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Proceedings of the Chemical Society. February 1961 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue February,
1961,
Page 33-92
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY FEBRUARY 1961 REPORT OF COUNCIL 1959-60 1. GENERAL were elected to the Fellowship than in any previous Period of Report.-The financial section of this year in the history of the Society. Moreover the loss Report relates to the twelve months ended September by death resignation or removal was smaller than in 30th 1960,and the record of appointments meetings any year since 1949 (Table 1). and other events covers a similar period. The Council is particularly encouraged to find that Statistical information on Fellowship or Publica- the number of Fellows under 27 years of age has tions however covers the calendar year 1960 since increased from 1,909 to 2,372 during the year. Al-this corresponds with the subscription period.though these younger Fellows include many post- graduate students in British Universities it may be noted that the number of Fellows resident outside 11. FELLOWSHIP the British Isles is increasing proportionately faster 1. Fellowship Statistics.-In 1960 more candidates than the Fellowship as a whole. TABLE1. Fellowship changes 1955-60. 1955 1956 1957 1958 1959 1960 No. of Fellows on Jan. 1st 9,123 8,936 9,074 9,389 9,539 9,943 Adlit ions Elections .. .. 678 656 765 595 802 1,326 Reinstatements . . 27 29 24 37 29 27 3 --Miscellaneous . . .. -1 705 -688 -789 -632 -831 -1,354 Deductions Deaths .. .. .. 60 61 52 54 73 67 .. .. 712 288 293 277 194 194 Resignations Removals . . ,. 117 199 129 150 159 127 2 -Miscellaneous .... 3 1 1 -892 -550 -474 -482 -427 -388 Net change in year .. -187 +138 +315 +150 +404 +966 ~~ ~ ~~~~~ No. of Fellows on Dec. 31st 8,936 9,074 9,389 9,539 9,943 10,909 33 TABLE 2.Geographical distribution of the Fellowship. 1958 1959 1960 British Isles United Kingdom .. 6,350 6,744 7,239 Republic of Ireland .. 54 60 71 6,404 6,804 7,310 The Commonwealth Australia .. .. 303 318 364 Canada .. .. .. 247 25 8 276 East Africa .. .. 23 21 21 HongKong .. .. 17 17 19 India .. .. .. 147 156 164 Malaya . . .. .. 22 21 23 New Zealand .. .. 74 76 83 Nigeria . . .. .. 14 19 26 Pakistan .. .. 32 30 29 Rhodesia and Nyasaland 12 12 17 South Africa .. .. 95 89 105 West Indies .. .. 25 25 26 Miscellaneous .. .. 38 33 42 1,049 1,075 1,195 Other Countries Argentine . . .. 12 11 11 Belgium .. ,. 20 20 22 Brazil .. .. .. 14 14 14 Czechoslovakia .. 23 17 21 Denmark .. .. 18 12 19 Egypt * -.. .. 31 25 23 France .. .. .. 58 53 68 Germany .. .. 48 51 62 Holland .. .. 34 34 38 Hungary .. .. 15 15 17 Israel .. *. .. 53 45 51 Italy . . .. .. 46 55 56 Japan .. .. .. 82 55 96 Jugoslavia .. .. 10 11 11 Mexico .. .. .. 16 15 15 Norway.. .. .. 13 11 12 Spain .. .. .. 16 15 14 Sweden .. .. .. 25 23 24 Switzerland .. .. 71 65 75 United States of America 1,417 1,454 1,698 Miscellaneous . . .. 64 63 57 2,086 2,064 2,404 World Total .. .. 9,539 9,943 10,909 Of a total Fellowship at the end of the year of nearly eleven thousand 536 were Life Fellows of whom 255 compounded before 1954and are entitled to receive the Journal without payment.PROCEEDINGS 2. Honours.-The congratulations of the Society have been conveyed to the following whose names were included in the New Year or Birthday Honours Lists Order of Merit Sir Cyril Hinshelwood C.B. Frederick Measham Lea C.B.E. David Christie Martin Thomas Gilbert Henry Jones Since the last report was issued the Council has been pleased to note the award of the Nobel Prize for Chemistry for 1959 to Professor Jaroslav Heyrovsky and the Nobel Prize for Medicine for the same year to Professor Arthur Kornberg with Professor Severo Ochoa. Congratulations have also been conveyed to Professor R. B. Woodward (Honorary Fellow) on the award of the Davy Medal by the Royal Society in November 1959.111. PUBLICATIONS 1. General.-At the beginning of 1960there were still some arrears of publication due to the trade dispute of the previous summer. During the twelve months January-December 1960,1,022Papers and Notes occupying 5,276pages were published; the number of pages constituted a record in the Society’s history though the number of Papers and Notes is just less than in 1957 (1,026); but it was not enough. The large issues of the beginning of the year were not maintained in the summer diffi- culties occurring this time in the Editor’s office and not primarily at the printer’s. The Editorial office moved from 9-10 Savile Row to 38 York Terrace N.W.l on June 9th 1960.The editorial work was hampered by this move and by staff difficulties.As a result there were at the end of the summer holidays over a hundred manuscripts awaiting editing. In September and October new staff began work and by the first week in December the editing had been brought completely up to date. Some of the arrears had been published by the end of this year but much remained with the printers who however hope that by means of abnormally large issues the whole publication position for the Journdl may be com- pletely restored in the opening months of 1961.Only the JournaZ was affected in this way the remaining publications of the Socioty being issued normally. 2. Journal.-The customary statistics are in Tables 3-6 from which the following are selected as significant FEBRUARY 1961 35 TABLE 3.Numbers of items in the Journal. 1956 1957 1958 1959 1960 Papers (General Physical and Inorganic). . .. 200 164 173 182 252 .I Papers (Physical Organic) .. .. .. 140 175 170 156 197 Papers (Organic) . . .. .. .. .. 508 550 476 394 461 Notes . . .. .. .. .. *. .. 123 137 157 108 112 *Lectures and Addresses . . .. .. .. 6 --*Obituary Notices .. .. .. .. .. 17 *Annual General Meeting . . .. .. .. 1 Editorial Nomenclature Report .. .. .. 1 1 --I.U.P.A.C. List of Atomic Weights. . .. .. 1 1 -1 997 1,028 976 840 1,023 * Now published in Proceedings. TABLE 4. Communications to the Journal. 1956 1957 1958 1959 1960 Papers and Notes received .... .. .. 1,05 1 1,048 1,005 1,056 1,084 ~ Less rejected or withdrawn . .. .. 56 67 57 51 56 995 981 948 1,005 1,028 Papers and Notes published. . .. .. .. 97 1 1,026 976 840 1,022 No. of pages (Papers and Notes) .. .. .. 4,864 5,099 4,784 4,141 5,276-No. of pages (total excluding Index Volume) .. 4,988 --Average no. of pages per Communication .. 5-01 4.97 4.90 4-93 5-14 TABLE 5. Communications from outside United Kingdom. (Parentheses indicate publication jointly with a British laboratory.) 1956 1957 1960 Australia .. .. .. .. .. .. 737) 56(8)b 740) Commonwealth (countries not separately listed) . . 14(2) 8(Ub 14(2) Canada.. .. .. .. .. .. .. gab 4 3 Egypt * -.. .. .. .. .. ,. 11 10 12 France . . .. .. .. .. .. .. 11 W)Q 6 Hungary .... .. .. .. .. 6 6 3 India Pakistan and Ceylon .. .. .. 2gC 22 14(1) Irish Republic .. .. .. .. .. 12(2) 12(4) 1 Israel . . .. .. .. .. .. .. 12(2) 14 27 Italy .. .. .. .. .. .. .. 3 5 3 New Zealand .. .. .. .. .. .. 5(2) 5(1) 11 South Africa . . .. .. .. .. .. 18 1 3c 8(1) U.S.A. .. .. .. .. .. .. . . 6(2)b 11(3)QC 24(1) Miscellaneous . . .. .. .. .. .. llUC 9(2) 1 1(2) 216(17) 183(20) 21 l(8) a b c indicate one each jointly. TABLE 6. Percentage distribution in the Journal. 1954 1955 1956 1957 1958 1959 1960 Papers (General Physical and Inorganic). . 14.0 18.5 21.1 16.0 17-7 21.6 24-7 Papers (Physical Organic) .. .. .. 13.0 16.9 14-4 17.0 17.4 18.6 19.2 Papers (Organic) .. .. .. .. 60.5 52.2 52-3 53.6 48.8 46.9 45.1 Notes ..*. .. .. .. .. 12.5 12.4 12.2 13.4 16.1 12.9 11.0 PROCEEDINGS The number of papers and notes received during 1960 was 1,084 which is exactly equal to the highest total for any previous year (1955). The proportion of organic papers in the Journal continued its slow decline being 45.1 % in 1960. There was a marked increase to almost a quarter of the whole in the number of papers classified as General Physical and Inorganic and a trifling in- crease (from 18.6 % in 1959 to 19-2%) in those classi- fied as Physical Organic; the substantial total of 449 Papers was contained in these two classes. (The term “Papers” here excludes “Notes” which are not classified.) Contributions from industrial laboratories and industrial research organisations published in 1960 were 108 (including 7 jointly with academic institu- tions); this represents 103% of the total (the figures for 1959 were 78 and 9.3 %).Published contributions from Government sources were 28 (including 3 jointly with academic institutions amounting to 2.7% of the total (1959 31 3.7%)). Published con- tributions from outside the United Kingdom during 1960 numbered 21 I which was 20.6 % of the total less than in 1959 (25.2%) but more than in the pre- ceding years (1958 18.0%; 1957 17.8%). 3. Proceedings.-The Society’s Proceedings con-tinued in 1960 in the form initiated in 1957. During the year 235 (1959,203) scientific short Communica- tions were submitted for publication 59 (1959 34) being rejected; 171 (1959 148) were published in the issues of the year.There were also 8 lectures 17 obituary notices and 23 short articles and reports on various topics in addition to the Report of Council and recurring items. 4. Annual Reports of the Progress of Chemistry for 1959,Volume LVI.-This volume contains 476 pages (466 in Volume LV). 5. Quarterly Reviews.-Volume XIV (1960) con-tains 19 articles occupying 452 pages. Volume XI11 (1959) contained 17 articles occupying 373 pages. 6. Current Chemical Papers.-Tables 7 and 8 give statistics about Current Chemical Papers. Note-worthy during the last year has been the increase in the proportion of Russian papers; it arises mainly from the larger number of Russian journals that has become available. TABLE 8.Languages used in papers included in Current Chemical Papers. Approximate percentages. 1956 1957 1958 1959 1960 English . . .. 55.1 55.8 56.8 55-4 53.9 German. . . . 13.0 11.8 13.6 13.5 12-0 Russian .. . . 12.1 11-5 11.8 14.0 17.1 Japanese French . . . . . 6.5 6-1 6.1 5-6 4.7 5-6 4-8 5.2 5-9 5.1 Czech . . . . 2.1 3.6 2.2 1.0 0.9 Italian .. . . 1.8 1.6 1.8 2.2 1-7 Polish . . . . 0-5 1.2 1.0 1.6 1.3 Miscellaneous . . 2.8 2.8 2.5 2.3 2.1 100.0 100.0 100.0 100.0 100.0 7. Special Publication.-Special Publication No. 14 the “Handbook for Chemical Society Authors,” became available in the Summer of 1960. It includes the Society’s brochure “Presentation of Papers,” the I.U.P.A.C. nomenclature rules on inorganic organic and steroid chemistry (with editorial explanations and comments) the US.-British agreements on nomenclature of carbohydrates and organophos-phorus compounds lists of physicochemical and spectroscopic symbols a note on crystallographic papers the collated editorial nomenclature reports of previous years and a list of abbreviations to be used for journal titles.This book of 224 pages of Journal size is available to Fellows of the Society for 6s. 8. Russian Chemical Journals.-Three Journals are now published in translation by the Society with the co-operation of the Department of Scientific and lndustrial Research. The Russian Journal of Inorganic Chemistry (Zhurnal neorganicheskoi Khimii) has been issued as a cover-to-cover translation since January 1959 with Professor P.L. Robinson as Scientific Editor. The Russian Journal of Physical Chemistry (Zhurnal fisicheskoi Khimii) edited by Mr. R. P. Bell was started with a translation of the July 1959 TABLE 7. Current Chemical Papers. Summary. Titles of papers listed .. .. . . Pages of C.C.P. .. .. *. .. Total no. of journals scanned . . .. Issues of journals yielding titles .. Issues not yielding titles .. .. 1955 1956 1957 1958 1959 1960 21,360 706 22,278 731 24,755 820 26,030 835 27,440 909 27,916 91 3 469 521 5 12 519 521 539 2,277 1,438 2,265 1,503 2,577 1,189 2,726 1,037 2,624 1,392 2,369 1,443 FEBRUARY 1961 issue of the Russian journal. Russian Chemical Reviews (Uspekhi Khimii) began with a translation of the January 1960 issue and Dr.J. N. Agar is prh- cipal Scientific Editor. Initially certain delays occurred in the production of these Journals because of a shortage of adequate translators. These are now being overcome and it is hoped that the interval between the receipt of the Russian original and the publication of the English translation can be reduced to three months. The circulation of these Journals is increasing as they become better known and more issues appear and it is hoped that as sales revenue increases it will be possible for D.S.I.R. to extend the coverage to other Russian journals not at present available in translations either in this country or in U.S.A. The agreement with D.S.I.R. provides that publication of these three Journals does not impose any cost to the general funds of the Society.Translations are supplied to the Scientific Editors by Infosearch Ltd. by whom the production is also undertaken by a lithographic printing process. Sales and distribution are handled for the Society by Cleaver-Hume Press Ltd. 1V. OTHERACTIVITIES 1. Anniversary Meetings,-The Anniversary meet- ings were held in conjunction with those of the Royal lnstitute of Chemistry in Belfast on April 5-8th 1960. In addition to a number of social events and to the Presidential Addresses of the two bodies scientific lectures were delivered by Professor A. Butenandt (Munich) Professor E. R. H. Jones (Oxford) Professor G. M. Schwab (Munich) Pro-fessor G. Schwarzenbach (Zurich) and Professor s.Winstein (California). 2. Symposium on Carbohydrate Chemistry.-A symposium on “Physical Chemical and Biological Methods in the Study of High Molecular Weight Carbohydrates” was held in Edinburgh on July 12-14th. Seventeen main papers were read and over 200participants registered for the meeting. 3. Scientific Meetings and Lectures.-Scientific meetings were held in London and under arrange- ments made by the Society’s local representatives at many other centres. These included meetings arranged jointly with local sections of other bodies and with local student chemical societies. The full programme has appeared in Proceedings. 4. Library.-CaIls upon the loan and photocopy- ing services have again increased during the year and more readers attended to consult books at Burling- ton House.In order to improve the service provided by the Library the Council has instituted with the approval of the Chemical Council a Scheme for Library Subscribers open to research and educational institutions and industrial firms. It had long been thought that the requirement of a personal signature for each item borrowed had become a nuisance to many Fellows working in establishments where the normal practice was to route requests for loans or information through the organisation’s librarian. Under the new arrangement such corporate bodies may obtain direct access to the Library. The scheme has already attracted eighty-six Subscribers. A complete list of the periodicals holdings of the Library was published during the year.It is hoped that this will prove a useful source of reference to those who use the Library and to the librarians at other institutions. The number of Journals taken by the Library continues to increase. Forty new titles were added in the year bringing the number of current periodicals to 656. The Library suffered a severe blow by the sudden death of Mr. Bird the Deputy Librarian in August 1960. He had been on the Library staff for over forty years and his unrivalled knowledge of the book stock enabled him to render exceptional assistance to many readers. His loss has been deeply felt. V. FINANCE AND ADMINISTRATION 1. General Purposes Account.-The income from Fellows subscriptions continues to increase and this year was augmented by a non-recurrent payment of ~€1,989 representing income tax recovered on sub- scriptions made under deed of covenant (see para-graph 6).Much of the Society’s income from sub- scriptions and from sales of publications is received in the period November-January whereas expendi- ture is spread more evenly over the year. This cash held in excess of immediate requirements is placed on short-term deposits and the high rates of interest earned during the year have helped to increase the Society’s income. Investment income was also greater than in the previous year partly as a result of the investment of surplus income from previous years and partly because increased dividends were received on many of the Society’s holdings of ordinary shares.The cost of administration was higher than in previous years but it remains unusually low in rela- PROCEEDINGS TABLE9. Administration costs of the Society. No. of Fellows at end of Administration Administration Year finan c i a I period costs costs per Fellow E s. d. 1951 1952 1953 1954 1955 1956 .. .. .. .. .. .. .. *. .. .. .. .. 1957 (9 months) .. 1957-58 .. *. 1958-59 .. .. 1959-60 .. .. .. .. .. .. .. .. .. .. .. *. .. .. .. .. I . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .* .. .. .. .. .. .. .. .. .. 8,616 9,083 9,249 9,123 8,936 9,074 9,376* 9,476* 9,874* 10,797* 9,072 8,484 8,948 8,666 7,024 8,079 5,934 8,200 9,154 10,593 110 18 8 19 4 19 0 15 9 17 10 12 8f 17 4 18 6 19 8 * At September 30th.t Equivalent to 16s. lld. for 12 months. tion to the total number of Fellows. Table 9 shows how with an increased Fellowship and as a result of the improved productivity of the administrative staff of the Society the cost per Fellow has remained con- stant over the past ten years despite the increase in costs during the period. The programme of improvements to the Society’s premises in Burlington House was continued during the year. With the complete refurnishing and re- equipment of the Council and Officers’ Rooms work on all the main apartments has now been completed. The Council remains confident that at least over the next few years it will be possible to continue to meet any expected increase in costs that can be fore- seen and also to increase the support given to Local Representatives and the expenditure on meetings and other activities as may be necessary.2. Publications Account.-This account shows a surplus of 21 1,465 after a transfer of &15,000to the General Reserve. The favourable result is due in part to an increase of &10,700 compared with 1958-59 in the income from sales and advertisements. An equally important factor however is the lack of any provision in the accounts for printing the arrears of unpublished papers. In the previous year a provision of &10,800 was made on account of some 250 papers delayed by the printing trade dispute. For various reasons it was not possible to reduce this accumula- tion as quickly as was hoped and the arrears at September 30th 1960 were still substantial.If as is expected a normal publication position is restored during the year 1960-61 a considerable increase in printing costs will arise during that year. It must be accepted that the size and hence the cost of the Journal will fluctuate from year to year but it is not intended to make any estimated provision for arrears of papers unless these are produced by events en- tirely outside the Society’s control. It appears that subject to unforeseen circumstances a satisfactory but not excessive surplus can be expected on the publications account as a whole over the next few years. The expenditure on the Journal includes a con- tribution of E1,OOO to the Special Publications Fund towards the cost of the “Handbook for Chemical Society Authors.” This publication is intended pri- marily to assist those who write papers for the Journal and it was decided that it should be sold to Fellows at an exceptionally low price in order that as many as possible might obtain a personal copy.Whilst all the Society’s publications had a larger circulation than in the previous year the increase for the Journal was due to more sales to non-Fellows. The number of copies sold to Fellows was virtually unchanged (see Figure) and now amounts to only 8.4% of Fellows in the United Kingdom and 29-5% of Fellows overseas. 3. Library Account.-The Council again records its grateful appreciation to the Chemical Council for a grant of ElOOO towards the costs of the library.FEBRUARY I961 \ Fellows NQv erseas) '*Ot Libraries and Non-feI lows \= I I I I I I I I 1953 1954 1955 1956 1957 1958 1959 1960 Sales of the Journal. 4. Trust and Lecture Funds.-These accounts do not call for any special comment except that the form of presentation has been simplified and the investments have now been consolidated into a pool described more fully in paragraph 5. The Council has decided to increase the honoraria paid to certain lecturers and medallists and to enable this to be done endowments have been augmented by a transfer of &1,060from General Purposes Account and apportioned as follows E Faraday Lecture .. .. 230 Harrison Memorial Prize ..50 Liversidge Lecture .. .. 70 Pedler Lecture . . .. .. 60 Research Fund (for Longstaff Medal and Hugo Muller Lecture). . .. *. .. 480 Simonsen Lecture *. .. 40 Tilden Lecture . . .. .. 130 El ,060 5. Investments.-The arrangement referred to in the report for 1958-59 whereby Messrs. Helbert Wagg and Co. Limited were appointed as investment advisers for the General Purposes investments has now been extended to cover all the invested funds of the Society. The General Purposes Fund has been augmented during the year by the investment of some &23,000 previously held as short term deposits and the re-adjustment of the ratio between the different types of security has now been substantially completed. The yield and the capital value of the in- vestments have both increased satisfactorily and it is not envisaged that further major investment changes will be made in the immediate future.The Staff Pensions Fund which is used to supple- ment at the sole discretion of the Council pensions secured under the Staff Superannuation scheme is the Society has been advised not subject to any specific trust but is merely an allocation of the general funds separated for the convenience of book- keeping and administration. As the fund does not have to meet definite monetary commitments at known dates in the future it has been decided that the fund should be governed by the same investment policy as the general funds of the Society. Under this policy 25 % of the capital is invested in fixed-interest securities and the balance is spread over a range of ordinary shares which it is hoped will produce over a period of years a growth of income and of capital value.The Publications Fund and the Special Publica- tions Fund are trust funds which by law are at present confined to a restricted range of fixed-interest securities. The investments of the other funds representing the endowments of the various Lectureships and the Medals awarded by the Society are now subject to scheme prepared by the Charity Commissioners which came into force on August 23rd 1960. Under this scheme the investments of the separate funds were consolidated in a combined pool of trust invest- ments and the income arising therefrom is divided in proportion to the value of the assets which each fund contributed to the pool at the date of consolidation.Power was granted under the scheme for the pool to be divided into two parts a Restricted part and a Free part equal in value at the date of division. In- vestments of the Restricted part are confined to fixed-interest trustee securities. The Free part may however subject to certain restrictions be invested in a wider range of securities inchding ordinary shares. At the date of consolidation investments in most of the funds had a value considerably lower than their original cost whereas the value of other funds PROCEEDINGS TABLE10. Trust Funds. Share in Profit or loss the combined on revaluation Fund pool of trust and re-investment investments Profit Loss (%) 2 2 Centenary Fund .... .. .. .. .. .. 31-30 -6,560 -Corday-Morgan Medal and Prize Fund .. .. .. 15.1 1 3,820 -Corday-Morgan Memorial Fund .. .. .. .. 19.13 2,461 Faraday Lecture Fund .. .. .. .. -. .. 0.36 -186 Robert John Flintoff Trust . . .. .. .. .. 0.8 1 -359 Edward Frank Harrison Memorial Trust .. .. .. 1-17 -167 Liversidge Lecture Fund .. .. .. .. . 0.63 -305 Pedler Lecture Fund .. .. .. .. .. .. 0.63 -305 Research Fund .. .. .. .. .. .. .. 27-18 -5,566 Simonsen Lecture Fund .. .. .. .. .. 0.63 -Tilden Lecture Fund .. .. .. .. .. .. 3*05 284 100.00 Totals . . .. .. .. .. .. .. 6,565 13,448 Deduct profit .. .. .. .. .. .. .. 6,565 Net loss .. .. .. .... .. 6,883 which had for some years included a proportion of ordinary shares had appreciated. After the scheme came into force substantial changes of investment were made and the list of investments held at September 30th is shown in the schedule attached to the accounts. The capital loss or gain in the various funds which resulted in the main from changes in the value of the investments which had taken place over a number of years is shown in Table 10 which also indicates the proportions in which the separate trusts have an interest in the pool. The endowments representing the Liversidge Pedler and Sirnonsen Lecture Funds which were previously combined in the Special Lectures Fund are now shown separately in the accounts. 6. Fellowship Subscriptions paid under Deed of Covenant.-For some six years before the Income Tax year 1955-56 Fellows paying British Income Tax at the standard rate could covenant for the amount of the annual subscription under a seven- year deed and the Society was able to recover In- come Tax on the grossed up value of the subscription.In 1955 and 1956 the Chief Inspector of Taxes con- tested certain claims submitted by other Societies and some Court actions were decided in favour of the Inland Revenue. Following these test cases the Inland Revenue refused payment for a claim repre- senting part of the tax recoverable in respect of the year 1955-56. In the light of the best information at that time the Council decided not to contest this ruling and the Chief Inspector was informed of this decision.During the year under review however the Society learned from the Inspector that the Board of Inland Revenue had reviewed the question of covenanted Membership Subscriptions in the light of recent decisions by the Special Commissioners in other cases and that the Society’s outstanding claim had been admitted in principle. It was also intimated that claims for subsequent years could also be considered. Claims were accordingly submitted and the sum of 21,989 representing this recovery is credited in the accounts. In view of the provisions of the Finance Act 1958 which made it possible in most cases for Fellows to obtain tax relief on subscriptions to the Society the Council has decided that Fellows should not in future be asked to enter into covenants in relation to the annual subscription.7. Underwriting.