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Proceedings of the Chemical Society. January 1964 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue January,
1964,
Page 1-36
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Proceedings of The Chemical Society LONDON THE CHEMICAL SOCIETY PROCEEDINGS OF THE CHEMICAL SOCIETY JANUARY 1964 THE CHEMICAL INDUSTRY OF THE MIDLANDS HISTORY AND DEVELOPMENT* BY GEORGE KING M.B.E. M.Sc. F.R.I.C. THEstructure of the chemical industry in the Midlands is firmer to-day than it was in 1934 when the Society last met in Birmingham under Sir Gilbert Morgan as President. Uneasiness following the depression of 1931 together with uncertainty in the European political situation was evident in the records of production and sales but the structure had firm foundations and has weathered the disturbances due to World War I1 and post-war expansion. The first essential for the foundation of chemical industry is obviously initiative and with this must be coupled the availability of labour and energy and raw materials or cheap transport and in the early days this meant canals.The ultimate success depends also on consumer demand and financial backing. Looking at the Midlands from this point of view we find that Birmingham in former times was not important enough to be considered as a borough or corporate town like Sutton Coldfield Lichfield or Warwick. It had no centre of culture or cathedral and the only really fertile land was around the River Rea and tributary streams. There were many of these coming down from the heaths-Small Heath King’s Heath Balsa11 Heath West Heath and Hamstead-and these streams by supplying water power for the small mills played an important part in the industrial history of the town.The manufacturing industry of the Midlands really began when following the Civil War in 1642 the Parliamentary forces ordered and actually paid for 15,000 swords to be made in Birmingham. By that date the in- habitants had developed the skill and know-how in working iron. In 1538 when John Leland Commissioner toured the Midlands iron had been worked for two hundred years and to quote from his report he found “many smiths who make knives and cutting tools and many lorimers that make billes and a great many nailors.” These were the men who had the initiative to use the water power from the small streams to drive their mills. The small mills were later driven by the steam engine-improved by *Published in connection with the Society’s Anniversary Meetings.Watt-followed in due course by oil engine and electric motor the products of Birmingham in- dustry. In the early days raw materials were to hand from the heathland around; charcoal and coal iron pyrites iron ore sand and particularly salt from Droitwich and limestone. At a later date Staffordshire clay was found to have special value. Two other factors influenced the rate of industrialisation in the Midlands firstly the schools and secondly the Five Mile Act. King Edward VI founded a Grammar School in Birmingham on the site of the earlier “Gild of the Holy Cross,’’ and at Bromsgrove Lichfield and Shrewsbury. These and other foundations like Bishop Vesey’s School provided a standard of learning.The second and important factor was the passing of the Five Mile Act in 1665. This was for Birmingham a most contributory agent to progress. The Act forbade any nonconformist minister to live within five miles of a corporate town. Birmingham was not a corporate town and so there came to Birmingham the persecuted of many sects; men with new ideas men with initiative. Many Quakers and Unitarians as well as Presbyterians came at that time because they were able to carry on their trade without hindrance and there were no craft companies to interfere with the establishment of new trades. The absence of such restraints allowed free scope for private enterprise.Unemployment was un- known in the Birmingham metal goods industry and the production was practically all sold abroad. In this connection-at a later date-the names of Boulton the administrator Watt the engineer and Murdoch the chemist are re-membered and somewhat belatedly Birmingham has recognised the work of the trio by erecting a monument in the Civic Centre. We shall refer to the chemist Murdoch later. They brought initiative and improved on the facilities already available and with their friends in the “Lunar Society” were virtually the founders of the In- dustrial Revolution. The Lunar Society so called because meetings were held on the night of a full moon had as members beside the above the chemist Joseph Priestley Dr. Withering Dr.Erasmus Darwin Capt. James Keir Samuel Galton John Baskerville Josiah Wedgwood John Smeaton John Wilkinson- all men of eminence and well known for their PROCEEDINGS achievements in science and industry. Considering next the availability of energy ; fortunately for the Midlands coal was plentiful even by surface working but it was not until James Watt came from Glasgow to Birmingham to join Matthew Boulton that energy from coal which was cheap was harnessed economically to drive a stationary engine. This enabled Matthew Boulton at his Soh0 works to provide for the first time in history enough power to drive machines for use by a large number of craftsmen working in the same building. These machines did away with much of the heavy manual work and made production of metal articles much cheaper.Birmingham buttons jewellery “toys”-a name given at that time to describe the buckles and other non-essential ornaments of the “nobility”-were produced at the Soh0 works and the factory was also recog- nised for the minting of money. To this was added the production of the large castings for the first steam engines to be sold to others thus introducing for the first time the steam engine for factory work which revolutionised manu- facturing industry throughout the world. Boulton and Watt were joined by Murdoch a chemical engineer by inclination and an in-genious felIow who when he came to be inter-viewed by Boulton for a job was wearing a top hat made of wood. No one had ever turned such a shape on a lathe before and it got him the job.Later he was the first in the world to make in- dustrial gas from coal between 1792 and 1802. The first gas holder in the world was built at the Soh0 works in 1792 and remained in use for 120 years. It had been so much repaired and altered and rebuilt that recently Messrs. Avery’s Ltd. considered it as of no true historical value and reluctantly cleared it away for works expansion. The first commercial gas works in the world was in Gas Street Birmingham in 1817 and the streets were lighted in 1826. In 1875 the Gas Company was purchased by the town. The firm of Boulton and Watt erected plants for many manufacturers and an employee named Clegg was the first gas engineer and inventor of mains seals meters etc.From 110 tons of worked coal he obtained 70 tons of coke and 11 to 12 ale gallons of tar per ton of coal and said that “it cannot be such as materially to influence the economic statement unless indeed new applica- tions of the tar should be discovered.” The JANUARY 1964 quantity of aqueous liquid was not ascertained. The coal used was not more than 128 tons a year. The gas industry developed actively in Birmingham as a chemical industry despite opposition by some leading clergymen who thought its use “profane and contrary to God’s law.” Iron for the metal trade came from the Black Country where charcoal from the Wyre forest was plentiful. Then came coal and in 1620 at the famous Cradley forge Dud Dudley claimed to have made 3 tons of iron per week using coal- and “so saved the nation’s timber for ships of war”! There was organised opposition and riots but in 1709 Abraham Darby at Coalbrookdale turned to coke derived from the coal instead of using charcoal and in 1770 John Wilkinson- brother-in-law of Dr.Joseph Priestley-made wrought iron by blowing air through cast iron pipes into his smelting furnace at Bilston. He built the first cast iron bridge-at Ironbridge-launched the first iron boat and was buried in an iron coffin! Copper and bronze are of great antiquity but brass was first made in 1740 and Birmingham became well known for its “brass casters.” Non- ferrous sheet metals were made at Selly Oak for the industry came from Bristol in 1831.Pebble Mill near Bristol Road was a silver “mill.” Muntz Metal Co. started in 1832 and the very first electrolytic refining of copper was done by the Elkington Works in 1869 and is still one of their interests. The nickel industry is the history of Henry Wiggin and Co. founded in 1832 by a veterinary surgeon Charles Askin in partnership with White Benson (father of Archbishop Benson). The first successful separation of cobalt and nickel was achieved in Birmingham and so we might continue up to the recent success of I.C.I. Metals in the commercial manufacture of titanium-a chemical as much as a metallurgical landmark. As the metal trades prospered they stimulated the demand for chemicals-acid for pickling (ackey waters) lacquer for brasswork.Salt for hydrochloric acid was available at Stoke Prior near Bromsgrove and the first vitriol factory in the world using the lead chamber process was undoubtedly Roebucks’-founded in Steelhouse Lane Birmingham in 1746. William Gossage a maker of soap known to our great-grandmothers had his alkali works at Stoke Prior in 1730 and later moved to Widnes. His assistant William Hunt set up his own works in 1851 and in 1868 joined Chance in the Chance and Hunt works- now I.C.I. Oldbury. In due course they ab- sorbed-or to use the modern term-took over other sulphuric acid works Shorthouse Peyton and others and so represented the heavy chemical industry in the Midlands. World War I was a period of awakening and readjustment especially in the administration of industry and the advantage of larger units en- visaged by Lord Melchett in his drive for rationalisation became effective in the formation of Imperial Chemical Industries Ltd.;thus many of the original names have been merged or entirely lost. This is particularly so in the acid and alkali branch of the heavy chemical industry and with the centralisation of research in this branch of I.C.I. Birmingham is no longer so much in the picture as in the days of the founders who have left “Blue Billy” behind as a memorial. The manufacture of gas and by-products in the heavy chemical field has changed from a rule-of- thumb operation in the days of the Gas Street works to a precise scientific technology.The Birmingham Corporation Gas Research Labora- tories at Nechells and the other departments such as the Industrial Research Laboratory directed by the late Sir Ernest Smith in its early days have contributed much to the chemistry of coal distillation and the use of the products. To-day the works are operated by the West and East Midlands Area Boards and the Research Station of the West Midlands Area Board is at Solihull near Birmingham. Various works have their own laboratories. Special facilities for re search are concentrated at Solihull and one hopes that all the knowledge and experience of the past are readily available. The Gas Council’s courageous decision to go ahead with the scheme for the conservation of coal resources in this country and to import natural gas from abroad where it cannot be fully utilised near to the wells will bring methane to the Midlands by 1964.Work at the Gas Board Research Station at Solihull is naturally connected with many problems which arise from the operation of the new Lurgi gasification plant at Coleshill. This type of plant will in some measure-but not for some time-have some influence on the amount of by-products available for the tar distillers. Near to the Nechells works in Birmingham Brotherton and Co. had a sulphuric acid and ammonia works which using by-products from the gas works was one of the heavy chemical producers. To-day in addition to the above they provide new chromium plating materials.On account of reorganisation as a subsidiary of the Associated Chemical Co. Ltd. the central research is now at Harrogate. In the Association of British Chemical Manu- facturers’ directory of members Midland Tar Distillers of Oldbury are classified as heavy and as fine chemical manufacturers. The company was formed in 1923 from Lewis Demuth and Co. who began business in 1867 Major and Co. Ltd. of Wolverhampton with whom Lunge was chemist in 1856 and Robinson Bros. Ltd. founded in 1869 at West Bromwich. Since nationalisation of the gas industry from their new head office and research laboratories at Oldbury they handle at their various works the output of some 350,000 tons of tar drawn from about 100 gas undertakings.These are now units of the West and East Midlands Wales and Eastern Area Boards. The products are pro-cessed and refined at Oldbury and at the new works at Four Ashes near Wolverhampton. In addition to tar crude benzol which is extracted from the gas forms a basic raw material for the production of motor spirit and solvents. The M.T.D. benzol refinery and motor spirit depot are operated in association with Benzoie Producers Ltd. Among the fine chemical pro- ducts is a range of hydrocarbon solvents and naphthalene; coal tar bases and their deriv- atives including pure pyridine a-,/3- and y-picoline 2,6-lutidine 2-vinylpyridine and other bases. The tar acids phenols cresols and their derivatives such as p-t-butylphenol are pre-pared for the plastics and paint industry and as anti-oxidants.The letters M.T.D. which were well known for many years to motorists in the area from barrels of road tar at the side of the road is now seen only on bulk transport. To-day M.T.D. are probably the largest producers of pyridine in Western Europe and a potentially large outlet is in the manufacture of Reglone an effective and safe potato haulm killer. The manu- facture of pyridine N-oxide and its anti-bacterial and fungicidal uses have been developed. From their own researches M.T.D. have achieved the commerical separation of /3-and y-picoline by azeotropic distillation PROCEEDINGS and are the only producers in the United Kingdom-possibly in the whole world-of 2-vinylpyridine the “versatile intermediate” which finds use in tyre cord adhesives.From this also is produced commercially the 2-methoxy- ethylpyridine the basis for the manufacture of “Promintic,” the I.C.I. anthelmintic for the treatment of a variety of internal parasites in sheep and cattle. Midland Tar in company with many other chemical manufacturers have con- tributed much to basic research both in the universities and indirectly through the Coal Tar Research Association British Road Tar and Water Pollution Research Association. Robinson Bros. of West Bromwich a private company was formed for the manufacture of special fine chemicals many of which are used in agriculture as fungicides. Their research laboratory has produced a range of products for specific purposes-rubber accelerators poly- urethane foam catalysts agricultural aids che- lating agents epoxy curing agents piperidines dithiocarbamates and tetrahydro t hiophen gas deodorant.Synthite Ltd. of the same address. have for many years produced hexamine and manufacture solvent paint removers and penetrating oils. Messrs. Albright and Wilson (Mfg.) Ltd. are listed as makers of heavy chemicals and of fine chemicals and under allied products. The works founded at Oldbury in 1851 have been much enlarged and with the factories at Widnes Portishead Kirkby near Liverpool and Strat- ford is the largest unit in the seven companies known as the Albright and Wilson group. Arthur Albright a Quaker had been with J. and W. Southall then in 1840 he joined his brother-in-law Edmund Sturge at the factory in Wheeleys Lane and at Selly Oak where fine chemicals and sulphuric acid were made.One product chlorate of potash was used with phos- phorus for making matches. In 1844 Albright proposed that the firm should make phosphorus which at that time was not made in this country but a small amount was imported. Its price was from E4 to &2 a pound and expensive matches made from it were kept in silver match boxes. Experiments were costly and by 1851 Sturge had lost interest but Albright had by then moved to Oldbury and was in partnership with Sturge. There he could get the sulphuric acid he required from Chance and Hunt. Ultimately he JANUARY 1964 produced non-poisonous amorphous phosphorus commercially for making matches and these were shown by Sturge and Albright at the Crystal Palace Exhibition in 1851 and the story is told of how some Swedish visitors took a sample of amorphous phosphorus and for an exhibition in Paris in 1855 decided to order a large quantity of amorphous phosphorus.So large an order was disturbing to Arthur Albright a Quaker because he thought that it must be intended for war-like purposes and he informed Sweden that if this was the case he could not supply. The Swedish buyers replied that the phosphorus was required “for peace and the enlightenment of mankind.” A year later in 1 856 Edward Wilson entered into partnership and the connection with J. and E. Sturge was dissolved and the firm of Albright and Wilson was established.To-day the A. and W. group of companies in addition to the manufacturing group already mentioned include the Electric Reduction Co. Canada (1902) A. and W. Australia (1939) Midland Silicones (1 950) Marchon Products Whitehaven (1955) A. Boake Roberts and Co. (1960) W. J. Bush and Co. (1961). The sons of the founders were chemists George Albright a double first at Cambridge-and worked in laboratories which were well equiped for their time. They encouraged attendance at scientific meetings in Birmingham and the firm has from the early days supported pure research at the uni- versities. The President Mr. K. H. Wilson is a member of the Council of Birmingham Univer- sity and there is an Albright and Wilson research scholarship there.The first director of research was Sir Richard Threlfall F.R.S. (1899) who created in the works a system of process control which might well have been called automation. All instruments required were designed by him and made in a workshop which was part of the research department. To-day there are five major research departments in the group and there are other development centres but the