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Proceedings of the Chemical Society. February 1963 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue February,
1963,
Page 33-72
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY FEBRUARY 1963 REPORT OF COUNCIL 1961-1962 I. GENERAL however refers to the calendar year 1962 as this Period of Report.-The financial section of this corresponds with the subscription period. report and the sections dealing with appointments 11. FELLOWSHIP meetings and other events relate to the twelve 1. Statistics.-The number of Fellows increased months ended September 30th 1962. Statistical in- during 1962 by 1,408 to a total of 13,177 (see Table formation dealing with Fellowship and Publications 1). The net growth is the highest in the Society’s TABLE1. Fellowship changes 1957-1962. 1957 1958 1959 1960 1961 1962 No. of Fellows on Jan. 1st 9,074 9,389 9,539 9,943 10,909 11,769 Additions Elections .... 765 595 802 1,326 1,246 1,797 Reinstatements . . 24 37 29 27 16 19 -1 -Miscellaneous .. .. -789 -632 -83 1 -1,354 -1,262 -1,816 Deductions Deaths . . .. .. 52 54 73 67 61 52 Resignations .. .. 293 277 194 194 198 21 8 Removals .. .. 129 150 159 127 142 138 -1 -Miscellaneous .. .. -1 1 -474 -482 -427 -388 -402 -408 Fellowship growth .. 315 150 404 966 860 1,408 No. of Fellows on Dec. 31st 9,389 9,539 9,943 10,909 1 1,769 13,177 Annual Fellowship changes expressed as percentage of total Fellowship at Jan. 1st each year % % % % % % Additions . .. . . 8.7 6.7 8.7 13.6 11.6 15-4 Deductions . . .. .. 5.2 5.1 4.5 3.9 3.7 3.5 33 history and the Council is particularly gratified to report the rising trend of elections and the decline in the percentage year by year of those whose Fellow- ship is terminated.The figures suggest that the steps taken in recent years to attract more enquiries for Fellowship have been well founded and the Council welcomes this influx of applications from suitable candidates since the larger the Fellowship the better can the Society fulfil its primary purpose of promoting the general advancement of chemical knowledge. An analysis has been made of the occupations of all the 1,797 Fellows elected in 1962 (Table 2). This clearly indicates that most Fellows are elected whilst they are still students at a University or Tech-nical College. The low level of resignations in recent years however suggests that a majority will retain their Fellowship after taking up appointments in industry or elsewhere.In most cases it is possible to tell how the applicant came to receive his application form. The largest group (35.6%) was introduced by Fellows. The other main sources were by direct applications to the General Secretary (26.5 x); through Local Representatives (15.2 %) ;and through Liaison Officers (6.9 %). A geographical analysis of the Fellowship (Table 3) indicates that the proportion of Fellows overseas has increased significantly over the past four years. This results from the exceptional growth of Fellow- ship in the United States of America. 2. Deaths.-Amongst those whom the Society has lost by death were Dr. E. VV. R. Steacie who was elected an Honorary Fellow of the Society in 1958; Dr.J. Kenyon a Vice-president from 1939 to 1942; and Mr. S. J. Pentecost who was elected in 1886 and was the senior Fellow of the Society at the time of his death. 3. Honours.-The congratulations of the Society were conveyed to Sir Alexander Todd on the award of a Life Peerage announced shortly before his re- tirement from the Presidency; to the President Professor J. M. Robertson on the award of the C.B.E.in the Birthday Honours List; and to the following whose names were included in the Birthday or New Year Honours List Baronet Sir Harry Jephcott K.B.E. Sir Charles Harington C.B. Edward Arthur Perren C.B. E. Norman Joseph Lane Megson PROCEEDINGS The Council also conveyed congratulations to Professor Melvin Calvin on the award of the Nobel Prize for Chemistry; to Sir Hans Krebs and Professor D.H. R. Barton on the award of the Copley and the Davy Medal respectively of the Royal Society; and to Professor V. Prelog Honorary Fellow on his election as a Foreign Member of the Royal Society. TIT. PUBLICATIONS 1. Journal,--(a) The customary statistics are given in Tables 4-7 for the Journal for the year January- December 1962. They show (Tables 4 and 5) that the number of papers and notes published was less than in 1961 (1962 1,019; 1961 1,094) though the average length was greater (1 962,523 ;1961,5.08 pp.). (There appears to have been a general increase in the average length of papers since 1958.) That the Journaf for 1962 was smaller than for 1961 was due to difficulties at the printers early in the year which led to small issues for the first four months of the year and were rectified later.The most notable feature of the year was however a sharp rise in the number of papers and notes sub- mitted which reached 1,269. The numbers from 1948 to 1962 are shown in Table 8. The receipts in 1961 had taxed the editorial office severely and the still larger figures of 1962 could not all be handled editorially during the period of the Summer holidays. The arrears of editing that accumulated were worked off by November whereupon the printers made special arrangements very large issues of the Journal for the first months of 1963 are assured and the position will be restored by about the April issue.A 1963 Journal of 6,000-6,500 pages is anticipated. The increased receipts for 1962 raise vital questions for the future financing and organisation of the Journal but prediction is at present very difficult. (h) Contributions published in 1962 from in-dustrial laboratories and industrial research organi- sations totalled 95 (including 7 jointly with academic institutions and 1 with a Government organisation); this represents 9.3 % of the total (the figures for 1961 were 123 and 11.2%). Published contributions from Government sources were 53 (including 5 jointly with academic or industrial organisations) amount- ing to 5.2% of the total (1961 45 4-1 %). Published contributions from outside the United Kingdom (see Table 6) during 1962 numbered 264 (including 17 jointly with British laboratories) amounting to 26.0 % of the total ( 1961 258 23-6 %).2. ProeeedinEs.-During 1962 Proceedings con-tained 197 scientific short communications the Presidential address and 6 lectures 8 special articles 8 reports of meetings 22 obituary notices the Annual Report of Council and various recurring items. The FEBRUARY 1963 35 TABLE 2. Occupations of newly elected Fellows. (Expressed as percentage of all elections for twelve months,January-December 1962) Academic Industrial Not known Total (%) (%) (%I (%) British Isles Age over 27 .. 6.2 3.6 0.3 10.1 Ageunder 27 . 40.8 6-5 1.3 48.6 Total .. . . 47-0 10.1 1.6 58.7 Overseas Age over 27 ..10.9 6.6 0.2 17.7 Ageunder 27 .. 21.8 1.6 0.2 23.6 Total .. .. 32.7 8-2 0.4 41-3 World Age over 27 .. 17.1 10.2 0.5 27.8 Ageunder 27 .. 62.6 8.1 1.5 72.2 Total .. .. 79-7 18.3 2.0 100*0 TABLE 3. Geographical distribution of the Fellowship. 1958 1960 1962 British Isles .. . . 6,404 (67.1 %) 7,310 (67.0'4 8,264 (62.7%) The Commonwealth. . 954 (10.0%) 1,090 (10.0%) 1,341 (10.2 %) U.S.A. .. .. 1,417 (14.9%) 1,698 (15.6%) 2,549 (19.3%) Other Countries . . 764 (8.0%) 81 1 (7.4%) 1,023 (74%) Total .. .. . 9,539 10,909 13,177 TABLE 4. Numbers of scientific items in the Journal. 1958 1959 1960 1961 1962 Papers (General Physical and Inorganic). . .. 173 182 252 236 237 Papers (Physical Organic) .. .. .. .. 1 70 156 197 201 197 Papers (Organic) .. .. .. .. .. 476 394 461 498 430 Notes .. *. .. .. .. .. .. 157 108 112 159* 155t 976 840 1,022 1,094 1,019 * Gen. Phys. Tnorg. 41 :Phys.-Org. I8 ;Org. 100. t Gen. Phys. Inorg. 36; Phys.-Org. 21; Org. 98. TABLE 5. Contributions to the Journal. 1958 1959 1960 1961 1962 Papers and Notes received .. .. .. .. 1,005 1,056 1,084 1,127 1,269 Less rejected or withdrawn .. .. .. 57 51 56 80 71 948 1,005 1.028 1,047 1,198 Papers and Notes published.. .. .. .. 976 840 1.022 1,094 1,019 No. of pages (Papers and Notes) .. .. .. 4,784 4,141 5,276 5,563 5,303 Average number of pages per contribution .. 4.90 4.93 5-16 5-08 5-23 PROCEEDINGS TABLE 6. Papers and Notesfromoutside United Kingdom. (Parentheses indicate publication jointly with a British laboratory.) Australia .... .. *. .. *. Commonwealth (countries not separately listed) .. Canada.. .. .. *. .. .. .. Egypt .. .. .. .. France .. .. .. .. .. *. .* .. .. .. Hungary .. *. .. *. .. .. India Pakistan and Ceylon. . Irish Republic. . .. .. Israel .. .. .. .. .. .. .. .. .. *. 1. .. *. Italy .. .I .. .. NewZealand .. .. .. .. .. .. .. *. .. South Africa .. .. .. .. .. .. U.S.A. .. .. .* .. .. .. .. Japan .. .. .* .. Belgium .. .. .. Romania . . .. .. *. .. .. .. .. .. .. .. *. Switzerland .. .. .. .. .. .. Miscellaneous . . .. .. *. .. .. 167 (20) 212 (26) 211 (8) TABLE 7. Percentage distribution in the Journal. Papers (General Physical Inorganic) .. Papers (Physical Organic) . . .. ..Papers (Organic) .. .. .. .. I. 0. Notes .. .. .. .. 1958 1959 1960 1961 A* B* . . 17.7 21.6 24.7 21-6 25.3 .. 17.4 18.6 19.2 18.3 200 .. 48.8 46.9 45-1 45.1 54.7 . 16.1 12.9 11.0 14.6 - - - - 100.0 100.0 100.0 100.0 100.0 * A Notes not classified. B Notes classified and included with papers. standard required for acceptance of communications was again raised during the year and the number and proportion published were slightly less than in 1961 (seeTable 9) averaging 14.7 pages a month; during 1962the total submitted was 347 slightly more than in 1961 but much less than the previous increases might have led one to expect. 3. Annual Reports on the Progress of Chemistry for 1961 Volume LVIDI.-This Volume contained 530 pages (572 in Volume LVII) and was issued in August 1962 the new printers achieving faster printing than had been possible in previous years.4. Quarterly Reviews.-Volume XVI contained 17 articles occupying 447pages. Volume XV (1961) had contained 17 articles occupying 460 pages. 5. Current Chemical Papers.-Tables 10 and 11 give statistics in the form of previous years. There were material increases in the numbers of titles listed and of journals scanned; the number of printed pages however did not change as a more compact typeface is now used. 6. Special Publications.-Specid Nos. 15 and 16 being reports of the Society’s Sym- posia held at Nottingham in July 1961 and at Sheffield in April 1962 were published in 1962. A supplement to Special Publication No.11 (Tables of Interatomic Distances) is in the press; and issue of a second (combined) edition of Special Publication Nos. 6 and 7 (Stability Constants) is expected in 1963. TABLE 8. Numbers ofPapers submitted to the Journal. Year No. Year No. 1948 .. 531 1956 .. 1,OS 1 1949 .. 720 1957 .. 1,048 1950 1951 . . . . 806 908 1958 1959 . . .. 1,005 1,056 1952 . . 1,046 1960 .. 1,084 1953 .. 946 1961 .. 1,127 1954 .. 1,019 1962 .. 1,269 1955 .. 1,084 264 (17) 1962 A* B* 23.3 26.7 19.3 21.3 42.2 52.0 15.2 -_I__-100.0 100.0 Publications FEBRUARY 1963 37 TABLE 9. Numbers of Communications for Proceedings. 1958 1959 1960 1961 1962 Rec.Publ. Rec. Publ. Rec. Publ.Rec. Publ. Rec. Publ. Total (year). . *. *. 128 93 203 148 236 170 326 218 347 197 100 x Publ./Recd. f. -73 -73 -72 -67 -57 TABLE 10. Current Chemical Papers summary. 1955 1958 1959 1960 1%1 1962 Titles of papers listed .. .. .. 21,360 26,030 27,440 27,916 28,433 31,101 Pages of Current Chemical Papers .. 706 835 909 913 1,091 1,090 Total no. of journals scanned .. .. 469 519 521 539 537 582 Issues of journals yielding titles .. 2,277 2,726 2,624 2,369 2,330 2,415 Issues not yielding titles .. .. 1,438 1,037 1,392 1,443 1,559 1,707 TABLE 11. Languages used in papers included in Current Chemical Papers (approximate percentages). 1956 1957 1958 1959 1960 1961 1962 EnglishGerman .. .I 4 . .. .. .. 55.1 13.0 55.8 11.8 56.8 13-6 55.4 13.5 53-9 12.0 55.9 12.1 55.6 11.6 Russian (.. .. .. 12.1 11.5 11.8 14.0 17-1 15.5 17-5 JapaneseFrench .. .. .I .. .. .. 6.5 6.1 6.1 5.6 4.7 5.6 4.8 5.2 5.9 5.1 5.6 4-8 5.1 4.8 Czech 1. .. .. 2.1 3.6 2.2 1.0 0.9 0.7 0.8 Italian .. .. *. 1.8 1.6 1.8 2.2 1.7 1 *7 1.7 Polish .. .. .. 0.5 1.2 1.0 1.6 1.3 1.9 1.3 Miscellaneous .. .. 2.8 2-8 2.5 2.3 2.1 1*8 1.6 - 100.0 100-0 100.0 100.0 100.0 100.0 100.0 IV. ~RAC”IV~S “Nitrogen Heterocyclic Chemistry,” arranged by the 1. Anniversary Meetings and Symposia.-The Hatfield College of Technology in May 1962; and Anniversary Meetings were held in Sheffield on in September 1962 it sponsored an informal meeting April 2nd to Sth 1962 and attracted a very high on “Deviations from Regular Structures” arranged attendance.In addition to Lord Todd’s Presidential in Oxford as the first of a series of annual “Oxford Address entitled “Some Observations on Organic Inorganic Discussions.” Phosphates,” Symposia on “The Structure Oxida- tion and Biosynthesis of Naturally Occurring 2. Other Scientific Meetings and Lectures.-Phenols,” on “Reactivity and Structure in Inorganic Details of meetings held in London and in other Chemistry,” and on “The Transition State” were centres arranged by Local Representatives have arranged and the last-named has been published as been published in Proceedings. As in former years No. 16 in the Society’s series of Special Publications. many meetings held outside London were arranged Sponsored jointly with the University of Birming- jointly with the local sections of other bodies and ham an International Symposium on “Carbohydrate local student chemical societies.Chemistry” to commemorate the life and work of It was decided that as an experiment scientific Sir Norman Haworth was held in July 1962 in the meetings held in London during the first part of the new Haworth Chemistry Building. This proved to be session 1962-63 should begin at 6 p.m. instead of a very successful meeting attracting many visitors 7.30 p.m. It appears that generally the earlier start from overseas. has been welcomed and the experiment is to be con-The Society also supported a Symposium on tinued for the remainder of the session. 3. Library.-An indication of the expansion of the size and use of the Library is given in Table 12.The growth since 1960 is a direct result of the Library Subscribers scheme started to enable insti- tutions and industrial organisations to have full use of the Library services on payment of a small annual subscription. The supply of photocopies has risen particularly steeply during 1961-62. This is due to the installa- tion of a Xerox photocopying machine which has enabled copies to be produced more quickly and since May 1962 at cheaper rates. Users of the Library have been quick to take advantage of this improved service which the Society also offers to other Societies in Burlington House. In a full year the total demands on the photocopy service may be expected to be substantially larger. Without the addi- tional demands to be expected from Library Sub- scribers it is doubtful if the installation of this equip- ment could have been justified economically by the requirements of individual users alone.The constant increase in numbers of periodicals taken further aggravates the accommodation prob- lem. Altogether 687 periodicals are taken in the library an increase of 29 in the year. The thanks of the Society are due to those who presented some 130 books and pamphlets. 4. Grants for Research.-Grants totalling E1,083 11s. Od. were made to 27 applicants. 5. Robert Robinson Lectureship.-The Robert Robinson Lectureship was founded during the year as a result of an endowment received from the Sir Robert Robinson Foundation Inc. which was created to receive the royalties donated by the authors of “Perspectives in Organic Chemistry” published in commemoration of Sir Robert Robinson’s seventieth birthday and supplemented by contributions from PROCEEDINGS other sources.The Lecture which should review progress in any branch of chemistry is to be given once during the Presidential term of office. The Lec-ture will be delivered at the Society’s Anniversary Meetings and it is intended to alternate with the Presidential Address. The inaugural lecture will be given at the Anniver- sary Meetings to be held in Birmingham in 1964. 6. Ethel Behrens Fund.