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Proceedings of the Chemical Society. January 1963 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue January,
1963,
Page 1-32
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摘要:
Proceedings of The Chemical Society LONDON THE CHEMICAL SOCIETY PROCEEDINGS OF THE CHEMICAL SOCIETY JANUARY 1963 UNIVERSITY COLLEGE CARDIFF* By Dr. GEORGE THOMAS (DEPARTMENT OF ENGLISH, UNIVERSITY COLLEGE CARDIFF) TOGETHER with its four sister institutions within approval of the Privy Council on March 7th the framework of the University of Wales 1883. Before the Royal Charter was graciously Cardiff University College stands as a memorial granted on October 7th 1884 the new College to the passion for education which dominated had already been in operation since October the thinking of many leaders of Welsh public life 20th 1883 at the Old Infirmary buildings in in the second half of the nineteenth century. The Newport Road with a Principal (who held the first practical outcome of their plans was the Chair of Physics) thirteen other teaching staff establishment of a University College of Wales and 151 students of whom 42 were women.at Aberystwyth in 1872; it catered for students Initially these students were prepared for degrees who wished to read for the external degrees of of London University in twelve departments the University of London and enabled many Greek; Latin; Mathematics and Astronomy; others to enter Welsh religious and public life Logic and Philosophy; English and History; often via Oxford and Cambridge. This brave Physics; Chemistry; Biology Welsh ; French ; kenture almost foundered between the Scylla of German; and Music. parsimonious government support and the J.Viriamu Jones the twenty-seven year old Charybdis of insufficient Grammar Schools to Principal had already spent two years as Profes-provide it with matriculated students. In August sor of Physics and Principal at Firth College 1881 a departmental committee-instituted by Sheffield. He devoted his remaining eighteen Gladstone’s administration and chaired by the years to the attainment of three objects the distinguished Welsh Liberal Lord Aberdare- organisation and co-ordination of intermediate published its report on “the present condition of and higher education in Wales (achieved in Intermediate and Higher Education in Wales.” 1889); the establishment of a degree-granting Among its recommendations was “the establish- University of Wales (achieved in 1893); and the ment of one College in Glamorganshire for South removal of his College to a suitable and worthy Wales” which was to be supplied by an annual site in Cathays Park Cardiff.The first pos- government grant of &4,000. Cardiff and Swansea thumous fruits of this third task was the opening were rivals for the new College. Generous local of the present Administrative buildings in 1909. support and an energetic committee backed by By today the Cathays Park site is fully occupied the Borough Council secured for Cardiff the the Old Infirmary site is the scene of new con- * Published in connection with the Society’s Anniversary Meetings. 3 struction-thanks to recent public generosity- and Viriamu Jones is known if at all to the average South Walian as the name of a Cardiff Primary School.His successor has left no tangible memorial and is elusive even to the diligent historian. Like Viriamu E. H. Griffiths was a physicist and an F.R.S. His difficult task was to consolidate exist- ing plans for expansion to guide the new depart- ments through the growing pains of a young University with strong centralising tendencies and to integrate the College into the educational industrial and professional life of South Wales and Monmouthshire. Few pen-portraits of him survive and most of them stress his aloofness. But the picture that emerges from his many recorded words before governmental committees is of a sharp decisive intellect with a tongue and temper to match.The development of techno- logical studies within the College was hampered at this time by poor public relations and the newly shaped Medical side of the College ran into many serious difficulties. The First World War saw a shrinkage of staff and students and an expansion of governmental enquiries into a Royal Commission. There were three major problems before the University of Wales could develop:first the relationship between a Faculty of Medicine the College and the University; secondly the grave unendowed financial state of the Colleges; and thirdly the demand for Lehrfreiheit on the part of academic staff who felt themselves restricted by the central control of a University Senate. Frequently at this time the Cardiff Senate voted for the establishment of a separate University at Cardiff.The Royal Com- mission which reported in 1918 as the Principal was about to retire granted the much deserved freedom to teachers and by establishing a “penny rate” from local authorities helped to solve some of the College financial problems even though it strengthened the financial control of the central University. The question of medical studies was not so easily settled. It remained as a nagging irritant throughout the eleven years that Principal A. H. Trow held office and was not resolved until the Welsh National School of Medicine was incorporated into the University of Wales by Royal Charter in 193 1-2. (Cardiff University College though retained its pre-clinical departments of Anatomy PROCEEDINGS and Physiology.) During this long triangular altercation the Treasury frequently lost patience the Principal received a bad Press and at one point medical teaching in Wales nearly came to an end.Trow was a determined and stubborn man; a graduate of the University who had taught Botany in this College for 28 years he seemed to identify himself with its all-round development. He seemed to encourage long argumentative sessions and was credited with the sole tenacious tactic of getting his own way when all his opponents were exhausted. But this public image must not be allowed to obscure the pro- gress maintained during his tenure of office the steady transfer of departments from the old Col- lege to Cathays Park the rapid post-war expan- sion of staff and student members and the increase of research facilities.Above all despite his brusque manner he encouraged the develop- ment of the social and sporting life of the student body. The legend remains alive that many Cardiff war-time millionaires were discouraged during this period from assisting the College’s financial difficulties but the harsh economic facts of a declining coal-trade must surely underlie the apparent arrest in the growth of the College between 19 18 and 1929. In such circumstances- and remembering the long “1926 strike”-the founding of new chairs and the even spread of post-gr adua t e work (and ex t ra-mur a1 teaching ) deserve special mention and praise. Trow’s successor Sir Frederick Rees was an old student of the College and he returned to control its affairs with a wide experience of uni-versities in England Ireland and Scotland.He soon made his mark in South Wales as a ready and able public speaker an even-tempered arbitrator and a willing servant of the com- munity. The economic depression and the Second World War cast their shadow over his twenty years as Principal. There were few benefactors about and a rush of students to the College. Building was at a standstill a few new depart- ments were created and a slight but constant increase in teaching and technical staff was main- tained. The immediate post-war period brought the twin problems of the student “bulge” and the insatiable demands for scientific research.During Sir Frederick’s period of office arrangements between the College and the Welsh National School of Medicine were smoothed out extra- JANUARY 1963 mural teaching was expanded an economic sur- vey of South Wales was undertaken and the Principal and his senior colleagues were in-creasingly involved in University administration and local affairs. Student numbers reached 1,400 the teaching staff was over 100 and there were clamant demands for new departments which would smooth the College’s “advances” towards independent University status. Throughout the 1930s the College was hampered by its chronic insolvency; the proportion of the support from the “penny rate” was small in comparison with the contribution of the new paymaster through the U.G.C.Like E. H. Griffiths our fifth and present Principal Dr. Anthony Steel came to us from Cambridge. Sir Frederick Rees an economist had broken the run of three scientists and he was succeeded by a distinguished historian. For 13 years Principal Steel has directed a steadily advancing building programme a clearly phased expansion of staff and student numbers and a vigorous attack on the problem of hostel and iodgings accommodation in an expanding capital city. The original site at Cathays Park has now been furnished with some modifications of the original plan; stark and blunt-nosed a new Arts Building stands close to it as the first promise of continued pre-clinical and library buildings on the “Ranch.” Sub-departments have hived off and reached parent status a new Faculty of Economic and Social Studies has been established and new Chairs are on the agenda.Already the present numbers (2,300 students and 240 teaching staff) is being considered an insufficient reply to the challenge of the contemporary demand for University places. The College too has entered into a close relationship with the recent develop- ment of St. David‘sCollege Lampeter which pro- mises to bring to an end the “yo-yo7’ dance that has been played between Lampeter and the Uni- versity of Wales since 1918. And as if to round off this tale of a successful principalship in the manner Viriamu Jones Dr. Steel’s influence has brought to the College a magnificent (&500,000) donation from South Wales industrialists and a handsome &75,000 grant from the City of Cardiff Corporation.“The strength of country lies in its academic disciplines” is a free translation of the College motto. For nearly 80 years now the University College of South Wales and Mon- mouthshire has tried to keep close to that ideal. Throughout that long span of years there has been a Department of Chemistry. The first Pro- fessor was Claude Metford Thompson and in the College’s first year 50 out of the total of 151 students were taking Chemistry. During this period the Department was housed partly in the Infirmary Building and partly in wooden huts at the rear. Thompson whose own work involved a study of the rare earths played an active part in departmental and College life; during Viriamu Jones’ last illness he became Acting-Principal and held this post until the new Principal E.H. Griffiths was appointed. On Thompson’s retire- ment in 1921 William Jacob Jones was appointed to the Chair of Chemistry. He had collaborated with Orton at University College Bangor and afterwards with Lapworth in Manchester on the mechanism of catalytic reactions. Seven years after his appointment the Chemistry department moved to the Tatem Laboratories in Cathays Park. These laboratories were named after William Tatem Lord Glanely President of the College who provided most of the money for the building and they were formally opened by the Prince of Wales in 1930.After the Second World War the large increase in student numbers led to the building of an extension containing addi- tional teaching and research laboratories and two lecture theatres. This extension begun in Pro- fessor Jones’ time was completed after he retired in 1951 when he was succeeded by A. G. Evans. It was opened in September 1954 by Dr. C.H. Latham President of the College and was named the Shandon Extension after Lord Glaneley’s son who died as a young man. The increase in teaching and research activities the expansion programme of the College and the initiation in 1961 of a new Faculty of Science Degree Scheme which offers a large variety of Joint Honours Courses necessitated a further extension to the Department.This further ex- tension known as the Shandon I1 Extension was opened by the Duke of Edinburgh on July 6th 1962. The building of the Shandon I1 laboratories was made possible by the generosity of the University Grants Committee and local industry; it has greatly eased the pressure on teaching space and allows for an increase in the variety of teaching which is implicit in the new degree scheme. At the moment there are some 470 students taking chemistry. The Final Honours Chemistry year numbers 28 and classes are provided at various levels for Pure Science Applied Science Medical and Pharmacy students. The depart- ment has an active and well equipped research PROCEEDINGS school; 28 students are being trained in research for the Degree of Ph,D.The special fields of study in the department include mechanisms of chemical reactions electron transfer reactions gas phase radical reactions study of natural products and radiation chemistry. THE INDUSTRIES OF SOUTH WALES THEIR HISTORY AND DEVELOPMENT* By P. VIVIANLLOYD F.R.I.C. SOUTHWALESis frequently referred to as “The Land of Castles.” There are over forty in Glamorgan alone now mostly in ruins and they were built principally to defend the country against invaders across the English border. In the same area are mountains and fertile valleys with meandering streams. The coast is beautiful and varied with sandy bays and rocky headlands. Away from the agricultural areas are drab regions peopled by a race of whom many speak their native Welsh language and have cultural interests and a passionate love for singing.South Wales always has been and still is mainly con- cerned with the heavier industries such as metallurgy and mining and very few of what are understood by purely chemical industries existed until after the 1914-1918 war. Nowhere in the world is there to be found such a variety of excellent coals within the confines of a comparatively small area. These types vary from the low volatility type (anthracite) in the west to the high volatility coals (bituminous and coking) in the east. It is upon these coals that the wealth and prosperity of the area has been built. Pioneering work in mining appears to date from 1249 when it is recorded the monks of Neath Abbey in West Glamorgan were actively engaged in the “mining” of coal.As a result of coal mining development in the adjacent valleys largely during the nineteenth century the Port of Cardiff docks and railways were built by the Bute family; earlier transport was by packhorse and canal iron rails being introduced by Sir Humphrey Mackworth of Neath. Just before and after the First World War Cardiff grew to be the largest coal-exporting port in the world. On the other hand Cardiff was importing anthracite coal from Pembrokeshire well over a century ago and by a queer twist of fate was im- porting American Pakistani and South African