main research is located at Oldbury in a new building designed originally by Mr. B. Topley who was at that time research director. The department has been much extended and has a staff of over 130. Associated with this is a process development section where chemical engineers design and esti- mate the cost of plant for full production and operate pilot plant to supply trial quantities.At Oldbury are also the Central Administration Technical Service and Central Engineering Department. The manufacture of phosphorus in com-mercial quantity and the production of pure phosphoric acids and their salts puts the firm into the heavy chemical industry but to-day it is better known for fine chemicals such as pure phosphates as aerators for cakes and confection- ery phosphate for water treatment-“Calgon” -tripolyphosphate an additive which makes modern synthetic detergents practicable. Since the war the organic phosphorus compounds made include insecticides; butyl and other alkyl phos- phates trimethyl and triphenyl phosphites and lower dialkyl phosphites and similar compounds.Much publicity has been given to the use of tetrakis(hydroxymethy1)phosphonium chloride as a constituent in the wash-proof flame- resistant finish for cotton and viscose rayon goods. The research department among its many recent publications has described the pro- duction and uses of phosphoronitrilic chloride. Although some of the heavy chemical pro- cesses which had their origin in the Midlands have for economic reasons (usually transport) gone elsewhere it is significant that so many fine chemical processes and those manufactures which depend upon a special type of chemical reaction e.g. polymerisation have selected the Midlands as the site for their central research and engineering departments.Such research is now financed by the industry to a degree not thought practicable in 1914. Many of these firms support pure research at the universities or through their associations and contribute papers to scientific meetings. Notable contributions have come from Messrs. Bakelite Messrs. British Industrial Plastics and Messrs. Courtaulds in the field of synthetic polymers and resins and Messrs. Dunlop on rubber and alternative products of similar physical character. A recent development by Messrs. Courtaulds of Coventry and Messrs. Celanese of Derby will lead to the production of building components such as P.V.C. pipes and gutters and wall panelling. Messrs. Courtaulds Ltd. founded at Coventry in 1904 achieved the first satisfactory commercial manufacture of artificial silk by the viscose process discovered by Cross and Bevan in 1891.The British public however would not ~ ~~ wear artificial silk until ten years later. With the decline in the use of nitrocellulose the major outlet for Celanese cellulose products to- day is probably for acetate fibres and films and moulded extrusion products. The use of methyl- cellulose as a thickener and of carboxymethyl-cellulose as a detergent additive and as an adhesive has increased considerably during the last few years. It is perhaps useful to remember that when the Chemical Society held its Annual Meeting in Birmingham in 1934 methyl methacrylate was in the laboratory stage and that Perspex was intro- duced by I.C.I.in 1936. Most early plastics were opaque or dark brown phenolics. From the pioneer work of E. C. Rossiter in the labora- tories of British Cyanides at Oldbury on the formation of thiourea by the fusion process from “ammonium sulphocyanide” were developed the thiourea resins in 1925 and their application to produce “Beetle” ware which was shown in many forms at Harrods’ in 1926. From this has grown British Industrial Plastics-now a Turner and Newall company-manufacturer of Beetle resins and moulding powders which are recognised all over the world. The main research centre of the group is at Oldbury where the works has been much extended and there are other factories at Streetly Maryport Cumberland and Erdington.The group not only produces the chemical moulding powders but a range of auto- matic presses and a system for the automatic control of the moulding cycle. At Streetly a lightweight translucent sheeting is produced from polyesterlglass fibre and also lightweight decora- tive trays. The present tableware known as Gaydon Ware-very different in appearance and design from the 1926 product-is made at Streetly. Birmingham can rightly claim to be the birth- place of the plastics industry for it was at the works of Messrs. Elkington that there was em- ployed a man named Alexander Parkes described by Lord Moulton as the greatest original inventor produced in this country up to the beginning of the twentieth century. In one of his inventions he added camphor to nitro-cellulose and produced “Parkesine.” This was similar to xylonite or celluloid invented much later.Parkes also found a way to vulcanise small articles of rubber with sulphur chloride and about 1850 Elkington and Mason (silversmiths) PROCEEDINGS ~ ~~~~~ manufactured raincoats. This process passed in 1852 to Charles Macintosh of Manchester (the name does not properly include a K). So early incidentally was Parkes’ work that he had to devise methods for the production of the raw materials sulphur chloride carbon bisulphide and-in connection with celluloid-the nitro-cellulose. Thus the initiative of a littleknown inventor (he called himself an artist) backed financially by Mason the founder of Mason College gave birth to what has now become the plastics industry.The history of Messrs. Bakelite Ltd. goes back to 1906 when the Fireproof Celluloid Syndicate was formed by Sir James Swinburne F.R.S. He purchased the patent rights of A. Luft (1 906) and from experiments stoving lacquers were made from phenol formaldehyde. These were covered by a patent of W. H. Story. The Damard Lacquer Co. was formed in 1910 at 98 Bradford Street Birmingham and Mr. H. V. Potter-later Chairman of Bakelite Ltd.-joined it in 1914. The Bakelite Co. at Cowley manufac- tured resins under the Baekeland patents and in 1916 the Bakelite factory was taken over by the Damard Lacquer Co. On January 2nd 1963 the Midland plastics firms celebrated the centenary of British plastics by an exhibition and re-membered Alexander Parkes.The Bakelite works to-day manufactures a variety of plastics of the thermoplastic and thermosetting type. Decorated laminates were used way back in 1937 for panelling and furnishing their new offices at Tyseley. The research centre is here and from their various factories the firm handles Wareite Wonder Board sheeting phenolic foam P.V.C. rainwater pipes and gutters as well as polyester resin products. Natural rubber came to Birmingham when Dr. Joseph Priestley received a gift of a small specimen of “caoutchouc” and found that it would remove pencil marks. He gave it the name “rubber-indiarubber.” The first synthetic rubber in the world was made at Mason College by Professor W.A. Tilden in 1892 by the cracking distillation of limonene when he produced iso- prene specimens of which are preserved in the University Chemical Department Museum. In the earlier stages of making his cycle tyres Mr. J. B. Dunlop used rubber some of which was supplied by Messrs. Byrne Br0s.l of Birming-D. F. Twiss Society of Chemical Industry Annual Meeting Birmingham 1930 Handbook p.119. JANUARY1964 ham. The process was first established at Coventry and afterwards moved to Birmingham. To-day the new extensive Dunlop Research Centre is situated at Erdington but is apart from the works and has contributed much to our knowledge chemically and physically not only of rubber products but also of other rubber-like synthetic materials.Messrs. Dunlop continue to contribute to the facilities for research at the universities by fellowships and by special arrangements for student vacation courses. The A.B.C.M. Directory classifies Messrs. John and E. Sturge as manufacturers of fine chemicals. The founder John Sturge started in 1822 at Bewdley making solutions for the dyers. Shortly afterwards he moved to Wheeleys Lane Birmingham near to the site of the present registered office. In 1830 he was joined by Edmund Sturge in the manufacture of citric acid and citrates tartrates potassium bicarbonate chlorate of potash. A works was established at Lifford near Selly Oak. The early manufacture of phosphorus by Sturge and Albright has been referred to under Albright and Wilson.In 1841 precipitated chalk was added to the list of manu-factures and the extensive and varied uses for this material to-day are largely due to the researches carried out in their laboratories on the character of fine powders. Products include mineral fillers for rubber suspending agents and dessicants. The original citric acid process has long been replaced by a fermentation process developed by the firm. Their interest in Birmingham University is traditional. A former Chairman F. C. Clayton was Pro-Vice-Chancellor and Treasurer from 1900 to 19 12 and Pro-Vice-Chancellor from 19 12 to 1921. The present Chairman of the Com- pany Mr. A. L. Wilson J.P. is a Life-Governor and Mr. A. R. Foxall Joint-Managing Director is a member of the University Council and Chairman of the Building Committee.Many galenicals were formerly made in Birmingham by Messrs. Southall Bros. and Barclay founded in 1820. The manufacture of special chemicals for the paint and varnish industry in Birmingham was stimulated by the demands of the metal industry. John Baskerville the printer who gave his name to a type introduced the art of japanning about 1720. It is said that the oldest varnish works was in Lionel Street in 1780 and known as John Meredith’s and at least four well-known paint manufacturers were established shortly after- wards. Llewellyn Ryland Ltd. occupied a site near to the Baskerville printing works; both sites are now part of the Civic Centre. Messrs. Mander Bros.of Wolverhampton is one of the oldest companies and the works opened every day with morning prayers. It was here that the pioneer researches of Dr. R. S. Morrell threw light on the chemical nature of linseed oil and with this came the key to the utilisation of other oils such as tung oil. With the shortage of the latter in 1936 chemists turned to others such as perilla oil. To-day prob- ably over 80% of paint production is from syn- thetic resins. Members of the research labora- tories at the above works and from Thornley and Knight Docker Bros. A. Holden and Sons Permoglaze Postans Merry and Minton and many others paid tribute on May 26th 1961 to Dr. J. Newton Friend at a dinner arranged by the Oil and Colour Chemists’ Association-of which he is senior surviving Past-President-and by the Royal Institute of Chemistry.The need for a new approach to the surface protection of metals has been made evident by the corrosion research work at the I.C.I. Metals Research Laboratory (Kynochs’). The difference in the technique used in the protection of the new Forth Bridge and that in the old Forth Bridge is a measure of the advances made by the paint industry over the years. Chemical plant An important branch of the chemical industry is the manufacture of chemical plant from suitable and sometimes most un-usual materials for the processing of the chem- ical. The Midlands supplied vessels for the Atomic Energy Authority and Messrs. Thomp- son Bros. of Bilston make special stainless steel lead-lined mixers and large 3,000 gallon tanks.Messrs. J. Thompson of Dudley make acid- resisting castings and tanks whilst Messrs. T. and C. Clark of Wolverhampton are well known for their enamelled iron chemical plant. Messrs. Prodorite Ltd. chemical engineers of Wednes-bury are pioneers in the making and erection of descaling tanks of special design for the metal- lurgical industry and large containers and they have been successful with their thin skin resin coating for a variety of containers and tanks used in pharmacy and in fermentation processes. PROCEEDINGS THE CHEMISTRY DEPARTMENT OF THE UNIVERSITY IOF BIRMINGHAM* ALTHOUGH the roots of the Chemistry Depart- ment of the University of Birmingham can be traced back to earlier institutions the creation in 1880 of the Mason College with Chemistry as one of the four foundation Departments of Science marks the beginning of its modern development.The task of building up this new department required a Professor of exceptional merit and he was found in the person of W. A. Tilden whose research activities had already resulted in important discoveries. In addition to his outstanding work on nitrosyl chloride and its applications in the investigation of terpenes and essential oils during his work in Birmingham he isolated isoprene and observed its polymerisa- tion. He announced this the first example of the formation of a synthetic rubber to the Birming- ham Philosophical Society in 1892.Before leaving for the Imperial College Chair in 1894 Tilden built up a thriving department and he later gained many honours including the Presi- dency of the Chemical Society (1903-1905) and a knighthood in 1909. Percy Faraday Frankland succeeded Tilden as the Second Mason Professor in 1894 and following the great traditions of his father Sir Edward Frankland he at once engendered a high standard of efficiency in the Department. His researches extended over wide fields and his lectures were a model of delivery and experi- mental exposition. During Frankland’s regime the Department experienced great changes. The granting of the Charter in 1900 which raised the Mason College to University status brought about a large increase in student numbers and following the ambitions of Joseph Chamberlain plans were made for transfer to the Edgbaston site.Frankland and his staff had responsibility for the general planning of the new laboratories and the move to Edgbaston took place in 1909. During the First World War these buildings were taken over for a military hospital making necessary a temporary return to the Mason Col- lege laboratories but despite the adverse condi- tions the teaching and research continued; in particular Frankland and his staff carried out valuable research for the Chemical Warfare Committee. The University of Birmingham owes much to Frankland’s strong personality and organising ability as Dean of the Faculty of Science and among the students and colleagues that he gathered round him were many who are now famous.In 19 19 following Frankland’s retirement the Mason Chair was occupied by G. T. Morgan F.R.S. who had wide experience in industry and in academic life. Under his guidance the Edgbaston Chemical Laboratories which had suffered severely during their military occupancy were re-equipped and made serviceable again for teaching and research. The formation of an active research school with wide interests was accelerated by the group of colleagues who had accompanied Morgan from Finsbury with whom he pursued investigations of aromatic dye- stuffs and the outstanding studies on the chem- istry of co-ordination compounds with which his name will always be associated.Morgan who became head of the National Chemical Laboratory and was later knighted was succeeded in 1925 by W. N. Haworth then Professor at King’s College Newcastle who came to Birmingham at a time when his mind was full of plans for new enquiries into carbo- hydrate structures. He was determined to build up a first-class department and like Morgan he brought with him a team of young men ex-perienced in carbohydrate research many of whom have since distinguished themselves. Haworth immediately plunged into his now classical investigations of the ring structures of the mono- and di-saccharides. He was shortly joined by E. L. Hirst and thus began the famous partnership that continued for the next decade and established the reputation of the Birmingham School of Carbohydrate Chemistry.Haworth early adopted a team system for the running of his research school which bore fruit in the successful work on the structure and synthesis of Vitamin C in 1933. Prominent in the team with Haworth and Hirst were the present Mason Pro- fessor M. Stacey R. J. w. Reynolds F. Smith and (the late) E. G. V. Percival. The period 1934-38 saw significant expansion of the carbo- hydrate researches on the organic physical and biological sides and in 1937 Haworth was * Published in connection with the Society’s Anniversary Meetings. JANUARY 1964 honoured with the Nobel Prize for Chemistry. It was during this time that a generous bequest from a local industrialist A. E. Hills made possible considerable extensions to the Depart- ment ;the new laboratories planned by Haworth and his staff were opened by Sir Frederick Gowland Hopkins in 1937.With the advent of the Second World War the Department became involved with militarily im- portant projects in collaboration with industry and Government laboratories. Prominent among these were problems relating to the preparation and purification of uranium and its derivatives (including the hexafluoride) in connexion with the pioneer separation of U-235 by the diffusion process. Subsequently Haworth as Chairman of the Chemical Panel with M. E. L. Oliphant had a major role in the organisation of the “Tube Alloys” British Atomic Energy effort and at a later date Haworth and Stacey played a prominent part in the chemical beginnings of Harwell and the organisation of the Canadian Chalk River project.In 194546 the interior of the Frankland laboratories was redesigned and modernised at a cost of nearly E20,OOO; this made it possible for the numbers of students in the Department to be almost doubled and thus to cope with the large influx of men and women from the forces. In 1946 as a first step to other planned expansions in Chemistry the Faculty of Science decided to create a second Chair of Chemistry within the Department and M. Stacey then Reader in Bio- logical chemistry was appointed to it. He took over most of the administrative duties from Haworth who at this time was carrying heavy responsibilities having been Dean of the Faculty of Science at the difficult period of expansion and then Vice-principal of the University.Haworth was elected Vice-president of the Royal Society and also knighted in 1947 and in his last year as Mason Professor he was also Acting Vice- Chancellor of the University. In 1948 Haworth was succeeded as Mason Professor and Head of the Department