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Proceedings of the Chemical Society. December 1963 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue December,
1963,
Page 357-392
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY DECEMBER 1963 CHEMISTRY AT CAMBRIDGE FROM 1901 TO 1910 By A. J. BERRY and E. A. MOELWYN-HUGHES PROFESSOR has directed our attention to NORRISH many interesting aspects of the study of chemistry in Cambridge during the first decade of the present century and has suggested that some of these should be more widely known. For this purpose he has placed the minute book of the Cambridge University Chemical Club from February 1901 to December 1910 in our hands. Its contents are full of interest in themselves and enable one to compare and contrast the teaching and research work done by Cambridge chemists during the first decade of this century with their present day activities. The origin of the Club is obscure.It had certainly been in abeyance for many years before its vigorous revival in 1901 of which the details are to be described later. The average attendance at its meet- ings was about thirty and approximately double that number when joint meetings were held with the Cavendish Physical Society. Its finances were on a diminutive scale. In the academic year 1902-1903 for example the balance sheet amounted to fll 17s. 5d. of which 5s. is entered opposite the word “lantern” and 21 0s. 8d. opposite the entry “tobacco.” Against this modest background there appear among the Club’s members and those who addressed them many notable men of science Prof. H. E. Armstrong Prof. H. B. Baker Sir James Dewar Dr. H. J. H. Fenton Sir William Hardy Mr.C. T. Heycock Sir Frederick Gowland Hopkins Mr. H. 0. Jones Mr. F. H. Neville Sir William Pope Sir Owen Richardson Sir J. J. Thomson and Sir William Dampier. The vast range of topics dis- cussed include absorption spectra (line and band) catalysis chemistry of proteids,” enzyme action metal carbonyls optical activity phosphorescence photosynthesis the position of tellurium in the periodic table radioactivity stereochemistry struc- ture of the atom tautomerism and the theory of colour. It is clear that liaison between physicists chemists and biochemists was closer then than it is or can reasonably be expected to be to-day. It is also clear that those who laboured sixty years ago to unravel abstruse problems in chemistry and physics came extraordinarily near to the modern views though differently expressed.The Revival of the Chemical Club.-The Chemical Club’s revival was a consequence of a circular issued by R. H. Adie. A. Hutchinson (afterwards Master of Pembroke College) and W. T. N. Spivey. A pre- liminary meeting was held in the rooms of T. B. Wood on February 13th 1901 “to discuss the desirability of reviving the old Chemical Club.” Altogether seventeen persons were present including G. Barger (later Professor of Medical Chemistry in Edinburgh University and afterwards Professor of Chemistry at Glasgow University) R. S. Morrell H. Ramage 0. W. Richardson W. T. N. Spivey (Demonstrator to the Jacksonian Professor) and H. 0. Jones (afterwards Jacksonian Demonstrator).It was unanimously agreed to revive the old Chemical Club. Other business such as the objects of the revived Club and the appointment of Secretaries was duly transacted. It was agreed to have two Secretaries-a Senior and a Junior. Spivey was ap- * The term “proteids” is retained instead of the modern term “proteins” for obvious historical reasons. 357 pointed as Senior Secretary. It was the regular practice to elect a Chairman by proposal and vote at each meeting. Three meetings were regularly held in the Michaelmas and Lent Terms and one in the Easter Term. The Chemical Staflof the University.-The Staff of the University Chemical Laboratory up to the year 1908 consisted of G. D. Liveing (Professor of Chem- istry) J.Dewar (Jacksonian Professor of Natural Experimental Philosophy) W. J. Sell and H. J. H. Fenton (University Lecturers) F. W. Dootson (Demonstrator) J. E. Purvis (Assistant to the Pro- fessor of Chemistry) and H. 0. Jones (Jacksonian Demonstrator after 1901). In addition to the University Chemical Laboratory the following Colleges had their own laboratories- St. John’s (Adie) Gonville and Caius (Pattison Muir) Sidney Sussex (Neville) Downing (Jackson) Girton (Miss Thomas) and Newnham (Miss Freund). Although these laboratories were concerned primarily with teaching research work of importance was carried out in some of them notably on alloys by Heycock and Neville in Sidney Sussex College and in organic chemistry by S. Ruhemann in Gonville and Caius College.The position of S. Ruhemann was a very curious one. He came to Cambridge in the capacity of Demonstrator to the Jacksonian Professor mewar) with whom he had a violent quarrel which ended ultimately with Dewar obtaining permission from the Vice-chancellor to secure his dismissal. Public feeling in the University was however highly un- favourable to Dewar and eventually recognition was given to Ruhemann’s valuable work as a teacher and investigator in organic chemistry by the creation of a University Lectureship in that subject for him. Thus arose the extraordinary situation of a University Lecturer in Organic Chemistry excluded from the University Chemical Laboratory by the ill-natured behaviour of the Jacksonian Professor.The situation was saved by the authorities of Gonville and Caius College where M. M. Pattison Muir Praelector in Chemistry provided a special part of their laboratory for Ruhemann’s work. It should be added that Ruhemann achieved considerable success as a teacher and director of research in that laboratory. This situation continued until the year 1908 when W. J. Pope succeeded Liveing as Professor of Chem- istry and Ruhemann was readmitted to the Univer- sity Chemical Laboratory. In that year one or two College laboratories were closed and the others were closed within a few years afterwards. Work of considerable importance and of much chemical interest was also being carried on outside the University and College chemical laboratories.Particular mention should be made of the work of PROCEEDINGS F. Gowland Hopkins in biochemistry of W. C. Dampier Whetham in electrochemistry of J. Reynolds Green on plant biochemistry and of W. B. Hardy on colloids. Papers were read by all these men to the Chemical Club during the decade 1901-1910. Notes on Some of the Papers read to the Club.