coal during the coal shortage following the 1939-1945 World War. The Rhondda Valley in 1847 was described as being beautiful but by 1860 coal mining develop- ments were in full swing.One of the pioneers in this area was Mrs. Lucy Thomas of Merthyr and a colliery bearing her name was operating until about five years ago. The development of what was to become a very large iron industry was mainly due to the plentiful local supply of coal limestone and clay band ironstone (30% Fe). Large plants for iron smelting were erected at Dowlais Cyfartha and Nantyglo (Mon.) around 1800 by pioneers such as Guest Bacon Homfray Crawshay and Menalaus. It was at Crawshay’s works at Cyfartha that Richard Trevethick in 1803 built the first steam locomotive to run on rails; it was used for haulage work to and from different parts of the works.Large iron works were also constructed at Ystalyfera with ten blast furnaces and Ynyscedwyn in the Swansea valley where the invention of the hot blast enabled George Crane to use the locally mined anthracite for his blast furnaces. Shortage of ironstone and its decreasing iron content caused these plants to be uneconomical and gradually all were closed. Only ruins and slag heaps now remain as evidence of what was once a very prosperous industry. It was at Blaenavon and Landore (Swansea) that Gilchrist and Thomas discovered the basic Bessemer process for handling iron ores of high phosphorus content. Today there are four huge iron and steel con- * Published in connection with the Society’s Anniversary Meetings JANUARY 1963 cerns in South Wales Richard Thomas and Baldwins’ plants at Newport (Mon.) (the Spencer Works) and at Ebbw Vale and the Steel Com- pany of Wales at Margam (Port Talbot) and Velindre near Swansea.The iron and steel and tinplate industries have been largely con-centrated into these works and consequently a number of smaller plants has closed. In 1876 the Swansea Vale Spelter Company was set up at Llansamlet four miles north of Swansea. Here zinc was smelted from Welsh zinc blende and foreign zinc carbonate ores. This works is today the sole survivor of the old zinc industry in the Swansea area. It was founded by Sir Richard Martin and in 1916 merged its interests with those of the newly formed National Smelting Company (now the Imperial Smelting Corporation recently amalgamated with the Rio Tinto Company Avonmouth).During the period 1951-53 modernisations and extensions were effected to improve output. Two other sub- sidiaries of the company in South Wales are Morris and Griffin Ltd. Newport Mon. (glues fertilisers sulphuric acid) later to merge with the South Wales Basic Slag Company and Fricker’s of Burry Port Carmarthenshire (zinc oxide). The latter firm was the pioneer of zinc oxide manufacture in the British Empire. The commodity is made by oxidation of zinc ores or metal. The Romans were occupied with copper mining and smelting in the Prescelly mountains Pembrokeshire with lead near Aberystwyth and with gold at Pumpsaint near Llandovery. Queen Elizabeth I granted a charter to the Mines Royal Society in 1564 and copper works were estab- lished near Neath Abbey.The Vivian family and subsequently Williams Foster and Pascoe Gren- fell were pioneers of large-scale copper smelting at Swansea and later added lead zinc (spelter) silver sulphuric acid and superphosphate plants. The copper ores came originally from Cornwall by sailing ship up the river Tawe to the plants. Very few of these industries are functioning to- day but the earlier activities are clearly marked bv ruins and slag heaps. Not far from these depressing ruins is the Mond Nickel Company’s works at Clydach in the Swansea Valley. Here a piece of pure chem- ical research has been translated into a highly successful industrial process.The pyrites ore (or matte) is roasted to the oxide then reduced to the metallic state by means of water gas. The crude metal is then purified by forming and sub- sequently decomposing the volatile nickel car- bonyl a very pure nickel being deposited. The aluminium industry is well represented in South Wales. At Newport (Mon.) the British Aluminium Company has erected a plant for the extraction of alumina from bauxite by leaching with caustic soda. Also at Newport the Northern Aluminium Company fabricates aluminium metal. The first chemical industry to be founded after the First World War was the oil refinery of the then Anglo-Iranian Oil Company (now British Petroleum) at Llandarcy near Neath. The crude oil delivered in tankers from the Middle East to Queen’s Dock Swansea is pumped directly therefrom to the refinery about three miles away.It was from the same dock that the first experi- mental underwater pipeline was laid across the Bristol Channel to Somerset. This pipeline was the prototype of the larger “Pluto,” laid across the English Channel in 1944 to supply petrol to the Allied Armies after the invasion of Nor- mandy. In more recent times the skyline of Milford Haven has been interrupted by the very modern refinery of the Esso Petroleum Com- pany and plans are afoot for the erection of a second in the same neighbourhood. Many plastics industries have come to South Wales and Monmouthshire. Monsanto Chem- icals have established themselves at Newport.At Sully near Penarth the Distillers Company have their Plastics Group consisting of British Resin Products British Geon and Distrene. At Barry Albright and Wilson have built a subsidiary Midland Silicones on the site of a plant which during the Second World War was used for ex- tracting magnesium from sea water. At Ponty- pool British Nylon Spinners (owned jointly by Courtaulds and Imperial Chemical Industries) have a modern plant fabricating nylon yarn into its many uses. In the same locality Pilkington Brothers have a large glass-manufacturing plant. One of the few plants in the United Kingdom manufacturing calcium carbide is that of the Distillers Company at Kenfig near Margam whilst there are several coking and by-product plants owned by the National Coal Board.Connoisseurs of china will be well aware of Swansea and Nantganv china and of Billingsley who was the artistic designer. Numbers of small industries are centred on four trading estates in South Wales. The largest glue and gelatine factory in the United Kingdom is located on the Treforest estate. Other products such as chemicals pharmaceuticals paper leather rubber glass metal products and instru- ments are fabricated on this and similar estates. The Metal Box Company has a large plant at Neath and the largest watch- and clock-making plant in the country is at Ystalyfera near Swansea. Finally brewing must be mentioned as PROCEEDINGS an important industry in many places throughout the area.Despite the continuing importance of heavy industry in the region the former extreme dependence on coal and iron has disappeared and new manufacturing industries such as the Rover car plant at Cardiff are bringing about a welcome diversification. At the same time a new consciousness of the natural beauty of South Wales has arisen and efforts are being made as in the lower Swansea Valley to restore and rebeautify areas made ugly by an earlier unheeding industrialisation. CHRISTMAS COMPETITION 1962 THEcompetition cited a verse The Fisherman’s Prayer God grant me strength to catch a fish So large that even I When telling of it afterwards May never need to lie. A prize (book token two guineas) was offered for a quatrain in any metre giving a Chemist’s Prayer.We are most grateful to the competitors all eighty-three of them who sent in 128 verses some from Australia Belgium Canada Chile Denmark E. Germany Israel Netherlands S. Africa Switzer- land and U.S.A. We hope that they had as much fun in composition as we had in reading their prayers. We assure them that they turned the table on us setting us the New Year puzzle of how to select from so much particularly as with a quatrain it must usually be all or nothing. We have used as criteria that so far as maybe the verse shall trip off the tongue have a punch at the end and include a bright idea neatly expressed. Other things equal-but they rarely are-we quote only one verse from multiple entries.To all whom we overlook we plead apologetically limitation of space. We start with the big battalions. In popularity the desire for crystals tied with that for priority. “Caivel” (from Australia) prays I am resigned to shattered flasks Dud reactions and hopeless tasks But oh before my patience dies Please tell this gum to crystallize! P.M. compresses two prayers into one so neatly When journals come in thick and fast God help me read them. When compounds fail to crystallise Lord let me seed them. From “Jade” we can quote only “Lord guide me through this vale of tars.” For the opposition a remarkable set of nine verses from a Belgian colleague includes Oh Lord when I lay down my load And terminate my stint May I find peace in my abode And be the first to print.and from M.P.B. (“a synthetic chemist’s prayer”) Lord we’re trying to get this done Before the other people so We wish You’d use Your power and tell The atoms where they ought to go. and very simply from “Riccardo” God grant that no one else has done The work I want to do And give me wit to write it up In decent English too. Great too was the praying for honour(s). Here is a neat verse from “Over the Hump” who in spite of his concentration on initials is not a spectroscopist of any sort May They grant me a B.Sc. A Ph.D. and then A D.Sc. an F.R.S. A Times Obit. Amen. And very jolly and Christmassy is It’s good to be a B.Sc. And a Ph.D. is swell But Lord please bless with F.R.S.And me and my mate the Nobel. Several verses took the final “lie” of the original as pattern; but only one (from Fiat Lux U.S.A.) punned it JANUARY 1963 God grant me strength to make a soap So fine that even I When washing with it afterwards May never feel the lye. *‘A. Fisher” (Canada) varied it in a good entry that comes nearer to a prayer than many others Grant oh God Thy benedictions On my theory’s predictions Lest the facts when verified Show Thy servant to have lied. Referees and the editor (“Whose ruddy pen is mightier than my word,” says C.J.W.B.) came in for their share of the fun so gently from P.Q. (“in submission”) Let not the hardened Editor With referee to quote Cut all my explanation out And print it as a Note.and from the “National Cynical Laboratory” Lord give me smartness to discern the work that’s in the fashion Some quick results and facile thoughts for plausible discussion; Then when I’ve rushed my paper in to claim priority Lord spare me the attentions of a thorough referee. How too can we fail to thank R.W. for sparing a prayer for us personally God grant there is never a paper So good that even I Without a stroke from my pencil Will have to let it by. By and large however the prayers of chemists are for things so various that we can now do no more than dip and offer some of our own favourites From azides and acetylides And organic peroxides And things that go bump in the night The Lord protect us.(A.G.D.) From absent professors And vacuous students And reactions which never go right Good Lord deliver us! (G.B.B.) More seriously Oh send us all the joy Divine The thrill of hope so shy and fine Through oil and tar a tiny sign Of cosmic order-crystalline. (-erg-) ”From the Natural Product Chemist” Oh Lord I pray forgive me please My unsuccessful syntheses. Thou know’st of course-in Thy position- That I’m up against such competition! (T.A.W.) Not so seriously Dear Lord I pray When tired and weary Let my last results Fit the Bl -dy theory. (C.H.) Oh Lord I fall upon my knees And pray that all my syntheses May no longer be inferior To those conducted by bacteria. (L.J.B.) Dear Lord if I mix sodium With conc.HNO, And add to it plutonium Will you take care of me? (“Ross”) I’m grateful Lord for NMR For IR and UV But may a technique ne’er be found That will dispense with me. (Occam) PRAYER Of a Chemist who was Old and wished to remain Pure. My Chymistry from rampant Physik free; From N.M.R. I.R. and O.R.D. From S.C.F. M.O. and specially From Braggart X-ray Crystallography. (J.C.S.) Impudently Lord give me leave to build a lab So large that when I’ve trod Its vasty nave and aisles I’ll think I’m in Thy house 0 Todd. (PH 6) An entry from “Efrog” is in a class by itself “in the englyn metre one of the 24 strict measures of alliteration and rhyme used in Welsh poetry”; here “monad” denotes one of the units of which the universe consists; note also that the first line “ends” at its penultimate word.The verse repays study May God grant me for my good-happiness Hope in my livelihood To shape as true chemist should Monads He left to manhood. But in a merely subjective judgement among so much we award the prize to W.V.F. for the first (or if you prefer another!) of the following three; they have all the technical efficiency of the:pattern and a charm and simple wit that are all their own. The author explains that they “range from simple piety Perkin Todd and Robinson Bless the bed that I lie on And while I slumber turn this gum To crystals bright as Kingdom Come. Amen. 10 PROCEEDINGS “through a demand for part-time supervision “to a perhaps unjustified cynicism Saints in Heaven hear my prayer Look down on my reaction there; Tranquil though it seems to be Watch it while I have my tea.Angels from the realms of glory Bless my latest bedtime story; And (though be careful what you do) Make it somehow. almost true.” COMMUNICATIONS The Deiodination of o-Iodobenzoic Acid Induced by Copper(@ Ions By M. ANBAR and S. GUTTMANN (ISOTOPE DEPARTMENT WEIZMANN INSTITUTE OF SCIENCE REHOVOTH ISRAEL) and C. FREDMAN COMMISSION RESEARCH REHOVOTH, (ATOMICENERGY SOREQ ESTABLISHMENT ISRAEL) IN a novel reaction o-iodobenzoic acid was de-iodinated by certain reducing agents in neutral aqueous solutions in the presence of copper(^^) ions. The extent of deiodination was determined by follow- ing the iodide originating from the acid labelled with 1311.Deiodination (t < 400 hours) did not occur in solutions containing o-iodobenzoic acid alone or in presence of copper ions; and there was no measur- able deiodination (without 48 hours) in the presence of adde or sulphite ions or with the other reducing agents when copper(n) was absent. Deiodination occurred only when the two additives were present simultaneously. Addition of sodium ethylenedi- aminetetra-acetate to a reaction mixture containing azide sulphite or ascorbic acid inhibited the de- iodination completely. The major product of de- iodination of o-iodobenzoic acid on reduction with ascorbic acid and copper was identified as benzoic acid. Univalent copper was not effective in the presence of azide ions or ascorbic acid; and deiodination was not induced by copper(n) in the presence of hydrogen peroxide or ferrous or ferrocyanide ions.Preliminary kinetic experiments were carried out with o-iodobenzoic acid in the concentration range 104-10-2~ and the experimental rate equation is given by R=.