摘要:

PROCEEDINGS OF THE CHEMICAL SOCIETY JULY 1957 THE PLACE OF CHEMISTRY-I. AT OXFORD* By F. M. BREWER (INORGANIC LABORATORY, CHEMISTRY OXFORD) THEearliest elements in English education lay discourage English clerics from going abroad. with the Church. Literacy belonged largely to the Instead they turned their steps to Oxford and as clerics and to those who were privileged to learn Sir Charles Mallet vividly says “AS Becket lay from them. As the earliest recorded foundations dead on the altar steps at Canterbury the life of of Public Schools are those associated with the first English University began.” Canterbury Rochester and York so our oldest For just about one hundred years the clerks University grew out of the “Schools” in which and scholars accumulated rights privileges and the clerks of Oxford expounded theological doc- endowments.Their frequent conflicts with the trine and discussed the principles of ecclesiastical citizens usually resulted in the assertion of and civil law. The early part of the twelfth the authority of the Church which backed by the century offers the first authentic records of such Crown gave the University still further strength. teaching which had probably developed how- It was all the same no doubt as a measure of ever through the preceding three hundred years safety that the students who came to hear the in which the city had been growing in political Masters preach and dispute were usually housed importance and this is why perhaps tradition in Halls of Residence often maintained by one connects the origins of the University with Alfred or other of the monastic orders or in houses set the Great.During the same period there had up by the friars; and as will appear later it is to grown up abroad notably in Paris and Bologna the Franciscans in particular that science in the associations of scholars or “Masters” who had University owes its origins. The fluctuating organised themselves into Universities with fortunes of these Halls is in marked contrast to established rights and many English had gone the steady growth and permanence of the Col- to these places to study; but in 1167 or there- leges which began to replace or absorb them. abouts foreign students were expelled from Paris Wealthy members of the Church the nobility while Henry 11’s quarrel with Becket tended to and royalty provided endowment and accom- * This article and that on Cambridge (p.190>,are the first two of a series which it is planned to extend in later issues of Proceedings. 185 modation for groups of scholars and it is possible to trace in the history of these foundations how the College developed from a small body of teachers into a larger group which embraced both teachers (Fellows) and students (Scholars) finally blossoming into much more elaborate institutions crowned by Wolsey’s “Cathedral Church of Christ.” Thus in 1249 William of Durham endowed the “College of the Great Hall of the University” (University College) for ten or more Masters while in 1458 Magdalen tenth in order of date was founded for a President forty Fellows thirty Scholars (demi-Socii) a school-master an usher four chaplains a steward an organist eight clerks and sixteen choristers ! By this time there had grown up also the habit of attaching to the Colleges students “not on the foundation,” or commoners as they became known.At Magdalen for example twenty “sons of nobles and worthy persons” were allowed to stay in College at their own expense. All Souls built essentially as a war memorial to those who had fallen in Henry V’s French wars has re- mained the only college not admitting under- graduates in this way. The most interesting and significant development of all perhaps was the founding of Corpus Christi College in 1509 in which three Professors whose lectures were to be open to the “University at large,” were included for the first time in a collegiate foundation.Now the centre of the University had always been the Church of St. Mary and it was here and in adjacent buildings that the University ad- ministration was carried on; nor was it until many of the colleges had been established that any further University building was begun. In the Colleges however it was the Hall which was the essential centre of the communal life for the Hall was not only the refectory but also the Lecture Room and the habit of lecturing in College Halls persists to this day. Each College had also its library chapel and garden and later (the first at Merton in 1661) “common rooms” for social and informal discussion.The pattern of the College was therefore that of a group of teachers surrounded by those who wished to learn from them. When the learners proved themselves capable of joining in the dis- putations they “graduated” or stepped up to the level of teacher though not necessarily becoming PROCEEDINGS fellows. As the disputations were mainly theo- logical graduation was in fact to begin with a licence to preach granted by the University. The University still holds the right to grant such licences and has exercised it this year for the first time since the seventeenth century. The Chancel- lor of the University was the Bishop’s deputy and it was therefore more a matter for the University than the colleges to grant degrees while Wolsey’s aim to create a Cathedral and a see of Oxford separate from Lincoln to which it had hitherto belonged indicated fairly clearly the power and place of the Church within the University.Yet such was the strength the colleges acquired that they ultimately dominated the University and membership of a college or hall became a sine qua non of University admission. It might seem unlikely that in such a com- munity fostered in the bosom of the Church and endowed largely for the study of theology and law that there should ever be the opportunity for scientific study. Yet science at Oxford is older than its colleges for its study was first stimulated by Robert Grosseteste who after serving as the first rector of the Franciscan School established in 1244 became Chancellor of the University and Bishop of Lincoln but who was also described as the “first mathematician and physicist of his time.” His most famous disciple was the friar Roger Bacon whose scientific work was carried out largely in Oxford and to whom the discovery of gunpowder is attributed-a discovery which may well have stirred in the hearts of his con- temporaries similar emotions to those which the activities of Harwell and the Clarendon Labora- tory rouse in their successors today.Nor is it difficult to see how these scientific studies took their place in the University curriculum. The Arts of which the scholars became Masters were the Seven Liberal Arts whose study was aug- mented by that of the three Philosophies.For the former there was the Trivium (curiously giving rise to the idea of trivialities) Grammar, Rhetoric and Dialectic together with the Quad- rivium of Music Arithmetic Geometry and Astronomy; while the latter comprised meta- physical moral and natural philosophy. Science and mathematics were therefore strongly repre- sented even if based on Aristotelian lines. Beyond all this lay the postgraduate studies re- sulting in the Doctorates of Theology Law and JULY 1957 Medicine still the three senior Faculties in the University. On such a basis and with such a beginning science in Oxford might well have flourished abundantly. It has often been remarked that in the period in which the colleges were developing there was a decline in the standards of learning and that scientific studies in particular practically disap- peared.The Renaissance gave a great impetus to classical studies and literature flourished with the Elizabethans but civil wars and religious controversies had not been conducive to the con- templation of Nature and even on the continent where physics and astronomy had made some progress there had been little development in chemistry. A new era began with Robert Boyle and in so far as Boyle is generally regarded as the father of modern chemistry Oxford may be re- garded as its birthplace. Boyle was not a member of the University but he was a member of the Philosophical Society which had moved from London at the end of the Civil War to find peace in Oxford and encouragement from Dr.Wilkins Warden of Wadham in whose College the Society first met. It is also significant that just about this time some of the most important pro- fessorial Chairs were established such as the Savilian Chairs in Geometry and Astronomy and the Sedleian Chair of Natural Philosophy. Boyle brought Stahl to Oxford and shortly after Mayow through his medical interest in respira- tion developed the technique of confining gases over water and anticipated by a century the oxidation theory of combustion. Mayow was typical of the majority of Oxford chemists untiI the middle of the nineteenth century in being primarily a medical man and he was also as were many other doctors of medicine of those days a Fellow of All Souls a College which has now lost its interest in science and has become the preserve of lawyers historians and philosophers.With the foundation of the Royal Society and the transfer of scientific leadership to London Oxford’s contribution to chemistry became erratic and at times negligible but the establish- ment of two centres of activity in the Physick Garden by Magdalen Bridge (1622) and the Ashmolean Museum (1683) which housed the collections of Elias Ashmole and had a chemistry laboratory in its basement enabled a curious assortment of medicine chemistry botany and natural history to be studied in a somewhat amateurish manner. There was nevertheless a number of interesting personalities whose work kept the spark alive such as Robert Plot the first curator of the Ashmolean Museum and the first Professor of Chemistry in the University Thomas Beddoes and William Higgins who claimed priority over Dalton in the matter of the atomic theory.But it was the benefactions re- ceived by the University from such persons as Dr. John Radcliffe physician to Queen Anne Matthew Lee and Dr. George Aldrich which paved the way for an academic revival by the foundation in 1850 of the Final Honour School of Natural Science and the building of the Science Museum in 1851-55. The establishment of the Final Honour School brought the colleges backinto the picture for they had to provide tuition and practical work for their students.Lee’s bequest of a School of Anatomy to Christ Church provided the building which was to become the chemistry laboratory at that college while Daubeny who held the Aldrichian Chair persuaded Magdalen in 1848 to let him build at his own expense a laboratory in the Physick Garden. Balliol built a laboratory in some cellars and extended them in amalgama- tion with Trinity and Brodie who succeeded Daubeny as Professor worked there until the University Laboratory was ready in the new Museum. The Queen’s College built a small laboratory in 1900 and Jesus built a much larger one in 1908. There is probably nothing more characteristic of the curious College-University complex at Oxford than this parallel development of Univer- sity and College Laboratories and it is interest- ing to compare the growth of the one with the rise and ultimate decline of the other.In the first place neither had much advantage in the matter of buildings or equipment. For the University the building of the new Science Museum was a matter of great controversy but eventually the party led by Sir Henry Acland and Ruskin won the day and the Museum was built under Ruskin’s influence in a Rhenish Gothic style not unlike that of the Natural History Museum at South Kensington. His idea of a suitable model for a chemistry laboratory however was the Abbot’s Kitchen at Glastonbury Abbey a thirteenth century octagonal structure containing a single room with a roof towering some fifty feet above the ground.Subsequently a fairly large and for its time (1875) modern addition was made in which undergraduate instruction in both inorganic and organic chemistry was given but in which little was done in the way of original research. Brodie it is true had done useful work on ozone and graphitic acid but his successor Odling although an important figure in his time and one who did much by his influence to put chemical theory on a sound basis has left little to posterity beyond an inaccurate formula for bleaching powder. He held the Chair of Chem- istry until 1912 when he was succeeded by W. H. Perkin. Perkin’s first act was to persuade Mr. Dyson Perrins to give him enough to build a new laboratory which was opened in 1915 and sub- sequently twice extended.In 1919 the Dr. Lee’s Readership became the Dr. Lee’s Chair and the first holder was an Oxford chemist of great dis- tinction Frederick Soddy who shortly after- wards received the Nobel Prize. With the legacy of an old and so far as research was concerned unequipped laboratory Soddy turned his atten- tion to the building up of a properly housed and equipped University Laboratory of Physical and Inorganic Chemistry. Partly on account of his personal attitude and possibly also because of the vested interests in the College laboratories his aims were largely frustrated; but the policy which he advocated in 1922 contained the germ of nearly all the advancements in the Chemistry school since that time. Acting as his own architect engineer and builder he reconstructed at very small cost the interior of the “Old Chem- istry Department” as it was called and was prevented only by lack of funds from building an extension foreshadowing that which has just been completed.On the organic side however Perkin accepting the inconsistency which arises from laboratories controlled by professors and faculties in which college tutors have a say as great as if not greater than the professors them- selves developed a research department of great strength but one in which a relatively high pro- portion of the teaching staff was ultimately im- ported from other universities. This develop- ment was continued with even greater distinction under Sir Robert Robinson.By comparison with the earlier achievements of the University laboratory the record of the PROCEEDINGS College laboratories is crowded with distin-guished names both in teaching and research indicating an extremely substantial contribution to contemporary chemistry. Vernon Harcourt who had worked at Balliol with Brodie went to Christ Church as Dr. Lee’s Reader in 1887. His pupils included H. B. Dixon Chattaway Chapman Sidgwick and E. G. J. Hartley (best known for his work with the Earl of Berkeley on osmotic pressure). He was succeeded by H. B. Baker who had been a pupil of Dixon’s and like Dixon had worked in the Balliol and Trinity Laboratory. H. B. Hartley and Nagel built up in these laboratories a formidable team of physical chemists including Hinshelwood Bowen and Bell.From the Magdalen Laboratory before 19 14 came publications by Sidgwick Tizard T. S. Moore and Manley while Chattaway and Chapman worked at Queen’s and Jesus respec- tively. Yet by 1948 all the college laboratories had closed down. Two main factors contributed to this consum- mation. In 1919 had been introduced Part I1 of the Final Honour School which required candidates for a Class in chemistry to do a short research and submit a thesis. This coupled with the almost phenomenal growth of the post- graduate school after 1919 led to demands for space which the Colleges were ill-placed to pro- vide and to expenditure on equipment for which college endowments did not exist. Had it not been for the strength of the personalities associated with the college laboratories and the fact that the University found in the subvention of these laboratories to do University teaching a relatively cheap and convenient way of meeting some of its growing obligations they could never have lasted as long as they did.So the wheel has come full circle; for chemistry began at Oxford before the Colleges were founded and after a valiant century of college laboratory teaching and research the University has once again taken over the major responsibility for the provision of the subject. Even the greater part of the re-muneration of scientific Fellows of Colleges is provided by the University. It is perhaps also curious to reflect that chemistry was the only science where the colleges bore a major part in the provision of laboratories.In this situation one has probably the most illuminating example of the interaction of the JULY 1957 University and College system at Oxford. Its strength lies in the fact that nearly everyone con- cerned in it has two masters and manages on the whole to serve them both effectively in spite of the biblical edict. Perhaps the theologians of an earlier day would have said that this could not be had not the University and Colleges been one and that service of the one was equally service of the other. This may well be for there is no doubt that the influence which