-Broadly speaking the papers which were read before the Club were of two kinds namely those on topics of current interest given by young graduates engaged in research work and those on subjects directly con- nected with research work carried out in the Uni- versity given by the senior people. Occasionally however it was customary to invite some distin- guished man of science from without to deliver a lecture on his own particular line of work.The first ordinary meeting of the Club was held in the University Chemical Laboratory on February 28th 1901. W. J. Sell presided and H. 0. Jones was appointed as Junior Secretary. A paper was read by H. J. H. Fenton entitled “Some Recent Investiga- tions,” which was followed by a discussion. There is no record as to the nature of the topics which Fenton presented to the Club. At a meeting of the Club on November 5th 1901 postponed from October 3lst fitting reference was made to the loss which the Club had sustained by the untimely death of Mr. Spivey. He had died as the result of an explosion when engaged in carrying out a preparation by Etard’s method. T. B. Wood succeeded Spivey as Senior Secretary.The papers which were read before the Club during the ten years 1901 to 1910 covered as we have seen a very wide range of chemical interests and it may be said that they reflect some of the most im- portant activities of those times and are therefore of historical importance. A modern reader would un- doubtedly regard them as “old fashioned,” but it must not be forgotten that some of the topics which were then discussed and later resolved represent permanent features of present day chemistry al- though doubtless viewed somewhat differently. It may be helpful to review the activities of the Club by considering the subjects which were discussed rather than by dealing with them in chronological order. Two papers were read on the atomic weight of tellurium one by A.Scott Director of the Davy- Faraday Research Laboratory of the Royal Institu- tion and formerly Demonstrator to the Jacksonian Professor and the other by H. B. Baker Student of Christ Church Oxford and later Professor at the Imperial College South Kensington. The atomic weight of this element had been a source of difficulty for some forty years because it was an apparent exception as regards its position in the Periodic Table with respect to that of iodine. The most DECEMBER 1963 reliable determinations of these atomic weights seemed to confirm this irregularity but most chemists doubted if really pure tellurium com-pounds had been prepared. Scott determined the ratio of iodine to silver using trimethyltellurium bromide (CH,),TeBr.His mean value for the atomic weight was 127.6. Scott’s paper which was read in 1902 was in the nature of a preliminary communication. Six years later (on May 18th 1908) Baker gave a very thorough account of his work carried out with the assistance of Bennett on material from widely different sources which had been purified with great care. By different methods he obtained a value for the atomic weight of 127.5. This was of great interest because Marck- wald had about that time obtained a value of 126.86 -very slightly lower than that of iodine. The accuracy of Baker’s result was however admitted by Marckwald afterwards. The inversion of tellurium and iodine as regards their positions in the Periodic Table was regarded at the time as an exception to the periodic regularity; but that was before the discovery of atomic numbers and isotopes after which the apparent anomaly disappeared completely.Alloys were a prominent subject of research by Heycock and Neville over a number of years. Heycock was a very gifted experimentalist but no theorist. Neville was a mathematician who became interested in heterogeneous equilibria as a result of his studies of the works of Willard Gibbs and their experimental applications by Roozeboom. Neville read a paper entitled “Intermetallic Solution and Alloys,” which was illustrated by lantern slides. At a later meeting Heycock read a paper on the copper- tin alloys. He explained that the relations were extremely complicated which he discussed with diagrams of the “liquidus” and “solidus” curves and drew attention to the changes which take place after solidification.This he did by showing photographs of microsections taken from ingots chilled at selected temperatures and etched by ferric chloride. These have been described as some of the finest micro- photographs ever produced. The equilibrium dia- gram showed the existence of the compound Cu,Sn. At a subsequent meeting of the Club W. G. Fearn-sides Demonstrator of Petrology read a paper entitled “Structural Analogies between Alloys and Ingeneous Rocks.” In this paper he adverted to Heycock and Neville’s work on the copper-tin series of alloys. A number of papers were read on subjects which might be described as belonging to “general” chem- istry.W. C. D. Whetham on November 3rd 1904 read a valuable paper entitled “Thermodynamics and Molecular Theory.” He indicated that it was chiefly historical accident which caused force and momentum to appear simpler and more important than work and energy and thereby delayed the acceptance of the latter. He claimed that force in mechanics is represented in chemistry by molecular theory. Force and momentum were Newton’s means of study of natural phenomena. Huygen’s approach was by means of energy and is represented by thermodynamics. But the conceptions of momentum and vis viva (kinetic energy) are nevertheless related. It was in 1904 that Ostwald delivered the Faraday Lecture before the Chemical Society in which he claimed that the fundamental laws of chemistry could be derived from thermodynamics and without the aid of the atomic theory.Paxt of Whetham’s paper was devoted to a discussion of Ostwald’s ideas. It should be noted that on more than one occasion Ostwald had given expression to his “dis- like” of mechanical theories and particularly to the kinetic theory of gases. Whether Ostwald’s claims to have established the fundamentals of chemical theory on thermodynamics without an atomic theory be admitted or not there was no question that the “reality” of atoms and molecules was demonstrated conclusively as the result of investigations of radio- active phenomena and the properties of colloidal solutions.In any case most physical and almost all chemical phenomena would be very difficult to understand without assuming a discontinuous structure of matter. 