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Proceedings of the Chemical Society. July 1962 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue July,
1962,
Page 237-264
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY JULY 1962 THE EVOLUTION OF THE STILL By PROFESSOR DR. IR. R. J. FORBES STILLS such as we commonly use in our technical and laboratory operations go back some twenty centuries but at a much earlier date we find a curious piece of apparatus in use in Mesopo- tamia in which distillation if unwittingly was achieved. The oldest vessel of this kind dating back to 3500 B.c. was found at Tepe Gawra in northeast Mesopotamia.* Dr. Martin Levey describing it in his “Chemistry and Chemical Technology in Ancient Mesopotamia” (Amster- dam 1959) as a double-rimmed earthenware pot of some 37 1. capacity the double-rim in which the distillate condensed against the lid (which might be a pot fitting none too closely in the double-rim of the lower pot) could be collected (capacity 2 1.).This apparatus was used by the ancient perfumers of Mesopotamia; the texts mention its careful heating and give Instructions on how to keep the heat from reaching the rim the primitive receiver of the distillate. It was the most primitive form of the later aludel the sublimatory and distillatory of the Arabs and later alchemists though they no longer stopped their work at intervals to collect the distillate collected in the rim but subjected the mass treated in the aludel to distillation in more appropriate stills. It should be mentioned that earthenware hearth bases for such stills were also found at Tepe Gawra. * See Plate facing p. 242. Of course neither these early perfumers and chemists nor those early chemists of Alexandria at the turn of our era who built the first adequate stills for recovering distillates understood the principle of distillation.In Latin “destillatio” olhmlo3Pl -Distillation apparatus of the Alexandrian chemists. means dripping and is used by the Roman physicians to describe the reaction of their patient’s nose to a bad cold. It is not applied to that complex of evaporation condensation and separation and recovery of the distillate to which we apply the word. To these early Alexandrian chemists this operation served to separate the “pneuma” or “spiritus,” the essential principle from the contaminating “somata” or “bodies.” They strove to separate such spirits in order to 237 study their reactions and to prepare pure metals such as silver and gold lead or iron being con- taminated but containing valuable “seeds” or principles which could be extracted and turned into gold provided one knew the essential operations.The excellent distillation apparatus developed during the first two centuries of our era con- sisted of the vessel holding the liquid to be dis- tilled the condenser fitting on top of this vessel the outlet-tube transporting the distillate from this condenser to the receiver and the receiver itself. The first of these was usually called “cu- curbit” because it was shaped like a calabash. The condenser was an inverted heart-shaped vessel fitting on the narrow mouth of the cucurbit.The rising vapours were condensed by the air cooling the condenser the condensate being collected in the inner rim and drawn off by the outlet-tube the “solen.” The condenser was sometimes called “bathos” (“cavity”) or “phiale” (kettle or cup) but usually “ambix.” This word came to denote the entire apparatus and through its Arabic form “al-anbiq,” became our “alem- bic” or “limbeck.” The receiver was usually a small vessel with a long thin neck called “bikos.” Certain alchemical diagrams show a “dibikos” or “tribikos,” but this has nothing to do with the type of fractional distillation apparatus in use in the laboratory now. The distillate was simply collected in two or three receivers simul- taneously the operation being described as “boiling” or “rising.” The difficulty of these early chemists was the lack of temperature control; the fire had to be watched very carefully and the use of earthen- ware or metal vessels did not enable them to watch the operation closely the types of glass then available not being able to withstand high temperatures or corrosion by chemicals.Their “distillations” were usually a combination of distillation and cracking of the natural impure primary material in their stills; they hardly ever recovered distillates unchanged nor could they recover low-boiling compounds because of the very primitive cooling of the ambix. Usually they had subjected their primary material to pro- longed heating in closed vessels in order to “loosen the spirit,” before applying distillation proper.Without proper analytical tools prepara- tion and reproduction of a good distillate was virtually impossible. PROCEEDINGS The Arab chemists inherited these distillation techniques through Syriac channels and deve- loped them mainly between the eighth and the twelfth century. They started using “distillation” in a far wider sense including filtration expres- sion of oils and extraction with water a proof that they were still ignorant of the basic prin- ciples. Their system was widely copied by mediaeval chemists and it still included a fairly rough treatment of primary material very often “distilled” in molten conditions at too high temperatures. Though the Arab chemists had better earthenware vessels they still had to “lute” their apparatus with mixtures of lime casein glue and white of egg such as the mediaeval alchemists called the “Lute of the Philosophers” which could seldom be removed without breaking the vessel! Though the Arab chemists designed various apparatus for different purposes these did not differ essentially.Only the “mass-oven,” a distillation furnace holding 16-25 cucurbits was a new contribution in which they produced “rose-water” (heating rose- petals with water) and even “nafta” from crude oil (to be used in removing stains from silk!). Closer attention to the cooling of the vapours rising from the still was a turning point in the history of distillation. By applying sponges or wet rags to the still-head low-boiling fractions could now be condensed before they escaped from the outlet of the still.Cooling was also applied to the outlet-tube and by such means the first alcohol was manufactured about A.D. 1100 in Northern Italy. This meant that extracts from herbs and the like could now be prepared and then subjected to distillation. Also when the manufacture of nitric acid and sulphuric acid started round A.D. 1300 means were available to prepare solutions to be distilled instead of molten salts and the like. A series of low-boiling com- pounds soon became available and this again necessitated more attention to the condensing of the evaporated contents of the still. Though the word “distillate” proper does not occur in literature before 1850 distillates being called “phlegm,” “spirit,” or “water,” the word “still” came into use in the sixteenth century.New types of stills were devised. The first was the “retort,” thus called because the upper-part of the still was bent backwards (“retortus”). The angle between the body of the still and the narrowing neck was more or less conventional JULY 1962 until Berzelius recognised its importance as a reflux-element. The second type was the “Moor’s head,’’ in which the still-head was enclosed in a basin or container which could be filled with a cooling liquid sometimes with arrangements for the use of running water. This was an invention of the fifteenth century the retort being some 150 years older.The third type the “Rosenhut,” popular in Central Europe retained air-cooling of a high conical alembic fitting over a wide-mouthed alembic. This was the apparatus of the distillers and apothecaries preparing liqueurs and alcoholic distillates as medicines or for home consumption. Proper cooling of the delivery- tube by leading it through a tub of water or extending it into a “cooling-coil” immersed in such a tub also dates back to the later Middle Ages the first illustration of such a still being given by Wenod in 1420 though mentioned much earlier. Leonard0 da Vinci is known to have worked on these problems throughout his life but his solutions remained buried with his notes until well into the nineteenth century. Sometimes exotic stills were designed by chemists such as Porta who believed that heavy distillates should be distilled from a still re-sembling a tortoise fractionation should be car- ried out with a “hydra,” and distillation with a constant reflux by means of a “pelican,” which LLRosenhut”(1478).animal was said to feed its children with its own life-blood. Up to the very end of the eighteenth century the series of “distillation-books” un-leashed by the invention of the printing press mention such special stills alongside the more common retort still with a cooling coil and “Serpentes.” Wenod (1420). ‘I Testudo” (Tortoise). G. P. Porta (1570). “Hydra.” G.P.Pavta (1 570). “Pelican.” G. P. Porta (1570). “Gallery oven.” G.Y.Porta (1560).Rosenhut and Moor’s head stills but without being able to improve on any of them. In some cases the law inspired the distillers into inventing new forms. Thus the heavy duties on whisky led the distillers to invent and use conical stills with a flat bottom which could be used and refilled more often a day than others whereas the law exacted a duty related to the surface of the still only and not to the amount of distillate obtained per day. Progress was possible only when science stepped in during the late eighteenth century. For only then the science of heat in its most simple form was taking shape after calorimetric experiments by Scottish Scandinavian and German scientists the most notable of whom was Joseph Black. All through this century sug- gestions were made for improving the common type of still and prizes had even been awarded for designs of more economic stills as fuel was becoming more expensive.Chemists such as Charas Glaser and Barlet had tried their hand at such designs; Baumk and Argand were more successful; and so was Millar’s design (1799). But as long as men such as Margraff and Boerhaave were quarrelling about the possibility of earth formed in distilled water little help could be got for the distillers from contemporary scientists. PROCEEDINGS However by 1800 such phenomena as boiling evaporation and cooling were properly under- stood specific and latent heats could be measured and good thermometers had been in- troduced to check the operation of distillation.Also good hydrometers were available to measure the strength of the distillate obtained or its specific gravity. Benjamin Thompson Count Rumford was to become the pioneer of the application of steam to distillation. At first steam-heating in closed coils was used until Savalle’s steam regulator of 1857 made the use of live steam during distillation possible. As men were now aware of such phenomena as vapour pressure distillation in a vacuum came natural to Philipe Lebon (1796) and its use spread gradually. In 1812 Howard invented the vacuum- pan using a steam-jacket for heating and an evaporation device which was the combination of the surface condenser and a barometric jet condenser an invention quickly adopted by most English sugar refineries.Multiple-effect evapora- tion is described in earlier patents but its first practical solution was the design by Norbert Rillieux of New Orlkans (1843). StiII designed by Cellier for an Amsterdam distillery (1839). JULY 1962 241 Countercurrent cooling of the vapours had been introduced by Magelhaens (1780) Von Weigel and Poisonnier long before the Liebig condenser appeared in the chemical laboratory. The modern still with its fractionating column was born at Montpellier when Adam tried to achieve good contact between the rising vapours and the refluxing condensate by placing a series of Woulfe bottles between the still-head and the condenser proper. His ideas were improved by Alkgre Bkrard and others until Jean Baptiste Cellier Blumenthal spurred by the large sums of AY The Egrot money offered by the French Government for a solution of the separation of alcohol from fer- mented pulp of sugar beets hit the target.He had also invented a method of producing white sugar by recrystallisation of raw sugar with al- cohol which personal invention doubled his interest in the matter of rapid and good distilla-tion methods for alcohol. Thus in 1813 he patented the first fractionating column in which rising vapours and condensate flowing back to the still achieved good contact by means of a series of trays with slits. He also used bubble- caps in his later patents. In 1816 he was given a gold medal and extension of his patent was granted.These designs were then improved by Lacambre Derosne and Dubrunfaut to name but a few of the most successful inventors in this field. Continuous fractionation was now well on its way to oust the older method of batch- distillation in many applications. New forms had to be found to deal with the heavy potato mashes from which alcohol was produced from 1820 onwards. Here the Coffey still (1830) was a good solution several of these stills being able to handle 40,000 gallons a week! None of these stills had been designed on scientific principles ; they were the work of practical distillers. Not until about 1850 were physics and thermo-dynamics sufficiently advanced for some of their results to be applied in constructing stills.Such stills were built for the rising tar and petroleum still (1 854). Champonnois still (1 854). industry the names