stoke Court Stoke Poges Bucks. Preis Seymour Ph.D. 4976 Long Branch San Diego 7, Calif. U.S.A. Price Michael George. 1 Uppingham Road Wallasey Cheshire. Quickenden Terence Ivan M.Sc. 22 North-Avon Road Christchurch New Zealand. Ranson Robert David. Troutbeck House Leeds Road Lightcliffe Halifax West Yorkshire. Rayworth Peter Malcolm. 37 Cropton Road Bricknell Avenue Hull. Reavill Roger Ernest B.A. 1 Adams Road Cambridge. Reid James Edward B.Sc.14 Appledore Close Weeping Cross Stafford Staffs. </p>
<p> Reynolds Arthur Andrew. 30-A Watermilk Way, Hanworth Feltham Middlesex. Richards Hugh Colin Ph.D. 104 Harrow Road West Bridgford Nottingham. Riggs Glenys Megan B.Sc. 203-A Gloucester Road Bishopston Rristol 7. Riley Vida Margaret Murray B.Sc. Chemistry Unit, Research Division Glaxo Laboratoris Greenford, Middlesex. Roberts William. 4 Hopfield Road Moreton Wirral Cheshire. Robertson George Heddle B.Sc. c/o Gordon 23 Upper Gray Street Edinburgh. Robertson Ross Elmore M.Sc. Ph.D. 317 Marshall Court Ottawa Ontario Canada. Rodrigo Russell Godfrey Alwyn B.Sc.Department of Chemistry The University Nottingham. Rogers Max T. M.Sc. Ph.D. Kedzie Chemical Labora- tory Michigan State University East Lansing, Michigan U.S.A. </p>
<p> Ruoff Paul M. B.Chem. Ph.D. Chemistry Department Syracuse University Syracuse 10 New York U.S.A. Safford Edward L. M.S. 1209 West Mains Street Urbana Illinois U.S.A. Salmon John. 79 Globe Road Hornchurch Essex. Sarma Kolachana Govinda M.Sc. Ph.D. Chemistry Department I hiversity of Delhi Delhi 6 India. Scharf Walter B.S. Ph.D. Chemistry Department The City College 17 Lexington Avenue New York 10, N.Y. U.S.A. Seaman David B.Sc. D.Phil. 93 Malton Avenue, Whitefield Manchester. Seel,Fritz Dr.ing. Institut fur Anorganische Chemie der Universitat des Saarlandes Saarbrucken 15 Germany. Selinger Benjamin Klaus M.Sc. 84 Lansdowne Pde. Oatley New South Wales Australia. Shah Sureshchandra. 2 Hartswood Road London W. </p>
<p>12. Sharp Christopher John B.Sc. Physical Chemistry Unit Glaxo Laboratories Greenford Middlesex. Sharp John Traquair B.Sc. Organic Chemistry Research Department King’s College Strand W.C.2. Shepherd Jan Stuart B.A. 117 Wallwood Road Leyton- stone E.11. Shields David John. Cripps Hall University Park Nottingham. Shreeve Michael Edward B.%. 258 High Town Road Luton Beds. Sim Keng Yeow M.Sc. Department of Chemistry, School of Pharmacy Brunswick Square W.C. 1. Slater Robert Anthony B.Sc. Department of Organic Chemistry University of Liverpool Liverpool. Smith Alan. 2 King Edward Road Hyde Cheshire. Smith David Macdonald B.Sc. “Howford,� 91 Main Road Elderslie Renfrewshire. Smith John Kaye B.Sc. Lab. E.46 College of Science and Technology Sackville Street Manchester 1. </p>
<p> Smithies Donald Ph.D. School of Chemistry The University Leeds 2. Somerville Sheena Margaret B.Sc. “Rosehill,� 14 Chillingham Way Camberley Surrey. Sovers Ojars B.S. Ph.D. 7 Stratfield Road Oxford. Spence James Allan. “Ridgeway,� Mitchell Walk, Amersham Bucks. Spillman Josephine Alice B.Sc. 15 Friary Road Friern Barnet N.12. Stansfield John Philip B.Sc. 41 High Street East, Glossop Derbyshire. Staunton James Ph.D. 58 Bentham Drive Liverpool 16. Stein Thomas Peter. 54 Dunstan Road London N.W.11. Stephens Philip Henry Peter. Christ Church Oxford. Sternberg Heinz W. Ph.D. 130 Sylvania Drive Pitts- burgh 36 Pennsylvania U.S.A. Sternhell Sever M.Sc. Ph.D. D.I.C. 2 Dorritt Street Lane Cove New South Wales Australia. </p>
<p> Stocks Robert Nigel. B.Sc. Llanfoist House Llanfoist Abergavenny Monmouthshire. Strang Jack D. B.A. M.S. 208 N. Portage Path Akron 3 Ohio U.S.A. Sutherland Shirley Anne Marguerite M.Sc. Ph.D. Chemistry Department The University Glasgow W.2. PROCEEDINGS Sutton Maxwell McLauchIan B.Sc. Gas Research Department Houldsworth School of Applied Science The University Leeds 2 Yorks. Swain Isobel Louisa B.A. 12 Cranley Gardens London s.w.7. Sykes Barry Law. 214 Cowcliffe Hill Road Cowcliffe Huddersfield Yorkshire. Tammar Anthony Richard BSc. 74 Edgware Way Edgware Middlesex. Teach Eugene Gordon B.S. Ph.D. 1200 S. 47th Street Richmond California U.S.A. Thomas Kenneth Emrys B.Sc. Chemistry Department University of Birmingham Edgbaston Birmingham 15. </p>
<p> Thorpe Frederick Gordon B.Sc. 6 Lytton Road, Droylsden Manchester. Todd Alexander Henry B.A. Oriel College Oxford. Townshend Alan B.Sc. Chemistry Department The University Edgbaston Bkningham 15. Truscott Terence George B.Sc. Department of Chem- istry University College Swansea Glam. Turner Ronald. 16 Normandale Avenue Loxley Sheffield. Venkata Rao Erraguntla M.Sc. D.Sc. A.R.I.C. Chemistry Department King’s College Newcastle- upon-Tyne. Verbiscar Anthony J. Ph.D. Regis Chemical Company 1219 N. Wells Chicago 10 Illinois U.S.A. Vidwans Dinkar Hari M.Sc. D/42 Tara Baug Estate Girgoam Bombay India. Vinal. Richard Sturtevant. B.S. 116 Lake Street. Ithaca. N.Y. U.S.A. Wahl. George Henrv. </p>