by H. W. Melville who had already achieved great dis- tinction having been elected to the Royal Society while still in his early thirties following his brilliant work in E. IS. Rideal’s Colloid Science Laboratory in Cambridge. Several changes were now made in the Department at Birmingham. For nearly twenty-five years the emphasis had been predominantly on organic chemistry and it had become necessary to achieve a more even balance.From Aberdeen where he had occupied the Chair since 1943 Melville brought a team of about a dozen lecturers and research students complete with apparatus to assist in the expansion of teaching and research particularly in physical chemistry. Among these newcomers was R. Belcher now Professor of Analytical Chemistry who had already started to build up a sub-department of analytical chemistry in Aberdeen which he was now able to develop extensively at Birmingham not only as an entity in itself but also to serve the needs of all sides of the Department. The Analytical School has become world famous and twice the Department has been host to Inter- national Congresses of Analytical Chemistry while Professor Belcher has held the Office of President of the Analytical Section of the Inter- national Union of Chemistry.In 1956 when Melville (now Sir Harry) resigned in order to become Secretary of the D.S.I.R. Professor M. Stacey was appointed to the Mason Chair and became Head of the Department. He has developed the Department in many directions especially in the research interests and was responsible for the initial general planning of the extensive new labora- tories the A. E. Hills Extension and the Haworth Laboratories which in all have cost about one million pounds. In 1957 J. C. Robb was ap- pointed to the Chair of Physical Chemistry and is now Administrative Head of the Haworth Buildings which will be the centre of the 1964 Anniversary Meetings.He is continuing to ex- pand the already powerful sub-department of Physical and Inorganic Chemistry. A new Chair of Organic Chemistry was created in 1958 and appointed to it was J. C. Tatlow who had long been leader of the Depart- ment’s group working in the field of organo-fluorine compounds. Professor Tatlow is Ad- ministrative Head of the Frankland and Hills Buildings Dr. G. A. Gilbert is Reader in Bio- physical chemistry Dr. J. C. Bevington (soon to hold the Chair of Chemistry in the University of Lancaster) is Reader in Polymer Chemistry Dr. J. Sheridan is Reader in Physical Chemistry Dr. J. B. Randles is Reader in Electrochemistry and Dr. A. S. Jones is Reader lin Organic 12 PROCEEDINGS Chemistry.There are 35 other Members of Staff 156 students reading for higher degrees 310 is provided for another 250 students from 12 other departments. These numbers may well be students reading Chemistry and service teaching doubled by 1980. CHEMICAL SOCIETY MEETING THEfollowing papers were read at a meeting held in the Society’s rooms on the evening of November 21st to celebrate the 70th birthday of Sir Christopher Ingold. The President congratulated Sir Christopher on behalf of those present. Sir Christopher replied later in the evening. T%e Kinetics and Mechanism of Heteroaromatic Nitration. Part I. Quinoline. By M. W. AUSTIN and J. H. RDD. Part 11. Pyrazole and Iniidazole. By M. W. AUSTIN,J. H. RDD and B. V. SMITH.MECHANISTIC studies of heteroaromatic nitration are frequently complicated by acid-base equilibria in- volving the substrate. These papers described the comparison of the reactivity of different hetero- aromatic systems under comparable mechanistic con- ditions and the efforts to obtain where appropriate a measure of the deactivation relative to the corre- sponding homocyclic systems. The nitration of quinoline in concentrated sul- phuric acid is first order with respect to the stoicheio- metric concentrations of both quinoline and nitric acid. The rate of reaction greatly exceeds the cal- culated encounter rate of nitronium ions with neutral quinoline molecules thus showing that the nitronium ion first interacts with the quinolinium ion.The variation of the rate of nitration with acidity indi- cates that the quinoline is still protonated in the transition state of the reaction. This transition state should be similar to that for the a-nitration of naphthalene and an indirect comparison of the two reaction rates indicates that the replacement of a -CH= group in $n a position of naphthalene by the isoelectronic -NH= group slows down the rate of a-nitration in the adjacent ring by a factor of -1010. The nitration of pyrazole and imidazole in con- centrated sulphuric acid occurs less readily than that of quinoline but the kinetic form is similar; both azoles undergo reaction through their conjugate acids. The nitration of imidazole is complicated by an oxidative side reaction leading to ring-opening.The rates of these reactions were compared with those expected from the corresponding localisation energies. The agreement was poor not only between the homocyclic and heterocyclic series but also among the heteroaromatic ions. Thus on this criterion the imidazolium ion should be more re- active than both naphthalene and the quinolinium ion but this was not observed; indeed it is less reac- tive than naphthalene by a factor of more than 1@O. In the discussion which followed Professor A. R. Katritzky mentioned that Dr. Ridd had used two criteria for showing that the nitration occurs on the protonated species instead of the free bases :(a)from the concentration of free base present and encounter rates; (b) from the variation of nitration rate with the acid concentration.He has assumed that the heterocyclic bases behave as Hammett bases in the absence of other data. However if the protonation of such bases occurred much less rapidly than for a Hammett base (as is the case for certain amides) both criteria would be invalidated. Professor Katritzky said that he and his colleagues depend on similar assumptions in related work and are there- fore investigating the nature of the protonation equi- libria of pyridines. Preliminary results (with Dr. B. J. Ridgewell and Mr. A. M. White) indicate that 2,3-dichloropyridine becomes protonated on in-creasing acid concentration at least as rapidly as does a Hammett base. Dr. Ridd replied that he thought it was safe to treat these heteroaromatic systems as Hammett bases because there was some evidence that the deviations for secondary and tertiary amines were in the direction of incieasing the dependence of the protonation ratio on acidity and such deviations would not affect the argument.However he was very glad to have direct information on this matter. Sir Christopher Ingold asked Dr. Ridd whether the picture of the ammonium proton in the transi- tion state should be that it stays there throughout the rate-controlling step or that its loss is concerted with the uptake of nitronium ion on carbon (SE2’) just as he has shown before that it is concerted with the uptake of nitrosoniuni ion on nitrogen (S,2). In reply Dr. Ridd said that there was no direct evidence on this point but that the comparison of the rate of nitration of the anilinium ion in sulphuric acid and deuterosulphuric acid indicated that the rate-determining step did not then involve any significant weakening of the N-H bonds.The acidity and reactivity of the anilinium ion are similar to those of the quinolinium ion and so the same result would be expected. Dr. C. W. Rees than asked (a) What measured or estimated parameters were used in the calculation of JANUARY 1964 the rate of encounter of nitronium ions with quinoline molecules ? Could not the simple picture of rate-control by diffusion of neutral quinoline molecules be complicated by the rapid equilibrium between them and the laige reservoir of quinolinium ions? (b) What approximate limits of accuracy should be set on the ratio of reactivity (4 x 10’) of benzene to quinolinium in view of the several inter- mediate ratios required to estimate it remembering that each was measured at a different sulphuric acid concentration.Dr. Ridd replied that the encounter rate was calculated from the viscosity of the medium using the equation discussed by Debye’ and given in the full paper. He thought that this was a valid measure of the maximum rate of reaction involving the neutral molecule providing one defined the reaction path from the form of the heteroaromatic system in which it first “saw” the nitronium ion. However it was possible for the nitronium ion to first interact with a quinolinium ion but for the N-H proton to be lost before the rate-determining stage had been reached.From the encounter criterion such a reaction path would be considered as involving the quinolinium ion but from the rate profile such a reaction path would appear to involve the quinoline molecule. The two criteria therefore refer to different stages of the reaction path. The calculation of the reactivity ratio assumes that relative reaction rates are independent of acidity and the known differences here could lead to an error by a factor of 5 in the final result. The combined experimental errors are difficult to esti- mate but there seems no reason to believe that the final value is out by more than a factor of 10. Professor A. W. Johnson enquired whether similar studies had been made on pyrroies and whether the introduction of a second nitrogen into the ring had a deactivating effect with regard to electrophilic substitutions.Dr. Ridd said that no kinetic studies had been carried out on the nitration of pyrroles but that the difference in the conditions of nitration suggested that the second nitrogen atom in azoles had a very marked deactivating effect towards electrophilic substitution. The problem was however complicated by the protonation of azole molecules and it was unfortunate that relatively little information was available on the reactivity of neutral azoles. Trans. Electrochem. SOC.,1942 82 265. Mechanisms of Octahedral Substitutions in Non-aqueous Solutions.Part 3. The Replacement of Co-ordinated Water in trans-Aquonitrobis(ethy1ene-diamine)cobaft(m) Ions. By M. N. HUGHES and M. L. TOBE. SOMEyears ago it was suggested that the potential electron-withdrawing capacity of the nitro-group promoted a bimolecular mechanism for the aquation of cis-and trans-[Coen,(NO,)Cl]+ but further in- vestigations of the reactions of these and similar complexes in non-aqueous solvents have not pro- duced any clear cut indication of this or other mechanisms. In an attempt to resolve these diffi- culties the reactions trans-[CO~~,(NO~)H,O]~+ + X-[Coen,(NO,)X]+ + H,O where X-= Cl- Br- NCS- and NO3- have been studied spectrophotometrically in acetone dimethyl- formamide (DMF) and tetramethylenesulphone (sulpholane).In acetone the rates of entry of NCS- and NO3-are independent of their concentration although NO3- reacts some 15 % more rapidly than SCN-. In sulpholane the reaction is also independent of the concentration of thiocyanate but in DMF there is a dependence of rate upon [SCN-] at low reagent concentrations. The limiting rates are dependent upon the nature of the solvent. Chloride and bromide ions enter the complex at rates that are dependent upon the concentration of reagent and which at lower concentrations can be represented by Rate = (k + k,[X-])[complex]. In DMF and sulpholane the rate becomes inde- pendent of mr] at higher reagent concentrations and the rates of reaction with bromide are almost identical in acetone and sulpholane although a limit- ing rate has not been observed in acetone solution since the solubility of the quaternary phosphonium salt is insufficient to produce the required bromide concentration.These varied behaviours were discussed in terms of ion-association between the dipositive cation and the anionic reagents. Once the ion-association pre- equilibria are taken into account it is found that the rate of “rearrangement” of the aggregate is not very dependent upon the nature of the entering group or the nature of the solvent and a classical bimolecular reaction would appear to be unlikely. Nevertheless the reaction is best described in terms of an associa- tive process. A discussion ensued during which Professor K. W. Sykes mentioned that the work which Dr.Tobe described provided a good illustration of the kinetic importance of ionic association. Although Dr. Tobe said that complexes of particular compositions had been detected there remained the further question of whether it had been possible to show that the forma- tions constant were quantitatively consistent with the rate expressions for the substitution reactions. An interesting possibility also arose in connection with the problem of the detailed structures of associated ions. One might have supposed that the bimolecular mechanism would have occurred only with anions in a particular position but that the unimolecular mechanism would not have been so specific. Was there thus a possibility of kinetic methods giving information about the distribution of associated anions among distinguishable positions in the solvation shell of an unsymmetrical cation? Dr.Tobe replied that (1) The formation constants of the ion aggregates of the trans-[Coen2N,H20l2+ cation could not be measured by the techniques at our disposal. The first and second formation con- stants were so large that the association was almost stoicheometric. In the region where the third anion joined the aggregate the assembly rearranged too rapidly (t+ = ca. 50 secs.) for any study of the initial spectra to be sufficiently accurate for the data to be used. A conductivity method was unsuitable. He wished to point out that they have just completed the study of another less labile system where the maximum ion aggregate is the ion-pair (Bosnich and Tobe to be submitted) and there is quantitative agreement between the kinetically determined value for the association constant and that determined from the initial conductivities.The system is chloride substitution in cis-[Coen,Cl,]+ where the rate of CI-exchange and the rates of the connected isomerisation and racemisation reactions are ex-plained in terms of a reaction involving the free ion and another involving the ion-pair with a formation constant in methanol at 35",of 300 M-l. A value of 275 f10%has been obtained for the same constant from a study of the conductivity. (2) It is possible to use a combined kinetic and spectrophotometric (stereochemical) study to pro- vide information about the stereochemical relation- ships within the ion aggregate provided one could be happy about the relationship between the observed stereochemical changes and the molecular processes involved.Because of the further deductive order of PROCEEDINGS magnitude required for the elucidation of mechanism and all matters appertaining thereto he would have been happier if one could use independently deter- mined information about the stereochemistry of the ion aggregate to elucidate the molecular stereo- chemical course of substitution. However if the equilibrium solution studies (including solution X-ray diffraction) have not been sufficiently developed to supply stereochemical data they will have to rely on deductions made on a reacting system.Gas-phase Eliminations. Part 6. Kinetics of the Pyrolysis of Neopentyl Chloride. By ALLAN MACCOLL and E. S. SWINBOURNE. GASEOUS neopentyl chloride decomposes in seasoned vessels at 444"by the following four simultaneous reactions:Reaction I (75 %) to hydrogen chloride and the equilibrium mixture of methylbutenes Reaction 2 (10 %) to methyl chloride and isobutene Reaction 3 (7 %) to methane and 1-chloro-2-methylprop-l-ene Reaction 4 (7 %) to methane and 3-chloro-2-methyl- prop-1-ene with subsequent rapid decomposition of the latter. Reactions 2 3 and 4 are in part hetero- geneous and are analogous to the pyrolysis of neo- pentane to methane and isobutene. Reaction 1 is homogeneous and unimolecular and involves a Wagner-Meerwein migration of a methyl group.For this reaction lo5 k = 2-8 sec.-l that is about one quarter of the rate for the dehydrochlorination of ethyl chloride. A similar rearrangement has been ob- served by Lewis and his co-workers in the case of the pyrolysis of neopentyl chloroformate. A brief description was also given of Bicknell's work on the pyrolysis of bornyl and isobornyl chlorides. These compounds also rearranged on pyrolysis as is shown by the fact that tricyclene and camphene are the major hydrocarbon products of reaction. The implications of the rearrangements in describing the transition state in gas-phase eliminations were described. COMMUNICATIONS Absence of a Primary Hydrogen Isotope Effect in the Sulphonation and Sdphonylation of Benzene By H.CERFONTAIN and Miss A. TELDER* THEabsence of a primary hydrogen isotope effect matic sulphonation moderate isotope effects have has been demonstrated for aromatic nitration and been reported (1.4 < k,/k < 2-1 at 25").l for certain halogenations and alkylations. For aro- We now report the kinetic isotope effect of * Laboratory for Organic Chemistry University of Amsterdam The Netherlands. l Berglund-Larsson,Arkiv Kemi,1957 10 549; Brand Homing and Thornley J. 1962 1374. JANUARY 1964 hydrogen in the sulphonation of benzene by sulphur trioxide without solvent. In a competitive study it was found that hexadeuterated and ordinary benzene are sulphonated at about an equal rate kH/kD= 1-14 f0.06 at 25.0”.Hydrogen exchange between benzene and benzenesulphonic acid is relatively slow and did not interfere with the determination of the kinetic isotope effect. The low selectivity between hexadeuterated and ordinary benzene is due to the substrate itself; it is not the result of statistical factors as the reactivity of toluene under similar conditions differs from that of benzene by a factor ten.2 The sulphonation of aromatic hydrocarbons with sulphur trioxide may proceed via arylpyrosulphonic acid.3 The observed isotope effect is thought a secondary one originating in the steps leading to the formation of ArHSO,OSO,. This secondary effect is likely to be the balance of hybridisation hypercon- jugation and inductive effect^.