-d [A]/dt = k [A] [C~(II)] [XI where A is o-iodobenzoic acid and X is N3- SO2- or ascorbic acid. Approximate specific rate constants for the three reactants at 25” are k(S032-)= 6 x lo2,k (N3-) = Bacon and Hill Proc. CAertr. Soc. 1962 113. 3 x lo3,and k (ascorbic acid) = 103 1.2 mole-2 sec.-l. p-Iodobenzoic acid is not appreciably deiodinated under identical conditions in the presence of 10-3~-copper(@ and 10-k-azide or -ascorbic acid within 100 hours ;thus the ortho-iodo-derivative undergoes deiodination at least lo00 times as fast as its para-isomer.It is evident that the transition state involves three compounds-o-iodobenzoic acid a bivalent copper ion and a third molecule which may be considered as a reducing agent namely an electron-donor. The great difference in the rates of deiodination of the ortho- and the para-isomer strongly suggests the formation of a complex between o-iodobenzoate and copper. ions; such a complex is expected to be con-siderably stabilised by chelation with the hydroxyl or carboxyl groups in ortho-position to the iodine. When the great stability of iodo-complexes of copper is taken into account this proposition seems reason-able.Next it should be recalled that cuprous iodide is considerably more stable than the cupric complex in other words the cupric complex may be considered as an oxidising agent. An electron-donor may at this stage supply an electron to the system resulting in cleavage of the C-I bond. The fact that the deiodina- tion does not take place in the presence of cuprous ions and the participation of ascorbic acid in the process make the Sandmeyer-type mechanism1 rather unlikely. It is suggested that the reaction reported here may serve as a model for the enzymic deiodination of physiologically active aromatic iodine com-pounds. A detailed kinetic investigation is in pro- gress. (Received,November 8th 1962.) JANUARY 1963 11 Trinitratoniobium(v) Oxide NbO(N03) By B.0. FIELD and C. J. HARDY (ATOMIC RESEARCH HARWELL, ENERGY ESTABLISHMENT DIDCOT BERKS.) SIMPLE nitrato-compoundsof niobium are unknown? We report the first preparation of trinitrato-niobium(v) oxide by reaction of anhydrous niobium pentachloride with liquid dinitrogen pentoxide at 30". An excess of dinitrogen pentoxide from the de- hydration of fuming nitric acid with phosphorus pentoxide was condensed on anhydrous niobium pentachloride at -180" and the mixture was warmed to 30" in order to melt the dinitrogen pent- oxide which then immediately reacted with the penta- chloride with evolution of a gas (nitryl chloride ?) NbCl + 4N205 -+ NbO(NOj) + 5N0,Cl. The reaction mixture was left overnight in an apparatus fitted with a pressure release valve.The product did not dissolve in the excess of dinitrogen pentoxide which was removed by pumping. The bulky white solid product was then pumped at a pressure of 21 "I5 x lo4 mm. for 20 hours after which no more gas was removed indicating absence of free oxides of nitrogen. It was then transferred to a dry-box containing phosphorus pentoxide for further operations. The white microcrystalline powder occupied about three times the volu,me of the original niobium penta- chloride fumed in moist air and was immediately hydrolysed by water into nitric acid and hydrated niobium pentoxide. It is slightly soluble in dry tri- butyl phosphate diethyl ether methyl cyanide or benzene.It is not volatile and when heated in vacuo begins to decompose at about 120". Analysis indi- cated contents of Nb 31.5 &-0.1% Nb (by ignition to Nb20,S and NO3 61.9% (as nitron nitrate) [NbO(NOj) requires Nb 31.4%; NO, 62-4%I. The infrared spectra of the complex in a Nujol mull between silver chloride plates showed the presence of co-ordinated nitrato-groups,2 v4 1646 vl 1213 v21004 vg 783,775,770crn.-l the difference v4 -vl = 433 cm? being the largest reported for a metal nitrato-complex. There was no indication of nitrate ion in the spectra but a strong peak at 906 cm.-l which we assign to a metal-oxygen bond. X-Ray powder diffraction showed the presence of a tetragonal cell with unit cell parameters a = 1 1.92 and c = 5.33 A values which are slightly larger than those of the tetragonal cell of the trichloroniobium(v) oxide.The crystal structure of the latter complex is consistent with Nb2C16 units with two oxygen bridges (Nb-0-Nb) from each niobium atom to adjacent niobium atoms.3 We therefore prepared a sample of this complex by the reaction of chlorine with a mix-ture of niobium pentoxide and carbon at 350" followed by fractional sublimation of the product and measured its infrared spectrum for comparison. The chloro-complex (in a Nujol mull between silver chloride plates) has a band at 769 cm.-l which is broader than that at 906 cm.-l in the nitrato-complex and can be assigned to Nb-0-Nb bridging oxygen bonds. We have also prepared samples by published methods and measured infrared spectra of the fluoro-complexes K2NbF,,5 K,NbOF, and K2NbOF,,H20.' The crystal structure6 of the hexa- fluoro-complex is consistent with the presence of a niobium-oxygen double bond and we find a band at 922 cm.-l for this complex and at 927 cm.-l for the pentafluoro-complex and no band in this region for the heptafluoro-complex ;we therefore assign this band to the Nb=O bond.This band lies within the range (900-1 100 cm,-l) considered diagnostic for metal-oxygen double bonds? It seems probable that the nitrato-complex con- tains a niobium-oxygen double bond (906cm.-') to-gether with bridging nitrato-groups rather than bridging oxygen atoms. We cannot exclude the possibility of some contribution from bridging oxygen atoms because of the coincidence of the expected band at about 770 cm.-l and nitrato-bands at 770-785 cm.-l.The thermal instability and lack of volatility of the nitrato-complex (compared to the trichloro-oxide) and its ease of hydration are probably connected with the bridging groups. The authors thank Mr. D. Scargill for obtaining the infrared spectra of the nitrato-complex and Mr. F. Moore and Dr. K. W. Bagnall for X-ray diffraction data. (Received November 23rd 1962.) Cotton and Wilkinson "Advanced Inorganic Chemistry," Interscience Publ. Inc. New York 1962 p. 773. Addison and Gatehouse J. 1960 613. Sands Zalkin and Elson Acta Cryst. 1959 12 21. * Sue Compt. rend. 1939,208 814. Hoard J. Amer. Chem. SOC.,1939 61 1252. Williams and Hoard J.Arner. Chem. Soc. 1942,64 1139. BaIke and Smith,J. Amer. Clzem. SOC.,1908,30 1637. Barraclough Lewis and Nyholm J. 1959 3552. PROCEEDINGS Electron Transfer in Some Solids containing Complex Ions By P. S. BRATERMAN and R. J. P. WILLIAMS P. B. P. PEXIPPS (INORGANIC DEPARTMENT, CHEMISTRY OXFORD) STUDYof the conductivity of a suitable solid offers a direct attack on the electron-transfer processes of oxidation-reduction which are normally examined indirectly in solution. Moreover electron transport in solids is readily studied by measuring conductivity. For these reasons we have examined the variation with temperature of the conductivity of a series of inorganic solids. We have chosen these (see Table) so as to contrast the oxidisable cation thallous with the cation potassium and the reducible anion ferri- cyanide with the anion cobalticyanide.Conductivity of the solids was measured by using an EIL vibrating-reed electrometer 33C with a gradient of 70-300 v/cm. The solids were prepared as single crystals or as compressed pellets; the activa- less than 20 cm.2 v-l sec.-l on a band-conduction model. The diffuse reflection spectra of the solids in the Table have also been measured. Thallous ferri- cyanide alone shows visible absorption in addition to the anion bands. The new broad band of this com- pound is centred on 600 mp and we assign it to a charge transfer from the reducing thallous cation to the oxidising ferricyanide anion. The table shows that the substance which contains both a reducing and an oxidising ion has the highest conductivity the lowest activation energy for con- duction and a low-energy optical excitation.We consider that all these properties are directly con- nected with the possibility of electron transfer but at present we cannot give a quantitative relation Conductivity of some complex cyanides. Compound Method of measurement X.Ag X.C Activation energy (kcal. mole-l) 15.3 13.0 -log. specific conductivity at 300”~ 12.5 11-1 18.2 11.9 12.7 5.7 12.4 7.8 12.0 8.5 15.4 10.0 17.0 11.2 6.8 6.5 6.3 6.2 6.2 6.6 12.9 X = Single crystal; P = Pellets; Ag C or Ni contacts. * Four-electrode assembly. Errors Ifi. 0.5. tion energy for conduction did not vary greatly between the different types of sample.Contacts were made with silver paste carbon or nickel contacts. All methods yielded essentially the same activation energies (see Table). The thallous ferricyanide crystals have also been examined with a four-elec- trode assembly to eliminate contact effects and at a pressure below cm. Hg so as to reduce surface absorption. The usual pressure for measurements was lo3 cm. The same low activation energy and high conductivity were found for this substance as in the standard experiments. We have attempted to measure a Hall coefficient on the same compound but no E.M.F. was detected. The result is consistent with a hopping mechanism or indicates a mobility of between the different energies involved.However we note that the activation energy for electron transfer in the ferricyanide-ferrocyanide exchange in solution is 4.7 kcal. mole-l (ref. 1j which is close to the value for electron conduction in thallous ferricyanide. It has been suggested that the energy for such exchange reactions may be largely a Frank-Condon barrier.2 We thank Dr. B. V. Rollin and Mr. J. Russell for their help with Hall-E.M.F. measurements and The Natural Rubber Producers’ Research Association for a Research Scholarship to one of us. (Received November 19th 1962.) Deck Microfilm Diss. Abs. 1956 16 1578 quoted in ref. (2). Stranks “Modern Co-ordination Chemistry,’y ed. Lewis and Wilkins Interscience Publ. Tnc. New York 1960. p. 148. JANUARY 1963 Nitrosoacetylenes By E.ROBSONand J. M. TEDDER OF CHEMISTRY SHEFFIELD, (DEPARTMENT THEUNIVERSITY 10) of dihex-1-ynylmercury and bis-3,3-di- Ymax 2280~~ SOLUTIOPUS (CZC) 1580s (N=O) cm.-l methylbut- 1 -ynylmercury in an inert solvent (chloro- CMe,.C=CN=O form or tetrahydrofuran) react with nitrosyl chloride Amax 654 mp (N=O n+n*) at low temperatures react to yield bluegreen solutions believed to contain the corresponding nitroso-Vmax. 2320/2280v~ (split CZEC),1560s (N=0) cm.-l compounds. NOCI The solutions are extremely reactive and qualita- (R CGC),Hg -__-+ R*CrC-N-0 tive evidence for condensation with aromatic arnines has been obtained. When the solutions are allowed The blue-green colour remains indefinitely at -78O to warm to room temperature the blue-green colour but is lost fairly rapidly at room temperature al- slowly fades and the acetylenic band disappears from though its disappearance can be retarded if the solu- the infrared spectrum while a strong carbonyl band tion is washed with aqueous sodium hydrogen develops.From the solutions of 1-nitrosohex-1 -yne carbonate. The presence of acetylenic nitroso-two compounds have been isolated namely a mer- compounds in these solutions has been inferred from cury derivative (C,H,NOHg) of the initial nitroso- their spectra and their reactions. compound and valeryl cyanide Bu*CO.CN which Me- [CH,],*C=C.N=O is the main product and is presumably formed Amax. 640 mp (N=O n47r*) through a dkter. (Received November 13th 1962.) Trimethyltin Salts Infrared Evidence for the Nonexistence of the Trimethyltin Cation By R.OKAWARA OF APPLIED OSAKA JAPAN) (DEPARTMENT CHEMISTRY UNIVERSITY and B. J. HATHAWAY and D. E. WEBSTER (DEPARTMENT THEUNIVERSITY, OF CHEMISTRY HULL) THEdimethyltin cation Me,Sn2f is known to exist anions that have much higher symmetry and are presumably solvated in aqueous solution and it has more likely to give ionic compounds than the car- been suggested on the basis of the infrared spectra boxylates and we have examined their infrared of some organotin carboxylates that this ion and the spectra. The relevant absorption frequencies of the trimethyltin cation Me,Sn+ can exist in the solid perchlorate nitrate and carbonate are reported in state.l This interpretation has been q~estioned,~,~ the Table; they were determined as mulls in Nujol the spectra being equally explained by assuming co- and hexachlorobutadiene with various polymer ordination of the carboxylate groups through both films to protect the potassium bromide plates.oxygen atoms to two tin atoms. This ambiguous The perchlorate and the nitrate were sublimed interpretation of the spectra arises from the low samples of m.p. 128” and 143” respectively (the symmetry of the acetate group (C,,) which applies nitrate has been reported as a high-melting solid of Infrared frequencies of trimethyltin compounds (cm.-l). C10 1202s 1125s 1005s 915s 633-609s 556s 470m NO 1425 1290s 1037s 81Os 553s 515w CO 1553 1534 1379 1072 839 741 705 546s 518 to the ion equally when free and when co-ordinated low vofatilitf).Trimethyltin carbonate is involatile. symmetrically through both of its oxygen atoms. For all three compounds the spectra are inconsistent In order to see if the trimethyltin cation can exist with the spectra of the free anion5 but indicate the in the solid state we have prepared salts involving presence of the covalently bonded groups.6-s For the Okawara Webster and Rochow J. Amer. Chem. Soc. 1960 82 3287. Beattie and Gilson J. 1961 2585. Van der Kerk Luijten and Janssen Chimia 1962 16 10; Rec. Trav. chim.,1962 81,202. * Coates “Organometallic Compounds,” Methuen and Co. Ltd. London 2nd edn. p. 184. Herzberg “Infra-red and Raman Spectra of Polyatomic Molecules,” D. Van Nostrand Co. Ltd. New York 1945. Hathaway and Underhill J.1961 3091. ’Gatehouse Livingstone and Nyholm J. 1957 4222; Addison and Gatehouse J. 1960 613. Gatehouse Livingstone and Nyholm J. 1958 3137; Fujita Martell and Nakamoto J. Chem.Phys. 1962,36,339. PROCEEDINGS perchlorate group it is possible to distinguish between the presence of the free ion (Td),a monodentate group (C,,) and a bidentate group (C2v).6Tri-methyltin perchlorate clearly contains the bidentate perchlorate group. The tin atoms must be five-co- ordinate in the solid probably with a trigonal bi- pyramidal configuration. Such a configuration seems very common in organotin corn pound^.^^^^^ Evidence for this comes from the carbon-tin frequencies the perchlorate giving only one band at 556 cm.