11. J. H. Fenton gave a paper on Colloids which he dealt with historically from the time of Graham and afterwards discussed the flocculating action of electrolytes on colloidal solutions discovered inde- pendently by several investigators notably by W. B. Hardy (Lecturer on Physiology). The flocculating power of an ion is a function of its valency; the charge on the ion is always of opposite sign to that on the colloidal particles. It was recognised that the relative coagulative powers of univalent bivalent and tervalent ions are approximately in the ratios 1:30 :1650. Fenton also discussed the classification of colloids viz.as suspensoids and emulsoids and went on to consider the nature of adsorption products. W. J. Pope (afterwards Professor of Chemistry 1908-1939) gave a paper on the “Nature of Valency.” Pope was accompanied by W. Barlow- a well-known crystallographer who collaborated with him. The Chair on this occasion was taken by the Cavendish Professor J. J. Thomson. The Barlow- Pope theory of valency was founded on crystallo- graphic ideas in which molecules were regarded as similar to closely packed assemblages of spheres of atoms. Valency was given volume significance-thus a sphere of unit volume corresponds to a univalent element a sphere of double the unit volume to a bi- valent element and so on.The valency volume was regarded as being constant in a series of related compounds. Although great interest was aroused by the Barlow-Pope theory particularly in the way of emphasising the importance of crystallography to chemists it was soon regarded as imperfect and after a few years was abandoned altogether very largely as a result of criticisms by T. V. Barker of Oxford. One paper was given by the Jacksonian Professor J. Dewar on low temperature research. This dealt with the properties of liquid oxygen and nitrogen. He showed experimentally that air could be liquefied by means of boiling oxygen under atmospheric pressure. He dealt in some detail with the differences between the two elements in the liquid state. Thus when evaporated under reduced pressure nitrogen solidi- fied but under these conditions oxygen remained liquid.Other physical properties notably the mag- netic properties of liquid oxygen and those of other kinds of matter were demonstrated. He also demon- strated the use of charcoal cooled by liquid air to the production of high vacua. It may be remarked that Dewar did very little if any low temperature re- search work in Cambridge. Practically all of his work was done at the Royal Institution. In earlier years he worked jointly with Liveing on spectroscopy. On May llth 1905 the Cavendish Professor J. J. Thomson read a paper on the “Structure of the Atom.” He dealt with the conditions of stability of an atom regarded as consisting of a uniform sphere of positive electricity with negatively charged cor- puscles (electrons) within it.He illustrated these con- ditions experimentally by the use of Mayer’s floating magnets-little vertical magnets afloat on water by corks and drawn together by a large magnetic pole placed above them. In this way the magnets assume various patterns according to their number and as the numbers are increased similar patterns are found to be repeated at various intervals. This illustrates in a general way the phenomenon of periodicity-the recurrence of similar elements when they are arranged in the order of ascending atomic weights. Similar conditions are applicable to the gradual change in electrochemical character-a gradual change from electropositive to electronegative followed by an abrupt return to electropositive.It may be noted that Thonison’s conception of atoms was founded on the idea of the electrons being dis- tributed within a uniform sphere of positive electri- fication. The later idea of the positive electricity being concentrated in a nucleus at the centre of the atom was introduced by Rutherford and Bohr. A paper was read on February 16th 1906 by 0. W. Richardson (later Sir Owen Richardson Yarrow Research Professor of Physics of the Royal Society) on atomic disintegration. He dealt with the different types of radiation given off from radio- PROCEEDINGS active substances and discussed the transformation of radium emanation into helium and the question of the origin of radium and of lead as the probable final product of radioactive change.On May 24th 1910 Sir J. J. Thomson discoursed on the “Origin of Spectra.” Sir Joseph Larmor occupied the Chair and Professor Newall was also present. The lecturer discussed the essential features of line spectra as distinct from those of band spectra. Line spectra are derived from atoms band spectra from molecules. He discussed the work of Zeeman and others (the effect of powerful magnetic fields on line spectra e.g. the resolution of single lines when the field is applied). “Colour and Constitution” formed the subject of an important paper given by Professor H. E. Armstrong. In this paper he elaborated his well-known views that colour is invariably associated with a quinonoid structure of the molecule and further that when a colourless substance assumes a colour by treatment with a reagent e.g.when a dissolved substance is colourless in acid and coloured in alkaline solution and vice versa this change is con-sidered as due to a reversible change from a benze-noid to a quinonoid structure. It should be added that many of the features of this theory of colour which Armstrong had propounded many years pre- viously have been regarded as fundamentally correct. Some of his elaborations of his theory are more questionable e.g. his “explanation” of the yellow colour of iodoform in terms of “residual affinity” of iodine leading to some sort of quinonoid constitu- tion arising from the unsaturated centres of the iodine atoms.Other papers in which questions of colour and constitution were raised were given by some of the younger graduates notably one by H. Bailes. He directed attention to the importance of the presence of double bonds first noted by Graebe and Lieber- mann and aIso groups known as chromophores and auxochromes by Witt. Much of the paper was con- cerned with work on absorption spectra notably that of Hantzsch and of Baly and Desch. From the wide survey of his subject Bailes was able to show that Armstrong’s views though modified in certain directions remained fundamentally unchanged. The subject of colour in minerals was discussed by A. Hutchinson. He stated that colour may be an inherent property or it may be an adventitious one.The latter may be subdivided according as the pro- perty is a physical effect due to structure e.g. as in opal or the colour may be due to minute particles or again it may be found where no particles can be discovered as in fluorspar (calcium fluoride). Colour may be due to traces of organic matter or it may be caused by traces of inorganic oxides e.g. Fe,03 DECEMBER 1963 Cr203 etc. Colour may be-varied or destroyed by heating. This may be due to actual destruction of organic matter or it may be due