^ The absence of a primary isotope-effect indicates5 that the intra-molecular proton shift (cf.ref. 3) is not rate-deter- mining. The kinetic isotope effect kH/kD,in aro- matic sulphonation with oleum at 25” varies from 1-4 to 2.1 indicating that the proton-removal step under these conditions is partly rate-determining.l The formation of diphenyl sulphone (N 9 mole- % relative to benzenesulphonic acid) enabled the determination of the kinetic isotope effect for the sulphonylation of benzene as well. For this reaction at 25.0” kH/kD= 0.88 f0.06. Therefore the proton removal in sulphonylation is also not rate-deter- mining. (Received November 2nd 1963.) Cerfontain and Vollbracht Rec. Trav. chim. to be published. a Gilbert Chem. Rev. 1962 62 549.* Halevi Tetrahedron 1957 1 174; Streitwieser Jr. Jagow Fahey and Suzuki J. Amer. Chem. Soc. 1958 80 2326; Klein and Streitwieser Jr. Chem. and Znd. 1961 180. Zollinger Experientia 1956 12 165; Melander “Isotope Effects on Reaction Rates,” The Ronald Press Company New York 1960 p. 107. The Photochemical Reaction of Benzene with Boron Trihalides By R. A. BOWIE and 0.C. MUSGRAVE* PHENYLBORON DIHALIDES have been obtained from reactions between boron trihalides and benzene catalysed by activated aluminium,l or by aluminium bromide,2 or by palladi~m.~ We have found that both boron tribromide and tri-iodide react with benzene & (I) BX2 in the absence of a catalyst when subjected to ultra- violet radiation. Exposure of the solutions to a “Hanovia” S 500 mercury-vapour lamp for 48 hr.resulted in the formation of phenylboron dibromide (25%) and of phenylboron di-iodide which was hydrolysed without isolation to phenylboronic acid (48%). No reaction occurred between boron tri- chloride and benzene under these conditions. A benzene solution of boron tribromide kept in dark- ness develops absorption maxima at 3150 and 4350 A which may be attributed to complex forma- tion as neither component shows selective absorp- tion above 2800 A. The photoaddition of maleic anhydride to benzene involves the formation of a charge-transfer complex which undergoes photo- activation followed by 1 ,Zaddition of the maleic anhydride to the benzene nu~leus.~ A similar sequence probably occurs in the photoreactions between benzene and boron trihalides photoactiva- tion of the complex resulting in the 1,Zaddition product (I) which eliminates hydrogen halide form- ing the phenylboron dihalide.The photoaddition of maleic anhydride or of acetylenes to benzene results in the formation of new carbon-carbon bonds.5 The formation of bonds between carbon and other ele- ments by this type of reaction has not been recorded previously. We are indebted to the D.S.I.R. for the award of a studentship (to R.A.B.). (Received November 9th 1963.) * Chemistry Department The University Old Aberdeen. Muetterties J. Amer. Chem. Soc. 1959 81 2597; 1960 82 4163. Bujwid Gerrard and Lappert Chem. and Ind. 1959 1091. Pace Atti Accad. naz. Lincei Rend.Classe. Sci. fis. mat. nat. 1929 10 193; Ruigh et a!. WADC Technical Re-port 55-26 Parts 111-IV US. Dept. of Commerce Washington D.C. 1956. Bryce-Smith and Lodge J. 1962 2675. See inter al. Angus and Bryce-Smith J. 1960,4791;Bryce-Smith and Lodge J. 1963 695. PROCEEDINGS The Origin of the Ethyl Side-chain in Spinasterol BADER,L. GUGLIELMETTI, By SYLVIA and D. ARIGONI* INCORPORATION of radioactivity from isotopically donor a compound with a zymosterol-type side- labelled acetate and mevalonate into phytosterols has been observed with a variety of plant systems by different authors in recent years.l Although no pertinent data on the distribution of the label have been reported2 these experiments are generally con- sidered to imply a close analogy with the well- established scheme of cholesterol biosynthe~is.~ Such an analogy cannot be extended to explain the origin of the “extra” two-carbon side-chain present in most sterols from higher plants and consequently sub- sidiary biogenetic hypotheses have been ~onsidered.~ We now report experimental evidence that both “extra” carbon atoms of spinasterol are derived from the methyl group of methionine.Administration of DL-[methyZ-14C]methionine to rhyzomes of Menyanthes trifoliata yielded a radio- active phytosterol fraction (0.02 % incorporation) purification of which afforded a main c~mponent,~ m.p. 169-170” [a] f0”,now identified as spina- sterol Ozonolysis of the labelled sterol followed by oxidation with silver oxide gave optically active a-ethylisovaleric acid isolated as the anilide (11) m.p.140-142” [a] + 21” containing all (112%) the activity of the starting material. Oxidation of the anilide (11) according to a modified Kuhn-Roth procedure8 furnished a mixture of propionic and acetic acid which could be separated by reverse phase chr~matography.~ Systematic degradation of the propionic acid involving successive Schmidt re- actionslO indicated that the carboxyl group was practically devoid of radioactivity (1 %) and that the methylene and methyl groups corresponding to C-28 and C-29 of spinasterol each carried 49% of the original activity. These results are consistent with the hypothesis that formation of the ethyl side-chain of spinasterol (and probably also of similar side-chains in other sterols) is the result of a double alkylation process (111) -+ (IV) -+(I) involving methionine as the methyl chain (111) as a precursor and a 24-methylene deriva- tive (IV) as an intermediate.Whereas the observed linkage of two C,-units appears to be without bio- genetic precedence each of the alkylation steps is clearly reminiscent of the process known to be operative in the formation of the “extra” methyl group of ergosterol.l2 ,A (n) We are indebted to Sandoz AG Basle for support of this work. The help of Dr. P. Jordan in the deter- mination of radioactivities and of Dr. C. Coscia and Mr. J.-P. Calame in the collection of the plant material is gratefully acknowledged. (Received October 28tl1 1963.1 Note added in proof (November 21st).Since the submission of our manuscript incorporation of radioactivity from ~-(methyZ-~~C)methionine into p-sitosterol in Pisunz sativum without direct evidence for the location of the label has been described by Castle Blondin and Nes J. Amer. Clzem. SOC. 1963 85 3308; cf. also Nicholas and Moriarty Fed. Proc. 1963 22,529. * Organisch-chemisches Laboratorium der Eidg. Technischen Hochschule Ziirich. Nicholas J. Biol. Chem. 1962 237,1476 1481 1485; Baisted Capstack and Nes Biochemistry 1962 1 537; Bennett Heftmann Purcell and Bonner Science 1961 134 671 and further references quoted therein. 2 Cf. however Gros and Leete Chem. and Znd. 1963 698. A recent review is given by Popjfik and Cornforth in Adv.Enzymology 1960 22,281. * Sir Robert Robinson “The Structural Relations of Natural Products,” Oxford University Press London 195s. p. 19; Arigoni in “CIBA Symposium on Terpene and Sterol Biosynthesis,” Churchill London 1959 p. 244. Lendrich Arch. Pharm. 1892 230,38; Zellner ibid. 1925 263,161. Barton and Cox J. Chem. Soc. 1948 1354; Fieser Fieser and Chakravarti J. Amer. Chem. Soc. 1949 71 2226. Spinasterol has been correlated with stigmasterol the configuration of which at C-24 follows from the work of Tsuda Kishida and Hayatsu J. Amer. Chem. SOC. 1960 82,3396. Bickel Schmid and Karrer Helv. Chim. Acta 1955 38,664. Bueding and Yale J. Biol. Chem. 1951 193 411. lo Phares Arch. Biochem. Biophys. 1951 33,173. l1 Alexander Gold and Schwenk J.Amer. Chem. Soc. 1957 79 2967; Alexander and Schwenk ibid. p. 4554; cf. also Danielsson and Bloch ibid. p. 500; Dauben Fonken and Boswell ibid. p. 1OOO. JANUARY1964 Light-induced Diene Migration:an Allene Synthesis By K. J. CROWLEY* 1~has been shown1 that certain 1,3-dienes can under- go reversible thermal isomerisation involving 13- hydrogen transfer coupled with migration of the diene system. We find that this change also takes place under the influence of light but without the thermodynamic limitations of the thermal reaction. One aspect of the photochemical change affords a synthesis of 1,2,4-trienes which may be of biogenetic significance. 4-Methylpenta-l,3-diene and cis-2-methylpenta-1,3-diene were reported to equilibrate thermally the latter being simultaneously isomerised irreversibly to the trans-isomer.On irradiation with ultraviolet light these three compounds are reversibly intercon- verted in dilute ethereal solution and the latter is at the same time irreversibly? photoisomerised to the expected2 1,3-dimethylcyclobutene.This compound which was obtained in 21 % yield had the expected infrared and ultraviolet spectra yielded only trans- 2-methylpenta-l,3-diene when heated and on hydrogenation gave 1,3-dimethyl~yclobutane.~ Similarly while prolonged irradiaticn of 1 -cyclo- hexylbuta-1 ,3-diene4 in ether gave 3-cyclohexylcyclo- butene in 43 ”/o yield, irradiation for shorter periods resulted in partial isomerisation to cyclohexylidene- but-2-ene ; the latter was transformed on prolonged irradiation into a farrago of isomers and polymer.The structure of the cyclobutene was indicated by its spectral properties and by thermal isomerisation to the starting diene and was confirmed by oxidation to cyclohexylsuccinic acid. The formation of hexa-l,2,4-triene (11) on irradia- tion of hexa-1 ,3,5-triene5 (I) provides another example of diene migration. In agreement irradia- tion of allo-ocimene6 (III) gave the unstable allene (IV); in this preparation a “Corex” glass filter was used and the irradiation continued until the absorp- tion at 270 mp had been reduced to 0.5% of its original value. This allene CI0Hl6 b.p. 24”/0-45 mm. isolated in 37% yield had A,,,. 225 mp (log E 4-39] and gave an infrared spectrum with a well- defined allene maximum at 1949 cm.-l as well as peaks indicative of trisubstituted ethylene methyl and isopropyl groupings (3010 817 1376 and 1362 cm.-l).It absorbed three equivalents of hydrogen to kRp & (V) RR RR (I ;R-ti) (n ;R-H) 6ll;R=Me) (N;R=Me) yield 2,6-dimethyloctane. After 8 min. at 115” the allene was (90%) isomerised to a mixture of two compounds showing the ultraviolet and infrared absorptions to be expected of the previously un-reported 4-cis,6-cis- and 4-cis,6-trans-allo-ocimenes. A mixture of these two trienes (b.p. 68”/10 mm.) absorbed three equivalents of hydrogen to yield only 2,6-dimethyloctane and on irradiation with visible light in the presence of iodine yielded a mixture of 4-trans,6- cis- and 4-trans 6- trans-a1 lo-ocimenes .When the allene (IV) was heated for 3 min. at 270” the cyclic compound (V) was as expected,’ the main (78 %) product. This diene migration taken in conjunction with our earlier reports of the photoisomerisation of con- jugated dienoic acids may indicate an alternativeg biogenetic route to some naturally occurring allenes. Thus we might expect that irradiation of the appropriate polyene acid would result in the forma- tion of the tetraene system of mycomycin although the geometry of the resultant 3,4-double bond is difficult to predict. (Received October 18th 1963.) * Department of Chemistry Instituto Venezolano de Investigaciones Cientificas (I.V.I.C.) Apartado 1827 Caracas Venezuela.t When a “Vycor” glass filter is used; we have found that in quartz with a high-pressure mercury-vapour lamp some cyclobutenes can be re-isomerised to 1,3-dienes. $ Irradiation under the previously described conditions’ gave only a low (ca. 5%) yield of the cyclobutene which was not readily separable by distillation from the polymeric products. Wolinsky Chollar and Baird J. Amer. Chem. SOC.,1962 84 2775. (a)Crowley Proc. Chem. SOC.,1962 334; (b) Srinivasan J. Amer. Chem. SOC.,1962 84 4141. * Caserio Parker Piccolini and Roberts J. Amer. Chem. SOC.,1958 80 5507. Grummitt and Mandel J. Amer. Chem. SOC.,1956 78 1054. Srinivasan,J. Chem. Phys. 1963 38 1039. Cf. G. J. Fonken Tetrahedron Letters 1962 13 549. Alder Brachel and Kaiser Annalen 1957 608 195.Crowley J. Amer. Chem. SOC.,1963 85 1210. Cf. Craig and Moyle Proc. Chem. SOC.,1963 56. PROCEEDINGS Poht-charge Crystai-field Calculations for Cupric Halides By PETERDAY* DESPITE the greater sophistication and flexibility of molecular orbital theory the simple point-charge crystal-field model remains a very useful approach to transition-metal spectra. Its advantages are two- fold. First when the crystal potential is expanded in spherical harmonics. v := 2 B’;.rj. y;(ei,+i) i,l,JlI B’;”are determined completely by crystallographic data. Secondly second- and fourth-order harmonics alone are required to calculated d-orbital spli ttings so that the matrix elements of V with the d-orbitals are linear functions of the two scale factors (r2> and {r4) only.When treated as empirical para- meters by fitting an observed spectrum these two variables contain implicitly all the effects of overlap between metal and ligands. x = Calc. CuXZ-*B2-,Al 8500 2B2-,B 7780 ,B2 3 2E 4280 cuxp 2” -,E’ 9500 CuX2-2B1 -2E 11,570 2B, -2B20 11,070 V = B$r2-Y? + B,O.fl-Yt leading to the diagonal matrix elements (0 1 VlO) = 1476(r2) + 1506(r4); (fl IVl&l) = 730{r2) -1007(r4); (f21Vl&2) = -1476(u2) + 257(r4 )in units of cm.-l when the observed4 interatomic distances in A for CUCI~~ are inserted. The transitions 2A,’ --t 2E” and ,A1’ -+ 2E’ are therefore expected at ?45(r2) + 2520(r4) and 2950(r2) + 1254(r4) respective-ly though the latter is not allowed by the dipole selection rules.In the same way inserting crystallographic data into the expressions for the diagonal matrix elements of the crystal potentials5p6 D,$ and D, we obtain calculated transition energies in terms of (r2) and (r4> which may now be chosen to give the best fit with the spectra of the three chlorides and three c1 X= Br Obs. (cm.-l) Calc. Obs. (cm.-l> 8300 8000 8000 -7200 7570* 5100 4810 4650 9500 9950 8700 11,800 11,650 11,500 -11,000 11,030 -1 1,000 *Ref. 5. The cupric halide complexes provide an excellent system for testing the transferability of empirical crystal-field parameters. With only one hole in the 3d shell no two-electron operators need be invoked. Furthermore there exist complexes of three different symmetries in which the cupric ion is entirely sur- rounded by chloride or bromide ions CuX,2- a flattened tetrahedron1*2 (point group DZd);CuX5> a trigonal bipyramid (D,,); and in solids such as CuCl, CsCuCl, and CuBr an elongated octa-hedron* (D4h).Bond lengths and angles are known in each case.A point-charge model has been used5 to interpret part of the low-temperature crystal-field spectrum of Cs,CuBr, and a generalised crystal-field treatment of Cu2+in Dqh symmetry has been given.g For the trigonal bipyramid not previously treated the basis functions are simply 10) (al’) 1311) (e”) and lf2) (e‘). The crystal potential contains only axially symmetrical components * Inorganic Chemistry Laboratory Oxford.bromides. The resulting values are 0.696 A2 and 3-570 A4for the former and 0.840 A2 and 4.360 A4 for the latter. Since each pair of parameters fits five bands the agreement with observation is satisfactory. Watson’s Hartree-Fock calculation’ for Cu2+ yields values for (r2) and (r4) of 0.288 A2 and 0-196 A4. Though empirical (rl) are therefore transferable the spectacular divergence from the Hartree-Fock values clearly illustrates the theoretical inadequacy of the electrostatic model. The lower energy bands in the tetrahalogen-complexes were placed by Gaussian analysis of the spectra in acetonitrile containing a large excess of halide ions.2 Solid spectra of CsCuCl, CuBr, and Cr(NH,),CuBr were each measured as hexachloro- butadiene mulls and by diffuse reflection.Co(NH,),CuCl was measured as a single crystal. I thank Drs. J. P. Hurrell R. Pappalardo and R. J. P. Williams for discussions. (Received November 14th 1963.) Barnes and Hume Inorg. Chem. 1963 2 444. a Furlani and Morpurgo Theoretica Chem. Act& 1963 1 102; Morosin and Lingafelter Acta Cryst. 1960 13 807. Mori Bull. Chem. Soc. Japan 1960 33 985; Mori Saito and Watanabe ibid. 1961 34 295. 4 Wells J. 1947 1662 1670; Helmholtz J. Arner. Chem. Soc. 1947 69 886. 6 Karipedes and Piper Znorg. Chem. 1962 1,970. 6 Belford Calvin and Belford J. Chem. Phys. 1957 26,1165. 7 Watson Phys. Rev. 1960,118,1036; Tech. Report 12 Solid State and Molecular Theory Group M.I.T. Cambridge Mass. 1959. Professor Sir Ewart Jones Ph.D.D.Sc. F.R.I.C. F.R.S. Waynflete Professor of Chemistry University of Oxford President Designate of the Society for the period 1964-66 The Council House Victoria Square (By courtesy City of Birmingham Information Department) Small brook Ringway (By courtesy City of Birmingham Information Department) Barber Institute of Fine Arts The University Entrance to the Great Hall The University Extension to Hills Block The University with Frankland Block in background The Haworth Building The University JANUARY 1964 Aeruginosin B-A Naturally Occurring Phenazinesulphonic Acid By R. B. HERBERT and F. G. HOLLIMAN* Pseudomonas aeruginosa produces two red pig-pared by alkaline treatment of the pigment) which mentsl of which one aeruginosin A has been shown gave in succession two compounds with character- to be 2-amino-6-carboxy-l O-methylphenazinium istic absorption spectra.Since aeruginosin A was betaine.2 We now present evidence that aeruginosin stable under these hydrolytic conditions the lability B is 2-amino-6-carboxy-10-methy1-8-su1phophen-of demethylaeruginosin B was clearly due to the azinium betaine (I). sulphonic acid group. In a series of 2-amino-phenazinesulphonamides and 2-amino-6-carboxy-phenazinesulphonamides synthesised as models on “B\ \ the hypothesis that sulphamoyl and sulphonic acid -03s\ 1 &NH* groups would show parallel electronic effects the (1) Me rate and pattern of the acidic hydrolysis was found The absorption of aeruginosin B in the visible and to be dependent on the position of the sulphamoyl ultraviolet spectra showed it to be a quaternary group.Only 2-amino-6-carboxy-8-sulphamoylphen-2-aminophenazinium salt. Infrared absorption and mine resembled demethylaeruginosin B in this electrophoresis indicated the presence of carboxyl respect; the products from the two compounds also and sulphonic acid groups. The carbonyl absorption had similar absorption spectra. frequency of aeruginosin B is at 1727 cm.