<p>Jr.. M.S. Chemistry DeDartment ‘ New Yo& university New York 53 N.Y.,-U.S.A. Walters Reginald Michael B.Sc. Chemistry Department University of Nottingham University Park Notting- ham. Wang Jui Hsin Ph.D. Department of Chemistry Yale University New Haven Connecticut USA. Warren John Henry B.Sc. Chemistry Department The University Edgbaston. Birmingham 15. Waters Kenneth. Hertford College Oxford. Webster Sydney James. 13 South Parade Worksop Notts. Wells Arthur Bernard B.A. 21 St. Andrew’s Road Bexhill-on-Sea Sussex. Wharmby Donald Henry Walter BSc. 62 Windsor Terrace South Gosforth Newcastle-upon-Tyne. Wilkins Anthony John Joseph. 95 Clarendon Gardens N. Wembley Middx. Wingrove Alan Smith B.S. Chemistry Department U.C.L.A. Los Angeles 24 Calif. </p>
<p>USA. Wolfe Saul M.A. Ph.D. Department of Chemistry Queen’s University Kingston Ontario Canada. Woolliams Peter Richard. 34 Carlton Road Little Thurrock Grays Essex. Yip Roderick Wing Jone B.Sc. University of Western Ontario London Ontario Canada. Young Anne Elizabeth B.Pharm. M.P.S. 3 Eagle Court Snaresbrook E. 11. Young Anthony Thompson B.Sc. 258 Hightown Road Luton Beds. Young Robert B.Sc. Chemistry Department West Mains Road Edinburgh 8. Youssef Hassan Zaki B.Pharm. Chelsea School of Pharmacy Manresa Road London S.W.3. FEBRUARY 1962 91 OBITUARY NOTICES ERNEST EDWARD AYLING 1900-I960 ERNESTEDWARD Anma was born in 1900 at Ashford Middlesex. He received his early education at the local grammar school and when barely sixteen years of age he gained the distinction of being the first pupil of the school to be awarded a Major County Scholarship. </p>
<p>A year later he became a student at King’s College London and graduated in 1920. For a short time he was a demonstrator in organic chemistry before his appointment towards the end of 1920 as an assistant lecturer at the newly founded University College of Swansea. By his death on March 30th 1960 the College teaching staff lost its longest serving member. During the forty years at Swansea he gave devoted service to the College and to the profession of chemistry. Staff students and others who had been associated with him during this period heard the news of his sudden death with regret and will remember his many sterling qualities. </p>
<p> The appointment at Swansea enabled him to renew his association with one of us who had been his tutor at King’s College. It led to a very happy collaboration fn both teaching and research. Earlier researches were concerned with the chemistry of chloro-o-xylenes and a number of publications appeared in the Journal between 1923 and 1934. In 1926 he was awarded the degree of M.Sc. (London). He collaborated in investigations including substi- tuted aromatic aldehydes in Hantzch’s pyridine con- densation Gattermann’s hydrogen cyanide aldehyde synthesis substituted dihydroresorcinols and p-aminodimethylaniline. A series of papers embodying these studies were published in the Journal during the period 193 1-1946. </p>
<p>Dihydroresorcinol chemistry continued to engage his interest in the post-war period. Other publications on miscellaneous topics included the chlorination of phthalic acid the Baeyer strain theory and the influence of alkyl groups in carbonyl compounds. His interest in the early application of the electronic theory of valency to organic reaction is in evidence in these publica- tions. With the outbreak of hostilities in 1939 he became a Senior Gas Identificat4on Officer. This appoint- ment which he undertook with customary zeal led to further responsibilities as Civil Defence Regional Scientific Officer and later Scientific Intelligence Officer. His long service to the College was fittingly recognised by his appointment as Acting Head of Department on the resignation of Professor C. </p>
<p>W. Shoppee in 1956. He was appointed a Senior Lecturer in 1958. At the time of his death he had been a Fellow of the Chemical Society for forty years and had held office as Honorary Secretary of the South Wales Section of the Royal Institute of Chem- istry for the record period of nearly twenty-one years. A great debt is owed to him for his contribution to the furthering of the profession of chemistry in South Wales. In his youth he was an excellent tennis player and even in recent years he could extend a very much younger player. Ayhg possessed an encyclopaedic knowledge of students who had passed through the Department. He undertook any duty conscientiously and with meticulous care. </p>