-The Society now participates in the underwriting of new issues of stocks and shares FEBRUARY 1961 introduced by means of a public offer for sale or by a rights offer to existing shareholders. The Society is only committed to underwrite stocks up to an agreed value and of a type which would in the opinion of the Society’s investment advisers be appropriate for the Society to hold as permanent investments. A commission of El98 was earned during the year 1959-60. 8. Council.-The following appointments were announced at the Annual General Meeting held in Belfast on April 7th 1960 President Sir Alexander Todd Honorary Secretary Professor K.W. Sykes Vice-president who has filled the Ofice of President Professor H. J. Emeldus Vice-presidents who have not filled the Ofice of President Professor E. R. H. Jones Professor J. M. Robertson Professor M. Stacey Elected Ordinary Members of Council Constituency I Dr. J. W. Linnett Dr. E. A. Moelwyn-Hughes Constituency N Professor J. C. Robb Constituency III Professor R. N. Haszeldine Constituency V Professor R. A. Raphael 9. Local Representatives.-The following changes among the Local Representatives were made during the year Bristol .. .. Dr. R. Parsons in place of Dr. P. Woodward Hull . . .. Dr. G. C. Bond in place of Dr. G. W. Gray Irish Republic . .Professor T. DilIon in place of Dr. D. O’Tuama Leeds .. .. Dr. W. Rigby in place of Dr. E. Rothstein Malaya and Singapore .. Professor R. L. Huang in place of Dr. R. A. Robinson St. Andrews and Dundee .. Dr. D. E. Hoare in place of Dr. C. Horrex VI. ACKNOWLEDGEMENTS The Council records is warmest appreciation of the many Fellows and others who have generously placed their services freely at the disposal of the Society and have assisted with its meetings publica- tions or other activities. FEBRUARY 42 PROCEEDINGS 1961 43 THE CHEMICAL SOCIETY AND EXPENDITURE FOR THE YEAR ENDED ~OTHSEPTEMBER, INCOME ACCOUNTS 1960 1958l59 1959160 1958159 1959/60 Expenditure Income E 6,575 750 1,324 505 General PurposesE Administration Salaries Superannuation etc... .. House Expenses etc. .. Stationery Postages and Office Expenses' Miscellaneous .. .. .. .. 899 Meetings . . *. .. .. .. 1,244 Local Representatives . . .. .. 616 Travelling . . .. .. .. ..-Capital improvements .. .. 9,154 3,000 Contribution to the Trust Funds .. .. .. .. .. .. .. .. .. .. .. *. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. a.*. .. f 7,039820 1,4751,259 E 10,5931,6651,475716 5,4151,060 f 19,068322 -€ General Purposes Fellows' Subscriptions:For 1959/60 .. .. .. .. .. .. For previous years .. .. .. .. .. Income Tax recovered on Subscriptions under Covenant 19,390 4,500 Income from Investments . . .. .. .. .. 2,257 Deposit Interest .. .. .. .. .. .. 809 Miscellaneous .. .. .. .. .. .. .. .. .. .. .. .. .... .. .. .. .. E 20,671235 1,989 E 22,8956,6182,7831,237 Transfers Publications Account- 2,315 2,6841,991800 7,790 4,253 Cost of free publications to Fellows under 27years of age .. Library Account- Books Periodicals etc. .. .. .. .. .. .. Maintenance .. .. .. .. .. .. .. 0 . Staff Pensions Fund .. .. .. .. .. .. .. Balance being Excess of Income over Expenditure carried to Balance Sheet, .. .. .. .. *. .. .. .. .. 2,698 3,1882,185950 9,021 3,588 E26,9 56 - E33,533 E26,956 E33,533- Staff Pensions Fund Staff Pensions Fund E E € s 800 Transfer from General Purposes Account .. .. .. .. .. 950 1,091 Pensions . . .. .. .. .. .. .. .. .. .. 1,os 1 210 Income from Investments .. .. .. .. .. .. .. .. 139 a. 10 Miscellaneous .. .. .. .. .. .. .. .. 12 2 Deposit Interest .... .. .. .. .. .. .. .. --Balance being Excess of Income over Expenditure carried to Balance Sheet. . 26 89 Balance being Excess of Expenditure over Income carried to Balance Sheet .. -E1,101 El,089 f1,101 El,089 - 44 PROCEEDINGS FEBRUARY 1961 45 AND EXPENDITURE INCOME ~ccomsFOR THE YEARENDED ~OTH SEPTEMBER,1960 1958159 1959/60 1958159 1959160 Expenditure Income Publications Publications E E € f € € 6 f Journal and Proceedings of the Chemical Society Sales and Revenue from Advertisements : 14,996 Salaries and General Expenses .. .. .. .. .. .. 17,000 75,422 Journal and Proceedings of the Chemical Society . . .. .. 82.663 50,175 Printing and Paper .. .. .. .. .. .. .. 44,115 7,500 Annual Reports on the Progress of Chemistry .. .. ..91355 7,975 Distribution .. .. .. .. .. .. .. .. 7,275 8,039 Quarterly Reviews .. .. .. .. .. .. .. 8,547 73,146* 68,390* 10,664 Current Chemical Papers. . .. .. .. .. .. .. 11,743 5,796 Annual Reports on the Progress of Chemistry .. .. .. .. 6,034 60 Other Publicat ions .. .. .. .. .. .. .. 86 5,415 Quarterly Reviews . . .. .. .. .. .. .. .. 5,890 101,685 112,394 7,774 Current Chemical Papers .. .. .. .. .. .. .. 8,6S1 368 Income from Investments .. .. .. .. .. .. .. 368 6,OOo Transfer to General Reserve .. .. .. .. .. .. 15,000 Transfer from General Purposes Account Balance being Excess of Income over Expenditure carried to Balance 2,315 Cost of free publications to Fellows under 27 years of age .. .. 2,698 6,237 Sheet .. .. .. .. .. .. .. .. .. 1 1,465 €104,368 * A provision for unpublished papers was made in 1958lt959 but no such provision has 5115,460 E104,368 El 15,460 been made for 1959/1960.Special Publications Fund Special Publications Fund € f ;f. 9,398 Sales and Royalties . . .. .. .. .. .. .. .. 6,577 E 6,548 Cost of Publications .. .. .. .. .. .. .. 5,174 146 Income from Investments .. .. .. .. .. .. .. 146 18 Miscellaneous .. .. .. .. .. .. .. .. 27 220 Deposit Interest .. .. .. .. .. .. .. 388 3,208 Balance being Excess of Income over Expenditure carried to Balance 10 Miscellaneous Receipts .. .. .. .. .. .. .. -Sheet .. .. .. .. .. .. .. .. .. 1,910 €9,774 E7,lll €9,774 f7,111 - E E Library E f E 764 € Library Grant The Chemical Council .. .. € E 999 E 2,522 852 74 3,448 Books and Periodicals Binding .... Furniture .. .. . . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 3,346876 58 4,280 2,684 - 3,448 Transfer from General Purposes Aiount' * Library Subscribers .. .. .. .. Less Transfer to Maintenance .. .. .. .. .. .. .. .. 3,188 186 93 93 -___. 4,280 Mah tenance 7,759 648 1,713 418 129 10,667 Maintenance Salaries Superannuation etc. .. .. Re-binding .. .. .. .. .. House Expenses etc. .. .. .. Stationery Postages and Office ExpensesMiscellaneous .. .. .. .. .. .. .. .. .. .. .. *. .. .. .. .. .. .. .. .. .. .. , 7,601 452 1,6801 403 275 10,411 1,991 4,561 1,411514 318 55 1 1,236 10,582 Contributions towards Maintenance Through the Chemical Council- Chemical Society .. Society of Chemical Industry . . Faraday Society .. Biochemical Society .... Royal Institute of Chemist& ... Society for Analytical 'Chemi'stry Chemical Council (Direct Grant) . . From other sources- .. .. .. .. .. .. .. .. .. ,. .. .. .. .. 2,185 5,005 1,549564 349 605 1 -10,258 25 Association of British Chemical Manufacturers .. - 50 10 85 Society of Dyers and Co1ou;i'sts Institute of Brewing .. . . .. .. .. .. .. 50 10 60 - 10,667 Library Subscribers . . .. .. 1. .. 93 10,411 E14,l 15- f;14,69 1 €14,115- E1 4,69 1 - FEBRUARY 46 PROCEEDINGS 1961 47 THE CHEMICAL SOCIETY GENERAL BALANCE SHEET ~OTHSEPTEMBER 1960 1959 1960 1959 1960 E € '€ Liabilities f 5 2 f. f Assets E f 4,852 24,538 34,339 6,OOo 6,10097 28,850 29,390 40,339 6,197 Sundry Creditors .. .. .. .. .. .. Fellows' Subscriptions .. .. .. .. ..Sales of Publications etc. .. .. .. .. Receipts in Advance General Reserve Balance at 1st October 1959 . . .. *. Add Transfer from Publications Income and Expenditure Account .. .. .. .. .. .. .. Life Composition Fees Balance at 1st October 1959 .. .. .. .. Add Receipts during year .. .. .. .. Special Funds Publications- 5,390 24,439 40,339 15,000 6,197 23 18,090 29,829 55,339 6,220 10,979 4,011 5,423 20,413 113,008 12,657 4,217 52,944 Investments as per Schedule at cost or value when acquired Special Funds- Publications .. .. .. .. .. .. Staff Pensions .. .. .. .. .. .. .. Special Publicati'dns .. .. .. ,. .. .. General Purposes . . .. .. .. .. .. .. Sundry Debtors and payments in advance . . .. .. Stock of Paper .. Balances at Banks (iniiuding bepos'its) and Cash inHand' . . (Stocks of publications are not included) .... .. .. .. .. .. 8,378 2,915 5,024 16,317 137,041 18,9414,710 45,225 10,979-8,691 3,208 10,979 1 1,899 Balance at 1st October 1959 .. .. .. .. 10,979 Deduct Loss on change of Investments .. .. 2,601 Special Publications- Balance at 1st October 1959 .. .. ..11,899 Deduct Loss on change of Investmen;; .. 1,095 Add Excess of Income over Expenditure for ;he year 1,9 10 Staff Pensions- 8,378 12,714 5,721 89 - 5,632 28,510 Balance at 1st October 1959 .. .. .. .. 5,632 Deduct Loss on change of Investments .. .. 399 Excessof Expenditure over Income for theyear -Add Excess of Income over Expenditure for the year 26 Accumulated Fund 5,259 26,351 62,791 3,879 58,912 51 500 4,253 6,237 10,490 -69,953 Balance at 1st October 1959 . . .. .. ..69,953 Deduct Net Loss on change of Investments ... Add Net Profit on change of Investments .. .. Sale of Surplus Library Books .. .. .. T.A. Henry Legacy .. .. .. .. .. -Excess of Income over Expenditure for the year- General Purposes .. .. .. . . 3,588Publications .. .. .. .. .. 11,465 69,953 592 807 -15,053 86,405 '€203,239 f222,234 €203,239- €222,234 MICHAEL W. PERRIN,Honorary Treasurer. We have examined the General Balance Sheet the Trust and Lecture Fund Balance Sheet and accompanying Income and Expenditure Accounts with the Books and Vouchers of the Society and certify them to be in accordance therewith and in our opinion correct. We have also verified the Balances with the Bankers and the Investments. FINSBURY HOUSE, CIRCUS BLOMFtELD STREET E.C.2 W.B. KEEN& Co. 1960. Chartered Accountants. 10th DECEMBER FEBRUARY 48 PROCEEDINGS 1961 49 SCHEDULE OF INVESTMENTS AT 3h-1-1 SEPTEMBER 1960 a Cost or Value Cost or Value when Acquired when Acquired E 6 or re-valued Publications Fund € s Brought forward.. .. 31,997 €4,366 5&% Funding Stock 1982/84 .. .. *. .. .. .. . . 4,189 General Purposes (Continued) €4,590 5% Conversion Stock 1971 .. .. .. .. .. .. .. 4,189 &8,378 Preference Stocks and Shares (Market Value E8,368) -1,0OO 44 % London Midland Associated Properties Ltd. Cum.Pref. Stock ;El Units 775 1,o@) 5% Peachey Property Corporation Ltd. Cum. Pref. El Shares . . .. 884 900 64% J. & N. Phillips & Co. Ltd. Cum. Pref. El Shares .. .. .. 930 800 6% Rotary Hoes Ltd.Red. Cum. Pref. El Shares 1973/78 .. 840 Special Publications Fund 750 7&% Scottish & Mercantile Investment Co. Ltd. Cum. Pref. €lShhres . 940 (Market Value $3,522) 4,369 &1,519 5$% Funding Stock 1982/84 .. .. .. .. .. .. .. 1,458 &1,597 5% Conversion Stock 1971 .. .. .. .. .* .. .. 1,457 €2,915 Ordinary Stocks and Shares (Market Value E2,911) 812 Boots Pure Drug Co. Ltd. Ord. 5s. Shares .. .. .. 625 1,199 Bowater Paper Corporation Ltd. Ord. Stock El’ Units .. .. 3,299 1,OOo British Assets Trust Ltd. Ord. 5s. Shares .. .. 801 3,445 Cable & Wireless (Holding) Ltd. Ord. Stock 5s Units’ .. .. 895 3,360 The Charterhouse Investment Trust Ltd. Ord. Stock 5s. Units .. 1,532 Staff Pensions Fund 1,200 The Charterhouse Group Ltd. Ord.f1 Shares .. .. .. 1,680 E2,200 5% Treasury Stock 1986/89 .. .. .. .. 2,016 1,500 Commercial Union Assurance Co. Ltd. Ord. 5s. Shares. .. .. 3,354 2,334 Ashdown Investment Trust Lid Ord.’5s. Shares .. .. .. .. 1,496 1,OOo Consolidated Zinc Corporation Ltd. Ord. El Shares . . .. 2,646 a. 420 Eagle Star Insurance Co. Ltd. Ord. 10s Shares .. .. .. .. 1,512 450 De Beers Consolidated Mines Ltd. Def. 5s. Shares .. .. .. 2,957 Distillers Co. Ltd. Ord. 10s. Shares . . .. .. .. .. 3,086 $3,024 2,500 (Murke! Value &5,284) __-1,875 Fremlins Ltd. Ord. Stock El Units .. .. .. .. .. 4,275 2,625 Gallaher Ltd. Ord. Stock 10s. Units . . .. .. .. .. 3,659 1,080 Glaxo Laboratories Ltd. Ord. Stock 10s. Units .. .. .. 701 1,000 A. Goldberg & Sons Ltd. Ord. 5s. Shares .... 3,062 2,666 Goodlass Wall & Lead Industries Ltd. Ord. Stock 10s Units .. 3,094 General Purposes 2.200 Great Universal Stores Ltd. “A” Ord. Stock 5s. Units .. .. 3,245 11500 Halevbridge Investment Trust Ltd. Ord. 21 Shares . . .. .. 3.618 .I ---British Government Colonial and Corporation Stocks i:is0 Imperial Chemical Industries Ltd.,-Ord. Stock $1 Units .. .. 2;994 &6,225 4% British Gas Guaranteed Stock 1969/72 .. .. .. .. .. 5,533 4,200 Inns & Co. Ltd. Ord. 4s. Shares . . .. .. .. .. 3,049 %1,500 3% Ceylon Stock 1959/64 .. .. .. .. .. .. 1,438 1,OOo Leyland Motors Ltd. Ord. Stock El Uni;; .. .. 2,408 &10,000 54% Glasgow Corporation 3-Year Mortgage ending December 1961 .. .. 10,000 4)500 Metropolitan Estate & Property Corporation Ltd. Oid.5s. Shares * 4,002 22,989 3&% Liverpool Corporation Stock 1961/66 .. .. .. .. .. 2,583 600 Northern & Employers Assurance Co. Ltd. Ord. €1 Shares . . .. 2,910 I. 21,000 3% Sheffield Corporation Stock 1967/69 . . .. ,. .. 962 2,500 Odhams Press Ltd. Ord. Stock 10s. Units 3,852 20,516 640 Peninsular & Oriental Steam Navigation Co. Ltd. Def.’ Stock ‘il Units 504 (Market Value E19,889) 350 E. Pollard & Co. Ltd. Ord. El Shares .. .. .. .. .. 827 250 Prudential Assurance Co. Ltd. “A” 4s. Shares .. .. .. .. 2,723 3,499 Radio Rentals Ltd. Ord. 5s. Shares .. .. .. .. *. 3,404 1,750 Rediffusion Ltd. Ord. Stock 5s. Units . . .. .. .. .. 3,138 Debenture and Loan Stocks 320 Rowntree & Co. Ltd. Ord. El Shares 788 400 The “Shell” Transport & Trading Co.’ Ltd.’Ord. Stock 21 Un% 2,307 ;f1,ooo 34% Agricultural Mortgage Corporation Ltd. Deb. Stock 1961 /63 .. 1,020 3,000 Shop Investments Ltd. Ord. 5s. Shares .. .. .. .. 3,722 €1,000 4% Cable & Wireless (Holding) Ltd. 10-Year Red. Unsec. Stock 1’660 .. 1,015 6,750 Smith & Nephew Associated Companies Ltd. Ord. 4s. Shares .. 3,210 E1,OOo 4% Canadian Pacific Railway Co. Perp. Deb. Stock .. .. .. 838 1,200 Smith’s Potato Crisps Ltd. Ord. 5s. Shares . . .. .. .. 3,901 E1,ooo 4% Covent Garden Properties Ltd. Red. Deb. Stock 1968 .. .. 95 1 2,750 Steel Company of Wales Ltd. Ord. El Shares .. .. .. .. 3,112 E1,000 4% Dominion & General Trust Ltd. Red. Deb. Stock 1959/64 .. .. 987 1,600 Tube Investments Ltd. Ord. Stock El Units .. .. .. 3,43 1 &3,0(3) 58% Hawker Siddeley Group Ltd.Conv. Deb. Stock 1979184 .. .. 3,113 E1,100 44% Nelson Financial Trust Ltd. Deb. Stock 1970 .. .. .. 982 750 United Dominion Trust Ltd. Ord. Stock El Uni& .. .. .. 4,726 €925 4% Olympia Ltd. 1st Mort. Red. Deb. Stock 1965/84 .. 853 1,750 United Wire Works Ltd. Ord. 5s. Shares .. .. .. .. 3,138 E1,m 44% Rugby Portland Cement Co. Ltd. Unsec. Loan Stock 1957/62 . .. . .. 1,040 (Market Value El 5 1,492) 100,675 E750 54% Wankie Colliery Co. Ltd. Mort. Deb. Stock 1962/78 .. .. 682 11,481 (Market Value €10,451) €137,041 Carried forward .. .. €3 1,997 FEBRWARY 50 PROCEEDINGS 1961 51 1-TRUST AND LECTURE FUNDS Income and Expenditure Accounts for the Year ended 30th September 1960 Combined Pool of Trust Investments Cost or Value Restricted Part when Acquired 1958159 1959160 E € f500 4% Defence Bonds .. .. .. .. .. .. .. .. 500 &20,000 5.St % Funding Stock 1982/84* .. .. .. .. .. .. .. 19,177 €23,248 5% Treasury Stock 1986/89 . . .. .. .. .. .. .. 19,934 (Market Value f 39,809) 39,611 Trust Funds Free Part f8,SOO 53% Borough of Chingford Loan on 7 days notice . . .. .. .. 8,501 f f 1,500 Babcock & Wilcox Ltd. Ord. Stock fl Units .. .. .. .. 2,756 -1,485 Cardinal Investment Trust Ltd. Def. 5s. Shares .. .. .. .. 1,400 1,135 484 +65 1 Centenary Fund. . 1,155 968 1,142 Commercial Union Assurance Co. Ltd. Ord. 5s. Shares .. .. 3,783 390 237 +153 Corday-Morgan Medal‘and Pr*& Fund 468 259 576 Courage Barclay & Simonds Ltd. Ord. f1 Shares .... 1,800 607 539 3. 68 Corday-Morgan Memorial Fund . . 669 555 3,500 Daily Mirror Newspapers Ltd. “A” Ord. Stock 5s. Units’ .. .. 2,608 17 1 + 16 Faraday Lecture Fund .. .. 37 1 796 Imperial Tobacco Co. (G.B. & I.) Ltd. Ord. Stock El Units .. .. 2,679 1. 38 91 2,472 Ind. &ope Ltd. Ord. Stock 5s. Units .. .. .. 2,596 36 2 + 34 Robert John Flintoff Trust 47 3 + 44 Edward Frank Harrison Trus; Fund’ ’ 50 8 387 Mitchells & Butlers Ltd. Ord. Stock El Units .. .. .. .. 1,137 26 1 + 25 Liversidge Lecture Fund .. .. 28 43 700 National Provincial Bank Ltd. €1 Shares .. .. .. .. .. 2,896 26 39 -13 Pedler Lecture Fund .. .. 28 2 356 Phoenix Assurance Co. Ltd. Ord. 5s. Shares . . .. .. .. 2,403 (I. 806 616 +190 Research Fund .. .. 983 883 2,500 Thomas Tilling Ltd.Ord. Stock 4s. Units .. .. .. .. 2.807 3,000 Trans-Oceanic Trust Ltd. Ord. Stock 5s. Units .. .. .. .. 21804 26 2 + 24 Simonsen Lecture Fund’ .. .. 67 2 88 94 -6 Tilden Lecture Fund . . .. .. 100 92 412 Watney Mann Ltd. Ord. Stock &1Units .. .. .. .. 1,725 39,895 (Market Value f39,729) €79,506 Balance Sheet 30th Segtemk 1968 1960 1959 1960 1959 E E E E Assets f. .€ € E Liabilities 3,259 Sundry Debtors .. .. .. .. .. .. .. .. 1,313 576 Sundry Creditors .. .. .. .. .. .. .. 172 Combined Pool of Trust Investments as per schedule a. 31,181 Centenary Fund-Capital Account . . .. .. .. .. 24,63 1 31,138 Centenary Fund .. .. .. 24,882 1,558 -Income Account .. .. .. .. 1,745 7,276 Corday-Morgan Medal’and P;;e Fund .. .. .. .. 12,016 a. 32,739 26,376 12,293 Corday-Morgan Memorial Fund .. .. .. .. .. 15,209 8,194 Corday-Morgan Medal and Prize Fund .. .. .. .. 12,223 469 Faraday Lecture Fund .. .. .. .* .. .. 283 13,197 Corday-Morgan Memorial Fund .. .. .. .. .. 15,780 1,m Robert John Flintoff Trust .. .. .. .. .. 641 47 1 Faraday Lecture Fund .. .. .. .. .. .. 530 1,101 Edward Frank Harrison Memorial Tkst .. .. .. .. 934 1,146 Robert John Flintoff Trust .. .. .. .. 733 808 Liversidge Lecture Fund .. .. .. .. .. .. 503 1,208 Edward Frank Harrison Trus; Fund ’ * .. .. .. .. 1,135 807 Pdkr Lecture Fund .. .. .. .. .. .. .. 503 92 1 Liversidge Lecture Fund . . .. .. .. .. .. 67 1 23,923 Research Fund .. .. .. .. .. .. .. 21,611 ’ 92 1 Pedler Lecture Fund .. .. .. .. .. .. .. 702 506 Simonsen Lecture ~unci .... .. .. .. .. 500 27,914 Research Fund .. .. .. .. *. .. 22,978 2,140 Tilden Lecture Fund . . .. .. .. .. .. .. 2,424 494 Simonsen Lecture Fund’ .. .. .. .. 565 -81,449 79,506 2,273 Tilden Lecture Fund .. .. .. .. .. 2,694 5,346 Baganm at Banks (including Deposits) .. .. .. .. 3,740 a. The investments of all Trust Funds were re-valued on the 23rd Aumst. 1960. when the Charity Corn-&84,559 .€90,054 f84,559 €90,054 ,g&$ope~5 appoyed the consolidation scheme. A net loss of f6.883 has been written off during the -, year and is analysed in the Report. PROCEEDINGS THE CHEMICAL INDUSTRY OF MERSEYSIDE By D. W. F. HARDIE, PH.D. A CONCERT of historical topographical tech- nical and chance circumstances has made Merseyside for over a century one of the world’s principal chemical industrial regions.At the present time it is the site of more than fifty important chemical factories. The type of chem- ical industry with which most of these works are concerned is heavy chemical manufacture i.e. large-tonnage conversion of widely available relatively simple naturally occurring substances into chemical commodities which may as such have final consumers but are more often inter- mediate facilitative or ancillary materials in other manufactures. Salt limestone sulphur sulphides and sulphates a few minerals such as borax and phosphatic rock air and water almost complete the raw material economy of heavy chemical industry. Coal in addition to providing energy for the processes serves as a source of carbon and simple hydrocarbons.In recent times petroleum has become increasingly a heavy chemical starting-point. Heavy chemical industry originated as a development of the traditional empirical techniques of metallurgy lime-burning saponification lye-making crystallisation and elutriation. There was little or no direct relation- ship between 18th century advances in scientific chemistry and the early phases of chemical industry. By 1800 potashes from forest clearance in the New World barilla from the Spanish littoral and kelp from the Scottish highlands and islands coming into Liverpool made it and its hinterland an early centre of soap manufacture second in importance to London which it later displaced from its primacy.At nearby St. Helens a glass industry was already in flourishing existence and hardly out of sight beyond the eastward horizon the powered looms of Lancashire were producing an ever-increasing vohme of textiles. As a con-sequence of the coupling of Eli Whitney’s gin with the most spectacular organisation of slavery in the mcdern world cotton was being grown and harvested in America on an unprecedented scale. Soap glass and textiles all require alkali in their manufacture. In part as a consequence of reduc- tion of potash supplies and the rise in prices occasioned by the American War of Independ- ence several Englishmen Irishmen and Scots devised processes more or less crude but effec- tive for producing alkali from salt via sodium sulphate ; indeed Nicolas LeBlanc by present- day standards would hardly have had subject matter for a patent in face of the extensive prior art! By the beginning of the third decade of last century natural alkalis were at last proving in- creasingly inadequate to meet demands between 1815 and 1825 output of cotton textiles doubled and hard soap output increased by 30 ”/o ;glass although a substantial user of alkali showed no increase of output during that period.Large- scale manufacture of alkali from salt had become a matter of national necessity. On Merseyside a sizeable vitriol works was operated at Garston in the 179O’s and before that the acid had been produced in Liverpool at a site still known as Copperas Hill.In the year of Waterloo Thomas Lutwyche and William Hill the pioneer in the use of pyrites instead of brim-stone were producing vitriol and Glauber’s salt near the bank of the Liverpool-Leeds Canal; as far as is known neither of these manufacturers made alkali. Synthesis of alkali from salt by LeBlanc’s process involved treating the salt with sulphuric acid to produce saltcake (sodium sul- phate) which was subsequently heated in admix- ture with crushed coal and limestone. The reactions which took place in the furnace were the subject of controversy for many years and still may require elucidation. The all-important fact was that a few saltcake pots and black ash furnaces could produce more alkali than thousands of peasants seasonally harvesting barilla or kelp along hundreds of miles of remote coast1 ands.Alkali manufacture in the United Kingdom arose in four regions-on the Clyde Tyne and Mersey and in the Midlands. Tennant’s St. Rollox works which was for a time the largest chemical factory in the world continued as the only chemical enterprise of importance in the Clyde region. Salt had to be brought by sea via Liverpool from Cheshire and local glass and soap industries afforded only a limited market after the disappearance of Glasgow’s short-lived cotton trade. The Tyne region was also remote FEBRUARY 1961 from salt importing it overland from the Cheshire field. Although the Midlands were near enough to salt and coal the region was remote (in those days) from exporting ports and the great alkali market of Lancashire.In the Mid- lands alkali was largely “captive” as a raw material in the regional glass and soap works. Merseyside was flanked by coalfields Derbyshire limestone quarries were a short haul away; brim- stone from Sicily and later pyrites from Ireland and Spain could be brought cheaply to the quays of Liverpool. Short canal distances linked the chemical factories with the vast saltfield of Cheshire; finally the very cradle of the Industrial Revolution was in the immediate neighbourhood. When in the early 1840’s the alkali industry began to export Liverpool was the natural port for shipments to America where indigenous production of heavy chemicals became com-mensurate with demand only in the last two decades of last century.While heavy chemical industry eventually vanished from the Clyde and Tyne and survived only to a limited extent in the Midlands it continued to diversify and expand on Merseyside. In Dublin James Muspratt son of an artisan cork-cutter became interested in chemical manu- facture and may have experimented there on a backyard scale with the LeBlanc soda process. In 1823 Muspratt transferred the scene of his activities to Liverpool where in an old glass- works in Vauxhall Road he was soon producing black ash and delivering it hot and odorous to Iocal soap-boilers. It is a gross over-simplification of historical facts to designate Muspratt the founder of the British heavy-chemical industry.His significance was that he thought in larger dimensions than his predecessors-his vitriol chambers were over 100 feet long and 24 feet wide instead of the 6-or 10-ft. cubical boxes up till then in use. Muspratt’s enterprise in Liver- pool and later at St. Helens was followed by others and by 1830 kelp and barilla were no longer in use on Merseyside. To secure their in- creasing salt requirements Muspratt and the Tennants of Glasgow jointly established in 1835 a saltworks near Winsford Bridge in Cheshire. At Runcorn alkali manufacture probably began as a soap raw material not long after Thomas Hazlehurst began soap manufacture there in 1816 on the north bank of the Duke of Bridge- water’s canal. In Warrington too alkali syn- thesis made its appearance as a department of soapmaking.During the period 1840-80 the greater part of all heavy chemicals used domestically and industrially in the United States came from Merseyside factories and Tennant’s St. Rollox. “Liverpool prices” for alkalis acids and bleach- ing powder were those quoted on the commodity exchanges of the world. Between the mid-century and 1880 the LeBlanc system rose steeply to its zenith. Apart from caustic soda the products of the heavy chemical industry in 1880 remained what they had been at its outset soda ash (sodium carbonate) saltcake sulphuric and hydrochloric acid and bleaching powder with alum and ammonium chloride as subsidiaries. Recovery of copper from the pyrites used as a source of sulphur for sulphuric acid became after 1850 an important branch development.Widnes and Runcorn were principal sites of copper recovery; this is in fact the historical reason why Widnes today produces most of this country’s copper sulphate. Hydrochloric acid was coproduced with the saltcake required for the alkali furnaces and chlorine for bleaching powder was in turn made from the hydrochloric acid. This process pattern was economically vul- nerable the relative demands for its products were often widely different from the ratios in which the laws of chemistry required that they should be produced. Since 18 1 1 it has been known that when carbon dioxide is passed into brine saturated with ammonia sodium bicarbonate separates out.The potentiality of this reaction as the basis for an industrial process for manufacture of alkali from salt was soon recognised. At Newton-le- Willows in 1840 James Young later of paraffin fame then Muspratt’s