-l a com- Finally the proton magnetic resonance spectrum parably high value being observed only with the (p.m.r.) of demethylaeruginosin B in alkaline D,O 4- and 6-compounds from the complete series of (r = 3-98,J = 2; r = 3.12 J = 2 and 9; r = 2.46 2-aminophenazinecarboxylic acids.3 Whereas 2-J == 9; and r r= 2-04,J = 2 in the ratio 1:1:1:2) amino-4-carboxyphenazinewas readily decarboxyl- required an 8-sulphonic acid group.The spectrum of ated by hot dilute mineral acid the corresponding 2-amino-6-carboxy-8 -sulphamoylphenazine was 6-carboxylic acid was table;^ this difference was closely similar although shifted to lower field. maintained when a sulphonamido-group was in-Aeruginosin B represents the first example of an serted into an available 4- 6- or 8-position in these aromatic sulphonic acid arising from natural sources. two acids. Aeruginosin B was not readily decar- boxylated in this way and is thus like its co-We thank Dr. Holcomb of Varian Associates for metabolite a 6-carboxylic acid. the determination and interpretation of the p.m.r.Aeruginosin B was sensitive to hot dilute mineral spectrum of demethylaeruginosin B. acids and so also was demethylaeruginosin B (pre-(Received November 8th 1963.) * The University Leeds 2. F. G. Holliman. Chem. and Ind.. 1957 1668. F. G. Holliman; S. African Znd. ?Chern:,1961 15 233. D. J. Brock F. G. Holliman and B. A. Jeffery Tetraheduon,in the press. D. J. Brock and F. G. Holliman unpublished work. The Structure and Absolute Configuration of Rosololactone and Related Diterpenoid Lactones By A. I. SCOTT,S. A. SUTHERLAND D. ARIGONI, D. W. YOUNG,L. GUGLIELMETTI and G. A. SIM* CONSIDERATION of stereochemical features of the relationship of the diterpenoid lactones from Tri-biogenesis of the family of diterpenoids in terms of chotheciumroseurn Link which represent a variant of an all-trans cyclisation mechanism1,2 has led to cor- the all-trans cyclisationl~* of the appropriate C, rection of previously accepted assignments of the precursor in that methyl migration has occurred absolute stereochemistry of gibberellic acid from C-10 to C-9.5 The absolute configuration of cafestol and kahwe01.~ We have examined the inter- resenonolactone (I) had been defined at centres 4 5 * (A.I.S.S.A.S. D.W.Y.) Department of Organic Chemistry University of British Columbia Vancouver 8 Canada; (L.G. D.A.) Eidgenossische Technische Hochschule Zurich Switzerland ;(G.A.S.) Chemistry Department The Uni- versity Glasgow W.2 Scotland. Scott McCapra Sytherland Young Ferguson and Sim Tetrahedron,in press.Birch and Smith CIBA Symposium on Terpene and Sterol Biosynthesis,” Churchill London 1959 p. 245; Arigoni ibid. p. 231 ;Ruzicka Eschenmoser and Heusser Experientia 1953 9 357. McCapra Scott Sim and Young Proc. Chem. SOC.,1962 185. Scott Sim Ferguson Young and McCapra J. Amer. Chern. SOC.,1962,84 3197. Birch Richards Smith Harris and Whalley Tetrahedron 1959 7 241; Britt and Arigoni Proc. Chem. SOC., 1958 224. PROCEEDINGS 8,9 and 10 but not at 13.6 The present communica- determined from Patterson syntheses and the carbon tion describes the chemical correlation of rosolo- and oxygen atoms were then located by evaluating lactone' (11) with (I) and provides evidence for the three-dimensional electron-densi ty distributions.The stereochemistry at C-13 in the latter. The complete stereochemistry thus derived for the three diter- penoid lactones of T. roseurns has been checked independently by X-ray diffraction studies of dibromorosololactone. pJjf 's. Dihydrorosonolactone7 011) formed a furfuryl-H idene derivative (IV),m.p. 193" [a]~ + 195" (all in CHCI,) Amax. 319 mp (E 23,130) (all in EtOH). 0 (I) Ozonolysis of (111)gave the diosphenol (V) m.p. 176" A,, 287 mp (E 11,500) [a],+ 220". The identical diosphenol was obtained by ozonolysis of furfuryl- idene dihydrorosenonolactone (VI),m.p. 19 1 ",Amax. 325 mp (E lO,OOO) [a] + 102". Thus rosololactone is 7-deoxy-6-hydroxyrosononolactone. Quantitative t- reduction of dihydrorosonolactone (111) to dihydro- @OH0 (V) rosololactone with sodium borohydride provided compelling evidence for the 6p-configuration (II).Treatment with methanolic sodium hydroxide of the nor-acidg (VII),m.p. 254" [aID-log" pK*,, t = 7~37,~~ from rosenonolactone gave the iso-acid (VIII) m.p. 258" [a] + 4" pK*,, 7.42.1° The acidity measurements are consistentll with the equa- torial conformation of the carboxyl group in both (VII) and (VIII). Reduction of (VIII) with sodium borohydride in dioxan furnished a 7-hydroxy-isoacid (IX) m.p. 253" [a],+ 3" which differed from a second 7-hydroxy-isoacid (X) m.p. 257" [a] + 17" obtained through ozonolysis of iso- rosenololactone7(XI). The two hydroxy-acids (JX) and (X)were converted into (VIII) upon oxidation with chromium(vr) oxide in acetone-sulphuric acid and therefore must be epimeric at position 7 only.Since both (IX) and (X) failed to undergo lactoniza- tion even under forcing conditions the 13p-con- figuration can be inferred for the carboxyl group of (VIII) and hence for the vinyl group of rosenono-lactone (I). Dibromorosololactone crystallises in the ortho- rhombic system with cell dimensions a = 11-12,b = 11 -42 and c = 15.74 A. There are four molecules of C,,H,,O,Br in the unit cell and the space group is P2,2,2 (Di). Three-dimensional X-ray intensity data were recorded on equi-inclination Weissenberg photographs and estimated visually. The co-ordinates of the bromine atoms were Whalley Green Arigoni Britt and Djerassi J.Amer. Chem. SOC., 1959 81 5520. Harris Robertson and Whalley J. 1958 1799 1807. The third lactone 7-deoxyrosenonolactone has been directly related to rosenonolactone (Scott and Young un- published) by reduction of the latter. Correlation was also made at the dihydrorosenonolactone state (ref. 6). Robertson Smithies and Tittensor J. 1949 879. lo For the definition and measurement of ~K*MCS values cf. Simon Helv. Chim..4cta 1958 41 1835. l1 Sommer Arya and Simon Tetrahedron Letters 1960 no. 18 20; Sommer Pascual Arya and Simon Helv. chim. Acta 1963 46 1734. JANUARY1964 molecule was found to have the constitution and relative stereochemistry shown in (MI); it follows that the constitution and stereochemistry of rosolo- lactone are defined by (XI) the absolute configuration shown being firmly established chemically.6 The average discrepancy between observed and cal-culated structure amplitudes is 19 %.The calculations were performed on the Glasgow University DEUCE computer with programmes12 devised by Dr. J. S. Rollett and Dr. J. G. Sime and on the IBM 1620 computer of the University of British Columbia with programmes devised by Dr. F. R. Ahmed. (Received October 14th 1963.) l2 “Computing Methods and the Phase Problem in X-Ray Crystal Analysis,” ed. Pepinsky Robertson and Speakman. Pergamon Press Oxford 1961 ; Rollett p. 87; Sime p. 301. The Structure of Dioxodi-8-quinolinolato-8-quinolinoluranium(w)-Chloroform By D. HALL,A. D. RAE,and T. N. WATERS* WHEN8-quinolinol is added to a neutral solution of the uranyl ion the red precipitate formed has the composition UO,(CloH,NO),,CIoH,N~OH.l This compound is stable and is converted into the “normal” green complex UO2(C1,H,NO) only slow- ly at 210”.Numerous investigations have been reported but several views are held on the structure of the red compound. These are that it is a solvate the extra molecule of 8-quinolinol being held by lattice forces only or alternatively that it is the acid of the ion U02(C10H,N0,)3- in which all ligand molecules are eq~ivalent.~ We have shown by crystal-structure determination that neither view is fully correct. The crystals used were grown from chloroform and contain one mole- cule of this solvent per molecule of uranium com- plex but this does not affect the conclusion.All three 8-quinolinol molecules are co-ordinated to the uranium atom but they are not equivalent. They are very nearly coplanar and perpendicular to the linear uranyl ion and all three phenolic oxygen atoms are co-ordinated but only in two ligand molecules is the nitrogen also bonded to the uranium. The U-0 bonds to the ligands are similar in length (2.25-2.32 A) while the U-N bonds are somewhat weaker with length 2.51 and 2.58 A. Some of the more important bond angles are shown in the Figure. It can be seen that the co-ordination of the uranium atom approximates to the regular 5 + 2 system as observed in e.g. K,U0,F,.5 The third 8-quinolinol molecule is twisted away from the uranium such that the two bonds involving the co-ordinated oxygen are almost collinear.The nitrogen atom is 4-1 A from the uranium but makes an approach of 2.79 A to the phenolic oxygen of the adjacent ligand molecule. It appears likely that the proton is associated with this bond and we suggest that this singly co-ordinated ligand exists as a zwitterion. The suggestion that the proton is involved in hydrogen-bond linkages between uranyl groups4 is certainly not correct. The crystals are monoclinic with a = 20.76 A b = 8.75 A c == 15-62 A 16 = 97-9” 4 molecules per unit cell space group P2,/n. The uranium atoms were located from Patterson projections and the remaining atoms from a three-dimensional Fourier synthesis. Refinement has proceeded by difference syntheses to a present reliability factor of 15-0%.The chloroform molecules are present as solvent of crystallisation only and have no interaction with the uranium complex. We are indebted to Professor D. R. Llewellyn for his interest in this work. (Received November 5th 1963.) * Chemistry Department University of Auckland New Zealand. Frere J. Amer. Chem. SOC.,1933 55 4362. See Horton and Wendlandt J. Inorg. Nuclear Cheni. 1963 25 241 for bibliography. Moeller and Ramaniah J. Amer. Chem. SOC.,1954 76 5251. Bullwinkle and Noble J. Amer. Chern. SOC.,1958,80 2955. Zachariasen Acru Cryst. 1954 7 783. PROCEEDINGS The Effect of changes in Oxidation State upon the e.p.r. Spectra of Dibenzothiophen Anion-radicals By D.H. EARGLE,~~~., and E. T. KAISER* A MARKED dependence of the conjugative properties with those measured recently by Gerdil and Lucken.2 of sulphur-containing groups on their oxidation These authors correlated observed spin splittings state has been observed in anion-radicals possessing with those of calculated values and with those the thiaxanthone and thianthrene ring.l Hence the observed for phenanthrene. dibenzothiophen system was suspected of being The complex overlapping of lines in the spectrum capable of similar behaviour. The anion-radicals of of anion (11) made complete determination of the the three oxidation states of dibenzothiophen (I) splittings difficult; however the total splitting lies (lI) and (111) were prepared by potassium reduction intermediate between those observed for the lowest e.p.r.measur-eme?its Anion of Anion Splittings (gauss)* Total colour (-*- compound width a a 8 "3 (gauss) (1) dk blue 5-04 4-60 1-45 1-05 25.5 (11) brownish >2-4 (2.4 indet. 0.20t 11.7 (111) yellow 2.36 1.84 0.24 0.12 10.4 * After tentative assignments by Gerdil and Lucken for the anion of (I).2 t At -70" and very low modulation splittings due to potassium (I = 3/2) were easily observed. in 1,2-dimethoxyethane at ca. -60°,and their e.p.r. and the highest oxidation state. This effect indicates spectra were examined for similar effects. It is that although the participation of the sulphoxide evident from comparison of the total widths of these group in conjugation is not so marked as that of the three spectra (see Table ) that there is a definite and sulphone it is much greater than that of the sulphide progressive narrowing of the total spectral widths group.It may be noted in addition that since the with increase in the oxidation state of the dibenzo- sulphoxide moiety possesses a greater electronega- thiophen nucleus. A progressive decrease in the tivity than the sulphide it should draw considerable splitting constants of each pair of protons is also electron density from the aromatic rings into the found. central heterocyclic ring. The authors acknowledge support from the Petroleum Research Fund (American Chemical Society) and assistance of the Naval Research Splitting constants measured for the dibenzo-Laboratory (Washington D.C.).thiophen anion itself are in fairly close agreement (Received October 28th 1963.) * The George Washington University Washington D.C. Washington University St. Louis Mo. and University of Chicago Chicago Ill. U.S.A. Kaiser and Eargle J. Amer. Chem. Soc. 1963 85 1821; J. Chem. Phys. 1963 39 1353. Gerdil and Lucken Proc. Chem. SOC.,1963 144. Metal Amines as Reagents for Synthesis of Organometallic Compounds By K. JONES and M. F. LAPPERT* WE have previously noted that the metal-N bond in particular we now report on reactions with protic amino-derivatives of Sn(1v) and other elements is reagents HA illustrated for the case of a dimethyl- responsive to attack by multiple-bonded compounds aminotriorganostannane (e.g. PhNCO CO, CS,) especially those normally R,Sn:NMe + HA+R,SnA + Me,NH susceptible to nucleophilic reagents.l Other examples of reactive unsaturated species have since been In this scheme A is OH OR c1 NH, NHR and demonstrated (see Table).NR, but of special interest are the cases where A is We now find that the range of reactivity of amino- PR, AsR, CI CR cyclopentadienyl and indenyl; derivatives of the more electropositive elements is acetylene affords Me,SnC i C-SnMe,. All these re- indeed comparable to that of Grignard reagents. In actions proceed in nearly quantitative yield and * Department of Chemistry Faculty of Technology University of Manchester. Jones and Lappert Proc. Chem. Soc. 1962 358. JANUARY1964 require mild conditions. The products have all been fully characterised and boiling or melting points are indicated in the Table.Acetonitrile and nitromethane behaved as protic reagents in this context but mixtures of products were obtained. A few tin-phosphorus compounds have recently been obtained but tin-arsenic compounds are novel. Results now reported together with earlier ones,l indicate that the Sn-N bond is highly polar. It is interesting that phosphine and arsine ligands should displace amino-groups from tin(Iv) a situation which we found unparalleled in aminosilanes where the Si-N bond is presumably stabilised by dn-pa interaction. The high reactivity of tin@)-amino-compounds indicates that they and those of other metals may be of value as synthetic intermediates. Thus we have found that ferrocene may conveniently be syn-thesised from iron(n1) chloride by conversion with lithium diethylamide into an iron diethylamide and then reaction with cyclopentadiene.Compound B.p./mm. (M.P.1 M [e,Sn.AsPh 136"/0.05 M re,Sn-PPh 150"/0-8 El:,Sn PPh 170"/0*7 M ,e,SnC i CPh 68"/0.3 M e,SnCi CPrn 172"/760 M e,Sn.Ci CBun 82"/12 El:,SnCi CPh 88"/O-1 PIi,Sn-C i CPh (62"1 M e3SnC5H 56-60 "/1 PIi,SnC,H (129") PIi,SnCgH (129") M e,SnNPh.CS.NMe liquid M e,SnN(p-Tol) CN(To1-p) * NEt 168"/O* 1 M[e,SnN :CPhNMe 79"/0-2 We are grateful to Professor G. E. Coates Dr. R. A. Shaw and Dr. J. C. McCoubrey [and Albright and Wilson (Mfg) Ltd.] for gifts of chemicals and to Pure Chemicals Ltd. for support. (Received November 8th 1963.) a Kuchen and Buchwald Chem.Ber. 1959 92 227; Brucker Balashova and Soborovskii Dokhdy Akad. Nuuk. S.S.S.R. Otdel khim. Nauk 1960 135 843; Schumann Kipf and Schmidt Angew. Chem. 1963 75 672. The Interaction of Radiolytically Produced Univalent Transition-metal Ions with Water By M. ANBARand D. MEYERSTEIN* ITwas reported by Baxendale and Dixon that certain transition-metal cations are reduced by hydrated electrons in radiolysed neutral solution.13 In the series reported manganese ions were exceptional as they did not diminish the yield of hydrogen produced from the radiolysed solution although a transient species formed on their interaction with e-aq was observed. It was suggested that manganese or the alkaline-earth ions can be reduced by electrons and that the absence of any effect is due to the formation of hydrogen atoms by their reaction with water.l We have found recently that transition-metal ions in- cluding manganese interact with the "residual hydrogen" in neutral radiolysed aqueous solutions? Alkaline-earth and alkali-metal ions were shown not to react with "residual hydrogen".It was of interest to check whether manganese ions interact with hydrated electrons and to examine the products of this reaction. 2-deuteropropan-2-01 (0.04~ in H,O) was irradiated by 8oCoX-rays at a dose rate of 11,800 rad/min. and the isotope com- position of the hydrogen produced was determined mass spectrometrically. The yield of hydrogen atoms was monitored by the HD formed.Mn2+ Co2+ Ca2+ and Ba2+ ions were added to the acid solutions; the effect of these additives on the ratio HD:H2 is given in Table 1. It is evident that Ca2+ and Ba2+ ions have no effect on the yield of HD. Co2+ ions diminish the yield of HD by competing with H,O+ for hydrated electrons. Mn2+ ions on the other hand decreased the ratio HD :H2by a factor of > 20. The total yield of hydrogen was however not decreased (cf. ref. 1). The effect of manganese on the HD :H ratio can be explained by the formation of hydrogen from water presumably involving the transfer of a hydride ion. Mn(H,O),+ + H,O+ + Mn(H,O),,OH+ + Ha + H,O If the reaction between Mn+ and water produced * The Weizmann Institute of Science and the Soreq Research Establishment Israel Atomic Energy Commission.Baxendale and Dixon Proc. Chem. Soc. 1963 148. Adams Baxendale and Boag Pruc. Chem. Suc. 1963,241. Baxendale Fielden and Keene Pruc. Chem. SOC.,1963,242. * Anbar and Meyerstein,J. Phys. Chem. in press. hydrogen atoms then these would abstract deuterium from the propan-2-01 and form HD. The formation of hydrogen by reduction of water by a hydride transfer mechanism was observed also in the oxida- tion of chromous ions by water in acid sol~tion.~ It is suggested that the reduction of water described herein is essentially the oxidation of Mn+ by H30+ ions. The absence of hydrogen formation from Co+ in acid solution can be explained either by a dis- proportion reaction to form Co0,l or by the inter- action of Co+ with the organic solute.These reactions may eventually proceed faster than the interaction with H30f ions. In neutral solution alkali-metal ions as well as those of the alkaline earths have no effect on the yield of hydrogen atoms (see Table). If they were to react with electrons to form either hydrogen atoms or hydride ions the ratio HD:H2 would be sub-stantially changed. As metal ions which were found to interact with electrons react at specific rates com- parable to the e-aq + H,O+ reaction the presence of 0-Oh-acetone added in order to scavenge e-sq in neutral solution is not expected to obscure their possible effect. Anbar and Neta unpublished results. PROCEEDINGS The yield of HD from 0.04~2-deuteropropan-2-01 irradiated by =OCo gamma rays.