<p>Students will recall his orderly presentation of a topic in lectures his charac- teristic jerky handwriting on the blackboard and his inexhaustible fund of anecdotes. Above all how- ever they will recall his sincere and sympathetic treatment of any problem which they presented to him whether academic or personal. The esteem with which he was held by all who came in contact with him is reflected in the list of subscribers to “The Ayling Prize� which has been established to per- petuate his name in the Department. He is survived by his wife and a grown up daughter. L. E. HINKEL R. H. DAVIES. SIR DAVID RIVETT 18 8 5-1961 SIRDAVIDRIVETT, K.C.M.G. F.A.A. F.R.S. who died in Sydney in his seventy-sixth year on April lst 1961 was a distinguished physical chemist and an outstanding scientific administrator. </p>
<p>His early career was in physical chemistry in which he achieved recognition both as a brilliant and stimulating teacher and for his research in the field of hetero-geneous equilibria. His book “The Phase Rule� is a standard text and will always remain a model to other authors for its clarity and conciseness of exposition. However what eventually became his real life’s work began probably rather unexpectedly for him in 1927 when he wasaged forty-one. He had occupied the Chair of Chemistry in the University of Mel- bourne for just three years when he was invited to accept appointment as the Chief Executive Officer of the newly formed Council for Scientific and In- dustrial Research an organisation created by the Commonwealth Government of Australia to con-duct research in science and its applications in both primary and secondary industry. </p>
<p>In 1927 Rivett accepted the new position only in a part-time capacity dividing his time between his duties to the C.S.I.R. and his duties to his university Chair. How- ever in the next year he resigned from the university and thereafter devoted his energies wholeheartedly to the development of the new infant. This organisation known since 1949 (the year of Rivett’s retirement) as the Commonwealth Scientific and Industrial Research Organ isa tion (C. S.I.R.O.) now occupies a dominating position in the Australian scientific effort with activities that range from radio- astronomy to wild life studies. </p>
<p>Its international prestige and the way in which it is pervaded by a spirit of fundamental science that is not always present in governmental research organisations are in large measure the result of Kivett’s wise and inspiring guidance during its early formative years. Rivett was a man of complete scientific integrity and of great imagination and he realised fully the kind of intellectual challenge that is needed to inspire the most able men to do their best work. From the out- set he encouraged his organisation to tackle funda- mental as well as “applied� problems although the successful solution of some of the latter (notably the prickly pear problem of north-eastern Australia) proved to be of the greatest publicity value to the young C.S.I.R. </p>
<p>Indeed he always insisted that the solution of practical or applied problems should be sought in their underlying fundamentals. He had the gift of selecting men of ability of inspiring them with his concept of the scientific attitude and of leaving them free to solve their problems in their own terms. Realising that the health and vigour of scientific research within the C.S.I.R. must depend ultimately on the health and vigour of the scientific schools of the Australian universities (which during this period were in a state of continuous financial impoverish- ment) he adopted a policy of close co-operation with them. The first regular budgetary provision for scientific research in the Australian State universities was in the form of an annual Commonwealth government grant administered by the C.S.I.R. </p>
<p> Although this grant has by now been merged in the much more substantial Commonwealth financial assistance administered by the Australian Univer- sities Commission the C.S.I.R. grant can be re- garded as marking the entry of the Commonwealth government into the field of State university finance. It is a tribute to Rivett that this fundamental PROCEEDINGS scientific policy of C.S.I.R. was established and maintained in a political and social climate that was on the whole rather indifferent to scientific research. Albert Cherbury David Rivett was born in Tasmania on December 4th 1885. After his second- ary education at Wesley College Melbourne he entered the University of Melbourne as a resident of Queen’s College and took chemistry as his major subject. </p>