to dehydration. Some minerals exhibit fluorescence; indeed the terms opalescence and fluorescence were actually derived from experimental studies on these minerals. Minerals may be caused to exhibit fluorescence or phosphorescence by subjecting them in exhausted glass bulbs to cathode ray discharges.This was largely stadied by Crookes in connection with his investigations on the rare earths. It has been fairly well recognised chiefly as the result of studies on these phosphorescence spectra that “pure” sub-stances do not phosphoresce under the influence of the cathode ray discharge. Very small traces of im- purities will however produce brilliant fluorescence or phosphorescence under these conditions but it should be added that the “impurity” must be very intimately mixed with the main substance-the con-dition should be that of dilute solid solution. It may be noted that Crookes approached very closely to the modern theory of lattice defects or “holes” in otherwise perfect crystals.On February 18th 1904 Miss M. B. Thomas (Fellow and Lecturer of Girton College) delivered a paper entitled “Factors which determine the value of Optical Rotatory Power.” She introduced the subject with a brief sketch of the stereochemistry of carbon compounds and then illustrated the com- plexity of the subject in the way of obtaining com- parable results having regard to such variables as the wavelength of the light used the solvent and the temperature. The law of Oudemans (1 885) which deals with the molecular rotatory power-the specific rotatory power multiplied by the molecular weight- originally developed in a purely empirical way was discussed. This law is concerned with the effect of dilution on the rotatory power of electrolytes con- sisting of either metallic salts of optically active acids or of acids of optically active bases or as it would be stated nowadays of salts of which either the anion or the cation {but not both) are optically active.Next the lecturer dealt with subjects such as lactone forma- tion the presence of certain groups and the effect of various inorganic substances. Finally Guye’s hypo- thesis (asymmetry product) and the experimental work arising therefrom was discussed. A valuable paper entitled “Double Salts” was given by Miss Ida Freund (Lecturer at Newnham College). At the outset she distinguished between double salts complex single salts and isomorphous mixtures. The greater part of the paper was con- cerned with the study of double salts in terms of the phase rule associated particularly with van’t Hoff Roozeboom and Meyerhoffer including methods for determining transition points and transition intervals and the formation and decomposition of 361 racemates.Various aspects of organic research figure in papers read at meetings of the Club. Sell dealt with the chlorine derivatives of pyridine and Ruhemann delivered papers on subjects such as unsaturated ketonic compounds. Several papers of biochemical importance were also read. Reynolds Green de- livered a valuable paper entitled “Chemical Trans- formation in germinating Seeds.” He described his own investigations on the changes in the oil of germinating castor oil seeds. His results showed that disappearance of the oil was associated with the appearance of cane sugar while lecithin was formed at the same time A very interesting paper was given by J.Parkin on the formation of carbohydrates in the green plant. This was chiefly a description of joint work of G. Dixon and himself. He discussed the views of Sachs on the formation of starch in the leaf followed by a consideration of the work of Brown and Morris in which he criticised their analytical methods for mixed sugars. Parkin and Dixon worked on the snowdrop (Galanthus nivulis). The leaf of this plant never forms starch so the problem is simplified. Their conclu- sions agree with those of Brown and Morris that sucrose is first formed. At the same time they pointed out that other work favoured an older view that glucose is the first product.H. J. H. Fenton read an interesting paper entitled “Synthetic Sugars.” He dealt with Baeyer’s theory that formaldehyde is first formed by the carbon dioxide which the plant assimilates from the air and pointed out various objections to it. In particular he showed that the demonstration of the presence of formaldehyde by qualitative tests is no proof that photosynthesis takes place via this compound-it may very well arise as a by-product. Fenton also discussed methods for ascending and descending in the aldose sugars in- cluding the formation of a-acrose by the threefold polymerisation of glycollic aldehyde-a substance first prepared by himself and the transformation of aldohexoses into aldopentoses by oxidation.An important paper entitled “Recent Progress in the Chemistry of Proteids” was read by F. G. Hopkins (later Professor of Biochemistry). He opened his subject with a discussion of the scope and meaning of physiological chemistry and described some of the degradation products of proteids which had been obtained in crystalline conditions including tryptophane a-amino-/%indolepropionic acid iso- lated in 1901 by himself and S. W. Cole. He sug-gested that such crystalline nitrogenous substances formed by the digestion of proteids are absorbed from the alimentary canal and then recombined in different proportions to form the various proteids in the body. S. W. Cole read a paper on enzyme action.He PROCEEDINGS dealt with the differences between ordinary catalysts and enzymes including the work of Croft Hill on the reversibility of the reaction between maltose and glucose. He also described some of his own experi- ments on the effects of acids and salts on the action of ptyalin and invertin and discussed the results. A paper on chlorophyll was given by F. F. Blackman who discussed the chemistry of this sub- stance and of other leaf pigments. Gowland Hopkins who occupied the Chair on this occasion adverted to certain similarities between certain blood and leaf pigments e.g. between haemoglobin and chloro- phyll the former containing iron the latter magnesium. An interesting paper entitled “A New Case of Tautomerism,” was given by VV.J. Pope shortly after he had taken up the professorship. This was a discussion of some work by himself and J. Read (later Professor of Chemistry in the University of St. Andrews) on oxymethylene camphor. This substance dissolved in benzene or alcohol exhibits mutarota- tion but the compound readily forms derivatives with secondary bases such as monomethylaniline and these do not show any mutarotation. Three possible formulz for oxymethylene camphor had been suggested by Claisen of which only the two following need be considered C:CHOH C-CHO C@M( and CSH,~</I co C-OH Tautomerism is clearly possible between two such compounds. But if the substance is condensed with a secondary amine the resulting derivative will have lost the mobile hydrogen atom of the enolic form and therefore the reversible isomeric change is no longer possible and consequently mutarotation is prevented.Oxymethylene camphor was used in other researches in stereochemistry by Pope and Read. Of other papers on organic chemistry delivered before the Club mention should be made of one by H. 0.Jones on metal carbonyls. This paper was the outcome of work by himself and Dewar the Jacksonian Professor on various iron carbonyls. These compounds are more difficult to prepare than the nickel compound Ni(CO) and have the formulae Fe(CO) and Fe,(CO),. Their properties and reactions were discussed. Spectroscopic Research in Cambridge.