of Bohm Paulmann Ilges and Heckmann being associated with these im- proved columns. Modern tube condensers were introduced by William Grimble (1825) and Savalle. Only a few of these stills used such economic devices now considered essential as preheaters to convey the heat of the residue to the intake and the like. In fact we must remember that the recognition of “chemical engineering” as a branch of applied science does not go back much further than the twenties of this century. When pioneer hand- books of the later nineteenth century such as those of Hausbrand and Sorel dealt with dis- tillation they were still baffled by the theory PROCEEDINGS of separating components from the distillate vapours.In fact the solution was proposed just some 45 years ago in the important paper by Thiele and McCabe and only during the twenties were methods of calculating fractionat- ing columns developed. In earlier centuries the inventors of different types of stills and auxilliary apparatus had to work on vague ideas of the basic principles involved. A general outline of this basic knowledge became available only some 150 years ago but native wit and practical routine had already achieved some important steps towards the design of the modern still. Lit R. J. Forbes “Short History of the Art of Distilla-tion,” Brill Leiden 1948. OBITUARY NOTICE IAN MORRIS HEILBRON 1886-1959 THE sudden death in London on September 14th 1959 of Professor Sir Ian Heilbron at the age of 72 removed from the chemical scene one who for nearly 40 years had exercised a profound influence on its development especially in Britain by his teaching his leadership and his original contributions to organic chemistry.The large number of his former collaborators who today occupy key positions in in- dustry research institutions and universities is in part a measure of this influence. He is remembered in the universities in which he worked not only for the urgent activity of the “Heilbron era” and his impatience with bureaucracy but also for his legacy of well organised and properly equipped laboratories an example which was followed far and wide.His advice cogent practical and clearly delivered was widely sought by government industry universities and innumerable individuals. Loyalty was one of his outstanding characteristics loyalty to his country to the organisations which he served and particularly to his family friends and colleagues. During two world wars he served his country with distinction. Already commissioned in the Territorial Army in 1910 in the fist he was on active service rising to the rank of Lieutenant-Colonel as an Assistant Director of Supplies in Salonika whilst throughout the second he was in London as Scientific Adviser first to the Director of Scientific Research Ministry of Supply and subsequently to the Minister of Production.He was mentioned three times in despatches was awarded the Distinguished Service Order the Greek Order of the Redeemer and the Medaille d’Honneur in 1918 and the American Medal of Freedom in 1947 and he was made a Knight Bachelor in 1946. The son of a Glasgow wine merchant Heilbron was born on November 6th 1886 into a family with wide cultural interests especially in music and the theatre but with little regard for the pursuit of chem- istry as a career. From the High School he went at the early age of 16 to the Royal Technical College Glasgow where he subsequently became a demon- strator and helped by a Carnegie Fellowship he spent the two years from 1907 at Leipzig where he obtained a doctorate. He was appointed lecturer at the Royal Technical College in 1909 and returned there as Professor in 1919 after his war service and a short interim period with the British Dyestuffs Corporation.In spite of strong Scottish family ties he accepted in 1920 the Chair of Organic Chemistry at Liverpool. He transferred his activities to nearby Manchester in 1933 and when Arthur Lapworth retired in 1935 he became the Sir Samuel Hall Pro- fessor and Director of the Chemical Laboratories. After much deliberation since he had established a particularly thriving research school in Manchester he agreed to follow Sir Jocelyn Thorpe as Professor of Organic Chemistry at the Imperial College of Science and Technology in London. Here his longer- range plans were largely frustrated after 1939 but as the College carried on in London throughout the war he was able whenever time could be spared from his more pressing duties to maintain contact with and provide continuous encouragement to those engaged The Tepc Gawl-a “still” (3500 H.C.).JULY 1962 there in work on an assortment of topics. In 1949 he resigned his chair to become the first Director of the Brewing Industry Research Foundation and though the challenge of establishing a research institute and organising basic research in a traditional industry appealed strongly to him there is little doubt that the prospect of an inevitable retirement from academic life in 1952 influenced his decision. G. G. Henderson introduced him to research putting him to work in the fashionable terpene field on addition and oxidation reactions of pinene bornene and camphene; this was followed by his two years with Hantzsch at Leipzig.This early acquaintance with both natural products and light- absorption spectroscopy may well have had a profound influence on his whole research career. Al- though his first independent work (191 1-1914) was on the isomerism of the semicarbazones of un-saturated ketones and the interconversion of the stereoisomers in ultraviolet light followed in Liver- pool by substantial contributions to the chemistry of benzopyrylium salts spiropyrans coumarins and chromones his return to natural-product chemistry in 1926 heralded a new and highly productive phase in his researches.Squalene an open-chain triterpene from fish-liver oils especially that of the shark was shown to be identical with spinacene he studied its cyclisation and his work helped appreciably in the elucidation of its structure. Prophetically he sug- gested the possibility that it might be the precursor of cholesterol a relationship which has been con- clusively established in recent times. These activities led on to structural work on selachyl and batyl alcohol and thence to an interest in another fish-liver oil constituent vitamin A. Here his light-absorption experience came in useful and the correlation (with R. A. Morton) of maximal absorption at 3280 8 with the antimony trichloride test and with biological activity made possible the estimation and purification of the vitamin as well as providing an all-important structural criterion.Although in the elucidation of the structure of vitamin A his work was anticipated by Karrer and his colleagues in Zurich the con- firmatory evidence was nevertheless valuable. There followed the isolation of vitamin A from the liver oils of freshwater fish and he was inevitably drawn into the fascinating realm of polyene synthesis where the difficulties were well-nigh insuperable with the techniques and knowledge then available. As with vitamin A so in steroid chemistry Heilbron was one of the pioneers in the field in Britain. His interest in vitamin D was aroused while listening to a Chemical Society lecture in London when it occurred to him that it could not be chole- sterol itself which contains no chromophoric group but some minor impurity which must be converted into biologically active material on irradiation with ultraviolet light.Crude cholesterol was then found to show very weak absorption bands identical with those of ergosterol; when the latter was irradiated the triplet of absorption maxima disappeared being replaced by a broader band at shorter wavelengths. Similar conclusions were reached simultaneously by the Windaus school in Gottingen where soon Windaus and Hess and simultaneously Rosenheim and Webster in London demonstrated by animal tests that ergosterol or a closely related sterol was the actual provitamin. The provitamin D work led to an extensive investigation into the chemistry of ergosterol and related sterols at a time when the whole structural situation in this group was in a state of turmoil.Particularly noteworthy in this period was the early attempt to correlate ultraviolet absorption and un- saturation in the steroid group which included the observation of the absorption of cholestenone and the conclusion that at least two double bonds were necessary for selective absorption. Had it only been realised at that time that cholestenone was an ccp-unsaturated ketone (this did not happen until 1932) the sterol structural problem might have been cleared up rather earlier. Various other steroid researches followed at Manchester (with F. S. Spring); attempts to obtain epicholesterol from cholesteryl methyl ether led to isocholesterol and to the determination of the location of the oxygen atom in this novel re- arrangement product bromination of steroid ketones in a search for routes to 7-dehydrocholesterol lumi- sterol structure and a vital contribution to the structure of vitamin D (calciferol) by oxidative degradation.In the 1930’s he became involved in an examina- tion of seaweed constituents; fucosterol the main algal sterol was isolated and its structure determined and some progress was made with the carotenoid fucoxanthin; in spite of its wide distribution the structure of the latter is still unknown. The work on myxoxanthin was most elegant and the detailed study (with B. Lythgoe and P. W. Carter) of the pigments and sterols of the various algal classes provided in- formation of much relevance to botanical classifica- tion an early example of the possibilities of chemical taxonomy.Heilbron collaborated with the late A. E. Gillam in analytical investigations on butter carotene and similar topics and he encouraged Gillam’s pioneering studies on both light absorption and carotenoid chemistry the isolation of “pseudo- a-carotene” presaging the extensive subsequent development of our understanding of stereochem- istry in the polyene field. During this period organic microanalysis became an essential adjunct to natural- product research and Heilbron very early established this and chromatographic techniques in his labora- tories. Throughout his career he was always quick to PROCEEDINGS realise the r81e which physical methods and new techniques could play in furthering organic chemical studies.Although since 1926 Heilbron’s main interests were focussed on natural-product chemistry he con- tinued work in the dyestuffs and related fields facilitated by his close association with the Dyestuffs Division of Imperial Chemical Industries Limited. In the Schorlemmer Laboratory at Manchester studies with almost invulnerable vat dyestuffs contrasted strangely with those with the labile polyenes and then and later at Imperial College (in association with D. H. Hey) studies on the Gomberg reaction furnished novel methods of coupling aryl and heterocyclic nuclei. Some feverish rehabilitation of the Whiffen Laboratory at Imperial College in the summer of 1938 made it possible for him to embark later that year on an ambitious programme of research with a large group of collaborators.The algal work was ex- panded to embrace an examination of the pigments of the male and female gametes and fungi were col- lected for a study of their “sterols,” the more interest- ing of which turned out to be triterpenes notably the polyporenic acids ; epi-ergosterol zymosterol from yeast and isocholesterol came in for detailed study and a major attack was launched on the objective of the synthesis of vitamin A. It proved possible to con- tinue some of these studies at least for a time after the outbreak of war in 1939 but urgent new activities were then undertaken in particular studies on a wide range of chemical warfare agents later the chemistry of the penicillins and a number of ad hoc investiga-tions for industry and government departments.Aspects of the vitamin A synthesis project con- tinued to be examined throughout the war but with more emphasis on acetylene chemistry (partly be- cause of potential industrial applications); here the discovery of the ubiquitous anionotropic rearrange- ment of acetylenic carbinols and glycols from ap-unsaturated carbonyl compounds opened up a new field and paved the way for the extensive post-war developments in polyene and carotenoid synthesis. The synthetic scheme envisaged in 1939 could not be pursued intensively inter alia because of the diffi- culty of obtaining pure p-ionone but it was some consolation to see it brought to fruition in 1946 in a superb manner by Isler and his colleagues at the laboratories of Hofmann-La Roche in Basle.From 1941 onwards (with A. H. Cook) the chern- istry of penicillin gradually became one of the major activities beginning with studies on the purification of the small supplies of extremely crude material which were at first available. A most significant advance was made by the application of a novel form of chromatography percolation of ethereal solutions through silica gel columns impregnated with barium carbonate a precursor of the phosphate buffer method which so convincingly demonstrated the plurality of the penicillins.Degradation and especially syntheses of degradation and transforma- tion products for example that of n-pentylpenil- lamine helped in the final elucidation of the structure and encouraged the belief that the antibiotics could be made available synthetically. Another important contribution of the Heilbron group was the recogni- tion of p-hydroxybenzylpenicillin and the