manager attempted to operate the Hemming-Dyar ammonia-soda pro- cess; at Widnes in 1853 Henry Deacon at-tempted to establish himself as an alkali-maker with another variant of the attractive ammonia- soda route. Both these attempts failed because of the inefficiency of the means of ammonia re- covery the step upon which depended the eco- nomics of the process. Ludwig Mond in 1873 on the eve of embarking upon LeBlanc soda- making at Widnes was informed by Henry Deacon of advances made by a Belgian gasworks engineer Ernest Solvay in development of an economic ammonia-soda process.Mond realised his opportunity he acquired Solvay’s British patent rights and with John T. Brunner who had been his colleague at Hutchinson’s works in Widnes set up an ammonia-soda factory on the River Weaver in the heart of the Cheshire salt- field. In 1877 their output of ammonia-soda was 9,000 tons and by the time that the LeBlanc system had reached its peak in the 1880’s they were producing over 100,000 tons of soda annually. The threat to the LeBlanc system had become fully apparent ; one Widnes manufac- turer (Edward Sullivan) wrote of it as “a grove of olives past bearing.” The LeBlanc system was maintained in a state of metastable economic equilibrium by its ability to make the chlorine “half” of sodium chloride into a marketable commodity-bleaching pow-der.Numerous attempts by the ammonia-soda makers to recover chlorine economically from their by-product calcium chloride failed to the temporary relief of the LeBlanc practitioners. So important did the bleaching powder side of their system become that the LeBlanc manufacturers abandmed competition amongst themselves in this commodity and formed in 1883 the Bleach- ing Powder Association. The groundwork of co- operation thus beicg laid it was only a matter of time before the entire LeBlanc heavy chemical industry with the exception of the firm of Chance in the Midlands amalgamated into the United Alkali Company. This 1890 merger was the first and for many years the largest of its kind in the history of the woild’s chemical industry.Many of the firms and these the prime movers in pro- motion of the merger were located on Mersey- side. From its outset the new combine was beset with troubles. There can be no doubt that it was grossly over-capitalised and many of the old concerns that it acquired at high cost operated at widely differing levels of technical efficiency. Over the thirty-seven years of its existence the United Alkali Company was never a very reward- ing investment for its shareholders. Brought into being in the quest for economic salvation the Company’s historical role was mainly technical it enabled the old LeBlanc system gradually to be replaced by modern processes.Had there been no merger it is reasonably certain that many heavy chemical enterprises would have gone out of PROCEEDINGS business in face of ammonia-soda competition and tariff barriers against alkali and bleaching powder rising everywhere between them and their traditional markets in America and Europe. In the 1890’s several inventors solved the physicochemical problem of decomposing brine electrolytically so that the liberated products (caustic soda and chlorine) did not react with one another and nullify the work of the electric cur- rent. Hamilton Y. Castner a young American solved the problem by removing sodium from the electrolytic decomposition in a flowing stream of mercury which also served as the cathode caustic soda and hydrogen being produced in a separate compartment by reaction of the amal- gamated sodium with water.Other inventors interposed a porous diaphragm between the electrodes at which chlorine and caustic soda were being liberated. Both methods of brine electrolysis had important developments on Merseyside. Castner and his assistant Harry Baker a former lecturer in chemistry at Owen’s College Manchester devised their successful mercury “rocking” cell at Oldbury near Birmingham but it was at Weston Point on the Weaver Canal Runcorn that the Castner-Kellner Alkali Company in 1897 brought the Castner mercury-Gel1 process into large-scale commercial operation in this country. The most advanced of the early diaphragm cells was developed in Widnes by James Hargreaves and a Liverpool electrical engineer Thomas Bird.The importance of introduction of brine electrolysis into heavy chemioal industry was that producing caustic alkali and chlorine in one continuous process stage from brine it dealt the coup de grace to the tottering LeBlanc system. Before the outbreak of the First World War Le- Blanc soda manufacture had all but ceased. At Widnes the United Alkali Company had developed its own variant of the ammonia-soda process and was contemplating brine electrolysis ; Hargreaves-Bird cells were operating on a large scale at Middlewich in Cheshire and at Weston Point the Castner-Kellner Company’s mercury- cell plant had been greatly improved and ex-tended.Brunner Mond and Company by that time had won much of the home and export markets for soda ash justifying Mond’a dying satisfaction with “the great Babylon” he had built above the ancient salt. Only the increased FEBRUARY 1961 demand for chlorine enabled the obsolescent Weldon and Deacon processes to survive the years of the war. During the last phase of the LeBlanc system Merseyside and particularly Widnes was the centre of a wave of inventiveness in that hitherto technically conservative industry. In St. Helens Walter Weldon evolved his chlorine process familiar to schoolboys from textbooks a genera-tion or so after its disappearance from the factory. At Widnes Deacon and Ferdinand Hurter evolved a rival chlorine process which as output of by-product hydrochloric acid mounts may now be revived in modernised form.In the same Merseyside town James Har- greaves developed his process for producing hydrochloric acid and saltcake directly in one stage from sulphur dioxide steam and salt. From his home in Widnes in December 1871 Mond wrote to his friend Merle at Salindres “YOU will find here all the important inventions the Deacon Weldon and Hargreaves processes the revolving kilns (for black ash) etc. . . . The journey from Paris here takes only 18 hours. . . .” Somewhat later George E. Davis devised a pro-cess which comprised the stages of treating salt with sulphuric acid and oxidising the hydro- chloric acid so produced with nitric acid. From 1890 to 1898 Davis’s process was operated at a small works at Lostock Gralam in Cheshire; technically it was fairly successful economically it failed-the price of bleaching powder was slumping heavily and the LeBlanc manufacturers already had disastrously idle saltcake capacity.Davis’s process integrated with neither the de- clining LeBlanc system nor the rising ammonia- soda and electrolytic processes. If George E. Davis failed to stay the decline of the old type of chemical manufacture based on batch reactions of salt with acid he made good use of the experience which he gained of chemical industry in the chemical factories or” St. Helens and Runcorn and in his own works at Lostock. It was Davis who first clearly formulated the principles of chemical engineering and his fruitful concept of unit processes became the systematic basis of chemical engineering instruction and practice.In the laboratory which as chief chem- ist he planned for the United Alkali Company in Widnes Ferdinand Hurter a pupil of Bunsen was one of the first to apply the principles of physical chemistry to the study of the problems and processes of heavy chemical industry. Up to the early 1880’s such practically important pro- cesses as the absorption of hydrogen chloride in water had not been subjected to scientific jnvesti- gation under industrial conditions and applica- tion of the theoretically advanced science of thermodynamics to the energy economics of the chemical factory had not begun. Before the First World War considerable diversification of chemical manufacture had taken place on Merseyside lead zinc and barium pigments aluminium sulpliate sodium sulphide (made by a modification of the old LeBlanc soda process) carbon disulphide sodium cyanide chlorinated solvents formic acid lactic acid sodium peroxide fatty acids and pharmaceutical chemicals were all well- established manufactures.In order to circumvent the provisions of the 1909 Patents Act the German dye firms of Meister Lucius and Bruning and Badische Anilin und Sodafabrik had set up factories in the region. Warlike needs during the years 1914-18 put new and urgent demands on the Merseyside chemical industry accelerating introduction of the contact sulphuric acid process and rapidly extending the production of electrolytic chlorine.The Castner-Kellner Company which had made small amounts of liquid chlorine in the pre-war years greatly increased its output of the liquefied gas. Brunner Mond and Company applied Willard Gibbs’s phase rule to the large-scale manufacture of the ammonium nitrate required by the Ministry of Munitions. After the war chemical industry on Mersey- side in common with the industry elsewhere underwent in 1920-21 a recession relatively greater than any in its history. In this immediately post-war period the United Alkali Company shut down its remaining operations in St. Helens. After the post-war depression increasing di- versification and other far-reaching changes took place in the Merseyside chemical industry; rapidly its present-day pattern began to emerge.In 1926 the United Alkali Company merged with the British Dyestuffs Corporation Nobel Industries Ltd. and Brunner Mond and Com- pany to form Imperial Chemical Industries Limited. As when the United Alkali merger took place thirty-six years previously formation of I.C.I. was followed by extensive measures of rationalisation in which the Castner-Kellner and United Alkali Companies were co-ordinated into an administrative grouping represented today by the General Chemicals Division of I.C.I. one of the two largest chemical producers on Mersey- side. The other large heavy chemical concern in the region Brunner Mond and Company be- came the Alkali Division.Later in 1937 the Cheshire salt interests which had been largely merged in the Salt Union in 1888 became the Salt Division which has now just been integrated with the Alkali Division. At the present time in almost a score of factories the I.C.I. Divisions on Merseyside produce some two-hundred heavy inorganic and organic chemicals. Very extensive research establishments are carried on by I.C.I. Alkali and General Chem- icals Divisions the former at Winnington and the latter at Widnes the Widnes Laboratory being the modern descendant of the former United Alkali Company’s Central Laboratory founded in 1890. Both establishments have made notable contributions to chemical industry amongst these being the Alkali Division’s dis- covery and early development of Polythene the first plastic to reach a world output of over a million tons a year.Chlorine and caustic soda are now produced electrolytically by I.C.I. General Chemicals Divi- sion at Wade (Central Cheshire) Rocksavage and Weston Point (Runcorn) Murgatroyd Salt and Chemical Company at Sandbach and the Associated Ethyl Company at Ellesmere Port. The I.C.I. Castner-Kellner factory at Weston Point has one of the largest mercury-cell plants in the world and generates its own electrical energy in the biggest privately-owned power station in this country. Weston Point power station is linked with the I.C.I. generating station in Widnes and together they generate annually energy equivalent to the total requirement of domestic consumers in a large English county.General Chemical Division and the Associated Ethyl Company also manufacture metallic sodium and chlorine by electrolysis of fused salt the latter concern using the metal for the produc- tion of the sodium-lead alloy used in making tetraethyl-lead (TEL). For almost twenty years PROCEEDINGS electrical energy has been consumed at Weston Point in the manufacture of calcium carbide required at that factory for making acetylene used in the manufacture of chlorinated solvents and vinyl chloride (the monomer of PVC). Pro- duction of these chlorinated solvents (trichloro- and perchloro-ethylene) was begun by the Castner-Kellner Company* as long ago as 1909 with the object of finding an outlet for its chlorine surplus :decline in demand for bleaching powder had temporarily consigned chlorine to the status of a partly marketable by-product.Tri- chloroethylene is today one of the most im- portant heavy organic chloro-derivatives. At Ellesmere Port the Associated Ethyl Company uses large tonnages of chlorine annually for the production of the ethyl chloride and ethylene di- chloride which it requires for the manufacture of TEL antiknock fluid. Caustic soda in addition to being coproduced with electrolytic chlorine is made in very large tonnages by 1.C.I. Alkali Division by reacting slaked lime with Solvay soda which that Division produces on a scale of some two-million tons annually. Thus the elec- trolytic chlorine-caustic and ammonia-soda processes are linked in a kind of technological symbiosis; fluctuations of chlorine demand which would affect supplies of electrolytic caustic soda are balanced by production of correspond- ingly more or less so-called “lime caustic”.Widnes and Runcorn are the acid-making centres. Sulphuric hydrochloric formic oxalic and lactic acid are all produced there. At Widnes the United Sulphuric Acid Corporation formed in 1951 by a group of acid-consuming concerns uses anhydrite (mineral calcium sulphate) as its sulphur raw material and is thus independent of imported brimstone or pyrites. An important feature of the Sulphuric Acid Corporation’s pro- cess is that cement is produced as a marketable by-product.In 1952 Albright and Wilson Ltd. began large-scale production of phosphoric acid and derived polyphosphates at a new factory on the Kirkby Industrial Estate near Liverpool. Polyphosphates are a general constituent of the domestic detergents the universality and adver-tising of which have become social phenomena of our time. The phosphorus used to make phos- phoric acid at Kirkby is transported north from * Originally as a partner with the Consortium fur Elektrochemische Industrie in the Weston Chemical Company at Weston Point. This concern was merged with the Castner-Kellner Alkali Company during the First World War. FEBRUARY 1961 57 Albright and Wilson’s factory at Portishead near Bristol. From 1934 to 1959 Albright and Wilson manufactured phosphorus at Widnes where they continue to produce phosphates and carbon tetrachloride.Hydrofluoric acid produced by re- action of sulphuric acid with calcium fluoride (fluorspar) is one of the raw materials used by Imperial Chemical Industries Limited at Run- corn for the manufacture of the now well-known chlorofluoromethane non-toxic non-inflamm-able refrigerants and aerosol-propellants. Production of phosphatic fertilisers has more than a century’s history on Merseyside dating from James Muspratt’s failure to put the revolu- tionary and all-but-correct notions of his friend Liebig into effect at his Newton-le-Willows factory. Today Fisons Ltd. on a Widnes site where fertilisers lave been made since 1873 pro-duct various types of phosphate and ammonium nitrate “compounds.” White lead was already a Merseyside chemical in the latter part of the 19th century ;today it is produced by Associated Lead Manufacturers at Bootle and the Mersey White Lead Company at Warrington; the Bootle factory is the largest of its kind in Europe.Hydrogen peroxide manufactured by Laporte Ltd. at Warrington in one of the largest and most up-to-date peroxygen factories in the world is a comparatively recent addition to the range of Merseyside chemicals. Although by long-established tradition soap-making is re-garded as a chemical-consuming industry rather than as a part of the chemical industry itself the vast soap and detergent manufacturing opera- tions of Unilever at Port Sunlight and Warring- ton provide a market for chemicals within Merseyside that has for many years been an important contributory factor to the prosperity of the chemical industry of the region.With the rise of petroleum refining on Merseyside at Stanlow and Partington have come the most recent and revolutionary develop- ments in the region’s chemical manufacture. It has been estimated that about one-third of all organic chemicals now being made in the U.K. is derived from petroleum. Hydrocarbon frac- tions and gases from Shell refineries at Stanlow are utilised for manufacture of chemicals at that site and for TEL production at the nearby works of the Associated Ethyl Company. Petroleum chemical operations at Stanlow are linked with related activities at Partington and Carrington to the east.Ethylene oxide production at Parting- ton where over eighty organic chemicals includ- ing Polythene are now produced accounts for about one-third of Europe’s output. Thornton Research Centre near Ellesmere Port estab-lished by Shell Ltd. during the Second World War to work on petroleum fuels and lubricants devotes a large part of its activity to the petro- leum chemical field; the same firm’s laboratory at Partington conducts long-term fundamental research in petrochemistry. Pharmaceutical and fine chemicals are produced by various firms in the region notably by W. J. Bush and Company and Boake Roberts and Company (now a sub- sidiary of Albright and Wilson Ltd.) at Widnes Brotherton and Company (now one of the Associated Chemical Companies) at Brom-borough Evans Medical Supplies at Speke In- dustrial Estate (Liverpool) and Ward Blenkin- sop and Company at Hale Bank near Widnes.The factors which have made Merseyside the scene of chemical manufacture for almost a hundred and fifty years are still largely operative and have now been augmented by the establish- ment of a great petroleum refining industry in the area. Salt must continue to be a principal heavy chemical raw material. Recent exploration has revealed Cheshire salt deposits estimated at 400,000 million tons doubling the hitherto known regional reserves. After the Second World War chemical manufacturers in the region have with very few exceptions greatly extended their operations and their sites and chemical concerns from outside the area have acquired interests within it.Chemical manufacture has now reached a maturity in which benign or threatening technological possibilities may gener- ally be foreseen through the eyes of the researcher and appropriately anticipated there is no prob- able prospect that any substantial part of con-temporary Merseyside chemical industry will become like the old LeBlanc system to the dis- may of its practitioners “a grove of olives past bearing.” PROCEEDINGS ~ ~~~~-A SHORT HISTORY OF LIVERPOOL UNIVERSITY By J. S. E. HOLKER, M.Sc. PH.D. (DEPARTMENT UNIVERSITY) OF ORGANIC CHEMISTRY LIVERPOOL THEfoundation of a College in Liverpool in 1878 followed closely upon similar foundations in Manchester (Owen’s College 185 l) Leeds (Yorkshire College 1874) and Bristol (Univer- sity College 1876).The Liverpool and Man- Chester Colleges joined in 1884 to form the federal Victoria University. Growth of the Liverpool College was rapid. Thus in 1884 there were fourteen Chairs and 300 students whereas by 1900 there were twenty-five Chairs and 600 students. At that time the federal system of the Victoria University was already becoming too cumbersome for the expanding organisation and in 1902 a Town’s meeting discussed proposals for a separate University. This led to a Royal Charter in July 1903 establishing the University of Liverpool. In spite of two World Wars and an intervening period of industrial depression the University expanded steadily.By 1953 the jubilee of the granting of the Charter there were fifty-nine Chairs 3,000 students and buildings land and equipment valued at E2,400,000. Throughout this period the rapid development of the Univer- sity was made possible by the generosity of lead- ing citizens and of the City which has not only given financial help but also provided land for development. In these respects Liverpool has been more fortunate than some other provincial Universities. There are many factors which influence the evolution of any University against a background of traditional academic disciplines. In some cases the eminence of individuals has been largely responsible for the development of branches of learning whilst in others external factors have played a part.Thus developments in oceano- graphy marine biology naval architecture and tropical medicine have occurred in Liverpool because of the importance of the City as a great port. More recently the growth of the Faculties of Science and Engineering has been affected by the demand for trained manpower in the modern age. Hence the history of the University can be surveyed most conveniently in terms of the in- dividual Faculties and Departments. If in this analysis some branches of learning seem to be highlighted it is not necessarily because of their intrinsic importance but rather that they may be specialised developments in Liverpool or have a particular interest for Fellows of the Chemical Society.The Faculty of Science.-Until recently the Faculty of Science was numerically second only to Arts. However the Barlow Report on scientific manpower in 1946 and subsequent White Papers have already resulted in Science becom- ing the largest single Faculty. Thus since 1954- 1955 student numbers in Science have risen by 65 % compared with 23 % in Arts. One of the main problems associated with this expansion has been the provision of more accom- modation for the various departments. Great progress is being made through governmental grants from the U.G.C. and D.S.I.R. As early as 1952 the new Nuclear Physics Laboratory housing the 156 in. synchrocyclotron and lt Mv high-tension set came into operation to promote the Government’s nuclear-research programme.In 1954 the first stage of the Donnan Labora- tories for Physical and Inorganic Chemistry were opened by H.R.H. the Duke of Edinburgh the second stage incorporating the lecture theatres and Radiochemistry Laboratories being occu- pied in 1958. The final stage to accommodate Organic Chemistry should be completed in 1962 when the present unfortunate geographical separation of the Chemistry Departments will end. Designed by Mr. R. R. Young of Stephen- son Young and Partners this extensive modern building will provide better accommodation for the Departments of Chemistry as a whole than at any time since the early days of University College. Although this project represents a vast capital expenditure of E 1,400,000 equivalent expansion of other Departments in the Faculty necessitated further building programmes.The new Chadwick Laboratories designed by Basil Spence for the Physics Departments and incorporating an im- pressive tower for Theoretical Physics were first used in 1959. A new building for the Depart- ments of Mathematics and Oceanography will be completed in 1961. It is hoped that these develop- FEBRUARY 1961 ments together with an expansion of other Departments into vacated premises will solve the main problems of accommodation in the Faculty . The rapid development in science has been due to the intrinsic importance of the disciplines studied and the distinguished men who have filled the Chairs.This has been particularly apparent in Chemistry which was first studied in Liverpool in 1867 when James Campbell Brown became a lecturer in Experimental Science in the Royal Infirmary School of Medicine. As joint secretary of the board set up in 1877 to create University College Campbell Brown played a leading part in raising funds for the establish- ment of the College. It was fitting that he should be the first holder of the Chair in Chemistry from 1881 until his death in 1910. Meanwhile in 1903 a separate Chair in Physical Chemistry was en- dowed. The first holder was F. G. Donnan who until 1913 carried out much of the work for which he became famous. In 1910 E. C. C. Baly was appointed to the Chair of Inorganic Chem- istry.Until his retirement in 1937 he developed and extended his work on ultraviolet spectro- scopy for which he already had a reputation when he came to Liverpool. One of his assistants R. A. Morton became interested in the use of spectroscopy in the assay of vitamin A and caro- tenoids. Later this developed into a wider interest in biochemical problems and in 1944 Morton was elected to the Chair of Biochemistry in the Faculty of Medicine. In 1913 when Donnan left Liverpool to go to University College London he was succeeded by W. C. M. Lewis who developed an active school in studies of chemical kinetics and later in the physicochemical behaviour of colloids. On the retirement of Baly in 1937 the Departments of Inorganic and Physical Chemistry were merged and the joint Chair was held by Lewis until his retirement in 1948.C. E. H. Bawn was then appointed to the Chair. Under his direction the research school has expanded rapidly and its reputation has been enhanced particularly by work on the principles of production of high- polymer systems. Although a separate Chair of Organic Chemistry was not founded until 1915 the distinguished line of occupants has more than compensated for the belated recognition of this field. When Robert Robinson became the first occupant of the Chair it was perhaps still early to recognise that he would later affect the development of organic chemistry so profoundly. The brilliant synthesis of tropinone which Robinson published from Liverpool in 19 17 provided one of the early signposts in this direc- tion.In 1920 Robinson was succeeded by I. M. Heilbron who until 1933 carried out much of his early work on the natural products squalene vitamin A the carotenoids and vitamin D. Emphasis on the study of natural products was continued by Heilbron’s successor Alexander Robertson. Robertson’s work on oxygen hetero- cycles and a wide variety of fungal metabolites considerably added to our knowledge of the chemistry of natural products. When Robertson retired in 1957 his successor G. W. Kenner had already built up a considerable reputation for his work in Cambridge on nucleotides and peptides. In Liverpool Kenner has not only extended his work on peptide synthesis but has also estab- lished an active group in the field of porphyrin synthesis.In 1923 a separate Chair of Industrial Chem- istry was endowed. The only occupant has been T. P. Hilditch who from 1926 until his retire- ment in 1951 led an active research group in the development of methods for the analysis of mixed fatty acids in natural fats. By using these refined techniques the whole pattern of glyceride structure in natural fats was elucidated and Hilditch became a world authority in the field. The School of Physics provides another example of a Department which has gained fame through a distinguished line of Professors. These include Sir Oliver Lodge L. R. Wilberforce Sir James Chadwick and H. W. B. Skinner whose untimely death in 1960 was a great loss to the University.The senior Chair is now occupied by J. M. Cassels who from 1956 to 1959 was Pro- fessor of Experimental Physics an office now held by A. W. Merrison. A third Chair in Theoretical Physics has been occupied by H. Frohlich since its foundation in 1948. The world- wide reputation of the Department in nuclear physics dates from 1938 when Sir James Chad- wick came to Liverpool. The work he initiated using the 37 in. cyclotron was later brilliantly continued by Skinner with the aid of the 156 in. synchrocyclotron and 1a MV high-tension set. The recent decision to build a 10-12 Mv horizontal Van de Graaff machine on a site adjacent to the south end of the Chadwick Laboratories suggests that further developments in the field may be expected.The Chair of Mathematics founded in 1882 was divided in 1919 when a separate Chair of Applied Mathematics was established. Both Departments together with the Department of Oceanography the only one of its kind in the British Commonwealth are to be housed in the new Institute of Mathematics in 1961. A feature of the Mathematics Departments is that they con- tain separate sub-Departments of Statistics and Numerical Analysis equipped with an Elec-tronics Computer Laboratory. The emphasis placed on numerical analysis in the undergradu- ate course has created a constant and increasing demand for Liverpool graduates trained in computational methods. The original Chair of Natural History en-dowed in 1881 changed its name to Zoology in 1894 when a separate Chair of Botany was en- dowed.These Departments now have a wide variety of research interests and are closely associated with the University’s Marine Bio-logical Station at Port Erin in the Isle of Man and with freshwater biological work on the shores of the Dee and at Lake Bala. A separate sub-Department of Genetics was established in 1960. Finally there is the Chair of Geology founded in 1916 and held first by P. G. H. Boswell who later became consulting geologist for the Mersey Tunnel. Although the School has never developed into a large one it has produced a distinguished line of graduates six of whom now hold Chairs in Universities. Faculty of Arts.