-Liveing and Dewar for many years carried on investigations on chemical spectroscopy.Their publications were collected together in a large volume published by the Cambridge University Press entitled “Collected Papers on Spectroscopy” in 1915. This volume con- tains 78 papers being reprints of their publications between 1877 and 1902 chiefly in the Proceedings of The Royal Society and in those of the Cambridge Philosophical Society. Liveing was appointed to the Professorship of Chemistry in 1861 and Dewar was appointed to the Jacksonian Professorship in 1875. Having regard to these dates it has been surmised by some that Dewar inspired Liveing to enter upon spectroscopic re- search (as the &st publication was in 1877). Others have thought differently namely that the initiative was with Liveing.J. E. Purvis (Assistant to the Professor of Chem- istry) worked closely with Liveing for many years and afterwards carried out work on his own account on this subject. Some of his researches were con- cerned with the effect of powerful magnetic fields on the spectra of the elements and others with absorp- tion spectra of organic compounds. Liveing and Dewar never founded anything in the way of a “school of research” in spectroscopy and it may be doubted if they even wished to do so. There was nevertheless some postgraduate research in this subject. Thus H. Ramage received the research B.A. degree for spectroscopic studies. For many years ending in 1909 Liveing conducted a practical class in spectroscopy for candidates taking Part I1 of the Natural Sciences Tripos.The Cambridge School of Stereocheinistry.-The stereochemistry of nitrogen tervalent and quin- quevalent was a subject which for many years had received attention from numerous chemists e.g. Le Bel Hantzsch and Werner Wedekind and Pope. Two questions were of outstanding interest namely the disposition of the three valencies of the nitrogen atom-whether in one plane or not and the realisa- tion of optical isomerism in compounds of quin- quevalent nitrogen of the type NabcdX where a b c and d are univalent organic groups and X is a halogen. These questions were investigated in great detail by H. 0. Jones who was undoubtedly the founder of the Cambridge School of Stereochemistry. The Hantzsch-Werner theory according to which the isomerism of the benzaldoximes is stereochemical not structural involved the doctrine that the three valencies of the nitrogen atom are not in one plane.This led Jones in 1904 to attempt the resolution of compounds such as benzylphenylhydrazine. These experiments yielded no positive results. He was how- ever highly successful with his researches on the optical isomerism of compounds of quinquevalent nitrogen of the type NabcdX. The first successful resolution of a compound of this kind namely phenylbenzylallylmethylammoniumiodide was made in 1899 by Pope and Peachey who used camphor- sulphonic and also bromocamphorsulphonic acid for resolving the quaternary ammonium bases. The use of these strong acids was an important advance because previous investigators including Wedekind DECEMBER 1963 had failed to resolve these compounds.Jones em- ployed these acids in his work on the quaternary ammonium compounds. Although Pope and Peachey had effected the first successful resolution of salts of this type it does not appear that Pope entered upon questions of the con- figurations of these compounds which exhibit optical isomerism in consequence of the asymmetry of the nitrogen atom-at any rate not at that time. Jones prepared a number of compounds of the NabcdX type and resolved them successfully. After due con- sideration he abandoned a suggestion of a double tetrahedron due to Willgerodt in favour of a pyramidal one due to Bischoff.According to this idea the configuration of a quaternary ammonium salt of the type NabcdX is to be represented as a nitrogen atom within a square based pyramid having the four organic groups at the corners and the halogen atom at the apex. Jones continued his researches on this subject and built up a small though highly successful school of stereochemistry. Pope followed Liveing as Professor in 1908. He came to Cambridge as the leading authority on stereochemistry in this country and soon built up a really brilliant “school” of the subject. Four years later Jones was killed by a fall in the Alps and was succeeded by W.H. Mills as Demonstrator to the Jacksonian Professor. Mills was also a stereochemist and he too attracted numerous research pupils to this branch of chemistry.A passing reference may be made to an important theoretical advance due to Mills. He showed con- clusively that the square-based pyramidal configura- tion of these quaternary ammonium salts which are good electrolytes and therefore regarded as totally ionised could not be correct. In 1925 he showed that the optical isomerism is due to the tetrahedral cation Nabcd+ and not to the molecule NabcdX. CHEMICAL SOCETY MEETING THE following papers were read and discussed at a Symposium on Peptide Chemistry held in the Lecture Theatre Middlesex Hospital Medical School Cleveland Street London W.1 on Thursday October 24th 1963 at 2.15 p.m. Recent Achievements in the Synthesis of Biological& Active Peptides.By R. A. BOISSONNAS. THE methods used for the synthesis of peptides have been greatly improved during the last few years and a whole array of condensation reagents and of pro- tective groups is now available to the peptide chemist. Several biologically active peptides are already obtained more economically by total syn- thesis than by isolation from natural sources and a large number of synthetic analogues of these pep- tides differing from the natural compounds by small structural modifications have been prepared and