practica- bility of increasing its production by adding p-hydroxyphenylacetic acid to the growth medium. In spite of tremendous efforts by workers in several laboratories the objective of a commercially feasible synthesis was not attained but Heilbron Cook and their enthusiastic collaborators fitted many pieces into this complex Anglo-American jigsaw puzzle; their more than 50 reports were subsequently hcor- porated (1949) into the monumental treatise on “The Chemistry of Penicillin.” As with other Heilbron studies the attempted syntheses of the penicillins were turned to good account and there emanated a series of 18 papers on heterocyclic (azole) syntheses of considerable versatility providing novel routes to certain amino-acids polypeptides and purines as admirably related in his 1949 Presidential Address.Reference has earlier been made to the advisory posts which Heilbron held during the second war. In the Ministry of Supply he was much concerned with the Chemical Defence Committee and the Chemical Board but it was in the Production Ministry that he was able to make a notable and characteristic con- tribution to the war effort.Having become con- vinced at an early stage of the potential value of the insecticide D.D.T. discovered in the Geigy labora- tories in Switzerland he spared no effort either his own or those of others to get it produced in adequate amount in the minimum of time. The provision of this protection for personnel operating in the Mediterranean and Far-Eastern areas reduced to un- believably small proportions the casualty rate in fly- infested areas. His public activities continued after the war in many ways perhaps most notably as Chairman of the Advisory Council on Scientific and Industrial Research and as one of those instrumental in re-establishing and reorganising the International Union of Pure and Applied Chemistry.To the Royal Institute of Chemistry and the Chemical Society he gave devoted service. He became President of our Society in 1948 at a time when post-war problems of publication costs the spate of papers and publication delays the future of British Abstracts and our shabby and over-crowded premises were most acute. Heilbron was the driving force behind many of the measures which have since dealt with these problems. In his 1950 Presidential Address he reverted to a practice in abeyance for 25 years ;his “The Chemical JULY 1962 Society-a Mid-Century Review” is a wholly excel- lent account of our organisation and its problems. In addition to his military decorations and knight- hood Heilbron’s achievements and services were widely recognised.He was elected to the Fellowship of the Royal Society in 1931 and awarded its Davy (1943) and Royal (1951) medals. The Chemical Society honoured him with the Longstaff Medal (1939) and he gave the Hugo Muller (1940) and the Pedler (1949) Lecture while from the American Chemical Society he had the great distinction of being the first recipient outside the U.S. of their Priestley Medal (1945). At a luncheon in London in 1956 to celebrate his seventieth birthday he was presented with an album containing signed photographs of 180 former col- laborators and the Journal for November of that year included 26 papers submitted in his honour. His original publications number over 300 and span the years 1908-1950 but the name of Heilbron will best be known to future generations of chemists through the “Dictionary of Organic Compounds.” This ven- ture “the poor man’s Beilstein,” undertaken in collaboration with H.M. Bunbury and with the assist- ance of many of his colleagues has been especially successful and a fourth edition is in preparation. Possessed of tremendous drive inspiring and imaginative yet realistic he was always exacting often impatient and occasionally intolerant de- manding much of those who worked with him. He knew almost instinctively when driving would no longer avail and persuasion was called for and he could be disarmingly persuasive. Rarely did he fail to get people to give of their best; those who helped him were thanked appreciatively and knew they had a friend on whom they could rely.Personally fastidious and invariably immaculate Heilbron car- ried over his meticulousness into all that he did. Letters speeches lectures and papers were prepared with the utmost care at times to the exasperation of his colleagues but the effort was invariably worth while for all were models of logical presentation and clarity. Naturally endowed with good taste he rarely neglected an opportunity of satisfying and develop- ing it. His interests were catholic ranging from music the theatre and cinema to paintings etch- ings antique furniture and china and in his home were many beautiful things in which he took great pride. Most of these interests were shared with his wife a beloved and loyal companion and a gracious hostess; her sudden death in 1954 was a cruel blow from which he never fully recovered.Heilbron was not the easiest of persons to live with but her sympathetic understanding quiet but constant en- couragement and almost inexhaustible patience made for him and their two sons a pleasant and com- fortable home where he could relax and shed the burdens of the day. In Lady Heilbron his colleagues found a staunch friend taking a kindly interest in all their activities and never far away in time of trouble. Although we mourn the passing of one who con- tributed much in many ways to his country and its scientific life his achievements and his example live on in our literature and in the hearts and lives of those who follow in his footsteps.E. R. H. JONES. COMMUNICATIONS A Photochemical Synthesis of /3-Pinene By K. J. CROWLEY VENEZOLANO CIENTIFICAS (INSTITUTO DE INVESTIGACIONES (I.V.I.C.) APARTADO VENEZUELA) 1827 CARACAS ULTRAVIOLET irradiation of a 1 % ethereal solution of myrcene (I) with a filter to remove light below 2200 A gives a large number of volatile products. One of these (9% of the total photo-products) was not separated from 19-pinene (II) by gas-chromato- graphy though a capillary column of 50,004) theoretical plates. A concentrate (61 %) of this com- ponent containing myrcene (14%)and many minor products had an infrared spectrum almost identical with that of a mixture of fl-pinene (80%) and Ruzicka Experientia 1953 9 357.(11 (a> myrcene (20%). This reaction is in agreement with the Proposed’ biogenetic formation of P-Pkene from mYrcene and suggests a simple method of SYn- thaising compounds of the CaVOPhYllene type. (Received May 7th 1962.) PROCEEDINGS Surface-potential Measurements during the Oxidation and Subsequent Reduction of Nickel and Iron Films By C. M. QUINNand M. W. ROBERTS (DEPARTMENT ,THEQUEEN’S OF BELFAST) OF CHEMISTRY UNIVERSITY MEASUREMENTS of surface potential by the capacitor technique with a gold surface as a reference elec- trode have enabled us to obtain a closer insight into the mechanism of the early stages of the oxidation and subsequent reduction of iron and nickel films. -0.6 r t t t + 08 L \\ \ FIG.1.Surface potential during the oxidation and subsequent reduction of a nickel film at 22”. Each oxygen dose (0-12) wasequivalent to -35 x c.c.; the numbers denote gas admission. Fig. 1 shows the variation of the surface potential of oxygen on nickel as a function of time with succes- sive additions of the gas The first dose results in a rapid increase in potential to about -0.15 v; there It is therefore significant to compare the form of the surface-potential curve for nickel with that for iron. Fig. 2 shows the variation of surface potential for iron with successive additions of oxygen as a function of time. Doses 1-25 were adsorbed to a pressure of -lo4 mm. within 1 min. of admission and the final potential of -1.64 v was virtually attained after only a third of the total oxygen uptake.Subsequent doses (8-26) resulted in an instan-taneous rise to the maximum value followed by a slower fall in potential the latter occurring after the oxygen uptake had ceased at a pressure of -low4 mm. After dose 26 the oxygen pressure was decreas- ing slowly corresponding to an oxidation rate of -C.C. min.-l. When this study of the oxidation of both iron and nickel was complete the oxygen (-mm.) was removed from the gas-phase and hydrogen was ad- mitted. In the case of oxidised nickel (Fig. 1,dose 12) there was a change in the surface potential to a value of + 0.2 v within 5 min. of hydrogen’s being ad- mitted and during this time 17 x C.C. was adsorbed. During the next 4 hr.the potential changed to + 1.2 v a further 16 x C.C. being adsorbed. This may be compared with values of -0.33 -0.35 -0-37 and -0-36 v obtained with hydrogen on “clean” nickel these being in agreement with n2 I 4 * Ph ‘a crease. This fall in potential persists long after the f -pressure had decreased to -mm the latter 5 occurring within 2 min. of oxygen’s being ad-lo -I mitted. When eleven doses of oxygen had been com- 4-0a -pletely adsorbed further oxidation occurred at a -Ob measureable rate (2-5 x C.C. min.-l). The surface potential at this stage is -0.76 v (values determined -04 P5 4: -J -’ in other similar experiments were -0.70 -0.72 -02 Mignolet Discuss. Faraday Soc. 1950 8 326. Anderson and Klemperer Proc.Roy. Soc. 1960 A 258 350. Ogawa Doke and Nakada J. Appl. Phys. (Japan) 1952 21 223. Klemperer and Stone Proc. Roy. Soc. 1957 A 243 375. Roberts Trans. Farada,v Soc. 1961 57 99. JULY 1962 established data.6 With oxidised iron a small change to -1.3 v occurred in 15 min. after hydrogen had been admitted (Fig. 2 dose 27) and during this period only 0.4 x C.C. of hydrogen was adsorbed. We attribute the initial rise and subsequent decrease in potential during oxygen interaction to chemisorption followed by incorporation. The latter process may be visualised as occurring at certain parts of the surface by a “place exchange”’ or “switching process,” so that the surface becomes This is in agreement with recent suggestions based on Culver and Tompkins Adv.Catalysis 1959 11 67. ’ Lanyon and Trapnell Proc. Roy. SOC.,1955 A 227 387. Quinn and Roberts Trans. Farahy SOC. 1962 58 569. a kinetic studys of the interaction of hydrogen with oxidised nickel. The large change in surface potential on addition of hydrogen to oxidised nickel to a value positive with respect to “clean” nickel probably reflects the presence of an intermediate state essential in the reduction of the oxide to the metal. The absence of any appreciable change with oxidised iron can be related to the well-known difficulty of reducing this oxide. (Received April 9th 1962.) Recognition of a General Reaction of Indoles By W. I. TAYLOR (RESEARCH CIBA PHARMACEUTICAL DIVISION DEPARTMENT COMPANY OF CIBA CORPORATION N.J.U.S.A.) SUMMIT has shown that the hydroperoxide from into the final products 2-acetyl-3-ethylindole and LEETE~ 2,3-diethylindole decomposes under acid-catalysis water. Analogous reactions have previously been to furnish 2-acetyl-3-ethylindole. A mechanism was observed with steroidal allylic hydroperoxides.3 In discussed which required a remote analogy2 for its support. It occurred to us that this transformation was actually a special case where X = Y = 0-OH of a reaction sequence (I -I1 + I11 -+IV) whose synthetic utility is under investigation in our labora- tories. According to this the hydroperoxide from 2,3-diethylindole suffers via (111) an internal re- arrangement to afford the secondary hydroperoxide (IV; Y = 0-OH) which is not stat12 and collapses ItH+ Leete J.Amer. Chem. SOC. 1961 83 3645. the decomposition of 2,3-dimethyl-3H-indol-3-yl hydroperoxide the imine (11) predominates over the enamine (111) since no alkyl group is present to stabilise the exocyclic double bond and the alternate reaction path is favoured leading to 2-acetamino- acetophenone as the major product. In fact Leetel was unable to obtain any 3-methylindole-2-aldehyde although we were able to isolate about 5% after careful chromatography. The course of other reactions on record are now clear including :the conversion4 of chloroyohimbine into d3-yohimbine (X = Cl ;Y = electron pair on Nb); the transformation of yohimbine into tetrade- hydroyohimbine by lead tetra-acetate in acetic acid5 [X = Pb(OAc),; Y = electron pair on Nb]; and the bromination and subsequent base-treatment of 2,3-dimethylindole to furnish 2-hydroxymethyl-3-methylindole6(X = Br; Y = OH).These and other reactions in more complex systems along with physical data will be discussed more fully elsewhere. (Received May 21st 1962.) Corey and White J. Amer. Chem. SOC.,1958 80 6686. Schenck Neumuller and Eisfeld Annalen 1958 618 202; Lythgoe and Trippett J. 1959 471. Godtfredsen and Vangedal Acta Chem. Scnnd. 