-Details of this Fund have been given in Proceedings 1962 p. 341 and the first awards of grants will be made in connection with the Anniversary Meetings in Cardiff in March 1963.7. 75th Anniversary Celebrations of the Belgian Chemical Society.-Lord Todd represented the Society at these Celebrations held in Brussels in June 1962 and presented a formal address of con- gratulation. He also gave a Plenary Lecture at the Symposium held in connection with the Celebrations. 8. 50th Anniversary celebrations of the Argentine Chemical Association.-Sir Robert Robinson repre- sented the Society at these Celebrations held in con- junction with the VIII Latin-American Congress of Chemistry in Buenos Aires in September 1962. 9. British Chemical Education.-Under the joint sponsorship of the Royal Society and the Royal Institute of Chemistry a Committee on British Chemical Education has been set up to promote im- provement in the teaching of Chemistry in schools.The Society has accepted an invitation to be associated with this activity and has nominated Pro- fessor C. C. Addison to serve on the Committee. 10. Dalton Bicentenary.-In collaboration with a number of other bodies the Society has initiated preliminary discussions concerning the celebration in 1966 of the bicentenary of the birth of John Dalton. An exploratory Committee on which the Royal Society the Manchester Literary and Philo- TABLE12. Library services. 1957-58 1958-59 1959-60 19-61 1961-62 Additions to the Library Books .. *. Pamphlets .. Attendances .. Books loaned In person .. By post. . .. Photocopies supplied Microfilm .. Prints .. .. I. .. I..* 315 45 299 35 262 36 317 56 368 43 *.*. 7,455 7,512 7,623 7,726 8,433 .. .. 4,186 4,086 6,546 6,861 7,283 .. .. 3,601 3,800 4,293 8,162 8,882 7,787 7,886 10,839 15,023 16,165 .. .. 2,794 3,686 3,565 2,388 1,779 .. f. 4,766 3,600 5,397 5,515 16,228 7,560 7,286 8,962 7,903 18,007 FEBRUARY 1963 sophical Society The Chemical Society the Royal Institute of Chemistry the Society of Chemical In- dustry and the Science Museum were represented has reported to the bodies concerned and an an- nouncement giving preliminary details of the proposed celebrations will be made in due course. 11. Index Chemieus.-The arrangement whereby Index Chemicus published by the Institute of Scientific Information Philadelphia U.S.A. was offered at reduced rates to Fellows of the Society was withdrawn by the Institute at the end of 1962because of the inadequate response.v. FINANCE AND ADMINISTRATION 1. General Purposes Account.-The growth of the Fellowship has yielded a further increase in income from subscriptions. This and the rising income from investments and short-term deposits has enabled the Society to meet the ever-growing cost of all its activities and still to maintain a reasonable surplus on the account without the need for an increase in the annual Fellowship subscription. Administration costs have again risen but the cost per Fellow of administration remains at a level which has grown very little over the past ten years (Table 13). A trans- fer has been made to an Accommodation Reserve for the reasons referred to in paragraph 6 (p.40). 2. Publications Account.-Revenue from publica- tions has grown during the year by about E6,000as a result of the increased circulation of all publica- tions (Table 14). There is however a further drop in the number of Fellows in the United Kingdom taking the Journal and the Council recognises that this is inevitable as a result of a combination of high prices increased size and greatly improved library facilities. The expenses of publication also unfortu- nately continue to rise and the Council is concerned at the prospect of further increases in cost which the future will most certainly bring. The reduced ex- penditure on the Journal and Proceedings and on Quarterly Reviews is due entirely to the fact that fewer pages were published in the financial year and has no significance for the future An exceptionally large Journal was produced in the year 1960-61 because of the publication of papers held up by the printing strike of 1959.The size and the cost of publications must inevitably increase substantially in 1962-63. Starting in 1962 the Society has assumed direct responsibility for the sale and despatch of the English translations of the three Russian Chemical Journals which it has published for the past few years under a contract with the Department of Scientific and Industrial Research (see also section 111). The sale and distribution of these journals can readily be integrated with the sale of the other pub- lications of the Society and should lead to economies for the Society in future years as well as to a reduc- tion in the cost to D.S.I.R.Under its contract the Society is able to recover full cost of the translation printing and distribution including the appropriate proportion of overhead expenses. After direct ex- penses for the work in 1961-62 have been met the balance amounting to &206 has been used to reduce the relevant overhead costs in the Accounts. This figure will rise considerably in 1962-63. 3. Library Account.-Expenditure on the Library has increased from El 7,809 to 21 9,998.Over f.1,OOO of this increase relates to the cost of new books and periodicals binding and other capital expenditure for which the Society carries the sole responsibility.Maintenance charges on the other hand have for many years been a joint responsibility since after a direct contribution from the Chemical Council and certain other receipts have been taken into account the balance is shared between a number of contribut- ing societies whose members are entitled to use the library. The apportionment is calculated on the basis of membership with allowance for overlap. TABLE 13. Administration costs. No. of Fellows at end of Administration Year financial period costs f. 1953 .. .. 1954 . . .. .. .. 9,249 9,123 8,948 8,666 1956 .. .. 1957,9 months 1955 .. .. 1957-58 1958-59 1959-60 1960-61 196142 .. .. .. .. .. .. .. .. .. .. .. .. .. 9,074 9,376* 8,936 9,476* 9,874* 10,797* 1 1,647* 12,882* 8,079 5,934 8,200 9,154 10,593 7,024 12,403 13,504 Cost per Fellow of administration S s.d. 19 4 19 0 15 9 17 10 12 8t 17 4 18 6 19 8 1 1 10 110 * At September 30th. t Equivalent to 16s. lld. for 12 months. The Council is pleased to acknowledge a grant of E2,OO awarded by the Chemical Council of which El3389 represents the normal contribution towards maintenance and the balance of $61 1 will reduce the Society’s liability for capital expenditure. 4. Trust and Lecture Fund Accounts.-The income of the trust funds has improved during the year and two new funds the Ethel Behrens Fund and the Robert Robinson Lecture Fund have been added. In accordance with an Order made by the Charity Commissioners the capital of these two new funds is now consolidated in the combined pool of trust investments.Altogether a total of E6,820 has been added to the pool on behalf of the following funds E .I Ethel Behrens Fund . . . . 2,350 Centenary Fund .. 750 Corday-Morgan Medal and Prize Fund 50 Corday-Morgan Memorial Fund . . 200 Robert John Flintoff Trust .. 50 .I Robert Robinson Lecture Fund . . 3,420 E6,820 5. Inv&ments.-During the year there have been no changes in investment policy for the Society’s funds and the Council remains well satisfied with the arrangements made with Messrs. J. Henry Schroder Wagg and Co. Limited for the supervision of its investments. If allowance is made for investment changes and for additional money invested by the Society it can be shown that the value of the Society’s General Purposes investments increased by approximately 5%.During the same period the Financial Times Index of Industrial Ordinary Shares fell by 9%. The Council regards this comparison as most satisfactory. The value of the Trust Invest- ments which however include a higher proportion of fixed-interest securities also appreciated by a comparable amount. 6. Accommodation.-In addition to the Rooms in Burlington House the Society occupies offices leased through the Ministry of Works in Savile Row and in Cornwall Terrace Regents Park and storage space in Savile Row leased independently. This accom- modation is grossly inadequate in total area in many ways inappropriate to the Society’s needs and in- convenient because it is so dispersed.Moreover the accommodation outside Burlington House is all held on leases which expire within 3-4 years. It will be recalled that as long ago as June 1958 it was an- nounced in Parliament by Lord Hailsham then Lord President of the Council that discussions were pro- ceeding between the Ministry of Works and the Learned Societies at present in Burlington House over the question of their future accommodation needs. Since then as announced in the House of PROCEEDINGS Commonson January 25th 1962 by the Chief Secre-tary to the Treasury an offer of additional accom- modation in Burlington Gardens was made by the Government to the Learned Societies.Confidential discussions on the accommodation difficulties continue and the Council is hopeful that a satisfactory solution will be found within the rela- tively near future. It may be necessary to refurnish and equip any accommodation which is made available to meet the varied requirements of the Library and the general administration of the Society as well as the issue of the Society’s publications including editing which requires an increasing amount of office space. Accordingly special allocations of f5,W from General Purposes Account and $5,000 from Publica- tions Fund Account have been made to a newly created Accommodation Reserve. 7. Council.-The following appointments were announced at the Annual General Meeting held in Sheffield on April 4th 1962 President Professor J.M. Robertson Honorary Secretary Dr. J. W.Linnett Vice-Presidents who have not filled the Ofice of President Professor D. H R. Barton Dr. J. Chatt Professor B. Lythgoe EZected Ordinary Members of Council Constituency I Dr. G. W. A. Fowles Dr. A. R. Katritzky Dr. A. I. Vogel Constituency II Dr. W.J. Orville-Thomas Constituency 111 Professor J. Baddiley Professor F. S. Dainton Dr. T. J. King In May Dr. L. Crombie was appointed to serve on the Council until the next Annual General Meet- ing to fill the vacancy caused in Constituency I by the election of Dr. J. VV. Linnett as an Honorary Secretary. It was decided that the business of the Council could be adequately conducted with fewer meetings during the year if the routine business were appropri- ately arranged thus making it unnecessary for Members to travel long distances for meetings that consisted mainly of formal business.Bye-Law 57 was accordingly amended at the Annual General Meeting in April to permit a minimum of five in place of eight meetings during the year. It is intended that when necessary additional meetings will be called to consider urgent matters that may arise. FEBRUARY 1963 ~ -~~ TABU14. Distribution of Publications. Home Overseas Total Fellows Non-Exchanges Fellows Non-Exchanges Fellows and free Fellows and free Journal 1953 .. .. .. .. 2,286 221 32 1,644 2,052 56 6,291 1954 .. .... .. 2,044 223 30 1,717 2,131 60 6,210 1955 .. .. .. .. 1,611 264 28 1,632 2,257 62 5,854 1956 .. .. .. .. 1,449 281 25 1,657 2,168 61 5,641 1957 .. .. .. .. 1,370 291 25 1,699 2,382 52 5,819 1958 .. .. .. .. 689 338 26 1,233 2,527 75 4,888 1959 .. .. .. .. 633 343 26 1,175 2,584 75 4,836 1960 .. .. .. 606 367 26 1,194 2,766 76 5,035 0. 1961 .. .. .. 580 381 26 1,200 2,885 83 5,155 *a 1962 .. *. .. 540 380 27 1,214 3,061 83 5,305 0. Proceedings 1957 .* .. .. .. 6,392 295 29 2,810 2,413 66 12,005 1958 .* .. .. .. 6,338 344 29 2,897 2,575 87 12,270 1959 .. .. .. .. 6,804 350 30 3,127 2,605 87 13,003 1960 .. *. .. .. 7,345 372 30 3,603 2,792 91 14,233 f. 1961 .. .. .. 7,662 385 29 4,501 2,925 98 15,150 1962 .. .. .. .. 8,290 385 30 4,824 3,082 99 16,710 Current Chemical Papers 1954 .... .. .. 95 1 227 43 426 540 31 2,218 1955 .. 823 197 37 484 760 42 2,343 1956 . 832 249 40 579 956 58 2,714 ___. .. f. .. 910 256 31 717 1,144 55 3,113 1957 -* . 1958 .. .. .. *. 821 276 38 693 1,186 82 3,096 1959 .. .. *. .. 861 295 41 734 1,293 90 3,314 1960 .. .. .. .. 902 320 44 830 1,444 93 3,633 1961 .. .. .. 935 335 42 898 1,468 100 3,778 1962 .. .. .. .* 947 356 40 972 1,652 100 4,067 Quurterl’ Reviews 1953 .. .. .-.. 4,417 202 14 1,598 666 12 6,909 1954 .. .. .. 4,376 235 14 1,778 762 18 7,183 .% 1955 .. .. .. 3,921 288 11 1,808 898 21 6,947 1. 1956 .. .. .. .. 3,886 311 12 1,932 1,091 22 7,254 1957 .. .. .. 3,981 321 10 2,133 1,270 23 7,738 .I 1958 .. .. .... 4,032 367 11 2,189 1,368 38 8,005 1959 .. .. .. .. 4,147 382 11 2,326 1,422 41 8,329 1960 .. .. .. 4,656 409 12 2,705 1,517 43 9,342 I. 1961 . .. .. .. 4,88 1 424 13 3,114 1,687 50 10,169 1962 .. .. .. .. 5,358 438 14 3,699 1,855 50 11,414 8. Local Representatives.-The following changes Glasgow . Dr. H. C. Wood in place of among Local Representatives were made during the Dr. G. H. Nancollas year Hull .. . . Dr. C. C. Barker in place of Dr. G. C. Bond Aberystwyth .. Dr. A. H. Price in place of Leicester .. Mr. R. W. Bott in place of Dr. W. J. Orville-Thomas Dr. E. R. A. Peeling Birmingham . . Dr. A. B. Foster in place of Melbourne . . Professor R. L. Martin in place Dr. A. S. Jones of Dr. J. F. Duncan Cambridge . Dr. E. A. V. Ebsworth in place Newcastle .. Dr. J. G. Buchanan in place of of Dr. A. R. Katritzky Dr. F. J. McQuillin Nottingham .. Dr. W. E. Addison in place of Dr. T. J. King Southampton .. Dr. G. W. A. Fowles in place of Dr. I. G. M. Campbell Swansea .. Dr. R. F. Curtis in place of Mr. R. H. Davies 9. Liaison Officers.-Liaison Officers have been appointed at a number of additional institutions and a list of those serving the Society in this way is given as an Appendix to this Report. The Council recog- nises that these appointments constitute a valuable link with Fellows at widely different types of institu-tions and they have done much to make known the facilities which the Society offers to its Fellows. 10. Free Publications for Younger Fellows.-The Council has decided that the age at which Fellows of the Society should cease to receive the Annual Reports and QuarterZy Reviews free of charge should be lowered from 27 to 25 years as from January lst 1964.It may be recalled that the age limit which was originally 25 years was raised to 27 because of the calls on students of National Service and the con- sequent delay in training in chemistry. 11. Staff.-On the retirement of the Finance Officer Mr. H. J. Morris after over 50 years of service new appointments among the existing staff of the Society were approved by Council as follows Finance Officer Mr. R. G. Theobald Administrative Officer Mr. A. Turpin Publication Sales Officer Mr. W. D. Broomhead Fellowship Recorder Mrs. G.M. Rosswick VI. ACKNOWLEDGEMENTS The Council records its warmest appreciation of the many Fellows who have freely placed their services at the disposal of the Society during the year. Particular mention is made of Local Repre- sentatives and Liaison Officers Members of Com- mittees Referees of contributions to the Society’s publications and Lecturers and others who have contributed so much to the success of the Society’s activities. Acknowledgement is also made of the many gifts from Fellows of books for the Library and of the Society’s publications. APPENDIX Liaison OJJicers as at December 3 1st 1962 Admiralty Materials Labora- tory Poole .. .. .. Dr. T. C. Ovenston Aero Research Ltd. (CIBA) Cambridge .. .. .. Dr. B. P. Stark Ashburton Chemical Works Manchester .. .. .. Dr. F. R. Basford Battersea College of Tech-nology London S.W.11 .. Dr. 5. E. Salmon PROCEEDINGS Bedford College London N.W.l .. .. .. Dr. M. M. Harris Belfast College of Technology Dr. D. Hamer Birkbeck College London W.C.1 .