most of the teachers of chemistry exert upon University policy comes not from their positions as Uni- versity readers and demonstrators but from the fact that they are members of the governing bodies of Colleges and it is the Colleges that make up the University.Nor in this capacity does the chemist deal only with chemistry for a College is concerned with all subjects taught in the University and with all aspects of University life. More particularly it is as a College Tutor that a chemist is likely to influence his students for he is in a strong and intimate personal rela- tionship with them. With increasing numbers the family spirit which existed in the whole chem- istry School at one time and was particularly strong in the college laboratories is proving hard to maintain but it is from the college tutorial system that the undergraduate usually derives the benefit of a personal contact with an eminent teacher often denied to others until the post- graduate stage is reached.The University could exist as it did in its earliest days without the undergraduate but no one would deny today that the impact of the University on the outside world is made largely by those who go out from it rather than by those who remain within its walls. The last reflection should therefore be on what the chemistry school means to the Oxford undergraduate what part he plays in the life of the University and what he does when he leaves the fold. It is not sur- prising that a School which numbers three Nobel Laureates among its more recent Professors should attract undergraduates from all over the country and research students from all over the world.It is in fact by far the largest individual school of chemistry in the country. Next October nearly 190 freshmen will begin the course for the Final Honour School and about 550 students will be on their way to a place in the chemistry class list. In the main they will be studying ostensibly nothing but chemistry. Together with post-graduate workers they will constitute about one-tenth of the whole University. Well might they become “subject-conscious,” thinking that chemistry was the important thing in their lives and not their relations with the world around them. It is the college which takes care of that danger. The laboratories let it be admitted are not very full in the afternoons when the youth of Oxford and a good many seniors too seek recreation.University teams and university clubs are not lacking in chemical members and the wise college tutor will hope to see his pupils taking their full share in college activities or winning the occasional blue. To win a cricket Blue and a soccer Blue to play for Sussex and for the Corinthians and unofficially to top the Chemistry list has been done by one man and may be done again. This it may be argued is because the Oxford chemist studies chemistry and nothing else on a syllabus so vague that it merely requires him to “show a knowledge of inorganic organic and physical chemistry.” This has resulted however in the production of a number of chemists who have filled chairs and many other posts in chemistry in other univer- sities as well as a host of directorships and managerial positions on the chemical side in in- dustry.But one of the more fascinating aspects of the School is in the fields outside chemistry where Oxford chemists have succeeded. On the academic side they have filled recently for instance one chair in Physics one in Metal Physics two in Chemical Engineering and two in Education. In industry they have shown them- selves competent not only in chemistry but in business administration salesmanship finance and in a host of other ways while the fact that a Canon of Rochester and the Venerable the Archdeacon of Sheffield the Headmasters of the two largest Public Schools in the country the Editor of “Endeavour,” the Chief Scientific Adviser to the Ministry of Agriculture Fisheries and Food His Excellency Her Majesty’s Ambas- sador to Denmark and two High Court Judges all read the Chemistry School when they were up at Oxford may go to show that the Oxford chemist still views the world with that same liberality of outlook with which Robert Grosseteste first inspired his students over 700 years ago.PROCEEDINGS THE PLACE OF CHEMISTRY-11. AT CAMBRIDGE By F. G. MANN (UNIVERSITY CHEMICAL LABORATORIES CAMBRIDGE) THE teaching of chemistry in Cambridge originated as an entirely private venture by J. H. Vigani a native of Verona who came to England in 1682 and in the following year settled in Cambridge as a private tutor in chemistry and pharmacy.He acquired so high a reputation as a teacher that the University in 1702 invested him with the title of Professor of Chemistry and thus inaugurated what is now the oldest Chair of Chemistry in Great Britain to have been con- tinuously occupied until the present day. The University however provided Vigani with neither stipend nor teaching facilities although Bentley the famous Master of Trinity seized the opportunity in his long and bitter feud with the Fellows of the College to build Vigani a labora- tory on the Fellows’ Bowling Green. This laboratory apparently fell into disuse after Vigani’s death. The first marked change in the treatment of chemistry followed the election in 1764of Richard Watson to the Chair of Chemistry.This remark- able man to whom justice cannot be done in this brief article had received solely the normal education in classics and mathematics. In his autobiography he says of this election “At the time this honour was conferred on me I knew nothing at all of chemistry had never read a syllable on the subject; nor seen a single experi- ment in it; but I was tired of mathematics and natural philosophy . . . I sent immediately . . . for an operator to Paris I buried myself as it were in my laboratory. . . and in fourteen months from my election I read a course of chemical lectures to a very full audience consisting of persons of all ages and degrees in the Univer- sity.” The University although granting no stipend to Watson did provide him with one room for teaching the laboratory to which he refers was presumably the one constructed in the garden of his private house where his charcoal furnace for analytical work remained up to the early years of this century.After much trouble he induced the Government to provide him with a stipend of El00 per annum (granted by the Prime Minister on the eve of the Government’s dissolution!). He wrote later “The ice being thus broken by me similar sti- pends have since been procured from the Crown for the Professors of Anatomy and Botany and for the recently established Professor of Com- mon Law. The University is now much richer than it was in 1766 and it would become its dignity I think to thank the King for his in- dulgence and to pay in future its unendowed professors without having resource to the public purse not that I feel the least reluctance to dipping into the public purse for such a purpose but I feel something for the independence of the University.” Watson’s vigorous chemical activities other than as a writer ceased in 1771 when he was elected to the Regius Professorship of Divinity “to take possession of the first professional chair in Europe .. . had long been the secret object of my ambition.” The Chair of Chemistry then received several undistinguished occupants- with the exception of the brilliant Smithson Tennant who was killed in an accident two years after election-until G.D. Liveing of St. John’s College became Professor in 1861. The University now took a step forward and provided Liveing with two rooms for teaching. He agitated vigorously for the construction of a University laboratory this was conceded in principle but it was proposed that the new laboratory should be “a building which was capable of standing violent explosions and as un- inflammable as possible containing a series of vaults.’’ This proposal which would have put the Cambridge teaching of chemistry largely into cellars as at Oxford was rejected by Liveing and a well-designed and equipped laboratory was ultimately provided by the University in 1887. It must be borne in mind that up to the middle of last century (or later !) the University teaching officers were largely limited to the professors who were few in number and often grossly neg- lected their duties and that by far the greater JULY1957 portion of the teaching was performed by College Fellows who gave instruction which sometimes was limited to the students of a Fellow’s own College but often was open to students of various Colleges.Consequently it is not surprising that the miserable facilities which the University pro- vided for the teaching of chemistry should have induced some of the more active Colleges to pro- vide their own facilities for teaching both theoretical and practical chemistry. In this respect pride of place goes to St. John’s College which in 1853 built its own laboratory consisting of two rooms with benches two smaller private rooms and a “ preparation room” at a cost of E511 and appointed Liveing “Lec-turer in Natural Science and Superintendent of the Laboratory.” This position was clearly a source of great strength to Liveing for when after his subsequent election to the Chair of Chemistry the University initially denied him a suitable laboratory he was able to fall back on his own College laboratory for the teaching facilities he required.Consequently he was able to bide his time until University opinion slowly veered round and the present laboratory in Pembroke Street was constructed. Without this College help he might have felt obliged to accept the “series of vaults,” from which the teaching of chemistry might subsequently have found escape both slow and difficult.Gonville and Caius College opened a College laboratory in 1873 and Pattison Muir was Praelector in charge from 1877 until he retired in 1908 and the laboratory closed. It provided a haven for Ruhemann after his quarrel with Dewar mentioned below. Sidney Sussex College built a laboratory in the late 1870’s Scott-Giles states that “A ground-floor room in Chapel Court was fitted up for practical studies in chem- istry and later a row of sheds (facetiously known as ‘the shooting gallery’) was built against the Sidney Street wall . . . to serve as a laboratory for both physics and chemistry.” It was in this laboratory that C. T. Heycock and F. H. Neville carried out their famous metallurgical work and E.H. Griffiths who was closely associated with this work developed the platinum resistance thermometer. This laboratory closed in 1908 when Neville retired and after lying derelict for a few years the wooden laboratory was torn down by undergraduates to provide extra fuel for a Bump Supper bonfire an act which did not arouse any acute disapproval among the College authorities although Heycock complained that many valuable experimental records were lost. The Girton College laboratory was opened in 1877 and remained open until Miss M. B. Thomas retired in 1935. The Newnham College laboratory was opened two years later and in 1887 Miss Ida Freund was appointed Demon- strator in charge of the laboratory an office which she held until the closing of the laboratory in 19 12.Downing College laboratory was opened in the 1890’s and closed in 1920 for several years Heycock ran private courses there and Mr. A. J. Berry was officially in charge in its later years. It is clear that as the scope (and consequently the expense) of practical chemistry steadily in- creased the maintenance of College laboratories became increasingly uneconomical moreover as the University laboratory became well estab- lished and University (as distinct from College) teaching became steadily better organised and more efficient the original purpose of these Col- lege laboratories slowly faded. In these circum- stances these laboratories often remained in use only until the retirement of a well-known and respected College teacher.Nevertheless there must be very many former students who still remember their undergraduate teaching in these laboratories. Dr. W. G. Palmer informs me that he received all his tuition in practical organic chemistry for Part I of the Natural Sciences Tripos in the St. John’s laboratory in 1911-13 when members of the College were allowed to choose attendance at the College or the Univer- sity laboratory for this purpose and Dr. Helen D. Megaw says that the students of Girton Col- lege in 1926-28 had almost all their practical organic and inorganic chemical instruction in the College laboratory and attended the University laboratory only for practical physical chemistry.When Liveing was elected to the Chair of Chemistry his duties entailed teaching “the pro- perties of substances ponderable and imponder- able” i.e. heat light and electricity in addition to chemistry and to lighten this load he urged successfully that Dewar should be elected to the Jacksonian Professorship of Natural Experi-mental Philosophy in 1875. The University Laboratory now had two professors neither of whom was primarily interested in organic chem- istry. Dewar therefore appointed Ruhemann (a former pupil of Hofmann) as a Demonstrator and also as his semi-private assistant. Ruhemann was a very active organic research chemist. Un- fortunately a violent quarrel ultimately ensued between Dewar and Ruhemann Dewar dis-missed Ruhemann from his office as Demon- strator but Ruhemann was re-instated after his appeal to the University.He then left the Univer- sity laboratory for the more congenial atmos- phere of the Caius laboratory-a striking example of the value of an independent labora- tory. When Pope succeeded Liveing in 1908 Dewar had already virtually left Cambridge for London (whilst retaining his Jacksonian Professorship) and paid only rare visits to his old University. Ruhemann returned to the University labora- tory and Heycock received his first University appointment so that with Fenton teaching general inorganic and physical chemistry and Mills returning shortly afterwards to Cambridge a period of steadily expanding activity set in. A particularly notable branch of this activity was the stereochemical research of Pope and Mills.The Pembroke Street laboratory had been extended at the time of Pope’s appointment and in 1919-20 was again considerably enlarged with the aid of a gift of E210,OOO from the British Oil Companies. A Chair of Physical Chemistry was created to which T. M. Lowry was elected. The historical sequence of two steps by which the University gave recognition by the award of Degrees to approved courses of teaching and research respectively should be noted. The Natural Sciences Tripos was inaugurated in 185 1 but not until 1861 when it had become well established did the University award the Degree of B.A. to successful candidates. In 1921 the Degrees of M.Sc.and Ph.D. were introduced (after much vigorous discussion) for approved research of two or three years’ duration respec- tively before this date the Degree of B.A. could be awarded for an investigation of more modest volume and quality but it attracted compara- tively few applicants for it was of value only to research workers coming from other Universities. The more recent and general conditions for the teaching of chemistry as they affect both students and staff must be outlined particularly PROCEEDINGS as the curriculum for students intending later to specialise in chemistry differs markedly from that at Oxford. A Cambridge student who intended to become a professional chemist would normally take Part I and then Part I1 of the Natural Sciences Tripos at the end of his second and third year respectively.For the Part I examination he would have to offer a minimum of three subjects. This arrangement was found to have an unfortu- nate result in that too many students read chem- istry physics and mathematics and thus had no occasion to widen their mental horizon beyond the subjects which they had studied at school. Consequently mathematics was made a “half-subject” and students therefore had to take one other subject which necessarily was almost al- ways a new subject for them. The prospective chemistry specialists were therefore not free to devote their whole time to chemistry until their third year which consisted only of 24 terms for the Part I1 examinations started in late May.The merits and demerits of this system have been discussed in innumerable committees and in many reports. Many Cambridge men considered that the Part I course gave students a much wider scientific education than that provided in many other Universities and in particular gave many students their first introduction to a biological subject furthermore it gave students two years during which they had time to evaluate their scientific interests and to make a final decision regarding the subject on which they intended ultimately to specialise. One great disadvantage however was that a course of 25 terms’ instruc- tion for