-l (the antisymmetric C-Sn stretching frequency) which also rules out the possibility that two oxygen atoms of a given perchlorate group co-ordinate to the same tin atom to form a four-membered ring-the tri-g Beattie McQuillan and Hulme Chem.and Ind. 1962 methyltin residue would then lack a centre of sym-metry and this should allow the C-Sn symmetric stretching frequency to be infrared-active. In trimethyltin nitrate and carbonate two Sn-C stretching frequencies occur indicating that the tri- methyltin group is not planar in these compounds. The carbonate is bidentate being bonded to two trigonal-pyramidal trimethyltin groups and the CZv symmetry of the nitrate group is consistent with either a monodentate or a bidentate nitrate group. The trimethyltin cation is clearly absent from these three compounds.Evidence in support of these con- clusions is being sought by X-ray methods by Dr. R. L. Sass of the Rice University Houston Texas. (Received November 12th 1962 .) 1429. Trimethyltin Tetrafluoroborate :Infrared Evidence of a Covalently Bonded Tetrafluoroborate Anion By B. J. HATHAWAY and D. E. WEBSTER (DEPARTMENT OF CHEMISTRY THEUNIVERSITY HULL) WE here report the first example of a compound containing a bidentate tetrafluoroborate group. The infrared spectrum of solid trimethyltin tetrafluoro- borate can be interpreted only by assuming covalent bonding through two of the fluorine atoms although previously the tetrafluoroborate ion has generally been considered to be a non-complexing anion as the required two co-ordination of the fluorine atom is rare? Trimethyltin tetrafluoroborate has been prepared as a white amorphous hygroscopic solid by reaction of boron trifluoride with tetramethyltin and also by the reaction of trimethyltin chloride with silver tetra- fluoroborate in methyl cyanide solution.It has m.p. 80” (lit. 89’). The infrared spectra were measured for mulls in Nujol and hexachlorobutadiene. The potassium bromide plates were protected by a suitable polymer film otherwise reaction occurred and the spectrum observed was of trimethyltin bromide and potassium tetrafluoroborate. The tetrafluoroborate ion has Tdsymmetry having nine vibrational degrees of freedom distributed between four normal modes of vibration of which only two (both triply degenerate) are infrared-a~tive.~ If co-ordination occurs through two of the fluorine atoms the symmetry is lowered to Czvand 7 bands are infrared-active (in the region 2000-400 cm.-l) the symmetric stretching vibration vl (of the ion) is now allowed and the degeneracies of the v3 and vp vibrations (each triply degenerate in the ion) are completely removed? In trimethyltin tetra- fluoroborate the symmetric stretching vibration now appears strongly at 758 em.-” (compared with 772 cm.-l in the Raman spectrum of potassium tetra- fluoroborate) and the broad 1100 cm.-l band of the ion is clearly resolved into three strong bands.The splitting of the 520 cm.-l band of the ion is not clear from the spectrum as the high-frequency side of this band is obscured by the trimethyltin antisymmetric stretching vibration at 562 cm.-l while the low- frequency side has a band at 447 cm.-l.This may arise from splitting of the 520 cm.-l band of the ion. Alternatively it may arise from the band observed at 353 cm.-l in the Raman spectrum of the ion (vz) where it is infrared-inactive though this vibration becomes infrared-active in C2vsymmetry. It is difFi- cult to believe that a shift to such a high frequency can occur as a negligible shift was observed in the related case of a bidentate per~hlorate,~ and it seems more reasonable to interpret this band as arising from the v4 mode of the ion. By analogy with trimethyltin perchlorate it is sug- gested that the tetrafluoroborate group forms a bridge between separate trimethyltin residues to give a chain structure and that it does not co-ordinate to the same trimethyltin residue to give a four-membered ring.Either structure would involve five co-ordinate tin. (Received November 12th 1962.) 1 Sharp “Advances in Fluorine Chemistry,” Vol. I Butterworths Scientific Publns. London 1960 p. 83. Burg and Spielman J. Arner. Chern. SOC.,1961 83 2667. Greenwood J. 1959 3811. * Hathaway and Underhill J. 1961 3091. JANUARY 1963 15 ~______ - Hazards in the Treatment of Carbon Halides with Sodium By E. R. WARD (COLLEGEOF TECHNOLOGY,LEICESTER) A RECENT Notel by us involved drying carbon pounds have exploded on contact with alkali metak2 tetrachloride with sodium and it appears that this The recommended method of drying is by fractional may be a hazardous procedure as other similar com- distillation? (Received November 9th 1962.) Piercey and Ward J.1962 3841. Staudinger,2.ungew. Chem. 1922,35 658; J. M. Bruce and W. Hieber personal communications. Timermans “Physico-chemical Constants of Pure Organic Compounds,” Elsevier Amsterdam 1950 p. 224; Riddick and Toops “Organic Solvents; Physical Properties and Methods of Purification,” Interscience Publ. Inc. New York 2nd edn. 1955 p. 413. Photolysis of l,l-Dimethyl-tran~-decalh-lO-carbonyl hide an AnaIogue of the A/B/E Rings of Diterpenoid Alkaloids L. MEYERand ALFRED By WALTER S. LEVINSON (DEPARTMENT INDIANAUNIVERSITY INDIANA) OF CHEMISTRY BLOOMINGTON ONEof the major structural units in many diter- chemically feasible in a rigid cyclic system (diter- penoid alkaloids is the tricyclic amine system (I; H penoid resin acid azides with an angular methyl and for 0).We here report a synthesis of compound (I) axial 4-carbonyl azide group) the photolysis took from carbocyclic intermediates of type (II).this course in preference to alternative y-lactam Ethyl 3,3-dime th yl-2-oxoc yclohexanecarbox yla tel formation (8:y = 5-10 1). In our case even though with methyl vinyl ketone afforded the octalin (IIa) the methyl and the azide group are in nearly the which was hydrogenated (Pd-C) to a single saturated keto-ester (IIb) in 91 % yield. By analogy it is likely that this compound has the tramfused rings.Conversion of the ketone (IIb) into the thio- ketal desulphurisation and cleavage of the ester pro-(IIb:R=CD2Et,R) 0.A* with lithium iodide in refluxing ~ym-collidine~ duced 1,l -dimethyl-trans-decalin- 10-carboxylic acid b :R=C02Et#RSO (IIc) which was transformed through the acid c :R=CO H ,R’=H2 chloride and hydrazide into the wide (IId). Irradia- d :bC& ,R’=H tion of the wide4 in hexane at 0”gave the isocyanate e :R=NCO ,R;=H (IIe) (35% based on starting crystalline hydrazide) f :R.CONl-$,R=H;! and three amidic products. One of these was the same juxtaposition (1,3-diaxial) the reverse selecti- desired 6-lactam (I) (10% yield) formed by attack vity obtains (8:y = 2 3). Further hydrogen abstrac- of the intermediate CON species on the 1-methyl tion from solvent was apparently not an important group and identified by infrared (N-H 6-lactam competing reaction with the 4-axial azides but it C=O) and nuclear magnetic resonance spectra (one clearly is when this group is at position 10.It thus C-methyl CH,.NH). appears that the structural selectivity of acyl azide The 6-lactam (I)was accompanied by the amide photolysis is a sensitive function of the steric accessi- (IIf) (10%) formed by hydrogen abstraction from bility of y-and &hydrogen for abstraction by the solvent and one of the three possible y-lactams intermediate nitrogenous species. (15%) resulting from attack at position 3 6 or 8. The result of this acyl azide photolysis is thus of We thank the National Institutes of Health U.S.interest in yet another respect. In the few previous Public Health Service for a grant. examples when &lactam formation was stereo-(Received December 3r4 1962.) Barraud Cornubert and Lemoine-Tressont Bull. SOC.chim. France 1957 1499; Fischer and Wunderlich Ber,, 1941,74 1544. Dauben Tweit and MacLean J. Amer. Chem. Sue. 1955,77 48; Dreiding and Tomasewski ibid. pp. 168,411; Minckler Hussey and Baker ibid. 1956 78 1009; Dauben and Rogan ibid. 1957 79 5002; Idelson and Becker ibid. 1958 80 908; Cocker and Halsall J. 1957 3441; Sondheimer and Elad J. Amer. Chem. SOC.,1957 79 5542 1958 80 1967; Gaspert Halsall and Willis J. 1958 624; Narang and Dutta J. 1960 2842; but see Haynes an Timmons Pruc. Chem. Suc. 1958 345 and Halsall Rodewald and Willis J. 1959 2798.Elsinger Schreiber and Eschenmoser Helv. Chim. Actu 1960,43 113. ApSimon and Edwards Canad.J. Chem. 1962,40 896. PROCEEDINGS The Molecular Formula of Cephalosporin P By T. G. HALSALL, E. R. H. JONES,and G. LOWE PERRINS OXFORD (THEDYSON LABORATORY UNIVERSITY) THE chemistry of the steroidal antibiotic cephalo- the laboratory of Professor C.Djerassi at Stamford sporin P has so far been discussed1 in terms of a University by mass-spectrometric examination of molecular formula C,,H,,O and a parent skeleton cephalosporin P methyl ester and dideacetyl-of 28 carbon atoms the molecular weight having cephalosporin Pl lactone using an improved in- been determined by the X-ray crystallographic jection technique. The parent skeleton has there- method.Recently a C, carbon skeleton has been fore 29 carbon atoms and an additional methyl proposed2 for fusidic acid a similar steroidal anti- group is presumably present probably at position 8 biotic. The molecular formula of cephalosporin P of the basic steroid ring system. The implications of has now been found to be C33H5008,the molecular this closer relationship of cephalosporin P to fusidic weight having been kindly determined for us in acid are being examined. (Received December 3rd 1962.) Burton Abraham and Cardwell Biochem. J. 1956 62 171; Baird Halsall Jones and Lowe Proc. Chem. Soc.. 1961,257. Godtfredsen and Vangedal Tetrahedron 1962 18 1029. A Kinetic Measurement for Fast Cation-Cation Oxidations in Solution By M. J. NICOL OF THE WITWATERSRAND, (UNIVERSITY SOUTHAFRICA) and D.R. ROSSEINSKY (UNIVERSITY OF EXETER) THEuse of rotating platinum electrodes in polaro- or from an inconstancy of activity coefficients with graphy hitherto confined to oxidations involving medium changes2). The rate constant k is 1-15 x only one ionic reactant, can be extended to kinetic lo6 1. mole-l sec.-l at O” Eabeing 3-60 kcal./mole investigation of fast calomel-cation oxidations pro- anddS2,* -33 e.u. These values are consistent with vided there exists a suitable applied voltage at which the view that predominantly electrostatic effects only one species gives a diffusion current. Thusif such accompanying the accumulation of charge. an electrode in the system Fe” + Vv%Ferlr + Vrv Further reactions apparently amenable to this (in M-perchlorate) is connected by perchlorate solu- technique are the interactions Mnlr~-VIV Mnr*r-FeII tion as a bridge to a standard calomel electrode and and CoIrI-FerI? The rate constant of the last reaction if a potential of 1.0~ is applied across the cell then does not conform with the Marcus equation ko = being 5 x loB,and kox (o~s.)~ a diffusion current id passes that is proportional only (k’k”K)#,kox(cal~.)~ to the iron(@ concentration.Tests for electrode being 23 1. molev1 sec.-l. Conformance is expected catalysis were negative. From second-order plots because of close simulation by such transition-ion based on pen-recorder traces of the diffusion current oxidations of the corresponding electron-exchange against time the rate constant k showed an approxi- reactions (k’ and k”) but it requires also a low mately 1.08th-power dependence on the (excess) equilibrium constant K.More favourable test re- where kox hydrogen-ion concentration indicating the following actions are VIIr-CrII and Co~~f-Mn~I mechanism (calc.)6 are 3 x 1W2 and 3 x 103 1. mole-l sec.-l. Hf + VO,+ + Fe2+-% HOVOf + Few respectively. We thank the South African C.S.T.R. for equip- H+ + HOVO+ -H,0V02+ (rapid) ment and a scholarship (to M.J.N.) also the donors (Protonation of VO,+ may actually occur in a pre- for a Leverhulme Commonwealth Fellowship and an equilibrium; the non-integral 1-08th order arises I.C.I. Fellowship (to D.R.R.). from marginal participation of diprotonated VO$ (Received November 23rd 1962.) Kolthoff and Reynolds Discuss.Faraday SOC.,1954 17 167. Higginson and Sykes J. 1962,2841. Bennett and Sheppard J. Phys. Chem. 1962,66 1275. Marcus Discuss. Faraday SOC.,1960,29,21. Bonner and Hunt J. Amer. Chem. Soc. 1960,82,3826; table 111; Stranks “Modem Co-ordination Chemistry,” ed. Lewis and Wilkins Interscience Publ. Inc. New York 1960 p. 163 ; Latimer “Oxidation Potentials,” Prentice-Hali New York 1952. New College Cathays Park Cardiff Chemistry Department New College Welsh Board of Health Arts Building ASSEMBLYHALL ABERDAREHALL College of Advanced Technology New College Temple of Peace College of Advanced Technology National Museum of Wales Glamorgan County Hall University Registry CITY HALL Law Courts Cardiff Castle Pen-y-Fan (2906 ft.) Brecon Beacons [By courtesy Tempest Ltd.] Caerphi 11y Castle [By courtesy Terence Soames (Cardiff)Ltd.] JANUARY1963 The Inter-relationship of (-)-Kaurene and (+)-Phyllocladene By B.E. CROSS and J. R. HANSON (IMPERIAL INDUSTRIES CHEMICAL LIMITED PHARMACEUTICALSDIVISION AKERSRESEARCH WELWYN, LABORATORIES HERTS.) and L. H. BRICCS R. C. CAMBIE, and P. S. RUTLEDCE (DEPARTMENT UNIVERSITY NEW ZEALAND) OF CHEMISTRY OF AUCKLAND AMONGST the tetracyclic diterpenes known at present the predominant stereochemistry is that of (-)-kaurene which has an antipodal A/B ring fusion and the complete stereochemistry (I; R = CH,).1-3 Thus not only the kaurenolides (11; R = Me or CH,.OH R' = CH,; and R = CH,*OH R' = OH,Me),2 (-)-kauranol (I; R = a-OH and steviol (III)ls5 but also the diterpene alkal~idsl*~ have been related to (-)-kaurene which therefore forms the parent hydrocarbon of this series of compounds.The synthesis6 from podocarpic acid of the enantiomer of a degradation product of atisine confirms the anti- podal A/B ring fusion of (-)-kaurene. (i)-Kaurene has recently been synthesised.' On the other hand (+)-phyllocladene8 (IV; R = CH,) which has been the subject of a total synthe~is,~ has the normal A/B ring fusion. We wish to report the inter-relationship of (-)-kaurene and (+)-phyllocladene. (-)-Kaurene nor-ketonelO (I; R = 0) on Baeyer-Villiger oxidation gave the &lactone (V; R = H) Ymax.1724 and 1216 cm.-l. Since the corresponding hydroxy-acid could not be obtained pure by hydrolysis of the lactone the latter was re- duced with lithium aluminium hydride to the diol which on oxidation afforded inter alia the corn- pound (V; R = OH) vmax. 3350 and 1703 cm.-l. Treatment of the last product with potassium car- bonate and methyl iodide in acetone gave the keto- ester (VI) m.p. 125-129". However use of sodium methoxide and methyl iodide in methanol gave an isomeric keto-ester (VII) m.p. 178-1795' [a]"," -24" Yma,. 1738 and 171 1 cm.