biologically investigated. The field of the posterior pituitary hormones has been intensively studied for several representatives of this class of peptides occur in Nature. Some interesting conclusions upon the interactions between these hormones and their recep- tors have already been established and several syn- thetic analogues have proved to be more potent or more selective than the natural parent compounds.Even in the field of peptides exerting an action on the blood pressure like angiotensin bradykinin eledo- isin and their analogues some of the structurally modified peptides have been found to be biologically superior to the natural products. Progress has also been impressive with the ACTH-like peptides despite the difficulty brought about by the greater size of these compounds. Methods insuring a total avoidance of racemisation are indispensable for the synthesis of large peptides and this problem remains one of the most important in peptide chemistry.Studies of Glyceraldehyde 3-Phosphate Dehydro- genases. By IEUAN HARRIS. GLYCERALDEHYDE $PHOSPHATE DEHYDROGENASE OC-curs widely in Nature and has been isolated in pure crystalline form from such diverse sources as yeast and mammalian muscle (review articles1s2). In most biological systems the enzyme in the presence of nicotinamide adenine dinucleotide (NAD) and orthophosphate catalyses the reversible oxidation and phosphorylation of glyceraldehyde 3-phosphate to 1,3-diphosphogIyceric acid. The enzyme isolated from rabbit skeletal muscle has been reported to possess a molecular weight of from 118,OOO-138,OOO and contains approximately three moles of firmly-bound NAD per mole. It is capable of functioning as an esterase as well as a dehydrogenase and both types of reaction have been shown to involve the formation of intermediate acyl- enzyme compounds.The dehydrogenase and esterase activities are mutually exclusive and both are in- hibited by iodoacetic acid under conditions which lead to the disappearance of approximately three of the twelve titratable sulphydryl (-SH) groups which are present per mole (base on a molecular weight of 120,000) of active enzyme. These observations sug- Czok and Bucher Adv. Protein Chem. 1960,15 315. * Velick and Furfine in “The Enzymes,” ed. Boyer Lardy and Myrback Academic Press New York 1963 Vol. 7 p. 243. gested that the two enzymic activities are mediated by the same chemical groups and that their inhibi- tion by iodoacetic acid occurs as the result of a direct competition between inhibitor and substrate for the same “reactive sites” in the enzyme protein.The aim of the present work has been to seek positive chemical identification of the “reactive sites,” by isolation and characterisation of the pro- ducts formed by reaction of the enzyme with the inhibitor iodoacetic acid and the substrate p-nitro- phenylacetate respectively and to determine the sequence of amino-acid residues in the immediate environment of these “reactive sites” within the con- text of the primary structure of its constituent polypeptide chain( s). The results obtained3 have led to the identification of the “reactive sites” as the SH groups of three out of the twelve cysteines which occur in the enzyme protein.These particular cysteines react selectively with the iodoacetic [l-14C]acid and replacement of the -SH group by the negatively charged S-carboxy- methyl side-chain prevents substrates such as glycer- aldehyde 3-phosphate and g-nitrophenylacetate from being attached to the enzyme. Nevertheless in the absence of inhibitor the same three cysteines partici- pate in the formation of the [1-14C]-S-acetyl enzyme compound which is formed as an intermediate during the enzyme-catalysed hydrolysis of p-nitrophenyl- acetate. Moreover these reactive cysteines occur in the same unique octadecapeptide sequence of amino- acids in the enzyme protein. These results raised the possibility that the active form ofglyceraldehyde 3-phosphate dehydrogenase is composed of at least three identical polypeptide chains and further studies involving amino-acid and end-group analysis and the characterisation of pep- tide fragments produced by cleavage of the enzyme with trypsin support the view that the active mole- cule consists of three and possibly four identical polypeptide chains each with a molecule weight of approximately 35,000.Similar studies have been carried out with the enzyme isolated from yeast5 and these and other results concerning relationships between chemical structure and enzymic activity will be discussed. The Synthesis and Some Properties of Partially Synthetic Ribonucleases. By KLAUSHOFMANN. IN creating a wide spectrum of physiologically active compounds Nature frequently utilises variants of a common architectural principle.One of these is em- bodied in peptides. Indeed polypeptides of medium molecular weight are known which possess a wide PROCEEDINGS spectrum of physiological activity and such activity seems to depend on a specific arrangement of certain amino-acids. Investigations designed to elucidate the underlying structural features for functions of pep- tides is bound to contribute to understanding of fundamental principles of biology. Despite much effort in this direction one may predict that comprehension of the biochemical function of physiologically active polypeptides will not come from routine biological testing of structural analogues. The available test systems are too highly organised and the biochemistry which underlies the observable physiological effects is not understood.It was for these reasons that we selected the 5’-peptide- S-protein system of F. M. Richards and P. J. Vithayathi16 for a study of peptide-protein interaction. In this system a peptide of low molecular weight pep- tide (S-peptide) has the ability to combine in a highly specific manner with a protein (S-protein) to generate an active modified ribonuclease. S-Peptide and S-protein are fragments of ribonuclease obtained from the enzyme by controlled proteolysis with subtilisin. S-Peptide is lysyl-glutamyl-threonyl-alanyl-alanyl-alanyl-lysyl -phenylalanyl-glutamyl-arginyl-gluta-minyl -histidyl -methionyl -aspartyl -seryl -seryl-threonyl-seryl-alanyl-alanine.A series of peptides corresponding to sections of this sequence have been prepared and tested for ability to activate 5’-protein.The results of these experiments will be discussed and will be compared to results of structure-function studies in the peptide hormone series. It will be shown that only a section of S-peptide is required for activation of S-protein just as only a section of ACTH a-MSH and parathyroid hor- mone is required for biological activity. The hypo- thesis’ “that the mode of action of the peptide hormones may involve their combination with a receptor protein to create an active enzyme” will be discussed in the light of the above findings. Methods of Peptide Synthesis the Present Position.By H. N. RYDON. THEmethods currently available for the stepwise synthesis of peptides from their component amino- acids will be reviewed with special emphasis on (a) those methods which have proved to be most generally useful and (6) new methods which seem particularly promising. The factors influencing the choice of methods for the synthesis of a given peptide will be discussed and an attempt will be made to indicate what further improvements in methods are desirable. Harris. Meriwether. and Park Nature 1963 197 154. * Harris’and Perham; Biochem. J. 1963 in the press. 