the Part I1 examination became in-creasingly inadequate for modern requirements. On the staff side a marked change followed the recommendations of the Royal Commission on Oxford and Cambridge Universities in 1926.To prevent recurrence of certain past abuses the Commission recommended the organisation of University teaching into various Faculties each controlled by a Faculty Board the membership of which was in the main elective. The Board recommended elections to lectureships and demonstratorships and these appointments in- volved solely teaching for a given number of hours per annum. A teaching officer in each grade was thus assured a measure of independ-ence and also a very reasonable amount of time for his own reading and research. JULY 1957 Very many teaching officers were also either Fellows of Colleges or held other College appointments and consequently directed studies and also gave weekly “supervisions” i.e.tuition classes in College whereby a much closer contact with students could be maintained. The teaching of chemistry in general and organic chemistry in particular received a great stimulus with the appointment of A. R. Todd (now Sir Alexander Todd) as Pope’s successor in 1944. It is primarily to his vision and his vigorous influence that we owe the magnificent new laboratories which are still under construction in Lensfield Road although the block for organic and inorganic research and third-year teaching has been in use since July 1956. The method and conditions of teaching chemistry in Cambridge are necessarily changing in order to maintain and increase their value in a changing world.With regard to the more de- tailed conditions the coming academic year will see the inauguration of an alternative Tripos course whereby men intending to take the Part I1 Tripos in chemistry may start some of their more advanced work in their second year with some compensating reduction in the amount of other work at present required during the first two years. This really represents one facet of a much larger and more significant-and apparently inevitable -change namely that whereas earlier in the century a student could read chemistry as part of a broad and liberal education he must now read chemistry primarily as a vocational training. This involves very much harder and more intensive work with the constricting intellectual influence that such specialisation must cause.I am greatly indebted to several of my colleagues for information particularly concerning the College laboratories. PRESIDENTIAL ADDRESS Some Aspects of the Chemistry of the Fructosans By E. L. HIRST* DURING the past decade structural investigations of naturally occurring high polymers have had a com-mon characteristic which is of special interest to all concerned with the chemistry of natural products. This is the emergence of recognisable patterns of molecular structure in which the chief features re- main constant although considerable variation in detail is encountered. The work of Sir Alexander Todd and his collaborators has demonstrated this very clearly for the nucleic acids.l A general pattern for the structure of the naturally occurring lignins is now becoming discernible based on Freudenberg’s demonstration of the formation of various poly- merisable units derived from free radicals which in turn have their origin in coniferyl alcoh01.~ In the carbohydrate group reference may be made to the pattern of molecular structure which is now known to be a characteristic of the xylan group of the hemi- celluloses.In this case there is a backbone of 1 :4’-linked xylopyranose residues to which are attached always in such a way that the same general structural pattern is maintaix~ed.~ Recent work on the molecular structure of poly- saccharides based on fructose has revealed that here again there are recognisable patterns underlying the detailed molecular architecture.Furthermore the importance of fructose derivatives in agriculture biology and chemistry has received increasing recog- nition during the past few years and it seems appropriate to review briefly the position which has now been reached. Fructose plays a prominent part in the chemical changes which accompany the life of plants. Together with glucose into which it is readily convertible by enzyme action it appears as one of the early products of photosynthesis. As shown by the work of Calvin and his collaborators one of the first products which can be recognised after the interaction of carbon dioxide and ribulose diphosphate is phosphoglyceric units of L-arabofuranose 4-O-methyl-~-glucuronic acid from which triose phosphates and then fructose acid and other sugars in varying proportions but diphosphate are derivable by known routes.A * Delivered at the 11 6th Anniversary Meeting of the Chemical Society at the University of Cambridge on April 11th, 1957. Todd Proc. Roy. Soc. 1954 A,226 70; “Nucleic Acids” (p. 245) in “Perspectives in Organic Chemistry” Inter- science Publ. New York 1956. Freudenberg Angew. Chem. 1956 68 84. Hirst J. 1955 2974. schematic summary of the changes involved and an indication of the pathway for the reversible intercon- version of glucose and fructose will be found in Scheme 1. CO + Ribulose diphosphate & (Photosynthesis) Phosphoglyceric acid J.? Triose phosphates J.? Fructose 1 :6-diphosphate .1T Fructose 6-phosphate -+Fructose J.? Glucose -+Glucose 6-phosphate -+ Glucose +ATP I= $1‘ Glucose 1-phosphate Scheme 1 When combined with glucose fructose gives rise to the disaccharide sucrose which provides a tempor- ary storage material.This is readily transported within the plant4 and serves as the starting material for enzymic syntheses of many products important in plant metabolism. In addition it is known that many monocotyledons and some dicotyledons lay down energy reserves in the form of oligosaccharides and polysaccharides based on fructose residues. These substances which are of special importance to the farmer in view of their occurrence in grasses will form the main subject of the present review.Fructose does occur in the free condition in the cytoplasm of plant cells but normally it is present only in small concentrations. In this state it has the pyranose ring structure (I) and is relatively inactive. This inertness applies also to other sugars which are H found in the free state in the cytoplasm including glucose and galactose and there is evidence that the plant can mobilise much more readily the combined sugars and will utilise these in preference to free sugars. Such a state of affairs is indeed readily under- standable if it is accepted that many of the enzymical- ly controlled changes in the plant are transfer reactions brought about by organic catalysts of the transglycosylase type.On the other hand when fructose residues occur in the combined state in natural products they are always found to possess the labile furanose ring PROCEEDINGS structure (11) and much of the difficulty which has been encountered in the investigation of fructose derivatives can be traced to the special reactivity of the fructofuranose residues. For instance in the HOH& 2:3:4:6-Tetra-O-methyl-HOQ Ho 0 glucose 1 Sucrose Me0 ‘ l:3.4:6 -Tetra -Ornet hyl-fructose Scheme 2 early work on the structure of sucrose when the methylation method of investigation was employed the tetra-0-methylfructose (see Scheme 2) obtained on hydrolysis of the methylated derivative of sucrose provided many troublesome problems before its structure was elucidated and even today the identifi- cation of this important reference compound is none too easy a task.If proof of the structure of sucrose by degradative methods was by no means readily obtained its synthesis was found to be very much more difficult and despite all the effort expended during many years no success was reported. Then only a few years ago the first synthesis of sucrose in the laboratory was achieved by Hassid with the aid of enzymic catalysts. Starting with glucose 1-phosphate and free fructose HO ’ Scheme 3. Enzymic synthesis of sucrose Hassid and his collaborators5 found that in the presence of a phosphorylase enzyme from Pseudo-munas saccharophila interaction took place between these two substances with the formation of sucrose (see Scheme 3).The reaction can be regarded as induced by a typical “transferase” enzyme which is Parkin Trans. Roy. SOC.,1899 B 191 35. ti Hassid Doudoroff and Barker J. Amer. Chem. SOC.,1944 66 1416. JULY 1957 not highly specific towards the glucosyl acceptor molecule since the same enzyme system can be used with other ketoses to make a series of disaccharides having analogous structures. It seems probable from the work of Calvin and Leloir that in the reactions which follow the photo- OH CH2-OH H -P-0 OH 6 U.D.C P Hb t)H U.D.P. 195 took place with opening of the anhydro-ring giving an a-glucoside. The product was a hepta-acetyl deri- vative of sucrose from which the well-known octa- acetate and then sucrose itself were readily obtainable (Scheme 5).In the course of structural studies of natural OH ' Fructose 6-Phosphate Sucrose Phosphate Scheme 4. Enzymic synthesis of sucrose phosphate (Leloir) synthetic reactions in plants fructose and glucose residues are combined to give sucrose by an entirely different enzymic mechanism. In the course of these reactions (see Scheme 4) glucose appears as uridine diphosphate glucose. Interaction with a fructose phosphate occurs in the presence of the appropriate enzyme system and the two products are uridine di- phosphate (U.D.P.)and sucrose phosphate. Further Leloir has shown that with the aid of these enzymes uridine diphosphate glucose (U.D.P.G.) can react products containing fructose residues the principal substances which are encountered as hydrolysis pro- ducts of the methylated polysaccharides are 1 :3 :4 :6-tetra-0-methyl-D -fructose 3 :4 :6-tri-0-methyl-D -fructose 1 :3 :4-tri-O-methyl-~-fructose and 3 :4-di-0-methy1-D-fructose.Modem methods of paper-strip chromatography have greatly facilitated the separation of mixtures of these and it is possible also to separate from such mixtures 2:3:4:6-tetra-O-methyl-D-glucose and some of the trimethylglucoses. Ac 0.H-C AcOH-C Aco*H2v CHiOAc CH2-OAc Aco-H2co AcO AcO Scheme 5. Synthesis of sucrose with free fructose giving sucrose directly-a remark-able transformation which involves a change from the pyranose to the furanose ring structure in the fructose moiety .The first synthesis of sucrose by purely chemical methods was reported by Lemieux and Huber' as recently as 1953. The materials used were 1:3:4:6-tetra-0-acetylfructose and the 1:2 anhydro-derivative of 3 :4 :6-tri-0-acetylglucose. When these substances were heated together for some hours combination Final proof of identity of the fructose derivatives still depends upon their transformation into crystalline reference compounds. In the case of the 1 :3 :4 :6-tetramethyl derivative the most readily available substance is the amide obtained by the route indi- cated in Scheme 6. Alternatively the crystalline tri- 0-methyl-D-arabonolactone can be utilised as a reference compound and these same two compounds serve for the identification of 3 :4:6-tri-O-methyL~-fructose.The 1:3 :4-trimethyl derivative of fructose is For a summary see Calvin J. 1956 1895; Buchanan Arch. Biochem. Biophys. 1953 44 140; Leloir and Cardini J. Amer. Chem. Soc. 1953 75 6084; J. Biol. Chem. 1955 214 157; Cardini Leloir and Chiriboga ibid.,p. 149. Lemieux and Huber J. Arner. Chem. SOC.,1953 75,4118. CH,-OH HO-6-1 MeO-H-C%OMe \ 50,Me \ c-7 H-F-OMe H-5 CH2*OMe CHiOMe Scheme 6. 1 :3 :4 :6-and 3 :4 :6-Methylated fructoses crystalline and is therefore readily identified. Proof of the structure of this sugar and also of the 3 :4-di-O-methyl derivative can be obtained by their trans- formation into the crystalline diamide depicted in Scheme 7.Complications are apt to occur in the case of materials which give rise to 3 :4:6-tri-O-methyb~-fructose when they are examined by the methylation method. These polysaccharides possess fructo-furanose residues linked in the 2 1‘-positions and it has been found that in these circumstances the forma- tion of a difructose anhydride can proceed with great ease. The one most commonly encountered has the 1:2’-1’ 2-structure (111) and the hexamethyl deriva- CH,-Scheme 7. 1:3 :4-and 3 :4-Methylated fructoses tive of this may be formed during the hydrolysis of all methylated fructosans in which there are chain linkages of the 2:l’-type. This poses some awkward problems in the end-group assay of these fructosans Bell and Palmer J. 1952 3763.@Boggsand Smith J. Amer. Chern. SOC.,1956 78 1878. PROCEEDINGS by the methylation procedure but modified methods of analysis which overcome the difficulty have been worked out by Bell8 and his collaborators. The tendency towards anhydride formation is clearly related to the geometrical arrangement in space of the reacting groups in 1’ :2-linked fructosans and a chain-reaction mechanism has been put forward by Boggs and F. Smithg in explanation. The reaction is acid-catalysed and appears to depend for its initiation on rupture of one of the 1‘ 2-fructosyl links with formation of a carbonium ion. In the subsequent course of reaction the neighbouring fructose residue is concerned and one mol. of difructose anhydride and a new carbonium ion are formed.From the latter the chain reaction can continue with successive liberations of units of difructose anhydride. The methylation method of investigation is still indispensable in the fructosan group since by its aid the nature of all the various residues present in the polysaccharide can be ascertained and quantitative assays of their proportions can be made on quite small amounts of materials. As with other groups of polysaccharides other techniques including oxida- tion by the periodate ion partial hydrolysis under carefully controlled conditions and enzymic studies are now playing an increasingly useful part in struc- tural investigation and it is worthy of note that the method of partial hydrolysis has been astonishingly successful in dealing with these highly labile mole- cules.One difficulty which has not yet been fully resolved is the estimation of molecular weights of these substances where the majority of them appear to be in the region 2,000-10,000 which is small for ultracentrifuge viscosimetric and osmometric studies but too high for the ordinary laboratory methods. Some determinations have nevertheless been made and it seems possible that much assistance may soon be gained by the application of modern methods of ebulliometry. One of the most interesting of the polysaccharides based on fructose is inulin the reserve carbohydrate which is stored in the tubers of the dahlia. A similar polysaccharide occurs in other members of the Com- positae family notably in the Jerusalem artichoke JULY1957 and in species of Inula but full chemical proof of structural identity is not as yet available.Inulin itself has a molecular weight of about 5,000. On hydrolysis it gives fructose together with a small amount of glucose. There has been much controversy over the significance of the glucose which persists despite the most rigorous fractionation of the polysaccharide and cannot be removed by acetylation followed by fractionation of the acetate or by fractionation of the methylated derivative of inulin.