* .. .. Dr. D. J. G. Ives College of Advanced Tech- nology Birmingham .. Dr. A. Holt Bolton Technical College .. Dr. G. W. Wood Boots Pure Drug Co. Not- tingham .. .. Dr. J. R. Marshall 0. Borough Polytechnic London S.E. 1 .. .. . . Dr. IT. R. Powell Bournemouth Municipal Col- lege .. *. .. Dr. D. 5. Collins f. Bradford Institute of Tech-nology .. .. .. Dr. G. Shaw Brewing Industry Research Foundation Nutfield Red- hill .. .. .. . . Dr. G. Harris Brighton College of Tech-nology .... . Mr. J. D. Donald University of Sussex Brighton Dr. R. A. Jackson British Hydrocarbon Chem-icals Ltd. Grangemouth .. Dr. M. M. Wirth British Nylon Spinners Ltd. Pontypool .. *. .. Dr. A. C. Davis British Resin Products Glamorgan .. .. .. Mr. R. A. Sutton British Titan Products Bil- lingham . . .. .. Dr. A. E. Comyns Brunel College of Technology London W.3 .. . . Dr. J. H. Skellon Sir John Cass College London E.C.3 .. .. Mr. D. W. Wilson Chelsea College of Science and Technology London s.w.3 . . .. .. Dr. J. F. J. Dippy Chemical Defence Experi-mental Establishment Salis- bury .. *. .. Dr. J. M. Wright Chester Beatty Research Insti- tute London S.W.3 .. Dr. C. L. Leese Chesterford Park Research Station Fisons Pest Con- trol Ltd.Saffron WaIden .. Dr. G. T. Newbold Clayton Aniline Company Manchester .. .. Dr. E. N. Abrahart University College Cork . . Professor F. L. Scott Derby and District College of Technology. . .. .. Dr. C. M. Atkinson Flintshire Technical College Chester .. .. .. Dr. C. G. Lyons University College Galway. . Professor P. O’Colla Glamorgan College of Tech- nology . . *. . . Mr. L. H. Thomas Glasgow University .. .. Dr. S. J. Thomson FEBRUARY 1963 43 Robert Gordon’s Technical College Aberdeen .. Royal Naval College Green- wich .. .. .. .. Harris College Preston .. Hatfield Technical College .. Heriot-Watt College Edin-burgh .. .. .. I.C.I. Ltd. Alkali Division Northwich .... .. I.C.I. Ltd. Dyestuffs Division Blackley .. *. .. I.C.I. Ltd. Heavy Organic Chemicals Division Belling- ham.. .. .. *. I.C.I. Ltd. Nobel Division Steventson .. .. .. I.C.I. Ltd. Pharmaceuticals Division Alderley Edge .. Imperial College London s.w.7 .. .. .. King’s College London w.c.2 .. .. *. Kingston -on -Thames Tech- nical College . . .. Lanchester College of Tech-nology Coventry .. *. Leicester College of Tech-nology and Commerce .. Lister Institute of Preventive Medicine London S.W.3. . Arthur D. Little Research Institute Edinburgh .. College of Technology Liver- pool .. .* .. .. Loughborough College of Technology. . .. .. University College London W.C.1 .... .. Manchester University ,. Medway College of Tech-nology Chatham .. .. Midland Silicones Ltd. Barry Glamorgan .. .. .. Monsanto Chemicals Ltd. Newport .. .. .. Monsanto Chemicals Ltd. Ruabon .. .. .. National Chemical Labora-tory Teddington . . .. Northampton College of Ad- vanced Technology Lon-don E.C.l .. .. .. Northern Polytechnic Lon-don N.7 .. .. .. Dr. M. B. Watson Dr. J. H. Pryor Dr. J. L. Latham Dr. R. F. Robbins Professor F. Bell Dr. H. L. Roberts Dr. G. de W. Anderson Dr. L. A. Duncanson Dr. R. C. Anderson Dr. R. Hull Dr. J. A. Elvidge Dr. C. W. Rees Mr. N. Lindop Dr. W. R. McGregor Dr. A. J. Nunn Dr. W. J. Whelan Dr. W. Banks Mr. C.B. F. Rice Mr. G. Oldham Dr. C. A. Bunton Dr. G. F. Smith Dr. C. E. Seaman Dr. F. C. Saunders Dr. T. T. Jones Dr. R. A. Baxter Dr. J. Idris Jones Dr. D. J. Alner Dr. W. Gerrard Nottingham and District Technical College .. *. Organon Laboratories Ltd. Newhouse-by-Motherwell.. Paint Research Station Ted- dington . . .. .. Paisley College of Technology Petrochemicals Ltd. Urmston The Technical College Ply- mouth . . .. .. Portsmouth College of Tech- nology .. .. .. School of Pharmacy London w.c.1 .. .. .. Queen Elizabeth College, London W.8 .. .. Queen Mary College London E.l ,. .. .. .. Royal Aircraft Establishment Farnborough .. .. Royal Holloway College, Englefield Green Surrey .. Royal Military College of Science Shrivenham ..Rutherford College of Tech- nology Newcastle .. .. Royal Technical College Sal-ford .. .. .. *. Shirley Institute Manches ter Slough College of Further Education .. .. .. South-West Essex Technical College London E.17. .. Stockport College for Further Education .. .. .. Sunderland Technical College U.K.A.E.A. Dounreay Ex-perimental Reactor Estab- lishment .. .. .. U.K.A.E.A. Risley Nr. Warrington Lancs. .. Dr. H. C. Dunn Unilever Ltd. Shambrook .. Mr. D. Welti Welsh College of Advanced Technology Cardiff .. Dr. V. Askam Westfield College London N.W.3 ,. .. .. Professor W. Klyne West Ham College of Tech-nology London E.15. .. Dr. F. L. Allen Whitehaven College of Further Education .... .. Mr. W. P. Thistlethwaite Woolwich Polytechnic Lon- don S.E. 18. .. . . Dr. A. I. Vogel Wrexham Technical College. . Dr. E. W. Claydon Dr. D. Harrison Dr. C. L. Hewett Dr. S. H. Bell Mr. G. R. Jamieson Dr. A. V. Mercer Dr. B. L. Tonge Dr. J. W. Griffin Professor W. B. Whalley Dr. P. F. G. Praill Dr. R. F. Garwood Mr. G. A. Earwicker Dr. T. G.Bonner Professor J. H. Turnbull Dr. R. Hemming Dr. H. Suschitzky Dr. F. S. H. Head Dr. B. W. V Hawes Dr. S. Lewin Mr. H. H. Armstrong Dr. W. R. Longworth Mr. P. Lees 44 PROCEEDINGSFEBRUARY1963 45 THE CHEMICALSOCIETY INCOME ANDEXPENDITUREACCOUNTS FOR THE YEAR ENDED~OTH SEPTEMBER 1962 1960/61 Expendittire 1%1/62 1960161 Income 1961/62 6 8,844938 1,5951,326 E 12,7031,4731,828803 1,723 General Purposes Administration Salaries Superannuation etc... .. House Expenses etc. .. Miscellaneous .. .. .. .. Stationery Postages and Office ExGnses Meetings .. .. .. *. Travelling . . .. .. .. .. Capi t a1 Improvements *. *. .. Local Represent&es .. *. .. .. .. .. .. .. .. .. .. me .. .I .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ,. E 991 1,6581,460 9,398 - € 6 22422,369 13,5072,093 1,929871 289 E 22,5938,5402,9 19 1,648 For previous years .. Jncome from Investments Fellows’ Subscriptions For 1961/62 .. .. Deposit Interest .. Miscellaneous .. General Purposes .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 5 24,662224 E 24.886 857 Transfers Publications Account- 3,522 4,8682,576 1 - 11,966 5,204 Cost of Annual Reports and Quarterly Reviews for Fellows under 27 years of age .... .. .. .. .. .. .. Library Account- Books Periodicals etc. .. .. .. .. .. .. .. Maintenance .. .. .. .. .. .. .. .. Staff Pensions Fund .. .. .. .. .. .. .. Accommodation Reserve . . *. .. .. .. .. *. Balance being Excess of Income over Expenditure carried to Balance Sheet .. .. .. .. .. *. .. .. .* 3,914 5,1833,104 800 5,000-18,001 1,273 E35,700- E37,963- E35,700 €37,963- Staff Pensions Fund 6 1,07816 120 Pensions .. .. .. .. .. .. .. Miscellaneous .. .. .. Balance being Excess of Income oiir Expkditurk ca$ed .. .. .. .. ..Sheet .. .. .. .. .. .. to Balance .. .. 6 1-004 -I--18 228 E Staff Pensions Fund 214 Income from Investments .... 1~o00 Transfer from General Purposes Account .. Refund of Premiums . . .. .. .. - .. .. .. .. .. .. .. .. .. .. .. .. E 224 800 226 €1,214 El ,250- E1,214- f 1,250 46 PROCEEDINGS FEBRUARY 1963 47 INCOMEAND EXPENDITURE MIR THE YEAR SEPTBMBER, ACCOUNTS ENDED 30~~ 1962 I 960/61 1%1/62 1960/61 1%1/62 Expenditure Income Publications Publications E E f E E f 90,298 Journal and Proceedings of the Chemical Society .. .. .. .. 88,417 Sales Advertisements and Transfer from General PurposesAccount 7,463 Annual Reports on the Progress of Chemistry .. .. .. .. 7,953 85,693 Journal and Proceedings of the Chemical Society .. .. .. 89,615 7,556 Quarterly Reviews . . .. .. .. .. .. .. .. 6,913 10,661 Annual Reports on the Progress of Chemistry .... .. 11,454 13,284 Current Chemical Papers .. .. .. .. .. .. .. 14,952 10,761 Quarterly Reviews .. .. .. .. .. .. .. 11,511 -Transfer to Accommodation Reserve .. .. .. .. 5,000 12,337 Current Chemical Papers .. .. .. .. .. .. 13,218 Balance being Excess of Income over Expenditure carried to Balance Other Publications .. .. .. .. .. .. .. 19 1,432 Sheet . . .. .. .. .. .. .. .. .. 3,051 -42 119,494 125,817 539 Income from Investments .. .. .. .. .. .. 469 E120,033 €126,286 €120,033 f126,286 -Special Publications Fund ;E € Special Publications Fund P E x. 611 Cost of Publications . . .. .. .. .. .. .. .. 2,014 2pygg Sales and Royalties .. .. *. .. .. .. .. 3,569 36 Miscellaneous .. .. .. .. .. .. .. .. 43 483 Income from Investments .... *. *. .. .. .. 164 Balance being Excess'of Tncome over Expenditure carried to Balance 2,790 Sheet .. .. .. .. .. .. *. .. .. 2,304 Deposit Interest .. .. .. .. .. .. .. .. 628 E3,437 E4,361 €3,437 Library Library € f f. E f. E ff 3,592 Books and Periodicals .. .. .. .. .. .. .. 4,369 Grant The Chemical Council .. .. .. .. 611 131 1 Binding .. .. .. .. .. .. .. .. 1,765 592 Library Subscribers .. .. .. .. .. 816 9. Less Transfer to Maintenance .. .. *. 408 Furniture .. .. .. .. .. .. .. .. .. 68 6,202 -296 296 -408 5,164 4,868 Transfer from General PurposesAccount .. .. 5,183-Maintenance -5,164 6,202 8,970 Salaries Superannuation etc. .-*. .. .. .. .. 9,989 Maintenance 405 Rebinding .. .. .. .. .. .. .. .. .. 97 Contributions towards Maintenance 2,294 House Expenses etc.Through the Chemical Council- .I .. .. 890 2,576 Chemical Society .. .. .. .. 3,104 0. 63 1 Stationery Postages and ofii'ce Expenses .. .. .. .. .. 2,547 345 Miscellaneous .. .. .. .. .. .. .. .. 273 4.438 Royal Institute ofChemisi& .. .. .. 5,349 13,796 Society of Chemical Industry .. .. .. 1,564 --12,645 Faraday Society . . .. .. 597 347 society for Analytical ChLAistry' ' .. .. 418 753 Biochemical Society .. .. 907 2,382 Chemical Council (Direct'Gmtj .. 1,389 a. 12,289 -13,328 From other sources- 50 Institute of Brewing .. .. .. .. 50 10 Society of Dyers and Colourists .. .. .. 10 7 60 60 -296 12,645 LibrarySubscribers ...... 0. .. -408 13,796 -f17,809 €19,998 €17,809 €19,998 I FEBRUARY 48 PROCEEDINGS 1963 49 THE CHEMICAL SOCIETY GENERAL BALANCE SHEET 3-SEPTEMBER 1962 1961 1962 1961 1962 € E Liabilities € € f.Assets E 5,86324,67 1 6,220 93 12,714 2,790 27,406 30,534 55,339 -6,3138,378 15,504 Sundry Creditors . . .. .. .. .. .. .. .. Fellows’ Subscriptions .. .. .. .. .. .. .. Sales of Publications etc. .. .. .. .. .. .. Receipts in Advance General Reserve . . .. .. .. .. .. .. .. Accommodation Reserve Transfer from General Purposes Income and Expenditure Account Transfer from Publications Income and Expenditure Account .. Life Composition Fees Balance at 1st October 1961 ,. .. .. .. .. ,.Add Receipts during year .. .. .. .. *. .. Publications Fund .. .. .. .. .. .. .. .. Special Publications Fund Balance at 1st October 1961 .... .. Add Excess of Income over Expenditure for the year. . .. .. Staff Pensions Fund 6,482 26,075 5,000 5,000 6,313 65 15,504 2,304 36,386 32,55755,339 10,Ooo 6,378 8,378 17,808 8,378 2,915 5,083154,853 17,771 5,561 48,789 Investments at cost or value when acquired Publications Fund (Market Value f.9,179) .. .. Staff Pensions Fund (Market Value E6,389) . . .. .. General Purposes (Market Value €219,443) .. .. .. Sundry Debtors and payments in advance .. .. .. .. Stock of Paper .. .. .. Deposits (E58,250) Current Balances at Banks and Cash in Hand Special Publications Fund (Market Value €3,194j .. .. .. .. .. .. (Stocksofpublications are not included) .. .. .. .. .. .. .. .. .. .. .. .. .. .. 8,3782,915 5,345172,589 21,132 5,353 62,801 5,2591 20 5,379 Balance at 1st October 1961 ..Add Excess of Income over Expendit& for thk year. * Accumulated Fund .. . . .. .. 5,379229 5,608 86,405 1,456 5,2041,432 94,497 Balance at 1st October 1961 .. .. .. General Purposes .. .. .. .. Publications .. .. .. .. .. Add Net Profit on change of Investmen; . . .. Excess of Income over Expenditure for the year- .. .. .. .. .. .. .. .. 94,4977,238 1,273 3,051 106,059 €243,350 f278,513 €243,350 &278,5 13 J. W. BARRETT Honorary Treasurer. We have examined the General Balance Sheet the Trust and Lecture Funds Balance Sheet and accompanying Income and Expenditure Accounts with the Books and Vouchers of the Society and certify them to be in accordance therewith and in our opinion correct. Overhead Expenditure onGeneral Purposes and Publications Accounts has been reduced by €206 received for work done under contract.We have verified the Balances with the Bankers and the Investments. W. B. KEEN& Co. FINSBURY CIRCUSHOUSE Chartered Accountants. BLOMFELDSTREET,E.C.2 17th January 1963. PROCEEDINGS TRUST AND LECTURE FUNDS Income and Expenditure Accounts for the Year ended 30th September 1962 196OJ61 1961162 -~ -n 1 -U t we! h Trust Funds Y E E If E 39 2 + 37 Ethel Behrens Fund .. .. .. 206 81 -_-t 125 1,214 891 3-323 Centenary Fund .. 1,296 749 -t547 562 403 +159 Corday-Morgan Medal and Prize Fund' ' 595 53 1 4-64 729 565 ++ +164 31 19 Corday-Morgan Memorial Fund .. 777 666 +111 *f 22 3 Faraday Lecture Fund .. 26 61 -35 35 4 Robert John Flintoff Trust ..38 3 + 35 53 128 -75 Edward Frank Harrison Trust Fknd .. 53 10 1-43 30 3 + 27 Liversidge Lecture Fund .. .. 32 64 -32 30 81 -51 Pedler Lecture Fund .. .. .. 31 2 +29 1,114 997 + -117 Research Fund *. .. 1,216 1,174 + 42 _. _. Robert Robinson ihcture'Fund . .. 133 38 + 95 24 62 -38 Simonsen Lecture Fund . . .. 26 2 +-24 114 + 16 1961 1962 E f f f Fund Balances 1,037 Ethel Behrens Fund .. .. .. .. 2,436 9. 24,849 Centenary Fund-CapitaiAw&t .. .. .. .. .. 24,860 2,068 -Income Account .. .. .. .* .. 2,615 269 17 27,475 12,435 Corday-Morgan Medal and Prize Fund .. *. .. .. 12,499 16,011 Corday-Morgan Memorial Fund .. *. .. .. .. 16,122 551 Faraday Lecture Fund .. .. .. *. .. *. 516 769 Robert John Flintoff Trust ...* .. .. 805 r. *. t. 1,062 Edward Frank Harrison Trust Fund .. .. .. .. 1,105 I. 700 Liversidge Lecture Fund .. .. .. .. .. 668 653 Pedler Lecture Fund . . .. .. .. .. .. .. 683 23,191 Research Fund .. .. .. .. .. .. 23,232 -Robert Robinson Lecture'Fund .. .. .. .. .. 3,514 529 Simonsen Lecture Fund .. .. .. .. .. .. 552 I. 2,709 Tilden Lecture Fund .. .. *. .. .. .. 2,725 €86,564 E92,332 -Represented by: 81,383 Combined Pool of Trust Investments .. .. .. .. .. 88,203 (Market Value E88,323) 4,638 Balances at Banks (including Deposit) .. .. *. .. 4,157 1,001 Sundry Debtors .. .. .. .. .. .. .. .. 740 87,022 93,100 458 Less Sundry Creditors . . .. .* .. .. 768 a. €86,564 &92,332 - FEBRUARY 1963 51 CHEMICAL SOCIETY MEETING ?ke following papers were read and discussed at a Scientific Meeting held in the Society's rooms at Burlingtoll House on Thursday December 13th 1962 at 6 p.m.Aromatic Reactivity. Part XXIII. Cleavage of Aryltricyclohexylstannanesby Iodine in Carbon Tetra- chloride. BY R. W. Bow C. EABORN and J. A. WATERS. THErate of cleavage of some aryltricyclohexylstan- nanes by iodine in carbon tetrachloride at 25" has measured (C,Hll),SnC,H4~X + Iz -+(C,Hll),SnI + I-C,H4*X.This reaction which is an electrophilic aromatic substitution is of the second order in iodine and of the first order in organostannane and appears to be homogeneous and chain-free. The Table shows the rate of cleavage krel of each compound relative to that of the unsubstituted corn- pound (C,H,,),Sn-C,H,.The substituent effects are krel X p-OMe 69 m-OMe 2-2 P-(c6H11)3sn 2o H 1*o p-Bu* 13.9 0-Ph 0.34 p-Pr' 12.1 P-F 0.22 p-Et 10.1 Pa o*lo p-Me 7.5 PBr ::::: m-Me 4.2 m-C1 p-Ph 2.9 pCO& 0.0145 not in accord with those in other electrophilic aro- matic substitutions (including acid cleavage of aryl- tricYclohexYlstannaneS)* Of Possible expfanations the Preferred one is that the transition state of the mte-detemg step has some ?r-comPlex character* The effects of varying R in R3Sn*C6H5 compounds are as follows R C6H11 Et Me Ph krel 5.4 5.1 1.0 0.018 Professor E. D. Hughes asked if a possible inter- action between the iodinating agent and the stan- nanes (at Sn in the initial state) could be of sig- nificance.The author said that he could not rule out the possibility that an iodine molecule co-ordinates with the tin atom as a first step of the reaction; this would provide an explanation of the function of one of the two iodine molecules which must be present in the transition state but high orders are normal in aro- matic halogenation in non-polar media and it seems unwise to postulate complex-formation specific to the tin compounds. Such complex-formation would not of course help to provide an explanation for the unusual subs ti tuen t effects. The Mechanism of the Substitution of Heteroaro-matic Compounds. Part I. Acid-catalysed Hydrogen Exchange of Lutidine and Collidine. Part II. Nitration of 1,2,4,6-'l"etramethy~ypyridiniuntSulphate.By A. R. KATRITZKY and B. J. RIDGEWELL. ~UWLY little is known about the quantitative aspects of the electrophilic substitution of hetero- cyclic compounds with six-membered rings. We studied first acid-catalysed tritiation of alkylpyridines because other electrophilic substitutions frequently proceed only under vigorous conditions and in poor yield. Our objects were (i) to elucidate whether it is the free base or conjugate acid that reacts and (ii) to determine