(Total dose 1.2 x loZOev/g.) Additive [Additive]M pH HD:H 1.1 2-02 1.1 2.09 1.1 2-10 1.3 1-28 1.6 1-90 1.6 0.093 6.0 0.58 5.9 0-53 5.9 0.58 5.7 0.54 5.3 Q.53 4.0 0.58 6-0 0.57 The reduction potential of e-aq is lower than required for the reduction of the alkaline earths to their univalent states. (Received September 1Oth 1963.) The Substituent Effects of Positive Poles in Aromatic Nitration By J. H. RIDDand J. H. P.UTLEY* THEsubstituent effects of the -+NH3 and -+NMe3 poles in aromatic nitration have been reported recent1y;l in 98 % sulphuric acid both poles give con- siderable amounts of para-substitution (38% and I1 % respectively). This second result has now been confirmed by the separation of the meta- and para- isomers by ion-exchange chromatography and the series has been extended in this way to the corre- sponding derivatives of phosphorus and arsenic (see Table).The results for the first three substituents refer to r,98 % sulphuric acid and those for the last two to less acidic media; however this should not affect the comparison for we have found that Ph+NMe gives almost the same percentage of para- nitration in fuming nitric acid as in 98% sulphuric acid. Substituent .. .. .. . . fNMe Overall relative rate (Ph.+NMe = 1). . para-Nitration (%) .. .. .. 11 1 The results for the phosphorus and arsenic poles are in fair agreement with those of earlier studies2 which indicated that such substituents are almost entirely meta-directing.However we suggest that the nitrogen pole should be considered as exhibiting the normal substituent effect of a positive -I group and that such substituents deactivate the meta- and para- positions to a rather similar extent. The substituent effect of the nitrogen pole is clearly very different from that of a strong -M group; compare the &meta:para ratio of 4 for Ph.+NMe3 with that of > 100 reported3 for PhNO (a substrate of similar overall reactivity). We attribute the higher *meta:para ratios associated with the phosphorus and arsenic poles to the incursion of an additional type of directing +PMe3 4-8 +AsMe 38.5 CH,-+NMe,*2,400 CH,-+PMe,* - 3 -4 15 >70 * Not yet studied by chromatography for references see text.* University College Gower Street W.C.l. Brickman Johnson and Ridd Proc. Chem. Soc. 1962 228; cf. Chem. Eng. News 1963,41,45. Ingold “Structure and Mechanism in Organic Chemistry,” G. Bell London 1953 Ch. 6. a Holleman Chem. Rev.,1925 1 187 cf. de la Mare and Ridd “Aromatic Substitution,” Butterworths London, 1959 p. 83. JANUARY 1964 effect. The high *nzeta:para ratios cannot be the result of the greater inductive and field effects of these poles for the overall reactivity of Ph.+PMe and Ph+AsMe exceeds that of Ph+NMe (see Table). Also the other results illustrated above show that the order +P > +N for the meta:para ratio is re- versed in the corresponding benzyl compound^.^ The expected screening effect2 of the extra electrons about the phosphorus atom is therefore manifested m the greater reactivity of the aromatic system but is apparently accompanied by a rather specific para- deactivating effect that operates only when the phosphorus atom is directly bonded to the aromatic ring.This additional effect can be understood as the conjugative donation of electrons from the aromatic system to the vacant d-orbitals of the phosphorus. Such an effect in the ground state would be facilitated by the contraction of the d-orbitals by the positive charge5 and would give these substituents some of the character of -A4groups. The high &rneta:para ratios then accord with the expected properties of such groups (compare with the results for nitro- benzene above).Although strongly electron-withdrawing -I and -M groups deactivate all positions of the aromatic ring it may be helpful to regard positively-charged -I groups as being meta,para-directing as a result of strong electrostatic deactivation of the ortho-posi- tions while such neutral -M groups as the nitro- group can be regarded as ortho,meta-directing as a result of strong conjugative deactivation of the para- position. The powerful meta-directing effect of positive -M groups can then be easily understood. We thank Sir Christopher Ingold F.R.S. Profes- sor D. P. Craig Professor P. B. D. de la Mare and Dr. C. A. Vernon for helpful discussions. One of us (J.H.P.U.) thanks the D.S.I.R. for a senior research fellowship.(Received November 21st 1963.) Brickman Ph.D. Thesis London 1963; Ingold Shaw and Wilson J. 1928 1280. Craig and Magnusson J. 1956 4895. Preparation and Properties of Difluoroborane By T. D. COYLE,J. J. RITTER, and T. C. FARRAR* FLUOROBORANES have been postulated as inter-mediates in the reaction of diborane with fluoro- olefinsl but have not been prepared although a number of boron hydrides are known containing atoms of the heavier halogem2 We have now ob- tained by two routes the first unequivocal example of a partially fluorinated boron hydride difluoro- borane HBF,. Difluoroborane is produced in small amounts by the pyrolysis of diborane or tetraborane at 100” in the presence of boron trifluoride or organoboron fluorides.A better preparative route is the reaction of boron trifluoride with dialkoxyboranes. Thus treating dimethoxyborane (45.6 mmol.) with boron trifluoride (90.8 mmol.) in a 1-1. Pyrex bulb at 0” for 30 min. gave a white solid involatile at -80”,and gas (32-7 mmol.) consisting of a mixture of difluoro-borane and boron trifluoride with traces of diborane. The contaminants were removed by repeated frac- tional condensation in the vacuum line although the similarity in the volatilities of the three compounds ied to a severe reduction in yield. Difluoroborane disproportionates slowly to boron trifluoride and diborane in the gas phase at room * National Bureau of Standards Washington 25 D.C. ’ temperature although in the presence of diborane the amount of disproportionation is negligible over several hours.The molecular weight (50.2)(from gas- density measurements on mixtures of difluoroborane and diborane) agrees with that calculated for mono- meric HBF (49-8). The compound adds smoothly to ethylene at room temperature to form ethylboron difluoride. The proton magnetic resonance spectrum (60Mc./sec.) of a solution of difluoroborane in boron trifluoride at -71” exhibits a quartet arising from spin-spin coupling of the hydrogen atom with the llB nucleus (JBH= 210 rt 2 c./sec.). Each member of the quartet is further split into a triplet (intensities 1 :2 1) by coupling with the two equivalent fluorine atoms (JHF= 108 2 c./sec.). The centre of the multiplet lies at slightly lower field (ca.0.1 p.p.m.) than the centre of the terminal proton multiplet in diborane. The infrared spectrum shows bands at 2645sh 263 1,2607m; l462,1455,1449sh s; 141 7,1405,1392sh vs; 1200sh,l176,1145s; 944m; 924s; 555,530~. (Received November 1 1 th 1963.) Bartocha Graham and Stone J. Inorg. Nuclear Chem. 1958 6 119; Phillips and Stone J. 1962 94. Stone “Advances in Inorganic Chemistry and Radiochemistry,” ed. Emeleus and Sharp 1960 Vol. 11 p. 279, and references cited therein. PROCEEDINGS A Mechanism for Triplet-state Relaxation of Aromatic Molecules in a Fluid Environment By BRIANSTEVENSand MICHAEL S.WALKER* THE first-order decay constants k for delayed fluorescence and kT for phosphorescence emission have been measured for an outgassed solution of 1,Zbenzanthracene in liquid paraffin over a range of temperatures as previously described.l The intensity of delayed fluorescence varied as the square of the incident light intensity under which conditions its origin in triplet-triplet state annihilation requires2 that kD/2 = kT as illustrated in the Figure.2.0lo>. I 9 Plot of' log k (solid circles) and log kD/2 (open circles) against T-l for an outgassed 2 x 10-3~-s01u-tion of 1,Zbenzanthracene in liquid parafin; curve is drawn according to eqriation (7). The variation of log k with T-l exhibits the characteristic regions 1 2 and 3 at high inter-mediate and low viscosities reported previously for similar systems and is kinetically consistent with a reversible quenching of the triplet state 3A of the solute by a solute impurity Q the overall scheme being k2 3A + Q +A +3Q 4kl k3 .1k4 A(+kv,) Q(+W If 3Q is lower in energy than 3A by an amount dE then k2/k3= exp (AEIRT) .. . (1) * Department of Chemistry Sheffield University. Stevens and Walker Proc. Chern. SOC.,1963 181. a Parker and Hatchard Proc. Roy. SOC.,1962 A 269 574. Porter and Stief Nature 1962 195 991. Stief private communication. Walker unpublished. whilst in accordance with the Debye equation k2 = 8RT/3MQ where the solvent viscosity 7varies with T as 9 = 90 exp(ED/RT)* For liquid paraffin EDvaries from N 12 kcal./moIe above Oo4 to N 23 kcal./mole from 0" to -14"~.~ The appropriate relaxation equations are -d[3Al/dt = k1[3A] + k2[3A][Q]-k3L3Q 1[A1 with kT = -dln[3A]/df == k + kz[Q] -k313Q1[AI/ 13AI ...(4) whereas the observed exponential decay of luminescence requires that dk,ldt = -d([3Q]/[3AJ)/dt= 0. Thus with [3Q]/[3A] from (2) and (3) (4) becomes k2 k [Ql ... k1 'k + 2k3[A]' since the negative term in (5) is important only at lower viscosities when k << k2[Q]. An analysis of the data provides the numerical expression k,/2 = kT = 3.0 + 1 -26 x 1013Texp(-15000/R7) sec.-l, 1 + 7.4 x 1O1'Texp(-16300/RT) . (7) which as shown by the solid line in the Figure expresses the temperature-dependence of kT and k over the whole temperature range investigated. A natural objection to an impurity quenching mechanism is based on the independence of kT of solute concentration and of solvent in the low viscosity range;3 however if under these conditions k4 < k3[A] (6) reduces to i.e.kT is independent of solvent viscosity and depends on the ratio of impurity to solute concentra- tions which is constant if Q is a solute impurity. JANUARY 1964 The following points may also be noted (i) a comparison of (6) and (7) leads to k,k4[Q]/2k3[A] = 17 exp(l300/RT) sec.-l whence according to (1) the triplet state of Q lies some 1-3 kcal./mole below that of A and [Q]/[A] = 34/k,(mole/mole). Thus either the impurity content of the solute is relatively large or 3Qis very short-lived in accordance with the failure to detect impurity phosphorescence; (ii) the quenching of 3A by a second impurity with Solvent k2 k4 (iii) the experimental rate constant ks for triplet- state transfer is given according to (6) and (1) by k2k4 ks = k4 + 2k3[A] = k2k4 -(8) k + 2k2[A] exp(- dE/RT)' Values of ks calculated from (8) are compared below with those measured6 for the system phen- anthrene-naphthalene where dE = 300 cm.-l.[A I(M) kS -v Found Calc. Hexane 2 x 1O1O 1.1 x 104 9.4 X 2.9 X lo6 2-4 x lo6 Ethylene glycol 3.3 x lo8 1.0 x lo3 6.9 x 2.3 x 106 3.0 x lo5 k2and k in mole-l I.:sec.-l and k in sec.-l a short-lived triplet state of higher energy should This research was supported by the U.S. Depart-produce a further increase in kT at still higher ment of Army (European Research Office).temperatures; (Received October 24th 1963.) IJ Porter and Wilkinson Proc. Roy. Soc. 1961 A 264 1. NEWS AND ANNOUNCEMENTS New Year Honours List.-Among those included in the New Year Honours List was E. G. Cox Secretary Agricultural Research Council who has been appointed K.B.E. Deaths.-We regret to announce the deaths of the following Mr. A. E. Fuller (Sept. 1963) Harrow a student and Mr. I;. Thomas (23.7.63) Ulverston a Fellow since 1907. Election Of New Fellows.496 Candidates were elected to the Fellowship in December 1963. Ethel Fmd*-The purpose of this Fund is to provide grants towards the tra\relling expenses including maintenance of Fellows of the Society studying at a University or Technical College in the British Isles for the first University degree Or other equivalent qualification to enable them to attend the Anniversary Meetings of the society and any Scientific Symposia or Discussions in conjunction therewith.The next awards are to be made in con- nection with the Anniversary Meetings to be held in Birmingham in April 1964. Forms of application together With reWlations governing the award Of grants may be Ob-tained from the Secretary and must be returned by February 15th 1964. Royal Society.-Among the Officers re-elected at the Anniversary Meeting of the Royal Society held on November 30th were Sir Howard Florey Presi- dent; Lord Fleck Treasurer; Sir Patrick Linstead Foreign Secretary; and Professor E. L. Hirst Pro- fessor w.T.J. Morgan and Dr.H. w.Thompson members Of Among the members Of was Professor c*A-Couzson* The of Fleck sir Patrick =instead Professor W.T.J.Morgan and Dr. H. W.Thompson also appear among the Vice-presidents appointed by sir Howard FZorey for the year ending November 30th 1964. E. W. R. Steacie Memorial Fellowship.-Dr. Neil Bartlett Associate Professor of Chemistry at the University of British Columbia has been designated as the first recipient of the new E. w. R. Steacie Memorial Feuowship. This is a senior research award established by the National Research Council of Canada in memory of the late Dr. Steacie who was its President from 1952-1962. The Fellowship is designed to give outstanding young members of staffs of Canadian Universities the opportunity to spend two or three years in unin- terrupted research.Further information regarding this Fellowship can be obtained from the National Research Council of Canada Ottawa 2 Canada. Scientists in the Public Service.-The Treasury has announced the names of individual research workers of exceptional merit who have received special merit promotions. Among those promoted are Dr. E. F. G. Herington and Dr. D. H. Whiffen who become Deputy Chief Scientific Officers and Dr. H. S. Turner who has been appointed Senior Principal Scientific Officer. All are at the National Chemical Laboratory. Salters’ Institute of Industrial Chemistry.-Appli- cations are invited for Salters’ Scholarships value E500-E600 p.a. according to circumstances (plus fees) for a resident in the United Kingdom with an Honours degree or equivalent qualification in Chemistry Biochemistry Physics or Engineering for the purpose of receiving either full-time instruc- tion in the principles of Chemical Engineering or further experience by research in Chemistry or Chemical Engineering.Applications may be made before graduation. The Scholarships will be tenable for one year and may be renewed year by year for two further years. Tenure abroad may be permitted in the third year. When a Scholarship is held abroad travel allowance not exceeding E60 will be made. Applications are also invited for Salters’ Fellow- ships of a value in the range of &l,OOe-&1,200 p.a. according to qualifications dnd experience (plus child allowance and 10% as contribution to F.S.S.U.).These Fellowships may be held by Honours graduates or holders of equivalent qualifi- cations in Chemistry Biochemiqtry Physics or Engineering who desire to obtain further training in research in Chemistry Biochemistry or Chemical Engineering. Candidates should have obtained a doctor’s degree or have had not less than three years’ post-graduate experience by the time of their taking up the Fellowship. Fellowships will be tenable in the United Kingdom or abroad for one year from September lst 1964 and may be renewed for one further year. When a Fellowship is held abroad travel allowance not exceeding f60 will be made. Application forms obtainable from the Clerk of the Salters’ Company 36 Portland Place London W.l must be returned by February 14th 1964.University of East AngIia.-The School of Chemical Sciences opened in October 1963 with a one-year M.Sc. course of advanced teaching and research in physical organic chemistry and a Ph.D. and postdoctoral research programme. The total re- search group now comprises eighteen research students and seven postdoctoral workers. Undergraduates (probably about fifty) will be admitted to the School in October 1964 and re- search will be greatly expanded one-year courses in both spectroscopy and physical organic chemistry will be mounted. The present academic staff are Professor A. R. Katritzky and Dr. R. A. Y.Jones. In 1964 they will be joined by Professor N.Sheppard at present PROCEEDINGS Fellow of Trinity College Cambridge and a further six academic staff. New Laboratory for Government Chemist.-The address of the Laboratory of the Government Chem- ist is now Cornwall House Stamford Street London S.E.I. The premises in Clement’s Inn W.C.2 Custom House E.C.3 Dudley House W.C.2 and in Barry Road N.W.lO have been closed. Dexter Award 1964.-The Division of the History of Chemistry of the American Chemical Society invites nominations for the Dexter Award for 1964. The Award which consists of a plaque and prize of $1,OOO is made on the basis of services which have advanced the history of chemistry in any of the following ways by publication of an important book or article; by the furtherance of the teaching of the history of chemistry; by significant contributions to the bibliography of the history of chemistry; or by meritorious services over a long period of time which have resulted in the advancement of the history of chemistry.Dr. Douglas McKie (University of London) was presented with the 1963 Award. All nominations in duplicate should be sent by March loth 1964 to Mr. Sidney M. Edelstein Secretary of the Division of History of Chemistry A.C.S. Dexter Chemical Corporation 845 Edge- water Road Bronx New York to whom enquiries should be addressed. Symposia etc.