*.l* Further there is evidence that partial hydrolysis of inulin by dilute acid gives rise to sucrose as one of the products.ll Since moreover the reducing power of inulin is far too small for a substance of molecular weight 5,000 with a terminal residue having a free reducing group it seems very probable that the glucose is an integral part of the molecule united through its reducing group to the reducing group of the first fructose residue in the chain.The alternative view that the glucose is present in a contaminating polysaccharide built up of glucose residues is much less attractive and fails to account for the non-reducing nature of inulin. Methylatedinulin gives 3 :4 :6-tri-0-methylfructose (91 %) on hydrolysis together with 1 :3 :4:6-tetra-0-methylfructose (3.2%) and 2:3 :4 :6-tetra-0-methyl-glucose (2-2%). Some tri-0-methylglucose is also present but no dimethylhexose. It follows that the chain of 2:1'-linked fructose residues is not branched and the most probable structure for inulin based on this evidence is that depicted in (IV) which shows a W%OH OH straight chain of about 33 2 1'-linked /3-fructo- furanose residues terminated by a sucrose residue.One remaining difficulty for which no complete explanation has yet been put forward is found in the trimethylglucose isolated from the hydrolysis pro- ducts of methylated inulin. There is too much of it to be accounted for by demethylation of tetramethyl- glucose during hydrolysis. On the other hand there is direct evidence that the particular trimethylglucose namely the 2:4 6-derivative which forms the bulk of this fraction has no structural significance so far as inulin is concerned. This follows from a study of the oxidation of inulin by periodate.12 After hydro- lysis of the oxidised polysaccharide no glucose is detectable and it follows that none of the glucose residues in inulin can be linked through the 3-posi- tion.Apossible explanation is that the 2:4 6-tri-0-methylglucose which at first sight would seem to indicate a linkage at position 3 arises through in- complete methylation and in this connection it may be recalled that the glucose residue in sucrose offers peculiar resistance to methylation-an observation which proved to be of great service in the early work on the structure of sucrose. It is of course a possi- bility which cannot be ruled out altogether at this stage that complete separation of inulin from con- taminating glucosans13 may not have been effected for all the samples examined but there seems little reason to doubt the occurrence of sucrose end- groups in at least the majority of the inulin molecules and as will appear below much collateral evidence in favour of this view is gained from the work of Bacon and Edelman and of Dedonder on the en- zymic synthesis and degradation of the related poly- saccharides found in the Jerusalem artichoke.Another structural type of fructosan is found in the leaves and stems of many monocotyledonous plants particularly amongst members of the Gramineae and similar structural features are present in the fructosans synthesised by many bac- teria for example Bacillus subtilis B. mesentericus and Pseudomonas prunicola.In all these polysac- charides the main linkage between the /3-fructo- furanoseresidues is 2:6' in contrast to the 2 1'-links characteristic of the inulin type of fructosan. These bacterial levans were first studied in detail from the chemical point of view by Hibbert and his col- laborator~,~~ who obtained on hydrolysis of the methylated derivative of the levan from B. subtilis 1:3 :4-tri-O-methyl-~-fructosein almost 99 % yield. The molecular weight of this levan is large and the structure therefore appears to involve a long un- branched chain of 2 :6'-linked /?-fructofuranose residues (see V) containing many hundreds of units. From the results of this early work little can be said about the nature of the end-groups but evidence Hirst McGilvray and Percival J.1950 1297. l1 Dedonder Compt. rend. 1950 230 549; Feingold and Avigad Biochim. Biophys. Acta 1956 22 196. l2 Aspinall and Telfer Chem. and Znd. 1953 490. l3Cf. Schlubach and Lubbers Annalen 1956 598 225. l4 See Evans and Hibbert Adv. Carbohydrate Chem. 1946 2 204. has been obtained from another sample of B. subtilis levan to the effect that it contains 1 part of glucose in 500 an amount almost at the limit of accurate measurement but nevertheless in accord with the general picture of a chain of fructose residues terminating in a sucrose residue. PROCEEDINGS action of the enzyme on sucrose.16 Similar results have been recorded by Hestrin and his col-laborator~~’ during investigations on the donor- acceptor specificity of a levan sucrase from Aero-bacter levanicum.As the molecular weight increases the detection of a glucose end-group becomes less Bacterial levans (V) Residues present 6F2 * * * ,F2 A very different problem is presented by the levans from B. mesentericus Pseudomonas prunicola and certain other strains of B. s~bti1is.l~ Here again the main linkage along the chain is 2 :6’ but the methyl- ated derivatives now give on hydrolysis approxi- mately 1 part of tetra-0-methylfructose 8 parts of 1:3 :4-tri-O-methyl-~-fructose,and 1 part of 3 :4-di-0-methyl-D-fructose. The molecular weights are known to be high and the molecule must therefore be highly branched with structural features of the type indicated in (VI).The branch points involve the FFFFFFFFFG F F F FFFFFFFFFF F F F F Main chain links -*6F2-* ;branch links -* -6F2. -...1 Bacterial levan (VI) primary alcoholic groups at position 1 of the appropriate fructose residues and it is of interest that all fructosans which have been examined up to the present possess either 2 1’- or 2 6’-linkages or both. In these macromolecular substances the presence of glucose as a terminal group is hardly discernible but there is strong evidence from the work of Dedonder that these levans are indeed built up by stepwise additions of fructosyl residues the initial starting material being a molecule of sucrose. By means of a levan sucrase from the strain of B. subtilis used by Bell and Dedonder he obtained an ascending series of glucose-terminated oligosaccharides during studies of the enzymic synthesis of levans by the certain and although this may well be due largely to analytical difficulties arising from lack of means to determine glucose accurately when it occurs only to the extent of 1 part in 1,OOO of fructose it is still just possible that in some levans the glucose may be lost during the synthesis or that synthesis may even originate not from sucrose but from a purely fructose derivative such as a difructose anhydride.In the grasses the levans which are found as short- term storage products in the leaves and stems have much smaller molecular weights and normally con- tain between 3 and 30 hexose residues per molecule.The levan from leafy cocksfoot grass (Dactylis glomerata) may be cited as typical. After extraction from the plant and fractionation by precipitation from aqueous alcoholic solution it gives on hydrolysis fructose (97 %) and glucose (3 %). The glucose can- not be removed by further fractionation and appears to be part of the molecular structure. The methylated derivative gives on hydrolysis 1 :3 :4-tri-O-methyl-~-fructose together with tetra-0-methylglucose (2 %) and tetra-0-methylfructose (4 %) (see Table 1). The TABLE 1. Hydrolysis of methylated fructosan from Dactylis glomerata Product Yield (%) 1:3 :4-Tri-0-methylfructose 93 1:3 :4 :6-Tetra-0-methylfructose 4 2 3 :4 4-Tetra-0-methylglucose 2 Residue present in fructosan * -6F2.F2** * Dime thylhexoses Trace only absence of dimethylhexoses shows that the molecule is unbranched and although the proportion of tetra- 0-methylglucose which was separated from the hydrolysis products is somewhat lower than that of tetra-0-methylfructose the analytical results are most readily interpreted in respect of the great majority of the molecules at any rate in the structure l6 Bell and Dedonder J. 1954 2866 where references to earlier work are given. l6 Dedonder and Noblesse Ann. Inst. Pasteur 1953 85 356. l7 Hestrin et al. Biochem. J. 1956 64 340 351. JULY1957 199 for the levan shown in (VII) which depicts an un- and his collaborators in Hamburg who have given branched chain of 2 :6’4inked p-fructofuranose residues terminated at one end by a fructose residue and at the other by a sucrose residue.18 An exactly similar picture can be given for the levan from perennial ryegrass (Lolium perenne).In H O-H2C@- -1-CHiOH CHiOH much attention to these problems have reported the isolation from L. perenne of a levan which after elaborate fractionation was found to contain no glucose. These investigatorsz0 envisage the possibility of ring-type molecules in some levans and they prefer H2C@-0-<y CHiOH OH OH 25-30 OH OH F2-6F2-+-. ,m-IG SUCrOS? residue (VII) Fructosans from Lolium perenne and Dactylis glomerat both instances the levans are essentially non-reducing and their chemical properties including oxidation by periodate ion are consistent with the presence of a non-reducing glucose residue in the molecule.A direct chemical proof of this has been obtained in the case of the levan from L. perenne.lg It has been observed that these levans undergo degradation when heated at 100”in aqueous solution giving rise to a series of smaller oligosaccharides. Amongst these there are found a trisaccharide which yields on further hydrolysis two parts of fructose and one of glucose and a non-reducing disaccharide which was shown to be sucrose. The trisaccharide on further hydrolysis catalyzed by the resin Amberlite IR-100 gave sucrose and fructose. There can be no doubt therefore that levan molecules containing to regard the longer-chain grass levans as being built up by stepwise addition of fructosyl residues to fructose or a fructose anhydride as starter molecules.On the other hand they agree with the British workers in accepting the hypothesis that the levans of shorter chain length found in various grasses con- tain glucose residues and are based on sucrose as a starter. In general the observed molecular weights of fructosans from grasses indicate a molecule corres- ponding in size to one unit chain as determined by end-group assay. In Table 2 details are recorded for five typical fructosans the chain length being given as the number of hexose residues present in the molecule for each terminal fructose residue. The proportion of glucose in these materials is roughly TABLE 2. Fructosans from grasses Source Linkage Chain Mol.wt. Glucose Dactylis glomerata18 D. glomeratd Lolium perenn8I L. perenng2 L. italicurns length (D.P.) content (%) 2 :6’ 15 15 2.9 2:6‘ 25 25 ca. 3 2~6’ 25-30 25-30 2 2:6’ 2:6’ 7 ca. 7 8 13 34-36 2.8 the same as the proportion of terminal fructose residues and it appears that most of the fructosan molecules in these samples but perhaps not all of them are terminated by a sucrose residue. For four of the samples the “chain length” by chemical methods and the molecular weight by physiqal measurements are in full agreement and it follows that the fructosan molecules are unbranched and terminal sucrose residues as inherent parts of their structure are present in L. perenne.Whether or not all the levan molecules contain the terminal glucose residue is a question still to be resolved. It is not impossible that in the plant itself or in the course of extraction and purification of the polysaccharides some of the levan molecules which are extremely labile may lose the glucose end group and Schlubach Aspinall Hirst Percival and Telfer J. 1953 337. l9 Aspinall and Telfer J. 1955 1106. 2o For a general review with references to earlier papers see Schlubach Experientia 1953 9 230. 21 Laidlaw and Reid J. 1951 1830. 52 Harwood Laidlaw and Telfer ,J. 1954 2364. small. Only in one instance namely a fructosan from Lolium italicum (Italian ryegrass) does the molecular weight (34-36 hexose residues) differ markedly from the chemically determined “unit chain length” (13 residues).In this instance the methylation experi- ments revealed that some di-0-methylfructose accompanied the tetra- and tri-0-methyl derivatives and it is probable that this fructosan has a branched- chain structure containing some three unit chains with two branch points. At present the nature of the linkage at these branch points is not known. PROCEEDINGS main chain linkages which are 2 :6’ in type and there has been a clear distinction between the inulin (2 1’-linked) and the levan group of fructosans. It is of special interest therefore to note that the occur- rence of 2:l’-linked fructose residues as a main structural feature has been observed in a group of monocotyledonous plants closely related botanically to the grasses.The fructosans in the stems and ears of a group of cereals have been studied in detail by Schlubach and his school at Hamburg.2o The results of these investigations are summarised in Table 3 TABLE3. Fructosans in stem and ear of cereals (Schlubach) Source D.P. Linkage Ratio of tetra- tri- Molecular and di-methylfructose structure Wheat (stem) 5 2:6‘ 1:3:1 Branched (ear) 12 2:l‘ 1:l:l Branched Rye (stem) 4 2:6’ 1:2:1 Branched (ear) 15 2:l’ 1:l:l Branched Barley (stem) 2 6’ (ear) 5 2:l’ 1:2:1 Branched Oats (stem) 7 2:6’ 1:5 1 Branched (ear) 7 2:6’ 1:3 1 Branched Timothy grass* 50 2 6’ 1:48:- Unbranched Rye grass* 34 2:6’ Unbranched * Leaf and stem. The range of molecular size amongst grass fructosans is by no means great and none of these described hitherto exceeds a D.P.of 50 residues which was recorded by Schlubach and his colleagues23 for an unbranched fructosan from Timothy grass. The 2 6’-linked fructosans of grasses differ markedly in this respect from the similarly linked polysac- charides of very high molecular weight synthesised by bacteria. At the other end of the scale fructosans of much lower molecular weight have been isolated from grasses.22 An examination of the carbohydrate content of mid-season perennial rye-grass (Loliurn perenne) revealed the presence of a series of short- chain fructosans having molecular sizes ranging between 5 and 10 hexose residues. Structurally they are built up of a chain of /3-2:6‘-linked fructose residues terminated at one end by a non-reducing fructose residue and at the other by glucose.It is likely therefore that the leaves and stems of grasses contain a series of fructosans in the form of “polymer homologues” which have been built up stepwise from sucrose by enzymically controlled transfructosyla- tion. All of the grasses which have been mentioned hitherto in this lecture contain fructosans having 23 Schlubach and Sinh Annulen 1940 544 101. from which it appears that the fructosans present in the stems of wheat rye barley and oats possess the levan type of structure with successive fructose residues mutually linked through the 2 :6’-positions. Nevertheless they differ in a remarkable way from the grass levans in that in each case the molecule although of low molecular weight is branched.For example the methylated derivative of the fructosan from the stems of wheat gives on hydrolysis 3 parts of 1:3 :4-tri-O-methyl-~-fructose 1 of tetra-0-methylfructose and 1 of di-0-methylfructose. The recorded molecular weight (D.P.5) is regarded by the authors as being probably too low but even if this is doubled it is apparent that some of the structural features of the branched molecule such as the pos- sibility of an annular form with side chain remain to be elucidated. This would apply also to the other cereal fructosans listed in Table 3 but for present purposes the main point of interest is that the fructosans in the stems and leaves were of the levan type and gave in every case 1:3:4-tri-O-methyl-fructose on investigation by the methylation method with no sign of the 3 :4:6-tri-0-methylfructosewhich is characteristic of the inulin type of structure.In striking contrast with these observations the fructo- JULY 1957 sans which were obtained from the ears of these cereals and were present in the endosperm of the developing grain gave rise after similar treatment to 3 :4 6-tri-0-methylfructose in the cases of wheat,rye and barley and it was only from the methylated fructosan extracted from the oat grain that 1 :3 :4-tri-0-methylfructose was obtained. In the oat there- fore the fructosans of stem and ear are all of the levan type with 2 6’-linked fructose residues whereas in wheat barley and rye the stem fructosans are of this type whilst the ear fructosans are of the inulin type.Some very recent work by F. Smith and his co-workers24 has shown that the position is even more complicated than this. These authors have examined in detail the carbohydrate components of wheat endosperm and have succeeded in isolating a fructosan which should have been similar to the material described by Schlubach. It turned out how- ever that the material was a fructosan of low mole- cular weight having a branched-chain structure with non-reducing terminal groups of fructose and glucose. Its methylated derivative gave 1 :3 :4-tri-O-methylfructose on hydrolysis and it must therefore belong to the levan type of fructosan.It is presum- ably derived from a sucrose molecule by stepwise transfructosylation and as an indication of the main features of its structure Smith has put forward the formula (VIII). F2-6F24F24F2-6F2-1 G 1 2 F 1 2 F (VIW(F. Smith) -1F2-1F2. * 6 2 (IX) (Schlubach) F Fructosan from wheat endosperm The occurrence of such diverse materials is perhaps not as surprising as might at first sight appear to be the case. There is evidence that these short-chain fructosans are extremely labile and readily undergo hydrolysis or synthesis according to conditions in the plant. The enzymes controlling these reactions strongly favour the transfer of fructose residues to primary alcoholic groups (positions 1 and 6 of fructose) and synthesis appears to originate in a sucrose molecule.Again it seems probable that carbohydrate material is transported within the plant mainly in the form of sucrose and it follows 20 1 that the fructosans resynthesised from glucose in the ear need not bear any close structural relationship to the stem fructosans which had served as temporary storage material. As pointed out by Smith it is pos- sible that both types of fructosan may occur in wheat endosperm or that different varieties of wheat may build up different types of fructosan. Still another contingency which cannot yet be excluded is that the type of fructosan may change with the age of the plant. During the development of the seed it is known that the amount of fructosan present diminishes rapidly and it may be that the type of structure required in the more mature seed differs from that needed during the stage of very rapid growth.What- ever may be the true explanation it is clear that there are here many problems of great interest still awaiting solution. Another and a much more complicated example of a fructosan which contains residues of both the inulin and the levan type is the material designated triticin found in quantity in the creeping under- ground stems of the couch grass (Triticum repens).