the Arrhenius parameters and relate the general Pattern Of reactivity in the PMdine Series to the wefl-established behaviour of benzenoid corn-pounds* Collidine lutidine and collidine methosulphate were separately heated with tritiated sulphuric acid at a known temperature for a known time.The base was recovered as picrate and analysed the tritium by scintillation counting. Three lines of evidence show that in the conditions studied it was the pyridine conjugate acids that re- acted (a) comparison with the rate for the 1,2,4,6- tetramethylpyridinium cation; (6) the acidity-dependence; (c) consideration of absolute reaction rates. hhenius were by measure-ments in the range 1fjO-425" for lutidine and c.1-lidine Extrapolations enable direct comparison with benzenoid analogues to be made and show the highly deactivating effect of the positively charged nitrogen atom this is manifested in the activation energy A factors being normal. From the above results it follows that a pyridinium metho-salt should undergo electrophilic substitution in acidic media as readily as the corresponding pyfidine tkis prediction has been rea&,ed for the nitration of collidine methosu~phate.Professor Hey asked Dr. Katritzky if it was possible to make a quantitative comparison of the ease of nitration of collidine and lutidine with that of nitrobenzene. Dr. Katritzky and Mr. Ridgewell replied "No because no kinetic experiments were done on the pyridines in nitration; however from the conditions employed it appears that the collidinium ion is some- what less reactive towards nitration than nitro- benzene." Dr. J. H. Ridd says "It may be helpful to mention that M. W. Austin and myself have recently obtained similar results for the nitration of quinoline in strong sulphuric acid.This reaction involves the quino- PROCEEDINGS linium ion and we estimate that the 5-and the spectrometer a singlet is observed in the spectrum 8-position of this ion are less reactive than the which is attributable to hydroxyl radical; it is re- corresponding a-position of naphthalene by a factor placed by signals due to other radicals when aro- of -1W0. This illustrates the great deactivating matic compounds are present in the reactant solu- effect of the -+N= group in an adjacent ring and tions. Toluene gives a triplet assigned to the benzyl accords with the still greater deactivating effect radical and bibenzyl is the main product of its re- reported by Katritzky and Ridgewell in the pyridine action.Benzene gives a spectrum compatible with the ring itself." adduct of a hydroxyl radical and the aromatic nucleus (coupling with two single protons coupling The Free-radical Hydroxylation of Benzenoid Com-constants 35 and 13.5 gauss and two pairs of pro- J. R. LINDSAY pounds. By W. T. DIXON Sm and tons coupling constants 9 and 3 gauss). Spectro- R. 0.C. NORMAN. scopic evidence for this adduct has been obtained THEsystem titanous ion and hydrogen peroxide previously during pulse-irradiation of aqueous behaves analogously to Fenton's reagent in its re- benzene. actions with benzenoid compounds (e.g. benzene The existence of this adduct as an intermediate gives phenol and biphenyl and chlorobenzene gives may also be inferred from quantitative studies of the phenol and chlorophenols).Evidence for radical oxidation of benzene by Fenton's reagent. The intermediates in such reactions has been obtained by results of these investigations are discussed with electron spin resonance spectrometry. When solu- reference to the mechanism by which the adduct is tions of titanous ion and hydrogen peroxide are converted into phenol by oxidising agents or into mixed just before entering a cell in the cavity of the biphenyl by dimerisation followed by dehydration. COMMUNICATIONS The Crystal Structure of Dihydro-b-erythroidine Hydrobromide By A. W. HANSON RESEARCH OTTAWA, (DMSIONOF Prrm PHYSICS NATIONAL COUNCIL CANADA) CRYSTAL-STRUCTURE analysis was undertaken in ficantly more intense than 1i1,and this inequality order to establish the hitherto unknown1 relative suggested the possibility of confirming the absolute configuration of dihydro-p-erythroidine.configuration by the methods of Bijvoet et aL2 The appropriate reflections were remeasured with greater precision on the General Electric XRDS spectro-goniometer and goniostat with Cu-K radiation and a scintillation counter. 1 1 1 was found to be 1a66 times as intense as lil ;this value was in agreement with that found by calculating structure factors; for the bromine atom the complex scattering factor f = fo -4-dfl + idfll was used where& is the conventional The crystals are orthorhombic P212,2 with a = atomic scattering factor and dfl and dfll are the real 10.22 b = 17.97 c = 8.72 A and 2 = 4.Intensity and the imaginary dispersion corrections. The values data were recorded on zero-and upper-level used for dfl and dfl1were -0.9 e and 1.5 e respec- Weissenberg photographs while the specimen was tively? The agreement establishes the absolute con- maintained at -110". 1580 independent reflections figuration by confirming that the set of atomic were evaluated. The structure was determined by co-ordinates belongs to a right-handed system of standard heavy-atom methods and refined with the axes. aid of differential syntheses. The final agreement The relative and absolute configurations of the residual (R = c1 IF0 I-IFc li/cIFo 1) is 0.13 and the molecule of dihydro-/h-ythroidine are shown in estimated standard deviations of co-ordinates are formula (I).The accuracy of the analysis suffices to for oxygen 0.011; for nitrogen 0.014; for carbon establish the distribution of double and single bonds 0.015 A. there indicated. It was observed that the reflection 111 was signi- (Received December 3rd 1962.) Wenzinger and Boekelheide Pruc. Chem. Suc. 1963 following Communication. Bijvoet Peerdeman and van Bommel Nature 1951 168,271. Dauben and Templeton Acta Cryst. 1955 8 841. FEBRUARY 1963 53 The Absolute Configurations of the a-and P-Erythroidines By GEORGE and V. BOEKELHEDE~ R. WENZINGER (UNIVERSITY ROCHESTER, OF ROCHESTER NEWYORK,U.S.A.) the overall structures and interconversion bined with the recent evidence of Hill and Schearer ALTHOUGH of a-and P-erythroidine have been known for some time their absolute and relative configurations have remained unsolved.We now report systematic de- gradation of p-tetrahydro-P-erythroidine(I) as out-lined below, methyl ethe?). to the isolated on oxidation of acid (111) (the enantiomorph (-)-P-methoxyadipic calciferol Mq3 -33 j/ Ww2*‘qH .&/ Me0 L2-W (m> with regard to the absolute configuration at position 12 in a-erythroidine,” this companion alkaloid can be designated (3R,5S,l2S)-a-erythroidine. paH2@2it 13 ___ 12 M.oH u I7 Me ,! (W (v) OS Fortunately the question of the relative con- figurations has now been settled by the X-ray studies on dihydro-P-erythroidine hydrobromide reported by Dr. Hanson in the accompanying Communica- tion.@ Indeed it has been possible for him to assign not only relative configurations but also the absolute H-W configuration of dihydro-p-erythroidine hydro- bromide.These assignments agree with the absolute configurational assignments for a-(IV) and p-ery-Reagents 1 LiAIH4,then H&’O4. 2 Successive Hofmann eliminations then hydrogenation. 3 KMnO,. throidine (V) annexed. Finally from the close cor- respondence of the optical rotatory dispersion data for derivatives of the erythroidines and the aromatic Although the degradative evidence does not Erythrina alkaloids it seems probable that the same permit a definite assignment of the relative con- absolute configurational assignments at positions 3 figuration at position 5 a logical interpretation leads and 5 apply to the aromatic Erythrina alkaloids.to the designation of (3R,SS)-P-erythroidine.4Com-(Received December 3rd 1962.) Present address University of Oregon Eugene Oregon U.S.A. Boekelheide Weinstock Grundon Sauvage and Agnello J. Amer. Chem. SOC.,1953,75,2550; Godfrey Tarbell and Boekelheide ibid. 1955 77 3342; Boekelheide and Morrison ibid. 1958 80 3905; Boekelheide “The Erythri~a Alkaloids” in Manske’s “The Alkaloids,” Academic Press New York 1960 p. 201. Bergstrom Lardon and Reichstein Helv. Chim. Acfa 1959,32 1617. * Wenzinger Ph.D. Thesis University of Rochester 1960. Hill and Shearer J. Org. Chem. 1962,27,921. Hanson Proc. Chem. SOC.,1963 preceeding Communication. Chang Ph.D. Thesis University of Rochester 1959. Tetramethyl-and Tetraethyl-ammonium Hydrogen Dibromide By D.G. TUCKand E. J. WOODHOUSE (DEPARTMENT OF NOTTINGHAM) OF CHEMISTRY,UNIVERSITY has been recent interest in the hydrogen di- prepared by condensing dry hydrogen bromide on to THERE chloride anion and stable crystalline compounds dry tetramethylammonium bromide at -190” incorporating it have been reported;l the only allowing the mixture to warm to room temperature evidence for the corresponding HBr,- species comes and distilling off the excess of hydrogen bromide. from conductometric titrations in pyridine solution? Analysis showed that the product contained 65.8 % of We have now prepared two crystalline compounds Br (Calc. for NBr, C,H,,Br 68.2 %). This compound containing this anion. is rather unstable at room temperature giving off Tetramethylammonium hydrogen dibromide was hydrogen bromide but a similar reaction with tetra- (a)West J.Amer. Chem. SOC.,1957,79,4568; (b)Waddington,J. 1958 1708; (c) Sharp J. 1958,2558; (6)Vallee and McDaniel J. Amer. Chem. Soc. 1962 84 3412. a Beattie and Leigh J. 1962 4762. PROCEEDINGS ethylammonium bromide gave the stable colourless tetraethylammonium hydrogen dibromide (Found Br 54.9. GH,,NBr requires Br 55.0%). The infrared spectra (Nujol mulls) of both the new compounds showed a broad band with a maximum at 1700 cm.-l which did not appear in the spectra of the starting materials; a similar band was reported by Waddingtonlb for HC1,-. The ultraviolet spectrum of the tetraethylammonium salt in methyl cyanide shows an absorption at 265 mp,not found with the simple bromide.Proton magnetic resonance spectra for dimethyl sulphoxide or methyl cyanide solution confirmed the presence of acidic protons in both the hydrogen dibromides; an analogous result was ob- tained with tetraethylammonium hydrogen di-chloride. We thank the Department of Scientific and Industrial Research for the award of a Research Studentship (to E.J.W.). (Received December 14th 1962.) On the Mechanism of Photochemicai Cycloaddition Direct Formation of the tra~-Bicyclo[4,2,0]octaneSystem By P. DE MAYO R. W. YIP and (in part) S.T. REID (CHEMISTRY DEPARTMENT CANADA) UNIVERSITY OF WESTERN ONTARIO LONDON INthe direct photochemically induced intermolecular addition of an excited ethylenic system to an isolated double bond' and related additions (including certain dimerisations) the question arises whether ring formation proceeds in one step or in two steps2 possibly separated for long enough to permit a con- formational change in an intermediate.We have investigated this problem in one instance. Irradiation of methyl maleate in cyclohexene (0.97~) gave five compounds? as well as polymer and bicyclohexenyl. One of these was shown to have structure (I) on the basis of spectral data and hydro- genation to cyclohexylsuccinic acid. Its mode of formation has ample ana10gy.~ The other four compounds gave crystalline saturated dicarboxylic acids on mild alkaline hydro- lysis [a fifth saturated acid was detected by careful examination but was present in too small amounts (0.2%) for further investigatio.111.The acids are con- sidered to be stereoisomers of the general structure (11). Acids A (m.p. 199-200") and B (m.p. 174- 176") are assigned structures having a cis-fusion of the carbocyclic rings with trans- and cis-carboxyl groups respectively acid A when heated with acetic anhydride and then hydrolysed with water gave acid B. Pyrolysis at 400-410" of the methyl ester of acid A gave methyl fumarate and cyclohexene. Oxidation of acid A by potassium permanganate gave in poor yield cis-cyclohexanedicarboxylicacid with no trace of the trans-acid. The remaining two acids constituting about 19% of the total saturated acids are assigned structures with a trans-fusion of the carbocyclic rings.These acids C (m.p. 181-182") and D (m.p. 201-202") were both converted into another acid E (m.p. 153-155') (111) through the anhydride. The methyl ester of acid C gave at 340-350" no trace of methyl fumarate or maleate but instead a mixture of cleavage products which on hydrogenation produced methyl sebacate. Fission in this instance because of the strained ring-fusion occurred in the opposite sense to that in the cis-fused series. This addition represents the first direct formation of the strained trans-bicyclo [4,2,0]octane system.6 Further since it is unlikely that methyl maleate should be acting as a sensitiser or that the vibration- ally excited cis-fused should be converted into the trans-fused product and since we find no evidence for the existence of a charge-transfer complex a two-step cycloaddition process at least in this instance is indicated.We thank the donors to the Petroleum Research Fund administered by the American Chemical Society for financial support. (Received December 28th 1962.) Mayo Takeshita and Sattar Proc. Chem. Soc. 1962 119. Eaton J. Amer. Chem. SOC.,1962 84,2454. The sensitised addition of maleic anhydride to a number of ethylenic systems has been reported by Schenk, Hartmann Mannsfeld Metzner and Krauch Chem. Ber. 1962,95,1642. Mayo Stothers and Templeton Canad.J. Chem. 1961,39 488; Pitts Letsinger Taylor Patterson Recktenwald and Martin J. Amer. Chem. Soc. 1959,81,1068;Schenck Koltzenburg and Grossmann Angew.Chem. 1957,69,1177. For the formation of 7-oxabicyclo-octanes see Kovacs Weisz and Schneider Chem. and Znd. 1961 1222; for the indirect formation of the trans-bicyclo[4,2,0]octanesystem see Cava and Moroz J. Amer. Chem. Soc. 1962 84 115, and Meinwald Curtis and Gassman ibid, p. 116. FEBRUARY 1963 55 HITHERTO, the electron spin resonance spectra of radical-anions (I) obtained from substituted nitro- benzenes by reduction have been investigated only in non-aqueous solvents. Maki and Geskel analysed the spectra of such radicals produced by electrical reduction in acetonitrile and Ward2 observed the spectra obtained from nitrobenzene deuterated nitrobenzene and [15N]nitrobenzene anions formed in dimethoxyethane by reduction with metallic potas- sium.We have used a flow technique similar to that Electron Spin Resonance Spectra of Some Nitrobenzene Radical-anions By P. L. KOLKER and WILLIAM @YSON hRRINS LABORATORY, OXFORD UNIVERSITY) dithionite. This has been noticed by Hodgson, Naves and Parkefl for solid sodium dithionite and has regularly been observed by us with alkaline aqueous solutions of sodium dithionite which had been exposed to air. The observed coupling constants are given in the Table. The values for are greater than those found previously1*2 and we suggest that this is due to the use of a different reducing medium. However ring-proton coupling constants differ only slightly from those reported earlier and we confirm that the sum of the ortho- and meta-coupling con- stants is approximately constant a negative spin density being assumed in the rneta-position.For each radical (RC,H,-NO,-)- the change in the nitrogen coupling constant a,(R-H) is proportional to the logarithm of the partial rate factor (Iogfj) for A. WATERS the Data for radical anions (I). Coupling constants (in oersteds) Partial rate factors5 for nitration of C,H5R* R C02Et 11.50 3.25 0.75 2.50 log10f2 -3.046 log fla (R-I-1)1.7 Br c1 12.80 12-90 3.40 3.30 1-00 0.90 2.40 2.40 -0.96 -0.85 1.9 2.1 I 13.15 3.35 1.10 2.25 -0.34 2.2 CHaC1 13.25 3.25 0.95 ‘2.30 -0.022 4.4 H 13.30 3.40 0.90 2.50 0 - CH,*CO,Et 13.65 3.25 0.85 2.40 1.017 2-9 Me 14.12 3-50 1.10 2-40 1-76 2.1 OMe 14.25 3.45 1-15 2.30 2.45 2.6 The probable error of the coupling constants is f0.05 oe.mentioned earlier? to produce radical-anions from para-nitration of the corresponding compound para-substituted nitrobenzenes in aqueous solution. C,H,R. Clearly the coupling constants at the nitro- For this a 10-2M-solution of the nitrobenzene in gen atoms of these radicals should be influenced by aqueous acetone was allowed to mix with a 10-2~- the substituent R but this correlation between free- solution of sodium dithionite in N-sodium hydroxide radical structure and the influence of R on the rate 1 cm. from the flattened section of an aqueous sample of a heterolytic reaction was totally unexpected; it cell in a Varian V4500 electron spin resonance holds for so many compounds that it cannot be spectrometer the spectra thus being examined cu.5 fortuitous. x 1W2sec. after mixing of the reactants. ascribe to the (.SO& radical-ion derived from the (Received December I 2th. 1962.) Maki and Geske J. Amer. Cheni. Sac. 1961 83 1852. * Ward J. Chem. Phys. 1959,30 852. Stone and Waters Proc. Chem. Sac. 1962 253. Hodgson Neaves and Parker Nature 178,489. de la Mare and Ridd “Aromatic Substitution,” Butterworths Scientific Publns. London 1959 p. 237. PROCEEDINGS An in Vitro Model for the Synthesisof Allenes By J. CYMERMAN CRAIGand M. MOYLE OF PHARMACEUTICAL UNIVERSITY SAN FRANCISCO (DEPARTMENT CHEMISTRY OF CALIFORNIA 22) THEdehydration step -COCH,-to -C C-can be (I) R.CH,-COCH,R' (a) R = R' = C0,Me carried out by treating enol phosphates with soda- (11) R.CH,C:CHR' (b) R = Ph R = C02Et I mide in liquid ammonia,' and acetylenic acids have O*PO(OEt) (c) R = Ph R' = CO,H been synthesised2 by the action of alkali on the enol (d) R = H R' = C02Et arenesulphonates of certain substituted diethyl (Ill) RCH:C:CHR' (e) R = Ph R' = H malonates.The widespread occurrence of acetylenes (IV) RCH2-Ci CR' and allenes in Nature3 and the evidence for their Whereas only the ester (IIIa) is expected5 from genesis from acetate units4 suggest that a natural acetonedicarboxylic ester (Ia) in the case of fg-polyketone system in which each methylene y-phenylacetoacetic ester (Ib) the product could be Temp. Reaction Products period 0" 10 sec. (IIIa) (42 %) 25 90min. (IIIa) (70%) 25 4 hr. (IIIa) (12 %) 5 2 min.