1956,10,1414; Finch and Taylor,J. Amer. Chem. SOC.,1962,84,1318. Hahn Kappes and Ludewig Ber. 1934 67 686. Plant and Tomlinson J. 1933 955. PROCEEDINGS Inversion Doublet Interactions in Formaldehyde By J. E.PARKIN H. G. POOLE, and W. T. RAYNES (WILLIAMRAMSAY LABORATORIES, AND RALPH FORSTER UNIVERSITY COLLEGE GOWERST.,LONDON, W.C.1) LIDE~ recently showed that vibration-rotation inter- actions of a hitherto unsuspected kind can occur between the member levels of an inversion doublet; he points out that his formulation is specifically for a molecule with the (non-planar) geometry of cyana- mide but that the qualitative conclusions should have a wider applicability. Millen Topping and Lide2 found evidence of such interaction in the micro- wave spectrum of cyanamide. In the ultraviolet absorption spectrum of formalde- hyde we have found in several places perturbations of some magnitude for which it is difficult to find an explanation other than such interactions.The first excited singlet state of formaldehyde is non-planar3s4 and is geometrically even more closely approximated by Lide’s model than is cyanamide itself; perturba- tions in quantitative agreement with the predictions of Lide’s theory may therefore be expected and are in fact found. A rotational level J,K of the 0-state active in a perpendicular band of this spectrum should be perturbed by interaction with the J,K -1 level and the J,K + 1 level of the O+ state. The perturba- tion is expressible in terms of three parameters one of which is the inversion frequency the other two do and eol being also associated with the potential function. Its magnitude is sensibly linear with respect to J(J + l) with the value very nearly zero for J = K and becomes large when (2K + 1){A -+(B + C)} approaches the inversion frequency.Our absorption frequencies have been obtained by an interferometric method5 to high precision generally of the order of 0.003~. Our analysis of the A2 band (Brand’s notation3) reveals a perturbation strong in sub-branches with K’ = 7 and K’ = 8 but not at all negligible over a considerable part of the band and a second perturbation which is strong in the sub-branches with K’ = 0 and is of markedly different appearance especially in that it is very much more localised in the J,K field. A complete numerical analysis has been made by using about 300 of the 9OO-lOOO recorded frequencies of this band; these were selected as being only singly assigned and free from near or overlapping neigh- bows.Simultaneous solution was made for the six rotational constants and ten centrifugal distortion constants of the ground and the excited state the band origin and the two sets each of three Lied parameters required for the two perturbations described. The fist of these perturbations gives 126~for the inversion frequency of the 2v’(CO) vibronic state involved in this band and do = 7.4 x e, is found to be so close to the level of significance that it can be ignored (the effect of a small eol would be to split the K-degeneracy of the high-K levels but for the value found at most a slight broadening (< 0.05~)of the most perturbed lines would occur; the lines concerned are weak (J’ -20 K’ = 8) and do not enable us to decide whether there is such broadening).Agreement between the pertur- bations observed and calculated with these values of the parameters is excellent-to about 0.01~for all singly assigned and apparently single-component lines and within the resolving limit of our equipment (0.09~)for practically all composite lines several hundreds of assigned frequencies in all. The second perturbation referred to above requires a somewhat more refined treatment. For a prolate near-symmetric rotor Lide’s formulation1 is adequate for levels of high K but is inadequate for describing a perturbation which is strong in levels of low K where there is large splitting between members of the asymmetry doublets. To deal with this case we have used a more extended treatment outlined by Lide.6 Tentatively we regard this second perturbation as arising from analogous interaction between the active 0-level and the Of level of a vibronically different state.On this assumption there is again good agreement with observation. The analogue of the inversion frequency here is about 14~, indicating the existence of a O+ level at 30,645~above the ground state (since the origin of the A band is 30,658.58~);this may belong to the v’(C0) + 8’(CH,) state. If so the corresponding 0-level according to our preliminary analysis of the per- pendicular C band is at 30,819~(in agreement with Brand’s recording3 of its R-head of K” = 3 at 30,875~).It would then appear that the inversion frequency of the vibronic state active in the C,band is about 174~; the considerable difference between this and the 126~for the 2v’(CO) state may well be the Lide jun.,J.Mol. Spectroscopy 1962,8 142. a Millen Topping and Lide jun. J. Mol. Spectroscopy 1962 8 153. Brand J. 1956 858. Robinson and DiGorgio Canad.J. Chem. 1958,36 31. Poole Raynes and Stace 4th Internat. Conference on Molecular Spectroscopy Bologna 1959 Pergamon Press London,in the press. Lide jun. personal communication. JULY 1962 249 effect of the replacement of a quantum of v'(C0) have been mapped but for the bands concerned a by a quantum of 6'(CH2). similarly complete numerical analysis has not yet Similar perturbations elsewhere in this spectrum been carried Out* (Received May 24th 1962.) The Vibrational Frequencies of Trimethylamine-gallane and -trideuterogallane By N.N. GREENWOOD A. STORR,and M. G. H. WALLBRIDGE OF CHEMISTRY NEWCASTLE (DEPARTMENT KING'SCOLLEGE UPONTYNE,1) VERY few authentic derivatives of gallium hydride infrared spectra of gaseous GaH,,NMe and have been reported in the literature and little is GaD,,NMe, m.p. 68.1" at about 3 mm. pressure are known of their properties despite their obvious im- shown in the Figure. In addition to the weak bands portance in relation to the hydrides of boron and directly attributable to the trimethylamine residue aluminium. During a general investigation into the there are a number of lines as listed in the Table which chemistry of gallium hydride we have prepared a can be assigned to the N-+GaH and N+GaD variety of adducts with ligands such as tertiary groups.As the gallium atom is essentially tetrahedral amines ethers and sulphides. Of these the trimethyl- these groups have local C, symmetry with six infrared amine complex is particularly noteworthy since it can active modes that have been assigned as in the Table Infrared bands (cm.-l). GaH,,NMe 1853 758 GaD,,NMe 1330 542 Assignment v1 and v4 sym and asym Ga-H stretch v5 asym H-Ga-H deformation 715 523 482 (510) (370*) 479 v2 sym H-Ga-H deformation v6 N-Ga_H bend v3 Ga-N stretch * Beyond range of instrument but observed in Raman spectrum.l 3000 2000 1500 1200 1000900 800 700 600 500 400 Wave number (cm?) Full line GaH,,NMe,. Broken line GaD,,NMe,.readily be prepared by the reaction of lithium gallium hydride on trimethylamine hydrochloride and has sufficient vapour pressure at room temperature to enable its gas-phase infrared spectrum to be recorded. It is therefore one of the few volatile compounds containing metal-hydrogen bonds which can afford spectroscopic information free from the complica- tions of solvent shifts or the splittings due to inter- action with crystal lattices. When purified by vacuum-sublimation trimethyl- amhe-gallane is obtained as colourless well-formed needles m.p. 70.5" (Found Ga 52.3 ; hydrolysable H 2.32; NMe, 46.6. GaH,,NMe requires Ga 52.9; hydrolysable H 2.29; NMe, 44-8%). The This assignment is consistent with the vapour-phase P.Q.R.structure of the band at 482 cm.-l and the expected factor of 42 in the ratio of H/D frequency for the other modes.The spectra are closely similar to those of gaseous trimethylamine-alane and -trideuteroalane observed by G. W. Fraser in these laboratories. Thus the Al-H and Al-D stretching modes at 1780 and 13 10 cm.-l and the Al-N stretching mode at 460 cm.-l are at somewhat lower frequencies than those observed for the gallanes whereas the deformation and bending modes are at somewhat higher fre- quencies. (Received May 14th' 1962.) Shriver hster and Taylor J. Amer. Chem. SOC.,1962 84 1321. PROCEEDINGS ~ ~~ The Contributions of n-Bonding to the Stabilities of Metal Complexes in Solution and a Correlation with Hammett’s a-Factor By H.IRVING (THE UNIVERSITY LEEDS) and J. J. R. F. DA SILVA (INSTITUTO T~~CNICO, SUPERIOR LISBON) THE effect of changes in the composition of a ligand Values of r shown in Table 1 (which extends data on the stability of complexes with a particular cation given in ref. 2) are invariably higher for ligands that or on the magnitude of the redox potential (where might be expected to form vbonds. The values of r different valency states are possible) can often be follow the Irving-Williams order for both ligands ; successfully correlated with changes in absorption but so does the difference dr contrary to what might spectra and interpreted in terms of various degrees of have been expected if +-bonding were alone respon- 0-and nb0nding.l There is some danger however sible for the additional stabilisation.of developing arguments in circulo probandu and a Anderegg6 recently compared the stabilities of a need for objective demonstrations of the reality and series of complexes of metals with a ligand capable extent of rr-bonding in systems that can only be of mbonding (e.g. picolinic acid or pyridine-2,6-di- investigated in solution. carboxylic acid) with those of an analogous ligand TABLE 1. Values of the stabilisation function r. Fe* co* Ni cu Zn I= 1 2 1 2 1 2 1 2 1 2 Et hylenediamine 2-Pyridylmethylamine Ar 0.25 0.30 0.33 0.36 0.08 0.06 0.34 0.47 0.13 0.28 0.40 0.12 0.44 0.37 0.61 0.52 0.17 0.15 0.62 0.81 0.19 0.54 0.67 0-13 0-33 0.30 0.44 0.36 0.11 0.06 The greater stability of complexes of Ag+ relative to those of the isoelectronic Cd2+ with ligands capable of forming nbonds is consistent with the greater availability of electrons from the univalent ion,2 but the most direct proof of the strengthening of a a-bond by back-donation of electrons is the increased strength of the acids R,M.C6H4-C02H as M is changed from C to Si Ge or Sn.3 Goldberg and Fernelius sought for direct evidence of n-bonding by comparing the stabilities of metal complexes of an aliphatic amine with those of a structurally related analogue containing a hetero- L I ~ cyclic nitrogen atom.3 Now changes in the structure -0 4 6 -04 of a ligand inevitably cause changes in its basic Hammett u values strength and hence in the strength of the a-bonds it forms.Fernelius attempted to overcome this by com- Values of (A) S and (B)APK calculated from data paring “the co-ordination stability of a ligand-metal in refs. 7 and 8 for pyridine derivatives and Ag+. bond per unit base strength (including the strength of 1 3-CN. 2 4-CN. 3 3-CO.NH2. 4 4-CO.NHp all donor atoms)” as measured by the function 5 H. 6 3-Me. 7 3-NH2. 8 4-Me. 9 4-OMe. 10 = dFi/{(AFH)l + (dFH)2f. 4-NH2. * Based on data for complexes of ethylenediamine in ref. 5 extrapolated to zero ionic strength and combined with data in ref. 4 valid for 30” and p -+ 0. Ref. 4 gives additional results for the pairs N-methylethylenediamine,N-methyl-2’-pyridylmethylamine and 1,3-diaminopropane 2-2’-aminoethylpyridine. Cf. James and Williams J. 1961 2207; James Parriss and Williams J.1961 4630. Ahrland Chatt Davies and Williams J. 1958 1403. Chatt and Williams J. 1954 4403. Goldberg and Fernelius J. Phys. Chem. 1959 63 1246. Bjerrum Schwarzenbach and SillCn. Tables of Stability Constants. Part I. Organic Ligands. Chem. SUC.Special Publ. No. 6 1957. Anderegg Helv. Chim.Acta 1960 43 414. JULY 1962 (e.g. glycine or iminodiacetic acid) in which such additional stabilisation is impossible. Contrary to expectation the stability relative to the aliphatic ligand is greatest not with the transition metals but with the alkaline earths. In an extensive study of n-bonding in metal corn- plexes we have considered the equilibria M + nH,L + ML + mnH+ for which LH KMLn = [MLnI [HImn/ [MI [HmLIn = PMLn/(PH,LT where the overall stability constants 18 have their usual significance and charges are omitted for simplicity.If a second ligand L' is considered which unlike L (or to a greater extent than L) is adapted to n-bond formation it is easy to see that KML', > KML,,,for its metal complex will be preferentially stabilised relative to hydrogen ions. In Fig. 1 we plot Basolo and Murmann J. Amer. Chem. SOC.,1955,77, Jaffe J. Amer. Chem. SOC.,1955,77,4441. 25 1 values of the stabilisation factor S = log KML'~-log KML~ for complexes of silver and substituted pyridines' against the Hammett a-factor for the sub- stituents. In this case the "reference" ligand is chosen as pyridine itself and m = 1 n = 2. It is easy to see that S reflects the algebraic sum of the enthalpy changes and is a measure of the stabilisation addi- tional to a-bond formation for differences in entropy changes are negligible or at least reasonably small and constant for a series of such closely related ligands and reactions.Also shown on Fig. 1 is the linear relation between the Hammett a-factor and values of pK for the corresponding pyridinium ions which had been previously noted by Jaffe.8 Since the increasing values of 0 correspond to increasing with- drawal of electrons. the linear correlation with in- creasing values of S is an impressive demonstration of the direction and extent of the n-bonding. (Received May 3 lst 1962.) 