% Hydrolysis of the methylated derivative yields tetra- (42 %) 1:3 :4-tri- (1 1 %) 3 :4:6-tri-(4 %) and 3 :4-di-0-methylfructose (39 %). Some glucose residues (4 %) are present also. It follows that the molecular struc- ture besides glucose comprises residues of structure F2.a .-6F2. -. . -.1F2.. * and . -1F2.. a. No .. .6 unique formula can as yet be advanced but some idea of the main structural features is indicated in (X). * .6F2-lF2-lF2-lF2* 9 6 6 6 (X) 222 FFF Residues also of * *1F2.-* and of glucose. Reference has already been made in passing to possible modes of synthesis of these fructosans by enzymes present in the plant cell. Much attention has been given to these problems and as the result of investigations by many workers including RabatC Fischer Hehre Hestrin Dedonder Bacon and Edelman it is now generally recognised that the synthesis of polysaccharides in plants proceeds by a series of enzymic “transfer” reactions.26 When this idea is applied to the fructosan series with sucrose as the substrate material the first stage of the reaction would be as follows Sucrose + Enzyme -+ Fructosylenzyme + Glucose 24 Montgomery and Smith J.Amer. Chem. SOC.,1957,79 446. 25 Arni and Percival J. 1951 1822. 26 A review with full references will be found in the article by Bacon on “Transfructosylation” in Ann. Reports, 1953 50 281. In the presence of a suitable acceptor molecule a second stage then provides the product and releases the enzyme Fructosylenzyme + Acceptor + Fructosyl Acceptor + Enzyme Acceptor molecules are of the-form ROH so that with R = H it is possible to regard enzymic hydro- lysis as one instance of such a transfer reaction.In general the product will be Fructosyl-0-R and in the case of the fructosans which are now under con- sideration the hydroxyl groups which feature most prominently are the primary alcoholic groups at posi- tions 1 and 6 of a fructofuranosyl residue located either in a sucrose molecule or in a fructose-contain- ing polysaccharide. The following picture of the building up of an oligosaccharide of the inulin type by this transfer mechanism may therefore be given F2-lG EnrymQ-F2-m~+ G Sucrose F2-en~p~ F2-IG FF!F2;1G + -t sucrose residue The process is continued by stepwise transfructos- ylation reactions which give successively F2-1F2-1F2-1G F2-1F2-1F2-1F2-1G and finally F2-( 1F2)X-1G. The overall reaction may be summarised by the equation n Sucrose + Sucrose (starter molecule) + (F),-F-G + nG In the fructosan series27 the experimental evidence on which these ideas are based comes largely from the work of Dedonder and of Bacon and Edelmann who discovered independently that the carbohydrate components of the tubers of the Jerusalem artichoke can be separated chromatographically into a series of substances extending regularly upwards from sucrose in molecular size each of which is non-reducing and gives on hydrolysis only fructose and glucose.They interpreted their observations as in- dicating a series of oligosaccharides produced origin- ally from sucrose by successive additions of a fructo- furanose residue. This work was followed by a more detailed examination of the properties of the inulin sucrase enzyme which is present in extracts of the tubers.It was found to be capable of transferring fructose residues from sucrose to fructose raffinose and melezitose as well as to sucrose but not to PROCEEDINGS glucose maltose or lactose. Many other enzymes are known to effect similar transfers and it seems prob- able that the very remarkable series of oligosac- charides examined during the past few years by Fleury Courtois Wickstram and their colleagues may owe their origin to a comparable mechanism.% These are found notably in certain plants of the Scrophulariaceae and Labiatae families. They all con- tain galactose residues and may be regarded as higher members of the series to which raffinose (Gal 1- 6Glu 1-2Fru) and stachyose (Gal 1-6Gal1-6Glu 1- 2Fru) belong.They are included in the general formula Gal 1-[6 Gal 1 1,-6 Gal 1-6 Glu 1-2 Fru and may be regarded as derived from sucrose by the step- wise addition of galactopyranosyl residues. In this connection it may be noted that raffinose occurs to an important extent in the endosperm of cereals and is found also amongst the oligosaccharides present in the stems and leaves of grasses. The views just outlined concerning the origin of the fructosans in Nature are in good agreement with observations on the changes which take place in the carbohydrate components of grasses during the period of growth. This is a subject which has been much studied because of its relevance to the nutri- tional value of grass in farming practice.It has important repercussions also on problems of fodder conservation including both haymaking and en-silage. The analytical procedure is far from easy even when all the resources of modern chromatographic methods are brought into play but sufficient is now known to permit at least a qualitative picture to be given for certain grasses. Quite apart from errors of sampling the possibility of enzymic degradation during the preparation of the sample for analysis and the difficulties encountered during the extraction and separation of the carbohydrates experiments with growing crops are liable to uncertainties due to weather conditions involving temperature moisture wind and sunshine which are not within the control of the investigator.Some experiments have indeed been carried out under completely sterile conditions with controlled temperature moisture and nutrients and although these have necessarily been on a small scale the results tend to substantiate the views derived from trials carried out in the open field. Investigations of the seasonal variation of the carbohydrate contents of grasses have been carried out in recent years by Waite and Boyd29 at the Hannah Dairy Research Institute by Schlubachm and his school at Hamburg and by Mackenzie and 27 Dedonder Compt. rend. 1951 232 1134 1442; Bacon and Edelmann Biochem. J. 1951 49 529. ts See for example HCrissey Fleury Wickstram Courtois and Le Dizet Bull. Soc. Chim.biol. 1954 36 1507 1519. sD Waite and Boyd J. Sci. Food Agric. 1953 4 197 257. 'O Schlubach and Lubbers Annulen 1956 598 228 (with references to earlier papers). JULY1957 Wylam3I at Edinburgh. It is clear that the various grasses show similarity in their general behaviour but considerable differences in detail. The pattern is perhaps best illustrated by reference to perennial rye- grass. During the growing season the content of fructosan in the stem rises from about 7 % of the dry weight of the material to the remarkably high figure of some 33 % towards the end of June. Then follows a rapid decline during the period of flowering and seed formation until by the end of October the value has fallen to about 4%. During the whole of this period the sucrose content of the grass remains low (about 3 %) except after long periods of bright sun- shine when figures as high as 12% were recorded.On the other hand even during periods of rapid growth after spells of sunless weather the rate of increase in the fructosan content fell to zero as the store of sucrose became depleted. There would appear to be therefore a close relation between the amounts of sucrose and fructosan by which the sucrose acts as a temporary storage product for the products of photosynthesis and then undergoes transformation at a slower rate into polymers of higher molecular weight and lower osmotic activity. These in turn are retained as reserve materials until their carbohydrate residues are required by the plant for growth and for the formation of flower and seed.These fructosans are important in other ways also. In agriculture success in the conservation of grass for fodder particularly in the form of silage may depend upon the proportion of fructosans present in the grass at the time of ensilage. Apart from the free sugars which are normally present in comparatively small amounts the fructosans are the carbohydrate materials most readily available for hydrolytic attack by the enzymes of the plant. Evidence obtained in some recent has indicated that after the grass has been cut rapid changes take place in the course of which the enzymes of the cytoplasm break down the fructosans and to a much smaller extent the hemicellulose constituents of the grass.If the carbo- hydrate content is sufficiently high conditions are particularly favourable for the establishment and growth of strains of lactobacilli and fermentation of the sugars to lactic acid takes place. Putrefactive de- composition of the protein material is then avoided and a palatable silage of high nutritive value is pro- duced. When the changes accompanying ensilage are essentially complete the sucrose and fructosan con- tents have dropped to zero owing in part to the action of plant enzymes in part to bacteria and in part to the hydrolytic action of the lactic acid pro- duced. It is significant that the free-sugar qontent of 51 Mackenzie and Wylam J. Sci. Food Agric. 1957 8 38. 82 Wylam ibid. 1953 4 527.ss Colin Compt. rend. 1921 173 852. the silage mainly fructose and glucose is still high. On the other hand if the protein content of the grass is high and that of the fructosan low the enzymic changes which follow cutting and ensilage provide conditions favourable to the formation of butyric acid instead of lactic acid and in these circumstances the pH value is high owing to decomposition of protein with liberation of ammonia. The silage so produced is extremely unpleasant to handle and is unpalatable as fodder. These reactions differ markedly from those which take place in the living cells of the plant during its period of growth. The enzyme systems responsible for the reversible transformation of sucrose into fructosans are delicately balanced so that changes take place in the forward or backward direction according to the photosynthetic activity and the call of the growing plant for energy reserves.There is evidence that separate enzyme systems are present in the various parts of the plant where fructosans are utilised and that in each case the starting material is sucrose which was referred to earlier as being in all probability the main form in which carbohydrate material is transported in many plants. Some years ago Colin33 described experiments with two species of Heliantltus namely H. annuus and H. tuberosus. If a cutting of the latter is grafted on to the rooted stem of H. annuus no inulin is found in the root portion although inulin is present in quantity in the stem above the position of grafting.On the other hand when a cutting of H. annuus is grafted on to the rooted stem of a plant of H. tuberosus inulin is freely deposited in the tubers but is completely absent in the portion above the graft region. Each portion of each species therefore appears to have its own set of enzyme systems and the fructosan which is syn- thesised by both species of Helianthus is produced only in the appropriate part of the plant and does not travel from one part to another as a polymer. Once again it seems probable that sucrose is the form in which the fructose residues are transported in the plant. It is understandable therefore that even within one plant fructosans of totally different structure may be found in different regions and a general picture emerges of fructose residues produced by photosynthesis and temporarily stored in the leaf cells in an active form as sucrose.This in turn gives rise in some plants to fructosans of the levan type stored in leaf and stem. These undergo the reverse transformation as required and are transported as sucrose down the stem to storage depots containing inulin or complex fructosans of mixed type such as PROCEEDINGS triticin. Alternatively transport may be upwards to contributing energy for the maintenance of the life regions where temporary stores of fructosan are processes of the cells. It will be seen therefore that required pending the utilisation of the hexose these studies of the chemistry of fructose derivatives residues for the synthesis of starch and other com- in plants have opened up a surprisingly wide and plex carbohydrates.Furthermore some of the varied group of problems which are of increasing fructose residues in all regions of the plant must be importance in biology and in chemistry. COMMUNICATIONS The Biochemical Origins of the Methyl Groups of Mycophenolic Acid By A. J. BIRCH,R. J. ENGLISH,R. A. MASSY-WESTROPP and HERCHEL M. SLAYTOR Smm (DEPARTMENT CHEMISTRY OF SYDNEY, OF ORGANIC UNIVERSITY AND CHEMISTRY UNIVERSITY DEPARTMENT OF MANCHESTER) Me R'O CO MYCOPHENOLIC ACID^ (I; R1= R2 = H R3= Me) from Penicillium brevi-compactum contains three methyl groups two attached to carbon and one to oxygen. The last would be expected to be introduced biochemically from methionine,2 and we have postulated that the nuclear methyl group in similar compounds should come from the same so~rce.~ This has now been confirmed on material obtained by feeding [methyl-14C]methionine to P.brevi-compactum which was degraded with the results given in the scheme. The number of active carbon atoms in each degradation product is shown. They are calculated strated may be of wide validity. Further examples of from the relative molar activities4 (the product of the natural products which may arise by the addition of molecular weight and counts/lQQ sec. for each sub- one or more methyl (or equivalent) groups to an stance) it being assumed that theacid (I;R1=R2=H acetate-derived chain are the group of mould meta- R3= Me) contains two active carbon atoms.bolites including fulvic acid citromycetin and fusarabin recently discussed by Robertson and his The activity of the 0-methyl group is rather higher colleagues,' and clavatol.8 The present work also than that of the C-methyl group which we attribute shows that there may be no necessity to postulate the to the presence of unmethylated phenol at the stage intervention of propionate units to rationalise the when the methionine is added. The incorporation of biosynthesis of the my~ins.~ the latter (about 75 %) is astonishingly high. Mevalonic acid5 provides the methyl group in the Grants from the Nuffield Foundation (Australia) side chain and acetic acid the carbon atoms of the (to M.S.) and the Cumberland Education Com-nucleus.6 The implications of these results will be dis- mittee (to R.J.E.) are gratefully acknowledged.cussed shortly. The biosynthetic route here demon- (Received May 28th 1957.) Birkinshaw Raistrick and Ross Bioclzem. J. 1952 50 630 and earlier papers. Challenger Quart. Rev. 1955 9 255. Birch Elliott and Penfold Austral. J. Chem. 1954 7 169. Birch Massy-Westropp Rickards and Smith J. in the press. Wolf Hoffman Aldrich Skeggs Wright and Folkers J. Amer. Chem. Soc. 1957 79 1486. * ' Birch English and Smith unpublished work. Dean Eade Moubasher and Robertson Nature 1957 179 366. * Hassall and Todd J. 1947 611. Flynn Gerzon Sigal Wiley Weaver Monahan and Quarck Chem. Eng. News 1956 34 5138; Woodward Angew. Chem.1957 69 50. JULY 1957 205 The Mechanism of the Light-catalysed Transformation of Santonin into 10-Hydroxy-3-oxoguai-44-en-6:1Zolide By D. H. R. BARTON,P. DE MAYO,and MOHAMMED SHAFIQ HE UNIVERSITY, GLASGOW) RECENTLY~ we described the light-induced conversion of santonin (I) into the azulene derivative (11; R = H) in aqueous acetic acid. The mechanism of this reaction has now been clarified. Irradiation of santonin (I) in ethanol gives an isomer (111) m.p. 153-155" [a] -169" A,,, 239 mp (E 5,800) with maxima in the infrared spectrum at 1765 (7-lactone) 1703 (cyclopentenone) and 1663 crn.-l (conjugated double bond).2 This substance when re- H fluxed in the dark with 45% aqueous acetic acid is converted into the compound (11; R = H);l with 1% perchloric acid-acetic acid the acetate (11; R = Ac)l is obtained.The constitution of the intermediate (110 is based on these observations and on the following facts. Ozonolysis gives formic acid but no acetic acid and hydrogenation affords a dihydro- compound containing no double bonds (stability to ozone) m.p. 160-162" [a],-59" showing Amax. 214 mp (E 4,600) indicative3 of a ketone conjugated with a cyclopropane ring. Treatment of the dihydro- compound with refluxing aqueous acetic acid gives the spiran (IV) m.p. 193-204' (decomp.) [a] + 106" with no high-intensity ultraviolet absorption but with an infrared maximum at 1726 cm.