(IIb); no allene or acetylene 5 24 hr. (IIIc) (65%); (Ie) (16%) 5 24 hr. (Id); no allene or acetylene 5 24 hr. (Ire) -50%; (Ie) -50%; no allene or acetylene * (a) Shaken in ether with aqueous N-sodium hydroxide; (6) shaken in ether with 10% aqueous sodium carbonate; (c)stirred with 5% aqueous sodium hydrogen carbonate in aqueous dioxan; (d)stirred with 0.5 N-sodium hydroxide in aqueous dioxan. group is doubly activated should be transformed into an acetylene or allene in vitro under even milder -~~iCoCHiCO.CHiCO-conditions. H ' c(2 The closest available model acetonedicarboxylic -CH,-C-CH~~~~-CO-ester (Ia.) gave the phosphate (Ha) (b.p. 127-129"/ "?%=P(0RLfO 0.005 mm.,n 1.4515) and we now report the ready J/ conversion of this into dimethyl penta-2,3-dienedio- ate5 (IIIa) ("glutinic ester") by aqueous base after QH -~2~~~2-cc-co-as little as 10 seconds at 0" (see Table).The absence O*PO(OR)2 of recovered enol phosphate indicates a competing substitution which involves displacement of phos- I phate by hydroxyl ion. Ethyl fg-oxoy-phenylbutyrate (Ib) gave the enol phosphate (IIb) (b.p. 162-1 64"/0-O05mm. n2,51-4960 end absorption only) but this was very much less reactive to base (see Table); complete reaction (24 hr.) gave 4-phenylbuta-2,3-dienoicacid6 (IIIc). Further removal of activating groups left aceto- acetic ester (Id) and phenylacetone (Ie). Their enol phosphates (IIId)' and (IIe) (b.p. 109-1 11O/0.005 ~ mm. FZ 1 e4840 prepared from 1-chloro-3-phenyl- acetone) afforded no allene or acetylene even after 24 hr.Craig and Moyle Proc. Chem. Soc. 1962 149. Fleming and Harley-Mason Proc. Chem. SOC.,1961 245; Chem. and Znd. 1962 560. Bohlmann and Mannhardt Progr. Chem. Org. Nat. Prod. 1957,14,1; Jones Proc. Chem. SOC.,1960,199; Sorensen ibid. 1961 98. Bu'iock and Gregory Biochem. J. 1959,72 322; Bu'lock Allport and Turner J. 1961 1654. Jones Mansfield and Whiting J. 1954 3208. Mansfield and Whiting J. 1956,4761. Stiles Reilly Pollard Tieman Ward Phillips Soloway and Whetstone J. Org. Chem. 1961 26 3960. FEBRUARY 1963 the allene (IIIc) or the acetylene (IVc). Only the allene was obtained ;4-phenylbut-2-ynoic acid (IVc) on identical treatment [condition (41 was com- pletely converted into the same allene (IIIc).The concurrent formation of both acetylene and allene in Nature may be explained if formation of a triple bond is accompanied by an intramolecular transphosphorylation giving an intermediate hemi- ketal phosphate. Dehydration of this could then give two different enol phosphates leading respectively to a stable diyne system (well known in Nature) or to an unstable diethynylmethane unknown while its rearrangement product the allene-acetylene system is relatively common. This work was supported by a grant from the National Institutes of Health U.S. Public Health Service. (Received November 26th 1962.) Structure and Synthesis of "Manninositose" By S. J. ANGYAL and B. SHELTON (SCHOOL THEUNIVERSITY N.S.W.) OF CHEMISTRY OF NEWSOUTHWALES KENSINGTON IN 1930 Anderson and Roberts1 showed that myoinositol is a constituent of a phosphatide present in tubercle bacilli and this was followed2 by isola-tion of a hydrolysis product containing myoinositol and two mol.of D-mannose which he named "manninositose." More recently Vilkas and LedereP provided strong evidence that in manninositose a 6-0-a-D-mannopyranosyl-D-mannopyranosegroup in linked a-glycosidically to myoinositol ;the posi- tion of attachment to the inositol ring was however not established. Vilkas4 isolated in addition to the dimannoside an a-D-mannopyranosyhyoinositol from the tubercle phosphatide. We have now syn- thesised both the mono- and the di-mannosylinositol and have shown that they have structures (I)and (11), respectively.Konigs-Knorr reaction of acetobromomannose with (f)-l,4,5,6-tetra-0-acetylmyoin~sitol~ gave two diastereomeric mannosylinositols in a total yield of 45%. One of the glycosides m.p. 233" (decomp.) [a]E + 435" (in H20),was converted into its nona- acetate m.p. 180" [a] + 20" (in CHCl,) which was identical with the nona-acetylmannosylmyoino-sitol? m.p. 178-180" [a] + 20.5" (in CHCl,) kindly presented to us by Mme. Vilkas. Complete methylation of the free mannosylinositol followed by hydrolysis gave (lS)-1,2,4,5,6-penta-O-rnethyl-myoinositole (111) m.p. 115-117" [a] -3.5" (in H,O) identical with a sample similarly prepared' from galactinol. The glycoside is therefore 1 -0-a-D-mannopyranosyl-(1R)-myoinositol (I).The diastereo- meric glycoside m.p. 237" (decomp.) [a] + 46" (in H,O) {nona-acetate m.p. 183" [a]? + 24" (in CHCI,)) was similarly degraded to the enantiomorphous pentamethylmyoinositol hence it is 1-0- a-D-mannopyranosyl-( 1 S)-myoinositol. HO QMe Me0 @re HO a (I)R=H '&I (P)R= a -o-MannopyranosyI The first mannosylinositol (I) was converted into the octa-acetate of its 6'-0-trityl derivative m.p. 141-143" [a] -8.0"(in CHCl& and this was condensed with acetobromomannose in the presence of silver perchlorate.8 The resulting dodeca-acetate of 0-a-D-mannopyranosyl-( I 36)-0- ar-~-manno- pyranosyl-(1-tl)-(1R)-myoinositol m.p. 134-1 37" [a] + 52.3" (in CHCl,) has the properties given by Vilkas4 for the acetylated manninositose m.p.135-137" [a]g + 54" (in CHCl,). The free dim- manosylmyoinositol (II) has m.p. 248-253 " (de-camp.) [a]z,O+ 77" (c 0.6,H20); Vilkas reported decomposition at about 260" and [a]:1 + 77" (c 1.33 H20). We thank Mme. E. Vilkas for samples Professor E. Lederer for valuable advice and Ciba Ltd. (Basle) for financial support. (Received November 9th 1962.) Anderson and Roberts J. Amer. Chem. Sac. 1930,52,5023. * Anderson Lothrop and Creighton J. Bid. Chem. 1938 125,299. Vilkas and Lederer Bull. SOC.Chim. bid. 1960,42 1013. Vilkas Bull. Soc. Chim.bid. 1960,42 1005. Angyal Tate and Gero J. 1961 4116. I) R and S used according to Angyal and Gilham J. 1957,3691. Kabat MacDonald Ballou and Fischer J. Amer. Chem. Soc.1953,75,4507. * Bredereck Wagner Faber Ott and Rauther Chem. Ber. 1959,92 1135. PRocleeDmGs Pyrolysis of Ally1 Ethers Hydrogenolysis of Ally1 Alcohols with SpeCitic Mlgmtion of the Double Bond By R.C. COOKSON and S. R.WALLXS (THE UNIVERSITY SOUTHAMPTON) ALDER’S‘‘ene-reaction” or “subs ti tut ing addition” furnace (8” long). In every case (except allyl 4-nitro-(1)l is the carbon archetype of a family of pyrolytic benzyl ether no. 7 where most of the balance was eliminations? in which one carbon atom or more recovered as unchanged ether) the expected carhnyl may be replaced by a hetero-atom (e.g. pyrolysis of compound was formed in high yield. The isolation carboxylic esters). The pyrolysis of allyl ethers of of phenylacetaldehyde so easily polymerised by acid primary and secondary alcohols constitutes a new or base in 82 % yield on pyrolysis of allyl phenethyl and potentially useful example of this sort of re- ether (no 9) at 600” is further testimony to the mild-action (2).The over-all change offers a way of ness of gas-phase molecular reactions. The Table reducing an allylic alcohol with specific migration of also gives the yields of olefins obtained by pyrolysis the double bond C=C-C-OH 3H-C-C=C or of in every case the product was that expected from a oxidising a primary or secondary alcohol in the gas cyclic molecular elimination (note especially nos. 1 phase CH-OH4 CO. We have found it a valuable 3,and 1 1). The freedom from by-products or polymer way of making ar-deutero-olefins. also tells against the intervention of free radicals.Ether Temp. Olefin Ketone Relative rate at 430” I. 1-Methylally1 diphenylmethyl 540” tram-But-2-ene* (82 %) Benzophenone (92 3.6f0.8 cis-But-2-ene (12YJ 2. Allyl fluorenyl 400 F%opene@O%) Fluorenone (83 %) 3.10 f0.27 3. But-2enyl diphenylmethyl 530 But-1-ene* (94 %) Benzophenone (91 %) 1.14f0.11 Buta-1,3-diene (6 %) 4. Allyl diphenylmethyl 540 Propene (91 %) Benzophenone (92 %) 1*OO 5. Allyl benzyl 500 Propene (97%) Benzaldehyde (82%) 0-81 f0.03 6. Allyl 4-methoxybenzyl 450 Propene (79’4 p-Methoxybenzaldehyde0.72 f0.08 (93%) 7. Allyl 4nitrobenzyl 430 Propene (34%) p-Nitrobenzaldehyde 0.64 f0.09 (33%) 8. 3-Cyclohexenyl diphenylmethyl 510 Cyclohexene (87%) Benzophenone (88%) 0.41 f0.06 9.Allyl phenethyl 600 Propene(94x) Phenylacetaldehyde 0.28 f0.02 (82%) 10. Allyl 2-methylallyl 390 Propene* (55%) -a0.4 Isobutene (45%) 11. 1-CyclohexenylmethyI 500 Methylenecyclohexanet Benzophenone (82x) - diphenylmethyl (70%I * Yields refer to C,and C4hydrocarbons. There were also traces of fragmental hydrocarbons e.g. CaH4. t Corrected for 33% of unchanged ether. The representative ethers listed in the accompany- The right-hand column in the Table gives the ing Table were pyrolysed by passage in nitrogen approximate rate of elimination compared with ally1 through a vertical tube packed with glass granules diphenylmethyl ether measured by simbeow and heated at the temperature stated in an electric pyrolysis of mixtures of pairs of ethers.The remark- able insensitivity to structural variation in the ether indicates that there is little change in polarity in pro-0-li “7 (1) gress from the initial to the transition state and the t> -8 3 0) very low kinetic isotope effect3 (rate for allyl di-phenylmethyl etherirate for allyl ar-deuterodiphenyl- methyl ether = 1.07 f 003 at 440”;the maximUm H possible ratio is 2.25) shows that in the transition Alder and Brachel AmZen 1962,651,141 ;Arnold and Showell J. Amer. Chem. Soc, 1957,79,419; Rondestvedt and Wark J. Org. Chem. 1955,20 368; and earlier papers by these authors; see also Huisgen and PohI Chem.Ber., 1960,93 527. * De Puy and King C em. Rev. 1960,60,431. a Westheimer Chem. lev.1961 61 265 FEBRUARY 1963 state the GH bond is hardly stretched and that therefore the C-O bond is presumably almost br~ken.~ (In fact the value of the isotope effect is in the range of those reported for several reactions in which the reactant is deuterated at positions adjacent to the reaction site but not directly involved in bond- bmaking. This contrasts with isotope effects of about 2 in the pyrolysis of carboxylic esters.z) Comparison of the rates of pyrolysis of ally1 horenyl (A) and diphenylmethyl 1-methylally1 ether (M) at various approximate temperatures gave these results kJk at 290" 1.44 f0.15; at 365" 0-98 f 0.02; at 430"0.86 f0.08. So if the ethers constitute a reaction series where changes in activation energy parallel changes in activation entropy5 (asis possible) 430" is above the isokinetic temperature.We are much indebted to Dr. H. M. Frey for help with gas chromatography. (Received December Nth 1962.) 'See also Wiberg Chem. Rev. 1955,55 717. ti Leffler J. Org. Chem.,1955 20 1202; Brown J. Org. Chem. 1962,27 3015. The Steric Course of Aromatic BromodesiIylation By C. EABORN and 0.W. STEWARD (DEPARTMENT RIE UNIVERSITY, OF CHEMISTRY LEICESTER) Tmwork of Sommer Frye and their co-workers has made available optically active methyl- 1-naphthyl-phenylsilyl compounds R3Si*X and has established the stereochemistry of some of their reacti0ns.l We have now used p-methoxyphenylmethyl-1 -naphthyl-phenylsilane R3Si*.C6H4.0Me-p in a study of the stereochemistry of the cleavage of aryl-silicon bonds by bromine in an inert medium.This represents we believe the first investigation of the stereochemistry of an electrophilic aromatic substitution. pMethoxypheny1-lithium in ether reacted with (i) the (-)-menthoxide (-)-R,Si*.OMenthyl-(-) to give the (-)-RBSi*.C6H4.0Me-p compound m.p. 7-72" [a] -6.17" (c 7.7 in benzene) in 95% yield (ii) the hydride (-t)-R,Si*H to give the (-)-&Si*-C6H,.0Me-p compound map. 70-73 " [a]? -6.0" (c 7.7 in benzene) in 77% yield and (iii) the chloride (+)-R3Si*Cl [not isolated but ob-tained by chlorination of the (+)-hydride in carbon tetrachloride] to give the (+)-R3Si*.C6HIL0OMe-p compound [a]1,9+ 5.72"(c 7.8 in benzene) in 98% yield; recrystallisation of the last product from hexane gave the ( +)-R3Si*C6H4.0Me-p compound m.p.69.5-73.5" [a]? + 6.13" (c 7.8 in benzene). Analogy with the results obtained by Sommer and his co-worked indicates that the aryl-lithium couples with the menthoxide and hydride with specific retention of configuration and with the chloride with predominant inversion and this accords generally with recent conclusions from couplings involving alkyl-lithiums and alkylmag- nesium halides? When bromine (in 20% excess) was added to a sohtion of the (-)-R3Si**C6H4-oMe-p compound in benzene the specific rotation changed from -6.17" to f13.4" (the result was similar when car- bon tetrachloride was used as solvent). Gas-liquid chromatography showed that p-bromoanisole 1-bromonaphthalene and anisole had been formed in a molar ratio of ca.4 1:1. After reduction of the mixture of bromosilanes with lithium aluminium hydride in ether the hydride R3Si*H m.p. 59-62' [m]? 4-30.9"(c 2.9 in cyclohexane) was isolated in 267i yield; the (+)-hydride obtained by reduction of the (-)-menthoxide with lithium aluminium hydride had [a]% 4-32.8" (c 4-0 in cyclohexane) m.p. 62+-64.5". The reduction of the bromide involves specific inversion1 and although 20% of the isolated hydride may have come from bromide formed by hydrogen bromide cleavage the bromine cleavage of the p-methoxyphenyl-silicon bond must involve at least 92% of inversion. The result shows that the organosilyl group is not detached from the ring as a free siliconium ion and indicates that nucleophilic attack at silicon assists cleavage of the aryl-silicon bond.Inversion of con-figuration is we believe consistent with an angle of 180" between the forming and the breaking bond to silicon or with one in the region of 120" the in- coming and the leaving group in the latter case occupying equatorial positions in an ~p~d-hybridised intermediate. This work was performed during the tenure by one of us (O.W.S.) of a National Science Foundation Postdoctoral Fellowship. (Received,January 9th 1963.) Sornmer and Frye U.S.P.3,024,262/1962; J. Amer. Chem. SOC.,1959 81 1013; 1960 82 3796 4118; Sommer, Frye Parker Rodewald Michael Okaya and Pepinsky ibid. 1961,83 2210; Sommer Angew. Chem. Internat. Edn., 1962 1 143.a Sommer Rodewald and Parker Tetrahedron Letters 1962 821; Brook and Warner ibid. 815. PROCEEDINGS A Reexamination of 1,6-DiphenyIhexatrienein Sulphuric Acid By J. A. LEISTEN and P. R. WALTON (THEUNIVERSITY, SHEFFIELD) A RECENT claim1 that 1,6-diphenylhexatriene (M) is immediately oxidised in 100% sulphuric acid to a dipositive ion (M2+)has lead us to carry out some further experiments. First we prepared solutions with different con- centrations of the triene in 100% sulphuric acid and immediately poured them on ice. Clear solutions were obtained from which no spectrophotometrically observable products were extracted by cyclohexane. The result suggests that M2+was not present in the original solutions since no water-soluble dilution products of this ion can be envisaged and in similar experiments other hydrocarbon cations give easily detected products? There is other evidence against the formation of the ion M2+.Oxidation of the triene M to the ion M2+in sulphuric acid would produce an equivalent quantity of sulphur dioxide; we found Specification of the cryoscopic solvent A 99.9%H,SO,; f.p. 9.82" B* (NH4),S04 (1.55 g. per 100 g. of oleum of f.p. 9.68") C* H3BO3 (1.64 g. per 100 g. of oleum of f.p. 5.73") scopic solvents two sulphuric acid solutions B and C the significant ingredients of which are hydrogen disulphate ion (HS20,-) and sulphuric acidium ion (H$04+) respectively. It can be understood from the following equations that the freezing points of these solutions are little affected by addition of water and therefore by sulphonation HS,O,-+ H,O -+ HS04-+ H,S04 H&O4+ + H,O + H,O+ 4-H,SO Consequently the difference of about four units between the i-values observed in the solvents A and B can be attributed to sulphonation.It shows that 1,6-diphenylhexatriene is sulphonated twice prob- ably once in each ring in the time required for dis- solution. The remaining two units of the i-value in Molality Molality i-Value for of HS20,-of H3S04+ 0.02m-addition of M 0.00 0.00 5.83 0.10 0.00 2.03 0.00 0.13 0.17 * Recommended compositions derived from studies with model s01utes.