PROCEEDINGS OF THE CHEMICAL SOCIETY APRIL 1961 CHEMICAL SOCIETY SYMPOSIUM Terpene Chemistry A CHEMICAL SOCIETY SYMPOSIUM on Terpene Chemistry was held at Imperial College on Thursday February 23rd. Sir Alexander Todd opened the meeting to a packed audience and extended a special welcome to the distinguished visitors from overseas. The morning’s session with Professor E. R. H. Jones in the chair began with a paper by Professor F. sorm on sesquiterpenes with ten-membered rings. Until recently compounds of this type were rare the first examples being pyrethrosin and germacrone. The speaker reviewed the chemistry of germacrone and showed how a combination of degradative and synthetic studies led to elucidation of its structure. The conversion of germacrone into p-elemone served as an example of the transannular cyclisations typical of this class of compound.A systematic sur- vey of plant material carried out in Prague has pro- vided interesting new examples of sesquiterpenes with ten-membered rings which now appear to be widely distributed in Nature. All these compounds contain y-lactone rings and can be related struc- turally either by cyclisation to a derivative of the santonin series or by hydrogenation to the basic ten- membered ring system. The chemistry of arctio- picrin cnicin and parthenolide provided examples of these methods. Work on the recently isolated balchanolide isobalchanolide hydroxybalchanolide and scabiolide has established the main structural features of these compounds balchanolide and iso- balchanolide may be represented by structure (I) differing only in the stereochemistry of the double bonds.Professor Sorm suggested that the ten-membered ring terpenes might serve as biogenetic precursors for compounds of the santonin type and in conclusion presented some quantum-chemical calculations on the anomalous ultraviolet spectra of germacrone and related compounds. In the next lecture Professor B. C. L. Weedon speaking on carotenoids showed in striking fashion how a combination of synthetic and spectroscopic methods may be used to elucidate the structures of these compounds. Nuclear magnetic resonance spectroscopy has proved particularly valuable ; the spectra are simple and it is possible to assign most proton bands with confidence.For example examinationof the proton spectrum of spirilloxanthin established the environment of its methoxyl groups while the position of the hydroxyl group in cap- sorubin (partial structure U) was indicated by the uniform deshielding of the three C-methyl groups in the corresponding ketone. In a similar way analysis of the nuclear resonance spectra of bixin spher- oidenone and spheroidene yielded valuable informa- tion. 129 Professor Weedon went on to describe recent synthetic work on the hydrolycopenes. Phytoene was obtained as a mixture of stereoisomers from which the trans-form was isolated. This differed from the natural material which probably has the cis-con- figuration about the central double bond.The all- transform of 5-carotene was also synthesised and shown to be identical with the natural product. In conclusion the conversion of canthaxanthin into astacene by autoxidation was described which com- pletes a total synthesis of this highly oxygenated carotenoid. The afternoon’s session was opened by Professor D. H. R. Barton who welcomed Professor 0. Jeger once more to Imperial College or as the speaker himself described it the “British Lions’ Den.” Ter- penes were first recognised as constituents of the essential oils used in perfumery and it seemed fitting that some reference to this application should be made at the Symposium. Professor Jeger’s paper concerned methods of degrading manool to give compounds having ambra odours.The stereochem- istries of manool sclareol and ambreinolide were outlined and oxidative degradation of these sub- stances described. The most potent ambra-smelling products were obtained by selective monoepoxida- tion of manool to give the a-epoxide (III) which after further transformations gave the spirocyclic ketal (I?/) together with an isomer differing only in the stereochemistry of the ketal rings. Paper strips impregnated with these ketals served to convince the audience of their value in perfumery. Professor Jeger concluded by showing how nuclear magnetic resonance spectroscopy was used to establish the stereochemistry of his compounds. As the chairman pointed out Professor Erdtman is an original man and he began by confessing to an early hatred of terpenes.Fortunately this dislike did not persist and for several years now a broad survey of the terpene constituents of conifer heartwoods has been in progress at Stockholm. During this work many important new sesqui- and di-terpenes have been isolated and their structures investigated al- though the isolation of even simple terpenes may be of taxonomic importance. The structure of thujop- sene (V) was convincingly demonstrated by a series of degradations and structures for the closely related hinokiic acid and widdrol were presented. The sesquiterpene p-himachalene is of special in- terest in that it is readily dehydrogenated to benzen- oid derivatives and like widdrol probably contains the unusual 6-7 fused-ring system.The chemo- taxonomic importance of the diterpenes was con- sidered next and the chemistry of torulosol and other compounds related to manool was discussed. Throughout his talk Professor Erdtman emphasised PROCEEDINGS the structural relations between compounds pro- duced by various orders of the coniferae and ended by appealing to natural-product chemists to study all species of a particular family and not merely the most accessible members. In recent years X-ray crystallographic analysis has been outstandingly successful in determining the structures of complex organic molecules. Professor J. Monteath Robertson gave an authoritative survey of X-ray techniques from the pioneering work of the Braggs up to the present time.The nature of the phase problem was discussed and the use of heavy atoms to overcome this difficulty explained. Com- putational difficulties may be surmounted with the aid of electronic computors and structures can now be determined with impressive speed. The recent work in Glasgow on limonin isoclovene caly-canthine and other complex molecules provided striking examples of the value of X-ray methods. Dr. G. A. Sirn followed with an enthusiastic account of an investigation of clerodin bromo-lactone. Pre- liminary examination of the X-ray data suggested a revision of the molecular formula to C,,H,,Br08 and this was supported by further analysis. Four cycles of calculations led to the complete structure (exclud- ing absolute configuration) of clerodin bromo-lactone and hence of clerodin itself (VI) although further refinement was needed to define the stereochemistry of the oxide ring unambiguously.The value of chemical insight during the early stages of an X-ray investigation was well illustrated by Dr. Sim’s talk. D 6Ac In answer to a question by Professor A. W. Johnson Professor Robertson explained that it is now possible to define the position of most hydrogen atoms in complex molecules though this is not normally necessary for structural purposes. Professor Barton’s paper was devoted to the terpenoid bitter principles and he began by referring to the structures of columbin and limonin. Non- alkaloidal bitter principles form an ill-defined class of natural products and the inclusion of clerodin in this class is therefore mainly a matter of taste.APRIL1961 Members of the audience courageously verified this by experiment. Chemical studies have established the main structural features of the clerodin molecule. The relative positions of the epoxide ring and acetoxyl groups were shown by an elegant series of transformations involving reduction with lithium aluminium hydride selective conversion into a mono- toluene-p-sulphonate oxidation and base-catalysed rearrangement. The presence of an enol ether sug- gested by infrared spectra was confirmed by the ready addition of acetic and hypobromous acid and clerodin hemiacetal acetate and bromohydrin could both be converted into y-lactones.Information about the carbocyclic rings was furnished by dehydrogena- tion of clerodin to 1,2,5-trimethyInaphthalene.Many details of the clerodin structure were revealed by nuclear magnetic resonance spectroscopy and Dr. Jackman followed with a lucid analysis of these spectroscopic findings. The value of nuclear mag- netic resonance techniques had been apparent throughout the Symposium and Dr. Jackman’s account re-emphasised their scope and importance in structural determinations. In the time remaining Dr. K. H. Overton gave a concise summary of work on the stereochemistry of columbin which has led to the structure (VII). The presence of the unusual C~S-A-B fusion presents a challenge to current theories of terpene biogenesis.The meeting adjourned in the evening to nearby Ayrton Hall for an informal dinner which was well attended. The success of the Symposium owed much to the quality of the papers presented and to the patient work of its organiser Professor Johnson. G. W. -BY. THE WINDAUS MEMORIAL LECTURE* By ADOLF BUTENANDT THEhistory of science can be built up from the biographies of those who by great discoveries in-fluenced the development of science and gave to their generation the problems for their research. The first half of our century is characterised by a rich harvest in the field of natural product chemistry many new classes of compounds were discovered and the constitution and physiological significance of many known substances were elucidated.Among these achievements the investigation of the sterols and steroids has an important place. We owe our in- sight into the structure and significance of these im- portant natural products largely to the work of Adolf Windaus in Gottingen who died on June 9th 1959 in the place where he had worked for so long. Adolf Windaus was born in Berlin on Christmas Day 1876 so that his life spans almost 83 years. He reached the zenith of his scientific career during the years 1923-1933 at Gottingen where at that time all branches of science were represented by men out- standing in research and teaching. In physics there were Max Born,James Franck Robert Pohl and Ludwig Prandtl ;in mathematics Richard Courant and Edmund Landau; in biology Alfred Kuhn Hermann Rein and Fritz von Wettstein; in geology Hans Stille; in astronomy Hans Kienle; and in mineralogy V.M. Goldschmidt.In chemistry Gustav Tammann Arnold Eucken and Richard Zsigmondy were active. The mathematician David Hilbert and the chemist Otto Wallach Windaus’s predecessor in the chair of chemistry once occupied by Friedrich Wohler were still alive. Adolf Windaus was working among these men when he achieved the great success that made his name famous outside the ranks of specialists the solution of the problem of the nature of the antirachitic vitamin D. In 1925 Alfred Hess of New York invited Windaus to take part in the investigation of the antirachitic vitamin D which would it was hoped cure rickets.Windaus who never forgot to accord to others the full credit due to them always used to point this out as the beginning of his work on vitamins and to emphasise that later as the work developed there was a frequent exchange of ideas between him and his English colleagues Heilbron Rosenheim Webster and others who were also working on vitamin D. We may ask ourselves how this invitation from Alfred Hess came about. It went to Adolf Windaus as the greatest expert of the time on the sterols and was the consequence of his painstaking investiga- tions of this class of substance. He had begun them at the age of twenty-five in 1901 at Freiburg-in- Breisgau in Killiani’s laboratory of medical chem- istry for his “Habilitation”; and he devoted himself primarily to them in the following decades at first alone and later with numerous pupils.“Uber Cholesterin” was the short title of the thesis that gained Windaus his “Habilitation” in the medicd faculty of the University of Freiburg. He had already passed his “Physikum” in his native city of Berlin in 1897 but then attracted by the problems of chem- istry he had done chemical research with Killiani and graduated Doctor of Philosophy in 1899. He received the honorary degree of Doctor of Medicine from Gottingen in 1927. * Delivered before the Society at Burlington House on May 5th 1960. 