<p>He was elected Victorian Rhodes scholar for 1907 and at Oxford continued his studies in physical chemistry in Lincoln College under the tutorship of N. V. Sidgwick. After a short period in the Stockholm laboratory of Svante Arrhenius he returned to the staff of the University of Melbourne in 1911 as lecturer in chemistry. He was appointed Associate Professor in 1921 and in 1924 he succeeded to the Chair of Chemistry which he occupied until his resignation in favour of the C.S.I.R. in 1928. He was knighted K.C.M.G. in 1935 and elected F.R.S. in 1941. In World War I he held rank as Honorary Captain in the Australian Army Medical Corps and later took part in munitions production in the United Kingdom. </p>
<p>He took a leading part in the scientific affairs of his country. He was President of the Australian and New Zealand Association for the Advancement of Science in 1937-39 and was twice President of the Royal Australian Chemical Institute in 1940 and in 1949 in which latter year he was also President of the Society of Chemical Industry (London). He took a prominent part in the founda- tion both of the Australian National University and of the Australian Academy of Science of which he was a Foundation Fellow. Rivett was short in stature with a spare athletic figure. One’s first and abiding impression of him was of his rather ascetic features dominated by blue eyes that were at once piercing intelligent and sym- pathetic. </p>
<p>His vigorous personality was such that even his private conversation gave an impression of abruptness and sometimes of impatience; but it was an impatience that even a nervous student could understand was pervaded by a fundamental kindli- ness and interest in his progress. His university lectures and public addresses were carefully prepared and brilliantly delivered and gave evidence of an original and imaginative mind that was prepared to seek the solution of new problems by quite uncon- ven tional methods. Within the organisation of the C.S.I.R. Rivett was a great believer in exposing a problem in one scientific discipline to the impact of brilliant minds trained in quite other disciplines. </p>
<p>This belief is an epitome of his own career. Trained as a physicai chemist he made few contributions in the conven- tional sense to the science of physical chemistry as such. His great work resulted from the impact of his own disciplined scientific intellect on the problems FEBRUARY 1962 of organising scientific investigation for the benefit of the community. His immediate community was Australia and he will be remembered in his country as a great Australian. However his personal scientific integrity and the reputation of the organisa- tion that he created have extended his influence far beyond the geographical boundaries of the Com-monwealth. Jn 191 1 he married Stella Deakin the daughter of Alfred Deakin one of the founders of the Australian Commonwealth. </p>
<p>He is survived by his widow and two sons. NOELS. BAYLISS. ROBERT EDWARD DODD 1925-1 961 ROBERTEDWARD DODD,son of Mrs. and the late Mr. E. R. Dodd was born in York on May 14th 1925. His sudden and quite unexpected death on February 25th 1961 in his thirty-sixth year came as a great shock to all who knew him and will remain a lasting sorrow to many of them. Dodd went to St. Peter’s School York where he held a Day Scholarship and always remained much attached to his school and to his native city and its Minster. There he began a life interest in swimming which led from captaining a school team to the Presidency of the Oxford University Swimming Club and in 1946 to a Blue. </p>
<p> He was awarded a Minor Scholarship at Trinity; there he read chemistry completing Part I in 1945 and Part LT in 1946 obtaining 2nd class Honours. Sir Cyril Hinshelwood was his tutor and with him he worked on gaseous free-radical reactions receiving the B.Sc. in 1947. He proceeded to the M.A. in 1950 and became an Associate in 1947 and a Fellow of the Royal Institute of Chemistry in 1958. From Oxford he came straight to a lectureship in the Chemistry Department of King’s College Newcastle upon Tyne on the staff of which he remained for the rest of his life. His service to King’s College was broken only by the academic year 1952-3; this he spent in Canada as a Post-Doctoral Fellow of the National Research Council. The visit to Canada he and his wife greatly enjoyed. </p>
<p>When- ever possible he grasped the opportunity of extending his experience by attending summer schools con- ferences and meetings; to some of these he con- tributed. By reason of his wide interests he became a valued member of the teaching staff of King’s College with the prospect of substantial advance- ment there or elsewhere. His teaching was principally in inorganic chemistry but its scope had been gradually extended to include quantum mechanics valency molecular structure and chemical spectro- scopy. In research Dodd’s interest lay in the reactivity of free radicals the study of which he began at Oxford; it was with this in mind that he went to Ottawa to work with Dr. E. W. R. Steacie. In a paper in the Proceedings of the Royal Society they showed from a study of the photolysis of acetone that the com- bination of methyl radicals to produce ethane occurs by the intervention of a third body which stabilises the excited molecule. </p>