~ that less than 2% of this amount is formed initially and since more is produced on storage it is likely that even this small amount is the result of a consecutive reaction.We have determined the behaviour of the triene in sulphuric acid by a relatively new cryoscopic pro- cedure3 which has been validated by application to solutes of known behavioufl and should be of interest in the study of carbonium ions. The van't Hoff i-values in the Table come from the formula i = d8/6-0m where m is the molality of M and d8is the freezing-point depression measured immediately after M is dissolved. The first i-value shows that in a freshly prepared solution in 99.9% sulphuric acid (solvent A) each molecule of the triene gives rise to about six foreign particles. This and the water-solubility of the product suggests sulphona- tion each stage of which by splitting out a molecule of water should contribute two units to the i-value M +-.LH,SO -+ M-SO + H,O+ + HS04-For more detailed information we used as cryo- De Boer and van der Meij Proc.Chem. SOC.,1961 139. * Gillespie and Leisten Quart. Rev. 1954 8,4549. Leisten J. 1961 2191. Leisten and Wright unpublished experiments. A and the whole i-value in B would be accounted for if the disulphonic acid were to split into two frag- ments; but this should lead to a two-fold depression of freezing point in the mixture C instead of the nearly zero depression which we observed. All these results can be understood however if the disulphonic acid behaves as a simple base and accepts one pro- ton. In A and B the protonated disulphonic acid contributes two foreign particles per molecule M(SO,) f H,SO -+ M(SO,),H+ + HS04-In C however the proton is supplied by the sulphuric acidium ion which is thereby converted into a solvent molecule.The predicted i-value of zero agrees with that determined (0.17) within the usual limits of cryoscopic measurements We believe that these conclusions follow unam- biguously from the cryoscopic results. All three results are necessary. (Received December 28th 1962.) FE~RUARY 1963 61 2-Halogenoakylphosphonic Acids A New Class of Phosphorylating Agent By JUDITH A. MAYNARDand J. M. SWAN (DIVISION CHEMISTRY RESEARCH OF ORGANIC C.S.I.R.O. C~EMICAL LABORATORIES, MELBOURNE, AUSTRALIA) 2-CHLOROALKYLPHOSPHONIC ACIDS RCHCICH,.PO(OH), are readily prepared by re- action of phosphorus pentachloride with aliphatic alk-l-enes followed by hydrolysis of the resulting complex with water.l We find that these acids (e.g., R = n-C8H1, n-CSHl3 or H0,C-[CH21s) decom- pose rapidly and quantitatively in aqueous solution at pH > 5 yielding chloride phosphate and the R-C H Br-CR' R".PR'"O.OH (I)a R == Bz R' = H R" = Ph R'" = OH b R = R" = H R' = Ph R"' = OH c R = H R' = Ph R" L-Br R'" = OH d R = Bz R = H R" = Ph R'" = OPh e R = Bz R' = H R" = R'" = Ph original olefin. A similar reaction has been ob-for the more complex 2-bromoalkylphos- phonic acids (Ia b and c) the monophenyl phos- phonate (Id) and the phosphinic acid (Ie). This easy and unexpected decomposition can be written either as an internal fragmentation leading to monomeric metaphosphate which then reacts with water giving orthophosphate [reaction (l)] or as a fragmentation initiated by attack of a water molecule on the phos- phonate dianion [e.g.reaction (2)]. c CL' + R.CH=CH + t Both equations imply that the 2-halogenoalkyl- phosphonic acids might be useful phosphorylating agents; this Communication reports the successful phosphorylation of alcohols and phenols by in particular 2-chlorodecylphosphonic acid. Reaction of 2-chlorodecylphosphonic acid with three mol. of cyclohexylamine in ethanol at room temperature gave decene in 89% yield together with cyclohexyl- ammonium chloride and ethyl phosphate isolated in 70% yield as its di(cyclohexy1ammonium) salt m.p.225-230" (decomp.). Ally1 alcohol cyclohexanol and t-butyl alcohol were similarly phosphorylated in good yield. t-Butyl phosphate has not previously been reported; it was isolated as its cyclohexyl- ammonium salt m.p. 205-206" (decomp.) which on being heated decomposed to cyclohexylammon- ium phosphate and isobutene. A mixture of cyclohexylamine phenol and 2- chlorodecylphosphonic acid on being melted gave di(cyclohexy1ammoniu) phenyl phosphate m.p. 212-215" in 83 % yield; p-chlorophenol was phos- phorylated similarly Cdi(cyclohexy1ammonium) salt m.p. 204-205" yield 77x1. The action of cyclohexylamine alone on 2-chloro- decylphosphonic acid gave decene (80%) and pre- sumably N-cyclohexylphosphoramidate,which on attempted purification yielded only di(cyclohexy1- ammonium) phosphate m.p.200" (decomp.). No metaphosphate was detected in the reaction mixture and no pyrophosphate was formed when the initial mixture contained also phosphate ions. The action of pyridine triethylamine dimethylaniline or aniline on 2-chlorodecylphosphonic acid gave only dec- 1 -enylphosphonic acid without fragmentation. It is possible that the phosphorylations proceed by direct attack of alcohol or phenol on the phosphonic acid [cf. reaction (2)] or through an intermediate phos- phoramidate. Fragmentation of monoesters of 2-halogenoalkyl- phosphonic acids could provide a new route to symmetrical or unsymmetrical phosphate diesters. So far the action of organic bases on monoesters of 2-chlorodecylphosphonic acid has led only to the corresponding ester of dec-1-enylphosphonic acid.2-Chlorodecylphosphonic monoesters were also found to be stable to cold alkali but they dwom- posed in hot solution to give either the dec-1-enyl- phosphonate or a 2-hydroxydecylphosphonate with no evidence of fragmentation. On the other hand the monoester (Id) was reported to fragment in warm sodium carbonate,2 so that extension of the phos- phorylation method reported here may be possible by suitable choice of 2-halogenoalkylphosphonicacid or other phosphonic acid with an appropriate leaving group at position 2. The formation of phenyl-acetylene from 2-bromo-1 -phenylvinylphosphonic Bergmann and Bondi Ber.1933 66 286; Kosolapoff "Organophosphorus Compounds," John Wiley and Sons, he.,New York 1950 pp. 59 127; Kosolapoff and McCullough,J. Amer. Chem. SOC.,1951,73,855. Conant and Cook J. Amer. Chem. SOC., 1920,42 830. Conant and Pollack J. Amer. Chem. SOC.,1921,43 1665. Conant and Coyne J. Amer. Chem. Soc. 1922,44,2530. acid4 and of p-methoxyphenylacetylene from 2- chloro-2-p-methoxyphenylvinylphosphonicacid5 by the action of alkali suggests that 2-halogenoalk-l- Bergmann and Bondi Ber. 1933 66,278. PROCEEDINGS enylphosphonic acids might also be useful phos- phorylating agents. These and other possibilities are being explored. (Received December 4th 1962.) Delayed Fluorescence in Aromatic Hydrocarbon Vapours By B. STEVENS and E.HUTTON M. S. WALKER (DEPARTMENT OF CkEMISTRY THEUNIVERSITY SHEFFIELD 10) PARKERandHATCHARDfrecentIyrepOrtedfluorescence components with lifetimes rD in the millisecond region for dissoh ed phenanthrene and anthracene. To account for their important observation that the intensity of these components varies as the square of the absorbed lig\t intensity these authors suggest that the decay of the triplet state principally by the first-order process (I) is monitored by the second- order process (2) 3A -+ A . . . (1) 3A + 3A -j. lA* 3-A * . * (2) the latter takes place to a much smaller extent and results in the formation of the lowest excited singlet state lA* which gives rise to the delayed component by radiative relaxation. This mechanism accounts for the exponential decay of the delayed fluorescence with rD= 1/2k1 .. . (I) since under conditions of low-intensity (non-flash) irradiation PA] < k1/k2 . . . (11) and explains the low intensity (< 1% of the total emission) of the delayed component. Moreover the values of rDobtained are in agreement with those expected from (I) and values of k obtained by flash absorption photometry2 for the same systems. We find a similar dependence of delayed fluorescence intensity on the square of the absorbed light intensity for anthracene perylene. and pyrene in the vapour phase excited by the group of mercury lines at 365 mp. A Becquerel phosphoroscope was used to isolate the delayed component of fluorescence emitted by the vapour in a heated Pyrex cell and its intensity ID was measured by means of a Mazda 27M3 photomultiplier tube.3 Wratten neutral density filters of known optical density D at 365 mp were placed between the light source and the cell to vary the incident-light intensity; plots of log ID against D were linear in each case with a slope of -1-9 f0.1.Values of rD obtained under the conditions described are given in the Table. Flash-photometric triplet decay data are not available for perylene and Lqetimes rDof delayed fluorescence it8 the vapour phase. Temp. Concn. 103rD 10-3k1 (sec.-l) (from I) (mole/ 1.) (sec.) Anthracene 220 0 1-2 220 2 x 10-4 0.4 220 4 x lo4 0.3 220 8 x 0.2 Perylene 362 b1.6 x 0.77 Pyrene 260 0-8 x lo4 2.7 0-42 1.2 1.7 1-9 0.65 0-18 pyrene in the vapour phase; indeed since k2 is some orders of magnitude larger in the vapour phase than in solution the inequality (11) obtains only when the triplet state concentration is reduced to the extent that it is not readily detected in absorption.However a detailed analysis of the composite triplet decay curves obtained by flash absorption photometry for anthracene vapour provides the estimate4 k = 1.08 & 0.20 x lo3 sec.-l at 160° which from (I) leads to r = 0-5 & 0.1 x sec. in good agreement with the experimental values obtained at 220". Our observations support the mechanism proposed by Parker and Hatchard for delayed fluorescence in fluid media. However in view of the fact that a doubly-excited singlet dimer of intrinsically long radiative lifetime5 may be an intermediate in process (2) a confirmation of the mechanism should be pro- vided by accurate measurements of r and k for the same system under identical conditions.Certainly the excimer dissociation mechanism based on an unrealistically long radiative lifetime of the excimer cannot account for the intensity dependence of delayed fluorescence reported here and previous1y.l This research has been made possible through the support of the U.S. Department of Army through its European Research Office. (Received December 12th 1962.) Parker and Hatchard Proc. Chem. SOC.,1962 147; Pruc. Roy. Soc. 1962 A 269 574. Jackson Livingston and Pugh Trans Faraday SOC.,1960 56 1635.Hutton Doctoral Thesis Sheffield 1961. West Doctoral Thesis Sheffield 1960. Colpa Fifth European Congress on Molecular Spectroscopy Amsterdam 1961. Williams,J. Chem. Phys. 1958 28 577; Stevens and McCartin Mol. Phys. 1960 3 425. FEBRUARY 1963 63 Mechanisms of Photoreactions in Solution. Part XV.l Photosensitised Addition of MaIeic Anhydride to Benzene By GEORGE and WILLIAM S. HAMMOND M. HARDHAM (GATES OF CHEMISTRY CALIFORNIA INSTITUTE OF TECHNOLOGY, AND CRELLIN LABORATORIES PASADENA U.S.A.) CALIFORNIA PHOTOADDITION of maleic anhydride to benzene gives quantum yields are essentially the same for benzo- the diadduct (I) under conditions of direct irradia- phenone and acetophenone indicates that inefficiency tion2p3 or on use of benzophenone as a photo-in the process arises after energy has been transferred sensitiser? Bryce-Smith and Lodge5 recently reported to maleic anhydride.There is probably a small de- that the sensitised reaction is successful only if the pendence of the quantum yield on the concentration system is irradiated with light absorbed in the second of maleic anhydride. This may indicate that reversion optical transition of the sensitiser. Although this of the monoadduct may compete with addition of the observation has not been reproduced by workers in second molecule of maleic anhydride. The reversion the same laboratory we now report quantitative might be either thermal or photochemical but cannot measurements which show that the sensitised re- account for a major portion of the inefficient action almost certainly involves transfer of excitation absorption of light (N 90%).from the lowest triplet state of the sensitiser as has been established in other cases.' Quantum yields for the sensitised reaction shown in Table 1 were measured by two techniques. TABLE1. Quantum yields in the photosensitisecl reaction of maleic anhydride with benzene. A preliminary estimate of the efficiency of maleic Series* [Maleic anhydridelt qr anhydride in benzene as a quencher for the photo- With benzophenone reduction of benzophenone by diphenylmethan~l~ A 0.50 0.088 f0.005 indicates that maleic anhydride is very effective as an A 1-00 0.092 f0.001 energy acceptor. Repetition of such experiments A 1-50 0-096 f0.007 with approximate correction of the results for maleic B 1.00 0.096 anhydride consumption gives a value of kq/kr,where B 1*50 0-106 kq is rate constant for the energy transfer process and C 0.50 0.064 kr is the rate constant for hydrogen abstraction from C 1-00 0.075 diphenylmethanol by benzophenone triplets of about C 150 0.082 700.This is close to the limiting value of kq/krwhich With acetophenone we believe to be characteristic of diffusion-controlled D 1.50 0.10 processes. Since at the concentrations used in the D 1-50 0.090 quenching experiments only about 30% of the maleic anhydride in benzene solution is in the form * In series A the collimated beam on our optical bench of the benzene complex,5 the result implies that was used with two glass filters which transmit a band with a broad maximum at 3800 A half heights at 3600 and energy transfer to both complexed and uncomplexed 3950 A and zero intensity at 3400 and 4200 A.The other material occurs. If only transfer to the complex were sxies were carried out with an immersion lamp at the involved the efficiency of quenching by that species centre of a rotating turntable which carried many samples would be higher than for any other non-metallic for simultaneous illumination ;filtering was provided by a cupric nitrate solution which does not transmit below quencher that we have studied. 3300 A. Absolute values obtained by the latter technique We have measured quantum yields in solutions in are less accurate but relative values determined in a single which the concentration of benzene was reduced by series are reasonably precise.7 Benzophenone 0.01h1 and acetophenone 1.OOM. Solutions degassed and then sealed dilution with dioxan. The results shown in Table 2 in vacuo. are consistent with the view that the quantum yield is determined primarily by competgion between Obviously long-wavelength light is effective in the addition of maleic anhydride triplets to benzene and sensitised reaction. Further the fact that the their non-radiative decay. While decay may occur Part XIV is Herkstroeter Saltiel and Hammond J. Amer. Chem. SOC.,in press. Angus and Bryce-Smith Proc. Chem. SOC.,1959,326; J. Chem. Soc. 1960,4791. Grovenstein Rao and Taylor J. Amer. Chem. SOC.,1961 83 1705. Schenck and Steinmetz Tetrahedron Letters 1960 No.21 1. Bryce-Smith and Lodge J. Chem. SOC.,1962,2675. Bryce-Smith Gilbert and Vickery Chem. and Ind. 1962,2060. Hammond Turro and Leermakers J. Phys. Chem. 1962,66 1144; Hammond and Leermakers ibid. 1148. from either free or complexed triplets the notion that free maleic anhydride triplets formed by energy transfer decay before they can enter into benzene TABLE 2. Effect of variation of benzene concentration. [C,H,]* 10.7 7.9 5.6 3.4 1.1 @ (approx.) 