132 PROCEEDINGS Cholesterol occurs in every animal cell but in 1901 related to the bile acids which occur in bile and are its significance had not been recognised; and its nature was quite unknown in spite of many attempts by able chemists to determine its structure.It could only attract a young scientist who was not concerned with quick and striking success but was convinced that a primary constituent of animal cells which also occurs in a similar form in plants must have great importance and a connexion with the other materials concerned in the cellular processes. For that very reason Windaus undertook the great labour of determining the complicated structure of a molecule of the composition C27H4@ a task which was only finally completed in the year 1932 after other labora- tories (notably those of Heinrich Wieland in Munich Otto Diels in Kiel and Rosenheim and King in London) had brought the work of many hands to bear on this intractable material.Chole- sterol proved first to be the prototype of a class of closely related compounds the so-called sterols of the animal and vegetable kingdoms which were sub- jected by Windaus to comparative study. The an- nexed Table gives the names and molecular formulae of some important sterols. The saturated hydro- carbons from which they are derived all contain eight hydrogen atoms less than a paraffin which indicates the presence of a tetracyclic skeleton as a common structural feature. Some natural sterols Saturated Double parent bonds hydrocarbon Cholesterol C27H460 C27H48 Zymos terol Brassicasterol C27H440 C2,H4,0 2 2 C27H48 C28H50 Ergosterol Stigmasterol Fucosterol C28H440 Cz 9H480 C29H480 2 C28H50 C29H52 C29H52 Windaus’s conviction that the tetracyclic carbon skeleton present in these substances must also be present in other natural products was verified by experiment for the first time eighteen years after the beginning of the work on cholesterol.Windaus who had gone to the chair of medical chemistry at Inns- bruck in 1913 was invited to Gottingen in 1915 as the successor to Otto Wallach; and there in 1919 he achieved the transformation of cholesterol into cholanic acid which had already been obtained by Wieland from the bile acids. The annexed formula show the experimental relation of cholesterol to the bile acids the formulae being those accepted today which were then un- known.Thus it was shown that cholesterol is closely important for its functioning; it then became possible to carry over the results of the structural investiga- tions of each-of the bile acids by H. Wieland and of the sterols by Windaus-to members of the other class. This great achievement was announced at a meeting of the Gottingen Scientific Society on May 16th 1919; its further development led to the pro- posal of partial formula= for the sterols and bile acids and at the same time to new types of problem con- cerning the arrangement in space of saturated con- - HO@-@ Cholesterol Copcostone c27H46 0 57 H48 Cholanic acid 24 H4002 H densed hydrocarbons and thence to fundamental generalisations of stereuchemistry. Saturation of the double bond of cholesterol gives rise to two dihydro- derivatives cholestanol and coprostanol which both occur in Nature.After lengthy investigations Windaus showed that the difference between these alcohols probably lay in cis-or trans-fusion of two saturated rings. Cholest a no i cdprost a noI A/B-trans A/ 0 -C~S This new conception stimulated W. Hiickel in Windaus’s laboratory to carry out his classical in- vestigations of the stereochemistry of the decalins. He was able to show that a cis-and a trans-decalin in fact exist and that the ideas derived from the APRIL1961 133 steroids on the stereochemistry of fusion of saturated pathologist Alfred Hess to take part in the work on condensed ring-systems had revealed a generalisation vitamin D.of universal validity. qJ a:.:::>H Quite independently and without recognisable H connexions with sterol chemistry there had de veloped a knowledge of vitamins substances that H must be taken up in very small concentrations in food if the processes of life are to proceed normally. If vitamin D is lacking irregularities of growth occur trans cis Decalin At the same time it became evident that the cholanic acid (from which the bile acids are derived) and coprostanol belong to the series in which rings A and B are cis-fused. During the investigations on cholesterol Windaus made incidentally the important discovery of the addition compound between cholesterol and digi- tonin. This finding explained Ransom’s earlier ob- servations that the hamolytic action of the saponins is abolished by choIestero1; Windaus recognised that complex formation is the cause of this phenomenon.In the meantime the number of natural products allotted to the sterols and bile acids increased rapidly but understanding of their complicated structure came more slowly. On May 30th 1919 Windaus proposed for the first time a possible type of struc- ture (A)-again to the Gottingen Scientific Society. Cholesterol OH 1919 (A) The time available in a short lecture allows one neither to follow the experimental route that led to the proposal of this first formula nor to trace the tortuous paths that led to its correction to that now established. It has already been mentioned that the fund of ideas of several groups of workers in England and Germany is reflected in the final structure of the so-called “sterane skeleton” composed of three six-membered and one five-membered ring.Today we even have several methods available for the total synthesis of cholesterol it was one of the highlights of the XIIth International Chemical Congress in New York (1951) when Sir Robert Robinson and R. B. Woodward reported the first total syntheses of the sterane skeleton and of cholesterol. Let us return however to the year 1925. Adolf Windaus could then indeed be regarded as the greatest expert on the sterols; and it was this that brought him the invitation from the New York on account of insufficient deposition of calcium salts in the bones of the young organism; the symptoms of rickets appear.Cod-liver oil had long been known as a cure for or preventative of rickets. But in 1919 the Berlin pediatrician Huldschinsky found a second protection against rickets ultraviolet irradiation of the child. It was not at first assumed that the two methods-oral administration of liver oil and ultra- violet irradiation-acted in the same way; and it was regarded as the classic example of a disease that could be cured either specifically with vjtamin D or unspecifically by raising the general level of resist- ance by irradiation. Then however Hess and Steenbock in the United States made independently the surprising discovery that it is not necessary to irradiate the sick child or the rat diseased with rickets but that it is sufficient to irradiate the food with ultraviolet light.This startling result could only be explained by assuming both the skin and the food contain a substance that is transformed by ultra- violet irradiation into vitamin D thus possessing the properties of a vitamin precursor a pro-vitamin D. The action of the therapy by light was thus attributed to a chemical process leading to the formation of a vitamin. The pro-vitamin that could be activated by ultraviolet light was found in the fractionation ex- periments of American and English authors (Hess Steenbock and Rosenheim) in the sterol fraction of the food. At first it seemed as though cholesterol it- self could be activated although curiously no chem-ically measurable changes could be observed on irradiation of cholesterol.That was the mysterious situation in which Windaus was asked for help and co-operation. In collaboration with the Gottingen physicist R. W. Pohl he was able to obtain the results that were published in 1926 and 1927. Independently of 0. Rosenheim and of Heilbron Kamm and Morton Windaus and Hess reported that it was not chole- sterol itself that could be activated but an impurity present in it in very small quantities. Cholesterol purified only by physical methods possesses a charac- teristic absorption at 280-300 mp which is destroyed by ultraviolet irradiation; it is due to the impurity. From the properties of the impurity Windaus concluded that it must be similar to the ergosterol that occurs in yeast.In fact the ergosterol present in yeast proved to be a pro-vitamin which at once was regarded by Windaus as a possible proto- type of further vitamin D precursors of similar struc- ture. A little later a dehydrogenated cholesterol with a structure similar to that of ergosterol the so-called 7-dehydrocholesterol was prepared by a chemical method from cholesterol and recognised as the pro- vitamin that is transformed into the vitamin D that occurs predominantly in cod-liver oil. PROCEEDINGS last two are formed by over-irradiation. The constitu- tions of vitamin D, lumisterol and tachysterol can now be discussed. Vitamin D2 HO HOw-:o&-' Windaus proposed for vitamin D the structural 6 - 6 ErgosteroI I"" 7-Dehydrocho lesterol Pv Vitamin D Vitamin D The annexed formulae show the established struc- ture of the fungal sterol ergosterol with its charac- teristic arrangement of two conjugated double bonds in positions 5,6 and 7,8 which are necessary for pro- vitamin properties.7-Dehydrocholesterol contains the same conjugated system and differs from ergo- sterol only in the structure of the side-chain. Both substances can be activated by ultraviolet irradiation; Windaus called the vitamin formed from ergosterol vitamin D2, that obtainable from dehydrocholesterol vitamin DS. In 1936 Brockmann in Windaus's labora- tory succeeded in isolating the natural vitamin from tunny-liver oil; it proved to be identical with itamin D3.After the discovery of the susceptibility of ergosterol to ultraviolet activation the remarkable investigations on the constitution of ergosterol and of the processes that take place on irradiation were carried out in the laboratory at Gottingen. From 1930 onwards it became apparent that irradiation of ergosterol leads to a series of transformation pro- ducts most of which were isolated as individual substances. Apart from vitamin D, which was called calciferol by the English group of workers at the National Institute of Medical Research lumisterol tachysterol and two suprasterols were isolated. The formula (I)which in the light of Dorothy Crowfoot's X-ray analysis is better written in the form (II) which certainly is present in crystallised preparations; in solution an equilibrium between the two forms may exist.It can be seen that ring B has been opened between the carbon atoms 9 and 10 with the forma- tion of a new double bond. Vitamin D is a tricyclic system with three conjugated double bonds. This constitution has been established by a series of unambiguous degradation reactions. o=c O/ H CH U Vitamin D2 HO With ozone vitamin D gives besides formalde- hyde and 2,3-dimethylbutanol the bicyclic keto-acid CI3H2,,O3 (III). By careful oxidation with chromic acid Heilbron obtained the $-unsaturated aldehyde CZ1H,,O (IV) which can easily be split out of vitamin D2by cleavage between carbon atoms 5 and 6. APRIL1961 Ring A of the vitamin was isolated by a particularly interesting transformation of the molecule vitamin D acetate reacts with maleic anhydride to give the adduct 0,which on dehydrogenation with selenium yields 2,3-dimethynaphthalene (VI) ; its formation could be explained by the unprecedented reduction of a carboxyl group to a methyl group which was demonstrated in model experiments.Thus the constitution of vitamin D was unambiguously established. The vitamin D3formed from cholesterol differs from the transformation product of ergosterol -as already stated-only in the structure of the sidechain; the recent total synthesis by H. H. Inhoffen sets the final seal on the chemistry of the anti-rachitic vitamin. ? F HO HO Ergostir0I (VII) Lumistero I R HO OH2 ?J OH Lumisterol is closely analogous in its chemical behaviour to the parent substance ergosterol; it proved to be a stereoisomer (VII) differing from ergosterol in the configuration at C(lol whereas tachysterol like vitamin D2 contains three con- jugated double bonds and three rings.To it was allotted structure (VIII) which was supported by the production of identical hydrogenation products from vitamin D and tachysterol. According to Inhoffen tachysterol has the stereochemical formula (VUI). 