-Chairs in the traditional disciplines of modern and ancient languages and literatures history and geography were estab- lished relatively early.From the beginning this Faculty has been strong in modern languages and history. The Chair of English Literature is note- worthy having been held by three outstanding scholars A. C. Bradley Sir Walter Raleigh and Oliver Elton. Of the other Departments Social Science and the School of Architecture are per- haps the most interesting to the scientific reader. The original School of Social Science founded PROCEEDINGS in 1905 was the first of its kind in the provinces. It became a University Department in 1918 and a Chair was established in 1925. This Depart- ment now has a large staff of lecturers and re- search workers and caters for Certificates and Diplomas in addition to Degree courses.In much of this work there is a close connection with the Department of Economics which has two Chairs. It is perhaps surprising that Psycho- logy which has such close ties with the Social Sciences was not included in the Faculty until 1939 and a Chair was not established until 1947. As early as 1894 a Chair of Architecture was founded the first of its kind in any University. Under the influence of Sir Charles Reilly who held the Chair from 1904 to 1933 the School earned world-wide fame and the Liverpool degree of B.Arch. was the first to be recognised as a qualification for election to the Associateship of the R.I.B.A. In 1909 a separate Chair of Civic Design was created.This Department housed in its own building since 1950 concentrates most of its effort on research and post-graduate courses. The Faculty of Engineering.-Although a Chair of Engineering had been in existence since 1886 the Faculty of Engineering was not empowered to award its own degrees until 1903. The Faculty then developed rapidly and separate Chairs of Electrical Engineering Civil Engineering and Naval Architecture were founded in 1903 1908 and 1909 respectively to supplement the original Chair of Mechanical Engineering. Finally in 1957 a separate Chair of Building Science was established to provide a link with the strong Architectural School. These separate Depart- ments together with the sub-Departments of Fluid Mechanics and Marine Engineering pro- vide for a wide range of specialised interests for undergraduates and research workers.The ex- panding scope of this Faculty and an increase in student numbers of 90% since 1954-1955 has created an acute pressure on available space only partially relieved by the separate building for Civil Engineering and Building Science com- pleted in 1959. The Faculty of Medicine.-This Faculty des- cended from the Royal Institution Medical School founded in 1834 became part of the Royal Infirmary in 1844 and was finally trans- ferred with its seven Chairs to the Liverpool College in 1881. From these beginnings the FEBRUARY 1961 Faculty progressed rapidly and has earned for itself an enviable reputation primarily through the fame of many physicians and surgeons associated with it.Although in such a distin-guished line it is not easy to select names mention must be made of Sir Charles Sherring- ton a President of the Royal Society and Profes- sor of Physiology from 1895 to 1913; Sir Robert Jones who founded the School of Orthopaedic Surgery; Thurston Holland a pioneer in X-ray therapy; Sir Ronald Ross and Warrington Yorke who held the Chair of Tropical Medicine from 1902 to 1912 and from 1929 to 1942 respectively. The Faculty now has twelve full-time and four part-time Chairs and ten sub-Departments. It continues to attract the best students from this country and overseas. Although adequate Clini- cal facilities are provided by the local hospitals the non-clinical Departments were for many years overcrowded in old buildings in the quadrangle.This situation has now improved with the completion of the first stage of the new Medical School in Ashton Street. The School of Dental Surgery was founded as a dispensary in 1860 but did not fully merge with the Faculty until 1921. Under the successive direction of PrQfessors W. H. Gilmour 1920- 1935 and H. H. Stones 1935-1957 the Depart- ment became one of the leading schools in the country. In the study of Veterinary Science Liverpool has been a pioneer. A Chair was founded in the Faculty of Medicine in 1904 and ten years later a separate degree in Veterinary Science was insti- tuted.In 1950 this degree was the first to be recognised as carrying with it professional membership of the R.C.V.S. The school became a full Faculty in 1952 the first of its kind in the country and fittingly it will occupy a new building in 196 1. The Faculty of Law.-The Faculty owes its foundation in part to the legal profession in Liverpool and there have always been close ties between the two. There are two Chairs founded in 1894 and 1903 respectively. Great pride is taken in the fact that four of its former students are High Court Judges. Present Expansion and Future Problems.-As recently as 1944 the University Post-War Recon- struction Committee reported to the U.G.C. that it would be unwise to contemplate a permanent full-time population of more than 2,500 students a 25% increase over the 1938-1939 numbers.This decision was taken before the material needs of the present era had become apparent. Since that time increasing external pressures from the Government have been brought to bear on the Universities to increase their rate of expan- sion particularly in the pure and applied sciences where it is recommended that about two-thirds of the total increase should occur. The dramatic impact of these recommendations in Liverpool is indicated by the following illustra- tion in 1946 the decision was taken to expand to 3,000 students as soon as possible and to 3,500 within ten years. By 1957 an increase in size to 5,000 full-time students by the mid 1960’s had been decided and the new building pro- gramme was designed with this in mind.Thus in 1959 the University Development Committee reported that “5,000 is the optimum size in rela- tion to the accommodation we are planning; and if we should be tempted or persuaded to go permanently beyond it we could safely do so only on the basis of a fundamental and costly revision of our programme or by makeshift addi- tion of bits and pieces which would be the negation of sound planning.” Despite these fore- bodings the University decided in 1960 that an ultimate figure of 7,000 students would have to be accommodated to satisfy National require- ments. The effect of doubling the size of the University in a little over ten years raises many problems. It is obvious that the University will have to made rapid provision of large Halls of Residence to supplement the already inadequate residential accommodation.In an expanding University the sense of belonging to a single academic comA munity is hard to maintain. In Liverpool each freshman is assigned to a senior member of the University who is responsible for the general welfare and progress but not academic teaching of the student. This tutorial system should become of increasing value. The University is aware of the magnitude of the task it has undertaken. In facing the chal- lenge of the future it realises that as long as it resists all encroachments on its academic freedom it will maintain its responsibility to the country and what is more important to learning itself PROCEEDINGS COMMUNICATIONS The Reactions of Echitamine By A.J. BIRCH H. HODSON B. MOORE,and G. F. SMITH OF CHEMISTRY MANCHESTER, (DEPARTMENT THE UNIVERSITY 13) PREVIOUSLY~ we criticised the three formula currently double m.p. 156-159" and 185-187" containing an discussed2p3 for echitamine chloride. We concluded extra C-methyl group and giving an ON-diacetyl deri- that the partial structure (I) must be present and vative. In accord with structure (UI) for echitinolide this could have been expanded on biogenetic grounds 00-diacetylechitamine chloride gives on hydrogena- to several possible formul~~ for none of which was tion an amorphous diacetyldihydroechitamine conclusive proof available. In a recent important C26H3106N2, with the C02Me group intact.Further note2 proof of the presence of a grouping hydrogenation (total 2 mols.) produces a-,double HOCH2C.CO2Me was provided together with m.p. 120-1 24" 195-197" and p-dihydroechitinolide essentially correct explanations of some of the re- C21H2,N,0, double m.p. 92-97 1 12-1 17", O actions of echitamine. The structure (II) determined which are probably diastereoisomers due to produc- by Robertson and his co-workers4 and kindly com- tion of a new asymmetnc centre on hydrogenation municated before publication includes the elements of the double bond. The low reactivity of the lactone (0 and on its basis the chemical evidence avail- grouping in these compounds is readily explained by able can be rationa1i~ed.l~~~ Almost all the recent steric hindrance.'NW H (Vl I> R CO,Me (VI II) evidence has been published in preliminary com-The action of 2~-hydrochloric acid at 100" for munications often with incomplete description several hours on echitinolide produces isoechitinolide of compounds and reactions; many reactions have (IV) C2,H2,N20, m.p. 182-184" which has a also been independently duplicated or triplicated. hydroxyl group and a double bond less than We therefore consider reactions which we have our- echitinolide. Hofmann degradation of echitinolide selves carried out or for which convincing evidence methiodide results in fission to a Hofmann base-A is available; for historical aspects the references (amorphous) readily converted on alumina into an given should be consulted.isomeric base-B C2,H3,N20, m.p. 182-187". The Hydrogenation (1 mol.) of echitamine chloride (or nature of this change we cannot at present explain base) (2H) gives echitinolide (In),C21H2,N203 but the base-B has the properties of the expected Birch Hodson Moore Potts and Smith Tetrahedron Letters 1960 No. 19 36. Conroy Bernasconi Brook Ikan Kurtz and Robinson Tetrahedron Letters 1960 No. 6 1. Chakravarti Chakravarti Ghose and Robinson Tetrahedron Letters 1960 No. 10 10; No. 11 25; Chatterjee, Ghosal and Mujundar Chem. and Ind. 1960 265. * Cf. Hamilton Hamor Robertson and Sim Proc. Chern. SOC.,following Communication. Govindachari and Rajappa Chem. and Ind. 1959 1549; Proc. Chem. SOC.,1959 224; Birch Hodson and Smith Proc. Chern.SOC.,1959 224; Chatterjee and Ghosal Naturwus. 1960 47 234. The Pierhead Liverpool (By courtesy Alfred Holt and Co.) Liverpool Cathedral (By courtesy Elsam Mann and Cooper Ltd ) The University-Vic t or ia Bu i Id i ng (By courtesy The University) Staircase-Donnan Laboratories (By courtesy The University) James Muspratt’s Vauxhall Road Works Liverpool ca. 1830 (From a contemporary engraving in possession of Liverpool Public Libraries.) The tall wide-based chimney was before Gossage in 1836 invented the film absorption tower the means adopted for dispersing hydrochloric acid from the saltcake pots. The windmill shown had probably no connection with the alkali works. In the background a ship in full sail breasts the Mersey.FEBRUARY 1961 compound 0.Conversion of base-A or base-B into the methiodide and further Hofmann degradation gives de-N-echitinolide-A C20H23N0,(V1) (amor-phous) converted on alumina into de-N-echitinolide- B C,,H,,NO, m.p. 176-179”. The de-base-A con- tains NH and OH groups (3422,3609 cm.-’) but the latter has disappeared in de-base-B which is also obtainable by a similar sequence of degradations from isoechitinolide. It must therefore contain the pyran ring of (IV) and result from an unexpectedly ready ring-closure presumably due to the favourable stereochemistry. A similar series of reactions can be carried out with a-or p-dihydroechitinolide except that a de- base-B is not produced since the requisite double bond is not present.The echitinolide Hofmana base-B can be reduced as expected from the presence of an NCOH group- ing to the deoxy-base C2,H3,N,0, m.p. 192-1 97 ’. In 6~-acid this base shows benzenoid absorption in accord with the presence of a simple indoline ring. The ultraviolet spectra of the Hofmann bases and the de-N-bases show only slight or no shifts of the maxima at -240 and -300 mp on dissolution in acid as would be expected from the presence of an NC.0 grouping. The nature of echitamine base C22H,,N,0, is still not certain; it is probably (VU) although either of the alternative structures involving ether forma- tion between a hydroxyl group and the CH of the C=CCH,.N system is sterically possible The ultra- violet spectrum of the base does not however agree with the presence of an NC-N grouping.Re-forma- tion of the quaternary base could proceed through the indolenine formation of which is sterically feasible in this series but not with echitinolide (VIII) -+ (X) -+ (11). The alloechitamine of Conroy et aL2 obtained by the action of the t-butoxide anion contains an addi- tional carbonyl group (vmax. 1689 cm.-l) and could have structure (IX) produced by loss of formaldehyde and a double bond shift in (X). (Received November loth 1960.) The Structure of Echitamine T. A. HAMOR ROBERTSON, By Miss J. A. HAMILTON J. MONTEATH and G. A. SIM DEPARTMENT GLASGOW, (CHEMISTRY THEUNIVERSITY W.2) RECENTdiscussion concerning the alkaloid echit- amine has led to the formulation of several different structures (I,l II, In3).Early this year after discus- sion with Professor A.J. Birch who kindly supplied HO the materia,; we commenced an X-ray .,ivestigation of the structure of echitamine bromide crystals. In his letter to us of December 21st 1959 Professor Birch suggested another formula (IV) with the quali- fication that “the positions of the OH groups and C0,Me are probably right but not certain.” It will be apparent that this formula is very closely related to the true structure (V) whkh we have now deduced from the results of our X-ray investigation. HO Echitamine bromide recrystallised from water was obtained as orthorhombic crystals of the di-hydrate C,2H,,BrN,0,,2H,0 with a = 9.5 b = 41.65 c = 17.25 A space group P2,2,2 and four molecules in the unit cell.A study of the Patterson Conroy Bernasconi Brook Ikan Kurtz and K. W. Robinson Tetrahedron Letters 1960,No. 6 1. ’D. Chakravarti R. N. Chakravarti Ghose and Sir Robert Robinson Tetrahedron Letters 1960,No. 10 10; 1960 No. 11 25. Chatterjee Ghosal and Ghosh Majundar Ckm. und Id. 1960,265. vector maps indicated a y co-ordinate near zero for bromine. Hence with 2 Br at y -0 and 2 Br at y -4 a well-known ambiguity is likely to arise in the course of phase determination based on bromine. We are proceeding with this analysis but the work was temporarily abandoned while a search was made for a more promising derivative. On recrystallisation from methanol4 orthorhombic crystals of the methanol solvate C,,H,,BrN,O,,MeOH were obtained with a = 14-72,b = 14.17 c = 11-09 A space group P212121 and four molecules in the unit cell.Three-dimen- sional data were collected the intensities being estimated visually from several series of Weissenberg photographs taken about the principal axes with Cu-K radiation. In all 2115 structure factors were finally evaluated. Analysis of the vector maps gave the bromine co-ordinates and structure-factor calculations based on the bromine positions alone gave R = 41 %. Successive three-dimensional Fourier syntheses were then carried out with the inclusion of further atoms a FIG.I. The fourth three-dimensional electron-density distribution for echitamine bromide as superimposed sectionsparallel to (001).Contours are at unit intervals beginning at the 2e A-3 level. The bromide ion and methanol molecule which lie beyond the field of this diagram have been omitted. PROCEEDINGS 6 a RG.2. The arrangement of the atoms corresponding to Fig. 1. in the phasing calculations as they became clearly defined. The fourth synthesis is shown in Fig. 1 by means of superimposed contoured sections projected on (Ool) and an explanatory diagram showing the arrangement of the atoms is given in Fig. 2. The resulting structure is a compact three-dimensional one in which the two five-membered rings are fused cis. The 6-ring is in boat form with the hydroxyl and acetate groups equatorial. There also result two interlocking 7-rings one in boat form and an 8-ring.At this stage the value of R is 19.4% with all the atoms except those of the methanol molecule in- cluded in the phasing calculations. Further refine- ment is proceeding but the essential details of the structure now appear to be quite clearly established. The extensive numerical calculations involved were carried out on the Glasgow University Deuce computer by using the programmes originally devised by Dr. J. S. Rollett and we are indebted to the Director of the Computing Laboratory Dr. D. C. Gilles and his staff for facilities. (Received November 9th 1960.) Goodson and Henry J. 1925 1640; Goodson J. 1932,2626. Perfluoroalkylnitroso-compoundsfrom Perfluoroacyl Nitrites By R.E. BANKS and M. K. MCCREATH R. N. HASZELDINE (CHEMISTRY DEPARTMENT OF TECHNOLOGY, FACULTY UNIVERSITY OF M ANCHESTER) A CONTINUOUS process has been developed for the This process is less expensive and more convenient preparation of a perfluoroalkylnitroso-compound by than the original photochemical route :l pyrolysis of the corresponding acyl nitrite NOCl A 12 Hghv NO RF-CO2Ag -+ RF.CO-O*NO-+ RF-NO+ CO2 RF.CO,Ag -+ RF.~-+ RF. --+RF-NO (where RF = CF3 C,F, CaF, etc.) Barr and Haszeldina J. 1955 1881. FEBRUARY 1961 It was found earlier2 that trifluoronitrosomethane was obtained in low yield (16%) when the product from the reaction between dry silver trifluoroacetate and nitrosyl chloride at -10" was pyrolysed in situ and the formation of trifluoroacetyl nitrite as an intermediate was postulated -1 0" CF &O,Ag + NOCl-+ AgCl + CF,.CO.O-NO A __?t CFS-NO + CO More detailed examination of these reactions for the silver salts of trifluoroacetic and heptafluoro- butyric acid has enabled the stable acyl nitrites CF,.CO-O.NO (b.p.101 "/750 mm. dyl.607) and GF,-CO.O.NO (b.p. 38"/14 mm. dyl.717) to be isolated in almost quantitative yields. Controlled Haszeldine and Jander J. 1953 4172. pyrolysis of these acyl nitrites gives high yields of the corresponding nitroso-compounds. For example pyrolysis in vacuo of heptafluorobutyryl nitrite at 175O in a platinum tube (100 cm. x 1 cm. i.d. ;heated length 56 cm.) gave an 85% yield of heptafluoro- nitrosopropane (based on starting material con-sumed) with 35 % conversion into the nitroso-compound per pass.The considerable difference in boiling point between a perfluoroacyl nitrite and the corresponding nitroso-compound (CF,.NO b.p. -86.6"; C,F,-NO b.p. -9.7") facilitates the separation and re-cycling of unchanged starting material. One of us (M.K.M.) thanks The Council of The British Plastics Federation for the award of a Bowen Scholarship. (Received,January 16th 1961.) The Nature of Tertiary Arsine-Halogen Adducts By G. S. HARRIS (THEUNIVERSITY W.2) GLASGOW TERTIARY arsine dihalides R,AsHal, have been referred to as covalent1 and ionic2 compounds but no structural or conductance investigations appear to have been made to distinguish between the two possibilities.This communication reports the results of electrolytic-conductance studies of non-aqueous solutions of triphenylarsine dihalides. It is found that these compounds are readily soluble in methyl cyanide [dielectric constant 36.7 (25")J and yield solutions which are good electrolytic conductors. Typical values of molar conductance are (at 25O) Ph,AsCI :/1 = 11.0 ohm.-1cm.2mole-1 (Cm = 0.0016) Ph,AsBr :A = 12.7 ohm.-1cm.2mole-1 (Cm = 0.0364) Conductometric analyses of the systems Ph,As-Br and Ph3As-I (in methyl cyanide) also indicate the presence of conducting species. In the latter system the only detectable conducting species is Ph,AsI, which is in accord with the reported stability of the tetraiodide and instability of the di-i~dide.~ In the system Ph,As-Br the conductance-composition graph shows two distinct discontinuities correspond- ing with the formula Ph,AsBr and Ph,AsBr, this new tetrahalide was isolated from the methyl cyanide solution.It is a yellow hygroscopic solid (m.p. 89")and is hydrolytically unstable (Found C 34.9;H 2.8;Br 50.6. C,,H,,AsBr requires C 34.5; H 2.4;Br 51.1 %). Molar conductance values of the tetrahalides are considerably higher than those of the dihalides Ph,AsBr :Am = 104.2 ohm.-1cm.2mole-1 (Cm = 0.0269) Ph3As14 (1 = 100.4 ohm.-1cm.2mole-1 (cm = 0.0117) It seems reasonable to suggest that the ions in- volved are of the type Ph,AsHal+ Hal- for the 1 :1 adduct and Ph3AsHa1+ for the I2 adduct, and it is hoped to Col"lfiIl"fl this by transference experiments which Will be reported when this work is published in Preliminary studies of the CoflesPonding Phos-phorus ComPo~ds Ph3PHal2 indicate that they too behave as electrob tes in methy 1 cyanide.(Received,January 13th 1961.) Mann J. 1945 65. Rochocv Lewis and Hurd "The Chemistry of Organometallic Compounds," John Wiley & Sons Inc. New York 1957 p. 215. Newton Friend (ed.) "Text Book of Inorganic Chemistry," Grifk & Co. Ltd. London 1930 Vol. XI Part 2 p. 125. PROCEEDINGS Radicals in Irradiated Formates and Oxalates By J. A. BRIVATI and P. A. TREVALIAN N. KEEN,M. C. R. SYMONS (DEPARTMENT THEUNIVERSITY, OF CHEMISTRY LEICESTER) As part of a study of oxyanions of the nonmetals,1*2 we have exposed various ionic formates and oxalates to y-rays from a 13'Cs source in an attempt to form and trap the radical-ion CO,-.This ion should have fair stability because it is isoelectronic with nitrogen .dioxide. Because of the mobility of hydrogen atoms in crystals and hence the chance of avoiding cage reactions we have concentrated primarily on for- mates for which the simplest sequence of reactions .to give C0,-would be H.COa-+ h~ -t He + COa-H-+ H*CO,-+ Ha + COB-It seemed possible that on irradiation oxalates would also form C0,-through breaking of the ?carbon-carbon bond but since C0,-is unlikely to be mobile the yield of radicals should be far smaller and if trapping occurs in pairs there might be specific magnetic effects between the partners of each pair.3 By analogy with the electron-spin resonance -spectrum of nitrogen dioxide we expected to be able to detect at room temperature a single nearly iso- tropic band with g-tensors equal to or slightly less than the free-spin value of 2.0023.(In addition if dhe concentration of radicals were sufficiently large a doublet from 13C0,-should be found having a very large almost isotropic hyperfine splitting "constant.) These expectations were fulfilled for poly- crystalline lithium formate the single line having a width between points of maximum slope of 14 gauss and a g-value of 2.0001. Spectra for ammonium and magnesium formate were similar except for a slight broadening on the high-field side.Unfortunately the signal-to-noise ratio did not permit detection of any doublet from 13C0,-. Spectra from irradiated calcium barium zinc and cadmium formate were complex and not readily interpretable although the general patterns were remarkably similar for all these salts. It appears that more than one radical is involved and it is hoped that present work on single crystals will contribute to our understanding of these results. The purpose of this Note is to call attention to some remarkable results for sodium and potassium formate. From the powders four lines of equal spacing and intensity but with broadening on the lMcLachlan Symons and Townsend J. 1959 952 Clark Horsfield and Symons J. 1961 7. Svmons. J.. 1959. 