-l (cyclo- pentanone) and the corresponding anhydro-com- pound with the double bond in the endocyclic posi- tion m.p.192-202" (decomp.) [a],+ 52" having three C-methyl groups and an infrared maximum at 1735 cm.-l (cyclopentanone). Reaction of the inter- mediate (111) with osmium tetroxide gave the ex- pected glycol m.p. 178-183" (decomp.) [a] + 35' showing Amax. 214 mp (E 4,250) cleaved by periodic acid (2 mols. uptake) to an aldehydo-acid m.p. 127-129" [aID-25" existing in the lactol form (no ultraviolet maximum) and consuming one atom-equiv. of oxygen on titration with chromic acid to give the corresponding five-ring anhydride m.p. 62-65" having infrared maxima at 1830 (anhydride) and 1770 cm.-l (anhydride and y-lactone). Treatment of the intermediate (111) with hydrobromic acid in acetic acid-benzene afforded the bromo- compound 0,m.p.111-114" [a] -130" with infrared maxima at 1792 (y-lactone) 1752 (uncon- jugated cyclopentenone) (both in CCl,) 1627 802 752 and 722 m.-l (triply substituted double bond); this product was dehydrobrominated with boiling pyridine to give back the intermediate (111) as well as the unconjugated dienone with the corresponding endocyclic double bond Im.p. 181-183" [aJD-200" showing infrared maxima at 1792 (y-lactone) 1752 (unconjugated cyclopentenone) (both in CCl,) 1643 815 741 and 727 m.-l (triply substituted double bond). It is possible that compound (III) is directly transformed into the azulene derivative (11) by a simple acid-catalysed process (see arrows); further intermediates of the type (IV) but con-taining a cyclupentenone component are however not yet excluded.All [a],are in CHC13 ultraviolet data in EtOH and infrared data in Nujol except where stated. Satisfactory analytical data have been recorded for all the new compounds. We thank Professor G. Biichi who is publishing his data on the intermediate (111) elsewhere for friendly discussion and helpful suggestions. (Received,May 21st 1957.) Barton de Mayo and Shafiq J. 1957 929. This compound has also been obtained by Professor Buchi (M.I.T.) and by Professor Cocker (Trinity College Dublin) personal communications. Eastman J. Amer. Chem. SOC.,1954,76,4115. PROCEEDINGS Total Synthesis of the Dinoronocerane Carbon Skeleton By Dov ELAD and FRANZ SONDHEIMER (THE DANIEL SIEFF RESEARCH INSTITUTE WEIZMANN OF SCIENCE ISRAEL) INSTITUTE REHOVOTH R @(I) Our first studies have been in the onocerin series and we have now succeeded in converting the ketone (I; R = H) into a compound which may be the racemate of dinoronocerane (VI; R = H R' = H,).4 The latter substance contains six of the eight asymmetric centres and all but two of the carbon atoms of cc-onocerin (a-onoceradienediol) (VI; R = OH R'= CH2).475 The ketone (I; R = H) with sodium acetylide in C liquid ammonia gave the acetylenic carbinol m.p.111 + 111 69-70" (all compounds gave correct analytical re- sults and showed infrared spectra compatible with the assigned structures) which was allowed to react in liquid ammonia with ca. 2 equivs. of sodamide and then with 1 equiv.of the ketone (I; R = H). The I i product was separated into two entities (m.p. 189-190" and 209-210"; large depression on ad- mixture; infrared spectra almost superimposable) one of which is presumably the racemic glycol (11) and the other the meso-glycol (111); the stereochem- C ical assignments have been made on the assumption Ill ii C C that attack from the less hindered side has taken place at position 1. Dehydration of the lower- melting glycol (probably the required racemic form if the m.p. generalisations made in the acyclic series* are valid also for semicyclic compounds) with potas- + sium hydrogen sulfate at 170-1 80" gave smoothly the dienyne (IV) or (V) (probably the former) m.p. 128-1 30" showing the typical ultraviolet maxima' at 265 (log E 4-24) and 279 mp (log E 4.1 1).Dehydra- tion of the higher-melting glycol under the same dPR conditions gave a complex mixture. Hydrogenation of the product (IV) was expected to occur stereospecifically from the less hindered a-side to give (&)-dinoronocerane (VI; R = H R' = H9). In fact with platinum in dioxan-acetic WE recently describedl the synthesis of 5 5 :9-tri-acid it yielded a saturated hydrocarbon m.p. methyl-trans-decale-1-on(I; R = H) as a possible 184-185" the infrared spectrum of which both in intermediate for the synthesis of certain di- and tri- chloroform and in carbon disulfide solution was terpenes. Independently Cocker and Halsal12 pre- virtually identical with that of authentic optically pared this ketone by a similar route and King active dinoronocerane.Unfortunately the spectra Ritchie and Timmons3 synthesized the 3p-benzoyl- exhibited little fine structure and the possibility that oxy-compound (I; R = OBz) by a different method. the synthetic compcund belongs to the meso-series Elad and Sondheimer Bull. Res. Council Israel 1956 5 A 269; J. Amer. Chem. Soc. in the press. Cocker and Halsall Chem. and Znd. 1956 1275. King Ritchie and Timmons ibid. p. 1230. Barton and Overton J. 1955 2639. ti Schaffner Viterbo Arigoni and Jeger Helv. Chim. Acfa 1956 39 174. Stern Abs. Papers 131st Meeting Amer. Chem. SOC. Miami Fla. April 1957 p. 5 0. Bastron Davis and Butz J. Amer. Chem. Soc. 1943 65 973. JULY 1957 or shows other stereochemical differences from the nat~al compound cannot be excluded.we are now attempting the synthesis with optically active sub- stances in order to eliminate the formation of com- pounds of the meso-series and to facilitate the final proof of identity. The authors are grateful to Professor D. H. R. Barton F.R.S. for a sample of optically active dinoronocerane. (Received May 21st 1957.) The Rate of Association of Ferric and Fluoride Ions By W. MAcF. SMITH (THEPHYSICAL LABORATORY, CHEMISTRY OXFORD*) As part of an investigation on the kinetics of the displacement of solvent around cations by various ligands it has been found that the reaction between ferric and fluoride ions in aqueous solution is sufficiently slow to be timed with a stop-watch; it follows expected second-order kinetics.The reaction was followed through the redox potential of the ferric-ferrous couple which appears to be potential-controlling during the approach to equilibrium. Measurements which were made with differential electrodes have been restricted as yet to the narrow range of conditions indicated in the accompanying Table. The acid content was adjusted with perchloric acid the ionic strength with sodium perchlorate. Hydrofluoric acid was the source of fluoride ferric perchlorate the source of ferric ions. Ferrous perchlorate was added until its concentration was 0.55 x or 1.1 x loF4molar. Both concen- trations led to stable and substantially the same cell e.m.f.s during reactions involving otherwise identical solutions.In the interpretation of the results it has been assumed that at 0" and ionic strength 0.050 the ionisation constant1 for hydrofluoric acid is 1-57 x lo3 and the hydrolysis constant2 for the reaction Fe3++ H20 = Fe(OW2++ H+ is 5-7 x lo4. In all experiments the initial molar concentration of total Fe(m) was in excess of that of total fluoride and the changes in redox potential between initial and equilibrium states were consistent with the assump- tions that all the iron engaged in complexes was present as FeF2+ and that the association constant for the formation of FeF2+ is (2.550.5) x lo5mole-ll. The kinetic results were satisfactorily interpreted on the assumptions that the ferric ion is removed by bimolecular reaction with free fluoride ion that the reverse reaction involving FeF2+ is of the first order that the contributions of reactions involving Fe(OH)2+,HF and the formation of FeF2+ are rela- tively unimportant and that the measured cell e.m.f.is due to the ferric-ferrous couple. The rate con- stants determined on the basis of these assumptions Bimolecular rate constants for the association of ferric and fluoride ions in aqueous solution at 0"and ionic strength 0.050 Total Total initial initial Concn. concn. of concn. of F Rate of HC104 Fe(rrr) (HF+F-) constant (M) (10-4~) (10-4~) (lo2 mole-l1. set.?) 0.010 2-28 1 -57 2-6 0.020 2.28 1.57 2-9 0.030 2-28 1-57 2.9 0.045 2-28 1-57 3.1 0.010 4-56 1.57 2.9 0.020 4-56 1-57 2.6 0.045 4.56 1.57 2.6 0-020 2-28 0.78 2-9 and the value for the ionisation constant of hydro- fluoric acid stated above are given in the Table.The rate constants do not depend significantly on the acid concentration over the range investigated which involves an associated change in the fraction of iron in the hydrolysed form Fe(OH)2+ of over fourfold. However in view of the rather low precision of the measurements a small dependence cannot be ruled out. The assumption that the slowness of the ferric- fluoride association is due to characteristics essential- ly those of ferric ion is supported by some pre- liminary measurements made with a Roughton-type flow system on the rate of association of ferric with chloride and with sulphate ions.These suggest that the rate constants for these associations are of the same order of magnitude as that for ferric and fluoride ions. The helpful advice of Mr. R. P. Bell and the receipt of a Royal Society and Nuffield Foundation Commonwealth Bursary are gratefully acknow-ledged. Thanks are also offered to Sir Cyril Hinshel- wood for making available facilities in the Physical Chemistry Laboratory Oxford. [Received June 24th 1957.1 * On leave from Queen's University Kingston Ontario. Broene and De Vries J. Amer. Chem. Suc. 1947,69 1644. Siddall and Vosburgh ibid. 1951,73 4270. PROCEEDINGS A Series of Stable Acetylene Complexes By J. CHATT,G. A. ROW and A. A. WILLIAMS (IMPERIAL INDUSTRIES LABORATORIES, CHEMICAL LIMITED,AKERSRESEARCH THE FRYTHE HERTS.) WELWYN AN attempt to prepare cyclobutadiene complexes of the type predicted by Longuet-Higgins and Orgell has lead to a new series of acetylene complexes of the general formula [Pt(PPh,),ac] (ac = acetylenic sub- stance).It is the most extensive series of mononuclear acetylene complexes known. Its members are pre- pared by the reduction of an alcoholic suspension of cis-[(PPh3),PtC12] in the presence of the acetylene and they separate without solvent of crystallisation. They crystallise well on addition of alcohol to their benzene or chloroform solutions and then usually contain one or two molecules of solvent of crystallisation. They are more stable to air and moisture than the well-known olefin complexes of platinum (11).Some have now been stored for over a year without decomposition. One acetylenic substance displaces another from its complex in solution at room temperature in- dicating ready equilibration of the type Pt(PPh,),ac + ac' + Pt(PPh,),ac' + ac A series of displacement reactions shows that the acetylenic complexes increase in stability in the order of acetylenes C2H2 < AlkC CH < C,(Alk) N Ph.C CH < C2Ph2 < C2(C6H4'N02-p)2 The acetylenes are not displaced by common mono- dentate ligands except those which are strongly dou ble-bonding e.g. carbon monoxide and phos- phorus trihalides. Indeed di-p-nitrophenylacetylene reacts with the very stable presumably three co- ordinated Pt(0) complex [PtPPh,,o-C,H4(AsMe~),] in solution at room temperature to eject the diarsine and gives the product [Pt(PPh,),,C,(C,H,-NO,-p),].Some acetylenes also react with [Pt(PPh,),] as pre-pared by Malatesta and Angoletta, to give [Pt(PPh,),ac]. The acetylenic complexes show no signs of a triple bond in the infrared spectrum but have absorptions in the region of 1,700 cm.-l indicating that the triple bond has been reduced in strength almost to a double bond. The acetylene is not functioning primarily as an electron-donor since the more electron-attracting the acetylene the more stable its complex nor as a bridging group as it is supposed to do in some binuclear cornplexe~.~~~ Possible structures are (I)and (11) [where --indicates a bond of the type which occurs in Pt(n) complexes with olefins 1.If structure (I)is correct it is evident that the back- donation of electrons from d-orbitals of the platinum into antibonding orbitals of the acetylene is more important than the donor character of the acetylenic n-bond. To accord with this structure we would expect to find the acetylenic bond perpendicular to the P,Pt plane and the platinum atom in the sp2 hybridised state as in [PtPPh,,o-C6H,(AsMe2)),].If (II) more accurately represents the structure the carbon atoms of the acetylenic bond are more likely to lie in the P,Pt plane with the platinum atom in the dsp2 hybridised state. Whatever the stereochemistry orbitals are available to allow one structure to take on part of the character of the other and the principal structure is probably (11).It is intended to examine the stereochemistry by X-rays. An analogous series of olefin complexes exists but its members are very unstable. These complexes may be of value for the separation of acetylenic substances from natural product mix- tures. The acetylenic substances could be recovered by displacement with diphenylacetylene or its di-p-nitro-derivative. We are indebted to Dr. L. A. Duncanson for investigating the infrared spectra. (Received,June 6th 1957.) Longuet-Higgins and Orgel J. 1956 1969; read at Burlington House December 1955. Malatesta and Angoletta Atti Accad naz. Lincei Classe Sci. fis. mat. nat. 1955 19 43. Greenfield Sternberg Friedel Wotiz Markby and Wender J.Amer. Chem. Soc. 1956 78 120 and references therein. Clarkson Jones Wailes and Whiting ibid. p. 6206 and references therein. Chatt and Duncanson J. 1953,2939. JULY 1957 209 A New Molecular Rearrangement By T. M. MOYNEHAN and D. H. HEY (KING'SCOLLEGE W.C.2) STRAND,LONDON AT the Meeting of the American Chemical Society in April 1957 Stiles Sisti and Libbey Jr.l reported that when the diazonium salt from 9-o-aminophenyl- fluoren-9-01(I) was decomposed in acid solution the normal phenolic product was formed together with a second compound which was isolated in 24 % yield and to which the structure of tribenzotropone (11) was assigned. In similar manner the diazonium salt prepared from 1-o-aminophenyl-1 -phenylethanol (111) gave 9-methylfluoren-9-01 and methyl 2-di- phenylyl ketone (IV) in 3.8% yield.In both these reactions the nuclear position from which the nitrogen is eliminated attacks a second nucleus at the point of attachment of the extra- nuclear carbon atom. This is followed by fission of the carbonarbon bond. During work on internuclear cyclisation carried out in our laboratories a new molecular rearrange- ment similar to but distinct from that described by Stiles Sisti and Libbey has come to light. Decom- position of the diazonium chloride prepared from N-o-aminobenzoyldiphenylamine(V; R = H) by addition of copper powder to the aqueous solution and chromatographic separation of the products gave the expected 10-phenylphenanthridone (m.p.225") in 40% yield together with the anilide (VI; R = H) (m.p. 109-110") of diphenyl-2-carboxylic acid in 45 % yield. The identity of the latter was con- firmed by mixed melting point with an authentic specimen. On the other hand the thermal decom- position of the diazonium chloride in aqueous solution in absence of copper powder gave 10-phenyl- phenanthridone in 60 % yield and N-salicyloyldi- phenylamine in 25% yield and no rearranged product. A similar reaction carried out with the diazonium chloride prepared from N-o-amino-benzoyldi-p-tolylamine (V; R = Me) gave 3-methyl- R 1 0-p-tolylphenanthridone (m.p. 175-1 76") in 28 % yield and the p-toluidide (VI; R = Me) (m.p. 134-135") of 4-methyldiphenyl-2-carboxylicacid in 58 % yield.The latter was identical with an authentic specimen prepared from p-iodotoluene and ethyl o-iodobenzoate by means of an Ullmann reaction followed by conversion into the acid and thence into the p-toluidide. Here again the nuclear position from which the diazonium group is eliminated attacks a second aromatic nucleus at the position of attachment of the nitrogen atom and this is followed by the fission of the carbon-nitrogen bond. This new rearrangement is being further investigated. (Received June 1 lth 1957.) Abs. Papers 131st Amer. Chem. SOC. Meeting Miami Florida Apr. 7-12 1957. The Solubility of Potassium and Sodium-Potassium Alloy in Certain Ethers By J. L. DOWN J. LEWIS,B. MOORE,and G. WILKINSON (INORGANIC LABORATORIES COLLEGE, CHEMISTRY IMPERIAL LONDON,S.W.7) THE observations by Wolthorn and Ferneliusl that of potassium are of course unstable liberating sodium and potassium showed a tendency to give hydrogen.However in certain ethers where decom- blue solutions in water were recently confirmed and position cannot occur so readily moderately stable extended in the case of potassium and a similar blue solutions of potassium or liquid sodium-potas- phenomenon with alcohol was reported at the sium alloys can be obtained; suitable ethers are e.g. same time.z These aqueous and alcoholic solutions tetrahydrofuran diethylene glycol dimethyl ether Wolthorn and Fernelius J. Amer. Chem. Soc. 1934 56 1551. Jortner and Stein Nature 1955 175 893. the cyclic tetramer of propylene oxide and ethylene glycol dimethyl ether the last being the most effec- tive.Tetrahydrofuran and ethylene glycol dimethyl ether have long been known3 as excellent media for reactions involving alkali metal~,~s~g~ which are often similar to those with metal-ammonia or -amine systems. Part of the reason for this may be accounted for and the similarity of the nitrogenous and ether media supported by the solubility of the metals in ethers. In ethylene glycol dimethyl ether and tetrahydro- furan the solutions of potassium or sodium-potas- sium alloy have a strong absorption band at about 7,000 A. Sodium alone does not appear to dissolve in these ethers even under ultrasonic ~timulation.