4 P -NO-EtOH H3C0*H 01I I) D1 hydrotachysteroI “AT 10” Reduction of tachysterol with sodium and alcohol produces among other products a dihydrotachy-sterol with two remaining double bonds in conjuga-tion.This compound shows no antirachitic properties according to investigations by F. Holtz in the labora- tory at Gottingen; but it raises the level of calcium in the blood-serum and is used in the treatment of idiopathic and hypoparathyroid tetany. In Germany it is called AT 10 (anti-tetanus preparation number 10). In what order and under what conditions are these products formed from ergosterol? In 1932 Windaus proposed a photochemical reaction sequence in Ergosterol -Lurnrsterol -Tachysterol Suprasterol I c ‘Vitamin o Suprasterol II. J which vitamin D2was supposed to be formed irre- versibly by way of lumisterol and tachysterol. Today we know more about this remarkable photoiso- merisation. From recent investigations by Velluz in Paris supplemented by the work of Havinga in Leiden it appears that the sequence of reactions should be written as shown in scheme A.The special Scheme A P Ergostero I (VII) Lurnisterot hvlt hv r OH HO (VII I> Tachysterol (I) Vrtamln D characteristics of this reaction scheme lie in the dis- covery of a further transformation product isolated in a pure state by Velluz pre-vitamin D (IX),which is considered to be formed together with lumisterol and tachysterol from a photochemically excited state of ergosterol postulated by Havinga. All the reactions are reversible. According to Velluz vitamin D is not formedin a direct photochemical reaction but exists in thermal equilibrium with the pre-vitamin. This scheme represents a considerable advance on our knowledge but it seems possible nevertheless that it does not yet give a complete expression of what happens.This chain of photochemical reactions is so far unparalleled in organic chemistry and therefore deserves special attention. It is hardly possible to decide where the greatest importance of this work lies in the determination of the constitution of vitamin D; in the extension of our knowledge of the importance of the sterols in the maintenance of life; in the analysis of photochemical processes; or in the practical effect that they had subsequently on the successful treatment of rickets with vitamin D preparations. We know that Adolf Windaus who sought to use his own words “not practical successes but scientific understanding,” felt with his characteristic modesty that each of these results was a gift.In the year 1928 this work was recognised by the award to him of the Nobel Prize for Chemistry. The further development of sterol chemistry after the determination of the structure of vitamin D has become almost a legend. Not only the bile acids and vitamin D proved to be related to cholesterol the supposition that was early expressed by Windaus that the animal and vegetable cardiac poisons the toad venoms and Digitalis substances which he in- vestigated at length together with some vegetable frothing agents the saponins are closely related to the sterols. The results of the research on the sex hormones and the hormones of the adrenal cortex were of particular importance for physiology and medicine both the indispensable male and female sex hormones oestradiol progesterone and testo- sterone which are necessary for the reproduction of man and higher animals that is for the perpetuation of the species; and also the hormones of the adrenal cortex the cortins including the clinically important cortexone cortisone and dehydrocortisone which are necessary for the continuance of an individual life proved to be sterols.Nowadays one includes all these compounds according to a suggestion by Callow and Young in a great new class of com- pounds the “steroids.” The chemistry of the steroids is today being investigated in many laboratories throughout the world in universities in research institutes and in industry.The number of publica- tions appearing daily which reflects the importance of these compounds to modern medicine has become almost too large to scan. The spring tapped by Windaus has developed to a great stream with many branches and we stand full of admiration and reverence before the conviction of this man who with the intuition of genius foresaw these developments from the beginning. At a time when many of his colleagues even distinguished ones PROCEEDINGS from whom this trait of genius remained hidden regarded Windaus as a chemist who “was only in- terested in cholesterol,” he himself was able para- doxically to declare that he was not interested in the chemical constitution of any particular substance but only in the great relationships between natural products.The great realm of the steroids has been conquered by many chemists since the ’thirties; some were Windaus’s pupils and all built on the founda- tions of careful research on the sterols that he had laid without which the investigation of the physio- logically important steroids would have been unthinkable. Even the development of the chemistry of the sterols in the hands and under the influence of Windaus that I have sketched makes it clear that he was anything but one-sided. He showed greatness in confining himself to the essential and the reasonable and he knew the limits of what was possible at the time; but he saw the breadth and depth of a room even before the outer door to it had been forced open.Apart from the field of research with which he was principally associated one should not forget how rich was the harvest that he gathered in other fields of natural product chemistry; nor the many subjects on which he stimulated his collaborators to work leaving them afterwards with exemplary selflessness to continue independently. In this way he helped his pupils forward left them to develop by themselves and founded a school of the first rank. We must remember the series of investigations that the young Privatdozent in Freiburg undertook at the same time as his work on cholesterol in col- laboration with Franz Knoop which indeed first made his name known. The idea that one might get on the track of the conversion of sugars into proteins by HF=O C,H,,O -$.=O + m,o CH3 Glucose Meth y I g I yoxa 1 H3N +O=$-CH -N-C-CH, -3H,O II u HCH=O O=CH HC\*I/~ IY // 4-Methyl imidazole HN-$*CH 5-Methyl imidazole I C~ C%N/ treating them with ammonia and that one might in this way be able to obtain the fundamental com- ponents of proteins the amino-acids led to a surpris- ing observation.The original idea was wrong but derivatives of imidazole were obtained. If glucose is treated with ammoniacal zinc hydroxide it is split first into methylglyoxal which can be trapped as the osazone and into formaldehyde. The two com-ponents then react with the molecules of ammonia APRIL1961 forming methy limidazole. This discovery was followed by closer investigation of this newly accessible class of compounds in the course of which the amino- acid histidine was recognised as an imidazolylalanine and histamine was discovered this tissue hormone is of particular interest in physiology and pharma- cology having a strong action which can still be detected at a dilution of I 2 x lolo.Histamine affects the peripheral circulation by dilating the capillary blood vessels appears in increased amounts in allergic reactions produces a contraction of the smooth muscles of the uterus and stimulates intestinal peristalsis. In 1929Windaus wished to return to the chemistry of the imidazoles to which he had devoted no atten- tion for a long time. The antineuritic vitamin B1 the absence of which is partly responsible for the symptoms of beri-beri was isolated by the Dutch workers Jansen and Donath and according to the first analyses it had a composition consistent with its being an imidazole derivative.In order to test this and to make use of his old experience Windaus took up the determination of the structure of vitamin B1 with a series of collaborators. It was soon shown that the formula proposed by the Dutch workers was not correct; they had overlooked the fact that the vitamin contained sulphur which was discovered in Gottingen. Although this result destroyed the hope of finding a new natural imidazole and an increased importance for this class of compound the structural investigation of vitamin B was continued and the group of workers in Gottingen made important con- tributions to the elucidation of its complicated consti- tution and the subsequent technical preparation of this important remedy.Of the remaining natural products on which Windaus worked some while he was still in Freiburg I shall mention only the alkaloid of the autumn crocus colchicine which was later recognised by other workers as representative of a new class of compounds with an unsaturated seven-membered ring with a tropolone structure; in colchicine was observed for the first time the genetically important activity of a so-called “mitotic agent” which pro- duces polyploids. I shall now leave the scientific work of Adolf Windaus. A man appears indeed most clearly in his life’s work but it cannot reflect every side of his being.Lastly I must try to complete the picture. One likes to ask how a distinguished scientist comes to start his work what led up to the hour in which he decided on his life’s work by the choice of his problem. It is remarkable that the tradition of his home did not point the way for him to scientific research. His paternal forefathers had been weavers clothiers and manufacturers for more than two hundred years and his mother’s family were mostly artisans. At the Gymnasium in Berlin there was practically no scientific instruction :German and foreign literature fully occupied the boy’s time; but the idea came to him that “literature provides an occupation for the dilettante but not a vocation.” In his last years at school he heard by chance of the discoveries of one Robert Koch and of one Louis Pasteur; they inspired him and made him resolve to study medicine.Al- though his widowed mother would have liked him to enter the family business she did not infiuence his choice of profession. He remembered her with grati- tude in his inaugural lecture before the Prussian Academy of Sciences in 1937 With the words “The good fortune was granted me to discover in my formative years that the work for which I was best suited was also the work which gave me the greatest pleasure.” The young medical student could not however muster any interest in the anatomical lectures and paper exercises; on the other hand the great chem- ical lectures of Emil Fischer thrilled him.It was he who aroused Windaus’s enthusiasm for chemistry and convinced him that this science was destined to elucidate the processes of life. Windaus decided after the Physikum to train himself thoroughly in chem- istry and he relates himself that the chemistry in Killiani’s institute attracted him more and more. “At the beginning,” he writes “I used to go to some of the usual medical lectures but I neglected medicine more and more and finally gave it up entirely.” Instead there developed a delight in finding out the composition of substances and there appeared a fundamental characteristic of the future experi- menter which he himself later describes as follows “The starting point of my work was always an experi- mental observation and not a theoretical deduction.It seems that the inductive method suits me best.” How characteristic of him is the objectivity and modesty of this self-analysis! We have already dared to speak of his intuition of genius but we must not do so without adding that Adolf Windaus himself would have disclaimed it. He taught his pupils per- severance and tolerance care and concentration as the qualities that promise success. Now we approach Windaus as a human being. His unassuming and amiable character his objective out- look and his way of giving everyone his due had a strong influence on those round him and especially on his pupils. He seldom praised and he reproved as a rule only by silence; he spoke clearly but little and rhetoric seemed to him repugnant and poetical quotations superfluous.In the Institute the power that radiated from him helped our work enormously