277. high-field side were obtained.Single crystals of sodium formate gave spectra comprising four well- resolved symmetrical lines with a splitting between any pair of lines ranging from 7.3 to 9.5 gauss in the manner expected for axially symmetrical radicals. The g-value varied in a more complex manner between 1,997 and 2.0025. The only reasonable ex- planation is that these quartets are hyperfine structures resulting from interaction between the unpaired electrons and the cation nuclei both of which have spins of 2. The results are compatible with the concept that C0,-radicals are formed (the g-value variations being a property of these radicals) in such a way that weak bonding occurs between the central carbon and one specific alkali-metal cation.If this is correct these results are novel in that previous studies on damaged ionic crystals have not shown specific interactions with individual cations. Adam and Wei~sman,~ however detected a similar quartet in the electron-spin resonance spxtrum of solutions of the sodium ketyl of benzophenone. Since the hyperfine splitting is so nearly isotropic we could postulate partial transfer of an electron from C0,-into the outer s-level of the cation. Using this approximation and the values of 317 and 82 gauss for the splitting to be expected for sodium and potassium atoms respectively we find that the un- paired electron is about 3% transferred to Na+ and 7% to K+. Thus the interaction increases with increase in the polarisability of the cation rather than its electron-affinity and lack of hyperfine splitting from lithium ions is in accord with this conclusion.However the slight anisotropy in hyperfine splitting means that there is some p-character in the orbital on the cations which would be expected if there is some specific covalent bonding between the cations and carbon. Spectra of irradiated oxalates were similar to the corresponding formates except that in no instance did we observe a quartet of lines such as those from sodium and potassium formate. The intensities for given periods of irradiation were far less than for corresponding formates and even after prolonged irradiation barium oxa-late showed no resonance absorption. Single crystals of ammonium oxalate gave a well-resolved triplet in certain orientations Ard J.Chem. Phys. 1955,23 1967. Adam and Weissman J. Amer. Gem. Soc. 1958,80 1518. FEBRUARY 1961 which is probably a hyperfine splitting from 14N this result will be discussed in detail elsewhere. In general two broad bands have been detected in the ultraviolet spectra of irradiated formates as measured by diffuse reflectance methods with maxima at about 350 and 270 mp. The low-energy band was not found for irradiated oxalates which could not be studied in the 270 mp region. The first absorption bands of NO are at considerably longer wavelengths; so if this absorption is a property of C0,-ions it seems likely that the transitions involve charge-transfer from oxygen towards nitrogen and carbon respectively.Our thanks are offered to Southampton Univer- sity and to Esso Petroleum Co.for grants (to J.A.B. and N.K.) and to the Department of Radiotherapy Royal Southants Hospital for use of their y-ray source. (Received November 25th 1960.) Carbonylation of Platinum and Palladium Organo-complexes By G. BOOTH and J. CHATT CHEMICAL LIMITED, (IMPERIAL INDUSTRIES AKERSRESEARCHLABORATORIES THE FRYTHE HERTS.) WELWYN OURknowledge of carbonylation has been consider- ably advanced by the discovery that carbon monoxide can be reversibly inserted between an alkyl or aryl group and a transition metal in organometallic carbonyls,lS2 for example co [MnR(CO),] + [Mn(COR)(CO),] Heat It has also been shown that the carbonyl portion of the acyl group is derived from the co-ordination sphere of the metal and not directIy from the gas phase.3 It was of interest therefore to see whether the tertiary phosphine complexes trans- [MXR(PEt,),] (M = Pd4 or Pt;5 X = C1 Br or I; R = alkyl or aryl) could be carbonylated although they contain no carbon monoxide.We find that carbonylation proceeds readily for the palladium compounds at atmospheric pressure and temperature and for the platinum compounds at 90"/50-100 atm. Typical acyl compounds ob- tained are listed in the Table. They form colourless to pale yellow crystals; those of platinum are rather more stable than those of palladium. They are all of trans-configuration as shown by their dipole moments tp) and have very strong sharp carbonyl stretching bands (vco) in the 1600-1700 cm.-l region.The halogen in the acyl derivatives is readily replaced by other anions and under the action of heat trans- [PtI(COMe)(PEt,),] reverts to the original methyl complex. The dialkyl and diary1 complexes [MR,(PEt,) J are also carbonylated but give less tractable products ; trans- [PtMe,(PEt,),] gave an unstable platinum carbonyl derivative and diacetyl (COMe),. The similar organo-nickel6 and -cobalt* aryl complexes undergo the same type of reaction and these are at present under investigation. It seems highly probable that these reactions occur through 5- or 6-co-ordinated intermediates. This would explain the greater reactivity of the palladium compounds since palladium is known to expand its co-ordination shell more readily than platinum.Attempts to prepare stable carbonyl complexes of the type [MX,(CO),(PEt,),] (M = Pt Pd or Ni) were not successful but we have obtained crystalline cobalt compounds [CoX,(CO)(PEt,),] and the cor- responding nitrosyls [CoX,(NO)(PEt,),]. Similar transient 5-co-ordinated carbonyl complexes might well be intermediates in the carbonylation of the platinum and palladium compounds. Acyl complexes trans- [MX(COR)CPEt,) J M.p. (c) PdCl(COMe)(PEt,) 65-67' PdBr(COMe)(PEt,) 50-52 PdItCO Me) (PEt3) 75-77 PtCl(COMe)(PEt,) 70-71 PtBr(COMe)(PEt,) 65-66 Ptl(COMe)(PEt,) 86-87 PtCI(COPh)(PEt,) 87-89 P* vcot (AO-2~) (cm.-l) 3.5 1665 -1667 -1668 2.55 1629 -1630 3.15 1635 2.8 1610 PtBr(COPh)(PEt,) 108-1 10 -1613 Ptl(COPh)(PEt,) 144-146 3.6 1613 * In benzene.t In CC14. (Received December 29th 1960.) Coffield Kozikowski and Closson J. Org. Chem. 1957 22 598. Breslow and Heck Chem. and Id. 1960,467; Heck and Breslow J. Amer. Chem. Soc. 1960,82,4438. Coffield Kozikowski and Closson Interna t. Conf. Co-ordination Chem. London 1959 Chem. SOC.Special Publ. No. 13 p. 126. Calvin and Coates J. 1960 2008. Chatt and Shaw J. 1959 705; 4020. Chatt and Shaw Chem. and Ind. 1959,675; J. 1960 1718. PROCEEDINGS The Reaction of Ethyl Radicals with Isopropyl Radicals By J. C. J. THYNNE (DEPARTMENT UNIVERSTY AT Los ANGELES, OF CHEMISTRY OF CALIFORNIA Los ANGELES U.S.A.’) 24 CALIFORNIA IT is not always feasible to study the disproportiona- tion and combination of higher alkyl radicals simply by photolysing mixtures of the appropriate ketones because of the occurrence of an intramolecular reaction leading to an olefin and lower ketone when the original ketone contains a-hydrogen atoms.Eg. for dipropyl ketone1 the two major primary reactions are C,H,-CO.C,H 3 2C,H7-+ CO . . . (la) -+ C2H + CHS-CO*C,H7 . . . (lb) However diethyl ketone2 and di-isopropyl ketone3 are excellent sources of ethyl and isopropyl radicals respectively;in addition their behaviour on photoly- sis is considered to be well understood. By photolys- ing at > 3000 A a mixture of diethyl and di-iso- propyl ketone each at pressures of about 50 mm.at temperatures from 34-1 50° the cross-combination and disproportionation of ethyl and isopropyl radicals have been studied. Three reactions are then possible C2HBm + C.3H7* C2H + C3H6 . . . (2) k* -+ C2H* + CSH . . (3) k3 -+ CiiHI . . . (4) k4 All three reactions were observed reactions (2) and (4) taking place to the greatest extent. The ratio of disproportionation to combination (k,/k = d) ranged from 0.60 at 34” to 0.81 at 144”. This is not in accord with expectation for with the possible ex- ception of butyl all reported values6 for these ratios have been independent of temperature. However photolysis sometimes lead to the produc- tion of “hot” radicals so it was desirable to compare the results of the reaction between possibly photo- lytically “hot” radicals with those obtained when one set of radicals is thermally equilibrated; for this another source of isopropyl radicals was chosen namely the decomposition of isopropyl formate sensitised by ethyl radicals; the same temperature range and similar reactant pressures were used.Diethyl ketone was again used as the ethyl-radical source at > 3000 8 where the formate is not photolysed. The major reactions (together with 2 3 and 4) are (5-1 1). All these products were found on CZH,. + H.C02-CaH7+ CZH + .CO,.C,H . (5) k C02C3H,+C0,+ C,H,* . . . . (6) k C,H,-+ H*C02C3H,-+ C,H + *C02*C3H7 . . m ZC,H,* 3 C2H4 + CSH * * (8) 3 C4Hm ... (9) 2C,H,* -+ C,H + C3H . . . (10) C6HlP .. . (11) analysis by gas chromatography dimerisation of the isopropyl radical producing 2,3-dimethylbutane. In this case k,lk = 0.43 0.03 and did not vary with temperature. This value can be compared with values of 0-14 for ethyl-ethyl,7 0.21 for methyl-iso- propyl,* and 0.63 for isopropyl-i~opropyl,~ none of which is temperature-dependent. The only direct comparison that can be made with k2/k comes from the work of Boddy and Robb,lo who used the mercury-photosensitised addition of hydro- gen atoms to mixed okfins to produce the appropri- ate radicals and so obtained values of 0.3 for k21k and 0.67 for k,/k,. In the work reported here when the ethylene produced by reaction (3) was measured a value of 0-15 was obtained for k,/k,.This is con- siderably lower than Boddy and Robb’s value but nevertheless is reasonable since it might be thought that an ethyl radical would be several times more likely to abstract a hydrogen atom from an iso- propyl radical than an isopropyl radical would abstract one from an ethyl radical. The discrepancy in the values of k,/k obtained on use of different sources of isopropyl radicals is curious. If it is assumed that the value 0.43 represents the actual value of A it appears that propene is produced by some other reaction possibly -f RH + .C,H6CO*C3H, R-+ C3H7-CO*C3H7 *C,H6*COC,H7-+ C,H + *CO*C,H7 * Present address Department of Chemistry The University Leeds 2. Masson J. Amer. Chem. Soc. 1952 74 4731. Kutschke Wijnen and Steacie J.AmPr. Chem. Soc. 1952 74 714. Heller and Gordon J. Phys. Chem. 1956 60 1315. Kerr and Trotman-Dickenson J. 1960 1602. Thynne Proc. Chem. SOC.,1961 18. t~ Trotman-Dickenson Ann. Reports 1959,55 36. James and Steacie Proc. Roy. SOC.,1958 A 244 289. Kerr and Trotman-Dickenson J. 1960 1609. Heller and Gordon J. Phys. Chem. 1958,62 709. lo Boddy and Robb Proc. Roy. Soc. 1959 A 249 518. FEBRUARY 1961 though using Heller and Gordon's results3 for the photolysis of di-isopropyl ketone for calculation of the possible yield of propene from such an abstrac- tion does little to reconcile the values. Although as shown by reactions (la and b) dipropyl ketone does not only yield propyl radicals when photolysed it was considered interesting to compare the value of d obtained for ethyl and propyl radicals produced by mixed ketone photolysis with the value obtained by using the decomposition of propyl formate as above.Only one experiment was carried out on each system and values of k,/k4 at 117" of 0.21 and 0-14 were obtained from the ketone and formate respectively. Substantially the same behaviour has been noted for butyl radicals. Thus it appears that the value of the disproportionation ratio obtained from purely photochemically pro- duced radicals is often higher than that observed when some of the radicals are generated in a state of thermal equilibrium. I thank Professor F. E. Blacet for helpful advice. (Received December 8th 1960.) Fluorocarbon Derivatives of the Metal Carbonyls By R.B. KING P. M. TREICHEL, and F. G. A. STONE (DEPARTMENT HARVARD CAMBRIDGE, OF CHEMISTRY UNIVERSITY MASS.) NEW fluorocarbon derivatives of cobalt iron manganese and molybdenum are now reported as examples of recently prepared transition-metal derivatives of this class. Reactions bet ween cyclopen tadienylcobal t dioar- bony1 and perfluoroalkyl iodides afford black com- pounds of the type C,H,Co(CO)R,I (e.g.,R,= C3F,). Perfluoroalkyl iodides and iron pentacarbonyl are known1 to give perfluoroalkyliron tetracarbonyl iodides; other examples of the similarity between cyclopentadienylcobalt dicarbonyl and iron penta- carbonyl will be described later. Tetrafluoroethylene and iron pentacarbonyl give the iron heterocyclic compound [CF,] >Fe(CO),.' This suggests that bis(perfluoroalky1)iron tetra- carbonyl compounds should exist.An obvious route to such compounds would involve treatment of disodium tetracarbonylferrate (-II)with perfluor-oacyi halides followed by decarbonylation of the per- fluoroacyliron tetracarbonyl derivatives in a manner analogous to that used to prepare perfluoroalkyl- manganese pentacarbonyls.2 However the tetra-carbonylferrate(+I) anion has been previously reported only in the unsuitable media liquid am- monia or water; it has now been prepared in ethereal solution. With perfluoroacyl halides it yields bis(perfluoroalky1)iron tetracarbonyls directly since the intermediate perfluoroacyliron compounds are unstable. An example of a compound thus made is (C,F,),Fe(CO), m.p.61-63". Bis(perfluoro-alky1)iron tetracarbonyls are stable to air and highly volatile. Above 100" in vacuo they decompose to carbon monoxide and fluoro-olefins; thus the com- pound (C,F,)2Fe(C0)4 affords perfluoro-but-Zene and -but-1-ene. Peduoroallyl chloride and C,H,-Fe(C0) ,Na yield the compound C,H,.Fe(CO),C,F (m.p. 70"). Infrared and fluorine-1 9 nuclear magnetic resonance studies however have established that the C3F5 moiety a-bonded to iron is a perfluoropropenyl group and not a perfluoroallyl group as might be expected. The course of this reaction is thus similar to that between perfluoroallyl chloride and the salt sodium pentacarbonylmanganate( -I) which gives a-perfluoropropenylmanganesepentacarbonyl.2 A reaction which can lead to a variety of fluoro-carbon-metal derivatives is the hydrometallation of fluoro-olefins.Manganese carbonyl hydride adds to tetrafluoroethyltne to afford the pale-yellow com- pound HCF,CF,.Mn(CO) (m.p. 30.5-3 1 -5O) which with bromine forms l-bromo-l,1,2,2-tetra- fluoroethane quantitatively. Cyclopentadienylmolyb- denum tricarbonyl hydride and tetrafluoroethylene form yellow-orange C,H,.Mo(CO),CF,-CF,H (m.p. 53-54'). For the two compounds derived from tetra- fluoroethylene the infrared spectra and the observed chemical shifts and fine structure in the nuclear mag- netic resonance spectra are in accord with the struc- tures suggested. Thus the fluorine nuclear magnetic resonance spectrum* of HCF,-CF,-Mn(CO) con-sisted of peaks of equal intensity at 63.8 and 122.8 (doublet) p.p.m.The proton spectrum was weak not unexpectedly because of the small percentage (0.3%) of hydrogen in the compound. However the pattern centred at 5.3 p.p.m. is consistent with the fluorine spectrum on the basis of the proposed structure. The Manuel Stafford and Stone J. Arner. Chem. Soc. 1961 83 249. Kaesz King and Stone 2. Naturforsch. 1960 156 in the press. * Fluorine nuclear magnetic resonance spectra were recorded at 56.4 Mc,and chemical shifts are given relative to trichlorofluoromethane. Proton spectra were recorded at 60Mc and chemical shifts are given down-field relative to tetramethylsilane. infrared spectrum of HCF,-CF,.Mn(CO) (carbon disulphide solution sodium chloride optics) shows a single C-H stretching band at 2930 cm.-l carbonyl bands at 2035 (s) 2015 (s) and 1972 (w) cm.-l and strong bands in the C-F stretching region at 1352 1093,1080,1012,and 991 cm.-l PROCEEDINGS We thank the National Science Foundation for the award of predoctoral fellowships (to R.B.K.and P.M.T.) and the United States Air Force for support of part of the work described. (Received January 3rd 1961.) A Study by Electron-spin Resonance of the Adsorption of Hydrocarbons on a Silica-Alumina Catalyst By J. J. ROONEY and R. C. PINK OF CHEMISTRY UNIVERSITY (DEPARTMENT THEQUEEN'S OF BELFAST) SPECTROPHOTOMETRIC technique has recently been successfully applied to the investigation of the ad- sorption of several types of hydrocarbon on silica- alumina cracking catalysts.Leftin and Hall1 have shown by this technique that triphenylmethane and related hydrocarbons are adsorbed as carbonium ions at Lewis acid sites on the catalyst surface while with diphenylethylene but-2-ene and ethylene two different species can be distinguished one probably a carbonium ion the other believed to be a charge- transfer complex formed by adsorption of the olefin activated at 100" were ineffective in producing radicals and active catalyst exposed to the atmos- phere lost its activity. No electron-spin resonance absorption was observed with the catalyst alone or with the catalyst-solvent systems or when chloro- form or dioxan was used as solvent for the poly- nuclear hydrocarbons.Radical formation was not detected at room temperature with olefins or triphenyImethane. Well-resolved spectra were obtained with anthra- cene (Fig. a) and perylene (Fig. c) and a partially 10GAUSS (a) Anthracene ahorbed from carbon disulphide. (b) Anthracene in 98 % H2S04. at a non-acidic site.2 A suggestion in the case of di-phenylethylene that the charge-transfer complex on the hydrated catalyst might be a positive radical ion was not confirmed by electron-spin resonance meas~rements.~ The present report describes the application of the electron-spin resonance technique to the study of the adsorption of a variety of hydro- carbons by activated silica-alumina. Strong electron-spin resonance signals were ob- tained when a number of polynuclear aromatic hydrocarbons were adsorbed from hexane or carbon disulphide on catalyst activated by being heated in air to 500".Hydrated catalyst or catalyst samples (c) Perylene adsorbed from carbon disulphide.(d)Perylene in 98% H,SO,. resolved spectrum with naphthalene. From dilute solutions adsorption of the hydrocarbon and con- version into the radical form appeared to be com- plete. Further addition of hydrocarbon resulted in saturation which for a particular catalyst sample occurred when the radical concentration had reached 6 x 10'' radicals per gram of catalyst cor- responding to -2 x loll active sites per cm.2 of catalyst surface. For a similar type of catalyst Leftin and Hall1 estimated the number of active sites to be 5 x 10l2 per cm.2 Addition of water to catalyst-hydrocarbon systems resulted in rapid decay of the electron-spin resonance signal which Leftin and Hall Reprint 65 Section 11 Second Internat.Congr. Catalysis July 1960. Webb Reprint 62 Section 11 Second Internat. Congr. Catalysis July 1960. Leftin and Hall J. Phys. Chem. 1960 64 383. FEBRUARY 1961 was only partly restored by drying at 100". Strong signals were also obtained when the hydrocarbons were warmed directly with the catalyst. The main result of this investigation is to show that certain polynuclear hydrocarbons are converted into a free-radical form when adsorbed on the surface of a strongly dehydrated silica-alumina catalyst.Radical formation with this type of hydrocarbon was suggested by Roberts Barter and Stone4 from a study of the oxidation of adsorbed anthracene in contrast to the accepted mechanism5 involving proton addition to the aromatic ring system. Comparison of the spectra of adsorbed anthracene and perylene with spectra obtained under identical instrumental conditions with the hydrocarbons in 98 % sulphuric acid (Figs. b and d) leaves no doubt that the radical species in the two cases are similar although the electron distribution in the adsorbed species par- ticularly in the case of anthracene may not be identical with that of the radical in acid solution. In view of this similarity the radical on the catalyst surface is formulated as a positive radical ion result- ing from the transfer of a single electron from the aromatic molecule to a positive hole in the surface probably located at a Lewis acid site.6 It is significant that the colour of the adsorbed species was found with each hydrocarbon to be identical with that of the corresponding sulphuric acid solution.The poorer resolution of the electron-spin resonance spectra in the case of the adsonbed species may be due to dipolar interaction between radicals on closely neighbouring sites on the catalyst surface. This is under further investigation. It seems likely that free radicals of the nature described may play an important part in many reactions of aromatic hydrocarbons under cracking conditions including disproportionation methyl shift and condensation.Catalyst samples coked during a cracking reaction did in fact give electron- spin resonance signals and it is probable therefore that oxidative regeneration of catalyst takes place by a radical mechanism. Electron-spin resonance measurements were made with a spectrometer operating at 9370 Mc./sec. and a magnetic field modulated at 100 Kc./sec. The authors thank Mr. R. K. Quigg for skilled assistance with the electronic instrumentation. (Received December 19th 1960.) Roberts Barter and Stone J. Phys. Chem. 1959 63 2077. Voge "Catalysis," Vol. VI Reinhold Publ. Corp. New York 1958 p. 453. Carrington Dravnieks and Symons J. 1959 947. Electron-spin Resonance Investigation of Trapped Hydrocarh-sulphonyl Radicals By P.B. AYSCOUGH, K. J. IVIN,and J. H. O'DONNELL (DEPARTMENT OF PHYSICAL CHEMISTRY UNIvERSfTY OF LEEDS) A RECENT investigation' has shown that the equi- librium constant for the reaction at room temperature should be of the order of lo1* atm.-I. Although there is considerable evidence for the addition of sulphur dioxide to alkyl radicals in the liquid phase to our knowledge there is so far none for its occurrence in the gas phase at room temperature. We have now demonstrated that it is possible to establish a heterogeneous equilibrium in which gaseous sulphur dioxide adds to trapped hydrocarbon polymer radicals. This equilibrium is set up rapidly and reversibly and at room temperature the equilibrium lies well to the side of the product radicals.Trapped hydrocarbon polymer radicals were pro- duced by irradiating degassed polypropene at -196" with 6oCo y-rays (2 hr. at ev mL-l min.-I). The polymer was kept at -196" and examined 1 hour later in a Varian E.S.R. spectrometer. A symmetrical line about 2 gauss wide was at first superimposed on that shown in Fig. l(a) but it decayed slowly and after about 12 hours only the spectrum shown in Fig. l(a) remained. This appears to consist of 8 lines and probably arises from -CH,-C(CH,)-CH,-radicals.2 Adding sulphur dioxide to the polymer and warming it to room temperature led at once to the narrow asymmetric signal shown in Fig. l(b).* (The spectra drawn indicate correct relative heights and widths and are centred on g x 2; exact g-values were not determined.) Keeping the polymer in a vacuum for 5 minutes at room temperature had no noticeable effect on the spectrum but evacuation for 15 minutes at 50" reduced the signal by a factor of 10.Further addition of gaseous sulphur dioxide immediately doubled the signal. This experiment indicates the reversibility of the reaction but that heating to 50" reduces the overall radical concentration. A similar reversible effect was observed at room temperature after 15 hours' evacuation. * This effect has been reported independently by Kurl et aLs Busfield Ivin Mackle and O'Hare Trans. Faraday Suc. in the press. Cf. Lawton Powell and Balwit J. Polymer Sci. 1958 32 257. Kuri Ueda and Shida J. Chem. Phys. 1960 32 371.The spectrum shown in Fig. l(b) is attributed to RSO,. radicals with the free electron largely on the sulphur atom. Its asymmetry indicates an anisotropic g-factor which may be associated as in the case of the RO,. radical with incomplete quenching of the FIG. 1. Derivative E.S.R. spectrum of y-irradiated polypropene (a) at -196” after 12 hr.; (b) at 20” after addition of SO,. orbital angular rn~mentum.~ The spectrum was not changed when the sample was exposed to air. R02. gives a much broader asymmetrical signal than RSO,. so that we conclude that oxygen neither adds to RSO,. nor displaces the sulphur dioxide at room temperature. Conversely it was found that sulphur dioxide neither adds to RO,. nor displaces the oxygen at room temperature.PROCEEDINGS ated at -196” in the hope of producing trapped (I) [-SO,-CH,.CMe,-] [-SO,.CHa*CH Et-fn (11) RSO,. radicals directly. However broad sym-metrical spectra such as that shown in Fig. 2 (a) were obtained which presumably result from trapped hydrocarbon-type radicals. When the samples were warmed to room temperature the spectrum changed to that shown in Fig. 2 (b) identical in form with 0 (b) i i I1 I -FIG. 2. Derivative E.S.R. spectrum of y-irradiated “but-1 -ene polysulplzone” (a) at -196”; (b) after warming to 20”. Fig. 1 (b) and attributed to RS02*radicals. This spectrum was stable for several weeks and unchanged at -196”. Speculation on the nature and reactions of the hydrocarbon radicals initially produced will be deferred until other reIated polysulphones have been examined.It appears that there is little or no homolysis of C-S bonds at -196” and that the RSO,. radicals are formed in secondary processes. We are indebted to Professor R. S. Dainton F.R.S. for permission to use the 2000 Curie 6oCo source presented to him by the Rockefeller Founda- tion. Degassed powdered “isobutene polysulphone” (I) and “but-1 -ene polysulphone” (11) were also irradi- (Received January 6th 1961 .) Abraham and Whiffen Trans. Faraday Soc. 1958,54 1291. Hydride-ion Substitution in Metal Complexes By G. WILKINSON CHEMISTRY LABORATORLES COLLEGE, (INORGANIC RESEARCH IMPERIAL LONDON,S.W.7) IF an aqueous solution of the yellow trans(or cis)-isomer of bisethylenediaminedichlororhodium(III) chloride1 is carefully treated at 0” with aqueous sodium borohydride there is effervescence and development of a pale brown colour.The brown species which is destroyed by air and deposits the metal on warming is not obtained with reducing agents such a dithionate hydrazine hypophosphite or molecular hydrogen in weakly acid neutral or basic solution. The solution shows a strong proton resonance absorption in the region associated with hydrogen atoms bound to transition metal atoms2 at 22.2 p.p.m. on the high-field side of the methyl line of an internal t-butyl alcohol reference (correspond- ing to r % 31). The line is a sharp doublet splitting 31 & 1 cycle/sec. owing to interaction with the lMRh spin confirming the presence of a Rh-H bond; the ethylenediamine lines are similar to those in the dichloro-complex Like the latter the brown species gives precipitates with Reinecke’s salt and with tetra- phenylborate ion.The tetraphenylborate in a Nujol mull shows a band in the infrared spectrum at Anderson and Basolo J Amer. Chem. SOC.,1960 82,4423. a For references see Green Angew. Chem. 1960 72 719. FEBRUARY 1961 73 2100 cm.