-l in which inversion at C-8 had taken place by intramolecular Claisen condensation at C-12 followed by fission of the resultant 1,3-diketone (cf. Grove and Mulhollandll). (+)-Phyllocladene nor-ketone (IV; R = 0)was oxidised with trifluoroperacetic acid to form the corresponding 8-1actonelb.Hydrolysis of the lactone := (cf. ref. 12). However the hydroxy-ester (VIII; R with methanolic potassium hydroxide followed by cautious acidification always led to relactonisation ,&OH a-H) was obtained by using methyl iodide and potassium carbonate in acetone and on oxida- tion it gave the keto-esteP (VIII; R = 0),m.p. 175-1 76" [a)","+ 23". The latter was also prepared by a reaction sequence analogous to that outlined above for the (-)-kaurene series. The two keto-esters (VIT) and (VIII; R = 0)were shown to be antipodes because although their infra- (a) Djerassi Quitt Mosettig Cambie Rutledge and Briggs J. Amer. Chem. Soc. 1961 83 3720; (b) Vorbrueggen and Djerassi ibid.1962 84 2990. Cross Galt Hanson and Klyne Tetrahedron Letters 1962 145. Briggs Cain Cambie Davis Rutledge and Wilmshurst J. in the press. Cross Galt and Hanson unpublished work; Briggs Cambie and Rutledge unpublished work. Mosettig Quitt Beglinger Waters Vorbrueggen and Djerassi J. Arner. Chem. Soc. 1961 83 3163. ti ApSimon and Edwards Canad. J. Chem. 1962,40 896. 'Bell Ireland and Partyka J. Org. Chem. 1962 27 3741. Briggs Cain Cambie and Davis J. 1962 1840. Turner and Ganshirt Tetrahedron Letters 1961 231. lo Briggs Cain Davis and Wilmshurst Tetrahedron Letters 1959 No. 8 8. l1 Grove and Mulholland J. 1960 3007. l2 Finnegan and Djerassi J. Amer. Chem. Soc. 1960 82 4342. red spectra were identical the mixed melting point was depressed and their Cotton effect curves were mirror images.The above data relate the absolute configuration of (-)-kaurene to that of (+)-phyllocladene and since the latter has been related13 to a degradation product of (+)-manool it constitutes a link between those natural products based on the (-)-kaurene l3Grant and Hodges Tetrahedron 1960 8 261. PROCEEDINGS skeleton and the bicyclic diterpenes of normal A/B ring fusion. It is of interest that both (-)-kaurene with an antipodal A/B ring fusion and agathenedi- carboxylic acid with a normal A/B ring fusion occur in Agathis australis ("Kauri"). We are indebted to Professor W. Klyne for deter- mining the rotatory dispersion curves. (Received November 12th 1962.) A New Synthesis of Aryl Esters of N-Acylated Amino-acids and Peptides By D.T. ELMORE and J. SMYTH (DEPARTMENT QUEEN'S UNIVERSITY BELFAST) OF BIOCHEMISTRY WE required a number of aryl esters of N-acylated amino-acids as substrates for various kinetic studies. Such compounds especially p-nitrophenyl esters are important intermediates for the synthesis of pep- tides. They have been obtained generally by reaction of an N-acylamino-acid with either a phenol in presence of dicyclohexylcarbodi-imide,' or a diaryl sulphite or triaryl phosphite.2 The first method is occasionally attended by various side-reactions in- cluding racemisation while the second is limited by the accessibility of the requisite diaryl sulphite or tri- aryl phosphite.For example the latter route did not appear suitable for the synthesis of 3-pyridyl esters which were particularly required for our kinetic studies. Two other methods have been briefly re- ported since this work was commenced but have not yet been widely used. In one di-p-nitrophenyl car- bonate was brought into reaction with an N-benzyl- oxycarbonylamino-acid; in the other an N-acyl- amino-acid was treated with p-nitrophenol in presence of eth~xyacetylene.~ Losse and Demuth6 have shown that the unsym- metrical anhydrides which are produced by reaction of an N-acylamino-acid with diphenylketen in presence of a catalytic amount of tertiary base are cleaved by amino-esters to give optically pure pro- tected peptides. Steric hindrance by the two phenyl groups directs fission in the desired direction.We have found that these anhydrides are attacked by phenols to give optically pure aryl esters. In general a solution of the N-acylamino-acid (0.01 mole) in pure dry tetrahydrofuran (10 ml.) at -15" was treated successively with triethylamine (2 ml. of a 0-001M-solution in tetrahydrofuran) and diphenyl- keten (0.01 mole). When the solution was colourless (30-60 seconds) the phenol (0.01 mole) in tetra- hydrofuran (10 ml.) was added and the mixture was allowed to warm to room temperature and left over- night. Solvent was removed under reduced pressure and the residue was dissolved in cold ethyl acetate. The solution was washed successively with ice-cold saturated sodium hydrogen carbonate solution and ice-cold water dried (MgSO,) and evaporated under reduced pressure.The product (60-65 % yield) was crystallised from methylene chloride-light petroleum (b.p. 60-80"). The following esters have been syn- thesised by this method :p-nitrophenyl hippurate,7 m.p. 167-168" alone and in admixture with a speci- men prepared by the dicyclohexylcarbodi-imidepro-cedure; N-benzyloxycarbonylglycine p-nitrophenyl ester m.p. 125O ;N-benzyloxycarbonyl-L-glutamine p-nitrophenyl ester m.p. 155" [a] -24" (c 2 in dimethyIformamide); N-benzyloxycarbonyl-L-phenylalanine p-nitrophenyl ester,9 m.p. 126" [alto -8.8" (c 2.2 in ethyl acetate); N-benzyloxycarbonyl- glycyl-D-phenylalanine p-nitrophenyl ester m.p. 144" [a39 + 6.4"(c 2 in chloroform) {the EL isomer^ had m.p.146.0-1465" [a] -6.5"(c 2 in chloro- form)1; N-benzoyl-DL-alanine 3-pyridyl ester m.p. 110"(Found C 66.4; H 5.1; N 10.0. C1,H1,N,O requires C 66.6; H 5.2; N 10.4%).The last com- pound was also prepared by the dicyclohexyl-carbodi-imide procedure and the two samples had identical m.p.s. and infrared spectra. (Received November 30th 1962.) Elliott and Russell Biochem. J.. 1957,66.49 P. Iselin Rittel Sieber and Schwyzer Helv Chim. Actu 1957,40,373. Bodanszky and Sheehan Chem. and Ind. 1960,1268;Iselin and Schwyzer Helv. Chim. Acta 1960,43 1760; Paul, Anderson and Callahan J. Org. Chem.,.1961,26 3347; Lubke and Schroder 2.Nuturforsch. 1961,16b 765. Wieland Heinke Vogeler and Monmoto Annulen 1962,655 189. Bodanszky and Birkhimer Chem.and Ind. 1962 1620. Losse and Demuth Chem. Ber. 1961 94 1762. McDonald and Balls J. Biol. Chem. 1957 227 727. * Bodanszky and du Vigneaud J. Amer. Chem. SOC.,1959 81 5688. Goodman and Stueben J. Amer. Chem. SOC.,1959 81 3980; 1962 84 1279. JANUARY1963 Hydrogenolysis of Enamines to Alkenes By J. W. LEWIS and P. P. LYNCH (LOUGHBOROUGH OF TECHNOLOGY LEKS.) COLLEGE LOUGHBOROUGH THE formation of allcenes by elimination from a-acetoxyalkylboranes (I) has recently been re-p0rted.l We now report an apparently analogous reaction in which enamines are cleaved to alkenes by the action of an equimolar mixture of lithium aluminium hydride and aluminium chloride. It seems likely that reaction proceeds via an a-pyrrolidinoallcylaluminiumchloride (11) (probably formed by cis-addition of AIH,C12 to the enamine) from which the pyrrolidine-AlHC1 complex is eliminated to give the alkene.Alternatively the inter- mediate may undergo hydrolysis to give a saturated Enamine 1-PyrrolidinocycIopentene 1-Pyrrolidinocyclohexene 1-Pyrrolidinocycloheptene 1-Pyrrolidinocyclo-octene 6-Methyl- 1 -pyrrolidinocyclohexene 4-Pyrrolidinohept-3-ene Products Cyclopentene (83 %) Cyclohexene (74 %); pyrrolidinocyclohexane (1 2 %) Cycloheptene (84 %) Cyclo-octene (20 %) ; pyrrolidinocyclo-octane (12 %) ;3 cyclo-octanone (40 %I 3-Methylcyclohexene (72 %) ;2-methyl-1-pyrrolidinocyclohexane(6 %) Hept-3-ene (30 %) ;4-pyrrolidinoheptane (45 %) The enarnine (see Table) (1 mol.) was refluxed in ether with lithium aluminium hydride (I mol.) and aluminium chloride (1 mol.) for 5-24 hours; the reaction was stopped with iced hydrochloric acid and the alkene was isolated from the ether extract.Ac0.C-C-B N*CC.Al(CI)H (1) (11) tertiary amine and products of this type were found in several of the reaction mixtures. We thank Dr. R. F. Phillips and Loughborough College of Technology for the provision of facilities and for a Research Assistantship (to P.P.L.). (Received November 29th 1962.) Caglioti Cainelli Maina and Selva Gazzetta 1962,92 309. Eliel and Rerick J. Amer. Chem. SOC.,1960 82 1367. Isolated as the picrate. The Thermal Decomposition of Alkyl~iphenylphospho~um Alkoxides By S. TRIPPETT (DEPARTMENT THEUNIVERSITY, OF CHEMISTRY LEICESTER) HEY and IN GOLD^ reported that tetra-alkylghosphon- ium alkoxides decompose above 120” to give phosphine oxides and hydrocarbons R,P+ R’O-+ R,PO + RR’ and Grayson and Keough2 showed that alkyltri- phenylphosphonium alkoxides (I) in which R is an activating group decompose in solution in the alcohol R’OH to give triphenylphosphine oxide hydrocarbon and ether.We now report a novel R*CH,.PPh,+ R’O-(I) + R’OH -+ Ph,PO + R.Me + R’,O decomposition of n-alkyltriphenylphosphonium alk-oxides which leads not to phosphine oxides but to phosphines. men n-alkyltriphenylphospho*um halides Ph3PR+X- are heated with dry sodium alkoxides to N 240°,an alkyl phenyl ether PhOR’ distils out of the mixture and distillation of the residue in vacido gives the n-alkyldiphenylphosphine Ph,PR+ R’O--+ Ph,PR + PhOR’ Varying amounts of triphenylphosphine are also formed (see Table).R X R’ Ph2PR PhOR’ Ph3P CH3 I Et (%)27 (%)29 (%I30 Bun Br Et 50 37 19 n-Cf& n-C,H17* Br Br Et Me 64 54 53 52 n-C8H17* Br Et 42 59 n-C1,H2,* Pr‘ Br I Me Me 66 70 78-93 * These salts were not obtained crystalline and the yields quoted are Overall from triphenylphosphine. In contrast to this isopropyltriphenylphosphonium iodide when heated with sodium methoxide decom- Hey and Ingold J. 1933 531. Grayson and Keough J. Amer. Chem. SOL,1960,82 3919. poses in the classical ’onium salt way to give tri- phenylphosphine and propene isolated as the di- bromide (51 %).This difference in behaviour between phosphonium salts derived from primary and from secondary halides is also shown on their reduction with lithium aluminium hydride? the former giving primarily alkyldiphenylphosphines and the latter tri- phenylphosphine and to a smaller extent on their reduction at a mercury cathode.* It suggests that the decompositions of n-alkyltriphemylphosphoniumalk-oxides and “hydrides” proceed by similar routes a possibility being the internal collapse of a quinque- covalent-phosphorus intermediate. An examination Gough and Trippett J. 1961 4263. * Horner and Mentrup Annalen 1961 646 65. PROCEEDINGS of the several minor products obtained in the above reactions may throw light on the mechanism.Benzyltriphenylphosphoniumbromide and sodium methoxide react in a more expected way to give inter alia triphenylphosphine (71 %) and stilbene (27 %) this presumably being formed by way of a carbene Ph,P:CHPh -Ph,P + CHPh + Ph,P:CHPh -f-CHPh -.c Ph,P,-yHPh / CGHPh J Ph,P + PhCH:CHPh (Received Decernbcr 7th 1962.) The Stereochemist ry of Flavan-4/3-ols By J. W. CLARK-LEWIS and L. R. WILLIAMS T. M. SPOTSWOOD (UNIVERSITY S. AUSTRALIA) OF ADELAIDE Roux and PAUL US^ recently reported the conversion of the dihydroflavonols (I; R = H or OH) into the corresponding optically active flavanones (11; R = H or OH) which were hydrogenated to the flavan-4P- 01s. These were represented as 2,4-trans-compounds (111; R = H or OH) as in the case of other flavan- 4/3-01s,~ but we now present evidence that they are 2,4-cis-flavan derivatives.The spin-spin coupling constants (J) for the 2- 3- and 4-protons in the epimeric 3-bromo-4‘-methoxy-6-methylflavan-4-ols3 are J2,,= 10.4,J,, =9.4 c./sec. for the trans-trans- racemate (IV) and J2, = 1.0 J3,4= 4.3 c./sec. for the cis-cis-racemate (V) which are close to values recorded for other flavan derivative^.^ The epimeric bromoflavanols previously debrominated by Kashi- kar and Kulkarni5 are thus the trans-trans- and the cis-cis-racemates(IV and V) and it follows that the 4’-me t hox y-6-methylflavan-4/3-01 obtained by de-bromination is the 2,4-cis-flavan derivative (VI). This compound (VI) had also been obtained by catalytic hydrogenation of the corresponding flavanone which is a general method for preparation of flavan- 4/3-01s so that these also may be regarded as 2,4-cis- compounds; hydrogenation of the flavanones pre- pared by Roux and Paulus should therefore yield the 2,4-cis-flavan-4/3-01~ (VII; R = H or OH).Roux and Paulus assigned the trans-structure (111; R = H or OH) to these flavan-4-01s by analogy with hydro- genation of dihydroflavonols to flavan-3,4-diols which were assumed to be 2,3-trans-flavan-3,4-cis-diols. The hypothzsis that these diols are cis has however proved untenable,6 and with the revised trans-trans-configuration their formation from di- hydroflavonols is analogous to the formation of 2,4-cis-flavan-4#3-01~ from flavanones. (Received November 19th 1962.) Roux and Paulus.Biochem. J. 1962,84,416. Mitsui and Kasahara J. Chem. SOC.Japan 1960 81 1583; Roux Chem. and Ind. 1962 278; Bognar Rakosi Fletcher Kehoe Phiibin and Wheeler Tetrahedron. 1962 18 135 (nuclear magnetic resonance measurements are however incompatible with the trans-configurations ;personal commun!cation from Professor Wheeler). 3 Clark-Lewis Spotswood and Williams Austral. J. Chem. 1963 16 in the press. Clark-Lewis and Jacean Proc. Chem. Soc. 1961 165. Kashikar and Kulkarni J. Sci. Ind. Res. India 1959 18 B 418. Bokadia Brown Kolker Love Newbould Somerfield and Wood J.,. 1961,4663;Fujise Hishida Onuma Adachi Fujise and Munekata Bull. Chem. Soc. Japan 1962,35,1245; Clark-Lewis Rev. Pure Appl. Chem. 1962,12,96. JANUARY 1963 ~ ~ The Preparation and Structure of Say1 hide By E.A. V. EBSWORTH, D. R. JENKINS,M. J. MAYS,and T. M. SUGDEN CHEMICAL LENSFIELD (UNIVERSITY LABORATORY ROAD CAMBRIDGE) WEhave prepared silyl azide SiH,N, by reaction of a silylamine (either trisilylamine or N-ethyldisilyl- amine) with a solution of hydrazoic acid in di-n- butyl ether. The compound is a colourless liquid m.p. -81-8”,which decomposes slowly in a vacuum-system forming monosilane ;the extrapolated b.p. is about 28”. The molecular geometry is of particular interest when considered in relation to the shapes of similar molecules. A microwave study has established that silyl isothiocyanatehas a linearheavy-atom skeleton,l and its infrared spectrum shows the “strong weak weak” rotational detail2 characteristic of a symmetric top with only three equivalent hydrogen atoms off the top axis.A preliminary study of the microwave spectrum of silyl isocyanate has revealed a number of closely spaced groups of lines similar in pattern to those found for the isothiocyanate indicating that the isocyanate too is a symmetric top; moreover its infrared spectrum also shows the characteristic “strong weak weak” rotational detail. In the infra- red spectrum of silyl azide between 4OOO and 650 cm.-l strong bands were observed at -2200 (SiH and N=NN stretching) 1325 (NNN stretch- ing) 950 (SiH bending) and -710 cm.-l (SiH rocking and SiN stretching) but none of these bands showed rotational detail even under a resolution of 0-4 cm.