and stilled every angry word and every unnecessary PROCEEDINGS quarrel. His sense of justice and his love of truth who repeatedly tried to injure him and his Institute. brought Windaus into dangerous opposition to the Adolf Windaus was one of those great personal- despots of National Socialism to whom he would ities whose existence one feels to bring bothablessing make no concession. The openness courage and and an obligation in the ordering of one's own life uprightness with which he confronted the years because the nobility of their lives sets an example to between 1933 and 1945 blunted the weapons of those others.COMMUNICATIONS cis-and trans-PerfluorodecaIin By B. J. K. SMITHand C. R. PATRICK (CHEMISTRY UNIVERSITY DEPARTMENT OFBIRMINGHAM) DURINGgas chromatography of the products of structural assignments are those based on the inter- fluorination1 of tetralin with cobaltic fluoride it was pretation of the nuclear magnetic resonance spectra observed that the elution bands corresponding to but it is noteworthy that the properties of the two perfluorodecalin were consistently unsymmetrical isomers of decalin differ in the same senses4 although and unexpectedly broad. It was thought that this the differences in boiling points and refractive indices might be due to the incomplete resolution of two are greater. components emerging almost simultaneously from the column.About 4 g. of perfluorodecalin were cis-trans-therefore passed through a preparative-scale gas- M.p. -7.0" f0.5" 17.5" f0.5" chromatography column (length 16' diam. 3"; 1:2 B.p. 142.5" f0.5" 141-0" f0.5" silicone elastomer E30l-kieselguhr; 90"; nitrogen nlSD 1-3179 1.3148 flow rate 41 IJhr.) and the leading one-third and the trailing one-third of the eluted band were collected The boiling points were measured by Siwoloboffs separately. Both these fractions gave analyses correct method but experiments with liquids having known for perfluorodecalin but they showed different infra- boiling points of about the same values confirmed red spectra melting points and refractive indices. that the small difference reported is significant.Nuclear magnetic resonance showed that the two fractions contained differing proportions of cis-and The trans-compound has the simpler infrared trans-perfluorodecalin. Subsequent more elaborate spectrum. The major differences between the two fractionation by gas chromatography almost com- spectra in the region 800-1000 cm.-l are that the pletely resolved the two isomers. This seems to repre cis-isomer shows bands at 820 863 and 985 cm.-' sent the fist report of a satisfactory resolution of a which are absent from or very weak in the spectrum saturated fluorocarbon into its stereoisomers. In the of the tram-compound. Other differences in the hydrocarbon field decalin has been resolved into its spectra in the nature of differing grouping or two isomeric forms by gas chromatography.2 How- relative intensities of the bands OCCUT in the region ever the separation of the isomers of decalin appears 1OOO-1400 cm.-l.to be easier than of perfluorodecalin owing to the The samples of perfiuorodecalin (b.p. 141-143") nearly complete resolution of the hydrocarbon into isolated from the products of the fluorination of two bands on elution from the gas-chromatography tetralin over cobaltic fluoride and usedfor the isola- columns used in the present work. tion of the isomers in the present work appear to be The properties of our purest isomers of per-slightly richer in the cis-isomer. fluorodedin are tabulated below. The purity of the cis-perfluorodecalin was estimated by nuclear mag- One of us (B.J.K.S.) is indebted to the Imperial netic resonance spectroscopy and by infrared Smelting Corporation for the award of a mainten- spectroscopy as greater than 95% and that of the ance grant.trans-perfluorodecalin was greater than 90 %. The (Received February 16th 196 1 .) Barbour Barlow and Tatlow J. Appl. Chem. 1952 2 127. a Kovats Simon and Heilbronner Helv. Chim. Ada 1958,41,275. * Homer and Thomas following Communication. Seyer and Walker J. Amer. Chem. SOC.,1938,60,2125. APRIL1961 139 The Nuclear Magnetic Resonance Spectra of cis-and trm-PerfIuorodecalin By J. HOMER and L.F. THOMAS (CHEMISTRY DEPARTMENT, UNIVERSITY OF BIRMINGHAM) IThas been shown1 that the high-resolution nuclear the nuclei most remote from the adjoining ring which magnetic resonance spectra at room temperature of have the large axial-equatorial shift (21.9 p.p.m.) cis-and trans-decalin differ in form because the comparable with the value of 18-2 p.p.m.for per- molecule of the former undergoes relatively rapid fluorocyclohexane? Assignment within the group is interconversion between two conformations whilst the latter has a more rigid structure. We have found 6 (PP-".) that the fluorine resonance spectra of the perfluoro- decalins2 show similar effects which afford a ready means of distinguishing the two isomers. In addition the greater chemical shifts characteristic of 19F spectra permit a more complete analysis. The spectra in the Figure were obtained from the undiluted liquids at 34" with a Mullard SL44 Mk 1 spectrometer operating at 30.107 Mc./sec.Frequency measurements were made by the usual side-band technique with a capillary of trifluoroacetic acid as external reference. For true comparison of chemical shifts between the isomers and with perfluorocyclo- hexane spectra were also measured in solution in carbon tetrachloride and extrapolated to infinite dilu- tion. All signals were broad compared with the reference absorption and this is attributed to un- Av (c./sec.) resolved coupling between nuclei in different positions in the molecule. based on the relative broadness of peaks 1 and 3 In the spectrum of the trans-isomer the group I compared with 6 and 7 which suggests that the absorptions form a type AB q~adruplet,~ the assign- former arise from nuclei which are more strongly ment of which is made on the assumption that it is coupled to those on adjacent carbon atoms.This is The fluorine magnetic resonance spectra of cis-and trans- per-uoro- decalin Peak dv" Assignment (c./sec.) 2 3 6 7 ax 60-4 62*gC 2 1192 47-0 (6) (1790) 8 3350 9 10 109-8 5 1643 impurity (cis) Cis 1 2 3 1363 1647 3375 1 4 5 8 pairs 2 3 6 7 pairs9,lO 42.6 52.1 109-7 53~8~ a From external reference in neat liquid. Absolute frequencies are f0*02% internal consistency f 2 c.1~~. b Extrapolated to infinite dilution in CCl (5 0-2 p.p.m.). c Data of Tiers (ref. 4) superimposed on extrapolated single peak value. Musher and Richards Proc. Chem. Soc. 1958,230. Patrick and Smith preceding Communication.a Bernstein Pople and Schneider Canud. J. Chem. 1957,35,65. Tiers Proc. Chem. SOC.,1960 389. most likely to occur with the axially disposed nuclei each of which is trans to a neighbouring nucleus. The geminal coupling constant JFp = 281 c./sec. is comparable with that observed in perfluorocyclo- hexane4 and other highly fluorinated cycl~hexanes.~ Group LT is probably another AB quadruplet in which the two centre components are merged into peak 4. The high-field component of this multiplet was resolved at the appropriate position to low field of peak 6 in a spectrum taken at 37.635 Mc./sec. and Jm is again about 280 c./sec. but the shielding difference in this case is small owing presumably to the proximity of the second ring.In contrast the spectrum of the cis-isomer Feeney and Sutcliffe Trans. Fmaday SOC.,1960,56 1559. PROCEEDINGS indicates rapid interconversion between conforma- tions resulting in loss of axial/equatorial identity of the nuclei so that ring position becomes the sole factor affecting shielding. It is assumed that the nuclei furthest from the ring junction have the shielding value closest to that in the interconverting perfluorocyclohexane molecule in which case the effect of the second ring is to decrease the shielding of the adjacent CF groups by about 10 p.p.m. We thank Mr. B. A. Evans of Mullard Research Laboratories for recording spectra at 37.635 Mc./sec. and D.S.I.R. for a grant towards the spectrometer and a maintenance grant (to J.H.).(Received February 16th 1961 .) THEinequality of phenyl and deuterophenyl groups can in principle be a source of asymmetry. We have used this difference in isotopic substitution of the two grwps to obtain asymmetry in the diphenylmethyl system and now report the optical resolution of C,H5-CH(OH).C6D5 and Of C,H5-CD(OH).C,D5. The former compound was resolved by repeated fractional crystallisations of the brucine salt of its hydrogen phthalate. To avoid autocatalysed decom- position and minimise contamination by brucine phthalate which is produced during the dispropor- tionation of the acid phthalate to the neutral phthalate ethyl acetate solutions of the hydrogen phthalate and brucine were kept in the cold and fre- quently filtered.The filtrate was then left in a desic- cator over light petroleum (b.p. 40-60"). After a few days a precipitate had been formed repeated re- crystallisation of which from acetone and methylene chloride yielded on decomposition a hydrogen phthalate m.p. 160" [a] + 1.4"(in C,H,) (Found equiv. 337. C21HllD504 requires equiv. 337). The ester was decomposed in strongly alkaline 96% ethanolic solution. Recrystallisation of the alcohol from light petroleum (b.p. 40-60") gave needles m.p. 69" [a] + 0-8 (in C,H,). For preparation of optically active C,H,-CHCl-C,D, the alcohol was treated with thionyl chloride in the presence of 2,6-lutidine at low temperature in absence of solvent. The resulting chloride had [a] -0.36". Resolution of C,H,-CD(0H) C,D and prepara- tion of optically active C,H5.CDC1.C6D has been achieved by similar methods.In 80% aqueous acetone at 25.0" the rates of loss of optical activity of the two chlorides were ca. 3 times greater than the initial rates of solvolysis and ca. 2.5 times greater than the sum of rates of radio-chlorine exchange and solvolysis. a-Deuteration de- creased the rate of solvolysis in 80% aqueous acetone at 25.0" by a factor e-DIc-H, of 0.865 and that of loss of optical activity by a factor k"iD/kTH of 0.87. The replacement of phenyl by pentadeuterophenyl increases the rate of i0nisation.l We find for solvolysis the factor k2D /k2Hbof 1.1 1 for each phenyl group. Indeed the replacement of both phenyl groups increases the rate of solvolysis by a factor of 1.23 = (l-ll)z.The alcohol isolated during the solvolysis of the a-deutero-chloride is optically inactive and the chloride isolated after 10% solvolysis is ca. 18 % racemised. The rate of radio- chlorine exchange accompanying solvolysis is some what larger than that associated with a mass-law effect and this difference increases with increasing concentration of chloride ions; even larger differences were observed with t-butyl chloride 3-chloro-3,7- dimethyloctane and 1-phenylethyl chloride.2 We suggest that the racemisation involves ion- pairs.3 At this stage of ionisation most ion-pairs return with retention of configuration but some of 1 Kresge Rao and Lichtin Chern. and Id. 1961 53; Klein and Streitwieser jun. ibid.p. 180. 3 Pocker unpubhshed work. * Pocker Trans. Furaduy Soc. 1959,55,1266; Winsteh Gall Hojo and Smith J. Amer. Chem. SOC.,1950,82,1010; Winstein Hojo and Smith Tetrahedron Letters 1960,22 12. APRIL1961 141 the pairs exist for long enough to allow one ion to rotate relatively to or to slide over its partner thus producing ion-pairs of opposite configuration faster {free energy lower) that the pairs can escape from their common solvation cage. As the capacity to dis- sociate decreases racemisation becomes progressive- ly faster than chemical capture. Thus while in more aqueous solvents the rate of loss of optical activity approaches the sum total of chemical capture in liquid sulphur dioxide the two chlorides racemke ca.100 times faster (and in nitromethane ca. 20 times faster) than they undergo radiochlorine exchange with tetraethyl- and tetrabutyl-ammonium radio- chloride. In accord with these conclusions we have also shown that an a-hydrogen atom is not necessary for relatively fast racemisation to be found in arylalkyl systems. Indeed the rate of racemisation of the tertiary chloride (-)-Ph-CClMeEt is faster in liquid sulphur dioxide and in nitromethane than the combined rates of elimination and radiochlorine exchange with saline radiochloride in these solvents. (Received March 1st 1961.) The Mechanism of the Gas-phase Claisen Rearrangement of AUyl Vinyl Ethers By Y.POCKER RAMSAY LABORATORIES COLLEGE and (WILLIAM AND RALPHFORSTER UNIVERSITY LONDON OF CHEMISTRY UNIVERSITY INDIANA, DEPARTMENT INDIANA BLOOMINGTON U.S.A.) THErearrangement of ally1 vinyl ether (I) to pent4 enal (IV) in the gas-phase in well-seasoned vessels has been found to be a homogeneous first-order reac- tion in the pressure range 150-4oOmm.l The negative entropy of activation -7.7 cal.deg.