-l and in acetone solution a high-field proton The aminerhodium hydride species are noteworthy resonance line as before. since with the exception of the hydridorhenium ion3 The interaction of [Rh en2Cl2]+ with borohydride all other complexes containing a transition-metal-to- ion thus appears to involve displacement of chloride hydrogen bond have also present n-bonding ligands by the highly nucleophilic hydride ion such as CO,n-C,H, R2S,R3P etc.although there is kinetic evidence4 for the transient existence of metal- [Rhllien,Cl,]+ + H-(BH,)= [Rhlllen,CIH]+ + CI-(++B,H,) to-hydrogen bonds in other cases. It now seems The interaction of borohydride with [Rh(NH,),Cl]+ possible that the 2,2’-bipyridylrhodium complexes also gives a brown solution but owing to the low prepared by using borohydride5 are hydrido-solubility of the pentammine salts and the very ready complexes and a search is being made for other conversion here into the metal no proton resonance hydride complex species with ligands of low n-bond- line could be detected; no line was detected when ing capacity.trans-[Co en,Cl,]+ was used. Since hydridic species are produced from halides such as (Pr3P),PtC12 and The author thanks Dr. L. Pratt for assistance with (Pr,P),NiCl by the action of borohydride these nuclear magnetic resonance measurements. reactions also must be considered as replacements. (Received,January 5th 1961.) Colton Dalziel Griffith and Wilkinson Nature 1959 183,1755; Ginsberg Miller Cavanaugh and Dailey Nature, 1960 185 528 Floss and Grosse J. Znorg. Nuclear CEem. 1960 16 36. See for example Halpern Czapski Jortner and Stein Nature 1960 186 629. Martin and Waind Proc. Chem. SOC. 1958 169; J. 1958 4284. The Structure of Dimeric Acetic Acid in Aqueous Solution By D. L. MARTIN and F. J. C. ROSSOTTI DEPARTMENT OF CHEMISTRY UNIVERSITY OF EDINBURGH) we have now THE existence of the hydrogen diacetate ion HA,-in In collaboration with Dr.S~hlyter,~ aqueous solution was suggested in 1930 by Dawson confirmed our description of proton-acetate catena- and Spiveyl in order to explain an unexpected cross- tion by a method of enthalpy titration5 at 25”’ using term [HA][A] in the expression for the rate of the Stockholm adiabatic calorimeter. Enthalpies4 and iodination of acetone in acetate buffers2 Preliminary entropies of association have been calculated and 0 thermodynamic functions for the relevant reactions R*C are listed in the annexed Table. O-H.-. O+ O-H-O C-R R-CO C-R Comparison of these values suggests that reactions (I H-0’ ‘0-H..,.o” (Dl (1) and (2) are strictly analogous and that the latter reports have been given3 of potentiometric evidence is not a cyclisation.This conclusion is reinforced by for this species and also for the neutral dimer H2A2 comparing the thermodynamic functions for re-together with formation constants valid in a 3M-actions (3) and (4). It is also noteworthy that AS and sodium (perchlorate) ionic medium at 25”. As the AS approximate to the value required by Pitzer’s. Reaction dG (kcal./mole) AH (kcal./mole) AS (e.u.) (1) H++A-+HA -6839 f0.012 -0.721 f0.006 20.53 f0.06 (2) H+ + HA,-+ H2A2 -6.315 f0.014 -0.596 f0.135 19.2 f0.5 (3) HA + A-+ HA2-0.46 f0.04 0.300 f0,106 -0.5 f0.5 (4) HA + HA + H2Az 1-00 f0-04 0.425 0.047 -1.9 f0.3 dimer proved to be a stronger acid than the monomer rule6 for monobasic acids in spite of the unconven- it was suggested that the dimer exists predominantly tional standard state.’ in the open (I) rather than in the cyclic form (LI).If the neutral dimer exists in the extended form (I) Dawson and Spivey J, 1930 2180. ’Cf. Rossotti. Nature 1960 188 936. * Martin and Rossotti Proc. Chem. SOC.,1959 60; Chem. SOC. Special Publ. No. 13 1959 p. 182. Schlyter and Martin Kgl. Tekn. Higskolans Handl. in the press. Schlyter Kgl. Tekn. Hogskolans Handl. 1959 no. 132; 1960 no. 152; Schlyter and SillCn Acta Chem. Scand. 1959 13 385. Pitzer J. Amer. Chem. SOC. 1937 59 2365. ’Cf. Rossotti in “Modern Co-ordination Chemistry,’’ ed. Lewis and Wilkins Interscience Publ. Inc. New York 1960. like the ion HA,- then the follawing approximate relationship might be expected between the partial molar entropies SoHoAL -SOHA SOHA -so (5) whence AS x AS,.(6) If we calculate the conventional partial molar entropies from Cobble's empirical equations for neutral and ionic organic solutes,8 the approximate eqns. (5) and (6) are exact and equal to 22 e.u. How- ever reactions (1) and (2) will be accompanied by an increase in the configurational entropy of the organic solutes and a release of water from the hydration spheres of the ionic reactants. The former effect will be expected to be more marked for reaction (2) whereas the latter effect should be less pronounced for reaction (2) owing to hydrogen-bonding of water to the centre of the dimer.Our experimental result AS > AS,,appears to be significant and indeed some analogous reactions suggest that the dehydra- tion factor is the more important of the two. The .entropies of protonation AS, of monomeric .acetate,9 b~tyrate,~ and methoxyacetate'O ions are * Cobble. J. Chem. Phvs.. 1953. 21. 1451. PROCEEDINGS 22.0 24.5 and 19-6 e.u. respectively in the conven- tional standard state. The increase in AS with in- creasing chain length has been ascribed to the con- figurational effect,ll and the lower value of AS in the methoxyacetate system to the dehydration effect.1° It is difficult to predict a value of AS for the formation of a cyclic dimer (II) by reaction (2) owing to the impossibility of assessing differences in hydration between molecules (I) and (II).However as SoHAO is 16.7 e.u.and the entropy of cyclisation about -14e.u. AS would probably be greater than AS,. It therefore appears to be most likely that dimeric acetic acid exists predominantly in the open form (I) in aqueous sdution. We thank the D.S.I.R. and the Post-graduate Studentship Committee of Edinburgh University for financial assistance and Dr. K. Schlyter and Professor L. G. Sillen for their help with the calorimetry. (Received,December 9th 1960.) Canady Papke and-h'idler 'Tr& Faraday SOC.,1958 54 502. lo King J. Amer. Chem. SOC.,1960 82 3575. Evans and Hamann Trans. Faraday Sac. 1951 47 34. The Synthesis of (&)-Cuparetie By W. PARKER and R. A. RAPHAEL R. RAMAGE (CHEMISTRY DEPARTMENT w.2) THEUNIVERSITY GLASGOW THErecent report1 of the conversion of (+)-camphonanic acid into cuparene prompts us to describe our total synthesis of this sesquiterpeneZ (I; R = Me).Condensation of 3-methylcyclohex-2-enone with toluene in the presence of aluminium chloride gave 3-methyl-3-p-tolylcyclohexanonewhich readily fur- nished a monofurfurylidene derivative (11; R = H). Treatment of this last compound with methyl iodide and potassium t-butoxide produced the gem-dimethyl homologue (11; R = Me) m.p. 146-148" Dxidative breakdown3 of which gave 01 cup-trimethyl-p-p-tolyladipic acid m.p. 222-224". Esterification Dieckmann cyclisation hydrolysis and decarboxyla- tion gave 2,2,3-trimethyl-3-p-tolylcyclopentanone which was converted by Huang-Minion reduction into (j-)-cuparene (I; R = Me) identical with the natural sesquiterpene in its infrared and ultraviolet spectra mass-spectrometric properties and retention time in gas-liquid chromatography.Mild oxidation of (&)-cuparene with chromium trioxide in acetic acid2 gave (5)-cuparenic acid (I; R = C02H) m.p. 151-1 54" essentially identical in infrared spectrum with natural (+)-cuparenic acid. We thank Professor H. Erdtman and Dr. C. Enzell for samples of natural cuparene and cuparenic acid. One of us (R.R.) acknowledges a D.S.I.R. maintenance grant. (Received,December 2nd 1960.) Nozoe and Takeshita Tetrahedron Letters 1960 23 14. Enzell and Erdtman Tetrahedron 1958 4 361. a Johnson Bannister and Pappo J.Amer. Chem. Soc. 1956 78 6336. FEBRUARY 1961 The Structure of clerodin By G.A. SIM,T. A. HAMOR ROBERTSON I. C. PAUL and J. MONTEATH DEPARTMENT GLASGOW, (CHEMISTRY THEUNIVERSITY W.2) CLERODM,the bitter principle of Clerodendron infortunaturn has been converted into the bromo- hydrin and thence into the bromo-lactone the crystal structure of which we have elucidated by an X-ray study. Our results define the constitution and stereochemistry (apart from absolute configuration) of the bromo-lactone as (I) and hence of clerodin as 01). OAC OAc w (1) (a> (1 v> At the outset of the X-ray work we were informed only that clerodin contained two acetate groups an epoxide group (III) and a dihydrofuran residue OV) and that analytical figures for various clerodin deri- vatives were consistent with a formula C21H3,OC for clerodin and consequently C2,H2,07Br for the bromo-lactone.The bromo-lactone belongs to the orthorhombic system space group P2,2,2, with cell dimensions a = 10-55 b = 10.12 c = 22-82. A. A careful determination of the density yielded d(meas.)= 1-432.With four molecules of C,,H2,0,Br in the unit cell d(ca1c.) = 1.290 a value clearly incompatible with the experimental result. Consid- eration of the crystal density of the bromo-lactone and of the C:H:O ratios for clerodin led us to propose C24H3407 for clerodin and C,,H,,O,Br for the bromo-lactone [d(calc.) = 1.4421. Confirmation of the CZ4formula was obtained from a preliminary crystallographic study of clerodin bromohydrin.This also belongs to the ortho-rhombic system space group P2,2,2, and the approximate cell dimensions are a = 11.44 b = 9-73 c = 22-50A. With four molecules of C2,H3,0,Br in the unit cell d(ca1c.) = 1-40 d(meas.) = 1.43 [C2,H3,07Br would require d(ca1c.) = 1 -26). From equi- inclination Weissen berg photographs taken with Cu-K radiation and visual intensity estimates 1514 independent structure amplitudes were obtained from the bromo-lactone. The bromine co-ordinates were determined without ambiguity from a study of the three-dimensional vector maps. I X fl Superimposed contour sections parallel to (001) showing the three-dimensional electron distribution over me molecule of clerodin bromo-lactone.Barton Cheung Cross Jackman and Martin-Smith following communication. PROCEEDINGS Successive three-dimensional Fourier syntheses calculated structure amplitudes at the present stage with increasing numbers of atoms included in the is 21.5 %. Further refinement is proceeding. phasing calculations served eventually to locate all Superimposed contour sections illustrating the the atoms other than hydrogen in the asymmetric seventh three-dimensional electron-density distribu- crystal unit. The distinction between oxygen and tion over one molecule are shown in the Figure. carbon atoms was based on a consideration of the Both cyclohexane rings of the trans-decalin have relative peak heights of the atoms concerned and of the chair conformation.The 19-methyl group is the interatomic distances involved. axial and the 20-group is equatorial. The 6-acetoxy- After four cycles of calculations the constitution of substituent is equatorial. the molecule was clearly established and the only Chemical evidence supporting the constitution doubtful stereochemical point (apart from the abso- 01) is also presented in the following communica- lute configuration) was the distinction between ti0n.l oxygen and carbon in the epoxide ring. In an ex- change of letters with Professor Barton in which we We are grateful to Professor D. H. R. Barton for announced our results we were informed of chemical suggesting the problem and for supplies of material. evidence that the epoxide-oxygen is probably cis to The calculations were carried out on the Glasgow the adjacent acetyl groups.Further refinement of the University Deuce computer using programmes de- crystal structure appears to confirm this for with vised by Dr. J. S. Rollett and we are indebted to the both atoms included as carbon atoms in the phasing Director of the Computing Laboratory Dr. D. C. calculations the peak height of the oxygen atom Gilles and his staff for facilities. We also thank the is consistently greater than that of the alternative Carnegie Trust for a Scholarship (to I.C.P.) and the atom 17 of the epoxide group in (I). University of Glasgow for an I.C.I. Research The average discrepancy between observed and Fellowship (to T.A.H.). (Received December 16th 1960.) The Constitution of Clerodin By D.H. R. BARTON A. D. CROSS and M. MARTIN-SMITH H. T. CHEUNG L. M. JACKMAN (IMPERIAL LONDON GLASGOW) COLLEGE and the UNIVERSITY THEconstitution and stereochemistry of clerodin to the contrary) clerodin hemiacetal acetate (IT ; R = the bitter principle of Clerodendron infortunatum has H R' = OAc R" = R"' = Ac) m.p. 208-210° been established as (I; R = Ac) by the X-ray [ a] -32" and the bromohydrin (I1; R = Br R' = crystallographic investigations described in the pre- OH R" = R"' = Ac) m.p. 186-187" [a],-13". ceding communication.l The molecular formula of With aqueous acetic acid the hemiacetal acetate was clerodin C,4H& was determined by the X-ray smoothly converted into the hemiacetal (XI; R = H work1 and by mass spectrometry for which we thank R' = OH R"= R"' = Ac) (which is also a major very cordially Dr.R. I. Reed of the University of constituent of Clerodendron infortunaturn) m.p. Glasgow. The following chemical and nuclear mag- 179-181 [a] -17". On oxidation by chromic O netic resonance results support the physically deter- acid the y-lactone (III; R = H R" = R"' = Ac), mined constitution (I; R = Ac). (For earlier chemical m.p. 192-193" [a],-23" with v,,,. (C=O)at 1795 work see refs. 2 and 3). cm.-l was obtained.7 Oxidation of the bromo- Clerodin contains two acetate residues two C-Me hydrin in the same way afforded the analogous groups and one vinyl ether grouping of the type bromo-y-lactone 011; R = Br R" = R"' = Ac) -CH = CH.0-(infrared) which readily added m.p. 168-169" [a] -37" used in the X-ray hydrogen acetic acid and hypobromous acid to investigations1 referred to above.give respectively dihydroclerodin-I* (11; R = R' = The substitution pattern of the vinyl ether ring is H R" = R"' = Ac) m.p. 169-170" [a] -20" revealed by the abwe work by nuclear magnetic (all rotations in CHCl at c = 1-2 unless specified resonance studies showing the presence of the * Reduction products are designated series -I if the vinyl ether group is hydrogenated and series -11 if ths 1,2-epoxide grouping is reduced. t The expected analytical infrared ultraviolet and nuclear magnetic resonance data have been recorded for all the compounds described in this communication. Reference to them is made here only if especially pertinent. Sim Hamor Paul and Robertson preceding Communication.Banerjee Science and Culture 1936 2 163; J. Indian Chem. SOC.,1937 14 51 ; Trans. Boss Res. Insf. 1935-36 11 71 ; 1936-37 12 75. a Chaudhury and Dutta J. Indian Chem. Soc. 1951 28 295; 1954 31 8. FEBRUARY 1961 system (IVa or b) and by the following experiment. The action of methanolic ammonia on the y-lactone (III; R = H R" = R"' = Ac) gave the correspond- ing amide which on acidification furnished the lactam (V; R" = R"'= Ac) m.p. 265-280" (de-camp.) [a] -6'. Such ready lactam formation is only rendered possible by the presence of the grouping (-04-OH) in the intermediate amide. The nuclear magnetic resonance spectra of clerodin and its derivatives showed the presence of one tertiary and one secondary C-Me group and that the two acetate residues were present as :CH.OAc and -CH,.OAc attached to a fully substituted carbon atom.Reductive cleavage of clerodin and dihydro-clerodin-I with lithium aluminium hydride afforded respectively the triols (VI; CH:CH in place of CHRCHR' R" = R"' = H) (dideacetyldihydro- clerodin-II) m.p. 218-225' [a] -566" (in pyri- /O\ X-CH dine) and (VI; all R's = H) m.p. 172-173" [aJD-15". Acetylation of the latter gave tetra- hydroclerodin (VI; R = R' = H R" = R"' = Ac) m.p. 145-147" [cc] -6" which has a tertiary hydroxyl group (stable to chromic acid). These com- pounds are formed with appearance of a new C-Me group (nuclear magnetic resonance) and therefore a 1,Zepoxide group of the type (A) must be present.Dideacetyltetrahydroclerodin (VI ; all R's = H) (see above) gave an internal carbonate ester (VI; R = R' = H R" = R"' = :C=O) m.p. 226-228" [ctID -49" with pyridine-ethyl chloroformate.* Dideacetyldihydroclerodin-I(I1;all R's = H) m.p. 188-195" [cc] -5' obtained by alkaline hydro- lysis of dihydroclerodin-I afforded a similar internal carbonate m.p. 276-281' [a] -49" and on treatment with toluene-p-sulphonyl chloride in pyridine gave a monotoluene-p-sulphonate (11; R = R = R"' = H R" = p-C,H,Me.S02) m.p. 149-1 5 1 ",[a],+35" oxidised to the corresponding cyclohexanone [vmax. (C=O) 1710 cm.-l] m.p. 152-153" [aID+75" by chromic acid. This ketone was stable to alumina (grade 111) in contrast to the ketone obtained in the same way from dideacetyl- tetrahydroclerodin monotoluene-p-sulphonate (VI ; R = R = R"' = H R" = p-C,H,Me.SO& m.p.152-1 53" [aID -8" which readily eliminated toluene-p-sulphonic acid to give in a reaction involving internal Michael addition by the inter- mediate (VII) the diketone (VIII) m.p. 183-186" [a],+9" shown to be a methyl ketone chemically and by its nuclear magnetic resonance spectrum. The mutual relationship of the 1 ,Zepoxide grouping and the two hydroxyl groups is thus established. Dehydrogenation of clerodin furnished 1,2,5-t rimethy lnaph t halene. All these facts and others that we shall present in (VI II) our full paper support the constitution established by X-ray crystallography. The biogenesis of the mole- cule clearly follows that proposed for c~lumbin.~ The absolute configuration of clerodin is probably R as indicated in formula (I;= Ac) since the ketone derived from dideacetyldihydroclerodin-I mono-toluene-p-sulphonate (see above) had an optical rotatory dispersion curve enantiomeric to that of a normal trans-A/B steroidal 6-ketone although of much enhanced magnitude.We thank Professor W. Klyne (Westfield College) for this determination. We thank Dr. K. N. Kaul (National Botanical Gardens Lucknow) and Messrs. Glaxo Laboratories for supplies of Clerodendron infortunaturn. We also acknowledge with gratitude financial assistance from the latter organisation (M.M.-S.) from the D.S.I.R. (A.D.C.) and from the British Council (H.T.C.). (Received December 16th 1960.) Fieser Hen Klohs Romero and Utne J.Amer. Chem. Soc. 1952 74 3309. Barton and Elad J. 1956 2085. PROCEEDINGS X-Ray Study of a Dicbloronaphthalene By J. TROTTER DEPARTMENT UNIVERSITY OF BRITISH COLUMBIA VANCOUVER OF CHEMISTRY 8 CANADA) CRYSTAL data have previously been outlined for several derivatives of naphthalene as a preliminary to complete structure determinati0ns.l Crystals of one of these that reported as 1,2-dichloronaph-thalene are monoclinic with four molecules in a unit cell of dimensions a = 15-11,b = 3-92,c = 14.86A, fi = 96.0° space group P2Jn. Detailed investigation of these crystals proceeded by examining initially the projection down the short b-axis. On the h02 Patter-son map however no peak could be found corre- sponding to the intramolecular Cl-Cl vector of the 1,2-derivative and it had to be concluded that the material being examined by the X-ray method was not 1,2-dichloronaphthaIene.An effort was then made to deduce the correct molecular structure directly from the X-ray data. There were two outstanding peaks on the Patterson projection and it seemed likely that these represented double Cl-Cl vectors. On this basis positions were found for two chlorine atoms and by setting the origin of the Patterson function in turn at these two C1 positions and at the positions related to them by the centre of symmetry at the origin of the cell a vector convergence (minimum) function was drawn up. This is shown in the Figure (contours being at equal and arbitrary intervals) and indicates clearly that the molecule is 1,3-dichloronaphthalene.The crystals used in the X-ray investigation had been obtained from a bottle whose original source was not known. The melting point was recorded roughly before any X-ray work was carried out as N 34". The sample having this melting point was however taken from the main bulk of material while the well-formed crystalline specimens used for the X-ray work were removed from the walls and neck of the bottle where they had been deposited by 'Trotter Acta Cryst. 1960 13 276. very slow sublimation. In view of the results of the X-ray structure analysis the melting points were re- checked and it was found that crystals from the bottom of the bottle melted over the range 30-34" while the sublimed crystals melted sharply at 60-61 '.This indicated that the crystals being 0 @ @ 0 examined by the X-ray method were as previously deduced directly from the diffraction data fairly pure 1,3-dichloronaphthalene (reported m.p. 61-5") but that the main bulk of the material was impure 1,2-dichloronaphthalene (the m.p. of the pure substance is 35") the impurity being of course the 1,3-derivat ive. Refinement of the structure is in progress. (Received December 6th 1960.) The Fractionation of Ribonucleic Acids by means of a New Typeof Exchanger By A. S. JONESand D. G. PARSONS (CHEMISTRY DEPARTMENT 15) THE UNIVERSITY BIRMINGHAM DEOXYRIBONUCLEIC ACIDS have been separated by the use of ion-exchangersl into fractions which differ in composition.Although some fractionation of ribo- nucleic acids has been achieved by precipitation counter-current e~traction,~ and chemical method^,^ fractionation with basic ion-exchangers gave only fractions of similar composition? We considered that better fractionation might be achieved if the exchanger could form hydrogen bonds with the purine and pyrimidine residues in- Brown and Watson Nature 1953,172,339; Bendich PahI Korngold Rosenkranz and Fresco J. Amer. Chem. SOC., 1958.80. 3949. Kirby Biochim. Biophys. Acta 1960 40 193. Kirby Biochim. Biophys. Acta 1960 41 338. * Brown "Microbial Genetics," 10th Symposium SOC. Gen. Microbiol. 1960 p. 222. Muria and Suzuki,Biochim.Biophys. Acta 1956 22 56S; Bradley and Rich J. Amer. Chem. SOC.,1956 78 5898. FEBRUARY 1961 79 stead of forming salt linkages with the phosphate ribonucleic acid” from solution in 0-24.5~-groups. An exchanger of this type has been made by sodium chloride at O” and they were eluted with forming a p-nitrobenzoyl ester of a partly acetylated distilled water. This behaviour is similar to that of a cellulose (Ac = 31-0%) reducing the mixed cellulose mixture of polyadenylic and polyuridylic acid which ester to the corresponding amine and coupling the forms a hydrogen-bonded double helix in 0.1~-diazotised amine with guanine. This coupling has sodium chloride but not in water.’ It appears there- Composition offractions of yeast ribonucleic acids. Ribonucleic acid of high molecular weight t Composition (mole per 100 moles of nucleotide) Total Fraction nucleic G 0 A Q C U U U acid (%) 1 35-8 25.3 *1*28 23.8 f0.65 20.3 &O-14 30.5 f0.65 2 20.8 26.0 f0.66 25.5 f0.41 19.2 f0.45 28.9 f0.18 3 15.0 26.0 fl.10 24-2 f0.53 19-9 f0-50 29.9 f0.33 4 7-0 24.5 fl.62 23.5 f0.23 22.0 f0.61 30-0 f0-41 5* 3.4 25.4 -22.4 -22-0 -30.2 -6 1.6 28.0 f0.10 21.8 f0-30 21.0 f0.60 29.2 f0.40 Recovery 83-6 “Soluble ribonucleic acid” $Composition (mole per 100 moles of nucleotide) Total Fraction nucleic G A C U #U MG acid (%) 1 39.9 27.9 18.1 33.3 17.4 1.2 2.1 2 17.7 29-1 20-7 28.5 17.5 1.4 2.8 3 9.4 26-1 22.4 31.2 20-3 - 4 1.9 29.0 27.7 26.0 17.3 - 5 1.5 ---Recovery 70.4 * Only one analysis.t Mean of four analyses for each fraction. 1Experimental error 5 % for purines and 3 % for pyrimidines. A = adenine; C = cytosine; G = guanine; MG = methylguanines; U = Uracil; #U = pseudouridine. been shown to occur at position 8 of the guanine.6 fore that the adsorption of ribonucleic acid on the The coupled product (1) contained one “guanine” exchanger is due to hydrogen bonds and not to salt residue per 15 glucose units. linkages. Partl Yeast ribonucleic acids were fractionated on a N+3-0-{met y Lted column of our material when a stepwise gradient of ;-i2N4’ cellulose decreasing salt concentration was used (see Figure). H (1) The fractionation of the “soluble ribonucleic acid” This material readily adsorbed yeast ribonucleic was reproducible but with ribonucleic acid of high acid of high molecular weight and yeast “soluble molecular weight different samples isolated by the Fischer Z.Physiol. Chem. 1909 60 69. Warner f.Biol. Chem. 1957,229 711. PROCEEDINGS same method behaved differently. The variability is thought to be due to changes occurring in the ribo- nucleic acid on storage. Analysis of the fractions for purines and pyrimidines by the method of Loring et a1.* for material of the high molecular weight and by an ion-exchange method for “soluble ri bonucleic acid” (see Table) showed significant differences in a composition particularly for the “soluble ribonucleic acid.” It would be expected that if the guanine residues of the exchanger formed hydrogen bonds with the cytosine residues in the nucleic acid the fractions Conc.NoCl richest in cytosine would be eluted last. That this is not so may be because the base in the exchanger is an 8-substituted guanine and because other factors such as molecular weight and nucleotide sequence b may play a part in the adsorption. This new type of exchanger can be used therefore to fractionate ribonucleic acids and may be of help in preparing homogeneous polyribonucleotides. It is clearly capable of modification in various directions. Fraction no. Fractionation of (a) yeast ribonucleic acid of high molecular weight (500 mg.) and (b) yeast “soluble The authors thank Professor M. Stacey,F.R.S.,for ribonucleic acid” (543 mg.) on a column (3 x 40 cm.2) his interest and British Celanese Ltd.for a Research at 0”.Fractions of 25 ml. were collected. Scholarship (to D.G.P.). Luring Fairley Bortner and Seagran J. Biol. Chem. 1952 197 809. The Mechanism of AUylic Bromination by N-Bromosuccinimide By B. P. MCGRATH and J. M. TEDDER OF CHEMISTRY SHEFFIELD, (DEPARTMENT THEUNIVERSITY 10) halogenation of an olefin can result in addi- long been recognised as a free-radical process and it ATOMIC tion (common at low temperature and with high is usually assumed to involve succinimido-radicals.s concentrations of molecular halogen) or substitu- Goldfinger has suggested an alternative mechanism tion usually allylic (occurring at higher temperatures in which the function of the N-bromosuccinimide is or in the presence of a low concentration of mole-to provide molecular bromine at very low concentra- Allylic bromination rather than addition is to cular halogen).1*2 The mechanism of the change from tion~.~ addition to substitution on rise of temperature and/or be expected provided the concentration of molecular change in the concentrations was elucidated by bromine is low and this low concentration is main- Goldfinger and his collaborator^.^ The key to this tained by the reaction of hydrogen bromide with mechanism is the high rate of dissociation of the N-bromosuccinimide initial addend (-CH2CHX-CH-).Recent studies of the halogenation of the butyl bromides have shown HBr + (.CH,CO),>NBr -+ (.CH,CO),>NH + Br, that the dissociation of the corresponding radical Br + 2 Br.when X is bromine is extremely rapid even at room Br. + -CH,-CH=CH-+ -CH,.CHBt-CH-temperat~re.