0.092 0.073 0.026 4 4 * Benzophenone 0.10~; maleic anhydride 1.00~. All solutions degassed. ~OCEEDINGS complexes is unattractive since it would imply either that the decay time is unusually short or that the rate of complex formation is unusually slow.We thank the National Science Foundation for partial support of this study. W.M.H. is also grateful for a summer stipend from the Shell Company Foundation Grant. (Received December I 7th 1962.) Bicyclo[3,2,l]octan-3-one By C. W. JEFFORD (DEPARTMENT UNIVERSITY PHILADELPHIA 22 PA. U.S.A.) OF cHEMISTRY TEMPLE A SIMPLEroute to bicyclo [3,2,1 loctan-3-one (IV) was needed in order to make feasible a study on sterically constrained or "pinched" cyclohexanone. Although the existence of bicyclo[3,2,1 Ioctan-3-one has been demonstrated by the formation of its dibenzylidene derivative the parent compound has not been isolated.lS2 This Communication reports the syn- thesis and preparation in good yield of bicyclo- [3,2,l]octan-3-one by a novel carbene addition to norbornene.It is known that the dihalogenocyclopropane adduct formed by the addition of a dihalogeno-carbene to a small cyclic olefin can undergo ring enlargement on subsequent heating.s Accordingly the synthesis of the ketone (IV) as indicated in the annexed scheme seemed reasonable. o X=Br x b XXC1 Dibromocarbene formed by the interaction of potassium butoxide with bromoform was allowed to react with norbornene in n-pentane at room temperature. Instead of the expected tricyclic product (I) an oil of b.p. 108"/1.75 mm. was obtained which was shown to be 3,4-dibromobicyclo [3,2,1 loct-2-ene (IIa) (40% yield). The structure of this dibromide was confirmed by its analysis and infrared and pro- ton magnetic resonance spectra.The presence of a band at 6.15 p is inconsistent with the cyclo- propane structure (I). Moreover the proton mag- netic resonance spectrum revealed a doublet centred at 3-75T (J = 6.6 c./sec.) and a doublet centred at 5.45 r (J = 2-7 c./sec.) which are due respectively to the vinyl and the allylic protons split by their neighbouring bridgehead protons. The other protons show as two complex areas centred at 7.30 and 8-34 T. The small value for the splitting exhibited by the allylic proton favours the stereochemical assign- ment shown in (IIa) which nevertheless is tentative. The uncertainty is apparent from an inspection of a Dreiding model which shows that the projected valency angles for the bridgehead proton with respect to quasi-axial and quasi-equatorial protons are nearly the same.Similarly it was found that di-chlorocarbene added to norbornene to yield 3,4-di- chlorobicyclo[3,2,1 Ioct-2-ene (IIb)? Lithium aluminium hydride reduced the di-bromide (IIa) in ether to 3-bromobicyclo [3,2,1 wt-2 ene (111) b.p. 63Of3.25 mm. (90% yield). Mild but prolonged hydrolysis which was successful for similar molecule^,^ was ineffective for this bromide. However a solution of the bromide in concentrated sulphuric acid when kept at room temperature for 2 days with occasional stirring and then treated with water gave a dark oil from which was sublimed bicyclo[3,2,1]octan-3-one (IV) (75 % yield) as a colourless waxy solid m.p. 132.5-133". The struc- ture was confirmed by characterisation as the di-benzylidene derivative,1e2 which was shown to be identical with an authentic sample.We are indebted to P. von R. Schleyer of Princeton University Princeton N.J. for providing a specimen of this derivative2 and to J. Gunsher for technical assistance. The work was supported by a Research Grant from the National Science Foundation. (Received November 23r 1962.) Alder and Reubke Ber. 1958 91 1525. a Schleyer and Nicholas Abs. 140th Meeting Amer. Chem. Soc.,Chicago Sept. 3--8th 1961 p. 754. Kirmse Angew. Chem. 1961,73 161. Independently Bergmann has reported the same findings (Abs. 142nd LMeeting Amer. Chem. SOC. Atlantic City, N.J. U.S.A. Sept. 9-14th 1962 p. 97Q.) Kwart and Kaplan J. Amer. Chem. Soc. 1954,76,4072. FEBRUARY 1963 65 Persulpbate Oxidation of carboxylic Acids A New Rearrangement By R.H. THOMSON and A. G. Wnm (UNIVERSITY OF ABERDEEN) THEproducts obtained by persulphate oxidation of carboxylic acids (RC02H) frequently simulate those formed by Kolbe electrolysis and are derived either directly from the initial carboxyl radical R*CO2- or from the radical R.after loss of carbon dioxide; e.g. o-benzoylbenzoic acid yields fluorenone,l and bi- phenyl-2-carboxylic acid affords 3,4-benzocoumarin. Both these cyclisations have been effected by electrolysis? By analogy oxidation of o-phenoxybenzoic acid (I) should yield the lactone (11) or more probably dibenzofuran (111). The lactone has been obtained3 (2%) by oxidation with manganese dioxide in chloro- form.But when persulphate was used neither com- pound (11) nor (111) was detected; the product (20 %) was then a phenolic ester C26Hls06 m.p. 145" (vmsx. 32OOw 1680s 835 753 690 cm.-l marked resembling data for phenyl salicylate > 1600 cm.-l), which formed a diacetate and a dimethyl ether. Alkaline hydrolysis of the ester gave phenol and a phenolic acid Cf4Hl0O6,m.p. 301-305" (vmax 3150sh 1680sh 1650 860 760 723 cm.-l) and similar treatment of its dimethyl ether followed by decarboxylation with copper in quinoline afforded 2,4'-dimethoxybiphenyl. The oxidation product is therefore the bisalicylate (VI). The compound (VI) was also obtained by per- (W sulphate oxidation of phenyl salicylate and we con- sider its formation from o-phenoxybenzoic acid to proceed by rearrangement of the initial carboxyl radical (IV) to the mesomeric phenoxyl radical (V) (for which good analogy exists4) followed by di- merisation.Intermolecular ortho-para-coupling of phenoxyl radicals is comparatively rare the classical example being the formation of PUmmerer's ketone. We thank D.S.I.R. for the award of a Research Studentship to one of us (A.G.W.). (Received December 15th 1962.) l Russell and Thomson J. 1962 3379. Bunyan and Hey J. 1962,2770; Kenner Murray,and Tylor Tetrahedron,1957 1,259. Lewis J. 1962 2533. De Tarand Hylinsky J. Anrer. Chem. Soc. 1955,77,4411; cf. Griffin and OConnell ibid. 1962 84,4148. Difluoro(pentafluorosuIphur)amine SF,*NF2 By G. H. CADY,D.F. EGGERS, and B. Tm OF CHEMISTRY OF WASHINGTON WASHINGTON, (DEPARTMENT UNIVERSITY SEATI-LE U.S.A.) TETRAFLUOROHYDRAZINE dissociatesf appreciably into .NF radicals at temperatures above about 100". Disulphur decafluoride S2F1 is stable at room temperature but decomposes into sulphur hexa- fluoride and tetrafiuoride at about 150" and above by a chain mechanism in which the first step is prob- ably dissociation into two SF radicals. It has now been found that the decafluoride and tetra-fluorohydrazine give difl uoro(pentafl uorosu1phur)- axnine SF,.NF2 in about 60% yield at 140" in a Monel tube the probable mechanism being that NF and SF radicals combine (there is no reaction at room temperature). The product is colourless has vapour pressures (over the range -63" to -20") expressed by the equation log P (mm.) = -1.241 x 103/T + 7.746 corresponding to a normal b.p.of -17.6" a heat of vaporisation of 5660 cal. per mole and a Trouton constant of 21.9 e.u. and it gave a molecular weight of 177 (F,SN requires M 179). Over the temperature range -60" to 0" the density (g./c.c.) of the liquid is given by 1.781 -3.546 X 1O4t ("c). Peaks in the mass spectrum with an ionisation voltage of 70,in order of decreasing intensity indi- cate fragments NFt SF,+ SF,+ NF$ SF+ S+ SF$ SF,+. Infrared bands at 912vs 885vs 699m 606s and 569m cm.-l are assigned as SFvibrations; corresponding bands for SF,CI are at 908vs 854vs SfJohnson and Colburn J. Arner. Chem. Soc. 1961,83 3043. Trost and McIntosh Canad.J.Chem. 1951 29 508. 706vs 602vs and 578m cm.-l. Bands assigned to NF vibrations are 1029m 946vs and 679m cm.-l; corresponding bands in NF occur at 1031m 907vs and 642m cm.-l. No bands were observed below 569 cm.-l even though one might expect to find there the analogue of the 497111 band in NF or possibly the b and b fundamentals of the SF group which are symmetry-forbidden in SF,CI but not in SF,.NF2. Weak bands observed in the 1000-2000 cm.-l region can be assigned as binary combinations and overtones of the fundamentals. The lgFnuclear magnetic resonance spectrum at 56.4 megacycles has the following chemical shifts with respect to CCI,F as standard for NF -3710 c./sec. for the apex atom of the SF group -2791 c./sec.for the four equivalent fluorine atoms of the SF group -2084 c./sec. The spin-spin coupling PROCEEDINGS constant for the two kinds of fluorine atoms in the SF group is 153.2 c./sec. Difluoro(pentafluorosu1phur)aminedoes not react at room temperature with water O*l~-sodium hydroxide or 0-lwhydrochloric acid. It is stable at room temperature but decomposes at 220" into sul-phur hexafluoride sulphur tetrafluoride and tetra- fluorohydrazine (found after cooling) the products expected from SF and *NF radicals. Photochemical decomposition by mercury-arc radiation in a Pyrex glass vessel gives sulphur tetrafluoride thionyl fluoride silicon tetrafluoride and nitrosyl fluoro- silicate (NO),SiF obviously glass enters into the chemical changes involved.This work was supported by the Office of Naval Research and the National Science Foundation. (Received January 9th. 1963.) The Thermolysisof Ally1 Cyanoacetate; Catalysis in the Vapour Phase By E. C. KOOYMAN, R. Louw and W. A. M. DE TONKELAAR OF ORGANICCHEMISTRY NETHERLANDS) (LABORATORY LEIDENUNIVERSITY WITHIN the scope of a general investigation on the thermolysis of allyl compounds we have studied the gas-phase thermolysis of allyl cyanoacetate (I). A mixture of toluene vapour and nitrogen or argon was used as the carrier gas in a flow system at atmospheric pressure. In the temperature range 360-440"~ this ester was found to decompose to pent-4-enenitrile (allylacetonitrile) (11) and carbon dioxide CH, CH.CH,*CO,.CH,*CN -+ CH, CH*CH,-CH,-CN + co (1) (11) The nitrile was identified on the basis of its ele- mentary composition infrared spectrum b.p.,l and n:;' the melting point of the amide obtained on reaction with dilute alkaline hydrogen peroxide? was 102.5-103.8" and showed no depression with a sample prepared from allylacetic acid and urea.3 Decarboxylation could be followed readily by mass- spectrometric determination of carbon dioxide in the exit gas as well as by gas-liquid chromatographic determination of unused ester with toluene as internal standard.Both sets of results tallied within the limits of experimental accuracy (a few per cent of the total conversion). Surprisingly decomposition appeared to be of the second order with respect to the ester in contrast to the first-order processes generally observed in ester thermolysis.* The Arrhenius parameters appeared to be E M 35.5 kcal.mole-l A x 2.5 x lo1* sec.-l ml. mole-l corres- ponding to a 25-fold increase in the rate constant over the temperature range investigated. Addition of acetic acid had a pronounced accelerating effect on the rate of decomposition (cf. Figure). Similar phenomena were observed with tri- ethylamine or pyridine. In the presence of more than 10moles of acid or base per mole of ester thermolysis proceeded as a first-order process and was practically independent of the amount of acid while forming the same products. The first-order rate constant was measured over the temperature range 310-385"; the Arrhenius parameters were E M 43 kcal.mole-l A x 2.2 x 101 sec.-l corresponding to a 65-fold increase in rate constant over this temperature range. These results may be interpreted as follows. In the absence of acid and base the primary step consists in self-enolisation of the ester (I) by a bimolecular reaction (a). The enol which is a substituted allyl vinyl ether (Ia) rearranges rapidly (b) in a cyclic reaction5 to form 2-cyanopent-4-enoic acid (111) which undergoes a fast decarboxylationfC (c) to form the product (11) and carbon dioxide. Under these conditions therefore the reaction is second order with respect to the ester (I). (a) Paul and Tchelitcheff Bull. Soc. chim. France 1949,470; (b) Kirrmann and Geiger-Berschandy ibid.1955,933; (c) Paul and Cottin ibid. 1937 4 934. Radziszewski,Ber. 1885 18 355. Cherbuliez and Landolt Helv. Chim.Acta 1946 29 1438. E.g. De Puy and King Chem. Rev. 1960,60,431. Schuler and Murphy J. Amer. Chem. SOC.,1950,72 3155; Pocker Proc. Chem. Soc. 1961 141. FEBRUARY 1963 67 Slow ester (I) and a molecule of the catalyst leading to the 2(1) -2(Ia) . . . (a) equilibrium concentration of the enol. Under these Fast conditions the rate of decomposition will be pseudo- (la) -+ (111) . . . (b) monomolecular with respect to ester (I) and in- Fast dependent both of the amount and of the nature of . . . (c) the catalyst (111) -+ (11) + coz (Acid or base) (I) <--(la) + AH . . . (a -1) The Arrhenius activation energy thus consists of two components viz.the activation energy of (b) and the heat of enolisation AHe. The above interpretation of the catalytic effect of acetic acid was supported by a detailed kinetic analysis at 359" with intermediate proportions of acetic acid (see Figure). Rate data could be satis- factorily interpreted in terms of the two enolising steps (a) and (a -l) ka-1 being about 18ka at 359". Packing of the reactor with glass tubelets (ten-fold increase in the surface:volume ratio) had only a small accelerating influence on the uncatalysed thermolysis. Glass wool however caused an increase in the decomposition rate even beyond the maxi- mum rate attainable with acetic acid. One of the authors (R.L.)is grateful for leave of absence from the Koninklijke/Shell-Laboratorium, Amsterdam.(Received December 20th 1962.) +5 Ib 1k ;rlo is io' Acetic acid (mol.) Plot of percentage decomposition of ally1 cyanoacetate ngainst moles of acetic acid per mole of ester. With high proportions of acid or base the primary step consists in the rapid reversible formation of the enol (Ia) by interaction (a- 1) of a molecule of NEWS AND ANNOUNCEMENTS Liaison Officers.--Dr. F. J. Smith (Monsanto Chemicals Limited) has agreed to serve as Liaison Officer for the Fawley area in place of Mr. K. 6. Bryant and Professor W. B. Whalley has agreed to serve at the London School of Pharmacy in place of Professor W.H. Linnell. The Harrison Memorial Prize 1962.-At the meeting of the Harrison Memorial Prize Selection Committee held on January 16th 1963 it was decided that the Harrison Memorial Prize for 1962 should be awarded to Dr.Alan Carrington in con- sideration of his contribution to the study of theoretical chemistry especially by virtue of his work on electron-spin resonance. Dr. Carrington is a graduate of the University of Southampton. He obtained the B.Sc. degree in 1955 and has subse-quently undertaken postgraduate research at the Universities of Southampton Minnesota and Cam- bridge where he now holds a Research Fellowship at Downing College. This prize may be awarded for outstanding merit in any branch of Pure or Applied Chemistry. It was created in 1922 to commemorate the services of the late Colonel Edward Frank Harrison formerly Deputy Controller of the Chemical Warfare Depart- ment for the protection of the British Forces from poison gas in the 1914-1918 war.It is awarded to the British chemist under 30 years of age who in the opinion of the Selection Committee has during the previous five years conducted the most meri- torious and promising original investigations in Chemistry and published the results. Research Fund.4rant.s for research have been awarded by Council to the following f. s. d. 1. Binks R. (Bristol) .. .. 56 0 0 Borrell P. (Keele) . .. .* 45 0 0 Chissick S. S. (Chelmsford) .. .. 