6 Perham and Harris J. Mol. Biol. 1963 in the press. Richards and Vithayathil J. Biol. Chem. 1956,234 1459. Hoffmann Brookhaven Symposia in Biology 1960 13 184. DECEMBER 1963 365 COMMUNICATIONS The Stabilisation of a Non-planac Benzene Nucleus in the Molecular Structure of n-Cyclopentadienylhexakistrifluoromethylbenzenerhodium By M.R. CHURCHILL and R. MASON* (INORGANIC LABORATORY COLLEGE S.W.7) CRYSTALLOGRAPHY IMPERIAL LONDON THEreaction of hexafluorobut-2-yne with transition- metal carbonyls has given a series of complexes con- taining a cyclic triiluoromethyl-substitutedligand.lV2 In both n-cyclopentadienyltetrakistrifluoromethyl-cycl~pentadienonecobalt~ and tricarbonyltetrakis-trifluoromethylcyclopentadienoneiron,4 the dienone is bonded to the metal via both o-and v-bonds this type of bonding being also present in the structures of n -cyclopentadienyl-1-phenylcyclopentadiene-cobalt5 and tricarbonyl-2,4,6-triphenyltroponeiron? n-Cyclopentadienylhexakistrifluoromethyl- benzenerhodium and v-c yclopen tadien yl te tra kis tri- fluoromethylcyclopentadienonerhodium are ob-tained in approximately equal yield by the reaction of hexa fluor o but-2- yne with dicarbonyl-n-cyclo-pentadienylrhodium.2 Crystals of the benzene complex are monoclinic with a = 9.48A b = 12.59 A c = 17.79 A /? = 114.8”; the space group is P2,lc (Cgh,No.14),2 = 4 pcalc. = 2.28 g.~m.-~ [pobs. (at 20”) 2-27 g.~m.-~). Patterson Fourier and least-squares analyses of 1622 independent reflexions have been used to determine the complete crystal structure the present reliability index after six cycles of least-squares refinement being 0.10. The molecular geometry is shown in the Figure and is similar to that expected from the infrared and nuclear magnetic resonance spectra.2 The rhodium ion is in an approximately octahedral environment the cyclopentadienyl ion being considered as a formal tridendate ligand.Only four atoms of the benzene nucleus are involved in bonding to the metal ion; C and C4 form o bonds a v bond from C&3 completing the metal co-ordination. The o-bonded atoms are at an average distance of 2.15 & 0.03 A from the rhodium the Rh-C2(C3) distance being 2-04 L-0.03 A. The remaining carbon atoms of the benzene nucleus C and c6,are 3-00A and 3.03 A from the metal. The benzene ring is “hinged” across C and C, the angle between the planes containing c, cz,c3,and c and c, c6 c, and c being 48 f2”.The non-co-ordinated double bond (C,-Cs> is 1-32 f0.05 A i.e. 0.13 A shorter than that in- volved in n-bonding to the rhodium. The distance of the rhodium from the centre of cyclopentadienyl ring is 1.83 A while that to the centre of the bonded “diene” is 1.68 A. This structure appears to represent the first unequivocal example of localised bonding from a benzene system to a transition-metal ion since bond- ing in dibenzenechromium remains contro~ersial.~ The formation of localised bonds from the hexakis- trifluoromethylbenzene ligand is shown by the con- formation of the ring and the fact that as in the dienone complexes the distance between the a-bond- ing carbon atoms C1 and C (2.56 A) is much shorter than would be expected for the free ligand (2.80 A).Localised bonding is only favoured from cyclic ligands with low resonance energies resulting from the highly electronegative substituents around the ring. As in the case of additions to aromatic hydro- carbons a-bonding in the present complex can be directly related to the electron localisation energies at the respective carbon atoms.8 It has been suggesteds that hexakistrifluoromethyl- benzene is itself non-planar as a result of steric inter- *Present address Department of Chemistry The University Sheffield 10. Boston Sharp and Wilkinson J. 1962 3488. a Dickson and Wilkinson Chem. and Inn. 1963 1432. Gerloch and Mason Proc. Roy. SOC.,in the press. Bailey Gerloch and Mason Nature in the press.Churchill and Mason Proc. Chem. SOC..1963 112. (I Smith and Dahl J. Amer. Chem. SOC.,1962,84 1743. Cotton Dollase and Wood J. Amer. Chem. SOC.,1963 85 1543. Churchill Gerloch and Mason Proc. Chem. Soc. 1963 107. * Harris Harder and Sausen J. Org. Chem. 1960,25 633. actions between adjacent CF groups. The present ring conformation would not markedly modify such steric effects which could be reduced most efficiently by alternate CF3 groups being symmetrically dis- placed above and below the mean plane of the benzene ring; this is not observed. The small difference in van der Waals radius between hydrogen and fluorine and the fact that the methyl groups in hexamethylbenzene are freely rotating at room temperature also suggest that the deviations from PROCEEDINGS planarity of hexakistrifluoromethylbenzenemust be quite small.We are grateful to Dr. R. S. Dickson and Professor G. Wilkinson for a sample of the complex to Mr. 0. S. Mills and Dr. J. S. Rollett for copies of their computer programmes for the Mercury computer and to the Department of Scientific and Industrial Research for a Research Studentship (M.R.C.). (Received October 8th 1963.) The trans-Effect in Octahedral Rhodium(Ir1) Complexes By F. BASOLO and A. J. PoG E. J. BOUNSALL (CHEMISTRY NORTHWESTERN EVANSTON AND DEPARTMENT UNIVERSITY ILLINOIS INORGANIC CHEMISTRY LABORATORIES IMPERIAL COLLEGE LONDON s.w.7) IN order to obtain unambiguous quantitative estimates of the kinetic trans-effect1 in octahedral complexes we have studied the reactions of trans- Rh en2X2+ (X = halide en = ethylenediamine) with other halide ions.The rates are independent of the nature and concentration of the incoming halide and involve no stereochemical change. They are not photosensitive and can easily be followed spectro- photometrically. The reactions CI-Br-Rh en,CII+ -+ Rh en,Cl,+ and Rh en,Brl+ -+ Rh en,Br,+ Rh(m) which are known to be labile is a further possibility. The kinetic parameters for the non-catalytic reactions are given in the Table. The rate-constants show that after allowance for purely statistical factors the trans-effect of I- is 850 times that of C1- when a Rh-Cl bond is being broken and 97 times that of Br- when a Rh-Br bond is being broken.The trans-effect of Br,- relative to C1- cannot be assumed to be 850/97 = 8.8 because the bond being broken is different in the two cases. In terms of AH$ the trans-effect of 1-is even larger. z Kinetic data for the reactions trans-Rh en,XY 4Rh en,= at 50’ X Y 2 10% (set?) AH (kcal. mole-l) AS (cal. mole-I deg.3 c1- Cl- I- 1-6* 23.8 -13.0 I- c1- I- 683 14.0 -31.8 Br- Br- I- 8.5* 20.0 -22.0 I- Br- I- 412 16.1 -26.3 1- I- Cl- Br and CN- 115 26-2 +2 * Obtained by extrapolation from higher temperatures. gave sigmoid rate curves and were catalysed by The order of reactivity of X in Rh en I X+ is Cl > hydrazine and more effectively by hydrazine-Rh(rI1) Br > I. Again the effect is larger in terms of dHz and mixtures.They are also inhibited by IrCl?