-l mole-l at 180° is consistent with the assumption that the activated complex is cyclic.2 The ring size cannot however be deduced from theoretical calculations because of the uncertainty as to what correction factor we should use in our rotational partition functions to account for the fact that rotations round each bond are partially restricted. In principle two independent intramolecular paths can be envisaged one involving a four- (11) and the other a six-membered activated complex (111).By unambiguous single and double isotopic labelling we have deter- mined the predominant reaction path.CH,= C,H ,CH2-CH H2C \O CH=CH (I") Pent-4-enal produced in the homogeneous gas- phaseisomerisationof CH =CH.0-14CH,CH =CH contains more than 97% of its label in the form of 14CH =CHCH,CH,CHO confirming that the rearrangement is intramolecular and indicating that the activated complex consists of a six-membered ring. In accord with this we find that the pent-6enal pro- duced similarly from CH =CH.O*CH,.CH =14CH contains > 1% of its label in the form of 14CH2=CHCH,CH,-CHO. Indeed on this evi- dence the isomerisation route via the four-membered activated complex if occurring at all cannot occur to an extent larger than 1%.Actu-ally the formation of very small amounts of lWH2 =CHCH,.CH,CHO accompanying the major product from CH2=CH.0CH2-CH=14CH might be due to the fact that even in well-seasoned vessels only 98 % of the isomerisation is intramolecular; intermolecular component of ca. 2 %couldin principle lead to equal amounts of 14CH =CHCH,CH,CHO and CH =CH.14CH ,.CH,.CHO. As additional mechanistic evidence concerning the intramolecular nature and the topological configuration of the activated complex we find (a) that the doubly labelled compound CH =CH.0*14CD2-CH =CH isomerises in the gas phase to give > 97 % of 14CD2=CHCH2-CH2CH0 and (b) that the doubly labelled compound CH2=CD-O.l4CH2-CH=CH isomerises predomi- nantly (> 96 %) to 14CH2=CH-CH,-CH,-CD0.By extending the kinetic measurements to low pressures we have established an enhancement in the fall-off in the first-order rate coefficients at pressures below 1 mm. Isotopic product analysis indicated that in this region the reaction is similarly intramolecular occurring predominantly through an activated six-membered-ring complex. The fall-off in the first- lSchuler and Murphy J. Amer. Chem. SOC.,1950 72 3155. Stein and Murphy J. Arner. Chem. Soc. 1952 74 1041. PROCEEDINGS order rate coefficients at these low pressures is thus unambiguously a true Lindemann-type fall-off con- firming the unimolecular nature of the isomerisation process. CH,= C,H The topology of the activated complex and the intramolecularity of the isomerisation process do not in fact tell us about the exact timing of the C-0 bond-breaking relative to the C-C bond-forming process.We have however shown that the rate of loss of optical activity in the homogeneous gas-phase reaction of optically active 1-methylallyl vinyl ether (V) at 180” is practically the same as that of its isomerisation to hex-4-enal (VI) so that the C-0 bond-breaking cannot be too far advanced over the C-C bond-making. This shows that these processes are sufficiently synchronous to allow them to be classified as concerted and indicates that there is no necessity to invoke “intimate” and “oriented” ion- pairs radical pairs or charge-transfer complexes to explain the homogeneous gas-phase isomerisation of simple ally1 vinyi ethers at temperatures around 200”.(Received February 13th 1961.) The Interaction between Aluminium Chloride and Aromatic Hydrocarbons By J. J. ROONEY and R. C. PINK OF CHEMISTRY THEQUEEN’SUNIVERSITY (DEPARTMENT OF BELFAST) THEformation of radical ions from hydrocarbons by the action of complexes of aluminium chloride with nitromethane or nitrobenzene has recently been reported by Buck Bloemhoff and Oosterhoffl and attributed to the strong electron-acceptor properties of the Lewis acid-nitro-compound system. We have now been able to show by the electron- spin resonance technique that aluminium chloride a itself acts as an electron-acceptor with aromatic hydrocarbons and that in suitable cases radical formation occurs in the absence of an additional electrophilic agent such as nitromethane.Anthracene chrysene or perylene when intimately mixed with freshly sublimed aluminium chloride rapidly de- veloped the characteristic colour of the hydro- carbon free radical and the coloured mixtures showed strong electron-spin resonance absorption. The partly resolved spectrum obtained with anthra- cene is shown in Fig. la. Similar results were obtained with a commercial grade of aluminium chloride and with a pure sample prepared from dry chlorine and aluminium containing less than 0004% of iron. Strong electron-spin resonance absorption was also observed when the freshly powdered chloride was added to solutions of anthracene or chrysene in carbon disulphide or chloroform (cf.Figs. lb and b lc) or when anthracene was added to a freshly pre- pared solution of aluminium bromide in benzene. Comparison of the spectrum obtained with anthracene in carbon disulphide with that obtained under identical instrumental conditions with the hydrocarbon in 98% sulphuric acid (Fig. Id) identifies the radical as the positive ion formed by direct transfer of an electron from the hydrocarbon molecule. This process is clearly analogous to the recently reported formation of radicals from hydro- Buck Bloemhoff,and Oosterhoff TetrahedronLetters 1960 No.9 5. APRIL1961 carbons at Lewis acid sites on the surface of a strongly dehydrated silica-alumina catalyst,2 and has certain formal similarities with the interaction between aluminium chloride and gra~hite.~ The interaction may involve two hydrocarbon molecules for each Al,Cl unit.Vapour-pressure evidence sug- gests that the compound which separates from a solution of aluminium bromide in benzene has the composition A1,Br,,2C,H6.* There seems little reason to doubt that free radicals of the type observed in these experiments are a Rooney and Pink PPOC.Chem. SOC.,1961 70. active intermediates in ring-closure reactions of aromatic hydrocarbons catalysed by anhydrous aluminium chloride of which the conversion of 1 ,l'-binaphthyl into perylene is one e~ample.~ Electron-spin resonance measurements were made with a spectrometer operating at 9370 Mc./sec.and a magnetic field modulated at 100 kc./sec. The authors thank Mr. R. K. Quigg for skilled assistance with the electronic instrumentation. (Received February 13th 1961 .) Croft Quart. Rev. 1960,14,40. 'Van Dyke J. Amer. Chem.SOC.,1950,72,3619; Eley and King Trans.Farahy SOC.,1951,47,1287. Scholl Seer and Weitzenbock Chem. Ber. 1910,43 2202. For other examples see Clar J. 1951,687; Zinke and Ziegler Chem. Ber. 1941 74 115; Clar and Willicks ibid. 1956 89 744; Reinlinger and Overstraeten ibid. 1958 91 2151. The Synthesis of Cyclic AUenes By W. J. BALLand S. R. LANDOR (WOOLWICH LONDON S.E.18) POLYTECHNIC A COMMUNICATION by Moore and Wardl prompts us to report our work on the synthesis of cyclic allenes. Cyclic allenes were l5st described by Favorskii and by Dominin who claimed to have prepared cyclohepta-1,Zdiene by the action of sodium on l-bromo-2-ch~orocycloheptene,but in this reaction we obtained only cycloheptene and polymers (cf.ref. 2c). Dropwise addition of 1 -chlorocyclohexene to sodamide in liquid ammonia gave an undistillable polymer but higher 1 -chlorocycloalkenes gave pro- ducts (all liquids) shown in Table 1 whose struc- tures rest on elementary analysis molecular-weight determinations quantitative hydrogenation and the absorption maxima listed in the Table. Compounds (I) and (II) gave maleic anhydride adducts and ozonolysis of compounds (III) and (IV) gave from (110 suberic (6 pt.) and azelaic acid (1 pt.) and from (IV) azelaic (6 pt.) and sebacic acid (1 pt.) confirm- ing the structures.Addition of dibromobicycloalkanes3 (V; n = 4 5 6 or 7) to sodium on alumina4 gave the liquid pro- ducts listed in Table 2. Structures rest on the same criteria as mentioned above and on ozonolysis to cis-cyclopentane-1 ,Z-dicarboxylic acid from (VI) cis-cyclohexane-1 ,Zdicarboxylic from (VU) suberic acid from (In),and azelaic acid from (IV). Clearly seven- and eight-membered cyclic allenes dimerise and polymerise rapidly when generated in liquid ammonia solution but rearrange internally when held on a solid surface of alumina. Models show little if any overlap of one pair of p-orbitals in cyclohepta-l ,Zdiene and only limited overlap in Moore and Ward J. Org. Chem. 1960,25,2073.* (a) Favorskii,J. Gen Chem. (U.S.S.R.) 1936 6 720; (6)Dominin ibid. 1938,8 851 ;(c) Dominin and Malysheva ibid. 1955 25 311. Doering and Hoffman J. Amer. Chem. SOC.,1954,76 6162. 'Doering and La Hamme Tetrahedron 1958 2 75. PROCEEDINGS TABLE 1. Products formed by sodamide in ammonia. 1-Chlorocycloalkene Product (%) Yield (E in parentheses) Ymax. (m~) band (cm.-l) Infrared Heptene Octene Nonene I I1 Lu" 32 23 43 260 (14,500) 254sh 270shC 250 (8800) 259 (11,O00) None 269 (8300) 1660111 162Om 196Om Decene IVb 39 None 1960m a Containing about 15% of cyclononyne; cf. Blomquist Burge and Sucsy J. Amer. Chem. Soc. 1952 74 3636; Blomquist Liang Huang Liu and Bohrer ibid. p. 3643. Containing about 15% of cyclodecyne. Cf. dimethylenecyclobutane Blomquist and Verdol ibid.1955 77 1806. TABLE 2. Products formed by sodium on alumina. Yield Ymax. (m~) Infrared Reactant n in (V) Product (%) (E in parentheses) band (cm.-l) 4 VI 50 None 1650m 5 VIP 24 228 (565)b 165Ow 6 me 44 None 196Om 7 Nd 64 None 1960m avogel Angew. Chem. 1953 65 346; Blomquist and Liang Huang Liu J. Amer. Chem. Soc. 1953 75 2153. Cyclo-octa-l,3-diene (VIII) formed 10% of this product according to the ultraviolet absorption (Cope and Ester ibid. 1950 72 1128). B.p. 160". Found C,88.8; H 11.7. C,H, requires C 88.8; H 11.5%. Absorbed 1.96 H,. d B.p. 70°/12 mm Found C 88.1; H 11.7. CloHle requires C 88.2; H 11.8%. Absorbed 1-99 Hs. cyclo-octa-1 ,2-diene. Models of cyclonona-and We thank the Chemical Society for a grant for cyclodeca-1,2-diene can be built in favourable chemicals and the D.S.I.R.for a maintenance grant conformations. to W.J.B. (Received February 17th 1961.) The Detection of the Phenalenyl Radical in Pyrolysed Hydrocarbons by Electron-spin Resonance By 3. E. BENNETT Lm. THORNTON CENTRE, ("SHELL"RESEARCH RESEARCH P.O.Box 1 CHESTER) THE products from the pyrolysis of petroleum hydro- unit and subsequently vacuum-distilled the fractions carbons have been examined by electron-spin being collected in tubes suitable for insertion into the resonance. A free radical has been observed in the electron-spin resonance spectrometer. Care was pyrolysis products and has been identified by this taken to exclude oxygen during the experiment the means as the phenalenyl (perinaphthenyl) radical (I).pyrolysis was carried out in an atmosphere of pure nitrogen and the samples were sealed under nitrogen. The phenalenyl radical was detected in the pyrolysis products from all the materials examined provided that the temperature was above a minimum value which depended on the molecular weight of the material. Materials of higher molecular weight Normally available petroleum products were used were pyrolysed at 650" but for those of lower mole as starting materials. The range was chosen to in- cular weight it was necessary to use temperatures up clude materials of low and high average molecular to 750" before the radical was observed. In one case weights (e.g. gasoline 80 and medicinal white oil a gas oil of average M 200,phenalenyl was detected 400) and of widely varying aromatic content.In in the material pyrolysed at 450". The free-radical addition spectroscopic-grade cyclohexane was content occurred mainly in the fraction of the examined. The materials were pyrolysed at tempera- pyrolysed material distilling between 120" and 140" tures from 