<p>On free-radical chemistry he published nine papers. Later he turned to infrared spectroscopy for which the Chemistry Department was then being equipped with modern instruments and more recently planned and brought into opera- tion a laboratory especially adapted for this work. He organised an infrared service largely used in organic research. His own use of infrared spectra was related to the structure of a number of fluorine com- pounds in which there was collaboration on the Raman side with Dr. L. A. Woodward; to the hydrogen bonding in maleic acid and potassium hydrogen maleate with Professor Wynne-Jones ;and to the characterisation of fluorine cyanide with Dr. </p>
<p>E. E. Aynsley. These researches appeared in twelve papers. He collaborated with the present writer in the Annual Reports on the Progress of Chemistry Inorganic Chemistry 1947-49 and in the book “Experimental Inorganic Chemistry� (Elsevier 1954). He has also written two other books which are just about to be published “Chemical Spectro- scopy� (Elsevier) a survey intended largely for use by undergraduates and non-specialists and in col- laboration with Dr. E. E. Aynsley “General and Inorganic Chemistry“ (Hutchinson) an advanced level text for schools. For the Royal Institute of Chemistry he has conducted the practical examina- tions held in Newcastle and has also examined for the Durham University Schools Examination Board. </p>
<p> Dr. Brewer then Senior Treasurer of the Oxford University Swimming Club records how Dodd as President in a difficult war-time period “ran the club with a skilful hand on the reins commanding both affection and respect.� For many years after coming to Newcastle he helped to organise inter-University swimming events. As a student he has been described as “competent and effective� and the above record shows that competence and effectiveness have re- mained dominant characteristics. Dodd had under- standable ambitions and was always prepared to accept responsibility but he never failed to shoulder the work which the responsibility entailed. </p>
<p>He may have spread his interests a little widely but if so this was only another expression of his energy and enthusiasm. His students had example as well as precept for he was an excellent experimentalist; he certainly gave them of his best. There was a touch of the artist in him; whether it was a sketch of a piece of apparatus or the working of a piece of glass it had just that turn about it which took it out of the ordinary. He had friends of long standing and many of these have written appreciatively of him. Music was a lifelong interest. At Oxford he arranged string quartets in which men joined for their mutual pleasure and in which he played the violin. He sang tenor in the Oxford Harmonic Society. </p>
<p>His interest in chamber music as a listener and an executant continued in Newcastle where he PROCEEDINGS was a member of the Chamber Music Group of the Pen and Palette Club. Religious drama attracted him and he devoted time to both acting and producing plays of this kind for the Drama Group of St. George’s Jesmond; here he was on the Parochial Church Council. Religion was a very real thing to him; he had been sensible of the Anglican ritual in his school days at York and had deepened his understanding of it at Trinity College. In 1946 he married Joan Player and they have had three daughters and two sons. To Dodd his home and family meant a great deal; to his wife and children he was deeply devoted and they brought much happiness into his life. </p>
<p>To them in the tragedy of his early death this may bring some consolation. P. L.ROBINSON. MILLICENT TAYLOR 1871-1 960 MILUCENT was born at Kingswood. Surrey TAYLOR on October 17th 1871 and died in Bristol on December 23rd 1960 in her ninetieth year. Until a few weeks before her death she paid almost daily visits to the Chemistry Departments of the Univer- sity of Bristol with which she was for so long associated and where aroom was provided for her use. Dr. Taylor was educated at Cheltenham Ladies’ College where in October 1893 she took the degree of B.Sc. of the University of London. Ln the same year she joined the staff of the College and was appointed Head of the Chemistry Department in 1894. </p>