~ Br. + -CH,CH=CH--t -CHCH=CH-+ HBr Allylic substitution by N-bromosuccinimide has -CHCH=CH-+ Br -f -CHBr-CH-CH-+ Br-Rust and Vaughan J. Org. Chem. 1940 5,472. Stewart Dod and Stenmark J. Amer. Chem. SOC.,1937 59 1765. Adan Gosselain and Goldfinger Nature 1953 171 704; Bull. SOC.chim. belges 1956 65 523. Fredricks and Tedder J. 1960 114. Bloomfield,J. 1944 144. FEBRUARY 1961 We hope at a later date to show in detail how the Goldfinger mechanism can give much better explana- tions of the previously reported reaction conditions and products of N-bromosuccinimide reactions. We now report two reactions which are predicted by the Goldfinger mechanism but are not consistent with the simple succinirnido-radical theory.If Goldfinger’s mechanism is correct then it should be possible to achieve allylic bromination by the slow addition of bromine to an olefin in refluxing carbon tetrachloride (the normal conditions for N-bromosuccinimide). There were two difficulties in this experiment (1) the need to prevent high local concentrations of bromine around the site of addi- tion and (2) the need to remove hydrogen bromide which reacts with N-bromosuccinimide in the normal reaction. Bromine was added in a stream of nitrogen bromine was added the larger was the yield of ethyl y-bromocrotonate at the expense of ethyl cup-di- bromobutyrate. These results are clearly consistent with the Gold- finger mechanism but a more exacting test was re- quired.It is implicit in the Goldfinger mechanism that a bromine atom will add to and dissociate from the olefinic carbon atoms several times before it abstracts a hydrogen atom. We have obtained evi- dence of such a process by taking a cis-olefin (hex-3-ene) and brominating it with N-bromosuc- cinimide under normal conditions. Each time a bromine atom added to the olefin and then dis- sociated again the regenerated olefin would be expected to be trans. The extent of bromination was followed by gas chromatography while the isomerisa- tion of the hexene (after separation by chromato- -CH,.CHBr.CH--+Brz -+ (-CH,CHBr.CHBr-) cis f \\ trans Br. + -CH,.CH=CH-CH,CH=CH-+ Bra I.I/ Br -CH.-CH= CH-5 -CHBrCH= CH- to a refluxing solution of cyclohexene in carbon tetrachloride. The nitrogen carried away a large pro- portion of the hydrogen bromide formed. Provided the bromine addition was even good yields of 3-bromocyclohexene were obtained but if the bromine was added rapidly or unevenly considerable addition occurred. The bromination of ethyl croto- nate was also studied but the experimental difficulties were much more formidable in this case. The original authors,6 using N-bromosuccinimide allowed the reaction to proceed for 14 hours and to ensure very gradual and even addition of bromine over this period proved extremely difficult as did the removal of the hydrogen bromide. However the slower the graphy) was followed by infrared spectroscopy.When cis-hex-3-ene (1 mol.) was brominated with a deficiency of N-bromosuccinimide (0.2mol.) 85 % of the recovered hexene had been converted into the trans-isomer. Failure to observe this rapid isomerisa- tion would have disproved the Goldfinger mechan- ism. The fact that it occurs does not unequivocably prove the Goldfinger mechanism though together with the direct bromination results described above it provides strong support for it and at the same time shows again the inadequacy of the simple SUC-cinimidyl radical mechanism. (Received December 5th 1960.) Ziegler Spath Schaaf Schumann and Winkelmann Annalen 1942 551 80. Kinetics and Equilibria of the Protonation of 1,3,5-Trimethoxybenzene in Concentrated Aqueous Acid By A.J. KRESGE~ and Y. CHIANG (BROOKHAVEN LABORATORY, NATIONAL UPTON,NEWYORK,U.S.A.) ACID-CATALYSED aromatic hydrogen exchange is considered to be unorthodox either in its mechanism or in its acidity-dependence in concentrated aqueous acid.2 For 1,3,5-trimethoxybenzene,however evi- dence which we now present indicates that the acidity-dependence is consistent with the orthodox mechanism. This evidence moreover suggests a general solution of the anomaly. The loss of tritium from 1,3,5-trirnetho~y[2-~H]-benzene is an “h,-dependent” reaction in the usual sense its rate obeys the relation kexch = 0.484(hO)1.07 in aqueous perchloric acid up to a concentration of 3~. The interpretation normally placed on such an observation is that the transition state is a fully pro- tonated species in which the transferred proton has lost all specific interaction with the conjugate base of Present address :Department of Chemistry Illinois Institute of Technology Chicago 16 Illinois.For a recent summary of the situation see Eaborn and Taylor J. 1960 3301. PROCEEDINGS the catalysing acid. But this interpretation is based on the assumption that the substrate is a Hammett base i.e. that its degree of protonation in concen- trated aqueous acid is governed by h,. The data in the Table show this assumption to be false for the present case the degree of protonation of 1,3,5- trimethoxybenzene in aqueous perchloric acid is proportional not to h, but to the different acidity function hR'.3 These equilibrium measure-ments were made in the usual spectroscopic manner; advantage was taken of the fact that in strongly acid solution the 2660 8,band (E 530) of 1,3,5-trimethoxy- benzene shifts to 2500 A (E 2-0 x lo4) and a new band appears at 3420 8 (E 1.32 x lo4).This spectrum of protonated 1,3,5-trimethoxybenzene has the same general features as the spectra reported for ring-protonated aromatic hydrocarbons in HF-BF solution4 and is different from that reported for anisole pro tonated on ~xygen.~ mechanism of this reaction is the orthodox one for electrophilic aromatic substitution,s the actual situa- tion at the transition state must be intermediate between no transfer and complete transfer of the proton.And of course the observed acidity-dependence is also intermediate between that predicted for these two extremes. Rates of hydrogen exchange in other aromatic substrates give H plots with slopes ranging from near 1.0 for phenols and aryl ethers to 1.5 and 2-0for the hydrocarbons toluene and benzene. This is con- sistent with a single mechanism for all aromatic ex- change similar to that established for triaethoxy- benzene but with varying degrees of proton transfer at the transition state. It is also consistent with a single mechanism but different acidity-dependencies for the degree of protonation of different aromatic compounds. Some support for the latter interpreta- tion comes from the fact that the degree of protona-Protonztion equilibria of 1,3,5-trirnethoxybenzenein aqueous perchloric acid at 25'.HClOQ I (%) (log CBH+/CB) I+Ho 58.0 2.02 -2.38 Z+H,' -77.45 56.1 1.58 -2.50 -7.28 53.3 0.85 -2.70 -7.23 51-1 0-24 -3.05 -7.28 50.3 0.17 -3.00 -7.15 These results indicate that were the transition .state for exchange in 1,3,5-trirnethoxybenzenea fully protonated species unassociated with the conjugate base of the catalysing acid the rate of exchange would be proportional to h'R(h'R= h;a,,). Since in the range of acid concentration used the empirical relation h,' = (hJ2 holds to a good degree of approx- imation this would appear as a linear plot of log k against -HH of slope 2.0. On the other hand had proton transfer not yet occurred to any appreciable extent at the transition state that is were the transi- tion state composed of an aromatic molecule and a nearly intact hydronium ion then a rate dependence on CHz0+ would be observed.This would give an H plot of slope considerably less than 1.0. Because the HC104 Z (%)44.8 (log C,,+/CJ-0.15 I+Ho -3.08 I+HR)-7.15 47-2 -0.43 -3.03 -7.10 45.6 -0.73 -3.25 -7.16 41.2 -9.72 -3.72 -7.34 39.5 -1-84 -3.70 -7.06 tion of rn-dimethoxybenzene increases more rapidly with acid strength than is required by dependence on itR'.The degree of protonation of toluene or benzene might be a still steeper function of acid strength in strong acid the protonated forms of these less polar substances should be salted in more strongly relative to the neutral molecules than is the case for the methoxybenzenes.This explanation accommodates the fact that a slope greater than 2.0 is observed in the H plot for the loss of tritium from benzene.2 This work was done under the auspices of the United States Atomic Energy Commission. (Received Decernhsr 16th 1960.) Deno Groves and Saines J. Arner. Chern. Suc. 1959 81 5790. h,' for perchloric acid was calculated by using the h values of Deno Berkheimer Evans and Peterson (ibid. pp. 2344 6535) and adlovalues of Pearce and Nelson (ibid. 1933 55 3075). Dallinga Mackor and Stuart Mol. Phys. 1958 1 123. Arnett and Wu J. Amer. Chem. SOC.,1960 82 5660. Kresge and Chiang J. Arner. Chem. SOC.,1959,431 5509; Abs. National Meeting Amer. Chem. SOC. Cleveland -Ohio April 1960 p. 31R.FEBRUARY 1961 83 The Reduction of Ascaridole with Ferrous Sulphate Solution By B. T. DAVIS, T. G. HALSALL,and A. R. HANDS @YSON hFUUNS LABORATORY OXFORD UNIVERSITY) THE action of aqueous ferrous sulphate on ascaridole (I) was shown by Nelson1 to give ascaridole glycol (III). This is formed by isomerisation of the epidi- oxide to isoascaridole2 (II)followed by hydrolysis no reduction occurring. We have re-investigated this reaction. Besides the glycol (28 %) and recovered ascaridole (3479,two reduction products have been isolated. They are the stereoisomeric hydroxy- ketones C10H1802,(IV) (6.5 % yield) m.p. 84",and (V)(2.5% yield) m.p. 113.5".The hydroxy-ketone (IV) is identical (mixed m.p. and infrared spectra) @I)R,= Pr' (Vl) (IV' R= H (V) R= H R'= Pr' (x I I) (XIII) R=Pr',R'=H (XIV) R-H R'= Pr' with a compound isolated by Paget3 after the action of titanous chloride in hydrochloric acid on ascari- dole and described as an unsaturated monocyclic glycol.The structures of the hydroxy-ketones are assigned as follows. Both contain one ketone group and one hydroxyl group. They are saturated and hence monocyclic. Both resisted attack by lead tetra- acetate and were reduced under Wolff-Kishner con- ditions to the saturated alcohols CloH,,O (VI) and (VII) which were characterised as their phenyl- urethanes. These reactions indicate the absence of an a-or /!?-hydroxy-ketone grouping. Dehydration of alcohol (VI) with phosphoryl chloride in pyridine gave a product which consisted essentially of one olefin (VIII) as shown by vapour- phase chromatography.Its infrared spectrum indi- cated that the double bond was tetrasubstituted. Similar dehydration of alcohol (VIJ) gave a product vapour-phase chromatography of which indicated that it was a mixture of three olefins one being identical with that from alcohol (VI). Infrared examination of the dehydration product showed that the second olefin (IX)had the grouping :C=CH and the third (X) the grouping -CH =C . Ozonolysis of the olefin (VIII) led to the isolation of a bis-2,4-dinitrophenyIhydrazone,C22H26N808 also obtained from the ozonolysis products of the olefin mixture from alcohol (VII) along with the 2,4-dinitrophenylhydrazone of 2-isopropylcyclohexan-one.These results led to structures (VI) and (VU) for the alcohols. The stereochemistry of alcohol (VI) is (XV) (XVI) (XVII) consistent with its dehydration mainly to the tetra- substituted olefin (VILI). 2-Isopropylcyclohexanone has been treated with methylmagnesium iodide the phenylurethane of the resulting alcohol was identical with that from alcohol (VI). In the Grignard reaction the stereochemistry of the product would be expected to be that of structure (VI). Since the keto-group in the hydroxy-ketones cannot be situated a or ,8 to the hydroxyl group structures (IV) and (V) follow. The formation of the hydroxy-ketones is explained by the transfer of one eIectron from the ferrous ion to ascaridole to give the radical ion (XI).This re- arranges to the unsaturated ketone (XII) and an isopropyl radical which then attacks the /%position of the double bond of the unsaturated ketone either cis or trans to the 4-methyl group giving the radicals (XIII) and (XIV). Acquisition of a further electron then leads to the hydroxy-ketones (IV) and (V). Support for this mechanism comes from the reduction of dihydroascaridole (XV) with titanous chloride in hydrochloric acid. Paget3 reported the Nelson J. Amer. Chem. SOC.,191 1 33 1404; 1913 35 84. Jacob and Ourisson Bull. SOC. chim. France 1958 734; Rundquist Diss. Abs. 1956 16 2313. * Paget J. 1938 829. formation of propane (90%) and a compound C,HI2O2 m.p. 45”,formulated as (XVI). If the above mechanism applies in this case this compound should be the ketone4 (XVII).We have shown that a hydroxy-ketone is indeed formed. Siege1 and Broll-Keckers Manatsh. 1957 88 910. PROCEEDINGS The authors thank Dr. H. T. Openshaw for Paget’s sample of hydroxy-ketone (IV). One of them (A.R.H.) thanks A. Boake Roberts and Co. Ltd. for a research bursary. (Received December 7th 1960.) NEWS AND ANNOUNCEMENTS Library.-The Library will close for the Easter Holiday from 1 p.m. on Thursday March 30th until 9.30 a.m. on Wednesday April 5th 1961. Chemical Society Liaison Officers.-The following additional Fellows have agreed to act as Chemical Society Liaison Officers Borough Polytechnic S.E.l .. Dr. J. R. Powell Portsmouth College of Tech- nology .... .. Dr. J. L. Latham South-West Essex Technical College E.17 .. .. Dr. S. Lewin Welsh College of Advanced Technology Cardiff .. Dr. V. Askam Royal Military College of Science Shrivenham . . Dr. J. H. Turnbull Local Representative for the North Staffordshire Area.-Dr. I. 7‘.MiZZur of the University College of North Staffordshire Keele has been appointed as Local Representative for that area. New Year Honours List.-Included in the New Year Honours List were Sir Alexander Fleck K.B.E. Chairman Advisory Council on Research and Development Ministry of Fuel and Power and the Nuclear Safety Advisory Committee (Baron) Dr. G. E. Watts M.A. Principal Brighton Technical College (C.B.E.) and Mr. A. H. Wilson M.A. Courtaulds Limited Coventry (Knight Bachelor).Biochemical Society Jubilee.-The Biochemical Society is to celebrate the 50th Anniversary of its foundation on March 27-29th 1961. The pro- gramme will include a Symposium on “Structure and Synthesis of Macromolecules,” to be held in The Senate House The University of London the third Hopkins Memorial Lecture to be given by Sir Hans Krebs and the Anniversary Dinner to be held in University College. Full particulars are available from Dr. W. J. Whelan The Lister Institute of Preventive Medicine Chelsea Bridge Road S.W. 1. Akers Research Laboratory :Changesin Administra-tion and 0rganisation.-Imperial Chemical Industries Limited are introducing changes in the administra- tion and organisation of their Akers Research Laboratory.This laboratory located near Welwyn was established fifteen years ago to conduct general long- range and fundamental research. Hitherto it has been administered centrally. It has been decided to associate its work more closely with the research carried out by 1.C.1.’~ manufacturing Divisions. To this end the two main activities of the laboratory-research on micro-biology (with the associated research in organic chemistry) and research in inorganic chemistry-will in future be the responsibility of the Pharma- ceuticals and Heavy Organic Chemicals Division respectively. Dr. P. W. Brian F.R.S. who becomes an associate research manager of the Pharmaceuticals Division will have charge of the work for this Division and will also be in general charge of the laboratory.Dr. J. Chatt will continue in charge of the In- organic Chemistry Department and is appointed Group Manager of the Heavy Organic Chemicals Division. The scientific work emanating from the Akers Laboratory is widely known. The laboratory will continue to be a centre for exploratory research in the selected fields. While the type and general charac- ter of the laboratory work will be unchanged it will be more aligned to the long term interests of the Company. The new organisation should facilitate the industrial development by other units of I.C.I. of new knowledge gained in the Akers Laboratory. Salters’ Institute of Industrial Chemistry.-Appli- cations are invited for Salters’ Fellowships of value in the range of f800-€1,000 p.a.(plus University fees and 10% contribution to F.S.S.U.). These Fellowships may be held by Honours graduates in Chemistry Biochemistry Physics or Engineering who desire to obtain further training in research in Chemistry Biochemistry or Chemical Engineering. Candidates should have obtained a doctor’s degree or have had not less than three years’ post-graduate experience by the time of their taking up the Fellow- ship. Fellowships will be tenable in the United Kingdom or abroad for one year from September lst 1961 and may be renewed for one further year. Applications are also invited for Salters’ Scholar- ships value E450-€550 p.a. according to circum- FEBRUARY 1961 stances (plus University fees) for a graduate resident in the United Kingdom with an Honours degree in Chemistry Biochemistry Physics or Engineering for the purpose of receiving either full-time instruc- tion in the principles of Chemical Engineering or further experience by research in Chemistry or Chemical Engineering.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 for both awards should be received by the Clerk of the Salters’ Company 36 Portland Place London W.l by March 28th 1961 from whom forms of application may be obtained. Royal Society and NufEeld Foundation Common-wealth Bursaries Scheme.-Awards have been made to the following Dr.M. M. Chukrubarty of the University of Calcutta to assist him in studying new techniques for Ihe investigation of fatty oils at the Prairie Regional Laboratory Saskatoon for six months from March 1961. Dr. W. H. Elliott of the John Curtin School of Medical Research Australian National University Canberra to assist him in visiting Cambridge for a year from September 1961 to study microbiological techniques. Dr. D. E. Hoare of Queen’s College University of St. Andrews to enable him to study reactions of hydroxyl radicals with hydrocarbons at the National Research Council Ottawa from April to September 1961. Conferences.-The Third Australian Spectroscopy Conference will be held in the Chemistry School University of Sydney from August 22nd to 24th 1961 under the sponsorship of the Standing Com- mittee on Spectroscopy of the Australian Academy of Science.The Conference is open to all with an interest in spectroscopy. Applications for registra- tion and all correspondence should be addressed to Dr. L. E. Lyons Conference Secretary Depart- ment of Physical Chemistry University of Sydney. The Sixth Salon International de la Chimie and the Conference Internationale des Arts Chimiques which had been planned for June 1962 will now be held from April 25th to May 4th 1962 at the Centre National des Industries et des Techniques (C.N.I.T.) Rond-Point de la Defence Puteaux-Paris. Infor- mation may be obtained from General Secretariat 28 rue Saint-Dominique Paris VIIe.Election of New Fellows.-1 52 Candidates whose names were published in the Proceedings for December 1960 were elected to the Fellowship. Deaths-We regret to announce the deaths of the folIowing Mr. W. A. Beattie (20.5.60) of the De- partment of Health for Scotland; Professor H. 7‘. S. Britton (30.12.60) Professor Emeritus of Exeter University; Mr. H. E. J. Cory (1 1.1 1.60) of the Eagle Chemical Works Oswaldtwistle; Dr. C. J. T. Cronshaw (5.1.61) formerly chairman of British Nylon Spinners Ltd. and former director of Imperial Chemical Industries Ltd. ; Dr. Millicent TuyZor (23.12.60) for many years Lecturer at Bristol University and one of the first lady Fellows of the Society; and Dr. R. Thomas (25.11.60) formerly Research Manager Unilever Ltd.Personal.-Dr. J. W.Bayles of the University College of South Wales and Monmouthshire Cardiff has been appointed Professor of Physical Chemistry in Natal University Durban. Dr. W. T. K. Braunholtz is to retire from his position as Secretary to the Institution of Gas Engineers with effect from the Annual General Meeting of the Institution to be held in May 1961. Mr. A. G. Higgins has been appointed as Secretary Designate. Mr. J. R. Davidson has assumed the position of Assistant Secretary with effect from January lst 1961. Mr. M. D. Farrow has been appointed chairman of Biting Rubber Estates and of Telogoredjo United Plantations. Dr. P. H. Given has relinquished his post with the British Coal Utilisation Research Association to take up an appointment as Associate Professor in the Department of Fuel Technology of Pennsylvania State University.Mr. F. A. Jones has been elected a Vice-president of the Institution of the Rubber Industry. Dr. D. H. Hayes formerly of University of Michigan has joined the staff of the Institut Pasteur Paris. Dr. A. B. Hurt has left the Royal College of Science and Technology Glasgow and is now head of a laboratory in the advanced projects division of the Central Electricity Generating Board’s research and development department. The Society’s Medal of the Society of Chemical Industry has been awarded for 1961 to Sir Cyril Hinshelwood. Professor W. Hume-Rothery Isaac Wolfson Pro- fessor of Metallurgy in the University of Oxford has been elected an Honorary Member of the lnstitute of Metals.Mr. J. R. Jarratt Boots Pure Drug Co. Ltd. Nottingham has been awarded the Lampitt Gold Medal of the Society of Chemical Industry. Dr. J. Leicester has been appointed Principal of Northern Polytechnic London. Dr. D. Mackuy has been appointed Lecturer in the Department of Pharmacology The University of Leeds from a date to be arranged. The Queen’s University of Belfast will confer an honorary D.Sc. on Sir Eric Rideal F.R.S. in July 1961. The title of Professor Emeritus of Biochemistry in the University of London has been conferred on Professor W. Robson on his retirement from the Chair of Biochemistry at King’s College London.The degree of Doctor of Science of the Univ- ersity of Liverpool has been conferred on Dr. W.A. PROCEEDINGS Sexton Research Director of the Pharmaceuticals Division of Imperial Chemical Industries Limited. Mr. R. B. Soufhall has been appointed to the board of British Hydrocarbon Chemicals Limited. Dr. P. H. Sykes Director of Research and Development of the Reed Paper Group has been appointed Deputy Managing Director of Albert E. Reed and Company Limited. FORTHCOMING SCIENTIFIC MEETINGS London Thursday March 16th at 7.30 p.m. Centenary Lecture “Charge Transfer in Organic Solids Induced by Light,” by Professor A. N. Terenin. To be given in the Rooms of the Society Burlington House W. 1. Aberdeen (Meetings will be held in the University Chemistry Department Old Aberdeen.) Wednesday March 8th 1961 at 8 p.m.Lecture “Infrared Spectra of Absorbed Molecules,” by Professor A. N. Terenin. Wednesday March 15th at 8 p.m. Lecture “The Lurgi Pressure Gasification Process,” by Mr. D. C. Elgin and Dr. J. Linton. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Wednesday March 29th at 2.30 p.m. Official Meeting and Lecture to be given by Professor E. Lederer Dr. Phil. Aberystwyth (Joint Meetings with the University College of Wales Chemical Society to be held in the Edward Davies Chemical Laboratories University College.) Thursday March 2nd 1961 at 5 p.m. Lecture “Polymer Kinetics,” by Dr. T. T. Jones. Thursday March 9th at 5 p.m.Lecture “Chemical Processing of Power Reactor Fuels,” by Dr. F. F. Kemp. Thursday March 16th at 5 p.m. Lecture “Cyclobutadiene-A Success Story,” by Dr. J. F. W. McOmie. Birmingham Friday March loth 1961 at 4.30 p.m. Lecture “Very Fast Chemical Reactions,” by Pro- fessor G. Porter M.A. Ph.D. Joint Meeting with the Birmingham University Chemical Society to be held in the Chemistry Department The University. Bristol (Meetings will be held in the Department of Chem-istry The University unless otherwise stated.) Thursday March 2nd 196 1 at 5.15 p.m. Lecture “Oxidation in Aqueous Solution,” by Pro- fessor F. s. Dainton M.A. Ph.D. F.R.S. Joint Meeting with the Student Chemical Society. Thursday March 2nd at 6.30 p.m.Lecture “Titrations in Non-aqueous Solvents,” by Mr. E. Minshall M.Sc. F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Technical College Brunswick Road Gloucester. Thursday March 9th at 6.30 p.m. Society of Chemical Industry Local Section Annual General Meeting and Film “Water Treatment.” Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Friday March 17th at 5.15 p.m. Lecture “Optical Sensitisation of Semiconductors by Organic Dyes,” by Professor A. N. Terenin. Thursday March 23rd at 6.30 p.m. Lecture “Frozen Foods (Ladies’ Night),” by Birds Eye Foods Ltd. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the College of Science and Technology Ashley Down.Cambridge (Meetings will be held in the University Chemical Laboratory Lensfield Road.) Monday March 6th 1961 at 5 p.m. Lecture “Some Molecular Structure Studies by Microwave Spectroscopy,” by Dr. J. Sheridan M.A. Friday March loth at 8.30 p.m. Lecture “Some Aspects of the Radiation Chemistry of Aqueous Systems,” by Professor J. Weiss Ph.D. Joint Meeting with the University Chemical Society. FEBRUARY 1961 Cardiff Monday March 13th 1961 at 5.30 p.m. Lecture “Some Aspects of the Chemistry of the Sesquiterpenes,” by Professor W. Cocker Ph.D. Sc.D. F.R.I.C. To be given in the Chemistry Depart- ment University College Cathays Park.Durham Monday March 13th 1961 at 5 p.m. Lecture “Aromatic Fluorocarbons,” by Professor M. Stacey D.Sc. F.R.I.C. F.R.S. Joint Meeting with the Durham Colleges Chemical Society to be held in the Science Laboratories The University. Exeter Friday March loth 1961 at 5 p.m. Lecture “Spectra of Gases and Vapours under High- frequency Excitation,” by Professor C. L. Wilson Ph.D. D.Sc. F.R.I.C. To be given in the Washing- ton Singer Laboratories The University. Glasgow (Meetings will be held in the Chemistry Department The University.) Friday March loth 1961 at 4 p.m. Lecture “Infrared Spectra of Addition Compounds with Metal Halides,” by Professor A. N. Terenin. Friday March 17th at 4p.m. Meeting for the reading of original papers and Annual General Meeting of local Fellows of the Society.Hull Thursday March 9th 1961 at 7.30 p.m. Lecture “Infrared Spectra,” by Dr. L. J. Bellamy. Joint Meeting with the Royal Institute of Chemistry to be held in the Department of Chemistry The University. Irish Republic Wednesday March lst 1961. The Official Meeting and Tilden Lecture by Professor R. A. Raphael originally arranged for this date has been postponed until Wednesday April 26th. Friday March 3rd at 7.45 p.m. Lecture “The Kinetics of Some Halogenation Reactions,” by Mr. R. P. Bell M.A. F.R.S. Joint Meeting with the Werner Society to be held in the Chemistry Department Trinity College Dublin. Leeds (Meetings will be held in the Chemistry Department The University.) Thursday March 9th 1961 at 6.30 p.m.Lecture “Phytol,” by Professor B. C. L. Weedon D.Sc. A.R.C.S. F.R.I.C. Joint Meeting with the Leeds University Union Chemical Society. Tuesday March 14th at 6.30 p.m. Centenary Lecture “Charge Transfer in Organic Solids induced by Light,” by Professor A. N. Terenin. Manchester (Meetings will be held in Room F1 The College of Science and Technology unless otherwise stated.) Thursday March 9th 1961 at 4.30 p.m. Lecture “Some Problems in the Chemistry of Phos- phorus,” by Dr. S. H. Pollard. Joint Meeting with the University Faculty of Technology Chemical Society. Monday March 13th at 6.30 p.m. Lecture “Organic Dyes as Semiconductors,” by Professor A. N. Terenin. Friday March 24th at 10.30 a.m.Symposium on “Organic Intermediates in the 1960’s.” Joint Meeting with the Society of Chemical Industry The Royal Institute of Chemistry and the Institute of Petroleum to be held in the Large Lecture Theatre Chemistry Department The University. Newcastle upon Tyne Friday March loth 1961 at 5.30 p.m. Bedson Club Lecture “Some Reflections on the Detergent Industry,” by Dr. A. Koebner. To be given in the Chemistry Department King’s College. Oxford Monday March 6th 1961 at 8.15 p.m. Lecture “Carbon-14 Compounds,” by Dr. J. R. Catch. Joint Meeting with the Alembic CIub to be held in the Inorganic Chemistry Lecture Theatre. The University. Sheffield (Joint Meetings with the Royal Institute of Chemistry and the University Chemical Society to be held in the Chemistry Department The University.) Thursday March 9th 1961 at 4.30 p.m.Lecture “The Electronic Orbitals Shapes and Spectra of Simple Molecules,” by Professor A. D. Walsh M.A. Ph.D. Thursday March 16th at 4.30 p.m. Lecture “Some Recent Developments in Agricul- tural Chemistry,” by Professor R. L. Wain Ph.D. F.R.I.C. F.R.S. Southampton Monday March 13th 1961 at 7 p.m. Lecture “Some Polysaccharides of the Human Body,” by Dr. A. B. Foster. Joint Meeting with the Portsmouth and District Chemical Society to be held in the College of Technology Portsmouth. Swansea Monday March 13th 1961 at 4.30 p.m. Lecture “Development of Modern Gas Kinetics,” by Professor A. F. Trotman-Dickenson Ph.D.Joint Meeting with the University College Chemical Society to be held in the Department of Chemistry University College. Tuesday March 21st. The Simonsen Lecture by Professor A. J. Birch PROCEEDINGS originally arranged for this date has been unavoid- ably postponed. Tees-side Tuesday March 14th 1961 at 8 p.m. Lecture by Professor F. D. Richardson. Joint Meet- ing with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Constantine Technical College Middlesbrough. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings. Such objections will be treated as confidential.The forms of application are available in the Rooms of the Society for inspection by Fellows.) Al-Baldawi Sadiq Abbas. 37 Whitburn Road London S.E.13. Altiparmakian Rodolf Haritoun. 22 Lees Hall Crescent Fallowfield Manchester 14. Amarasingham Rajasingam Duraisamy B.Sc. Depart- ment of Chemistry Jalan Sultan Petaling Jaya Selangor Malaya. Archer Sydney B.A. Ph.D. 52 Wisconsin Avenue Delmar New York U.S.A. Armitage Phillip Terance B.Sc. 41 Orchard Road East Cowes Isle of Wight. Arya Vishwa Prakash Ph.D. B.Pharm. Institute of Organic Chemistry Royal Institute of Technology 33 Kemistvagen Stockholm 70 Sweden. Atkinson John Richard M.Sc. Balliol College Oxford. Beattie Ian Alexander Moore B.Sc.Laharna Hotel Lame Northern Ireland. Bellamy Anthony John B.Sc. 103 Grove Road Blaby Leicester. Beyer Hans Hermann Max Dr.habi1. Steinbeckerstrasse 15 Greifswald Germany. Black Donald Noman. 56 Cardinal Street Cheetham Manchester 8. Blake Peter Gerald B.Sc. D.Phi1. St. Salvators Hall St. Andrews Fife. Bland Ian Kenneth Henry. The Woodlands Bamford Rochdale Lancs. Bloch Jean-Claude. 14 Place de 1’Hotel de Ville Erstein (Bas-Rhin) France. Bolon Donald Allen B.S. Ph.D. Department of Chem-istry Harvard University 12 Oxford Street Cambridge 38 Massachusetts U.S.A. Borowitz Grace Burchman Ph.D. 3890 Sedgwick Avenue New York 63 New York U.S.A. Brannan Sydney John Henry B.Sc. 6 Buckhurst Hill House Queen’s Road Buckhurst Hill Essex.Breuer Miklos Moshe M.Sc. Ph.D. 44 Harcourt Drive Earley Reading Berks. Brickman Madeline Ruth B.Sc. 22 Heriot Road, London N.W.4. Brimacombe John Stuart Ph.D. Department of Chem- istry The University Edgbaston Birmingham 15. Brown John Michael B.Sc. 23 Buckingham Road Heaton Moor Stockport Cheshire. Brown Weldon G. M.Sc. Ph.D. Dzpartment of Chem-istry University of Chicago Chicago 37 Illinois, U.S.A. Buchanan Ronald Leslie B.Sc. Department of Chem- istry University of Western Ontario London Ontario Canada. Burke John Findlay. 136 Felbrigge Road Goodmayes Essex. Burwood Ralph. 200 Southend Lane London S.E.6. Bushweller Charles Hackett. Delta Kappa Epsilon House Hamilton College Clinton New York U.S.A. Byrom Philip B.Sc. 10 Brownlea Avenue Dukinfield Cheshire.Calderazzo Fausto D.Chem. 58 Austin Street Cam- bridge Massachusetts U.S.A. Chadha Mohindra S. M.Sc. Ph.D. Department of Chemistry Cornell University Ithaca New York U.S.A. Chaykovsky Michael M.S. Department of Chemistry University of Michigan Ann Arbor Michigan U.S.A. Chodroff Saul MA. Ph.D. 243 McDonald Avenue Brooklyn 18 New York U.S.A. Chong Vee Yong B.Sc. 38 Gayville Road London s.w.ll. Church Robert FitzRandolph M.S. 2877 Bellwood Avenue Ann Arbor Michigan U.S.A. Clark James B.Sc. 1724 Great Western Road Glasgow w.3. Coe Paul Leslie Ph.D. Department of Chemistry The University Edgbaston. Birmingham 15. Collins Guy Robert B.S. M.A. Department of Chem- istry Indiana University Bloomington Indiana, U.S.A.Cooke David Michael B.Sc. 33 Abbey Drive Rhos-on- Sea Colwyn Bay Denbighshire. Cotterill William David B.Sc. 4 Milton Terrace High- town Congleton Cheshire. Creighton John Alan B.A. Jesus College Oxford. Cullis Charles Fowler M.A. D.Phil. D.Sc. Department of Chemical Engineering Imperial College London s.w.7. Datby Joan Shirley B.Sc. 36 Queen’s Road Vicar’s Cross Chester. Davis Robert Earl A.M. Ph.D. Department of Chem-istry Purdue University Lafayette Indiana U.S.A. Dean Harvey Grosvenor. 10 Eachard Road Cambridge. De Reuck Anthony Vivian Smith M-Sc. D.J.C., A.R.C.S. A.1nst.P. 18 Heber Mansions Queens Club Gardens London W.14. FEBRUARY 1961 Diassi Patrick A. M.S. Ph.D. Squibb Institute for Medical Research New Brunswick New Jersey, U.S.A.Drago Russell S. Ph.D. Department of Chemistry University of Illinois Urbana llli~ois U.S.A. Drake John Edward Ph.D. Department of Chemistry University of California Berkeley California U.S.A. Drew Paul Geoffrey. 7 Oak Street Bentleigh S.E.14 Melbourne Victoria Australia. Edwards Robert Harry M.Sc. 18 Earl’s Road White- haven Cumberland. Eggins Brian Robert B.A. 31 Pitcairn Road Warley Smethwick 41 Staffs. Eilxs Kenneth L. B.S. Department of Chemistry Iowa State University Ames Iowa U.S.A. Emanuel John David B.A. 17 Court Lane Gardens London S.E.21. Endres Gerard Francis Ph.D. Research Laboratory General Electric Company Schenectady New York U.S.A. Falk Richard John B.A. Department of Chemistry, South Dakota State College Brookings South Dakota U.S.A.Fare Godfrey B.Sc. Cancer Research Laboratories, Medical School The University Edgbaston Birming- ham 15. Feast Alan Arthur John B.Sc. 7 Dornton Road, London S.W.12. Feldman Martin Robert A.B. Department of Chemistry University of California Los Angeles 24 California U.S.A. Fdseth Stephen Vincent B.S. Department of Chemistry University of Wisconsin Madison 5 Wisconsin U.S.A. Finch Arthur Ph.D. D.I.C. Department of Chemistry Royal Holloway College Englefield Green Surrey. Forrester Alexander Robert A.R.I.C. 3 Castleview Drive Bridge of Allan Stirling. Fothergill Graham Alwyn B.Sc. 13 Ashley Grove Aston Sheffield. Franta William Alfred B.A. M.S. 112 W. Pembrey Drive Wilmington 3 Delaware U.S.A.Freeman Robert D. B.S. Ph.D. Department of Chem- istry Oklahoma State University Stillwater Okla- homa U.S.A. Frost John Lawrence. Rosebank Trundle Mead, Horsham Sussex. Garraway James Lynton B.Sc. Wye College Wye nr. Ashford Kent. Geer Richard Perlee B.Sc. Department of Chemistry University of Rochester Rochester 20 New York U.S.A. Gerns Fred R. M.S. Ph.D. Wellcome Research Labora- tories Tuckahoe 7,New York U.S.A. Gortler Leon Bernard M.S. Department of Chemistry, Harvard University Cambridge Massachusetts U.S.A. Graham Colin Leslie B.Sc. 32 Marondale Avenue Walker Newcastle upon Tyne 6. Grant Louis Russell Jr. M.S. 4602 8th Avenue Los Angeles California U.S.A. Gray Alan. 4 Waterloo Road Poynton Cheshire.Grenda Victor Joseph B.S. Ph.D. 25 Manor Drive Newark 6 New Jersey U.S.A. Grim Samuel O. B.S. Ph.D. Department of chemistry University of Maryland College Park Maryland U.S.A. Groom Alan Thomas. 5 Capstone Avenue Oxley Wolverhampton Staffs. Grotewold Juan. Dil-Kusha Portland Street Aberyst- Wh. GUSS Cyrus O. Ph.D. Department of Chemistry Colorado State University Fort Collins Colorado U.S.A. Haim Albert Ph.D. Department of Chemistry Univer- sity of Southern California University Park Los Angeles 7 California U.S.A. Hancock Richard Anthony. 42 Chaffers Mead Ashstead Surrey. Hamdam Ali A, M.S. Department of Chemistry Seton Hall University South Orange New Jersey U.S.A. Hanson Jennifer May B.Sc. 11 Newton Drive Accring- ton Lancs.Hardy Paul Martin B.Sc. 12 Coleshill Road Sutton Coldfield Warwickshire. Harihara Krishnan Perambavoor Subramonia Iyer, B.Sc. Superintendent Laboratory Travancore Rayons Ltd. Rayonpuram P.O. Kerala State India. Harris John E. B.S. Ph.D. 36 Dietz Road Hyde Park 36 Massachusetts U.S.A. Harvey James Frederick B.Sc. 75 Elmore Street, London N.l. Hassan Ghulam M.Sc. Ph.D. Pathology Department Liaquat Medical College Hydcrabad West Pakistan. Hausser Jack Walter B.S. Ph.D. Department of Chem-istry Iowa State University Ames Iowa U.S.A. Heaton Brian G. Ph.D. Department of Chemistry Indiana University Bloomington Indiana U.S.A. Hebbourn Richard George Frederick. 101 Madden Avenue Chatham Kent. Heppell Gerald Ernest B.Sc.Department of Chemistry University of California Los Angeles 24 California U.S.A. Hepworth John David B.Sc. 21 Wellington Street Oakes Huddersfield. Hibbert Peter Glynn B.Sc. 82 Brodrick Road London s.w.17. Hodge Philip B.Sc. 5 Derwent Drive Sale Cheshire. Hodgson Anthony Malcolm B.Sc. A.R.C.S. Beverley Lodge Coombe Lane Kingston-upon-Thames Surrey. Hopkins Theodore Emo B.Sc. Ph.D. Stanford Research Institute Menlo Park California U.S.A. Hopkins Paul Donald B.S. Department of Chemistry University of Pittsburgh Pittsburgh 13 Pennsylvania, U.S.A. Huang Samuel Jienshek B.S. 275 Henry Street Brook- lyn 1 New York U.S.A. Hughes Elizabeth Eleanor Glenda B.Sc. Pandy Half- way Bridge Bangor Caerns. Hughes Gordon Ph.D. Department of Physical and Inorganic Chemistry The University Liverpool.Huibers Derk Theodoor Adriaan Ph.D. 42 Wabash. Avenue Kenmore Baffalo 17 New York U.S.A. Hutchinson David Wesley Ph.D. A.R.I.C. Department of Chemistry Massachusetts Institute of Technology, Cambridge 39 Massachusetts U.S.A. Janes John Francis. 64 Charles Street Bower Hill Epping Essex. Jayne Gerald John Joseph. 81 St. Kilda Road London W.13. Jenkinson Stuart Clifton. 20 Wilton Drive Whitley Bay Northumberland. Jones Merlyn. 65 High Street Hirwaun Aberdare Glamorgan. Kader Ali T. B.Sc. Department of Chemistry The Queen’s University Belfast Northern Ireland. Kadunce Raymond E. B.S. 275 Aubert Hall University of Maine Orono Maine U.S.A. Kaplan Leonard. 606 West Ohio Street Urbana, Illinois U.S.A.Katner Allen Samuel. 6 Island Hall Godmanchester,- Huntingdon. Ketcham Roger Ph.D. School of Pharmacy University of California Medical Center San Francisco 22, California U.S.A. Kiser Robert W. B.A. Ph.D. Department of Chemistry Willard Hall Kansas State University Manhattan Kansas U.S.A. Klopman Gilles Ph.D. 8 rue des LiIas Geneva Switzerland. Koong Kin Fatt B.Sc. Fugard Hall The University Hong Kong. Lavigne Joe Bryson Ph.D. California Research Corpora- tion 576 Standard Avenue Richmond California USA. Law Henry. 101 Hanover Road London N.W.lO. Laye Peter George B.Sc. 148 Wadham Gardens Green- ford Middlesex. Lehrian George Henry. 68 Folkestone Road London E.6. Lissi Eduardo Alejandro.FitzRoy 1750 Buenos Aires Argentina. Lock Helen Elaine B.Sc. 7 Bullen Court New North Road Hainault Ilford Essex. Loh Lucy Yung-Sen BSc. 43A Kimberley Road Kowloon Hong Kong. McCarty Richard Norman B.S. Department of Chem- istry Indiana University Bloomington Indiana U.S. A. McDonald Walter Stanley BSc. 24 Selwood Road Chessington Surrey. Macfarlaae Calum Brechin BSc. 156 Arbroath Road Dundee. McGregor William Herbert M.S. Ph.D. Union Carbide Research Institute. 32 DeDot Plaza White Plains New York USA. McIntosh. Donald Stevenson. B.Sc. 10 Colauhoun Drive Bearsden Glasgow. Mah Raymond Wei Hsien B.S. Department of Chem- istry Washington State University Pullman Washing- ton USA. Maheshwari TCrrishna Kumar MSc. Department of Chemistry Indiana University Bloomington Indiana U.S.A.Maine Francis William M.Sc. 5 Tenison Avenue, Cambridge. Mak Danny Shiu Hung B.Sc. Department of Chemistry University of British Columbia Vancouver B.C. Canada. Marsden Colin John. 36 Bexhill Road Adswood Stock- port Cheshire. Mason Ernest Arthur B.Sc. Ph.D. Davrine Hillcrest Place Kilwinning Ayrshire. Mehta Prakash Purshottamdas M.Sc. Department of Organic Chemistry The University Liverpool. Mendelson Wilford Lee M.A. 3831 Oakford Avenue Baltimore 15 Maryland USA. Miller Melvin Paul M.A. Loyola College Baltimore 10, Maryland U.S.A. Montgomery Anthony James B.Sc. Ph.D. 63 Freegrove Road London N.7. Montgomery Lawrence Kernan B.S. Ph .D. Depart- ment of Chemistry Harvard University Cambridge 38, Massachusetts U.S.A.Moodie Roy Brian Ph.D. Department of Chemistry Washington Singer Laboratories Prince of Wales Road Exeter Devon. Morton-Blake David Antony B.Sc. Department of Chemistry The University Glasgow. Mulvaney James E. Ph.D. Department of Chemistry University of Illinois Urbana Illinois U.S.A. Nelson Norman Stuart M.S. 2147 Columbine Avenue Boulder Colorado USA. PROCEEDINGS Newberry Robert Anthony. 69 Chaplin Crescent, Sunbury-on-Thames Middlesex. Oliveto Eugene Paul B.S. Ph.D. Schering Corporation Bloomfield New Jersey USA. Pan Hsi-lung M.S. Department of Surgery University of Washington School of Medicine Seattle 5,Washing-ton USA. Pannbacker Richard G. 925 Bluemont Manhattan Kansas U.S.A.Partch Richard E. B.A. Lattimore Hall University of Rochester Rochester 20 New York U.S.A. Partos Richard D. B.S. Department of Chemistry University College of Los Angeles Los Angeles 24, California U .S.A. Pethybridge Alan David. B.Sc. St. Patrick's Hall Reading Berks. Peyronel Giorgio Dr. Sc. Via S. Eufemia 19 Modena, Italy. Pilipovich Donald B.A. Ph.D. 6633 Canoga Avenue 591-356 Canoga Park California U.S.A. Pitcher Emily M.A. 91 Somerset Street Belmont 78 Massachusetts U.S.A. Pitt Colin Geoffrey Ph.D. Department of Chemistry Florida State University Tallahassee Florida U.S.A. Plambeck James A. B.A. 606 W. Ohio Street Urbana Illinois U.S.A. Porritt Christopher John. 5 Beresford Avenue Tolworth Surbiton Surrey. Porter Roger David BSc.74 Furniss Avenue Dore Sheffield. Quan Peter Michael B.Sc. 10 Lymeborne Avenue Heavitree Exeter Devon. Raleigh James Arthur B.Sc. 5040 Victoria Drive, Vancouver 16 British Columbia Canada Ralph Philip David B.A. University College Oxford. Rathbone Peter B.Sc. 25 Princess Road Shaw Oldham Lancs. Reid Philip Edward M.Sc. Department of Chemistry Queens University Kingston Ontario Canada. Rhodes Yorke Edward. Jr. M.S. 152 Noyes Laboratory University of Illinois Urbana Illinois U.S.A. Ripley Robert Allison Ph.D. National Research Council Pure Chemistry Division Ottawa 2 Ontario Canada. Roberts David Gordon BSc. Department of Chemistry, The University Edgbaston Birmingham 15. Robinson Howard Clem B.Sc. Exeter College Oxford.Sabet Claude Raymond B.Sc. 27a Kensington Place Campden Hill London W.8. Sach George Sidney B.Sc. A.R.I.C. 287 Hornblower Avenue Belleville New Jersey U.S.A. Salinger Rudolf M. M.S. Department of Chemistry University of Cincinnati Cincinnati 21 Ohio USA. Salvagnini Luciano D.Chem. Camposampiero Padova Italy. Saunders Robert Montgomery B.k. 36 Dulverton Avenue South Shields Co. Durham. Schulze Arthur William B.S. 1815 Bluebell Avenue Boulder Colorado U.S.A. Schweizer Martin Paul B.A. 11965 Davis Street Sunny- mead California U.S.A. Searle Roger A.B. 219 Noyes Laboratory University of Illinois Urbana Illinois U.S.A. Sharp David Charles B.k. 8 Algiers Road London S.E.13. Shelton Bertram M.Sc. A.R.I.C. Department of Chemistry Gordon Hall Queen's University Kingston Ontario Canada.Sissons Christopher Robert B.Sc. 40 Abbey Road Westbury-on-Trym Bristol. FEBRUARY 1961 Sleater Gerald A. B.S. 904 East Lake Avenue Baltimore 12 Maryland U.S.A. Smalley Robert Kenneth B.Sc. 44 Ashbourne Road Eccles Manchester. Smith James Gregory. 72 Rupert Road Sheffield 7. Smith Peter Brian B.Sc. 21 Foston Avenue Burton upon Trent Staffs. Spiggle David Warner M.S. University of Connecticut, Storrs Connecticut USA. Sprague Michael Jolyon. 4 Linden Terrace Benton Forest Hall Newcastle upon Tyne 12. Staab Heinz A. Dr.rer.nat. Chemisches Institut der Universitat Tiergartenstrasse Heidelberg Germany. Starratt Alvin Neil B.Sc. Department of Chemistry, University of Western Ontario London Ontario, Canada.Steck Warren Franklin. 207 Crescent Towers Saskatoon Saskatchewan Canada. Stocker Jack Hubert M.S. Ph.D. Department of Chem-istry Louisiana State University Lake Front New Orleans 22 Louisiana USA. Stoodley Richard John M.Sc. Gordon Hall Queen’s University Kingston Ontario Canada. Stratmann Wilfried. Kampstrasse 17 Oer-Erkenschwick (2 la) Germany. Strumza Jacob D.Sc. 13D Pinsky Street Mount Camel Haifa Israel. Sugden John Kennedy B.Pharm. M.P.S. 2 Holmesdale Road Kew Richmond Surrey. Tait Malcolm John B.Sc. 214 Tamworth Road, Newcastle upon Tyne 4. Tebby John Caesar. Department of Chemistry The University Nottingham. Thayer Gordon Littlefield Jr. A.B. Baker Laboratory Cornell University Ithaca New York U.S.A.Thompson Clifford John B.Sc. 70 Maidavale Crescent Styvechale Coventry Warwickshire. Thornley Ian Anthony. 8 Withington Road Whalley Range Manchester. Tribbeck Terence Donald. Queen’s College Oxford. Turner Malcolm Frederick. 465 Footscray Road, London S.E.9. Unrau A. M. Ph.D. Department of Chemistry Univer- sity of British Columbia Vancouver 8 Canada. Vass John David Ritchie B.Sc. 12 Church Hill Place Edinburgh 10. Vogt Herwart Curt M.S. Ph.D. Research Building Wyandotte Chemicals Corporation Wyandotte, Michigan USA. Wardale Harold William. 7 Hurtbank Holmbury St. Mary Dorking Surrey. Waters Owen John M.Sc. c/o National Bank of Australasia Ltd. Australia House London W.C.2. Watthey Jeffrey William Herbert B.Sc.A.R.C.S. 45 Kingston Road Oxford. Watts Alan Thomas B.Sc. 22 Gooding Avenue, Braunstone Leicester. Webster Dennis Edward B.Sc. 10 Bruin Street Leicester. Weiss Martin Joseph A.B. Ph.D. 975 Phyllis Lane Oradell New Jersey USA. Weiss Ronald M.S. Kedzie Chemical Laboratory Michigan State University East Lansing Michigan U.S.A. Weller Paul Franklin B.S. Baker Laboratory Cornell University Ithaca New York USA. White Dwain Montgomery B.S. Ph.D. 2045 Arkona Court Schenectady 9 New York U.S.A. White William N. M.A. Ph.D. Evans Chemical Laboratory The Ohio State University 88 West 18th Avenue Columbus 10 Ohio USA. Whiter Paul Francis B.Sc. 69 New Road South Darenth Dartford Kent. Whittingham Michael Stanley. Swallow Hill House Thurlby nr.Bourne Lincs. Wilde Marion Ilse Hedwig Ph.D. Department of Organic Chemistry The University Liverpool. Williamson Joseph Maclean BSc. 9 Scotstoun Street Glasgow W.4. Wilson Joseph William B.S. Department of Chemistry Indiana University Bloomington Indiana U.S.A. Wilson Raymond B.Sc. Department of Physical Chem- istry The University Leeds 2. Wong Ka Wing B.Sc. I.L. No. 7551 Sylvanbrook Block C Pokfulam Road Hong Kong. Wong Edmon Ph.D. 233 Broadway Avenue Palmerston North New Zealand. Wood Frank B.Sc. 50 Sprin&eld Road Baildon nr. Shipley Yorks. Zerner Burt M.Sc. Ph.D. A.R.A.C.J. Department of Chemistry Northwestern University Evanston, Illinois U.S.A. Ziderman Diane Gladys. 125 Church Drive London N.W.9. OBITUARY NOTICE WILLIAM HENRY CADMAN 1880-1 WILLIAM who was born at Silver- HENRYCADMAN dale Staffordshire on August 12th 1880 and died on February 20th 1960 at his home in Market Drayton Shropshire attained considerable note for his investigations into the manufacture and uses of carbon black and into the utilisation of waste gases from oilfields.Son of an eminent mining engineer in the Mid- lands and the younger of the two brothers of the late Lord Cadman formerly Chairman of the Anglo- Persian Oil Company (now The British Petroleum Company) he was educated at Newcastle-under- 960 Lyme High School and took his degree of B.Sc. at the University of Wales. In 1905 he entered the Egyptian Civil Service from which he was released on the outbreak of the First World War to join the Army.Wounded at Gallipoli in 1915 while serving with the Manchester Regiment he afterwards joined Allenby’s staff as Assistant Chemical Adviser and Commandant of the Central Gas School until the end of 1918. After the war he returned to Egypt becoming Professor of Agricultural Chemistry in Cairo Uni- versity. Later he was appointed Research Chemist to the Egyptian Government. He left Egypt in 1924 to join the Anglo-Persian Oil Company. After spending six months in the Company’s Sun- bury Research Station Cadman was posted to the pioneer oilfield in Iran at Masjid-i-Sulaiman where considerable developments were in progress. Cadman was put in charge of the process for the pyrolysis of hydrocarbon gases and at Bibian he established a plant which proved that aromatic derivatives could be produced from methane and its homologues.In 1930 Cadman returned to the United Kingdom to join the Production Department in the Head Office. There his main duties were concerned with the study of the production of carbon black. He also maintained a close interest in coal utilisation in rela- tion to its effect on the oil industry. During the ~ ~ ~~~ ~ ____~ Second World War in which he gained the M.B.E. (Military) Cadman was an enthusiastic member of the Home Guard. He later undertook work in Allied- occupied Germany investigating German methods of manufacturing and utilising carbon black. He retired aged 67 from service with the oil com- pany at the end of 1947.Cadman was a man of wide interests and great pertinacity. He contributed many papers on pure and applied chemistry to learned societies both at home and abroad. For a paper on the production of carbon black he was awarded the silver medal of the Royal Society of Arts. He was a Member of the Institution of Chemical Engineers and a Fellow of the Royal Institute of Chemistry. M. A. L. BANKS. ADDITIONS TO THE LIBRARY 1959 Supplement to the Bibliography of spectrophoto- metric methods of analysis for inorganic ions; prepared by M. G. Mellon and D. D. Bly. (Special Technical Publication No. 125-A.) Pp. 27. A.S.T.M. Philadelphia. 1959. Ullmanns Encyklopadie der technischen Cheniie. Edited by W.Foerst. Vol. 12. 3rd edn. Pp. 800. Urban &Schwarzenberg. Munich. 1960. Supplementary formula index for Microwave Spectro- scopy (by C. H. Townes and A. L. Schawlow). E. B. Wilson and J. R. Holton. Pp. 17. 1960. (Presented by the Royal Naval Scientific Service (A.C.S.I.L. Library).) United States. National Research Council. Sub-committee on Radiochemistry. Source Material for radio- chemistry. (Nuclear Science Series-Report No. 27 (rev. l).) Pp. 39. National Research Council. Washington. 1960. (Presented by the publisher.) Titration in non-aqueous solvents. A. H. Beckett and E. H. Tinley. 3rd edn. Pp. 56. British Drug Houses Ltd. Poole Dorset. 1960. (Presented by the publisher.) New uses for gas-liquid chromatography in plastics. W.H. Parriss and P. D. Holland. (Ressarch Laboratory Reprint from British Plastics August 1960.) Pp. 4. A.E.I. Research Laboratory. Rugby. 1960. (Presented by the publisher.) Chemistry technology and uszs for derivatives of pyridine and quinoline. (In Russian.) Pp. 299. Latvian Academy of Sciences. Riga. 1960. (Presented by the publisher.) A history of platinum from earliest times to the eighteen-eighties. D. McDonald. Pp. 254. Johnson Matthey &Co. Ltd. London. 1960. (Presented by the publisher.) I.C.I. Titanium 3 Corrosion resistance. Pp. 186. I.C.I. Metals Division. Birmingham. 1960. (Presented by the publisher.) Demineralization by electrodialysis. Edited by J. R. Wilson. South African Council for Scientific and In- dustrial Research.Process Development Division. Pp. 378. Butterworths Scientific Publications. London. 1960. Chemical engineering practice. Edited by H. W. Cremer and S. B. Watkins. Vol. 10. Pp. 606. Butterworths Scientific Publications. London. 1960. (Presented by the publisher.) Practical organic chemistry. F. G. Mann and B. C. Saunders. 4th edn. Pp. 585. Longmans. London. 1960. (Presented by the authors.) Organic chemistry of bivalent sulfur. E. E. Reid. Vol. 3. Pp. 486. Chemical Publishing Co. Inc. New York. 1960. The nucleic acids. Edited by E. Chargaff and J. N. Davidson. Vol. 3. Pp. 588. Academic Press. New York. 1960. The enzymes. Edited by P. D. Boyer H. Lardy and K. Myrback. Vol. 4.2nd edn. Pp. 631. Academic Press. New York. 1960. The plasma proteins.Edited by Frank W. Putnam. Vol. 2. Pp. 518. Academic Press. New York. 1960. The chemistry of lignin. Supplement volume covering the literature for the years 1949-1958. F. E. Brauns and D. A. Brauns. Pp. 804. Academic Press. New York. 1960. Laboratory handbook of toxic agents. Edited by C.H. Gray. Pp. 170. Royal Institute of Chemistry. London. 1960. (Presented by the R.I.C.) Toxic phosphorus esters :chemistry metabolism and biological effects. R. D. O’Brien. Pp. 434. Academic Press. New York. 1960. The Pharmacopeia of the United States of America (the United States Pharmacopeia). Pp. 1148. Mack Publishing Co. Easton Pa. 1960. Schweizerische Arbeitsgemeinschaft fur Spektral-aiialyse. VIII. Colloquium Spectroscopicum Interna- tionale held in Lucerne 1959.Edited by H. Guyer. Pp. 319. H. R. Sauerlander &Co. Aarau. 1960. The determination of gases in metals report of a symposium organised by the Society for Analytical Chemistry in conjunction with the Iron and Steel Institute and the Institute of Metals. (Iron and Steel Institute Special Report No. 68.) Pp. 308. Iron and Steel Institute. London. 1960. (Presented by the Iron and Steel Institute.) Proceedings of the fourth conference on carbon held at the University of Buffalo Buffalo New York 1959. Sponsored by the American Carbon Committee and the University of Buffalo. Pp. 778. Pergamon Press. Oxford. 1960. Symposium on steric aspects of the chemistry and bio- chemistry of natural products held by the Biochemical Society in London in 1959.Edited by J. K. Grant and W. Klyne. Pp. 137. University Press. Cambridge. 1960. (Presented by the Biochemical Society.) NEW JOURNALS Polymer Science U.S.S.R. (English translation of Vysokomolekulyrnya Soedineniya) from 1960 1.
ISSN:0369-8718
DOI:10.1039/PS9610000033
出版商:RSC
年代:1961
数据来源: RSC
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