-The Fifth Agrochimica Inter-national Symposium (Sulphur in Agriculture) will be held in Palermo and Catania on March 12th-21st 1904. Further enquiries should be addressed to Pro- fessor 0.T.Rotini Director Institute of Agricultural Chemistry University of Pisa Via S. Michele degli Scalzi 2 Pisa Italy. A Symposium on Organic Reactions in the Field of Natural Products will be held in Gamagori Japan on April 20th 1964. Further enquiries should be addressed to Professor Yoshimasa Hirata Department of Chemistry Nagoya University Chikusa Nagoya Japan. This meeting follows the I.U.P.A.C. Symposium which will be held in Kyoto on April 12-18th 1964. A Symposium on the Chemistry of Microbial Products will be held in Tokyo on April 24-25th 1964. Further enquiries should be addressed to Professor H. Umezawa Institute of Applied Micro- biology University of Tokyo Hongo Tokyo Japan. The Fourteenth Annual Meeting of the Society of Physical Chemistry will be held in Bordeaux on May 25-29th 1964.Further enquiries should be addressed to Prolessor G. Emschwiller Secretaire GknCral SociCtC de Chimie Physique 10 rue Vauquelin Paris 5e France. A General Assembly of the International Organisa- tion for Pure and Applied Biophysics will be held in JANUARY 1964 Paris on June 22nd-27th 1964. Further enquiries should be addressed to Professor A. K. Solomon Biophysical Laboratory Harvard Medical School Boston 15 Mass. The Eighth International Conference on Co-ordination Chemistry sponsored by the International Union of Pure and Applied Chemistry will be held in Vienna on September 7-1lth 1964. Further enquiries should be addressed to Profess? A.Maschka Secretary VIll .I .C.C.C. Verein Oster-reichischer Chemiker 1 Eschenbachgass 9 Vienna Austria. The Thirty-fifth International Congrxs of In- dustrial Chemistry sponsored by the Polish Society of lndustrial Chemistry will be held in Warsaw on September 13-1 8th 1964. Further enquiries should be addressed to Stowarzy szenie Inzynierow i Technikow Przenysla Chemiscznego (NOT) VI. Czackiego 3/5 Warsaw Poland. A Symposium on the Application of Chemical Engineering in Newly Developing Countries will be held in London on September 29th 1964. Further enquiries should be addressed to Mr. 0. G. Weller The Institution of Chemical Engineers 16 Belgrave Square London S.W.1. Personal.-Mr. A. B. Angus formerly of Sheffield College of Technology has been appointed Head of the Chemistry Department at Widnes College of Further Education.Dr. C. M. Atkinson has been appointed Vice- Principal of the Liverpool College of Technology. Dr. R. R. Raldwin and Dr. J. J. Kipline ha\le been appointed to Readerships in Physical Chemistry at the University of Hull. Dr. L. C.F. Blackman has been appointed Director of the Basic Research Laboratories of the British Coal Utilisation Research Association from February 1964. Dr. J. Cliatt has been appointed to the new Chair of Inorganic Chemistry at Queen Mary College University of London. He will combine this aupoint- ment with the Directorship of the Agricultural Research Council‘s Unit of Nitrogen Fixation which is being established at Queen Mary College.Dr. V. M. Clnrk and Dr. T. C. W(ld&ngton University Lecturers at Cambridge and Fellows of Gonville and Caius College Cambridge have been appointed to Professorships in the School of Mole-cular Sciences at the new University of Warwick. The title of Senior Visiting Research Fellow in Chemistry has been conferred on Dr. A. .I. Ellis at the University of Southampton. Dr. A. C. M. Finch has been appointed to a Lectureship in Pharmaceutical Chemistry at the College of Advanced Technology Birmingham. Dr. M. J. GaZZug?ier has been appointed to a Lectureship in Organic Chemistry at the University of New South Wales. Dr. L. J. Harris has retired as Director of the Dunn Nutritional Laboratory Cambridge.At the Annual Statutory Meeting of the Royal Society of kdin burgh Professor E. L. Hirst was elected President and Dr. M. Ritchie was elected Vice-president of the Council. Mr. J. M. konard has been appointed Chairman of Carless Cape1 & Leonard Limited and Mr. F. A. Jackman has been appointed Deputy Chairman and will continue as Commercial Director. Dr. Leo Marion Vice-president (Scientific) of the National Research Council of Canada has been awarded the “Prix Jecker,” the most important chemistry prize of the Academy of Sciences of Paris for his work on the structure of alkaloids. Dr. 1. A. Menzies has been appointed to a Senior Lectureship in Corrosion Science in the Department of Chemical Engineering Faculty of Technology University of Manchester.Professor F. L.M. Pattison has just returned from a world tour which included lectures to the Czech Polish and Soviet Academies of Science and to Universities and research groups; part of the trip was under the N.R.C.-Soviet Academy Exchange Agree- ment. Professor V.Prelog (Honorary Fellow) will deliver the Andrews Lectures for 1964 at the University of New South Wales in March. Dr. I. H. Qirreshi has taken a one-year Post- doctoral Fellowship in the Department of Chem- istry University of British Columbia Canada. Dr. W. Schneider has been appointed Professor of Inorganic Chemistry at the E.T.H. Berne from April lst 1964. Mr. J. A. Semlyen has been appointed to a Research Lectureship in Chemistry at Christ Church Oxford.Dr. J. N. Smith formerly of St. Mary’s Hospital Medical School London University has been appointed to the Chair of Biochemistry 2t Victoria University of Wellington. Dr. R. Spence has been appointed Director of the Atomic Energy Research Establishment Harwell from February 10th. Dr. T. M. Sugden has been appointed Research Director of the Thornton Research Centre Shell Research Limited Chester. Projessor J. C. Tatlow recently visited the Univzr- sity College of Rhodesia and Nyasaland in Salisbury and gave one lecture. His visit was in connection with a medical degree course which has been started under the auspices of the University of Birmingham. Dr. H. W. Thompson was elected President of the Council for lhe next two years of the International Council of Scientific Unions.P ROCEEDINGS ~~ ~ ~ ~ ~ ~~~~~ Lord Todd has accepted an invitation to join the board of Fisons Limited as an independent outside Director. Dr. M. Vajdaof the Eotvos University of Budapest is now at Loughborough College of Technology on a one-year Research Fellowship in the Department of Applied Chemistry. Dr. W. J. Whelan formerly of the Lister Institute of Preventive Medicine has been appointed to the Chair of Biochemistry tenable at the Royal Free Hospital School of Medicine. Dr. C. L. WiZson has been appointed Head of the Chemistry Department at High Point College High Point North Carolina U.S.A. FORTHCOMING SCIENTIFIC MEETINGS London Thursday February 13th 1964 at 6 p.m.Simonsen Lecture “Molecular Rearrangements of Terpenes,” by Professor G. Ourisson Ph.D. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology Imperial Institute Road S.W.7. Thursday February 27th at 6 p.m. Tilden Lecture “A Glow in the Dark-The Rationale of Phosphorylation,” by Dr. V. M. Clark M.A. To be given in the Lecture Theatre School of Pharmacy Brunswick Square W.C.l. British Railways are offering concessionary fares (single fare plus one half for the return journey) for London meetings; a travel voucher for any meeting will be sent by the General Secretary on receipt of a stamped and addressed envelope.] Aberdeen (Joint Meetings with the Royal Institute of Chem- istry and the Society of Chemical Industry to be held in the Medical Physics Lecture Theatre Marischal College unless otherwise stated.) Thursday February 13th 1964 at 8 p.m.Liversidge Lecture “Some Contemporary Problems in Solid-state Chemistry,” by Professor J. S. Ander-son Ph.D. F.R.S. To be given in the Chemistry Department The University. Thursday February 27th at 8 p.m. Lecture “Some Aspects of the Chemistry of Flames,” by Dr. T. M. Sugden M.A. F.R.S. Aberystwyth (Joint Meetings with the University College of Wales Chemical Society to be held in the Edward Davies Chemical Laboratory.) Wednesday February 5th 1964 at 5 p.m. Lecture “Flames Cool and Hot,” by Dr. C. F. H. Tipper. Thursday February 20th at 5 p.m. Lecture “Tetraterpenes,” by Professor B.C. L. Weedon Ph.D. F.R.I.C. Thursday March 5th at 5 p.m. Lecture “The Stability of Lanthanide Chelates,” by Dr. F. J. C. Rossotti M.A. Birmingham Friday February 14th 1964 at 4.30 p.m. Lecture “Naturally Occurring Acetylenic Com-pounds,” by Sir Ewart Jones D.Sc. F.R.S. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University. Friday February 28th at 5.30 p.m. Lecture “Some Applications of n.m.r. Spectro-scopy in Organic Chemistry,” by Professor A. R. Katritzky D.Phil. Sc.D. Joint Meeting with the Chemical Society of the College of Technology to be held in the College of Advanced Technology. Bristol (Joint Meetings with the Royal Institute of Chem- istry and the Society of Chemical Industry to be held in the Department of Chemistry The University unless otherwise stated.) Thursday February 13th 1964 at 6.30 p.m.Lecture “The Catalytic Activation of Hydrogen,” by Professor D. D. Eley O.B.E. Ph.D. Sc.D. Tuesday February 18th at 7.30 p.m. Lecture “Polymerisation Mechanisms with Ionic Catalysts,” by Professor A. G. Evans D.Sc. F.R.I.C. To be given at the Technical College Gloucester. Thursday February 27th at 5.15 p.m. Lecture “Tarnishing Reactions,” by Dr. S. J. Gregg. Joint Meeting with the University Student Chemical Society. Thursday March 5th at 6.30 p.m. Lecture “Freeze Drying of Pharmaceuticals and Food,” by Mr. T. W. G. Rowe. Also joint with the Institute of Fuel.JANUARY1964 Cambridge Friday February 28th 1964 at 8.30 p.m. Lecture “Liquid Sodium,” by Professor C. C. Addison D.Sc. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the University Chemical Laboratory Lensfield Road. cardif€ Monday February 3rd 1964 at 5 p.m. Lecture “The Infrared Spectra of Surface-adsorbed Molecules,” by Dr. N. Sheppard M.A. To be given in the Department of Chemistry University College Cathays Park Cardiff. Dublin Friday February 7th 1964 at 7.45 p.m. Lecture “The Chemistry of the Pneumococcus Immuno-polysaccharides,” by Professor M. Stacey D.Sc. F.R.S. Joint Meeting with the Werner Society to be held in the Department of Chemistry Trinity College. Friday February 14th.It is regretted that the Simonson Lecture by Professor G. Ourisson arranged for this date has been cancelled. Monday February 24th at 7.45 p.m. Lecture “Protonation of Some Transitional-metal Complexes,” by Professor G. Wilkinson Ph.D. F.R.I.C. Joint Meeting with the Werner Society to be held in the Department of Chemistry Trinity College. Durham (Joint Meetings with the University Chemical Society to be held in the Science Laboratories South Road unless otherwise stated.) Monday February 3rd 1964 at 5 p.m. Lecture “Organometallic Chemistry-Some Recent Studies,” by Professor F. G. A. Stone M.A. Ph.D. Wednesday February 12th at 3 p.m. Meeting for the Reading of Original Papers in Inorganic Chemistry. Joint Meeting with the Chemical Societies of Newcastle and the Tees-side to be held in the Chemistry Department The University Newcastle-upon-Tyne.Monday February 24th at 5 p.m. Lecture “Modern Developments in Free-radical Chemistry,” by Dr. W. A. Waters F.R.S. Dundee (Meetings to be held in the Chemistry Department Queen’s College.) Tuesday February 18th 1964 at 5 p.m. Lecture “The Stereochemical and Spectroscopic Aspects of Optical Rotatory Power,” by Dr. S. F. Mason M.A. Tuesday February 25th at 5 p.m. Lecture “Excitons and the Spectra of Molecular Crystals,” by Professor D. P. Craig D.Sc. F.R.I.C. Edinburgh Thursday February 20th 1964 at 7.30 p.m. Lecture “How Poppies Make Opium,” by Professor A. R. Battersby D.Sc. Ph.D. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College.Tuesday March 3rd at 4.30 p.m. Lecture “Simple and Complex Metal Nitrates and Nitrites,” by Professor C. C. Addison D.Sc. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University. Exeter Friday February 28th 1964 at 5.15 p.m. Lecture “Biogenesis of Some Alkaloids,” by Professor D. H. R. Barton D.Sc. F.R.S. To be given in the Department of Chemistry The University. Glasgow Thursday February 13th 1964 at 4 p.m. Lecture “Modern Chemical Applications of Infrared Spectroscopy,” by Dr. N. Sheppard M.A. Joint Meeting with the Alchemists’ Club to be held in the Chemistry Department The University.Wednesday February 19th at 4 p.m. Simonsen Lecture “Molecular Rearrangements of Terpenes,” by Professor G. Ourisson Ph.D. To be given in the Chemistry Department The University. Hull (Joint Meetings with the University Students Chemical Society to be held in the Department of Chemistry The University.) Thursday February 13th 1964 at 4 p.m. Lecture “A New Family of Antibiotics,” by Professor W. D. Ollis Ph.D. Thursday February 27th at 4 p.m. Lecture “Infrared Spectra of Molecules Adsorbed on Surfaces,” by Dr. N. Sheppard M.A. Leeds Thursday March 5th 1964 at 6 p.m. Lecture “Electron Transfers in Aprotic Solvents and some Chain-transfer Complexes,” by Professor M. Szwarc Ph.D. D.k. Joint Meeting with the University Union Chemical Society to be held in the Chemistry Department The University.Leicester Monday February loth 1964 at 4.30 p.m. Lecture “Co-ordination Complexes and Organic Chelating Agents in Modern Analytical Chemistry,” by Dr. T. S. West F.R.T.C. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University. Tuesday March 3rd at 3 p.m. Lecture “Stereochemistry in lnorganic Chemistry,” by Dr. W. E. Addison. Joint Meeting with the Colleges of Art and Technology Chemical Society to be held in the Lecture Theatre The Union Building College of Technology Loughborough. Liverpool Monday February 17th 1964 at 5 p.m. Simonsen Lecture “Molecular Rearrangements of Terpenes,” by Professor G.Ourisson Ph.D. Joint Meeting with the University Chemical Society to be held in the Donnan Laboratories The University. Manches ter [Meetings to be held in the Lecture Theatre R/G7 Renold Building (Lecture Room Block) Manchester College of Science and Technology.] Thursday February 20th 1964 at 6.30 p.m. Lecture “Catalytic Reactions of Aromatic Mole- cules on Metals,” by Professor C. Kemball M.A. Sc.D. F.R.I.C. Thursday February 27th at 6.30 p.m. Lecture “Recent Developments in Anionic Poly- merisation,” by Professor M. Szwarc Ph.D. D.Sc. Newcastle-upon-Tyne (Meetings to be held in the Chemistry Department The University.) Wednesday February 12th 1964 at 3 pm. Meeting for the Reading of Original Papers in Inorganic Chemistry.Tuesday March 3rd at 5.30 p.m. Lecture “Chemical and Biochemical Studies on the Cephalosporins,” by Dr. E. P. Abraham M.A. F.R.S. Northern Ireland (Joint Meetings with the Royal Institute of Chem- istry the Society of Chemical Industry and the Andrews Club to be held in the Department of Chemistry David Keir Building Queen’s University Belfast.) Thursday February 6th 1964 at 7.45 p.m. Lecture to be given by Professor M. Stacey D.Sc. F.R.S. PROCEEDINGS Tuesday March 3rd at 7.45 p.m. Lecture “The Synthesis of Polypeptides,” by Professor H. N. Rydon D.Sc. F.R.I.C. North Wales Thursday February 13th 1964 at 5.45 p.m. Lecture “Some Unusual Electrophilic Aromatic Substitutions,” by Professor C.Eaborn D.Sc. F.R.I.C. Joint Meeting with the University College of North Wales Chemical Society to be given in the Chemistry Department University College of North Wales Bangor. Norwich (Meetings to be held in Lecture Room 2 The University of East Anglia Wilberforce Road.) Thursday February 6th 1964 at 5.30 p.m. Lecture “The Kinetics of Nitration of Heterocyclic Compounds,” by Dr. K. Schofield F.R.I.C. Thursday February 13th at 5.30 p.m. Lecture “Recent Developments in Petroleum Pro-duct Technology,” by Mr. J. B. Berkeley M.A. A.F.1nst.Pet. Thursday February 20th at 5.30 p.m. Lecture “Reactions of Carbon-Silicon Bonds,” by Professor C. Eaborn D.Sc. F.R.I.C. Thursday March Sth at 5.30 p.m. Lecture “Sulphoxide Oxidations,’’ by Dr.D. N. Jones. Nottingham (Joint Meetings with the University Chemical Society to be held in the Chemistry Department The University.) Tuesday February 11 th 1964 at 5 p.m. Lecture “The Structure of Some Simple Inorganic Radicals,” by Professor M. C. R. Symons D.Sc. Ph.D. F.R.I.C. Tuesday February 25th at 5 p.m. Lecture “Kinetic Theory of Gases Old and New,” by Professor P. Gray M.A. Ph.D. Oxford (Joint Meetings with the Alembic Club to be held in the Inorganic Chemistry Laboratory.) Friday February 14th 1964 at 3.30 p.m. Simonsen Lecture “Molecular Rearrangements of Terpenes,” by Professor G. Ourisson Ph.D. (Heme note the amended date of this Lecture.) Monday March 2nd at 3.30 p.m. Tilden Lecture “Activated Molecules,” by Professor A.F. Trotman-Dickenson Ph.D. JANUARY1964 Reading (Joint Meetings with the Royal Institute of Chem- istry and the University Chemical Society to be held in the Large Chemistry Theatre The University.) Monday February loth 1964 at 5.30 p.m. Lecture “Liquids and Solids,” by Professor D. H. Everett M.B.E. M.A. D.Sc. Tuesday March 3rd at 5.30 p.m. Lecture “Chemistry of the Excited State,” by Profes- sor G. Porter Sc.D. F.R.I.C. F.R.S. Southampton Friday February 7th 1964 at 5 p.m. Lecture “Aliphatic Electrophilic Substitution,” by Sir Christopher Ingold D.Sc. F.R.S. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University. Friday February 14th at 7 p.m.Lecture “Fuel Cells,” by Dr. A. B. Hart. Joint Meeting with the Portsmouth and District Chemical Society to be held in the Department of Chemistry College of Technology. Portsmouth. Swansea (Joint Meetings with the Student Chemical Society to be held in the Department of Chemistry Univer- sity College.) Wednesday February 12th 1964 at 4.30 p.m. Lecture “Organic Semi-conductors,” by Professor D. D. Eley O.B.E. Sc.D. Ph.D. Monday March 2nd at 4.30 p.m. Lecture to be given by Professor B. Lythgoe M.A. Ph.D. F.R.S. Tees-side Wednesday February 19th 1964 at 8 p.m. Tilden Lecture “A Glow in the Dark-The Rationale of Phosphorylation,” by Dr. V. M. Clark M.A. Joint Meeting with the Royal lnstitute of Chemistry and the Society of Chemical Industry to be held at the Constantine College of Technology Middlesbrough.OBITUARY NOTICES ROBERT FERGUS HUNTER 1904-1963 ROBERT HUNTER was born at Beckenham FERGUS Kent on March 18th 1904. His early education was in Brussels but on the outbreak of the First World War in 1914 he returned to England completing his pre-university courses at The Regent Street Poly- technic. From there he went to Imperial College of Science and Technology where he remained until 1929. He graduated in Chemistry with First Class Honours in 1924 obtained his M.Sc. degree in 1925 and his Ph.D. in 1926. In that year he was appointed as a Ramsay Fellow a distinction of which he was justly proud. During the period 1929-1930 he was a lecturer at Brighton College of Technology.Following the conferment on him of a D.Sc. degree in 1930 he accepted the post of Nizam Professor of Chemistry Aligarh University India at the early age of 26 a Chair which he held for six years. He relinquished the position in 1936 and was success- ively a lecturer at Manchester University (1936- 1937) research biochemist at the London School of Hygiene and Tropical Medicine (1938-1939) Senior Organic Research Chemist and Section Manager with Lever Bros. and Unilever Ltd. (1 939-1946) and Research Manager Bakelite Ltd. (1946-1958). At the time of his death he was Research Co-ordinator Bakelite Ltd. Hunter’s chemical interests were broad and he published over a hundred papers. By 1930 when he was still only 26 he had written no less than twenty-five original contributions.His first interest which he maintained for many years was in aromatic heterocyclic compounds mainly of the benzthiazole type and on this topic he prepared some twenty-seven papers. He also found time to examine the use of thiocarbonyl chloride in the synthesis of such compounds as nuclear methyl- substituted aromatic thiocarbimides. His investi-gations of benzthiazoles led him to examine the tautomeric mobility of heterocyclic compounds in general. The directive effect of substituents on cyclisation of substituted diarylthiocarbamides also claimed his attention. In 1934 he became actively interested in the problems associated with chemical linkages and in collaboration with Samuel gave an interpretation of valency on the basis of wave mechanics and band spectra.