<p> She remained a member of the staff until 1919 becoming Head of the Science Department in 191 1. Over a period of twelve years between 1898 and 1910 Dr. Taylor devoted much of her spare time to research work first in organic chemistry and then in physical chemistry at the then University College of Bristol often cycling to Bristol at week-ends a round trip of over eighty miles. As a result of her work she was awarded the degree of M.Sc. of Bristol in 1910 and the following year the degree of D.Sc. Duringthe First World War she worked for the Ministry of Munitions under Dr. Harker at University College London and in 1917 was appointed a research chemist at H.M. Factory Oldbury. In 1919 she returned to her post at Cheltenham but left to take up an appointment as Demonstrator in Chemistry at the University of Bristol in 1921. </p>
<p>In 1923 she was appointed Lecturer a post which she held until her retirement in 1937. Millicent Taylor was one of the first women to be admitted to the Fellowship of the Chemical Society her election taking place on December 2nd. 1920. In the previous year she was elected an Associate of the Institute (now the Royal Institute) of Chemistry and in 1922 was admitted to the Fellowship. Dr. Taylor’s published work covers a period of nearly fifty years. Her first paper was published in Berichte in 1903’ on ths addition products of benzylideneaniline with ethyl acetoacetate and ethyl methylacetoacetate and demonstrates her early interest in organic chemistry; her twelfth and last with Dr. </p>
<p>W. J. Dunning on the measurement of the vapour pressures of pure sucrose solutions at rela- tively high temperatures appeared in the Journal of the Cheinicaf Society in 195 1 .2 During the intervening years she was associated for a short time with Professor Francis Francis and later with Professor J. W. McBain and her published work was mainly concerned with the physical chemistry of soap solu- tions. In contrast with her scientific work she also wrote a most interesting monograph entitled “The Mining Camps of Cobalt and Porcupine,� describing a visit she made to these places in Northern Ontario Canada in the summer of 1911. At that time trans- port facilities in these regions were meagre and such a journey unaccompanied as she was must have been a considerable undertaking. </p>
<p> Millicent Taylor’s life was a full one. She had many outside interests and travelled widely. As a teacher she was known to be strict but always fair and she maintained her interest in research until failing sight obliged her to cease work. Her former pupils and colleagues will greatly miss her. W. BAKER. Ueber die Additionsprodukte aus Benzylidenanilin und Acetessigshernethylester Ber. 1903,36 941. The Vapour Pressure of Concentrated Aqueous Sucrose Solutionsup to the Pressure Of 760 111111. (with W. J. Dunning and H 6.Evans) J. 1951,2363. FEBRUARY 1962 95 STANLEY ERNEST CARR 1875-196 1 STANLEY CARRwas born at Croydon on December 26th 1875 the eighth of twelve children of Henry and Ada Carr; an older son Francis Carr,has also become well known to several generations of chemists. </p>
<p> Cam was at first educated privately and later he attended the Whitgift School Croydon. At the age of 15 however the family business having ceased to prosper he left school. Being ambitious and hard- working he attended evening classes while occupied in unsatisfying work. In 1896 as a result of replying to an advertisement he became a junior assistant to R.B. Pllcher in the Institute of Chemistry and later he was appointed Assistant Secretary carrying on during Pilcher’s long absence on sick leave in 1901-1 902. In 1902 Carr was appointed Assistant Secretary to the Chemical Society and for 43 years he devoted himself wholeheartedly to the welfare of the Society. </p>
<p> His designation was changed in 1939 to General Secretary; although the change was nominally due to a recognition of the increasing responsibilities attached to the office his friends regarded it rather as a further tribute to his work which had already been acknowledged in 1927 on his completion of 25 years of service by the presentation of a cheque and a clock from the Council and Fellows. Carr’s early days at Burlington House were uphill work for a young man but he worked hard and over- came many difficulties not the least of which was the friction between the younger Fellows and the innate conservatism of successive Councils. The war of 1914-18 however was a great stimulus to chem-istry and its aftermath created a new spirit among British chemists. </p>