~ For the sodium-potassium eutectic which shows a negative temperature coefficient of solubility elec- trically conducting blue solutions are obtained even at 25” by stirring or shaking the alloy with ether in absence of oxygen.The solubility of the metals in the ether suggests that neither a very high dielectric con- stant nor hydrogen bonding of the solvent is a prime factor in formation of the blue solutions and that more important are the solvating power of the solvent towards cations i.e. the donor properties of the oxygen or nitrogen atoms and factors probably steric allowing the formation of holes for the accom- PROCEEDINGS modation of electrons as required in electron-cavity theories6 of metals in liquid ammonia and amines such as that originally proposed by Ogg. There seems thus no reason to attribute the insolubility of alkali metals in trimethylamine to the absence of a hydrogen atom on the nitrogen atom.The sodium-potassium alloy-ethylene glycol di- methyl ether system is interesting from a preparative standpoint ;although similar reactions can be carried out by using sodium shot dispersion or amalgam in ethers reactions may here be carried out more expeditiously with advantages such as operation at room temperature and increased solubility of react- ants; one particular advantage over metal-ammonia or -amine solutions is the freedom from ammonolysis when for example compounds with reactive halogen atoms are used. Reductions we have studied in a preliminary way include those of titanium tetra-chloride (to give lower halides and the metal) boron trichloride and benzyl chloride (to give dibenzyl) the rapid conversion of iron and manganese car- bony1 into salts of Fe(CO),% and M~(CO)S and of hydrocarbons such as naphthalene into anion salts and the polymerization of isoprene styrene and acrylonitrile.(Received,May 29th 1957.) Scott Walker and Hansley J. Amer. Chem. SOC.,1936 58 2442. Chu and Weismann ibid. 1956 78,23 3610; Paul Lipkin and Weissman ibid. 1956 78 116. Slough and Ubbelohde J. 1957 918. 6 For references see Becker Lindquist and Alder J. Chem. Phys. 1956 25 971. Some Properties of Nickel Cyanide Ammonia Clathrate Compounds By E. E. AYNSLEY and R. E. DODD W. A. CAMPBELL (KING’SCOLLEGE UPON TYNE) NEWCASTLE WEhave recently examined further the physical pro- perties of Ni(CN),,NH3,C6H2v2 and similar clath- rate compounds containing aniline pyridine pyrrole thiophen and furan.Rayner and Powell3 showed that the benzene molecules are imprisoned within the Ni(CN),,NH lattice. Contrary to previous asser- tion~~.~ we have found that the benzene can be re- moved in vacuo (without removal of ammonia) slow- ly at room temperature and rapidly (50 % in 1-3 hr.) at 40-60”. Up to at least 80% removal of benzene the decomposition is of zero order varying in rate from sample to sample. This suggests that the rate- determining step (approximate activation energy 11 kcal./mole) is escape from the surface and that migration within the lattice is comparatively easy In an attempt to determine the heat of dissociation we measured the vapour pressure and found a behaviour similar to that reported by Wynne-Jones and Anderson4 for the compounds of methanol and sulphur dioxide with quinol.Equilibrium is readily approached from lower temperatures (and pres- sures) an increase in temperature of 10-20” being accompanied by a rapid rise in pressure (complete within 24 hr.) to a value which remains steady for at least 4 weeks. The vapour-pressure curve so obtained indicates a heat of dissociation of -10 kcal./mole (cf. 10.5 for the evaporation of solid benzene). Lower- ing the temperature leads to a considerable lowering in pressure but to values always in excess of the curve for rising temperature. Presumably liberation of benzene (albeit less than 5% in the vapour- pressure measurements) is accompanied by a partial collapse of the lattice which is then not wholly avail- able for re-absorption of benzene.Further experi- 1 Hofmann and Hochtlen Ber. 1903,36 1149; Hofmann and Arnoldi Ber. 1906 39 339. Palmer “Experimental Inorganic Chemistry,” Cambridge Univ. Press 1953 pp. 516 561. Rayner and Powell J. 1952 319. 4 Wynne-Jones and Anderson “Changements de Phases,” SOC. de Chimie physique 1952 p. 246. JULY 1957 ments may reveal similar behaviour in the other clathrate compounds and the extent to which this behaviour is complicated by kinetic effects and by adsorption of benzene on the finely divided powder. X-Ray powder photographs (kindly taken by Dr.K. H. Jack) of the benzene compound at various stages of decomposition up to 90% removal of ben- zene indicate progressive changes in the unitcell dimensions and not a complete breakdown of the lattice The material of composition Ni(CN),,NH obtained by the (almost complete) dehydration of the hydrate5 Ni(CN),,NH,,H,O bears only superficial resemblance to that obtained by almost complete removal of benzene from its clathrate compound. A striking difference in property is the fact that the de- hydrated hydrate re-absorbs water from the atmos- phere very rapidly but the decomposed clathrate compound shows no tendency to absorb water. We are investigating the infrared spectrum for comparison with the work of Halford et aL6 and of Mair and Hornig' on crystalline benzene.The dis- position of the benzene molecules (site symmetry Ci) in the two solids is similar. The most striking features are as follows. There is a pronounced reduction in intensity of the C-H stretching modes compared 21 1 with those in either liquid or solid benzene. Bands occw at two frequencies (1573 and 1166 cm.-l the latter very strong) which appear to correspond most closely with two E, vibrations (1595 and 1178 cm.-l) which for the vapour state (molecular sym- metry D6h) are active only in the Raman spectrum. Relaxation of the selection rules for the liquid phase permits these frequencies to appear in the infrared spectrum of liquid benzene (1587 and 1179 cm.-l) but in the solid the correlation Ezg(D6h) -+2Ag(C,) re-imposes the restriction and the frequencies do not appear in the infrared spectrum of benzene crystals.It would be expected that the same restriction would apply to benzene in the nickel clathrate compound and yet the band at 1166 crn.-l is the strongest band in the region 2-15 p. The other in-plane C-H deformation frequency at 1481 cm.-l appears with unchanged intensity as do the bands at 1037 (C-C stretching) and 707 cm.-l (out-of-plane C-H deformation). A similar comparison between Ni(CN),,NH,,C,H,.NH and liquid aniline demon- strates the reduction of intensity of the C-H stretch- ing vibrations and both the N-H stretching and the N-H deformation modes. (Received June 24th 1957.) Aynsley and Campbell J. 1957 in the press.* Halford and Schaeffer J. Chem. Phys. 1946 14 141; Zwerdling and Halford ibid. 1955 23 2221. Mair and Hornig ibid. 1949 17 1236. ERRATUM 0 FROMthe communication entitled "Hexanitroso-0 NAo benzene (Benzotrifuroxan) A Complex-forming Reagent for Aromatic Hydrocarbons" by A. S.Bailey and J. R. Case (Proc. Chem. Soc. 1957 176) formula (III) was omitted. It is printed alongside. (rn) SCIENTIFIC MEETING OF THE SOCIETY THE following papers were read at a Scientific Meeting held at Burlington House on Thursday June 6th 1957. The President was in the Chair. The Vapour Pressure of Anhydrous Copper Nitrate and its MoZecuZar Weight in the Vapour State. By C. C. ADDISON and B. J. HATHAWAY. Pure anhydrous cupric nitrate is readily prepared in the form of blue-green crystals by thermal de- composition of the compound Cu(NO,),,N,O, followed by vacuum-sublimation at 200".The un- expected volatility implies some unusual structural feature and for this reason vapour-pressure and molecular-weight measurements have been made. The method used to determine vapour pressure (which were described) has to allow for the rapidity with which copper nitrate vapour condenses and for the slight decomposition of the vaporising solid. From the variation of vapour pressure over the tem- perature range 1 50-225 * various thermodynamic properties for the Sublimation process are calculated. For sublimation into a vacuum vapour-phase decomposition of copper nitrate begins at 226"-By using the vapour-pressure values the molecular weight has been obtained by direct determination of the copper nitrate contained in a known volume of vapour; the compound is found to be monomeric.A sandwich structure for copper nitrate monomer is an attractive possibility. The failure of molecular-weight determinations carried out at atmospheric pressure 2 12 by the transport method is interpreted in terms of the lower stability of copper nitrate vapour in the presence of other gases. The compound has a high solubility in a number of oxygen-containing solvents and some properties of these solutions (spectra conductivity molecular weight) were described. DISCUSSION Professor L. Hunter.-The most remarkable pro- perty of this compound is its colour.One would expect an anhydrous copper salt to be either colour- less or very pale green. The blue colour of copper salts is usually associated with a co-ordinated ion e.g with water molecules or ammonia or amine molecules. Does this throw any light on the structure of the compound? Is there any evidence that the vapour is blue? Dr. Addison.-The rich blue colour of the an- hydrous nitrate is certainly unusual and is probably to be explained on the basis of co-ordination as Professor Hunter suggests. An X-ray crystallo- graphic examination of the solid is being carried out by Dr. S. C. Wallwork and Dr. W. E. Addison at Nottingham but this is not yet completed. There is no obvious colour in the vapour apart from that of a little nitrogen dioxide produced by decomposition of the solid.Dr. S. E. Livingstone.-The sandwich type of structure proposed by Dr. Addison for copper nitrate in the vapour phase would seem unlikely for the solid. Dr. Livingstone and Mr. Gatehouse at University College London had examined the infra- red spectra of a number of covalent nitrates. These compounds in contrast to ionic nitrates give an absorption corresponding to y1 of the NO group normally forbidden in the infrared region for the plane symmetric ion. If the nitrato-group were bound through an oxygen to the copper atom the symmetry would be destroyed and absorption corresponding to y1 should arise. Dr. Addison.-The environment of copper and nitrate ions in the solid state is very different from that existing in an isolated copper nitrate molecule in the vapour phase and we are very ready to believe that different structures apply in the two cases.Aromatic Reactivity. Part II. The Cleavage of Aryl-trimethylsilanes by Bromine in Acetic Acid. By C. EABORNand D. E. WEBSTER. The cleavage of the aryl-silicon bond in aryltri- methylsilane by bromine (bromodesilylation) ArSiMe + Br -+ ArBr + Me,SiBr is an electrophilic aromatic substitution process related to aromatic halogenation. However in the medium used (1.5 wt.% of water in acetic acid) at the bromine concentrations employed (initially ca. PROCEEDINGS 0.004-0.04~)bromodesilylation is of first order in bromine whereas aromatic halogenation e.g. of anisole is of an order of ca.1.25 in bromine so that processes involving two or more bromine molecules are relatively unimportant in the former reaction. The second-order rate constant falls off during a run becaose bromide ion produced by solvolysis of the trimethylsilyl bromide formed removes bromine as tribromide ion. The effects of added hydrogen bromide and salts (lithium chloride perchlorate and bromide and sodium acetate) are very similar to those in aromatic halogenation and indicate that the effective reagent is molecular bromine. The absence of significant catalysis by sodium acetate suggests that removal of the trimethylsilyl group is not involved in the rate- determining process. Except for ortho-substituents with which steric effects cause complications the effects of nuclear sub-stituents in bromodesilylation may be quantitatively correlated with those in protodesilylation but not with those in molecular halogenation.These sub- stituent effects are in general qualitative agreement with those in molecular halogenation in acetic acid (for example para-alkyl groups activate according to the hyperconjugative order Me > Et > Pr’ > But and para-halogens deactivate in the “mixed” order Br >I > Cl) but there are significant differences which point to somewhat different charge-distributions in the rate-determining transition states of bromination and bromodesilylation. The Kinetics of the Oxidation of Ethane by Nitrous Oxide. By R. KENWRIGHT and A. B.TRENWITH P. L. ROBINSON. The oxidation of methanel by nitrous oxide takes place at temperatures above 600” and involves an initial split of the latter followed by attack of atomic oxygen on the hydrocarbon. With hydrocarbons from propane to nonane2 oxidation occurs at temperatures beIow that at which nitrous oxide decomposes and probably results from reactions between hydrocarbon radicals and nitrous oxide. Ethane belongs to the second class oxidation occurring at 530”.At this temperature nitrous oxide is stable but ethane decomposes. The empirical rate equation is Rate= k [C2H,l+k2[C,H61“201 The principal products are H, N, CH, CO and C,H,; small amounts of CO and CH,O are also formed but water was not detected. Experimental evidence was described which indicates that the oxidation of ethane by nitrous oxide involves the reactions normally postulated for the decomposition of ethane together with the following C2H5 + N2O -+ C2H5O + N2 C2H50-+ CH + CH20 Robinson and Smith J.1952 3895. Smith J. 1953 1271. JULY 1957 213 NEWS AND ANNOUNCEMENTS The Research Fund.-The Research Fund of the Chemical Society provides grants for the assistance of research in all branches of Chemistry. About seven hundred pounds per annum is available for this purpose. Applications for grants will be con- sidered in November next and should be submitted not later than November 15th 1957. Applications from Fellows will receive prior consideration. Reports on grants outstanding from previous years should be made by November 1st.Forms of application together with the regulations governing the award of grants may be obtained from the General Secretary. Imperial Chemical Industries Transfer Scholarships Scheme.-Imperial Chemical Industries Limited is to extend its Transfer Scholarship Scheme and has offered three new Scholarships for the academic year 1957-58 to each of the Universities of Bristol Birmingham and Sheffield. The Word “Isotope”.-The Glasgow and West of Scotland Section of the Royal Institute of Chemistry is making arrangements for the erection of a plaque on the house at No. 11 University Gardens Glasgow W.2 to commemorate the coining within those walls about 1912 of the word isotope to fit Frederick Soddy’s radiochemical concept evolved in Glasgow.The house was then the home of Sir George Beilby the metallurgist who was Soddy’s father-in- law and is now the property of the University of Glasgow. The arrangements are being made with cordial support from the Chemistry Department of the University and affixing of the plaque will be by permission of the University. No public subscription is contemplated. Elections to the Fellowship.-52 Candidates for the Fellowship whose names were given in Pro- ceedings for May were elected on June 6th. Deaths.-We regret to announce the death of Professor A. P. Cheng (23.2.57) of Shanghai a Fellow of the Society since 1912; of Mr. Albert Ernest Judd (24.6.57) Senior Research and Development Chem- ist with Messrs.Erinoid Limited; of Dr. Alexander Killen Macbeth (29.5.57) who was until his retire- ment a few years ago Professor of Chemistry at the University of Adelaide South Australia; and of Mr. Thomas Workman Orr (28.4.57) associated for over 50 years with the Nitrate industry in Chile. Personal.