(J. Chern. Soc. 1934 1180). During this year he also published a book on “The Electronic Theory of Chemistry.” While he was at Manchester University Hunter worked on the “trimethylene biradical.” On joining Lever Bros. in 1939 he developed fresh interests this time in carotenoids and Vitamin A; he published something like thirteen papers in this important field and additionally wrote the section on “The Caretenoid Group” for Vol. I1 of “The Chemistry of Carbon Compounds,” 1953. He was always interested in spectroscopy and in particular utilized ultraviolet absorption spectra and X-ray techniques as tools for elucidating structures.When Hunter became associated with Bakelite Ltd. in 1946 he showed his versatility by concen- trating on the difficult subject of phenol-formal- dehyde resins. He was impressed with the paucity of information on prototype compounds of known structure even of a comparatively simple kind and he initiated “rational syntheses” designed to fill some of the gaps. Precisely defined compounds were essential if maximum value were to be achieved from chromatographic studies of the resinous conden- sation. Hunter’s first noteworthy achievement in the field was the synthesis in 1950 of 2,4,6-trimethylol- phenol the presence of which in phenolic resins had previously been inferred but which had never been isolated. Carpenter and Hunter (J.Appl. Cltem.1951 I 217) relied on the reduction of the triethyl ester of hydroxytrimesic acid by lithium aluminium hydride in this first synthesis but later (1954) they described improved methods based on 2,4-diformylphenol and the dichloromethyl derivative of salicylaldehyde. Carpenter and Hunter in 1950 additionally described the preparation of certain methyl01 derivatives of dihydroxydiphenylmethanes. Later PROCEEDINGS Hunter with various collaborators carried out the preparation of numerous “Novolaks” (phenolic nuclei linked by methylene groups). Many of these were of large size; for example tetra penta hexa hepta octa and deca-nuclear compounds were synthesized varying through linear branched bridged and cross-linked forms. Perhaps of special interest was the demonstration that such compounds could in fact exist many in crystalline form.Finally Hunter turned to the possibility of polymerising acetylene and ally1 derivatives to give useful resins. Although unsuccessful from a practical point of view the work provided scope for elegant syntheses of a wide range of new compounds. Hunter’s numerous contributions to chemistry are the more impressive when the handicaps under which he suffered are realised. Few even of his friends were aware that for 25 years he suffered acutely with bronchial asthma aggravated later by heart trouble. He was forced to give up virtually all physical exercise and used his leisure time in reading the classics and history being his main preoccu- pations.For a time he was actively engaged as a sidesman at the parish church of St. Margaret’s Olton but had to give up this activity because of ill-health. He died as the result of a cerebral haemorrhage on May 2nd 1963 leaving a wife who had shared his difficulties and rejoiced in his successes and to whom sympathy is extended. N. J. L. MEGSON. LEONARD ERIC HINKEL 1882-1 LEONARD ERICHINKELwas born at Croydon on November 15th 1882 the fourth son of naturalised parents of German origin. Educated at King’s College School Wimbledon he entered King’s College London in 1900. Here he was awarded a Daniell Scholarship and he graduated with First Class Honours in Chemistry. He remained at King’s in the capacity of Research Assistant in the Chem- istry Department and in 1905 he was appointed Assistant Demonstrator serving first under Pro- fessor J.M. Thomson F.R.S. and Sir Herbert Jackson K.B.E. F.R.S. and after 19 14 under Pro- fessor A. w. Crossley C.M.G. F.R.S. In 1907 he became a Fellow of the Institute of Chemistry and in 1911 an Associate of King’s College. He was appointed Lecturer at King’s in 1912 and Senior Lecturer in 1919. His teaching duties afforded little time for research more particularly during the First World War when in 1916 the demands made on his senior colleagues left Hinkel in sole charge of the Honours work and evening classes in Chemistry. 962 When the University College of Swansea was established in 1920 Hinkel was appointed Senior Lecturer in Organic Chemistry and he continued to hold this post until his retirement in 1949.The planning and equipment of the new laboratories organised in collaboration with Professor J. E. Coates had to be conducted under conditions of exceptional difficulty but Hinkel was at last able to engage in a certain measure of research. At King‘s College he had become deeply interested in Cross- ley’s work on the chemistry of the dihydroresorcinols and xylenols and when Crossley resigned in 1920 to become Director of the British Cotton Industry Research Association he assigned to Hinkel all his chemicals and interests in these lines the develop- ment of which became the basis of the organic chemical research initiated by Hinkel at Swansea. It was a source of deep satisfaction to Hinkel that one of his earliest research students later became the present Daniell Professor of Chemistry at King‘s College.JANUARY1964 In 1924 the University of London conferred on Hinkel the D.Sc. degree. He had meanwhile de- veloped an intense interest in his work in conjunction with Professor Coates on the chemistry of hydrogen cyanide. His extensive investigations in this field included Gatterman’s aldehyde synthesis reactions between hydrogen cyanide and hydrogen halides and the polymerisation of hydrogen cyanide. He further initiated studies on substituted aromatic aldehydes in Hantzsch’s pyridine condensations and on p-aminodimethylaniline. Some fifty original papers covering these researches have appeared in the Journal.Hinkel was always an enthusiastic experimentalist and worked regularly at the bench until his retire- ment. He took a keen interest in the local activities of the Chemical Society and of the Royal Institute of Chemistry and served on the Council of the R.I.C. from 1930 to 1933. It was however as a teacher that Hinkel was supremely successful. He combined a contagious enthusiasm for his subject with a deep human interest in his students. To attend his lectures was stimulating and to engage in research under him was a demanding but highly rewarding experience. Anything short of the highest standards of intellectual and personal integrity evoked his most devastating disapproval. Yet his rare sympathy with individual creative effort aroused an equally rare response and Hinkel had the ability to inspire in students interests they would never have thought to share for Hinkel was a man of that wide general culture which he held it the function of a University to instil.He further pro- moted the careers of his students in strictly practical ways in one case at least drawing on his own financial resources for this purpose. Hinkel’s courteous friendliness and ebullient good humour were well adapted to life in Wales. He was insatiably curious about the language and traditions of the country and when he considered it necessary to censure an insincere or hypocritical attitude was quite capable of producing a barbed epigram in the vernacular.Hinkel was an accomplished pianist and a lover of classical music. This must have been a consolation to him in his later years for his health never robust deteriorated during his retirement and his sight eventually failed completely. He then had the gratification of discovering that his former students remained keenly conscious of their indebtedness to him and undertook considerable journeys in order to visit him. This is perhaps the greater tribute in that the vitality of the man was such that even when approaching 80 his zest for life lent him a force of personality which could prove exhausting to those of more limited capacity. For he held tenaciously to an idea and could be exasperating in the way only a forceful yet lovable man can be.He died on November 18th 1962 and his passing leaves us the poorer. R. H. DAVIES, J. H. GORVIN. ADDITIONS TO THE LIBRARY Harrap’s standard German and English dictionary. Edited by T. Jones. Part 1 German-English Vol. I A-E. Pp. 117. Harrap. London. 1963. Organic electronic spectral data. Vol. 4 (1958-59). Edited by J. P. Phillips and F. C. Nachod. Pp. 1179. Interscience. New York. 1963. Beilsteins Handbuch der organischen Chemie. Edited by H. G. Boit. 3rd Supplement. Vol. 4 Part 11. 4th edn. Pp. 1097-2237. Springer-Verlag. Berlin. 1963. (Pre-sented by the Beilstein Institut.) Gmelins Handbuch der anorganischen Chemie. System-Nummer 3,Lieferung 5.8th edn. Pp. 1185-1732. Verlag Chemie. Weinheim. 1963. Ullrnanns Encyklopadie der technischen Chemie.Edited by W. Foerst. Vol. 14. 3rd edn. Pp. 810. Urban and Schwazenberg. Munich. 1963. Determination of beryllium handbook of chemical and radiometric methods for its determination in ores, concentrates and low-grade sources. Issued by the Department of Scientific and Industrial Research, National Chemical Laboratory. Pp.. 31. H.M.S,O. London. 1963. (Presented by National Chemcal Laboratory.) Atomic and nuclear physics an introduction. T. A. Littlefield and N. Thorley. Pp. 436. Van Nostrand. London. 1963. (Presented by the publisher.) Infrared spectroscopy and molecular structure an outline of the principles. Edited by M.Davies. Pp. 468. Elsevier. Amsterdam. 1963. Characteristic frequencies of chemical groups in the infrared.M. St. C. Flett. Pp. 98. Elsevier. Amsterdam. 1963. Analyse der Tenside infrarotspektroskopische und chemische Methoden. D. Hummel. 2 Vols. Pp. 480. Carl Hanser Verlag. Munich. 1962. Radiation effects on organic materials. Edited by R. 0. Bolt and J. G. Carroll. Prepared under the auspices of the Division of Technical Information of the United States Atomic Energy Commission. Pp. 576. Academic Press. New York. 1963. Atomic structure and chemical bonding a non-mathematical introduction. F. Seel. (Translated from the 4th German edition.) Pp. 112. Methuen. London. 1963. Mass transfer process calculations. H. Sawistowski and W. Smith. Pp. 518.Interscience. New York. 1963. Komplexometrie. R. Pribil. Vol. 2. Pp. 112. VEB Deutscher Verlag fur Grundstofhdustrie.Leipzig. 1962. Elimination reactions. D. V. Banthorpe. (Reaction Mechanisms in Organic Chemistry. Vol. 2.) Pp. 215. Elsevier. Amsterdam. 1963. Matheson gas data book. 3rd edn. Pp. 420. Matheson Co. Inc. East Rutherford N.J. 1961. Recent progress in microwlorimetry. E. Calvet and H. Prat. (Trunslatedfrom the French.) Pp. 177. Pergamon Press. Oxford. 1963. Chemical aspects of nuclear reactors. J. K. Dawson and R. G. Sowden. Vols. 1-3. Butterworths London. 1963. Gas phase chromatography. R. Kaiser. (Translated from the German.) Vol. 1. Pp. 199. Vol. 2. Pp. 120 and Vol. 3. Pp. 162. Butterworths. London. 1963. Thin-layer chromatography. K. Randerath. (Trans-lated from the German.) Pp. 250. Verlag Chemie.Wein- heim.-1963. High pressure physics and chemistry. Edited by R. S. Bradley. Vol. 1. Pp. 444. Vol. 2. Pp. 361. Academic Press. London. 1963. Solubilities of inorganic and organic compounds. Edited by H. Stephen and T. Stephen. (Transfafedfrom the Russian edition.) Edited by V. V. Kafarovs and issued by the Academy of Sciences U.S.S.R. Vol. 1 Parts 1 and 2.) Pp. 1933. Pergamon Press. Oxford. 1963. Chemical compounds of the noble gases. C. L. Chernick. (Record of Chemical Progress 1963 24 (3).) U.S.A. 1963. (Presented by the publisher.) Inorganic polymers. D. N. Hunter. Pp. 110. Blackwell Scientific Publications. Oxford 19 6 3. Inorganic polymer chemistry. F. G. R. Gimblett. Pp. 452. Butterworths. London. 1963. Stabilization of polyvinyl chloride.F. Chevassus and R. de Broutelles. (TransZatedfrorn the 2nd French edition.) Pp. 385 Edward Arnold. London. 1963. Methoden der organischen chemie (Houben-Weyl). Edited by E. Miiller. Vol. 6 ii. Georg Thieme Verlag. Stuttgart. 1963. Techniques of organic chemistry. Edited by A. Weissberger. Vol. 11. Elucidation of structures by physical and chemical methods. Edited by K. W. Bentley. Part. 1. PP. 642. Part 2. P. 643-1181. Interscience. New -_._ ~ York. 1$63. Alicyclic chemistry. G. H. Whitham. Pp. 119. Old-bourne Press. London. 1963. Die Photochemie der organischen Farbstoffe. H. Meier. Pp. 471. Springer-Verlag. Berlin. 1963. Chemie und Technologie aliphatischer fluororganischer Verbindungen. D. Osteroth. (Sammlung chemischer und chemisch-technischer Beitrage no.59.) Pp. 195. Ferdinand Enke. Stuttgart. 1964. Principles of sugar technology. Edited by P. Honig. Vol. 3. Pp. 711. Elsevier. Amsterdam. 1963. Modem chemical processes a series of articles describing chemical manufacturing plants. Editors of Industrial and Engineering Chemistry. Vol. 6. Pp. 126. Reinhold. New York. 1961. (Presented by Dr. M. A. Phillips.) Enzymes. Edited by P. D. Boyer H. Lardy and K. Myrbiick. Vol. 8.2nd edn. Pp. 484. Academic Press. New York. 1963. Chemical constitution and biological activity. W. A. Sexton. 3rd edn. Pp. 517. Spon. London. 1963. Organic constituents of higher plants their chemistry and inter-relationships. T. Robinson. Pp. 306. Burgess Publishing Co.Minneapolis. 1963. Detection and determination of antioxidants in food (Association of Public Analysts Special Report no. 1.) Pp. 27. Association of Public Analysts. London. 1963. Biochemistry of industrial micro-organisms. Edited by C. Rainbow and A. H. Rose. Pp. 708. Academic Press. London. 1963. Dynamic aspects of biochemistry. E. Baldwin. Pp. 554. University Press. Cambridge. 1963. ~ Experimental immunochemistry. E. A. Kabat and M. M. Mayer. 2nd edn. Pp. 905. Charles C. Thomas. Springfield Illinois. 1961. Medicinal chemistry a series of reviews prepared under the auspices of the Division of Medicinal Chemistry of the American Chemical Society. Vol. 6. Edited by E. E. Campaigne and W. H. Hartung. Pp. 356. J. Wiley and Sons. New York.1963. Chemical effects of nuclear transformations proceed-ings of the Symposium on Chemical Effects of Nuclear Transformations sponsored by the International Atomic Energy Agency held in Prague 1960. Vol. 1. Pp. 569. Vol. 2. Pp. 390. International Atomic Energy Agency. Vienna. 1961. Polyamino acids polypeptides and proteins proceed-ings of an International Symposium held at the University of Wisconsin 1961. Edited by M. A. Stahmann. Pp. 394. University of Wisconsin Press. Madison. 1962. BNF Analytical Conference Malvern 1961 proceed-ings of a conference on analytical methods held at Malvern 1961. Pp. 120. British Non-Ferrous Metals R.A. London. 1962. Ultracentrifugal analysis in theory and experiment a conference sponsored by the National Academy of Sciences held at the Rockefeller Institute 1962.Edited by J. W. Williams. Pp. 282. Academic Press. New York. 1963. Peptides proceedings of the Fifth European Sym- posium Oxford 1962. Edited by G. T. Young. Pp. 269. Pergamon Press. Oxford. 1963. Status of quantum chemistry in the interpretation of organic chemical phenomena (Tetrahedron Contributed Symposia on Recent Developments in Organic Chem- istry no. 4.Convened by E. Heilbronner.) (Tetrahedron, 1963 19 Supplement 2.) Pp. 477. Pergamon Press. Oxford. 1963. Catalysts for the cyclic gasification of hydrocarbons. J. D. F. Marsh and J. H. Wylde. Presented at the 29th Autumn Research Meeting of the Institution of Gas Engineers 1963. (Gas Council Research Communication GC98.)Pp.18. Gas Council London. 1963. (Presented by the publisher.) Nickel and iron carbonyls in town gas. L. S. Cooper, A. B. Densham and M. W. Tanner. Presented at the 29th Autumn Research Meeting of the Institution of Gas Engineers 1963. (Gas Council Research Communication GC94.) Pp. 18. Gas Council. London. 1963. (Presented by the publisher.) Proceedings of the Symposium on the interaction be-tween fluids and particles held in London at the third Congress of the European Federation of Chemical Engineering 1962. Edited by P. A. Rottenburg and N. T. Shepherd. Pp. 351. Institution of Chemical Engineers. London. 1963. Cosmetic Science 1962 proceedings of the Second Congress of the International Federation of Societies of Cosmetic Chemists London 1962.Edited by A. W. Middleton. Pp. 270. Pergamon Press. Oxford. 1963. Aspects of protein structure proceedings of a sym- posium held at the International Symposium on Protein Structure and Crystallography held in Madras 1963 and organised by the Department of Physics University of Madras. Edited by G. N. Ramachandran. Pp. 380. Academic Press. London. 1963. Effluents from the carbonising industries an investiga- tion of the amount of additional percolating filter capacity required for the treatment of spent liquors in admixture with sewage. W. H. Blackburn and M. Kershaw. Presented at the 29th Autumn Research Meeting of the Institution of Gas Engineers 1963. (Gas Council Research Communication GC96.) Pp. 39. Gas Council.London. 1963. (Presented by the publishers.)
ISSN:0369-8718
DOI:10.1039/PS9640000001
出版商:RSC
年代:1964
数据来源: RSC
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