<p>One result for instance was the admission of women to full FeIlowship in 1920 after many years of unseemly wrangling. Another was the creation of the Bureau of Abstracts which took over what had hitherto been a section of the Journal this involved co-operation with the Society of Chemical Industry. A third result was the Joint Library Scheme which allowed the use of the Library upon certain conditions by members of several kindred societies. Still another was a change in the nature of the Annual Meetings; until 1926 these had been held only in London and occupied only one day but in 1926 1929 1932 and thereafter biennially they were held in alternate years in provincial centres and usually extended over three days with many visits recep- tions and other social attractions which were very popular. </p>
<p>Further the year 1932 saw the inception of the scheme for Local Representatives who organised local meetings in collaboration with kindred societies. AU these changes involved the (then) Assistant Secretary in much work often far into the evening. When it is realised that all this work together with such complex operations as for instance arrange ments for the Annual Dinner had to be done in one small room accommodating Carr and his two chief assistants his difficulties can be imagined but can only be fully realised by those who saw the condi- tions. In fact this great pressure on accommodation persisted until after Carr’s retirement and typists had to use makeshift conditions in the meeting room when it was available. </p>
<p> The outbreak of war in 1939 created further difficulties. Provisional arrangements had to be made for the transfer of the whole office to Lincoln College Oxford but in the event only the finance section under the Assistant General Secretary (H. J. Morris) was moved. All the upsets and changes due to the war coupled with the strain of working in London throughout-a strain which can never be fully appreciated by those who did not have to experience it-took their toll on Carr and he had a serious illness in 1944. Although his friends were shocked at its apparent effect on him he ultimately made a fairly good recovery but it was a relief that he was able to retire shortly afterwards at the age of 70. </p>
<p> A former Honorary Secretary pays tribute to the loyalty with which Carr carried out any Council policy with which he might disagree and to the value of his help based on long experience. In 1908 Carr married Florence Fagg also of Croydon who together with two married daughters and three grandchildren survives him. The happiness of the 53 years of married life was often commented upon by friends and in recent years Carr’s devotion to his wife in her increasing infirmity was very touch- ing. His interests were many and varied; he was a keen gardener and a great reader particularly of Shakespeare. Also he was Secretary of the hrley Cottage Hospital for many years Secretary and later President of the Purley and District Scientific Society and Secretary of the F’urley Lawn Tennis Club. </p>
<p>His long and busy life ended at Purley near his native Croydon on October 25th 1961. We may conclude by quoting the words of Alexander Scott who had served for long periods as Honorary Secretary Treasurer or President in making the presentation already referred to “Cam has thrown his whole soul and energy into everything that he could do to promote the welfare of the Society utterly regardless of the amount of work any new departure might bring upon himself.� Those words applied in 1927 were if possible still more applicable in 1945. A. D. MITCHELL. ERNEST CHAPMAN 1898-1 961 ERNESTCHAPMAN was born in Worsley near Manchester on January llth 1898. </p>
<p>He attended Salford Secondary School leaving in 1915 for Victoria University Manchester with a Lancashire County Council scholarship. From July 1916 to December 1918 his studies were interrupted by a period spent on war work with Sneyd Bycars Co. Ltd. in Burslem Staffordshire. He then returned to the University and graduated with First Class Honours in 1920 obtaining the degree of M.Sc. in 1921 and of Ph.D. in 1924. In 1920 he was awarded the Leblanc Medal in 1921 the Beyer Fellowship and in 1923 the Sir Clement Royds Memorial Scholarship which last he held for two years. During his postgraduate period at the University he carried out research on reactions of resorcinol and phloro- glucinol on phthalamic acids and their conversion into anthranilic acids and on the colouring matters of carajura the red pigment of Bignonia chica. </p>
<p>All this work is reported in the Journal. In 1925 he joined the Research Department of British Dyestuffs Corporation now the Dyestuffs Division of Imperial Chemical Industries Limited where he remained till his retirement in January 1960. Much of his early work in his industrial career as indicated in patents often in collaboration with the late James Baddiley was on the preparation and uses of surface-active agents particularly those based on sulphonated mineral oils. Some later patents con- cerned sulphur dyestuffs made from novel indo- phenols. For a long time he was in charge of research work on sulphur dyestuffs on which he was an authority as shown by the article “Sulphur Dye- stuffs� which he contributed to Thorpe’s “Diction- ary of Chemistry�. </p>