3484. The Structure of Pentaphenyl-phosphors -arsenic and -antimony By P.J. WHEATLEY (MONSANTO S.A. BINZSTRASSE RESEARCH 39 ZURICH3 145 SWITZERLAND) and G. WITTIG (ORGANISCH-CHEMISCHES DER UNIVERSITAT GERMANY) INSTITUT HEIDELBERG WE have undertaken an investigation of the struc- tures of the pentaphenyls of phosphorus,l arsenic and antimony2 by X-ray diffraction and dipole moment measurements. The dipole moments measured in solution in ben~ene,~ are Ph,P 1.25 f 0.05 Ph,As 1.32 and Ph,Sb 1.59 D. The crystallo- graphic constants are as tabulated Ph,P Ph,As Ph,Sb a 10-029 10.075 10.277 8 b C 17.215 14.170 17.412 14.227 10.574 8 13.594 A NP 90" 112" 03' 90" 111" 57' 79" 00' 79" 34' Y 90O 90O 119" 37' 4 1 -220 1a225 1.412 Space group CC cc Pi Z 4 4 2 which has been elucidated by two-dimensional X-ray- diffraction techniques is based on a square pyramid as shown in the Figure.Refinement has not pro- X? LY gressed sufficiently to afford reliable bond lengths and angles (R is about 15 % for the Okl and the h01 projection) but the general features are well estab- lished. The molecule which is not required to have symmetry has in fact a two-fold axis coinciding with the axial Sb-Ph bond. The Sb atom lies within the pyramid about 0.58 above the base. It will be seen that pentaphenyl-phosphorus and -arsenic are isomorphous but that the molecules adopt a non-centrosymmetric distribution in the crystals. Pentaphenylantimony however is different from the other two a centrosymmetric distribution being present. The structure of pentaphenylantimony Wittig and Rieber Annalen 1949 562,187.Wittig and Clauss Annalen 1952 577,26. Preliminary results communicated by Prof. Dr. R. Mecke Freiburg. The systematic trend in the dipole moments suggests that pentaphenyl-arsenic and -phosphorus also have square-pyramidal structures. It is hoped to check this conclusion by a three-dimensional analysis of the latter. Although a similar square-pyramidal structure has Alderman Owston and Rowe J. 1962 668. GrdeniC and SCavniEar Pruc. Chem. SOC.,1960 147. PROCEEDINGS been found for a cobalt c~mplex,~ this appears to be the first time that a square-pyramidal structure with the central atom lying within the pyramid has been found in five-co-ordinated compounds of the Group V element^.^ (Received May 28th 1962.) Electron Spin Resonance Spectrum of the Radical ~CHF*CO.NH By R.J. COOK and D. H. WHIFFEN J. R. ROWLANDS (BASICPHYSICS DIVISION PHYSICAL TEDDINGTON, NATIONAL LABORATORY MIDDLESEX) THERE are only a few examples1p2 known of hyperfine coupling to fluorine nuclei in organic free radicals. This note summarises the couplings for the radical CHF-CO-NH and draws attention to the large anisotropic and the positive isotropic coupling to the fluorine nucleus. A single crystal of monofluoroacetarnide CH,FCO-NH, was irradiated with 1 Mev y-rays and its electron spin resonance spectra as a function of crystal orientation were measured at 9O00 Mc./sec. These indicate a dominant trapped radical with hyperfine coupling to a nucleus of spin 1/2 with principal values of the coupling tensor of -96 -62 and -36 Mc./sec.which are characteristic3 of a hydrogen atom attached to the free-radical centre; the negative signs attributed on theoretical grounds4 are by now well established. There is hyperfine coupling of the electron to one other nucleus also of spin 1/2 with principal tensor components of 530,47,and 22 Mc./sec. Such aniso- tropy is impossibly large for a second hydrogen and this nucleus must be that of the fluorine; the most probable radical is CHFCO-NH,. The large value 530 Mc./sec. is found in a direction perpendicular to the plane of the radical since it is 3" f5" from the axis of the hydrogen tensor of magnitude -62 Mc./sec.This is confirmed by occurrence of the maximum 13C coupling of 238 Mc./sec. in this direction. Were the fluorine anisotropy due solely to a 2p-electron on the carbon atom a spread of only 50 Mc./sec. would be ex- pe~ted.~ The ten-fold greater spread observed implies considerable fluorine 2pcharacter for the unpaired electron and a consequent large positive value of the tensor parallel to this 2p-orbital. The sign of the smaller elements of 47and 22 Mc./sec. are in doubt though probably positive but for any sign choice the isotropic coupling is positive in agreement with the preferred6 sign for the chlorine atom in CHCI-CO,H. The 2p-unpaired electron in the fluorine must polarise the spin in the 2s-shellY since the positive sign is contrary to that for hydrogen where such a mechanism is impossible.The discussion by Ander-son et aL2of tetrafluoro-p-benzosemiquinoneimplies a negative coupling for such fluorine but ignores this additional mechanism. With positive signs for all elements the fluorine tensor has effectiveJy cylindrical symmetry since its principal elements can be approximately expressed as A + 2B A -ByA -B with A = +200 and B = + 165 Mc./sec. The isotropic coupling A is small com- pared with the value 47,910 Mc./sec. expected for an electron in the SCF 2s-orbital of neutral ground- state fluorine atom.' The value of B is appreciable compared with the value 1515 Mc./sec. for the SCF 2p-orbital and indicates a spin population of 0.1 1 in this orbital. This implies 11 % contribution of a structure C--F.+ in a valence-bond description of the n-electrons; this charge distribution will be more than neutralised by the o-electrons.After slight ad- justment for the amide group the molecular-orbital description of these results requires that the unpaired electron will be in a one-electron n-orbital indicated by (0.94# -0.35#,). These coefficients would be obtained by a simple Huckel treatment with olP -aC = 2.3pc-F overlap being neglected. These experi- mentally based values should be reasonably valid for fluorine atoms attached to aromatic systems. (Received May 30th 1962.) Rexroad and Gordy J. Chem. Phys. 1959,30 399. Anderson Frank and Gutowsky J. Chem. Phys. 1960,32 196. Whiffen Pure Appl. Chem.1962,4 185. McConnell and Chesnut J. Chem. Phys. 1958 28 107. McConnell and Strathdee Mul. Phys. 1959 2 129. Pooley and Whiffen Spectrochim. Acta 1962 18 291. Roothan and Clementi personal communication. JULY 1962 253 lifetimes ranging down to 5 minutes but often found Coupling constants of transient aryloxy-radicals. Substituen ts Coupling constants (oersteds) Substituents Coupling constants (oersteds) 246 o-H 0-p-H p-m-H 2 4 6 0-H 0-p-H p-m-H Alkyl Alkyl Alkyl H Me H 6-1 11.9 1.7 H CO,Et H 7.0 2.2 H Et H 6.1 10.4 1.7 H C02H H 7.0 2.3 H Prn H 6-2 8.4 1.6 H COMe H 7.0 2.2 H Bug H (6.1) (6.5) -H CHO H 7.0 2.3 H But H 6.3 -Me COPh Me 6-8 2-2 Me H H 6.0 6.0 11-5 1.9 Me C02H Me 7-0 2.2 Pri H H 6.1 4-1 10.2 2.0 Pr’ H Prl 3.8 9.6 1.9 The probable error of the above data is 5% but may be larger for the figures given in parentheses.spin resonance spectra of a number of complex re- obtained by the oxidation in this way of aromatic acting mixtures,2 but hitherto flow techniques do not amines. seem to have been used for the detection of transient The spectrum of the phenoxy-radical gives the aryloxy or arylamino radicals. I . -.. -L We now report that if streams of aqueous solu- tions of phenols (ca. 10-3~)and of ceric sulphate (ca. 10-3~ in M-sulphurk acid) are allowed to mix just outside the flattened section of an aqueous solu- tion cell of a 100 kc./sec. Varian V4500 electron spin resonance spectrometer then a well-defined reson- ance spectrum of even the unsubstituted phenoxy- radical can be obtained (Fig.1). We estimate that FIG.2. Spectrum (haff) of the radical-cation(I ;R = radicals of lifetimes of the order of 1W2 sec. can be Me R’ = CHO) and reconstruction based on the studied by this method. Radical spectra can also be coupling constants given in the text. Becconsall Clough and Scott Trans. Furuday Soc. 1960,56,459. Piette Yamazaki and Mason “Free Radicals in Biological Systems,” ed. Blois et al. Academic Press,New York, 1961 p. 195. PROCEEDINGS following values for the coupling constants (in hyde has given the spectrum shown in Fig. 2 This can oersteds) aH-2= 6-6 = 1.9 a,+ = 10.4. be attributed to radical (I; R = Me R' = CHO), Corresponding coupling constants for a number of and the coupling constants are found to be aN-Me = substituted phenols are given in the Table.They show 12.7 aN = 10.9 ~H-Z = 5.4 aH-3 = 1.8. coupling that alkvl substituents other than the methyl group constants for the similar radical from p-amino- in either the ortho-or the para-position reduce the benzoic acid (I; R = H R' = C02H) are aN-H= values of both the ortho-and the para-coupling con- 9.2 a~= 7-39 a~-2 = 5-53 aH-3 = 1.8. stants from those of the unsubstituted phenoxy- We are engaged in the investigation of further radical whereas electrophilic substituents such as substituted analogues of both types of radical. carbonyl or carboxyl groups in the para-position increase the ortho-and meta-coupling constants. We thank the D.S.I.R. for a grant for the purchase The oxidation of p-NN-dimethylaminobenzalde-Of the spectrometer.(Received May 25th 1962.) The Absolute Configuration of Mycarose T. D. INCH,J. LEHMANN J. M. WEBBER, By A. B. FOSTER L. F. THOMAS and J. A. WYER (CHEMISTRY DEPARTMENT, THEUNIVERSITY BIRMINGHAM 1 5) a component of the macrolide antibiotic 2-01 (111) b.p. 75-85"/0.1 mm. This had [a]D ca. MYCAROSE magnamycin,' is a 2,6-dideo~y-3-C-methylhexose.~0.0"(c 1.6 in H20) changing on acidification rapidly We now report evidence in favour of a total ~-xylo- f 7.5" which corresponds to [a] f 17-6" with configuration. respect to propane- 1,2-diol. Similar treatment of the The magnitude and sign of the optical rotations alcohol (IV) (obtained4 by successive periodate ([a]D + 54" and -141" in CHCI,) recorded2 for the oxidation and borohydride reduction of methyl anomeric methyl mycarosides suggest an L-sugar.a-L-rhamnopyranoside) caused [a] to change from +38-7" -+8*95" corresponding to [a]D + 17-2" Confirmation was obtained as follows Oxidation of methyl a/3-mycaroside2 ([a] -14.4"; c 2.0 in H,O) with respect to (+)-propane-l,2-diol. Since propane- with periodate in Paul and Tchelitcheff's conditions2 1,2-diol (containing as its asymmetric centre the gave the dicarbonyl compound (11) b.p. 66"/0.1 mm. C-5 carbon atom of the parent sugar) is the only [a]~-19.3" (C 2.6 in HZO) (Found C 55.05; H optically active product formed on hydrolysis of the 7.9. C8H1404 requires C 55.05; H 8.05%); Vmax. alcohols (111) and (IV) the correspondence in [a] (liquid film) 1730s (C = 0),2720w (aldehyde C-H) values indicates that mycarose is an L-sugar.Satura- tion of the hydrolysate of the alcohol (111) with salt followed by prolonged ether-ex traction and p-OHC&> H,OMe H,OMe phenylazobenzoylation5 of the ether solute gave Me .CO (+)-propylene-di-p-phenylazobenzoate [a15461 + 25" (c 0-14 in CHCl,). Smith and his co-workers4 observed that (+)-propane-l,2-diol gave a dextro- rotatory di-0-p-nitrobenzoate. Control experiments indicated that aldol the second product of the hydrolysis of alcohol (111) was dehydrated during HO-MeHC-p-phen ylazo benzoylation. ,IV> With acetic anhydride in pyridine methyl U-L-and 3500w cm.-l (OH) indicated predominant mycaroside2 gave the 4-0-acetate (V). The acetyl existence as structure (11).Guthrie records no other group may be assigned to position 4 on the basis of example of a dicarbonyl compound formed by the known6 resistance to acetylation of tertiary periodate oxidation which contains a free aldehyde alcohol groups in other branched sugars. The signal group. Reduction with sodium borohydride then for the protons on C-6 occurred at r 9.02 in the gave 4-(2-hydroxy- 1 -methylethoxy)-4-methoxybu tan-nuclear magnetic resonance spectrum of a solution Regna Hochstein Wagner and Woodward J. Amer. Chem. Soc. 1953 75 4625. Paul and Tchelitcheff Bull. SOC. chim. France 1957 5 443. a Guthrie Adv. Carbohydrate Chem. 1962 16 105. Abdel Akher Cadotte Montgomery Smith Cleve and Lewis Nature 1953 171,474; Goldstein Lewis and Smith. J.Amer. Chem. SOC. 1958 80 939. Baggett Foster Haines and Stacey J. 1960 3528. Shafizadeh Adv. Carbohydrate Chem. 1956 11 263. JULY 1962 255 of the 4-O-acetate in dimethylformamide. By com- propylidene derivative whereas the trans-isomer does parison with the signals for the protons on C-6 in not react.’ Assignment of the trans-arrangement of methyl 2,3,4-tri-O-acetyl- a-L-fucopyranoside (T 9.02 the 3,4-diol unit together with the preceding results cis4-OAc,S-Me) and methyl 2,3,4-tri-O-acetyl-a-~- permits the allocation of a total L-xylo-configuration rhamnopyranoside (T 8.91 trans-4-OAc,S-Me) a to mycarose and its glycoside (I). The D-glum-&-relation and hence the L-threo-configuration of configuration has been assigned8 to the amino-sugar the acetoxy- and 5-methyl groups in methyl 4-U-portion of magnaniycin.acetyl- a-L-mycaroside (V) may be assigned. The failure of methyl a-L-mycaroside to yield an The authors thank Professor M.Stacey,F.R.S.,for isopropylidene derivative with acetone and zinc his interest and Dr. F. A. Hochsteir of Pfizer Ltd. chloride indicates a trans-disposition of the 3,4-diol for a gift methyl aa-mycaroside isovalerate. unit 1-methylcyclohexane-cis- 1,2-diol forms an iso- (Received May 28tl2 1962.) ’Boeseken Ber. 1923 56 2409. Richardson Proc. Chem. Soc. 1961,430; Foster Tnch Lehmann Stacey and Webber Chenz.andInd. 1962 142. The Existence of Tetrahedral Nickel(1r) Chelates By L. SACCONI P. PAOLETTI P. L. ORIOLL and M. CIAMPOLINI (ISTITUTO GENERALE DELL’UNIVERSITA DI CHIMICA E INORGANICA DTFIRENZE FLORENCE, ITALY) No unambiguous evidence has yet been advanced for co-ordination for this nickel chelate attained by the occurrence of tetrahedral chelate nickel@) com- polymerisa tion plexes.Therefore many authors have expressed Crysoscopic measurements of benzene solutions doubt about the existence of complexes with this of the isopropyl- and s-butyl-nickel(r1) complexes structure proposing instead for the paramagnetic show that the association can account for only a part nickel(1r) chelates the octahedral structure obtained of the solution paramagnetism. This is particularly by po1ymerisation.l According to this view the buff- evident for the t-butyl derivative. coloured form of bis-N-methylsalicylaldimino-This complex paramagnetic in the solid state nickel(@ which was the first paramagnetic com- (peff= 3.3 B.M.) has the highest solution paramag- pound discovered in the series of nickel@) chelates netism (,ueff= 3.2 B.M.in xylene) which corresponds with N-alkylsalicylaldimines,2was attributed octa- to -90% of its being in the paramagnetic form. hedral structure attained by intermolecular associa- The molecular weight in benzene 431 on the con- tion.2 The same hypothesis was advanced to explain trary corresponds to only 5-10% of associated the paramagnetism of some &-branched nickel(I1) species. The reflectance spectrum of this complex is complexes of this series in the solid state as well as in quite similar to those of the isopropyl and the s-butyl s~lution.