-l.Also a preliminary study of the micro- wave spectrum at -78” between 28,000 and 32,000 Mc./sec. revealed at least 30 widely spaced lines all of which showed a second-order Stark effect. It is therefore clear that silyl azide is an asymmetric top molecule with a non-linear heavy-atom skeleton. In methyl azide4 and methyl isocyanate5 the (M,)CNX angles are both close to 120”;presumably (p-4)~-interactions are responsible for the linearity of the heavy-atom skeletons in silyl isocyanate and isothiocyanate. The difference in structure between the isoelectronic silyl azide and silyl isocyanate im- plies that the influence of such n-interactions on molecular geometry is difficult to predict. (Received November 21st 1962.) Jenkins Kewley and Sugden Trans.Faraday Soc. 1962,58 1284. Ebsworth Mould Taylor Wilkinson and Woodward Trans. Faraday Soc. 1962,58 1069. Ebsworth and Mays J. 1962,4844. Pauling and Brockway J. Amer. Chem. Soc. 1937 59 13. Eyster Gillette and Brockway J. Amer. Chem. SOC.,1940 62 3236. The Biosynthesis of Riboflavin By THOMAS ROWANand €3. C. S. WOOD (THEROYALCOLLEGE AND TECHNOLOGY, OF SCIENCE GLASGOW) studies1 have established that 6,7-di- 0 BIOCHEMICAL methyl-8-ribityl-lumazine(I) is the precursor of ribo- flavin (11) in organisms such as Erernothecium ashbyii and Ashbya gussypii. More recent work2indi-Me cates that all the carbon atoms of the o-xylene moiety of riboflavin are derived from the same lumazine (I) at least two molecules of which are converted enzymically into one of riboflavin.We now report the conversion of 6,7-dimethyl-8-ribityl-lumazine (I) into riboflavin (11) in vitro in the absence of any other source of carbon. 6,7-Dimethyl-8-ribityl-lumazine(I) dissolved in phosphate buffer at pH 7.3 was refluxed under nitrogen for 15 hr. in the absence of enzyme. On cooling riboflavin separated in 55% yield. We sug- gest that the mechanism of this transformation and CV) Maley and Plaut J. Biol. Chem. 1959 234 641; J. Amer. Chem. Soc. 1959 81 2025. Plaut J. Biol. Chenz. 1960 235 PC41. PROCEEDINGS presumably of the corresponding enzyme reaction Addition of metal ions accelerates the conversion involves the following steps (a) ring-opening of the of 6,7-dimethyl-8-ribityl-lumazine (I) into riboflavin pyrazine ring in the “quinonoid” pteridine initiated (II) in vitro in our system.Since metal ions are known by nucleophilic attack at position 7 (I -j. 111 3IV) to promote the hydration and hence the ring- [we have recently3 described experiments which indi- opening of “quinonoid” pteridine~,~ this observa- cate that the pyrazine ring-closure in “quinonoid” tion supports the mechanism suggested above. We pteridines such as (I) is reversible]; (b) aldol con- have isolated from the mother-liquors of the reaction densation involving two molecules of (IV) to give a a small amount of a pyrimidopteridine identical with derivative cv)of dimeric biacetyl as suggested by that obtained6 from self-condensation of 5-amino- Birch;* and (c) cyclisation of the intermediate (V) 4-~-ribitylaminouracil.This indicates that the di- with loss of one diaminopyrimidine portion to give aminopyrimidine portion eliminated in the final riboflavin (II). A related cyclisation of a derivative cyclisation is not degraded further in our reaction in of dimeric biacetyl to give riboflavin has previously vitro. We understand however that this may not be been reported by US.^ the case in biological systen~s.~ (Received November 13th 1962.) Rowan Wood and Hemmerich Proc. Chem. Soc. 1961 260. * Birch Proc. Chem. SOC.,1962 11. Cresswell and Wood J. 1960,4768. Cresswell Neilson and Wood J. 1960 4776. Plaut personal communication. A Further Total Synthesis of (Estrone By D. J. CRISPIN and J.S. WHITEHURST (CHEMISTRY THEUNIVERSITY DEPARTMENT OF EXETER) PRELIMINARY experiments on the alkylation of 1,3-dione (IV) b.p. 180-182”/0*005 mm. Amax. 2-methylcyclopentane-1,3-dione1~2 with a series of 268 mp (ci lO,oOO) I/max. 2925 1732 1602 1566 alkyl halides gave in two instances only the C-alkyl 1490 1450 1315 1250 1156 1133 991 883 and R compounds (I;= Me or CH2=CHCH2). When 827 cm.-l (Found C 76.4; H 7.4. C19H,203re-6-methoxy-1-vinyl-1-tetraloP(II) was treated with quires C 76.5; H 704%).A greatly improved yield phosphorus tribromide4 in chloroform-pyridine at was obtained by the direct action of the allylic -60” it gave after chromatography the substituted alcohol (11) on the dione (I; R = H)in xylene- ally1 bromide (III) which by reaction with the dione Triton B.S Gentle warming of a solution of the di- (I;= H) produced albeit in poor yield 2-methyl- ketone (IV) in methanol containing dilute hydro- R 2-(6-methoxy-1 -naphthylidene)ethyl cyclopentane-chloric acid promoted rapid and efficient conversion into the bisdehydrooestrone cv)which has been re- duced to oestr0ne.B Toluene-p-sulphonic acid in benzene and phosphorus pentoxide in phosphoric acid were unsatisfactory reagents for this cyclisation (cf.refs. 6 7). The syntheses of cestrone by way of the bisdehydro- compound (V) are the simplest yet devised.Bs7 The elegant synthesis by Johnson and his colleagues: when coupled with Sheehan’s method9 of forming ring D is also highly efficient. (Received October 24th 1962.) Panousse and Sannie Bull.SOC.chim. France 1955 1036. Boyce and Whitehurst J. 1959,2022. Normant Compt. rend. 1954,239,1510 1811 ;Nazarov Torgov and Verkholetova Doklady Akad. Nauk S.S.S.R., 1957,112,1067; Cole Johnson Robbins and Walker Proc. Chem. Suc. 1958,114; Robbins and Walker J. 1962,244. * Ruzicka and Muller Helv. Chim. Acta 1939,22,416; Sarett J. Biol. Chem. 1946 162 601. Ananchenko Leonov Platonova and Torgov Doklady Akad. Nauk S.S.S.R. 1960,135,73. Hughes and Smith Chem. and Ind. 1960 1022. Crispin and Whitehurst Proc. Chem. SOC.,1962 356 and present paper. Johnson and Christiansen J. Amer. Chem. Soc. 1951,73 5511; 1957,79 1995,2005. Sheehan Coderre and Cruickshank J. Amer. Chem. SOC. 1953,75,6231; 1957,79 147. JANUARY1963 Alternation of Line Width in the Electron Spin Resonance Spectrum of the Alkali-metal Radical-ion Complex of Pyracene By E.DE BOERand E. L. MACKOR (KONINKLIJKE/SHELL-LABORATORIUM SHELLINTERNATIONALE AMSTERDAM RESEARCH MAATSCHAPPIJ, N.V.) THEelectron spin resonance spectra of the alkali- metal derivatives of pyracene (I) studied in solvents of various ion-associating power shows changes in spin densities caused by electric fields1 and alterna- tions of line width2 (Figure) caused by an intramole- cular exchange. H#H H*H ~4-4-H H @ H (I) d~"]dHversus H for the sodium-pyracene complex in tetrahydrofuran at -30". Analysis of the hyperfine pattern of the ion pair revealed two aliphatic coupling constants (Table). As in the sodium-naphthalene system the sodium splitting decreases with temperature indicating that the metal ion is near the nodal plane of the 7~,.+~ molecular orbital.* If the different values of ]aNaI observed for the two systems are taken into account (Table) position A or B appears to be the most likely position of the counter-ion.The figure shows the spectrum of the ion pair in tetrahydrofuran (cf. Table). The odd-numbered quintuplets exhibit a well-resolved quartet structure whereas in the even quintuplets the quartet structure is not resolved. This alternating effect arises from the dynamic equilibrium consisting between the two possible conformations of the ion pair M-Na+ + Na+M-. The counter-ion interchanges between two sym-metrical positions (e.g.A and B) introducing time- dependent modulations in the isotropic coupling constants. If the lifetime T is short compared to {y(aul -arz))-l where y is the gyromagnetic ratio of the electron a sharp averaged spectrum will be observed with za = &(aal+ a,z). The spectrum illustrated almost meets this condition on the un-a ha I *Taken from ref. 4. DME = Spritting constants (gauss) Pyracene-Naphthalene-DME 2Me-THF THF 2Me-THF THF -80" -30' +27" +27' +6.58 $6.93 f6.65 {t6.37 GU) -1-58 -1.63 -1.63 -1.865* -1*865* -0.176 0.146 1.115* 1-05* 1,2-Dirnethoxyethane. 2Me-THF =Tetrahydro-2-methylfur an. THF =Tetrahydrofuran. The spectrum of the "free" ion in 1,2-dimethoxy- ethane resembles that of the positive ion3 and consists of nine quintuplets.The magnitudes and signst of the splitting constants are given in the Table. In tetrahydro-2-methylfuran strong ion association occurs:4 Na+ + M-+ Na+M-; K = [Na+][M-]/[Na+M-] < 5 x lo-* rnole/l. at -8O"c. sharp quintuplets incipient alkali-metal splitting is already observed. In intermediate cases when 7(aal -a,& x 1 complex spectra are obtained. By using the strong-field approximation it can be shown that the line widths of the hyperfine lines in the first quintuplet and the most intense ones in the third and fifth quintuplets are independent of T 7 Signs are determined from the anomalous line-width broadening occurring at temperatures lower than -70" (see ref. 3). Stone and Maki J. Chem. Phys. 1962 36 1944; Ayscough and Wilson Proc.Chem. Soc. 1962 229; Heineken Bruin. and Bruin. J. Chem. Phvs.. 1962.37.452. Maki J. Cheh.Phys. 1961; 35,761 Bolton and Carrington Mol. Phys. 1962,5,161; Freed and Fraenkel J. Chem. Phvs.. 1962. 37. 1156. De Boer and Mackor Mol. Phys. 1962,5,493. Atherson and Weissman J. Amer. Chem. Soc. 1961 83 1330. PROCEEDINGS whereas the line widths of all the lines in the second and fourth quintuplets do depend on T. By varying the solvent (using if necessary mixed solvents) and the temperature spectra corresponding to different values of r have been obtained. The spectrum in tetrahydro-2-methylfuran consists of sharp lines consequently r >> (Y(G,~-a,z)>-l; the average line width AH (between points of extreme slope) is 65mG.This value sets a lower limit to the lifetime of the ion pair. Taking into account the other mechanism contributing to the total line width we estimate r to be larger than second. The nature of the exchange process may be explained by the following reasoning. Although the mean lifetime T of the ion pair in tetrahydrofuran at -3O"c. (Figure) is w lo-' sec. sharp alkali-metal lines are observed in the odd quintuplets (AH = 90 mG). These observations can be reconciled only if during the exchange the spin state of the alkali- metal nucleus is preserved. Therefore the reactions responsible for the line width alternation must be intramolecular. Intermolecular reactions such as M-X*+ + X+ + X+M-+ X*+ and M*-X+ + M-+ X+M-+ M*-in which X represents the alkali metal are excluded since they lead to a random distribution of the spin states of the metal nucleus.Preliminary experiments have shown that addition of an alkali-metal halide to the solution or an increase in the dissociation constant brought about by changing the solvent causes the alkali-metal splitting to disappear. The authors acknowledge experimental assistance by Mr. A. P. Praat and Mr. A. R. Korswagen. (Received December 3rd 1 962 .) Formation of Isomeric Bromohexosyl Fluorides from 3,4,6-Tri-0-acetyl-D-glucal By P. W. KENT,F. 0.ROBSON, and (in part) \I. A. WELCH (DEPARTMENT UNIVERSITY OF BIOCHEMISTRY OF OXFORD) AN interesting route to the synthesis of ap-fluoro- bromo-compounds previously employed in the steroid field1 has now been extended to carbo-hydrates.In this method triacetylglucal reacted smoothly with N-bromosuccinimide and anhydrous hydrogen fluoride in ether to give two isomeric pro- ducts (I) and (11) in good yields. Isomer (I) C,,H,,BrFO, m.p. 139" [a]? -32" in CHCI, was stable and crystalline. It was shown to be 2-bromo-2- deoxy-3,4,6-tri-O-acetyl-/3-~-mannosyl fluoride on the following evidence .. (1) iII> Br (a) Treatment with methanolic hydrogen chloride at 100" resulted in quantitative expulsion of fluoride ion in 5$ hours (a -0.32" + +O.l" const.) and the formation of a methyl bromoglycoside from which a crystalline benzylidene derivative (methyl 4,6-0- benzylidene-2-bromo-2-deoxy-a-D-mannoside) m.p. 84-86' [a:]?+ 15.3" in CHCl, was obtained. The latter was stable towards sodium methoxide and gave no evidence of anhydro-sugar formation. (b) After methanolysis the isomer (I) absorbed 1 mol. of hydrogen in the presence of Raney nickel at room temperature giving methyl 2-deoxy- a-~-glucoside (m.p. 89" lit.? 91") which after acidic hydrolysis was converted into N-benzyl-N-phenyl- 2-deoxy-~-glucosylhydrazine(m.p. 158" alone or in admixture with the authentic substance3). Isomer (11) obtained from the mother-liquors of the first had m.p. 113" and [a] + 67-3"in CHCI,. This substance was shown to be 3,4,6-tri-O-acetyl- 2-bromo-2-deoxy- a-D-glucosyl fluoride in the follow- ing way. Methanolysis under the foregoing condi- tions (a +0.73" -+0+1" const.; 6 hr.) gave a syrupy bromoglycoside which with benzaldehyde gave methyl 4,6-0-benzylidene-2-bromo-2-deoxy-/3-D-glucoside (m.p.174"; [SIT+ 1" in CHCI,). Sodium methoxide readily converted this into methyl 2,3-anhydro-4,6-0-benzylidene-/3-~-mannoside (m.p. 182-183"; [a]%-30" in CHCl,; lit.? m.p. 183" [a] -30.7" in CHCI,). Whereas other additions5 to substituted glycals e.g. as with halogens in an alcohol leads to 2-frans-halogeno-glycosides in the present isomers Bowers Ivanez Denot and Becarra J. Amer. Chenz. SOC.,1960 82 4001 ; Bowers Denot and Becarra ibid.. p. 4007. Hughes Overend and Stacey J. 1949 2846. Bergmann and Schotte Ber. 1921 54,440. Peat and Wiggins J. 1938 1088. Lemieux personal communication. JANUARY1963 the fluorine is located at the anomeric carbon atom and bromine at position 2 in the cis-configuration.There was no evidence of deacetylation or ring contraction as reported6 for the action of hydrogen fluoride on fully acetylated sugars. It is of interest that the different positions of the halogen atoms confer distinctive reactivity such that the fluorine can be displaced selectively by methan- olysis and the bromine by hydrogenolysis. Both bromofluoro-compounds appear to be stable in neutral or mildly alkaline solutions. The addition appears to be of wide application in the carbohydrate series and similar products have been obtained from 3,4-di-O-acetyl-~- and -L-arabinal 3,4-di-O-acetyl-~-xylal,3,4,6-tri-Q-acetyl-D-galactal and $-glucalo (Received November 22nd 1962.) Pederson and Fletcher J.Amer. Chem. Soc. 1960 82,946. NEWS AND ANNOUNCEMENTS Ethel Behrens Fund.-This is a new fund the purpose of which is to provide grants towards the travelling expenses including maintenance of Fellows of the Society studying at a University or Technical College in the British Isles for the first University degree or other equivalent qualification to enable them to attend the Anniversary .Meetings of the Society and any Scientific Symposia or Dis- cussions in conjunction therewith. The first awards are to be made in connection with the Anniversary Meetings to be held in Cardiff in March 1963. Forms of application together with regulations governing the award of travel grants may be ob- tained from the General Secretary and must be returned by February 15th 1963.Deaths.-We regret to announce the deaths of the following Mr. F. M. Dyke (28.7.62) of Deal formerly Research Chemist with Unilever Ltd. ; Mr. H. B. Hammond (9.1 1.62) of Shoreham-by-Sea a Fellow for over 60 years; and Professor T. S. Wheeler (13.12.62) Professor of Chemistry and Dean of the Faculty of Science of University College Dublin. Election of New Fellows.-267 Candidates were elected to the Fellowship in December 1962. New Year Honours List.