<p>His knowledge and experience however extended into other fields. He was a worker of great thoroughness care and pertinacity and expected these qualities in the work of those in his charge. Difficulties were for him things to be overcome and not shelved. In the Dyestuffs Division of l.C.1. he was known as a loyal and respected colleague and friend. A deeply religious man he did much work for young people in his earlier days and was a valued worker in the Methodist Church. He was very interested in nature particularly in gardening and in the amenities of the Lake District. Dr. Chapman was a bachelor and lived with his sister who survives him. </p>
<p>His sudden death at his home in Worsley on February 22nd 1961 so soon after his retirement came as a shock to his friends and colleagues. A. KERSHIAW. ADDITIONS TO THE LIBRARY A history of technology. Edited by C. Singer E. J. Holmyard A. R. Hall and T. 1. Williams. 5 Vols. Clarendon Press. Oxford. 1954-58. (Presented by the publisher.) I chimica italiani e le lor0 associazioni. A. Coppadoro. Pp. 349. Associazioni Scientifiche e Tecniche. Milan. 1961. (Presented by the publisher.) Handbuch des Chemikers. Edited by B. P. Nikolski. Vols. 1-3. VEB Verlag Technik. Berlin. 1956-59. (Presented by the N.B.L.) Theoretische Chemie. K. Lothar Wolf. 4th edn. Pp. 813. Barth. Leipzig. 1959. </p>
<p>(Presented by the N.B.L.) Selected constants relative to semiconductors. C. Eknoit A la Guillaume et al. Tables of constants and numerical data. No. 12. Pp. 65. Pergamon Press. Oxford. 1961. Die radioaktiven elemente. S. J. Bresler. Pp. 346. VEB Verlag Technik. Berlin. 1957. (Presented by the N.B.L.) Chemistry of heterocyclic compounds. G. M. Badger. Pp.498. Academic Press. New York. 1961. Ergebnisse der Alkaloid-Chemie bis 1960 unter besonderer Berucksich tigung der Fortschri t te seit 1950. €3. G. Boit. Pp. 1082. Akademie Verlag. Berlin. 1961. Cahiers de synthese organique methodes et tableaux d’application. J. Mathieu and A. Allais. Edited by L. Velluz. Vol. 9. Pp. 325. Masson et Cie. Paris. 1962. (Presented by the publisher.) Tutorial questions in qualitative organic analysis. </p>
<p>P. A. Ungley. Pp. 96. University of London Press. London. 1961. (Presented by the publisher.) Chemie der Silikone. A. Hunyar. 2nd edn. Pp. 343. VEB Verlag Technik. Berlin. 1959. (Presented by the N.B.L.) Einfuhrung in der Petrokhemie. F. Asinger. Pp. 428. Akademie Verlag. Berlin. 1959. (Presented by the N.B.L.) Zement-Chemie. H. Kuhl. Vol. 3. Pp. 522. Verlag Technik. Berlin 1952. (Presented by the N.B.L.) Some recent developments in the chemistry of phos-phate esters of biological interest. H. G. Khorana. Pp. 141. John Wiley & Sons. New York. 1961. Proceedings of the Third International Congress on Rheology held in Bad Oeynhausen 1958. 2 Vols. Dietrich Steinkopff Verlag. Darmstadt. 1961. Submicrogram experimentation. </p>
<p>Edited by N. D. Cheronis based on a symposium sponsored by the National Academy of Sciences and the National Research Council Arlington Virginia 1960. Pp.351. Interscience Publ. Inc. New York. 1961. Joint symposium on fertiliser analysis; held under the auspices of the Fertiliser Society and the Society for Analytical Chemistry London 1960. Pp. 215. Fertiliser Society and Society for Analytical Chemistry. London. 1961. Powders in industry papers read at a symposium organised by the Surface Activity Group of the S.C.I. held in London 1960. (S.C.I. Monograph No. 14). Pp. 447. Society of Chemical Industry. London. 1961. (Presented by the publisher.) Biological structure and function proceedings of the First International Symposium held in Stockholm 1960. </p>
<p> Edited by T. W. Goodwin and 0. Lindberg. Vol. 1. Pp. 363. Academic Press. London. 1961. Preprints of papers read at the Fifth International Symposium on Free Radicals Institute of Physical Chemistry University of Uppsala. 1961. Almqvist & Wiksell. Stockholm. 1961. Proceedings of the Congress of Analytical Chemistry Budapest 1961; held under the auspices of the Society of Hungarian Chemists. 3 vols. (Acta Chimica Hung. 1961, vols. 26,27,28.) Akademiai Kiado. Budapest. 1961. Fungicides in agriculture and horticulture papers read at a symposium organised by the Pesticides Group of the S.C.I. London 1961. (S.C.I. Monograph No. 15.) Pp. 145. Society of Chemical Industry. London. 1961. (Presented by S.C.T.) </p>
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