~ complex showing in particular the characteristic The isopropyl and s-butyl complexes have now band of tetrahedrally co-ordinated nickel(@ at been found isostructural and practically isometric -6800 ~ni.-~*~ The spectra of solutions of this com-with the cobalt(@ and zinc@) analogues.On the plex in various inert solvents are similar to the re- other hand the reflectance spectrum of these cobalt flectance spectrum. The value of its orientation chelates are equal to that of the n-butyl-cobalt com- polarisation in benzene at 25” 461 c.c. is very close plex which was found to be tetrahedral.* Therefore to that of the analogous cobalt($ complexes which a tetrahedral structure must be assigned to these have been found to be tetrahedral.4 The greater part nickel(I1) chelates.Further from two-dimensional of the t-butyl complex therefore must be present in Patterson syntheses the shortest distance between solution as tetrahedral species. the nickel atoms in the isopropyl complex was found The spectra of the isopropyl and s-butyl complexes to be -7 A. This result rules out an octahedral in solution are intermediate between those of the Nyholm “Quelques Problkmes de Chimie Minerale,” Proc. 10th Solvay Conference Brussels 1956 ed. R. Stoops, Brussels 1956; Poray-Koshits Russ. J. Inorg. Chenz. 1959 4 332. Sacconi Paoletti and Cini J. Inorg. Nuclear Chem. 1958 8 492; Sacconi Paoletti and Cini J. Amer. Chem. Soc. 1958 80 3583. Holm and McKinney J. Amer. Chem. Soc. 1960,82,5506;Holm Proc. 6th Internat. Conference on Co-ordination Chemistry MacMillan Co.New York 1961 p. 341. Sacconi Ciampolini Maggio and Cavasino J. Amer. Chem. SOC.,in the press; Frasson and Panattoni 2. Krisi., 1961 116 154. Liehr and Ballhausen Ann. Phys. (New York) 1959 6 134; Goodgame Goodgame and Cotton J. Amer. Chem. SOC.,1961 83 4161. n-alkyl and that of the t-butyl derivative. The orientation polarisation values for these complexes are also intermediate between those of the planar n-alkyl complexes which are practically zero and that of the t-butyl. With increase in temperature the percent of the paramagnetic species in xylene and bibenzyl as calculated by magnetic measurements increases for the isopropyl complex from 37 % at 20" to 70% at 180". Likewise the absorption spectra of PROCEEDINGS these xylene and bibenzyl solutions more nearly approach that of the t-butyl complex on changing from 20"to 160".In conclusion the paramagnetism of these a-branched complexes in solution of inert solvents must be mainly attributed to a conformational equi- librium where the percentage of tetrahedral species increases with increasing temperature. (Received April 24th and May 14th 1962.) Sacconi et af.,J. Amer. Chem. SOC.,1957,79,4062; 1960,82 815. The Geometry of Binuclear Iron Carbonyl Complexes (RC =CR')H,Fe,(CO) By R. CASE,E. R. H. JONES N. V. SCHWARTZ, and M. C. WH~G (DYSONPERRINS THE UNIVERSITY LABORATORY OXFORD) THEcomplexes obtained from the anion Fe,(C0)2- and various acetylenes1 were shown in 19562to have structure (I).In 1958 one such complex was shown to exist in the crystal lattice in the unsymmetrical form (IIa),3 and later chemical evidence4 suggested that the dissimilarity of the iron atoms was maintained in solution. By a hypothetical rotation of the ligand VI I v (H0)C-CR-CR'-C(0H) in (IIa) about an axis per- pendicular to the Fe-Fe bond but not passing through it the form (IIa) could in principle go through a more symmetrical arrangement (IIb) to a form (IIc) in which the 0-and n-bonded iron atoms HYL'7' (m) \/ I I \/ OR m=HOC-CR-CR'COH had interchanged roles. In the energy profile for this process form (IIb) might be (i) a minimum neces- sarily shallow in view of the X-ray results;3 (ii) a maximum of height ca. 15 kcal. mole-l or less of "conformational" type over the asymmetric arrange- ment (IIa/c) ; (iii) a maximum of "configurational" height; or (iv) a maximum higher than that for the disruption of the complex.In cases (i) and (ii) the complex (I; R # R') would be incapable of optical activity; in case (iii) it would be resolvable but sub- ject to thermal racemisation; in case (iv) it would be optically stable below its decomposition temperature. The complex (I; R = Et R' = H) was converted into its mono-( -)-menthoxyacetate which on re- peated crystallisation changed in rotation from [a];* -44" to [a]kg -397" without significant change in infrared spectrum. Alkaline hydrolysis however gave the parent complex without detectable optical activity. The t-butyl complex (111; R = R' = H) was then prepared and converted into its (+)-camphorsulphonate methyl ether which after chromatography had [a],+ 14" f1" (all rotations in alcohol) and on repeated crystallisation finally gave a more sharply melting product [a]D -153" f3" with an unchanged infrared spectrum in solu- tion.Treatment successively with methanolic sodium methoxide at -40" and then diazomethane gave the dimethyl ether (111; R = R' = Me) with rotation varying in different experiments between [a]D + 10" and [alD+ 25". This racemised at 76.0"(96 % of the initial rotation 3 % of initial ultraviolet absorption lost k rac = 1-1 rt 0.1 x sec.-l) or at 52.4"(loss of rotation 86% and of absorption 4% krac = 5.1 + 0.5 x sec.-l). These values lead to an activation energy for the process (IIa + IIc) of 29 f2 kcal.mole-l log A = 14-6 0.6. A very rough estimate was also made of the rate of racemisation of the anion of the monoether (111; R = Me R' = H) giving k raC = 1-5 f0.5 X sec.-l at -23". This would correspond to an energy barrier of ca. 21 kcal. mole-' if the temperature-independent Reppe and Vetter Annulen 1953 582 133; Wender Friedel Markby and Sternberg J Amer. Chem. SOC., 1955, 77,4946; 1956 78 3621;Case and Whiting J. 1960 4632. a Case Jones Wailes and Whiting J. Amer. Chem. SOC.,1956 78 6206. Hock and Mills Proc. Chem. Soc. 1958 233; Actu Cryst. 1961 14 139. Case Clarkson Jones and Whiting Proc. Chem. SOC.,1959 150. JULY 1962 factor were the same as for the dimethyl ether.The earlier isolation of racemic complex (I; R = Et R' = H) after alkaline hydrolysis of the menthoxy- acetate is understandable if its dianion has an energy barrier of only -13 kcal. mole-l as extrapolation would suggest. We conclude that the distinction between the a-bonded and n-bonded iron atoms simultaneously Hubel and Bray J. Znorg. Nuclear Chem. 1959 10,250. present in complexes (I) is real but that the inter- mediate type of bonding typified by (IIb) is also possible; that is cases (i) and (iv) are excluded for these complexes and cases (ii) and (iii) are exempli- fied. These results are probably valid also for related binuclear iron complexes notably of the type (2RCICR')Fe,( CO) g.6 (Received May 8th 1962.) A New Heterocyclic Rearrangement By A.J. BOULTON and A. R. KATRITZKY (THEUNIWRSITY LABORATORY, CHEMICAL CAMBRIDGE) NITRATION of 5-methylbenzofuroxan (I; R = Me) yields the 4-nitro-derivative (11; R = Me) m.p. 98-100" (rapid heating) which rearranges when heated to the more stable (sterically less hindered) Drost Annulen 1900 313 299. 7-methyl isomer (111; X = Me) m.p. 167-169" which is also obtained by direct nitration of 4-methyl- benzofuroxan (IV; X = Me). Drostl made the com- pound (111) by the two methods without isolating its isomer (11) but considered that the products were different compounds. The structures (11) and (111) are supported by ultraviolet and proton resonance spectra. The conversion of (11) -(111) represents a new heterocyclic rearrangement Bailey and Case2 postulated that compounds of types (11) and (111) were mesomers.The present work suppoi ts previous evidence from this laboratory3s4 that this plausible suggestion is incorrect. Preliminary work indicates that successive nitration and rearrangement of 5-chlorobenzofuroxan (I; X = Cl) gives the chloro- analogues (11; X = CI) and (111; X = Cl). This work will be reported in full in the Revue de Chimie (Roumania). (Received May 22nd 1962.) Bailey and Case Tetrahedron 1958 3 113. Katritzky 0ksne and Harris Chem. and Znd. 1961 990. * Harris Katritzky 0ksne Bailey and Patterson J.,in the press. NEWS AND ANNOUNCEMENTS Library.-The Library will be closed for the Bank Holiday from 6 p.m. Friday August 3rd until 9.30 a.m.Wednesday August 8th 1962. Liaison Officers.-The following Fellows have agreed to act as Chemical Society Liaison Officers Bradford Institute of Tech- nology . . .. . . Dr. G. Shaw Harris College Preston . . Dr. J. K. Latham I.C.I. (Heavy Organic Chem- icals Division) Billingham Dr. L. A. Duncanson. Deaths.-We regret to announce the deaths of the following Mr. R. L. De (4.4.62) of the Research Section of Chittaranjan Cancer Hospital; Lord HenZey (21.4.62) a Fellow since 1901; Mr. W. H. TayZor (8.6.62) formerly Works Chemist Wellcome Foundation Ltd. Dartford; and MI-.C. T. Webster (14.6.62) Senior Experimental Officer D.S.I.R. Election of New Fellows.-1 11 Candidates whose names were published in Proceedings for May have been elected to the Fellowship.Birthday Honours List.-Included in the Birthday Honours List were Sir Charles Robert Harington Director National Institute for Medical Research (K.B.E.) Dr. N. J.L. Megson Director of Materials Research and Development Ministry of Aviation (C.B.E.) and ProfessorJ. M. Robertson President of the Society and Gardiner Professor of Chemistry Glasgow University (C.B.E.). Royal Commission for the Exhibition of 1851.-The Royal Commission for the Exhibition of 1851 has awarded the following Overseas Scholarships for 1962 Mu. R. E. Burton (Trinity College Dublin) for research in theoretical chemistry at Oxford; Mr. J. D. Cotton (Melbourne) for research in inorganic chem- istry at Cambridge; Mr.M. C. L. Gerry (British Columbia) for research in physical chemistry at Cambridge; and Mr. J. F. Young (Canterbury) for research in inorganic chemistry at Oxford. Van’t Hoff Fund.-The Committee of the Van’t Hoff Fund for the endowment of investigations in the field of pure arid applied chemistry invites applications for grants from the fund. The amount available for next year is about 2,000 Dutch guilders. Applications should be sent by registered post to Het Bestuur der Koninklijke Nederlandse Akademie van Wetenschappen bes temd voor de Commissie van het “Van’t Hoff Fonds,” Trippenhuis Kloveniersburgwal 29 Amsterdam before December lst 1962. The purpose for which the grant is required the reasons for the application and the amount desired must be stated.Grants from the Fund for 1962 were awarded to Dr. Ernst Gottinger (Austria) Dr. 0. P. Malhotra (India) and Dr. L. Petit (Seine France). Symposia etc.-The Third International Sym-posium on Batteries sponsored by the Inter-Departmental Committee on Batteries will be held at Bournemouth on October 2nd-4th 1962. Further enquiries should be addressed to the Secre- tary Mr. D. H. Collins Admiralty Engineering Laboratory West Drayton Middlesex. A Symposium on the Chemistry and Biochemistry of Fungi and Yeasts organised by the Irish National Committee for Chemistry under the auspices of I.U.P.A.C. will be held in Dublin on July 15-20th 1963. Further enquiries should be addressed to The Secretary Irish National Committee for Chemistry Royal Irish Academy 19 Dawson Street Dublin.The 1963 Federal Scientific and Medical Congress will be held in Lusaka Northern Rhodesia on August 26-30th 1963. Further enquiries should be addressed to The Honorary Secretary 1963 Federal Scientific and Medical Congress P.O. Box 844 Lusaka Northern Rhodesia. The Twenty-second Session of the International Geological Congress will be held in Calcutta India on October lst 1964. Further enquiries should be addressed to the General Secretary Twenty-second International Geological Congress Geological Sur- vey of India 27 Chowringhee Calcutta 13 India. Personal.