-For reasons of health Dr. J. F. J. Dippy will now not take up his appointment as Principal of the Bradford College of Advanced Technology (Proceedings March p. 100). The Queen has appointed Dr. R. A. Raphael to be Regius Professor of Chemistry in the University of Glasgow in place of Professor D. H. R. Barton whose resignation will take effect on September 30th. Professor H. 7‘.S. Britton who is retiring from the Chair of Chemistry at the University of Exeter in October has been awarded a Leverhulme Research Fellowship to do further work on applications of physicochemical methods in inorganic chemistry.Mr. T. Kennaway has been appointed Director of Research of Messrs. Simon-Carves Ltd. Mr. W. E. Dick has been appointed Editor of Chemistry and Industry the weekly news organ of the Society of Chemical Industry. Mr. Dick who was formerly Editor of Discovery will succeed the present Editor Mrs. Bush on her retirement at the end of June. Dr. B. M. W. Trapnell Lecturer in inorganic and physical chemistry at Liverpool University has been appointed headmaster of Denstone College Staffs. The Perkin Centenary Trust has awarded the Perkin Centenary Fellowship to Mr.John Edward Bloor of Manchester for study in the Department of Chemistry Manchester College of Technology on the structure and properties of merocyanine dyes and related compounds. Perkin Centenary Scholarships have been awarded to Mr. James McCartney of Newtownards Northern Ireland tenable at Queen’s University Belfast; to Mr. Clive Milne of East Ardsley near Wakefield Yorkshire tenable at Bradford Technical College; and to Miss GabrieZle Grifin of Withington Man- Chester tenable at Manchester University. The Fourteenth Meeting of the European Federa- tion of Chemical Engineering and the Second Con- gress of the European Federation of Corrosion will be held on May 31st to June 8th 1958 in Brussels Belgium and Frankfurt Germany respectively.Enquiries should be addressed to the European Federation of Chemical Engineering Frankfurt (Main) 7 Germany. The German Society for Chemical Engineering (DECHEMA) Meeting and Twelfth Chemical En- gineering Exposition (ACHEMA) will take place at Frankfurt (Main) Germany on May 31st to June 8th 1958. Details may be obtained from the Deutsche Gesellschaft fur chemisches Apparatewesen Rhein- gau-Allee 25 Frankfurt (Main) Germany. The Seventh International Symposium on Com- bustion will take place on August 28th to September 3rd 1958 at the Royal Institution London and at Oxford University. The Symposium whose main theme will be “The Physics and Chemistry of Flames,” is the second to be held under the auspices of the new permanent society The Combustion Institute and is in collaboration with the Council of the Institute of Fuel.Further particulars may be obtained from the Chairman The Combustion Insti- tute Committee c/o The Institute of Fuel 18 Devonshire Street Portland Place London W. 1. The Third InternationaI Seaweed Symposium will be held in 1958 at University College Galway on the west coast of Ireland during the period August 13-19th. Further particulars may be obtained from the Secretariat University College Galway Ireland. The Fourth International Congress of Biochem- istry will be held in Vienna on September 1-7th OBITUARY PROCEEDINGS 1958 under the auspices of the International Union of Biochemistry. Further information can be ob- tained from Mr.0.Hoffmann-Ostenhof Wahringer- str. 42 Vienna IX. An International Conference on Scientific Infor- mation will take place in Washington D.C. during November 1958 under the sponsorship of the American Documentation Institute National Acad- emy of Sciences National Research Council and the National Science Foundation. Enquiries should be addressed to the Office of the Executive Secretary International Conference on Scientific Information NAS/NRC 2101 Constitution Avenue Washington 25 D.C. NOTICE MALCOLM PERCIVAL APPLEBEY 1884-1957 M. P. APPLEBEY was born at Brierley Hill Stafford- shire on May llth 1884. From Stourbridge Grammar School where he received his early educa- tion he was elected an (Open) Millard Scholar of Trinity College Oxford and was admitted on October 16th 1903.He read chemistry and took a “first” in the Final Honour School of Natural Science and was elected a Fereday Fellow of St. John’s College shortly after- wards. This Fellowship enabled him to continue research work combined with some teaching for a number of years. In this period the research which interested him most was the measurement of the osmotic pressure of concentrated solutions. He worked for some time in the private laboratory of the Earl of Berkeley at Boar’s Hill. In the war of 1914-1918 he was largely engaged on work for the Ministry of Munitions. In 1919 he was elected an official Fellow of the College and continued as Tutor in chemistry until he left Oxford in 1928.Those who were fortunate enough to be among his pupils in these post-war years retain the liveliest and happiest memories of him. He commanded respect and affection and his teaching was an intellectual delight. He worked very hard on his own subject and yet managed to find time to take a wide interest in College affairs. He lectured regularly on inorganic chemistry and the large Museum Lecture Room was always filled throughout his two-year course. His lectures were a mode1 of their kind. They were pre- pared with great care and the experiments performed had been meticulously rehearsed and timed before- hand. A subject which might have degenerated into a tedious recital of reactions and resulting com- pounds became alive and stimulating through a judicious mixture with the more general problems of physical chemistry physics and thermodynamics.The teaching of science at Oxford and chemistry in particular which had fallen to a low ebb twenty years before had made an astonishing recovery owing to the efforts of men like Nagel Tizard Sidgwick and Hartley. Applebey was a worthy colleague and follower of these. Applebey also found time to continue his own research and a visitor late at night to the College Laboratory at Jesus where during the day he was a Demonstrator would often find him quietly at work. Here too as a result of his interests in the hypo- chlorites he did some work of industrial importance on the problem of stabilisation. This brought him into contact with the United Alkali Company and was I think the first of his connections with the chemical industry of the United Kingdom.But it is as a private College Tutor that his pupils will always remember him. The hour or two one evening a week in his rooms at St. John’s must live in all their memories. His facility for encouraging individual interests his insistence on reference to original papers to the exclusion of text books brought out to the full any spirit of original enquiry which they possessed. Many of his pupils too must have been profoundly influenced in their later life by Applebey’s keen interest in the philosophy of JULY 1957 scientific thought and the application over wide fields of the principles of scientific method.In 1928 Applebey left Oxford to go to the I.C.I. Division at Billingham as Research Manager. At that time the Billingham factory was in a phase of rapid expansion but within three years the “great depres- sion” of the thirties with its disastrous effect on the agricultural industry and on fertiliser manufacture in particular had struck a cruel blow at the hopes and plans of those in charge. Drastic reorganisation and the re-orientation of much research effort was necessary. So Applebey soon after leaving the academic calm of Oxford was faced with formidable problems of administration and research direction. Among the staff at Billingham were a number of his former pupils; some in the Research Department and others engaged in production work or the planning of new developments.Encouraged by them it was not long before Applebey took a wide interest in the affairs of the Division and within a few years the scope and sweep of research was substantially widened. Primarily a manufacturing unit for the production of ammonia for fertiliser purposes Billingham now not only undertook the production of industrial nitrogen compounds and methanol but by entry into the field of hydrogenation of coal and creosote laid the foundations of the production by high-pressure synthesis of a whole range of aliphatic compounds based on coal creosote and later oil. With all this work to interest him Applebey never lost touch with the academic world. He soon became a Governor of two of the local Grammar Schools and it was not long before his contact with Durham University was forged into a strong link which was to last for the rest of his life.In 1937 he became Chairman of Council for the Durham Division of the University-and a most admirable Chairman he proved to be. In 1945 when he retired from Imperial Chemical Industries Limited he devoted the whole of his time to the affairs of the University and soon went to live in Durham itself. Just as his house in Museum Road was always open to his undergraduate friends in the Oxford days so his house in South Street Durham became a centre of the social life of Durham University for graduate and undergraduate alike. This combined with the admirable administrative work he did and his interest in all the activities of the colleges did much to weld them into a corporate whole and advance still further the status of the University in the outside world.He died after a lengthy illness on January 7th and his friends will long cherish his memory. J. L.S. STEEL. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings. Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Allen John Michael BSc. 26 Burniston Road Hull Yorks. Blake William Edward B.Sc. 64 Holt Drive Lough- borough Leks.Boone James L. B.S. Ph.D. 663 W. 34th Street Apart- ment 301 Los Angeles 7 California. Brasch Donald James B.Sc. M.Sc. 28 Hamilton Street Kingston Ontario Canada. Clark Robin Jon Hawes B.Sc. 16 Huntsbury Avenue St. Martins Christchurch S.E.2 New Zealand. Delpierre Georges Robert. 201 Milner Road South Claremont C.P. Union of South Africa. Dignum George B.Sc. 30 Church Road Northwich Cheshire. Dorer Frederic Edmund A.B. M.S. Department of Bio-chemistry New York State University College of Medicine 450 Clarkson Avenue Brooklyn 3 New York. Dutton John Varley B.Sc. A.R.I.C. 1 Newcastle Court Newcastle Circus The Park Nottingham. George Manapurathu Verghese M.Sc. Ph.D. Depart- ment of Chemistry University of Toronto Toronto-5 Canada.Goehring John Brown B.S. 951 Indian Rocks Road Belleair Clearwater Florida U.S.A. Habib Muhammad Saleem M.Sc. Chemistry Depart- ment Birkbeck College Malet Street London W.C.l. Jones Harry Robert B.Sc. F.R.I.C. 46 Croft Avenue Bromborough Cheshire. McKenzie Ian Grant B.Sc. Ph.D. A.R.I.C. 17 Hillary Road Eastham Wirral Cheshire. Rippie Wallace Larimer A.B. 21 1 Noyes Laboratory of Chemistry University of Illinois Urbana Illinois U.S.A. Robbins John B-Sc. D.Phi1. 12 Wake Green Road Moseley Birmingham 13. Sekera Ales D.Sc. D.Pharm. Bulharska 48 Brno 12 Czechoslovakia. Truce William Everett Ph.D. Department of Chemistry, Purdue University Lafayette Indiana U.S.A. Vossius Volker Dip.Chem. Dr.rer.Nat. 56 Wendell Street Cambridge 38 Massachusetts U.S.A.ADDITIONS TO THE LIBRARY Encyclopedia of chemistry. Edited by G. L. Clark. Pp. 1037. Reinhold Publ. Cow. New York. 1957. Biographisch-literarischesHandworterbuch der exakten Naturwissenschaften. J. C. Poggendorff. Vol. VIIa. Part 2 F-K. R. Zaunick and H. SaliC. Pp. 384.Akademie- Verlag. Berlin. 1957. Imperial College Inaugural Lectures 1955-56. Pp. 21 8. Imperial College of Science and Technology. London. 1957. (Presented by Imperial College.) Chemistry in the service of man. A. Findlay. 8th Edn. Pp. 326. Longmans Green & Co. 1957. Safety in the chemical laboratory. H. A. J. Pieters and J. W. Creyghton. 2nd Edn. Pp. 305. Butterworths Scientific Publ. London. 1957. Lecture experiments in chemistry.G.Fowles. 4th Edn. Pp. 629. G. Bell & Sons Ltd. London. 1957. Physical chemistry. E. A. Moelwyn-Hughes. Pp. 1295. Pergamon Press. London. 1957. (Presented by the publishers.) La chimie nucldaire et ses applications. M. Haissinsky. Pp. 651. Masson & Cie. Paris. 1957. (Presented by the publishers.) Quantum mechanics. H. A. Kramers. Pp. 496. North- Hdland Publ. Co. Amsterdam. 1957. Crystal structures. R. G. Wyckoff. Vol. 11. Chapters XI and XII. Interscience Publ. Inc. New York. 1957. Thermodynamics :an advanced treatment for chemists and physicists. E. A. Guggenheim. 3rd Edn. Pp. 476. North-Holland Publ. Co. Amsterdam. 1957. Thermodynamic properties of the elements. (Tabulated values of the heat capacity heat content entropy and free energy function of the solid liquid and gas states of the first 92 elements for the temperature range 298” to 3,000” K.) Compiled by D.R. Stull and G. C. Sinke. Advances in Chemistry Series. No. 18. Pp. 234. American Chemical Society. Washington. 1956. Chimie organique gCnCrale. J. Vhe. Pp. 349. Masson & Cie. Paris. 1957. (Presented by the publishers.) Problems in theoretical organic chemistry. F. G. Arndt. Sponsored by the Pennsylvania State University (28th Annual Priestley Lectures). Pp. 57. Pensylvania State University. 1954. Organic synthesis. 2 vols. V. Migrdichian. Pp. 1822. Reinhold Publ. Corp. New York. 1957. Synthetic methods of organic chemistry. W. Theil- heimer. Yearbook. Vol. 11. Pp. 494. S. Karger. Basle.1957. E. Gildermeister and F. Hoffmann’s “Die atherischen ole.” 4th Edn. Vol. IV. W. Treibs and K. Bournot. Akademie-Verlag. Berlin. 1956. Heterocyclic compounds. Edited by R. C. Elderfield. Vol. VI. Six-membered heterocycles containing two hetero atoms and their benzo derivatives. 14 contributors. Pp. 753. John Wiley & Sons Inc. New York. 1957. First European Symposium on Vitamin BIZ,Hamburg. Pp. 576. Edited by H. C. Heinrich. Ferdinand Enke Verlag. Stuttgart. 1957. The structure of nucleic acids and their r61e in protein synthesis a symposium held in London 1956. Edited by E. M. Crook. Biochemical Society Symposia No. 14. Pp. 74. Cambridge University Press. 1957. Progress in biophysics and biophysical chemistry. Edited by J.A. V. Butler and B. Katz. Vol. VII. Pp.362. Pergamon Press. London. 1957. (Presented by J. A. V. Butler.) Biological polymers. P. Doty. Sponsored by Pennsylvania State University (29th Annual Priestley Lectures). Pp. 62. Pennsylvania State University. 1955. Fundamentals of immunology. W. C. Boyd. 3rd Edn. Pp. 776. Interscience Publ. Inc. New York. 1956. Lectures in immunochemistry. M. Heidelberger. Pp. 150. Academic Press. New York. 1956. British Pharmaceutical Codex 1954 with supplement 1957. Pp. 124. Pharmaceutical Press. London. 1957. Mathematics and statistics for use in pharmacy, biology and chemistry. L. Saunders and R. Fleming. Pp. 257. Pharmaceutical Press. London. 1957. (Presented by L. Saunders.) Chromatography a review of principles and applica- tions.E. and M. Lederer. 2nd Edn. Pp. 711. Elsevier Publ. Co. Amsterdam. 1957. Fusion methods in chemical microscopy. W. C. McCrone Jr. Pp. 307. Interscience Publ. Inc. New York. 1957. Official methods of analysis (1957) of the Society of Leather Trades’ Chemists. 3rd Edn. h.200. Society of Leather Trades’ Chemists. Croydon. 1957. Mises au point de chimie analytique pure et appliquk et d’analyse bromatologique. Edited by J. A. Gautier. 4th series. Pp. 209. Masson & Cie. Paris. 1956. (Presented by the publishers.) Handbuch der analytischen Chemie. Edited by W. Fresenius and G. Jander. Part 3. Quantitative Analyse. Vol. 5a alpha. Elemente der funften Hauptgruppe (Stickstoff). W. Leithe. Pp. 244. Springer-Verlag. Berlin.1957. Chemical engineering practice. Edited by H. W. Cremer. Vol. 111. Solid systems. 12 collaborators. Pp. 534. Butterworths Scientific Publ. London. 1957. (Presented by H. W. Cremer.) Chemistry in the metallurgy of iron and steel. J. Chipman. Sponsored by the Pennsylvania State Univer- sity (31st Annual Priestley Lectures). Pp. 95. Penn- sylvania State University. 1957. Extraction and refining of the rarer metals proceedings of a symposium arranged by the Institution of Mining and Metallurgy London 1956. Pp. 444. Institution of Mining and Metallurgy. London. 1957. Varnish manufacture and plant. H. W. Chatfield. 2nd Edn. Pp. 443. Leonard Hill (Books) Ltd. London. 1957. Chemistry of lithography. P. J. Hartsuch. Pp. 254. Lithographic Technical Foundation.New York. 1952. Particulate clouds dusts smokes and mists. H. L. Green and W. R. Lane. Pp. 425. E. & F. N. Spon Ltd. London. 1957. (Presented by the publishers.) Air and water pollution the position in Europe and in the United States. (Project Nos. 136 and 145.) Pp. 218. Organisation for European Economic Co-operation. Paris. 1957. (Presented by the publishers.) Aspects of river pollution. L. Klein. Pp. 621. Butterworths Scientific Publ. London. 1957. (Presented by Mr. Cremer.) Disposal of sewage and other water-borne wastes. K. Imhoff W. J. Muller and D. K. B. Thistlethwayte. Pp. 347. Butterworths Scientific Publ. London. 1956. Methods of chemical analysis as applied to sewage and sewage effluents. 2nd Edn. Pp. 96. H.M.S.O. London. 1956.

ISSN:0369-8718    

DOI:10.1039/PS9570000185

出版商:RSC    

年代:1957

数据来源: RSC