450" to 750" by passing them through an at 0.5 mm. The amounts of phenalenyl found cor- unpacked silica tube heated by an electric furnace. responded to concentrations of between 104~ and The products were condensed into a small distillation 10% in the total products of pyrolysis. APRIL1961 The same electron-spin resonance spectrum was obtained from each of the pyrolysed products and the free radical was identified as the phenalenyl radical by comparison of this spectrum with that from the pure compound; it was essentially that observed by Sogo Nakazaki and Calvin.' However we found that the hyperfine splitting constants were 6.3 f0.1 and 1.82 f0-05 oersted which were about 15% lower than the values quoted by them.The production of the phenalenyl radical during pyrolysis and its subsequent survival during distilla- tion at 140"show that it is unusually stable for a free radical. This confirms the suggestions by Bockelheide and Goldman,e and Gold and TY~,~ that the radical should be extremely stable owing to its high sym- metry. Also Pettit" has shown from molecular-orbital calculations that there is a considerable gain in resonance energy when the radical is formed from the parent hydrocarbon.In contrast Reid6 claims that the radical decomposes rapidly in boiling benzene whereas we find that in an inert atmosphere a solution of phenalenyl in propylbenzene is stable at 150". The presence of phenalenyl in all the pyrolysed materials suggests that it is formed fairly generally during the pyrolysis of hydrocarbons. Our observa- tion is in agreement with the results of Badger et al.,6 who have found a wide range of polycyclic aromatic compounds in pyrolysed hydrocarbons. (Received February 28th 1961 .) Sogo Nakazaki and Calvin J. Chem. Phys. 1957,26 1343. a Bockelheide and Goldman J. Amer. Chem. SOC.,1954 76 604. a Gold and Tye J. 1952 2184. Pettit J. Amer. Chem. SOC.,1960 82 1972.Reid Chem. and Znd. 1956 1504. For leading reference see Badger and Spotswood J. 1960,4431. Tbe Optical Resolution of EthylphenylphosphinothiolicAcid By M. GREEN and R. F. HUDSON (CYANAMIDEUROPEAN INSTITUTE?,GENEVA) RESFARCH SEVERALmethods have recently been developed for resolving phosphonyl compounds containing one or more replaceable groups into their optical enantio- morphs. The resolution of thiolic acids first described by Aaron and Miller' is one of the most convenient for obtaining good yields of a variety of optically active phosphorus compounds. This method has been used by several workers,2 but in all cases acids of the general type RO-RPOSH or RO(R0')POSH were prepared. These have the disadvantage that in subsequent reactions the ester groups may be attacked in addition to the other replaceable group.We decided therefore to attempt to resolve com- pounds of the general type RR'POSH and now report the partial resolution of methylphenylphos- phinothiolic acid (I). Phenylphosphinous dichloride Ph*PCI + PhEtPCl + PhEtP(S)CI -+:PhEtPOSH (I) with tetraethyl-lead at 120" gave phenylethylphos- phinous chloride b.p. 76"/2mm. which with sulphur in the presence of aluminium trichloride gave ethyl- phenylphosphinothionyl chloride. Hydrolysis gave the acid (I) characterised as the dicyclohexylamine salt m.p. 158" (Found C 65.3; H 9.4; N 3.9. C,,H,,NOPS requires C 65.3; H 9.3; N 3.8 %). The free acid (I)(75 9.)in hot acetone (1.5 1.) was treated with anhydrous quinine (128-5g.).Gradual addition of light petroleum resulted in crystallisation of the quinine salt in fractions (1) 0.5 g. (2) 46 g. (3) 3 g. (4) 83 g. and (5) 20 g. The free acid (I)was liberated from each fraction and converted into the dicyclohexylammonium salts whose optical rota- tions were (2) [(u]D~O -6.6" (c 6 in MeOH) (3) [CX]D~'-6.5" (c 5 in MeOH (4) [cx]D~O + 1.3" (c 5 in MeOH) and (5) [a]~~~ + 1-1" (c 5 in MeOH). The dicyclohexylammonium salt from fraction (4) with methyl methanesulphonate gave the S-methyl ester (n)(70%) b.p. 120"/0*3mm. [a]DZo + 10.4" (homogenous) that with exactly 1 equiv. of sodium PhEtP(0)i &H2(C5H1Ja-+ PhEtP(0)-SMe -f PhEtP(0)-OMe (11) (111) methoxide in methanol at -10" (2 hours) gave the O-rnethyl ester (LII) (68 %) b.p.106-108"/0~8 mm. ror]~~O-3.49"(homogenous). (Received February 9th 1961 .) l Aaron and Miller J. Amer. Chem. SOC.,1956,78,3538; 1958 80 107; 1960,82 597. * Hilgetog and Lehmann Angew. Chem. 1957 69 506; J. prakt. Chem. 1959,8 1224; Michalski and Ratajczalc Chem. and Ind. 1959 539; 1960,241. PROCEEDINGS NEWS AND ANNOUNCEMENTS Nominations to Honorary Fellowship.-The Coun-cil has made the following nominations for election to Honorary Fellowship. Subject to Bye-Law 13 these elections will be made on June 8th next. Sir Howard Florey (Oxford) President of the Royal Society Nobel Laureate. Sir Howard’s pioneer work on penicillin compounds has opened up to chemists the whole study of antibiotic com- pounds.Professor Henry Gilman (Iowa State University of Science and Technology). Distinguished for his work in the field of organometallic chemistry. Professor Alexander Nicolai Nesmeyanov (Mos-cow) President of the Academy of Sciences of the U.S.S.R. Distinguished for his contributions to organic chemistry. Professor Nesmeyanov has played a leading part in promoting international co-operation between chemists. Professor Vlado Prelog (Eidg. Technische Hoch- schule Zurich). Distinguished for his contributions to many aspects of organic chemistry. Corday-Morgan Medal and Prize.-The Council has awarded the Corday-Morgan Medal and Prize to Dr. A. R. Battersby Lecturer in Chemistry at the University of Bristol in consideration of his out- standing work published in the year 1959 on the stereochemistry of emetine and its congeners and also his contributions to the chemistry of curare alkaloids and the biogenesis of papaverine.This Award consisting of a Silver Medal and a monetary Prize is made annually to the chemist of either sex and of British Nationality who in the judgment of the Council of the Chemical Society has published during the year in question the most meritorious contribution to experimental chemistry and who has not at the date of publication attained the age of thirty-six years. Copies of the rules governing the Award may be obtained from the General Secretary of the Chemical Society Burlington House London W. 1. Applica- tions or recommendations in respect of the Award for the year 1960 must be received not later than December 31st 1961 and applications for the Award for 1961 are due before the end of 1962.Local Representatives-Dr. D. R. Hogg has been appointed as the Local Representative for Aberdeen in succession to Dr. P. Meares who has resigned and Dr. C. T. Greenwood is to succeed Dr. G. 0. AspinalZ as Local Representative at Edinburgh. Library.-The Library will close for the Whitsun Holiday from 5 p.m. Saturday May 20th until 9.30 a.m. Wednesday May 24th 1961. Election of New Fellows.-21 8 Candidates whose names were published in Proceedings for February were elected to the Fellowship. C.S.M. J. Clarke.-We regret to announce the death on March 9th of C.S.M. J. Clarke who was appointed the Society’s Commissionaire in 1926 and retired from that post in 1956.Royal Society.-The following were included amongst those elected to the Fellowship of the Royal Society on March 16th Professor James Baddile-v Professor of Organic Chemistry in the University of Durham King’s College Newcastle upon Tyne. Distinguished for his researches in organic chemistry and biochemistry particularly in the field of co-enzymes nucleotides and bacterial cell-wall constituents. Dr. Joseph Chatt Head of the Inorganic Chem- istry Department Akers Research Laboratories Imperial Chemical Industries Limited Welwyn Hertfordshire and Group Manager of the Heavy Organic Chemicals Division. Distinguished for his work on the chemical and physical constitution of co-ordinated metallic compounds.Dr. Leo Marion M.B.E. Senior Director National Research Council of Canada and Director Division of Pure Chemistry Ottawa. Distinguished for his work in organic chemistry particularly in the field of alkaloids. Symposia etc.-A Symposiumon “The Physics of Sectioning and the Embedding Process,” has been arranged by the Joint British Committee for Electron Microscopy on which the Chemical Society is represented. It will be held in the University of Nottingham on Friday July 14th 1961. Full particulars may be obtained from Dr. R. Reed. The 5th International Symposium on Radioactive Isotopes will be held at Bad Gastein Austria in January 1962. Particulars may be obtained from Dr. R.Hofer 11 Garnisongasse 13 Vienna 9 Austria. The 6th Congress of the International Society for Fat Research (I.S.F.) will be held in London on April 9-13th 1962. The programme will cover the following subjects on which recognised authorities are being invited to submit papers (1) The chemistry of oils and fats fatty acids and associated natural products. (2) New research techniques including analytical methods. (3) Recent developments in the technology of oils and fats including new processes the utilisation of new raw materials and the ex- ploitation of new outlets. The Congress Secretariat is at the headquarters of the Society of Chemical Industry 14 Belgrave Square London S.W.l and the Joint Organising Secretaries are Dr. F. Bradley and Dr.H. Jasperson. APRIL1961 The 10th Congress of the International Federation of Associations of Textile Chemists and Colourists will be held in Amsterdam on April 25-27th 1962. Details may be obtained from the President of the Federation Mr. John Boulton Dean House 19 Piccadilly Bradford 1 Yorkshire. The 14th International Symposium on Crop Protection will be held at Ghent Belgium on May 2nd 1962. Details from Professor J. Van den Brande Institut Agronomique de l’Etat Coupure Gauche 233 Ghent Belgium. Symposium on Desalting Sea Water will be held under the auspices of the European Federation of Chemical Engineering in Athens on May 24th 1962. Particulars will be available from Professor Dr. A. A. Delyannis Secretary c/o Union of Greek Chemists Rue Kaningos 10 Athens K Greece.The 6th International Congress on Glass will be held in Washington D.C. on July 9-14th 1962. Particulars from Pierre Gilard Honorary Secretary 24 Rue Dourlet Charleroi Belgium. The 8th International Cancer Congress will take place in Moscow from July 22-28th 1962 under the auspices of the International Union Against Cancer. The Congress will meet at the Moscow State University (the new building on Lenin Hills) and will consider both experimental and clinical aspects of the problem. Foreign members of the Congress will be serviced by the Soviet travel agency “Intourist.” Applications for reading papers will be considered only on condition that both the application and the abstract of the paper (not exceeding 250 words) are submitted not later than November lst 1961.Further information as well as enrolment forms and applications to read papers may be obtained from ProfessorL. Shabad General Secretary of the Soviet National Organising Committee Academy of Medical Sciences of the U.S.S.R. 14 Solyanka Moscow U.S.S.R. The 21st International Congress of the Pharma- ceutical Sciences will be held at Pisa on September 4-8th 1961. Further particulars from the Inter- national Pharmaceutical Federation 1 1 Alexander- straat The Hague Netherlands. The 5th International Congress of Electron Microscopy will be held in Philadelphia on August 29th-September 5th 1962. The programme will be available from Professor Thomas F.Anderson President International Federation of Electron Microscope Societies Institute for Cancer Research Philadelphia 1 1 ,Pennsylvania. Deaths.-We regret to announce the deaths of the following Dr. E. de Barry Barnett (23.3.61) formerly Head of the Chemistry Department of the Sir John Cass Technical Institute; Dr. R. E. Dodd (25.2.61) of King’s College Newcastle-upon-Tyne ;Professor C. E. Fawsitt (1 6.1 1 .a), formerly Professor of Chemistry of the University of Sydney; and Dr. B. N. Feitelson (4.12.60) of Expandia Paris. Personal.