-Dr. W. Blakey Deputy Chairman of British Industrial Plastics has been appointed PROCEEDINGS Chairman of the Trustees of the Plastics Industry Education Fund.Dr. G. C. Bond Senior Lecturer in Chemistry in the University of Hull has been appointed by Johnson Matthey and Co. Ltd. as Head of Catalyst Research in their Research Laboratories Wembley as from October 1st next. Miss Juliann Calder is to take up the post of Principal of Glasgow and West of Scotland College of Domestic Science at the end of the year. Dr. J. Clark formerly a Senior Lecturer at the Royal College of Advanced Technology Salford has taken up a Research Fellowship in the Department of Medicinal Chemistry Australian National Uni- versity Canberra. Mu. H. A. Collinson Managing Director Leicester Love11 & Co. Ltd. has been elected Vice-chairman of the British Plastics Federation.Dr. F. M. Dean and Dr. J. S. E. Holker have been appointed Senior Lecturers in Organic Chemistry at the University of Liverpool as from October 1st next. Dr. V. S. Grifiths and Dr. J. E. Salmon have been nominated by the Academic Board and elected to serve as Governors of Battersea College of Tech- nology. Dr. R. D. Guthrie has been appointed to a Lecture- ship at the University of Leicester from October next. The earlier reference to him in Proceedings 1962 p. 33 is incorrect. The Honorary Degree of Doctor of Science will be conferred upon Sir Charles Harington by the University of London on November 29th 1962. Mr. J. D. Hemingway has been appointed Research Fellow in Radiochemistry at the University of Durham. Dr. H. S. Hirst has been appointed a Director of Imperial Chemical Industries Limited Billingham Division.The Council of the Royal Society has appointed Mr. R. W. J. Keay at present Director of the Federal Department of Forest Research in Nigeria to be Deputy Executive Secretary to the Society from October next . Mr. D. G. 1. Kingston has been elected to a Research Fellowship at the University of Cambridge. Dr. A. J. Lindsey who has resigned as Head of the Department of Chemistry Sir John Cass College has been appointed Director of Research Carreras Ltd. Basildon. Dr. M. L. McGlashen and Dr. J. E. Prue have been appointed Readers in Chemistry at the University of Reading as from October 1st next. Mr. P. McGregor has retired from his position of Senior Principal Scientific Officer Laboratory of the Government Chemist D.S.I.R. Dr. S. R. Mohanty Banaras Hindu University has JULY 1962 been promoted to a Readership in the Department of Chemistry. Dr. J. N. Murrell who has been appointed Lec- turer in Chemistry at the University of Sheffield has also been appointed to a Mr. and Mrs. John Jaffe Donation Research Fellowship by the Council of the Royal Society from October 1st next. Dr. S. C. Nyburg and Dr. P. H. Plesch have been appointed Senior Lecturers in Chemistry at the University of Keele with effect from October 1st next. Dr. C. A. Ponnamperuma has been awarded a post-doctoral research fellowship with the National Aeronautics and Space Administration Ames Research Center Mountain View California.Dr. L. C. Roselaar has been appointed Senior Lecturer in Physical Chemistry in the Department of Chemistry and Biology South-East Essex Technical College Dagenham from September 1st next. Dr. R. A. Shaw Birkbeck College will be on a lecture tour of the United States and Canada from early July to the middle of September. Dr. H. M. Stanley Controller of the Development Division of The Distillers Co. Ltd. has been ap- pointed to the board of British Hydrocarbon Chemicals Ltd. Mr. W.P. Thistlewaite has been appointed Vice- Principal of Whitehaven College of Further Educa- tion. APPLICATIONS FOR FELLOWSHIPS (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings.Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Adler Michael Edward. Brasenose College Oxford. Bailin Lionel J. A.B. Ph.D. 1492 Ebener Street Red- wood City Calif. U.S.A. Bidinosti Din0 Ronald Ph.D. Department of Chemistry, University of Western Ontario London Ont. Canada. Bloom Percival B.Sc. SKF Laboratories (Pty.) Limited P.O. Box 38 Isando Tui South Africa. Bosnich Brice Ph.D. Chemistry Department University College of London Gower Street W.C.1. Bowman William Russell B.Sc. 1 Woodlands Upper Tree Road Camps Bay Cape Town South Africa. Boxall Brian Alfred B.Sc.564 Staines Road East Bedfont Feltham Middlesex. Brewster Anne Isabel B.Sc. Apt. 404 No. 5 Biggin Court Toronto 16 Ontario Canada. Burling Eric Douglas B.Sc. A.M.C.T. 54 Daisy Bank Road Victoria Park Manchester 14. Cairns Thomas B.Sc. 4 Avon Drive Bellshill Lanark- shire Scotland. Cameron Euan Hamish Donaldson B.Sc. Biochemistry Department Queen’s College Dundee Scotland. Carmichael Jack Blake B.A. Kedzie Chemical Labora- tory Michigan State University East Lansing Mich. U.S.A. Carter Robert Everett B.A. Ph.D. K. .Vetenskaps-akademiens Nobelinstitut Avd. for Kemi Stockholm 50 Sweden. Chadwick Ann. 4 Hardy Street Blackburn Lancashire. Daly William Howard B.S. 273 Henry Street Brooklyn 1 New York U.S.A. Dinius Robert H. Ph.D.Chemistry Department, Auburn University Auburn Alabama U.S.A. Downs Anthony John Ph.D. University Chemical Laboratory Lensfield Road Cambridge. Dugar Sumer Mal M.Sc. 13 Vivekanand Road Jaipur India. Falk Robert A. Ph.D. Sperry Gyroscope Co. LOC.C-2, Great Neck Long Island New York U.S.A. Fragman Zvi. P.O. Box 11 151 Tel Aviv Israel. Glasgow David Gerald A.B. 370 Howell Avenue Cincinnati 20 Ohio U.S.A. Gurney John Joseph B.%. 75 Forest Drive Pinelands Cape Province South Africa. Hackett James Walter Ph.D. O.P. Department of Chemistry Providence College Providence 8 Rhode Island U.S.A. Heicklen Julian Phillip B.Chem. Ph.D. Department of Chemistry Aerospace Corporation Box 95085 Los Angeles 45 Calif. U.S.A. Himoe Albert B.A. Department of Chemistry Univer- sity of Chicago Chicago 37 Illinois U.S.A.Hirshfeld Fred Lurie Ph.D. Weizmann Institute of Science P.O. Box 26 Rehovoth Israel. Kennewell Peter David. 24 Plumpton Lea Wrose Bradford 2. Li Kuang-pang B.S. 76 Hsin Tien Tapei Taiwan Formosa. Lykiardopulos Anthony B.Sc. 210 Bordeaux Flats, Beach Road Sea Point Cape. South Africa. Macrea Alasdair Robin B.Sc. A.R.C.S. University Chemical Laboratory Lensfield Road Cambridge. Masumoto Eleanor Mitsue M.S. Lockheed M.S.C., Dept. 52-30 Bldg. 204 3251 Hanover Street Palo Alto Calif. U.S.A. Matsuura Teruo D.Sc. Faculty of Science Osaka City University 12 Minamiogimachi Kitaku Osaka Japan. Moulden Harvey. 247 Ratcliffe Road Sileby Nr. Loughborough Leics. Odham Lars Goran.Inst. for Medicinsk Biokemi Medicinargatan 7 University of Gothenburg Sweden. O’Shea John Martin B.Sc. B.P. Australia Limited 196 North Terrace Adelaide Australia. Pence Harry E. M.S. Department of Chemistry, Washington and Jefferson College Washington, Pennsylvania U. S.A. Penny Gerald Glyn. 75 Valetta Road Acton W.3. Pratt Gwyneth Margaret M.Sc. 38 Salmon Avenue Essendon W.5 Victoria Australia. Raval Arvind Anantrai Ph.D. 10 Hirabang Ellis-bridge Ahmedabad-6 Gujarat State India. Sample Thomas Earl Jr. Ph.D. 2208 Morse Street Apt. 2 Houston 19 Texas U.S.A. Savage David Samuel Ph.D. 3 Castleton Drive Broom Estate Newton Mearns Renfrewshire Scotland. Simon Lawrence Edward B.S. Dept. 52-30 Lockheed Missiles and Space Co. 3251 Hanover Street Palo Alto California U.S.A.Singh Jauhal Gurcharan M.Sc. 11 Simon-Side Terrace Heaton Newcas t le-upon-T yne . PROCEEDINGS Spackman John William Charles B.Sc. Royal Military College of Science Sbrivenham Wilts. Stephens Diana Lynne Joplin B.S. Lockheed Missiles and Space Co. 3251 Hanover Street Palo Alto California U.S.A. Stoneman Colin Frank B.Sc. 54 Courtfield Gardens London S.W.5. Suhadoinik Robert J. Ph.D. Albert Einstein Medical Center York and Tabor Roads Philadelphia 41, Pennsylvania U. S.A. Thomas John Arthur B.Sc. 4 Thornton Way Golders Green N.W.11. Ticktin Saul B.Sc. 12 Marmion Road Oranjezicht Cape Town South Africa. Tobia Sami Kirollos Ph.D. D.I.C. Faculty of Science A’in Shams University Abbassia Cairo Egypt.Todesco Antonio Bernard0 Joao Batista Ph.D. Univer- sity Chemical Laboratory Lensfield Road Cambridge. Trecker David J. A.B. Ph.D. 4214 Rosemont South Charleston 3 West Virginia U.S.A. Wayland Bradford Britton A.B. Chemistry Department University of Illinois Urbana Ill. U.S.A. Wimp. Peter Olaf B.Sc. 307 Norton Road Hastings, New Zealand. Woolhouse Beatrice Anne. 9 Glebe Avenue Woodford Green Essex. Worsdall Julia Margaret. “Ingledene,” Norton Brom-yard Herefordshire. OBITUARY NOTICES* H. V. A. BRISCOE INProceedings for May (1 962 p. 191) quite a detailed account is given of much of the excellent work carried out by the late Professor Briscoe. May I add a reference to another of his extremely valuable con- tributions to scientific literature namely his book entitled “The Inert Gases,” iiicluded as Part I1 of Volume I of my “Textbook of Inorganic Chemistry.” It was first published in 1914 and a second edition was called for in 1916 by which time Briscoe had obtained his doctorate.At the time of its publication this was by far the best account of the gases that had as yet appeared in the English language and the greatest credit is due to Briscoe; it cost him an immense amount of work. Mention might also be made to his useful little book “First Aid in the Laboratory and Workshop,” written in conjunction with his colleague A. A. Eldridge and published in 1915. I gladly pay tribute to the memory of so great and modest a chemist whom I had the pleasure of knowing for upwards of forty-eight years.J. NEWTON FRIEND. HARRY WILLIAM WEBB 1893-1 962 THEdeath occurred in Stoke-on-Trent after a short illness of Dr. Harry W. Webb at the age of 68. Many people in North Staffordshire read the announcement of his death on February 8th with great surprise and with much regret. Surprise because he had been active in his consulting work and in his attendance at Committees until shortly before his death. Regret because Dr. Webb had been a well known and popular figure in the educa- tional and industrial life of the Potteries for the second half of his life and the value of his work had been widely recognised. Harry W. Webb was born in Boston U.S.A. in 1893 but he came to England in his early youth and in fact received his formal education in this country.He entered Birmingham University in October 1910 and graduated with a First Class honours degree in Chemistry three years later. He received his M.Sc. degree in June 1914. He saw service in the ranks in the 1914-18 war but his chemical training was soon utilised for in 1915 he was given a responsible posi- tion with H.M. Factory Oldbury which was con- * See also p. 242. cerned in the production of sulphuric acid-so essential to the manufacture of TNT and the other explosives of the period. From 1916-19 he was Superintendent of Research Departments H.M. Factory Site A Oldbury. His experience at this time was subsequently drawn on to provide the material for his book on “The Absorption of Nitrous Gases” which was published in 1923.At the conclusion of the war Webb took up Tech- nical Education as a career. He was appointed Head of the Department of Industrial Chemistry at Cardiff Technical College in 1919 and Principal of Aston Technical College Birmingham in 1926. Despite his teaching and academic duties he was able to carry out research in pure chemistry in the field of co-ordination compounds and in 1931 he submitted a thesis for the degree of D.Sc. which he was awarded later in the year. Some of these papers may be seen in the Transactions of the Chemical Society. In 1931 Dr. Webb was appointed lecturer in the Pottery Department of the North Staffordshire Tech- nical College at which time Dr.J. W. Mellor was JULY 1962 the Head. Dr. Webb succeeded Dr. Mellor on his retirement in 1934 and was at the same time ap- pointed to be the nist Principal of the College a posi- tion which he held until his retirement from the College in 1958. On his arrival in the Potteries Dr. Webb took up the study of the technology of ceramics with enthusiasm and he was soon engaged in investigating both personally and with the assistance of students the fascinating problems pre- sented in the manufacture of clay ware. These experi- ments are described in the Transactions of the Ceramic Society in the period 1932-39. He received the O.B.E. in 1945 for his technical services to the Government during the war. He was Vice-chairman of the Working Party on the Pottery Industry which published its report in 1946 and President of the British Ceramic Society for the year 1956-57.Although Dr. Webb became an acknowledged ceramics expert it was in the field of technical educa- tion that he achieved his life’s work. When he arrived at the North Staffordshire Technical College in 1931 it was relatively small in numbers despite its inter- national reputation in ceramics among the know- ledgeable few. When Dr. Webb left in 1958 the College while still possessing a Pottery Department unique in the country had grown eightfold with Departments of Engineering Mining Chemistry Physics and Catering and Food Technology as well 26 1 as Ceramics enabling it adequately to serve the needs of the area in full-time day part-time day and part-time evening courses.To accommodate the con- siderable increase in student population much new building was required. Today the large and impres- sive buildings of the College now known as the North Staffordshire College of Technology with their manifold activities can in large measure be considered to owe their existence to Dr. H. W. Webb whose energy foresight and organising ability brought them to pass. Of dignified appearance and courteous in address Dr. Webb had great personal charm. Keen in debate a first class committee man he had the ability to make his points clearly and succinctly and at times with a dry humour. As a committee chairman he was excellent. His passing will be keenly felt by a whole genera- tion of students and by many friends in the pottery industry most of whom were his stud.ents of former years.Of Sir Christopher Wren it was said “If you desire a monument look around you.” With the setting transferred from London to Stoke-on-Trent one might say the same of Dr. Webb and it would not be solely in buildings that his memory would be perpetuated; it will live on in the minds of the manufacturers and people of the area. F. H. CLEWS. CHARLES EDWARD FAWSITT 1878-1960 CHARLES FAWSITT EDWARD was born in Glasgow in 1878. His father C. A. Fawsitt was a chemical manufacturer in that city and his mother a niece of Dr. James Young F.R.S. the founder of the Scottish Shale Oil industry.l As a boy he was educated at the Glasgow High School.Because of the opinion of his father that chemistry in the Uni- versity of Edinburgh under Professor A. Crum-Brown F.R.S. was superior to that in the University of Glasgow Charles proceeded for his first degree to the former University. In 1900 with a Science Re- search Scholarship from the Royal