35 0 0 Coysh R. H. (Blandford) .. .. 40 16 0 Cremlyn R. J. W. (Hatfield) .. .. 14 7 0 Downs A. W. (Birmingham) ,. .' 50 0 0 Dutta P.C. (Calcutta) .. .. .. 30 0 0 I. Elmore D. T. (Belfast) .. .. 15 0 0 Frey H. M. (Southampton) . .. 70 0 0 Gibson M. S. (Manchester) .. .. 15 0 0 Graham R. J. T.(Salford) .. .. 20 9 0 Hathaway B. J. (Hull) . .. .. 100 0 0 Jones N. (Coventry) .. .. .. 18 0 0 Kettle S. F. A. (Sheffield) .. .. 45 0 0 Landor S. R. (London). . *. .. 25 0 0 Longworth W. R. (Sunderland) .. 10 0 0 Moody D. P. (London). . .. .. 26 4 0 Munday L. (Birkenhead) .. .. 10 10 0 Parr C. W. (London) .. .. .. 45 0 0 Peacocke T. A. H. (Leatherhead) .. 100 0 0 Spaull A. J. B. (London) .. .. 15 0 0 .I Spencer M. (Leeds) .. .. 40 0 0 Tandon S. G. (Jabalpur) . .. 25 0 0 Tyrrell H. J. V. (Sheffield) .. .. 20 0 0 West B. 0. (Adelaide) .. .. .6500 Whalley W.B. (London) .. .. 89 10 0 Whippie R. 0. (Ghana). . .. .. 45 0 0 Election of New Fellows.-245 Candidates were elected to the Fellowship in January 1963. Deaths.-We regret to announce the deaths of the following Dr. W. Charlton (14.12.62) of Man- Chester a Fellow for nearly forty years; Mr. J. H. Dyson (1 3.1.63) Managing Director J. H. Dyson and Son Limited Halifax; Dr. E. Frankel (5.1.63) of Metal Alloys Limited Treforest; Mr. R. N. Johnson (17.9.62) of A.W.R.E. Aldermaston; Dr. A. M. Moore (26.8.62) of Atomic Energy of Canada Limited; Dr. 7'. G. Pearson (29.12.62) Director of Research British Aluminium Company Limited; Professor J. Read (21.1.63) of the Univer- sity of St. Andrews; and Mr. R. H. Spencer (1 3.12.62) Process Development Chemist of Sidcup.Royal Society.-Among the Vice-presidents ap- pointed by Sir Howard Florey President of the Royal Society for the year ending November 30th 1963 are Lord Fleck Sir Patrick Linstead and Professor W. T.J. Morgan. Symposia etc.-The Fifth International Pesticides Congress will be held in London from July 17th- 23rd 1963. Further enquiries should be addressed to the Honorary Secretary Fifth International Pesti- cides Congress 14 Belgrave Square London S.W.1 and not as indicated in Proceedings 1962 p. 393. hOCEEDiNGS A symposium on the Chemistry and Biochemistry of Fungi and Yeasts sponsored by the Irish National Committee for Chemistry will be held in Dublin on July 18-20th 1963. Further enquiries should be addressed to Professor Eva M.Philbin Honorary Secretary of the Symposium Department of Chem- istry University College Dublin. Personal.-Ah-. D. H. BelZ has retired as Chemical Production Manager of British Drug Houses. Ltd. Laboratory Chemicals Division. Professor A. J. Birch has been awarded the 1963 Fritzsche Award of the American Chemical Society and the Edward Curtis Franklin Memorial Award for Outstanding Contributions to Chemistry. As recipient of the latter award Professor Birch has been asked to deliver the Memorial Lecture at Stanford University. Mr. P. F. Cooke has left the American Oil Com-pany of Indiana to become Chief Chemist of Petro- quimica Argentina S.A. Dr. F. Albert Cotton has been awarded the 1963 Leo Hendfik Baekeland Award which is ad-ministered by the North Jersey Section of the American Chemical Society.Dr. P. J. C.Counsel1 has joined the Research Staff of Evode Limited. Dr. B. Dickens formerly with the Chloride Electrical Storage Co. has taken a post in the Department of Chemistry Harvard University. Mr. L. A. Dickinson formerly with the Defence Research Board is now Chairman Solid Propellant Department Propulsion Sciences Division Stamford Research Institute Menlo Park California. Mr. W. Gardiner formerly of Winthrop Labora- tories has joined Glaxo Laboratories Ltd. Barnard Castle. Dr. R. G. A. Ginman formerly with the Distillers Company is now Lecturer in Physical Chemistry in the Pharmacy Department Brighton College of Technology.Dr. E. B. Hughes has retired as Chief Chemist of J. Lyons and Co. Ltd. and has been succeeded by Dr. J. H. Bushill. Dr. D. T. Hurst has been awarded a National Research Council Fellowship tenable at the Atlantic Regional Laboratory Halifax Nova Scotia. Prufessor G. A. Jefrey University of Pittsburgh has been elected President of the American Crystallo- graphic Association for 1963. Mr. E. I. Johnson has joined the Food Standards Committee and its Food Additives and Con-taminants Sub-committee representing the Govern- men t Chemist Mr. R. M. Johnson formerly of the National College of Food TechnoIogy is now Lecturer in Analytical Chemistry at the Chelsea College of Science and Technology. FEBRUARY 1963 Mr. R. H.Henriksen has been made a Vice-Chairman of Roussel Laboratories Ltd. Mr. J. M. Locke is now a N.A.T.O. Research Fellow at the Dyson Perrins Laboratory University of Oxford. Dr. R. H. McDougaZZ has taken a post in the Department of Chemistry and Biology West Ham College of Technology. Miss Mamie OZliver has been appointed research investigator and consultant to the Schweppes Group of Companies. Mr. C.J. Panton has been appointed to a Research Fellowship at the University of California Davis California. Dr. A. R. Parkinson has joined the research divi- sion of the Goodyear Tyre and Rubber Co. Akron Ohio. Lt.-CoZ. F. W. Pinkard has retired as Senior Lecturer in Chemistry University of Birmingham. Dr. R. H. Sahasrabudhey has taken up the appoint- ment of Reader in Chemistry at the Banaras Hindu University Banaras.Dr. C. A. SZater has been appointed Head of the Basic Research Section of Schweppes Research Laboratory. Dr. L. E. Sutton has been appointed to a Reader- ship in Physical Chemistry at the University of Oxford. Dr. G. A. Swan has been appointed to a Personal Readership in Organic Chemistry at King’s College Newcastle-upon-Tyne. Mr. B. TopZey relinquished his executive duties with Albright & Wilson Ltd. on medical advice but remains a Director of the Company and Deputy Chairman of the Board. Dr. F. L. Tye formerly of The Permutit Company Limited is now Research Manager with The Ever Ready Company (Gt. Britain) Limited. Dr. P. F. R. Venables has been appointed to the Advisory Council on Scientific Policy.Dr. H. S. Venkataraman formerly at the Indian Institute of Technology Bombay is now pool Officer -in -Charge Corrosion Section Central Electro-chemical Research Institute Karaikudi India. Dr. K. 1;. Watterson formerly of Cornell Univer- sity is now Senior Research Chemist Pennsalt Chemicals Corporation. Dr. I. WeZZings has joined the staff of the Depart- ment of Chemistry Johns Hopkins University Baltimore. Sir Alan Herries Wilson and Mr. A. E. Bide have been elected to the Board of Glaxo Laboratories Ltd. Mr. J. Wood has been appointed General Manager (production) of Bakelite Ltd. Dr. S. H. Zaheer Director of the Regional Research Laboratory Hyderabad India has been appointed Director-General of the Indian Council of Scientific and Industrial Research.FORTHCOMING SCIENTIFIC MEETINGS London Thursday March 14th 1963 at 6 p.m. Meeting for the Reading of Original Papers “Some ortho-phenanthroline complexes of yttrium and the lanthanides,” by F. A. Hart and F. P. Laming. “Stabilisation of some organic systems by complex- formation with transition metals,” by M. Green P. L. I. Nagy and J. K. P. Ariyaratne. “0-and n-Bonding from cyclic ligands to transition- metal ions in organometallic compounds,” by M. R. Churchill M. Gerloch and R. Mason. To be held in the Rooms of the Society Burlington House W.l. (Abstracts of papers can be obtained from the General Secretary.) Aberdeen Thursday March 7th 1963 at 8 p.m.Lecture “Aromatic Reactivity,” by Professor C. Eaborn D.Sc. F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Medical Physics Lecture Theatre Marischal College. Aberystwyth (Joint Meetings with the University College of Wales Chemical Society to be held in the Edward Davies Chemical Laboratory.) Thursday March 7th 1963 at 5 p.m. Lecture “Nuclear Magnetic Resonance,” by Prof- essor E. R. Andrew M.A. Ph.D. Thursday March 14th at 5 p.m, Tilden Lecture “Biosynthesis of Alkaloids,” by Professor A. R. Battersby Ph.D. Birmingham Friday March lst 1963 at 4.30 p.m. Lecture “Ionic Polymerisation,” by Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University.Bristol (Joint Meetings with the Royal Institute of Chem- istry and the Society of Chemical Industry to be held in the Department of chemistry The University un- less otherwise stated.) Thursday March 7th 1963 at 6.30 p.m. Annual Meeting and Lecture “Ceramic Fuels for Nuclear Reactors,” by Dr. J. K. Dawson F.R.I.C. Joint Meeting with the Institute of Fuel. Friday March 22nd. Annual Dinner and Dance. Bristol College of Science and Technology. Cambridge Friday March lst 1963 at 8.30 p.m. Lecture by Professor R. C. Cookson F.R.I.C. Joint Meeting with the University Chemical Society to be held in the University Chemical Laboratory, Lensfield Road.Cardiff Thursday March 21st 1963 at 5.30p.m. Lecture “Stereochemical Factors in Biological Activity,” by Dr. A. H. Beckett F.R.I.C. F.P.S. To be given in the Welsh College of AdvancedTech- nology (Pharmacy Department) Cathays Park. Dublin Wednesday March 20th 1963 at 5.30 p.m. Lecture “Recent Developments in Molecular Spectroscopy,” by Dr. H. Rubaclava. To be given in the Department of Chemistry University College. Durham Monday March 11th. 1963 at 5 p.m. Lecture “Some Chemical Aspects of Polymerisation Reactions,” by Professor C. H. Bamford Ph.D. F.R.I.C. To be held in the Science Laboratories South Road. Edinburgh Thursday March 7th 1963 at 7.30 p.m Lecture “Developments in the Field of Nucleic Acids,” by Professor J.N. Davidson D.Sc. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Exeter Friday March Ist 1963 at 5.15 p.m. Lecture “Polysaccharides as Energy Reserves in Plants,” by Professor E. L. Hirst C.B.E. LL.D. F.R.S. To be given in the Washington Singer Laboratories. Glasgow Friday March Ist 1963 at 4 p.m. Tilden Lecture “The Biosynthesis of Alkaloids,” by Professor A. R. Battersby Ph.D. To be given in the Chemistry Department The Royal College of Science and Technology. PROCEEDINGS Friday March 15th at 4 p.m. Annual General Meeting of Local Fellows followed by Meeting for Reading of Original Papers. To be held in the Chemistry Department The University.Keele Tuesday March 5th 1963 at 8.30 p.m. Lecture “The Expert in the Witness Box Samples Old and New,” by R. P. Moore LL.B. Barrister-at- Law. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University. Leicester (Joint Meetings with the University Chemical Society to be held in the Department of Chemistry The University.) Monday March 4th 1963 at 4.30 p.m. Lecture “Addition Accompanying Substitution in Aromatic Systems,” by Professor P. B. D. de la Mare D.Sc. Monday March 18th at 4.30 p.m. Lecture “Degeneracy and Magnetic Resonance Experiments,” by Dr. L. E. Orgel M.A. F.R.S. Manchester Thursday March 21st 1963 at 6.30 p.m. Lecture “Big Rings,” by Professor R.A. Raphael Ph.D. F.R.S. To be held in Room FlyManchester College of Science and Technology. Newcas tle (Meetings to be held in the Chemistry Department King’s College.) Tuesday March 5th 1963 at 5.30 p.m. Lecture “Some Fast Halogenation Reactions,” by R. P. Bell M.A. F.R.S. Friday March 15th at 5.30 p.m. Lecture “Some New Natural Phenolic Compounds -Structural and Biosynthetic Studies,” by Dr. W. D. Ollis. North Wales Thursday March 14th 1963 at 5.45 p.m. Lecture “The Peculiarities of Radical Polymerisa- tion in Solution,’’ by Professor G. M. Burnett D.Sc. F.R.I.C. Joint Meeting with the Society of Chemical Industry to be held in the Chemistry Department University College Bangor. Nottingham Tuesday March 12th 1963 at 5 p.m.Nottingham University Chemical Society Presiden- FEBRUARY 1963 tial Address by Dr. T. J. King M.A. To be held in the Chemistry Department The University. Oxford Monday March 4th 1963 at 8.30 p.m. Lecture “The Chemistry of Bacterial Walls and Membranes,” by Professor J. Baddiley D.Sc. F.R.S. Joint Meeting with the Alembic Club to be held in the Inorganic Chemistry Laboratory. Reading Tuesday March 5th 1963 at 6 p.m. Lecture “Molecular Vibrations and Chemical Prob- lems,” by Dr. H. W. Thompson C.B.E. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the University Chemical Society to be held in the Large Chemistry Lecture Theatre The University. Southampton Friday March 8th 1963 at 5 p.m.Lecture “The Visible and Infrared Spectra of In-organic Chemistry,” by Dr. T. M. Dunn. Joint Meeting with the Royal Institute of Chemistry to be held in the Department of Chemistry The University. Friday March 8th at 7 p.m. Lecture “Some Aspects of the Chemistry of Fungal Products,” by Dr. C. E. Stickings. To be given at the Portsmouth College of Technology. Wednesday April 3rd at 7 p.m. Lecture “Recent Trends in the Study and Utilisation of Coal,” by A. R. Middleton. To be given at the Portsmouth College of Technology. Swansea Friday March lst 1963 at 4.30 p.m. Lecture “The Place of Kinetics in Chemistry,” by R. P. Bell M.A. F.R.S. Joint Meeting with the Student Chemical Society to be held in the Depart- ment of Chemistry University College.Tees-side (Joint Meetings with the Royal Institute of Chem-istry the Society of Chemical Industry and Society for Analytical Chemistry.) Thursday March 7th 1963 at 8 p.m. Lecture “Coal Research,” by Dr. R. R. Gordon. To be given at the Billingham Technical College. Thursday March 14th at 8 p.m. Lecture “The Nature of the Genetic Code,” by Dr. R. J. Watts-Tobin. To be given in the Con- stantine Technical College. ADDITIONS TO THE LIBRARY Use of the chemical literature. Edited by R. T. Bottle. Pp. 23 1. Butterworths Scientific Publications. London. 1962. Electrochemistry of fused salts. In. K. Delimarskii and B. F. Markov. (Translated from the Russian by A. Peiperl. Translation edited by R. E. Wood.) Pp. 338. Sigma Press.Washington. 1961. Les triterphnes tttracycliques. G. Ourisson and P. Crabbe. Pp. 194. Herman. Paris. 1961. Die quantitative Bestimmung der Alkaloide in Drogen und Drogenzubereitungen. 0.-E. Schultz and F. Zymalkowski. (Die Chemische Analyse. Vol. 47.) Pp. 295. Enke. Stuttgart. 1960. Die Flammenspektralanalyse; grundlagen und ver-fahren von Flammenphotometrie und Flammenspektro-graphie. W. Schuhknecht. (Chemische Analyse. Vol. 48.) Pp. 258. Enke. Stuttgart. 1961. Statistik in der quantitativen chemischen Analyse. G. Gottschalk. (Die chemische Analyse. Vol. 49.) Pp. 220. Enke. Stuttgart. 1962. Neutronenaktivierung als analytisches Hilfsmittel. W. Schulze. (Die Chemische Analyse. Vol. 50.) Pp. 320. Enke. Stuttgart. 1962. Analytik des Kaliums; Klassische und moderne Tren- nungs und Bestimmungsmethoden mit Leistungsver-gleichen in kritischer Sicht.H. Tollert. (Die chemische Analyse. Vol. 51.) Pp. 416. Enke. Stuttgart. 1962. Chemical carcinogenesis. D. B. Clayson. Pp. 467. Churchill. London. 1962. Paint Technology Manuals. Part 3. Convertible coatings. Edited by I. C. Bews. Pp. 318. Chapman and Hall. London. 1962. IP standards for petroleum and its products. Part 1. Methods for analysis and testing. 21st edn. Pp. 799. Institute Petroleum. London. 1962. The chemistry and manufacture of cosmetics. Maison G. de Navarre. Vol. 2. 2nd edn. Pp. 413. Van Nostrand. Princeton New Jersey. 1962. (Presented by the pub- lisher.) Second Report of the toxicity sub-committee of the main technical committee 1962 with methods of analysis of representative extractants.Pp. 65. British Plastics Federation. London. 1962. (Presented by the publisher.) Peroxide reaction mechanisms. Edited by John 0. Edwards. Based on a conference held at Brown Univer- sity Providence Rhode Island 1960 and sponsored by the Office of Ordnance Research U.S. Army. Pp. 245. Interscience Publ. lnc. New York. 1962. Gas chromatography proceedings of the third Inter- national Symposium on Gas Chromatography held at Michigan State University; under the auspices of the Instrument Society of America 1961. Edited by N. Brenner J. E. Callen and M. D. Weiss. Pp. 719. Academic Press. New York. 1962. Developments in applied spectroscopy. Edited by W.D. Ashby. Proceedings of the 12th Annual Sym- posium on Spectroscopy held in Chicago 1961. and sponsored by the Society for Applied Spectroscopy. Vol. 1. Pp.247. Plenum Press. New York. 1962. ERRATUM 1962 Page 327. Col. 1 line 24 For C32H20010 read C32H24010'
ISSN:0369-8718
DOI:10.1039/PS9630000033
出版商:RSC
年代:1963
数据来源: RSC
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