-Dr. G. M. Blackbum of St. John’s College and Dr. D. W. Cameron of Churchill College have been appointed to University Demon- stratorships in the Department of Organic and Inorganic Chemistry at Cambridge.Dr. G. C. Bond has been appointed to a Senior Lectureship in Chemistry at the University of Hull from October 1st next. Dr. Helena Bradbury of the Liverpool School of Technology has been chosen to take part in the English-Speaking Union’s plan for the exchange of technical teachers between Britain and the U.S.A. Dr. R. Chikd retired from the post of Director Tea Research Institute of East Africa on March 31st 1961. Mr. J. S. Clapham who has been Chairman of Metals Division Imperial Chemical Industries Limited since January lst 1960 has been appointed a Director of Imperial Chemical Industries Limited. He is to be an Overseas Director vice Dr. J. S. Gourlay who is to be Group A Director (responsible for Alkali and General Chemicals Divisions).Dr. J. F. Duncan (University of Melbourne) will be on sabbatical leave from June 1961. The first part ofthis period will be spent mainly at Chalk River Ontario Canada but he will be in the United Kingdom from October 1961 to February 1962. Correspondence during this period should be sent to him at Jesus College Oxford. Professor D. H. Everett and Professor D. E. Eley have recently been appointed by the American Chemical Society to serve as members of the Advisory Board for the Journal of Physical Chemistry. Dr. Dorothy M. Farmer has been elected the first woman Fellow of the Plastics Institute. Professor D. M. Hodgkin is to receive the honorary degree of D.Sc. of the University of Manchester on May 17th and of the University of Cambridge on June 8th next.Dr. M. V.Luck has taken up an appointment with the Deering Milliken Research Corporation Spartanburg South Carolina U.S.A. Sir Patrick Linstead and Mr. R. B. Southall have been appointed to serve on the Prime Minister’s Committee of Enquiry into Higher Education. Mr. G. F. J. Moir has taken up an appointment as Lecturer in Agricultural Biochemistry in the Univer- sity of Malaya in Kuala Lumpur. Dr. T. P. Nevell has been appointed lecturer in textile chemistry at the Manchester College of Science and Technology. The title of Reader in Chemical Pathology has been conferred upon Dr E. M. F. Roe at the Institute of Cancer Research Royal Cancer Hospital. Dr. W.D. Scott Managing Director of B.T.R. Industries Ltd.has been appointed chairman of three of its subsidiaries Artrite Resins Ltd.; Glass Yarns and Deeside Fabrics Ltd.; and Microcell Ltd. Mr. M. A. Short who is to receive the degree of Ph.D. of the Pennsylvania State University in June next has joined the technical staff of Bell Telephone Laboratories Murray Hill New Jersey U.S.A. Mr. Harold Smith who has been Chairman of their General Chemicals Division for the past two PROCEEDINGS years has been appointed a Director of Imperial Chemical Industries Limited with effect from March 23rd. He will take over as Technical Director from Dr. Richard Beeching on June 1st when Dr. Beeching becomes Chairman of the new British Transport Board. Dr. K. Wade has been appointed Lecturer in Chemistry at the University of Durham from October 1 st next.FORTHCOMING SCIENTIFIC MEETINGS London Thursday May 4th 1961 at 7.30 p.m. Simonsen Lecture “Some Pathways in Biosyn-thesis,” by Professor A. J. Birch D.Phil. F.A.A. F.R.S. To be given in the Rooms of the Society Burlington House W. 1. Thursday June Sth at 6.30 p.m. Reception and Conversazione. To be held by kind permission of the Director in the Science Museum South Kensington S.W.7. (Details have been circulated.) Birmingham Friday May 5th 1961 at 4.30 p.m. Lecture “Synthetic Applications of Metal Car-bonyls,” by Professor R. C. Cookson M.A. Ph.D. Joint Meeting with the Birmingham University Chemical Society to be held in the Chemistry Department The University.Cambridge (Meetings will be held in the University Chemical Laboratory Lensfield Road.) Monday May Sth at 5 p.m. Lecture “Constituents of Acacia Species; Leuco- anthocyanidins and 4-Hydroxypipecolic acid,” by Dr. J. W.Clark-Lewis Ph.D. F.R.I.C. Wednesday May 17th at 5 p.m. Lecture “The Total Syntheses of Tetracyclines,” by Dr. J. H. Boothe. Durham Monday May 8th 1961 at 5 p.m. Lecture “Recent Advances in the Chemistry of D Vitamins,” by Professor B. Lythgoe Ph.D. F.R.I.C. F.R.S. Joint Meeting with the Durham Colleges Chemical Society to be held in the Science Labora- tories The University. Newcastle upon Tyne Thursday May 4th 1961 at 5.30 p.m. Bedson Club Lecture “Anatomy of Haemoglobin,” by Dr. M. F. Perutz F.R.S.To be given in the Chemistry Department Kings College. Oxford Monday May 29th 1961 at 8.15 p.m. Lecture “Photochemical Reactivity and Molecular Structure,” by Professor J. N. Pitts. Joint Meeting with the Alembic Club to be held in the Inorganic Chemistry Lecture Theatre The University. Swansea Monday May Sth 1961 at 4.30 p.m. Simonsen Lecture “Biosynthetic Routes to Phenolic Compounds,” by Professor A. J. Birch D.Phil. F.A.A. F.R.S. Joint Meeting with the University College Chemical Society to be held in Department of Chemistry University College. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedinps.Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Atherton Neil Manning B.Sc. Ph.D. Department of Chemistry The University Sheffield 10. Bailey E. Thomas B.S. 808 South Wood Street Chicago 12 Illinois U.S.A. Barrett Sonja Irene B.Sc. 4 Riverbank Laleham Road Staines Middlesex. Bean Leonard William B.Sc.,A.1nst.P. 23 Oldborough Road. North Wembley Middlesex. Bensted John. 37 Heversham Road Bexleyheath Kent. Booth Donald Harold B.Sc. A.R.I.C. 23 Cordys Lane Trinley-St,-Mary Ipswich suffolk. Borders Ih~ald Bruce B-S. MA. 12064 N. Goodwin Avenue Urbana Illinois U.S.A. Briggs Frank. 26 Thatch Leach Chadderton Oldham Lancs.APRIL1961 Bunker Philip Robert. 57 Woodmansterne Road, London S.W.16. Burrows Ian Edward B.Sc. 22 Beech Avenue Up- minster Essex. Chadwick Peter Howard B.%. Greengarth Hall, Holmrook Cumberland. Clark Peter Wilson. 40 Bland Road Prestwich Man- Chester. Clarke Wilbur Bancroft M.S. Ph.D. Southern Univer- sity Box 9745 Baton Rouge Louisiana U.S.A. Cohen Fredric Sumner A.B. 86 Oliver Road Belmont 78 Massachusetts U.S.A. Cook Clarence Edgar B.S. Ph.D. 96 Barton Road Cambridge. Cordes Arthur Wallace M.S. Ph.D. Chemistry Depart- ment University of Arkansas Fayetteville Arkansas U.S.A. Coutts Ian George Cormack BSc. 197 Victoria Road Aberdeen. Crampton Michael Richard. 125 Pitts Lane Earley Reading Berks.Dance. Ian Gordon. B.Sc. 22 The Promenade. Chelten- ham; N.S.W. Australia. Davidson John Michael B.Sc. Ph.D. 127 Hughenden Road St. Albans Herts. Davies Derek Ivor B.%. 75 Withycombe Drive Ban- bury Oxon. Davies Gareth Morse B.Sc. 33 Alexandra Terrace Brynmill Swansea Glam. De Rycke Douglas August Charles F.R.I.C. F.P.S. Domus Beaconsfield Road Woolton Liverpool, Lancs. D’Orazio Vincent Thomas B.S. 1209 G University Village E. Lansing Michigan U.S.A. Downes Michael Barrie. Students Union University College of North Staffordshire Keele Staffs. Dybvig Douglas Howard Ph.D. Minnesota Mining and Manufacturing Co. Central Research Department 201-2 2301 Hudson Road St. Paul 19 Minnesota U.S.A. Dyer John. 140 Underhill Crescent Abergavenny, Mon.Eargle Dolan Hoye Jr. B.A. Ph.D. 7540 Dale Avenue St. Louis 17 Missouri U.S.A. Ellis Ian Angus B.Sc. 174 Skene Street Aberdeen. Eyton William Bryan B.Sc. Department of Organic Chemistry The University Woodland Road Bristol 8. Farragher Anthony Leslie. 526 Green Lane Small Heath Birmingham 9. Feniak George B.Sc. Ph.D. Apt. 3 204 Boteler Street Ottawa 2 Ontario Canada. Fielden Edward Martin. 18 Chester Road Akroydon Halifax Yorks. Figov Murray B.Sc. 61 Tanfield Avenue Neasden London N.W.2. Fleischfresser Barry Edwin B.Sc. C/o The Overseas Visitors Club 180 Earls Court Road London S.W.5 Foley William Michael Jr. B.S. Ph.D. 3027 Regent Street Berkeley 5 California U.S.A. Gardella Libero Anthony B.S. 5023 W. Gunnison Street Chicago 30 Illinois U.S.A.Gardiner William B.Sc. 11 1 Seatown Cullen Banff- shire. Garriock Elizabeth Kathrin B.Sc. St Ambrose Vicarage Halton View Road Widnes Lancs. Gerratt Joseph B.A. Hertford College Oxford. Gore Brian Alfred. 15 Keildon Road Battersea London S.W.11. Graham James Aloysius S.J. M.A. Loyola College 7141 Shcrbrooke Street West Montreal 28 Canada. Grisebach Hans Dr.rer.nat. Chemisches Laboratorium der Universitat Freiburg i. Br. Germany. Hasty Robert Armistead B.S. Chemistry Building University of Texas Austin Texas U.S.A. Hatfield William Emerson M.S. Chemistry Department University of Arizona Tucson Arizona U.S.A. Heinemann Gunther Dr.rer.nat. Department of Chem- istry University of Indiana Bloomington Indiana U.S.A.Heraud Valda May B.Sc. Chemistry Department Uni- versity of Melbourne Parkville N.3 Victoria, Australia. Herbert Paul Arthur. 28 Worcester Road Sutton, Surrey. Hill John B.Sc. 15 The Priory Salford 7 Lana. Hillyer Martin James B.Sc. Chemistry Department University of Western Ontario London Ontario, Canada. Hughes Allan. 104 Barker Road Strathfield Sydney N.S.W. Australia. Iketubosin George Obene B.Pharm. School of Phar- macy University of London Brunswick Square, London W.C.l. Jacobsen Noel William M.Sc. Department of Medical Chemistry Australian National University Canberra A.C.T. Australia. Jeffries Denis John. 34 Water Lane Totton Southamp- ton. Jenkins Dennis R. Ph.D. 7 Carlton Way Cambridge. Jones Alan John.University College of North Stafford- shire Keele Newcastle-under-Lyme Staffordshire. Jones Alan Rodney B.Sc. Pharmacy Department, University of Sydney N.S.W. Australia. Kaempfen Henry Xavier B.S. Ph.D. Department of Chemistry Queen’s University Belfast Northern Ireland. Karipides A. G. B.A. M.S. 360 Noyes Laboratory Urbana Illinois U.S.A. Katague David B. B.S. University of Illinois College of Pharmacy 833 S. Wood Street Chicago 12 Illinois U.S.A. Kilner Melvyn B.Sc. 10 Willoughby Avenue Lenton Boulevard Nottingham. Kitto George Barrie B.Sc. Chemistry Department Victoria University of Wellington Wellington New Zealand. Lang Jean Fernand Albert D.es.Sc. Laboratoire de Chimie Minerale C. Faculte des Sciences Rennes (IV) France.Levy Ezra M.Sc. Department of Inorganic Chemistry Hebrew University Jerusalem Israel. Lewis Cyril John. 29 Cherry Lane Sale Cheshire. Linker Alfred Ph.D. Veterans Hospital Ft. Douglas Salt Lake City Utah U.S.A. McAdam. Brian William B.Sc. Branksome 36 Stocks Lane Chester Cheshire. Maher John Patrick B.Sc. A.R.C.S. Shamrock Villa Nine Mile Ride Wokingham Berks. Margerison Donald B.Sc. Ph.D. 31 Mosslands Drive Wallasey Cheshire. Marov Gaspar J. M.A. B.S. 86-09 25th Avenue Jackson Heights 69 New York U.S.A. Mathews F. Scott B.S. Ph.D. Department of Chemistry Harvard University 12 Oxford Street Cambridge 38, Massachusetts U.S.A. Maxwell Hazel Marjorie B.Sc. 4 Oakwood Drive, Heaton Bolton Lancs. Middaugh Richard L. A.B. 606 West Ohio Street Urbana Illinois U.S.A.Murray Kenneth Ph.D. 40 Del Monte Avenue Los Altos California U.S.A. 150 Newns Denis Merton. 12 Milborne Grove London s.w.10. Nitecki Danute E. M.S. 5617 S. Drexel Chicago 37, Illinois U.S.A. Noreyko John Michael BSc. Chemistry Department University of Alberta Edmonton Alberta Canada. Osborne Anthony George. 8 Hartwell Road Roade Northamp ton. Osborne John Anthony B.Sc. C/o Aluminium Produc- tion Corporation Ltd. Bell Bay Tasmania Australia. Pal Bimal Chandra M.Sc. P.O. Box 996 Tuskegee Institute Alabama U.S.A. Panton Christopher James B.Sc.Chemistry Department University College of North Staffordshire Keele Staffordshire. Penfold David Keble College Oxford. Percival Albert B.Sc.Ph.D. Organic Chemistry Department Fisons Pest Control Chesterford Park Research Station near Saffron Walden Essex. Perkins Arthur Wilson Jr. B.A. 10,208 Lexington, N.E. Albuquerque New Mexico U.S.A. Pledger Bryan Edward George B.Sc. 12 Stoke Place Old Oak Lane London N.W.lO. Porgess Paul Victor Kraus Ph-D. A.R.C.S. 3 Cromford Way New Malden Surrey. Prakobsantisukh Biravana B.Sc. c/o Thai Government Students’ Office 28 Princes Gate London S.W.7. Rawles Richard Edwin. 16 Winsford Road London S.E.6. Richardson Davis B. M.S. Ph.D. 10326 Old Orchard Road La Porte Texas U.S.A. Rothwell Michael Tom B.Sc. 1 Garden City Langport Somerset. Saxby Michael John B.Sc. Ph.D. A.R.I.C. Royal College of Surgeons Physiological Department, Lincolns Inn Fields London W.C.2.Senior John Brian B.Sc. Department of Chemistry McMaster University Hamilton Ontario Canada. Siegel Bernard B.S. Ph.D. 1015 Glenview Road West Covina California U.S.A. Sinclair Robert Andrew B.Sc. 14 Ferryhill Place, Aberdeen. Skancke Per Njal. Mathematical Institute 10 Parks Road Oxford. Spanier Edward J. B.A. 11064 Proctor Road Phila- delphia 16 Pennsylvania U.S.A. PROCEEDINGS Stirling George Coulson B.Sc. Chemistry Department University of Melbourne Parkville N.2 Victoria, Australia. Straub Dare1 K. Ph.D. Department of Chemistry, University of Florida Gainesville Florida U.S.A. Thompson Michael B.Sc. A.R.C.S. 27 Bartholomew Road London N.W.5. Thompson Neville Ramsden Ph.D. 6 Beech Grove, Beverley Road Hull Yorks.Thornely Philip Roger Wilson. 