-Among those included in the New Year Honours List were J. W. Cook Vice-chancellor of the University of Exeter who became a Knight Bachelor F.M. Brewer Chairman Southern Region Advisory Council for Further Education J.B. Speakman Professor of Textile In- dustries University of Leeds and A. R. J. P. Ubbelohde Professor of Thermodynamics Imperial College of Science and Technology University of London who were appointed C.B.E.S. Royal Society.-At the Anniversary Meeting of the Royal Society held on November 30th Sir Howard Florey was re-elected President Sir Patrick Linstead Treasurer and Professor W. T. J. Morgan and Dr. H. W. Thompson members of Council. Among the newly elected members of Council was Professor E. L. Hirst. Salters’ Institute of Industrial Chemistry.-Appli- cations are invited for Salters’ Scholarships value &500-600 p.a. according to circumstances (plus fees) for a resident in the United Kingdom with an Honours degree or equivalent qualification in Chemistry Biochemistry Physics or Engineering for the purpose of receiving either full-time instruc- tion in the principles of Chemical Engineering or further experience by research in Chemistry or Chemical Engineering.Applications may be made before graduation. The Scholarships will be tenable for one year and may be renewed year by year for two further years. Tenure abroad may be permitted in the third year. Applications are also invited for Salters’ Fellow- ships of value in the range &900--1,200 p.a. accord- ing to qualifications and experience (plus 10% as contribution to F.S.S.U.). These Fellowships may be held by Honours graduates or holders of equivalent qualifications in Chemistry Biochemistry Physics or Engineering who desire to obtain further training in research in Chemistry Biochemistry or Chemical Engineering.Candidates should have obtained a doctor’s degree or have had not less than three years’ postgraduate experience by the time of their taking up the Fellowship. Fellowships will be tenable in the United Kingdom or abroad for one year from September lst 1963 and may be renewed for one further year. Application forms obtainable from the Clerk of the Salters’ Company 36 Portland Place London W.l must be returned by March lst 1963. Symposia etc.-A Symposium on Inorganic Fluorine Chemistry will be held in Argonne Illinois on September 4-6th 1963. Further en-quiries should be addressed to Dr.L. Stein Argonne National Laboratory 9700 S. Cass Avenue Argonne Illinois U.S.A. A Conference on Plasma Physics sponsored by the Institute of Physics and the Physical Society will be held at the Culham Laboratory United Kingdom Atomic Energy Authority on 2627th September 1963. Further enquiries should be addressed to the Administrative Assistant The Institute of Physics and The Physical Society 47 Belgrave Square London S.W. 1. Personal.-Dr. D. M. Adam who resigned his position with Imperial Chemical Industries Limited Heavy Organic Division The Frythe Welwyn is now a Lecturer in Inorganic Chemistry at Leicester University. Dr. J. S. Anderson Director of the National Chemical Laboratory Department of Scientific and Industrial Research has been appointed to the Chair of Inorganic Chemistry at Oxford with effect from October lst 1963.Mr. M. H. Briggs has been awarded the degree of D.Sc. by the University of New Zealand. He has relinquished his position as lecturer in Biochemistry at the Victoria University of Wellington in order to accept the newly-created position of Senior Lecturer in Pedology at the same institution and has been given six months’ leave of absence to join a space- biology group in the Jet Propulsion Laboratory of the California Institute of Technology. Dr. C. L. Chakrabarti formerly of The Queen’s University of Belfast is now Visiting Assistant Pro- fessor at Louisiana State University. Dr. J. W. Covran has retired as Chief Chemist of J.and J. Colman Limited. PROCEEDINGS Mr. J. G. N. Drewitt has been appointed a Director of Courtaulds Limited. The Court of the University of Manchester has conferred the title of Professor Emeritus on Professor F. Fairbrother. Mr. W. Johnstone has been appointed Managing Director of Plant Protection Limited. Mr. J. P. Koppel has resigned as Director of British Cellophane Limited. Dr. J. N. Milne formerly with Du Pont Company (United Kingdom) Limited has taken up an appoint- ment in the Chemicals Division of Esso Petroleum Company Limited. Professor J. Packer University of Canterbury New Zealand has had the honorary degree of D.Sc. conferred upon him at the first public degree con- ferring ceremony of that University. Professor C.W. Shoppee of the University of Sydney is a visiting Professor in the Chemistry Department at Duke University U.S.A. until June 1963. Professor R. Truscoe Victoria University of Wellington is visiting Departments of Biochemistry of overseas universities and research establishments. Dr. R. F. Webb has been appointed Technical Director of the Plastics Division of Allied Chemical Corporation. FORTHCOMING SCIENTIFIC MEETINGS London Thursday February 14th 1963 at 6 p.m. Centenary Lecture “Problems of Cumulenes and Acid Hydrocarbons,” by Professor Dr. R. Kuhn. To be given in the Lecture Theatre The Royal Institu- tion Albemarle Street W.l. Thursday February 28th,at 6 p.m. Tilden Lecture “The Biosynthesis of Alkaloids,’’ by Professor A.R. Battersby Ph.D. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington s.w.7. Aberdeen Wednesday February 13th 1963 at 8 p.m. Lecture “The Importance of a Quantitative Ap- proach at all Stages in the Development of a Chemical Process,” by A. J. Young. 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 February 7th 1963 at 5 p.m. Lecture “Seeing Molecules with Microwaves,” by Dr. J. Sheridan M.A. Thursday February 21st at 5 p.m.Lecture “The Active Centres of Enzymes,” by Professor H. N. Rydon D.Sc. F.R.I.C. Birmingham (Joint Meetings with the University Chemical Society to be held in the Chemistry Department The University.) Friday February 8th 1963 at 4.30 p.m. Lecture “Phytol-The Cinderella of Natural Pro- ducts,” by Professor B. C. L. Weedon D.Sc. F.R.I.C. Friday March lst at 4.30 p.m. Lecture “Ionic Polymerisation,” by Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. Bristol (Joint Meetings with the Royal Institute of Chem- istry and the Society of Chemical Industry to be held JANUARY 1963 in the Department of Chemistry The University un- less otherwise stated.) Thursday February 7th 1963 at 6.30 p.m. Lecture “Applications of X-Ray Crystallography in Chemistry,” by H.M. Powell M.A. F.R.S. Tuesday February 19th at 7.30 p.m. Lecture “Luminescence,” by Professor G. F. J. Garlich D.Sc. F.1nst.P. To be given at Gloucester Technical College. Cambridge (Joint Meetings with the University Chemical Society to be held in the University Chemical Laboratory Lensfield Road.) Friday February lst 1963 at 8.30 p.m. Lecture “Molecular Shapes and Sizes,” by Dr. L. E. Sutton M.A. F.R.S. Friday February 15th at 8.30 p.m. Centenary Lecture “Problems of Cumulenes and Acid Hydrocarbons,” by Professor Dr. R. Kuhn. Friday March lst at 8.30 p.m. Lecture by Professor R. C. Cookson F.R.I.C. Cardiff CORRECTION Professor C. H. Bamford’s Lecture entitled “Metal Carbonyls and Other Novel Initiators of Polymerisa- tion,” will be given on Monday February 25th at 5 p.m.and not on March 25th as announced. Dundee Tuesday February 26th 1963 at 5 p.m. Lecture “Some Applications of Nuclear Magnetic Resonance to Organic Chemistry,” by Dr. A. R. Katritzky M.A. To be given in the Chemistry Department Queen’s College. Durham (Meetings to be held at The Science Laboratories South Road.) Monday February 11 th 1963 at 5 p.m. Lecture by Dr. R. E. Richards M.A. F.R.S. Joint Meeting with the Durham Colleges Chemical Society. Monday February 25th at 5 p.m. Tilden Lecture “The Biosynthesis of Alkaloids,” by Professor A. R. Battersby Ph.D. Edinburgh Thursday February 14th 1963 at 7.30 p.m. Lecture “Pesticides,” by Dr.R. A. E. Galley F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Thursday February 21st at 4.30 p.m. Official Meeting and Centenary Lecture “Problems of Cumulenes and Acid Hydrocarbons,” by Prof-essor Dr. R. Kuhn. To be given in the Department of Chemistry The University. Tuesday February 26th at 4.30 p.m. Lecture “The Co-ordination Chemistry of Gallium,” by Professor N. N. Greenwood Ph.D. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University. Exeter Friday March lst 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 Thursday February 14th 1963 at 4 p.m. Lecture “Substituent Effects in Electrophilic Aro- matic Substitution,” by Professor C. Eaborn D.Sc. F.R.I.C. Joint Meeting with the Alchemists’ Club to be held in the Chemistry Department The Univer- sity. Friday March lst 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. Hull Thursday February 28th 1963 at 5 p.m. Lecture “Aromatic Character in 4Membered Rings,” by Dr. J. F. W.McOmie. Joint Meeting with the University Students Chemical Society to be held in the Organic Lecture Theatre The University.Keele Tuesday February Nth 1963 at 8.30 p.m. Lecture “The Development of Anaesthesia,” by Dr. E. Isaacson M.Sc. M.B. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University. Lee& Thursday February 28th 1963 at 5.45 p.m. Lecture “Chemical Basis of the Injury of Cells by Tonising Radiations,” by Dr. P. Alexander. Joint Meeting with the University Union Chemical Society to be held in the Chemistry Lecture Theatre The University. Leicester (Joint Meetings with the University Chemical Society to be held in the Department of Chemistry The University.) Monday February 4th 1963 at 4.30 p.m. Lecture “Recent Studies of Unimolecular Re- actions,” by Professor A.F. Trotman-Dickenson M.A. D.Sc. Tuesday February 19th at 7.30 p.m. Lecture “Chemistry of the Hemicellulose Group,” by Professor E. L. Hirst C.B.E. LL.D. F.R.S. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry. Monday March 4th at 4.30 p.m. Lecture “Addition Accompanying Substitution in Aromatic Systems,” by Professor P. B. D. de la Mare D.Sc. Manchester (Meetings to be held in Room Fl Manchester College of Science and Technology unless otherwise stated.) Tuesday February 5th 1963 at 4.30 pm. Lecture “Exploring Surface Reactions on the Atomic Scale,” by Dr. J. S. Anderson F.R.S. Joint Meeting with the University of Manchester Faculty of Technology Chemical Society. Thursday February 21st at 6.30 p.m.Lecture “Oxidative Cyclisation,” by Professor G. W. Kenner Sc.D. Newcastle (Meetings to be held in the Chemistry Department King’s College.) Friday February lst 1963 at 5.30 p.m. Bedson Club Lecture “Chemotherapy and the Organic Chemist,” by Dr. F. L. Rose O.B.E. ,F.R.S. Monday February 18th at 5.30 p.m. Centenary Lecture “Problems of Cumulenes and Acid Hydrocarbons,” by Professor Dr. R. Kuhn. Tuesday March 5th at 5.30 p.m. Lecture “Some Fast Halogenation Reactions,” by R. P. Bell M.A. F.R.S. North Wales Thursday February 28th 1963 at 5.45 p.m. Lecture “Mass Spectrometry in Chemistry,” by Dr. J. H. Beynon A.R.I.C. Joint Meeting with the University College of North Wales Chemical Society to be held in the Chemistry Department University College Bangor.Nottingham Tuesday February 12th 1963 at 5 p.m. Lecture “Tetraterpenes,” by Professor B. C. L. Weedon DSc. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University. Oxford (Joint Meetings with the Alembic Club to be held in the Inorganic Chemistry Laboratory.) PROCEEDINGS Monday February 4th 1963 at 8.30 p.m. Lecture “Infrared Spectra of Surface-adsorbed Molecules,” by Dr. N. Sheppard M.A. Monday February 25th at 8.30 p.m. Lecture “Microcalorimetry of Living Processes,” by Dr. H. A. Skinner B.A. Monday March 4th at 8.30 p.m. Lecture “The Chemistry of Bacterial Walls and Membranes,” by Professor J. Baddiley D.Sc.F.R.S. Reading (Joint Meetings with the Royal Institute of Chem- istry and the University Chemical Society to be held in the Large Chemistry Lecture Theatre The University.) Wednesday February 6th 1963 at 6 p.m. Lecture “The Study of Bond Properties by Infrared Spectroscopy,” by Dr. L. J. Bellamy. Tuesday March Sth at 6 p.m. Lecture “Molecular Vibrations and Chemical Problems,” by Dr. H. W. Thompson C.B.E. F.R.S. St. Andrews (Joint Meetings with the University Chemical Society to be held in the Chemistry Department St. Salva- tor’s College.) Friday February Sth 1963 at 5.15 p.m. Lecture “The Simplest Chemical Reaction,” by Professor G. Porter Ph.D. F.R.S. Friday February 22nd at 5.15 p.m. Lecture “Some Recent Aspects of Inorganic Fluor- ine Chemistry,” by Dr.D. W. A. Sharp. Joint Meet- ing with the University Chemical Society and the Royal Institute of Chemistry. Sheffield Thursday February 21st 1963 at 7.30 p.m. Lecture “The Way Ahead with D.S.I.R.,” by Sir Harry Melville K.C.B. D.Sc. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the University Chemical Society to be held in the Department of Chemistry The University. Southampton Friday February 22nd 1963 at 5 p.m. Lecture “Recent Developments in the Measure- ment of Surface Area Adsorption,” by Dr. s. J. Gregg F.R.I.C. Joint Meeting with the Royal Insti- tute of Chemistry to be held in the Department of Chemistry The University. Swansea (Joint Meetings with Student Chemical Society to be held in the Department of Chemistry University College.) JANUARY 1963 Monday February llth 1963 at 4.30 p.m.Lecture “Recent Advances in Aromatic Fluorine Chemistry,” by Professor M. Stacey D.Sc. F.R.S. Friday March lst at 4.30p.m. Lecture “The Place of Kinetics in Chemistry,” by R. P. Bell M.A. F.R.S. Tees-side Tuesday February 5th 1963 at 8 p.m. Lecture “Unusual Properties of Metal Nitrates,” by Professor C. C. Addison D.Sc. F.R.I.C. Joint Meeting with the Royal Institute of Chemistry the Society of Chemical Industry and Society for Analytical Chemistry to be held at the Constantine Technical College. OBITUARY NOTICES SYDNEY SMITH 1886-1962 SYDNEY SMITHwas born in London on September 27th 1886.His death occurred suddenly on May 23rd 1962 at Dartford after only a few hours’ illness. The third and youngest son of Alfred Smith he received his early education at the Stockwell Train- ing College School and later entered the Westminster City School. On leaving school he was apprenticed to a chemist and druggist Mr. F. H. Glew who was an early worker with X-rays and radium. On the completion of his apprenticeship he gained some further experience in pharmacy as an assistant and then matriculated in the University of London at the same time gaining a Jacob Bell Scholarship at the School of Pharmacy of the Pharmaceutical Society. At the end of the first year’s course in the School he was awarded the medal for chemistry and the Martindale Memorial Medal for pharmacy.Im-mediately after passing the “Major” examination for the diploma of pharmaceutical chemist he was awarded the Pereira Medal of the Society. For the next three years he was a demonstrator under Professor A. W. Crossley F.R.S. and passed the Branch E (Analysis of Foods and Drugs) examination of the Institute of Chemistry. He gained a Neil1 Arnott Scholarship in chemistry and gradu- ated B.Sc. (London) with First Class Honours. During