Commission for the Exhibition of 1851 he went to Leipzig and joined the laboratory of Wilhelm Ostwald. There he had as fellow 1851 scholars J. C. Irvine W. G. Smeaton R. D. Abell G. Senter F. A. Lidbury H. L. Heath-cote F. W. Skirrow A. Slatcr and others who sub- sequently held senior academic or industrial posts in the United Kingdom United States of America or Canada; he had also opportunities of contacts with J.H. van’t Hoff J. Wislicenus G. Bredig M. Read Endeavour 1942 36. Le Fkvre Clzem. and Ind. 1953 736. Bodenstein L. Boltzmann G. N. Lewis and many more of the scientific leaders of the period. With two years’ experience of such an environ- ment it is not surprising that Fawsitt was attracted more to academic than to an industrial career. Re- turning to Scotland with a Leipzig Ph.D. he first became assistant to Professor Crum-Brown in Edin-burgh but soon during 1904 accepted an invitation from Professor J. Ferguson F.R.S. to transfer to the University of Glasgow as Lecturer in Metal- lurgical Chemistry. This position he held until his election in 1908 to the Chair of Chemistry in the University of Sydney from which Professor Archi- bald Liversidge F.R.S.had just retired. Fawsitt was thus third in line from the foundation of the University. Liversidge’s predecessor the Hon. John Smith from Aberdeen taking up duties in 1852-some years before valency or the formula of benzene was understood-had formed a modest chemistry department2 apparently adequate for 25 years. Liversidge in the early 188O’s expanded this into new buildings and developed courses of a general kind emphasising consistently with his research interests the mineralogical and analytical aspects of his subject. Professor Fawsitt arrived during 1909 to inherit a staff of about eight and a curriculum of lectures3 on metals and non-metals engineering chemistry organic chemistry and on the History of Chemical Philosophy and Discovery.The Iaboratories3v4 were for the day perhaps more modern than the course. They included “separate rooms for spectroscopic and gas analysis for photography and for research work.” The building was provided with electric light throughout the upper floor with a gas engine for driving the dynamos and through an attached shaft- ing a liquid-air machine various grinders rollers and crushers and “similar appliances necessary for a large laboratory.” It contained also “44 fusion and muffle assay furnaces . . . an experimental revet- beratory furnace with a bed 6 feet by 4 feet . . . a magnetic concentrator. ..vats. . .for the extraction of gold and silver ores by . . . leaching processes.” The practical courses3 were heavily inclined towards analysis and metallurgy.Fawsitt immediately introduced two changes organic chemistry was made a compulsory part of the first-year syllabus for students in all Faculties and a course of practical physicochemical measure- ments was started for 3rd year B.Sc. students. Lec- ture programmes were replanned for 1910 rewritten under the now familiar three adjectival headings and based on Newth’s “Inorganic Chemistry,” Senter’s “Outlines of Physical Chemistry,” and Cohen’s “Organic Chemistry.” For the laboratory Fawsitt prescribed Perkin’s “Qualitative Analysis,” Clowes and Coleman’s “Quantitative Analysis,” Cohen’s “Practical Organic Chemistry,” and his own “Tables of Quantitative Chemical Analysis.” Dr.J. W. Hogarth a student under Liversidge and a demonstrator under Fawsitt remembers the first years of the latter in Sydney. He writes “Professor Fawsitt possessed a brief and lucid way of expressing himself and what he said was definite. I attended his series of lectures in physical chemistry. They were a model to imitate being clearly and logically ex- pressed and any fomulz were given in logical sequence from their derivation to the final stage. He spoke at such a rate that by the use of abbreviations it was possible to take down his statements verbatim and when later perused they read like a book. He lectured mostly without notes with dry humour and a Scots accent.” Fawsitt himself has told the writer how in the PROCEEDINGS early years of his Professorship he thought that Organic Chemistry deserved recognition by a Chair but that the governmental advisers of the day con-sidered that what was needed was a Professor of In- dustrial Chemistry; since the Government was largely to provide the funds a compromise was accepted and thus the University of Sydney came to have a Chair with the unusual title “Organic Chem- istry Pure and Applied.” The first occupant of the new position was Dr.Robert Robinson introduced in the words of the University Calendar for 1913 as “the author of many original papers on chemical subject including contributions to the chemistry of dyeing processes.” The post continued with the an- notation “Pure and Applied” until 1947 when an independent Department of Chemical Engineering was created.A third example of Fawsitt’s long-range prevision as a Departmental Head occurred just before his re- tirement. In 1944-5 anticipating-correctly as events proved-a great increase of student numbers following demobilisation he arranged the erection of capacious elementary laboratories. These if not beautif~l,~ were efficient and made it possible for the University to provide Chemistry I courses for 2000 and more students from 1946 onwards. Fawsitt’s research interests during his thirty-seven years as a Professor lay mainly in the fields of metallic corrosion and chemical kinetics. In Leipzig he had studied the decomposition of urea a matter he took up again with C. J. Burrows about 1913. While in Scotland he had concerned himself with the reaction between iron and sulphuric acid and a number of publications on various aspects of this and related matters such as the corrosion of steel in water and the corrosion of bore-casings appeared during his Sydney period in the Journa1 Trans.Faraday Soc. J. Proc. Roy. Soc. New South Wales and elsewhere. Other papers in the same journals described investi- gations on the miscibilities of liquids and the freezing points of solutions. In 1918 Fawsitt pro- posed cineole as a crysoscopic solvent-a proposal which however does not seem to have received much acceptance. Professor Fawsitt perhaps deserves remembrance and gratitude for more general reasons than merely his research activities.From 1923-29 he was Dean of the Faculty of Science. Throughout all his time in Sydney he maintained a keen interest in educational affairs and established a very friendly liaison with the New South Wales Education Department and the secondary schools of the State. Moreover he co-operated willingly and understandingly with the University of Sydney Calendar 1908 pp. 135-142. Tilden “Chemical Discovery and Invention in the Twentieth Century,” Routledge London 1916 pp. 44-46. Le Fkvre Chem. and Znd. 1951,415. JULY 1962 senior staff members of the Sydney Technical Col-lege. Fawsitt took an effective part in the most h-portant of the wider developments concerned With chemistry and science in Australia. He was one of the original members of the Royal Australian Chem- ical Institute of which he was Federal President 1924-25.For a number of years he was Chairman of the Australian National Committee of Pure and Applied Chemistry. He joined the Council of Science and Industry on its formation in 1916 and was honorary secretary of the New South Wales Branch of the Council for several years. In 1919 he presided over a meeting of scientists representing all the States of the Commonwealth at which it was agreed to found the Australian National Research Council; this was the body which voluntarily disbanded itself to make space for the Australian Academy of Science in 1953. Like his predecessors Smith and Liversidge Fawsitt was a strong supporter of the Royal Society of New South Wales serving it in many ways and being its President 1919-20.When the New South Wales Government created its “Pure Food Advisory Committee’’ in 1909 Fawsitt became a member and remained actively associated with the Committee until 1947. Professor Fawsitt was a musician of quality and a performer of high standard on the piano. Old students have often spoken of the pleasure he gave by his playing at social functions connected with the University. His taste in general literature was catholic and he particularly enjoyed works of a bio- graphical kind. Through his attendance at a lecture on Dickens given by the Reverend Dr. M. Gardner in Glasgow he met Lena G. Gardner whom he married in 1909. Professor and Mrs. Fawsitt were a musical pair she being a singer and a composer and like him a keen golfer.Dr. Hogarth writing about his impressions of Professor Fawsitt says “My seven years of associa- tion with him convinced me of his straightforward- ness and forthright manner. He was very trusting towards others and was quite free of guile. He did not seem to bear any ill-will towards anyone.” Everything seen and heard by the writer from 1947 onwards confirms this. Fawsitt was a loyal Scot and a quietly religious man possessed of old-world courtesy considerateness friendliness and helpful- ness to all. He died in the Scottish Hospital Sydney about midnight on November 16th 1960 Mrs. Fawsitt and their one daughter (Mrs. J. A. Cosh) surviving him. R. J. W.LEF~VRE. ADDITIONS TO THE LIBRARY Great chemists.Edited by E. Farber. Pp. 1642. Inter-science. New York. 1961. Small particle statistics. G. Herdan. 2nd edn. Pp. 418. Butterworths. London. 1960. An ultraviolet multiplet table. C. E. Moore. Sponsored by the United States Dept. of Commerce National Bureau of Standards. (Circular 488 parts 3 4 5.) U.S. Govt. Printing Office.Washington. 1962. (Presented by the publisher.) Fluorescent protein tracing. Edited by R. C. Nairn. Pp. 280. Livingstone. Edinburgh. 1962. Ion association. C. W. Davies. Pp. 190. Butterworths. London. 1962. Catalysis by metals. G. C. Bond. Pp. 519. Academic Press. London. 1962. Anodic oxidation of aluminium and its alloys issued by the Aluminium Development Association. (Informa- tion Bulletin 14.) 2nd edn.Pp. 187. A.D.A. London. 1961. (Presented by the publisher.) Progress in polarography. Edited by P. Zuman. Vols. 1 2. Pp. 807. Interscience. New York. 1962. Gas chromatography. J. H. Knox. (Methuen’s mono- graphs on chemical subjects.) Pp. 126. Methuen. London. 1962. Introduction to advanced inorganic chemistry. P. J. Durrant and B. Durrant. Pp. 1171. Longmans. London. 1962. An introduction to the chemistry of complex com- pounds. A. A. Grinberg. Translated from the 2nd edn. (1951) by J. R. Leach. Edited by D. H. Busch and R. F. Trimble. Pp. 363. Pergamon Press. Oxford. 1962. The manufacture and use of fluorine and its com- pounds. A. J. Rudge. Pp. 87. Oxford University Press. London. 1962. The chemistry of rhenium.K. B. Lebedev. (Translated from the Russian bv L.Ronson.) PD.105. Butterworths. London. 1962. ,A Glossarv of organic chemistrv. S.Patai. PD. 227. Inter-science. Nkw YoFk. 1962. Grundriss der Technischen Organischen Chemie. A. Rieche. 2nd edn. Pp. 549. Hirzel Verlag. Leipzig. 1961. Stereochemistry of carbon compounds. E. L. Eliel. Pp. 486. McGraw-Hill. New York. 1962. Mechanisms of sulfur reactions. W. A. Pryor. Pp. 241. McGraw-Hill. New York. 1962. Mechanisms of organic and enzymic reactions. S. G. Waley. Pp. 365. Clarendon Press. Oxford. 1962. Methods in hormone research. Edited by R. I. Dorfman. Vols. 1 and 2. Academic Press. New York. 1962. Phenolics in plants in health and disease proceedings of a Plant Phenolics Group Symposium Bristol 1959.Edited by J. B. Pridham. Pp. 131. Pergamon Press. Oxford. 1960. Biochemical applications of gas chromatography. H. P. Burchfield and E. E. Storrs. Pp. 680. Academic Press. New York. 1962. Synthetic materials from petroleum. A. V. Topchiev, M. F. Nagiyev and T. N. Shakhtakhtinskii. Translated from the Russian by J. Burdon. Pp. 128. Pergamon Press. Oxford. 1962. Coal typology chemistry physics and constitution. D. W. van Krevelen. Pp. 514. Elsevier. Amsterdam. 1961. Electrolytes proceedings of an International Sym-posium held in Trieste 1959 arranged as part of the Congress of the Societa Italiana per il Progress0 delle Scienze. Pp. 360. Pergamon Press. Oxford. 1962. Retardation of evaporation by monolayers :transport processes.Edited by V. K. La Mer. Papers presented at the symposium held by the A.C.S. in New York 1960. Pp. 277. Academic Press. New York. 1962. First International Congress on Metallic Corrosion held in London 1961 under the auspices of the Inter- national Union of Pure and Applied Chemistry. Pp. 712. Butterworths. London. 1961. Cellular regulatory mechanisms :symposium organised by the Biological Laboratory Cold Spring Harbor 1961. (Cold Spring Harbor Symposia on Quantitative Biology Vol. 26.) Pp. 408. Long Island Biological Association. New York. 1961. Titrimetric methods proceedings of the symposium on titrimetric methods held 1961 Cornwall Ontario sponsored by the Chemical Institute of Canada. Edited by D. S. Jackson.Pp. 185. Plenum Press. New York. 1961. Report of the Commission on Enzymes of the Inter- national Union of Biochemistry 1961. (International Union of Biochemistry Series Vol. 20.) Pp. 159. Per-gamon Press. Oxford. 1961. NEW JOURNAL Scientific Reports of the Instituto Superiore di Sanita. Rome. From 1961 1. (Presented.) A PRETTY PACKET in the Editor’s Mail Dear Sir Submitted as a Communication for Proceedings I enclose a manuscript entitled . . . Yours faithfully . . .
ISSN:0369-8718
DOI:10.1039/PS9620000237
出版商:RSC
年代:1962
数据来源: RSC
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