265 Bramhall Lane South Bramhall Stockport Cheshire. Thurston Elvin Frederick William. 10 Thor Road, Thorpe St. Andrew Norwich Norfolk. Towns Donald Lionel B.Ch.E. Chemistry Department University of Wisconsin Madison 6 Wisconsin U.S.A. Treloar Francis Edward Ph.D. Department of Chem-istry University of Malaya Paulai Valley Kuala Lumpur Malaya. Truax David Rodney Walkerton Ontario Canada. Turner Fred Allen M.S. Dept. of Pharmaceutical Chemistry University of Illinois 833 S. Wood Street Chicago 12 Illinois U.S.A. Vinciguerra Anthony B.S. Department of Chemistry Florida State University Tallahassee Florida U.S.A. Walker Francis Harry M.S. Apartment No. 5 542 55th Street Oakland 9 California U.S.A.Webb Graham Alan B.Sc. A.R.J.C. Chemistry Depart- ment University College Gower Street London W.C. 1. Weinberg David Samuel B.S. Chemistry Department University of Arizona Tucson Arizona U.S.A. Weiss Jonas B.S. 1721 Grand Avenue New York 53, New York USA. Whitney Robert B. Ph.D. 1 Stratton Audley Manor Bicester Oxon. Williams Andrew. Keble College Oxford. Williams Brian Jos B.Sc.,Ph.D. A.R.I.C. 1333 Leek Road Abbey Hulton Stoke-on-Trent Staffs. Woods Harry B.Sc. 2 Cherry Tree Avenue Penketh Warrington. Wristers Harry Ian A.B. Apt. 14A East State Street Athens Ohio U.S.A. Yablonsky Harvey A. M.A. M.S. 550 East Zlst, Brooklyn 26 New York U.S.A. Zand Robert M.S. 71-5 Middlesex Road Waltham 54, Massachusetts U.S.A. OBITUARY NOTICE BAWA KARTAR SINGH BAWAKARTAR SINGHwho died of heart attack on June 16th 1960 at Chandigarh was one of the pioneers of chemistry in India.He was born on April 17th 1886 at Verowal district Amritsar Punjab. His father Colonel Bawa Jiwan Singh I.M.S. was a descendant of the third Sikh Guru. Bawa Kartar Singh inherited the tradition of tenacity of purpose from his Sikh Guru ancestors and carried it to the end of his life. He received his early education from 1895 to 1900 at the D.A.V. School Lahore. His father then called him to Burma where he joined the Rangoon Col- legiate School. In the Entrance Examination of the Calcutta University in 1903 he was seventh in order of merit in Burma. His father was a man of very advanced views and he took him to Cambridge and got him admitted to Downing College in 1904 for further studies.He was a Prizeman of the College in 1905 took his Tripos in Natural Sciences in 1906 and from then to 1910 did postgraduate work at Cambridge and London where he had the good fortune to be taught by such well-known scholars as W. J. Pope H. J. H. Fenton W. J. Sell H. 0.Jones and T. M. Hughes and where also he worked in close association with Dr. Ruhemann. Returning from Cambridge in 1910 he joined the Dacca Government College as professor of chem-istry. There he came in close contact with the Iate Dr APRIL 1961 151 E. R. Watson. He stayed from 1910 to 1918 at Dacca where he did research on optically active nitrogen compounds.The facilities for research at Dacca were very meagre and when in 1918 he was appointed Head of the Department of Chemistry at Government College Lahore a spurt of research activity was witnessed in Punjab. As a result in 1920 he was elected President of the Chemistry Section of the Indian Science Congress (Nagpur Session) President of the Lahore Philosophical Society and a Fellow of the Punjab University. Next year he became a Fellow of the Institute of Chemistry (U.K.) by research and was awarded the degree of Sc.D. by Dublin University. It was at this time that he was selected for appointment in the Indian Educational Service and was posted at Patna. The University of Punjab wanted him to remain in the Punjab and so created a University Professorship in Organic Chem- istry and offered the post to him on June 17th 1921 but were unable to obtain his services on loan from the I.E.S.Singh joined Patna College in April 1921 but remained only till November when he was trans- ferred to Ravenshaw College Cuttack. His stay at Cuttack was a long one from 1921 to 1936. There despite lack of proper facilities he carried out a con- siderable amount of research and established a small but vigorous school. In 1925-26 he went on study leave to Europe and U.K. working at Paris St. Andrews and Cambridge. Back again at Cuttack he resumed research with vigour. He soon attracted the attention of the Indian scientific world. He was elected President of the Indian Chemical Society for 1931-32 Vice-president of the Indian Academy of Sciences for 1934-38 and additional Vice-president of the National Institute of Sciences.In addition to his post as Head of the Department of Chemistry he was Principal during 1934 and 1935. In 1935 he represented the Universities of U.P. Bihar and C.P. in the Council of the Indian Institute of Sciences Bangalore. In January 1936 he was transferred to the Science College Patna as Head of the Department of Chem- istry and Chemical Adviser to the Department of Industries Bihar. His activities in Patna from 1936 to 1940 were diverse. On the one hand as Head of the Department of Chemistry he held the administra- tive charge of a large department and was teaching and guiding research in chemistry.On the other as Chemical Adviser to the Department of Industries his work involved analyses of materials of different kinds preparation of schemes for the development of chemical industries and industrial research. Up to this time he had published fifty-five original papers. These he submitted to the Cambridge University and was awarded the Sc.D. degree in 1941. In July 1940 he was appointed Professor and Head of the Department of Chemistry Allahabad University where he remained until 1946. At last he had ample opportunity for research publishing more than forty papers. He was re-elected Additional Vice-president of the National Institute of Sciences for 1940-46 acted as Foreign Secretary National Academy of Sciences India for 1944-46 and was appointed Emeritus Professor of Chemistry by the Allahabad University from May lst 1946 on his retirement.Dr. B. K. Sin& was now sixty years of age but was still full of vigour and planned to continue his researches. He decided to spend the rest of his life at Lahore purchased a plot of building land at Model Town and asked the Punjab University to offer him research facilities. The University was very happy to have him and on May 6th 1946 appointed him temporarily Honorary Professor of Organic Chemistry and Associate Director Punjab University Institute of Chemistry. However he could stay there only during 1946-47 being forced to leave Lahore on the partition of Punjab. For some time he stayed in Delhi but his restless spirit could find no satisfaction without research.Fortunately the Banaras Hindu University offered him an Honorary Research Professorship in Organic Chemistry and promised him facilities. He promptly shifted to Banaras Hindu University in 1948 and continued working there till March 1960. During this period he published more than fifty papers and made Banaras an active centre of research in stereochem- istry. He left Banaras in March 1960 and decided to settle at Chandigarh for the rest of his life. He was now seventy-four years of age. He had an attack of paralysis during his stay at Banaras. He was very weak in body but still quite vigorous in intellect. He was actively collaborating with the author in writing a monograph on “Optical Activity and Chemical Constitution”-a project sponsored by U.P.Scientific Research Committee in November 1959. He had also not given up research completely. The Council of Scientific and Industrial Research had given him a grant for the year 1960-61 and he was planning further research as soon as the Chem- ical Laboratories and the Chemistry Section of the Punjab University shifted from Hoshiarpur to Chandigarh in July 1960. He died suddenly of heart attack on June 16th 1960. His name in India was synonymous with stereo- chemistry. He was an eminent figure in Indian chem- istry and was a restless helper of every good scientiiic cause in the country. The void created by the passing of this veteran willbe difficult to fill. 0.N. PERTI.ADDITIONS TO THE LIBRARY Library administration. R. Northwood Lock. Pp. 135. Crosby Lockwood. London. 1961. The structure of the atom an electromagnetic theory. H. M. Dowsett. 2nd edn. Pp. 109. Stephen Austin. Caxton Hill Hertford. 1960. (Presented by the author.) Crystals and crystal growing. A. Holden and P. Singer. Pp. 320. Heinemann. London. 1961. (Presented by the publisher.) Applied thermodynamics. S. H. Bransom. Pp. 230. Van Nostrand. London. 1961. (Presented by the pub- lisher.) Noble metal thermocoEples. H. E. Bennett. 3rd edn. Pp. 44. Johnson Matthey & Co. Ltd. London. 1961. (Presented by the publishers.) The radiochemistry of iron. J. M. Nielsen. Tssue by the United States National Research Council Subcommittee on Radiochemistry.Sponsored by the United States Atomic Energy Commission. (Nuclear Science Series NAS-NS 3017.) Pp. 42. Subcommittee on Radio-chemistry National Academy of Sciences. Washington. 1960. (Presented by the publisher.) The radiochemistry of protactinium. H. W. Kirby. Sponsored by the United States Atomic Energy Com- mission. (Nuclear Science Series NAS-NS 3016.) Pp. 80. Subcommittee on Radiochemistry. Washington. 1959. (Presented by the publisher.) The radiochemistry of zinc. H. G. Hicks. Sponsored by the United States Atomic Energy Commission. (Nuclear Science Series NAS-NS 3015.) Pp. 58. Subcommittee on Radiochemistry. Washington. 1960. (Presented by the publisher.) H,SO, sulphuric acid and related chemical plant. Issued by the Power-Gas Corporation Limited.Pp. 12. Power-Gas Corp. Ltd. Stockton-on-Tees. 1961. (Pre-sented by the publisher.) Toxicology and biochemistry of aromatic hydro-carbons. H. W. Gerarde. Pp. 329. Elsevier. Amsterdam. 1960. Organometallic chemistry. Edited by H. Zeiss. (American Chemical Society Monograph Series No. 147.) Pp.549. Reinhold. New York. 1960. Chemistry of carbon compounds. Edited by E. H. Rodd. Vol. 4. Part C. Pp. 2201. Elsevier. Amsterdam. 1960. Transactions of the Connecticut Academy of Arts and Sciences. 1871-73. Vol. 2 (2). Vol. 3 (1-2). (Bound in one vol.) Connecticut Academy of Arts and Sciences. New Haven Conn. (Presented by Prof. H. A. Robinson.) Kinetics equilibria and performance of high tempera- ture systems proceedings of the first conference of the Western States Section of the Combustion Institute Los Angeles California 1959 edited by G.S. Bahn and E. E. Zukoski. Pp. 255. Butterworths Scientific Publications. London. 1960. Production and application of enzyme preparations in food manufacture a symposium organised by the Food Group held in London. 1959. (S.C.I. Monograph No. 11.) Pp. 180. S.C.I. London. 1961. (Presented by the pub- lisher.) The biochemistry of mucopolysaccharides of connec- tive tissue a symposium held in London 1960 organised by J. K. Grant and edited by F. Clark and J. K. Grant. (Biochemical Society Symposia No. 20.) Pp. 125. University Press. Cambridge. 1961. (Presented by the Biochemical Society.) Saline Water Conversion a symposium presented before the Division of Water and Waste Chemistry at the 137th National Meeting of the American Chemical Society Cleveland Ohio 1960.(Advances in Chemistry Series-No. 27.) Pp. 246. A.C.S. Washington. 1960. Gas chromatography 1960 proceedings of the third symposium organised by the Society for Analytical Chemistry and the Gas Chromatography Discussion Group of the Hydrocarbon Research Group of the Institute of Petroleum held at the Assembly Rooms, Edinburgh. Edited by R. P. W. Scott. Pp. 466. Butter-worths. London. 1960. NEW JOURNALS Uchenye Zapiski Kazanskogo ordena trudovogo krasnogo znameni Gosudarstvennogo Universiteta imeni V.I. Ul'yanova-lenina. (Archives of Kazan State University) 1957 117 (9). Pure and Applied Chemistry 1960,l. Arzneimittel-Forschung 1961 11. Zeitschrift fur Chemie 1960 1.