this period he published two papers with Professor Crossley. Smith was then offered a Re- search Fellowship at the School but preferred to study in Germany. There he worked with Geh. C. Harries on the ozonisation of organic compounds and obtained his Ph.D. (Kiel) in 1914.On his return to England Smith joined Burroughs Wellcome and Company at Dartford under the late Dr. H. A. D. Jowett and after a period in the analytical laboratories was transferred to the Ex-perimental Department on the outbreak of war. Thus began a life-time association with the company during which he was responsible for the organisation of original research and the development of manu- facturing processes in the whole field of medicinal chemistry He soon became head of the Experimental Chemical Laboratories and then Head of the Experi- mental Department a post he retained for the next twenty years. Here he organised a team of workers dealing with alkaloids glycosides hormones and vitamins and many fundamental researches were carried out.During this period he developed the production of insulin from the research to the manufacturing scale; he investigated the lesser alkaloids of Ephedra and discovered the nor- and methyl-ephedrines. Ergot alkaloids remained a major interest. Smith intro- duced the use of ergotoxine ethanesulphonate in- vestigated the subsidiary alkaloids and the isomerism between them and the degradation product ergine. When ergometrine was discovered he and his col- leagues developed the published preparation to a commercial process in a very short time and ergo- metrine was available to clinicians in a matter of days. To Smith’s regret it fell to others to determine the structure of these alkaloids. In 1930 he discovered digoxin developed it to commercial production from DigitaZis Zanata and saw it take an outstanding place in the treatment of cardiac insufficiency.In 1936 Smith was appointed Works Manager at The Wellcome Chemical Works in succession to Dr. Jowett. He always regretted the divorce from research work and did not take kindly to administration feel- ing that much time was being wasted on petty decisions. In 1940 on the retirement of Dr. T. A. Henry he accepted an invitation to become Director of The Wellcome Chemical Research Laboratories. A new laboratory was established at Beckenham and a new research team assembled. Here he soon became ab- sorbed in the British effort on the production de- gradation and synthesis of penicillin and was the first to isolate a crystalline derivative penillic acid.A new chemical block was built and the research team expanded considerably. When work on penicil- lin slowed down he began the extension of activities into all the fields of drug research associated with The Wellcome Foundation. He retired in 1948 having published over 30 papers. As an individual Smith was always modest and unassuming in manner and shunned publicity. He served on various committees on pharmaceutical matters but at these and other committee meetings he never said two words if one would do and often contributed little or nothing to the “public” part of the discussion. For the same reasons he rarely attended scientific meetings though he always en- couraged his people to do so arguing that only in that way could they know and be known.PROCEEDINGS As a research worker he was exact and exacting but scmpulously fair in his dealings with those who worked with him. He was always willing to help both in private and business life. He was a good friend. He insisted on keeping his laboratories in magnificent condition and those who have succeeded him are very grateful for the standards he set and are endeavouring to maintain them. For many years and up to the time of his death Smith was a very keen golfer and held various offices in the Dartford Golf Club sharing his enthusiasm with Mrs. Smith who survives him. W. M. DUFFIN. CECILIE MARY FRENCH 1915-1 962 DR.C. M. FRENCH was born in London on October 23rd 1915 and educated at Walthamstow County High School.From there she went in 1934 to Uni- versity College London where she held a Founda- tion Scholarship. In 1936 she obtained First Class Honours in the B.Sc. General degree in chemistry botany and zoology a rare achievement in these three subjects and a year later she obtained First Class Honours in the B.Sc. Special degree in chem- istry. She remained at University College to work under Professor C. K. Ingold and Dr. C. L. Wilson for her Ph.D. on the preparation and properties of hexadeuterodiborane. During this period she took a course at Sir John Cass College which enabled her to pass intermediate physics and was then admitted to the A.R.I.C. When subsequently she specialised in physical chemistry few realised that her consider- able knowledge of physics and mathematics was largely acquired by her own efforts in later life.With the advent of the war Dr. French spent a few months with Imperial Chemical Industries Limited General Chemicals Division Widnes. before taking up her first academic appointment as a demonstrator at Bedford College then evacuated to Cambridge. It was here under Professor J. F. Spencer that she began her work on magnetochern- istry. It was here too that she met Professor J. R. Partington and other members of the staff of Queen Mary College also evacuated to Cambridge. At a time when the war made experimental work difficult she gave Partington valuable assistance in the preparation and revision of his books.In 1945 she was appointed a Lecturer at Queen Mary College where she remained until her death. She was elected F.R.I.C. in 1947 became a Recognised Teacher of the University of London in 1948 and was awarded a London D.Sc. in 1956. In 1961 she became a Senior Lecturer at the College. Dr. French was an outstanding University teacher and will be remembered with gratitude by genera- tions of undergraduates in whose welfare she took a keen personal interest. She proved her ability during the difficult post-war years when classes were swollen with ex-servicemen and for a number of years she was also responsible for teaching the 1st M.B. students of the London Hospital. The energy she devoted to research may be judged by the fact that nearly fifty papers bear her name and twenty-three students working under her super-vision gained higher degrees.She had the knack of selecting research problems which were both in- teresting and fruitful and she was highly skilled in the lucid presentation of material for publication. Her research students would be the first to acknow- ledge the debt they owe her. She had great faith in their ability and they were left to work without inter- ference. At the same time she kept a close watch on the progress of each by frequent discussions written reports and group seminars. Until a Gouy balance was installed at Queen Mary College in 1951 Dr. French in association with Dr. V. C. G. Trew continued to use the apparatus at Bedford College for the measurement of diamag- netic susceptibilities of homologous series and ob- tained improved values for the CH increment.Then with D. Harrison using the new apparatus she developed a bond-additivity system in which the structural correction terms of Pascal were replaced by “bond interactions.” The success of the method was demonstrated by measurements on a series of oximes and an “end-effect” due to the characteristic groups in homologous series was observed. Magnetochemistry was also used to study the forces involved when transition-metal ions were ad- sorbed by silica gel. More recently in work with 3. H. JANUARY1963 Garside some diamagnetic complexes of molyb- denum in various valency states were shown to have an underlying temperature-independent paramag- netism thought to be compatible with ring structures involving oxygen bridges.Parallel with magnetochemistry Dr. French developed an extensive scheme of research into the electrochemistry of non-aqueous solvents. A series of papers was published on the conductance of solu-tions in which the solvent molecules were “large”. The solutions used were tetra-alkylammonium picrates or sulphonates dissolved in trialkyl and tri- aryl phosphates or phosphites. Observed anomalies were explained in terms of solvent-solvent and solvent-ion interaction. Conductance measurements were also carried out on tetra-alkylamrnonium salts in solvents of high dielectric constant namely N-methylformamide and N-methylacetamide.Large deviations of the slopes of the X-JC curves from the theoretical Onsager values were ascribed to the de- polymerising action of the tetra-alkylammonium ion. A series of e.m.f. measurements were carried out with D. Feakins to determine standard electrode potentials and activity coefficients in aqueous solu-tions of glycols and ketones (S) using the cell H,(Pt) [ HCI(m),x %S(lW-x) %H20IAgC1-Ag and the corresponding one with sulphuric acid as electrolyte and a mercurous sulphate-mercury elec- trode. The inadequacies of the Born equation were demonstrated and a striking correlation of the standard electrode potential on the molar scale with the volume fraction of water in the solvent medium was achieved on the basis of a model depending on specific solvation of the acid by water.Her most recent work in the electrochemical field was directed towards the deposition of boron and uranium from non-aqueous solvents. Dr. French was also active on the preparative side of chemistry and with J. M. Davidson she returned to a study of the compounds of boron the element which was the subject of her first research. By means of the ultraviolet absorption spectrum she was able to demonstrate the existence in solution of a solvated organic cation containing boron. This diphenyl-boronium ion was later isolated in a solid perchlorate salt as an adduct with 2,2‘-bipyridyl and diaryl- boron hydrides were investigated as a new class of electrolytes. With J. M. Smith she studied the syn-thesis from Grignard reagents of diarylchloroborines and their polymerisation in the presence of alumin- ium chloride.Some of Dr. French’s most recent research was sponsored by the British Empire Cancer Campaign. A combination of magnetic and electrochemical measurements was used in an attempt to correlate carcinogenic activity with physical properties. Sub- stances investigated included azo-compounds alkyl anilines azines and fluorenes as well as the com- pounds they form with the transition metals. Finally she turned her attention to enzymically catalysed reactions in order to see whether carcinogenic sub- stances could act as inhibitors. For this work her early training in biology provided a useful back- ground. It was when Dr.French was barely forty that the first signs of encroaching illness came. With great courage and determination as well as cheerfulness she continued her work as usual despite partial blind- ness and increasing disability. At this stage her long- standing practice of lecturing without notes was in- valuable to her. She learnt Braille and characteristi- cally gave her services to the National Institute for the Blind in advising them about the transliteration of scientific and mathematical symbols. Always a great traveller she lectured both in the Far East and in the U.S.A. where she spent a year at Pennsylvania State University. She was honoured by an invitation to return there to give the 1962 Marie Curie Lecture but did not live to make the journey.She died in an Epsom hospital on August 6th 1962. Dr. French lived almost the whole of her life with her parents and is survived by both of them. She was devoted to them and they in their turn gave her every assistance in her work. Her father a retired surveyor drew the diagrams for her papers. Their sense of loss wjll be shared by colleagues and former students now scattered in many parts of the world. D. M. GROVE. ADDITIONS TO THE LIBRARY Fourcroy chemist and revolutionary (1755-1 809). W. A. Smeaton. Pp. 288. W. A. Smeaton. Cambridge. 1962. Topics in chemical physics based on the Harvard Lectures of P. Debye A. Prock and G. McConkey. Pp. 277. Elsevier. Amsterdam. 1962. Spectroscopy.S. Walker and H. Straw. Vol.2. Pp. 386. Chapman and Hall. London. 1962. Chemical spectroscopy. R. E. Dodd. Pp. 340. Elsevier. Amsterdam. 1962. Tables of spectral-line intensities. W. F. Meggers C. H. Corliss and B. F. Scribner. (NBS Monograph 32.) 2 Vols. National Bureau of Standards. Washington. 1961. (Presented by the publisher.) Physical adsorption of gases. D. M. Young and A. D. Crowell. Pp. 426. Butterworths Scientific Publications. London. 1962. Experimental physical chemistry. W. G. Palmer. 2nd edn. Pp 321. University Press. Cambridge. 1962. (Pre-sented by the publisher.) Gas-liquid chromatography theory and practice. S. Dal Nogare and R. S. Juvet. Pp. 450. Interscience Publ. Inc. New York. 1962. Regular solutions. J. H. Hildebrand and R. L. Scott. Pp.180. Prentice-Hall. New Jersey. 1962. The principles and applications of cathode-ray polaro- graphy. R. C. Rooney. Southern Analytical Ltd. Camber- ley Surrey. 1962. (Presented by the publisher.) Autoxidation and antioxidants. Edited by W. 0. Lundberg. Vol. 1. Pp. 450. Interscience Publishers Inc. New York. 1962. Hydrogen compounds of the Group IV elements. F. G. A. Stone. Pp. 112. Prentice-Hall International. London. 1962. Clathrate inclusion compounds. Sister Martinette Hagan. Pp. 189. Reinhold. New York. 1962. Physical organic chemistry. J. Hine. 2nd edn. Pp 552. McGraw-Hill. New York. 1962. Solvolytic displacement reactions. A. Streitwieser. Pp. 214. McGraw-Hill. New York. 1962. Short chain branching in hydrocarbon polymers. D.A. Boyle W. Simpson and J. D. Waldron. (A.E.I. Research Series no. 83.) Pp. 10. Associated Electrical Industries. Manchester. 1962. (Presented by the publisher.) Polyethers. Edited by N. G. Gaylord. High Polymers. Vol. 13 (3). Pp. 303. Interscience Publ. Inc. New York. 1962. Acrolein. Edited by C. W. Smith. Pp. 273. J. Wiley and Sons. New York. 1962. Les cyclitols. T. Posternak. Pp. 491. Hermann. Paris. 1962. (Presented by the publisher.) Recent progress in the chemistry of natural and synthetic colouring matters and related fields. Edited by T. S. Gore et al. (Dedicated to Prof. K. Venkataraman in commemoration of his 60th birthday.) Pp. 659. Academic Press. New York. 1962. Methods of organic elemental microanalysis. G. Ingram. Pp.511. Chapman and Hall. London. 1962. The applications of organic bases in analytical chem- istry. E. A. Ostroumov. (Translated from the Russian by D. A. Paterson.) Pp. 159. Pergamon Press. Oxford. 1962. Analyse chimique; interpretation des resultats par 1e calcul statistique. Y. Lacroix. Pp. 68. Masson et Cie. Paris. 1962. (Presented by the publisher.) Comparative biochemistry a comprehensive treatise. Edited by M. Florkin and H. S. Mason. Vol. 4. 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ISSN:0369-8718
DOI:10.1039/PS9630000001
出版商:RSC
年代:1963
数据来源: RSC
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