- a*+,the order suggests that partial solvation of X- as it is removed from the complex plays a larger part in and Fe3+. The other reactions studied were also catalysed in this way but without added catalyst they were not inhibited by IrC162- and we therefore consider them to be non-catalytic. The nature of the catalytic reactions suggests Rh(n) catalysis [cf. Pt(m) catalysis of reactions of Pt(rv) complexes2] or reduc- tion to Rh(1) and reaction via a Rh(1)-Rh(n1) bridged intermediate [cf. Pt(n) catalysis of reactions of Pt(rv) complexes3]. The intervention of hydride species of determining AH$ than does the energy needed to stretch the Rh-X bond. The fact that of the di- halogeno-complexes Rh en212+ reacts most rapidly but has the highest AH$ shows again the necessity for temperature variation studies.We are grateful to the U.S.A.E.C. for partial support of this work. (Received September 12th 1963.) Basolo and Pearson Progr. Znorg. Chem. 1962 4 381. Rich and Taube J. Amer. Chem. Soc. 1954 76 2608. Basolo Wilks Pearson and Wilkins J. Znorg. Nuclear Chem. 1958 6 161. * Gillard and Wilkinson J. 1963 3594. DECEMBER 1963 367 The Mechanism of the Removal of the N-Benzyloxycarbonyl Group by the Action of Hydrogen Bromide By R. B. HOMER R. B. MOODIE,and H. N. RYDON (WASHINGTON THEUNIVERSITY, SINGER LABORATORIES EXETER) TREATMENT with solutions of hydrogen bromide in + kl anhydrous acetic acid is widely usedl for the removal R.CH2.0*COH.NH*CH,*COzEt -of the N-benzyloxycarbonyl group2 in peptide syn- R.6H2 + CO + HzNCH,-C02Et .. . (2) theses but the mechanism of this important reaction + k2 has not been fully investigated. We now report a RCH2.0.COH.NHCH2C02Et+ Br-kinetic and mechanistic study using the model sub- strates N-benzyloxycarbonylglycineethyl ester (I ;R RCH2Br + C02 + H2N-CH2C02Et. . . (3) = Ph) and its p-nitro-derivative (I; R = Concurrent operation of the two mechanisms would p-NO,.C,H,); the reactions have also been studied lead to an observed first-order rate constant by using solutions of sulphuric acid in anhydrous kobs = Rate/cs = Ka,+ys(kify23 4-~ZCB,-~B~-/Y~$) acetic acid. where the subscript s refers to the substrate and The reactions were followed by colorimetric y2$ and y3$ are the activity coefficients of the estimation of the liberated amino-group with nin- transition states of reactions (2) and (3).h~drin.~ Good first-order plots were obtained up to In HzS04-AcOH the marked dependence of kobs at least 60% reaction. Some selected results are on acidity compared with the protonation equilibria given in the Table. of structurally similar N-methyl-amides is con-First-order rate constants kobs for removal of the arybxycarbonyl group porn N-benzyioxycarbonyi- and N-p-nitrobenzyioxycarbonyi-glycineethyl ester. Solvent anhydrous acetic acid at 50". Substrate concentration 1.14 X 10-3~. Concn. (molesfl.) io5k0bS(sec.-l) HBr H2S04 Et4N)Br-Et4N)HS04-(I; R = Ph) (I ;R = NO,*CBHa) 0 0.138 0 0 0.318 -0 0.455 0 0 2.46 -0 0.455 0 0.091 2-25 -1 0 0.455 0-09 0 41.2 -0 0.455 0.0228 0 17.4 -0 0.455 0.0228 0.0682 9-2 -0 0.864 0 0 10.28 0.01* 0 4.52 0 0 341.0 0.14 0-031 0 0 0 14.7 1 a02 0.077 0 0 0 43-7 3.60 0.077 0 0 0.0455 21.6 -0.154 0 0 0 103.4 8.58 5.25 0 0 0 541-0t 28.0t 0 0 0.091 0 O* -* Approximate values.t at 20". The results suggest that in H2S04-AcOH the A-1 sistent with the A-1 mechanism if benzylcarbonium mechanism4 (equations 1 and 2) is operative whereas ion separation has proceeded far enough in the transi- the A-2 mechanism (equations 1 and 3) predominates tion state to release hydrogen-bonded solvent mole- in HBr-AcOH cules thus leading to a decrease of y2S and a con-+ K comitant increase in kobs with increasing acidity. R.CH,.O.CO.NH.CH,.CO,Et + H+ + The two-thousand-fold decrease in kobs resulting (1) + from p-nitration of the substrate is likewise con- RCH2*O*COH.NHCH2-C02Et.. . (1) sistent with the A-1 mechanism.6 Addition of tetra- * Anderson Blodinger and Welcher J. Amer. Chem. SOC.,1952 74 5309; Ben-Ishai and Berger J. Org. Chem. * Bergmann and Zervas Ber. 1932 65 1192. 1952,17 1564; 1954,19 62. Rosen Arch. Biochem. Biophys. 1957 67 10. Long and Paul Chem. Rev. 1957,57,935. Homer Moodie and Rydon unpublished results. Streitwieser Chem. Rev. 1956 56 571. PROCEEDINGS ethylammonium hydrogen sulphate has little effect on the rate but the bromide increases the rate to an extent too great to be attributed solely to the result- ing increase in acidity;5 this suggests the incursion of the A-2 mechanism in the presence of bromide ion and is supported by the large and negative neutral salt effect and the slight dependence of rate on acidity since y~~/y~$decrease with in- should creasing electrolyte concentration.Furthermore the residual rate after subtraction of the estimated A-1 contribution shows an approximately first-order dependence on bromide-ion concentration. Cf. Weygand and Hunger Chem. Ber. 1962,95 1. In HBr-AcOH the predominance of the A-2 mechanism is shown by the large negative neutral salt effect and the lesser dependence as compared with H,SO,-AcOH on acidity and is confirmed by the small effect of p-nitration of the substrate which causes only a twelve-fold decrease in kobs.The application of these findings to the develop- ment of selective methods of N-protection by vary- ing not only the nature of the N-aryloxycarbonyl group' but also the reagent used for its removal is under investigation. (Received October 15th 1963.) Microwave Spectrum and Barrier to Internal Rotation in Acetylacetylene By 0.L. STIEFVATER and J. SHERIDAN (DEPARTMENT THEUNIVERSITY, OF CHEMISTRY BIRMINGHAM) THE structures and barriers to internal rotation of several substances of the type CH,CO-X where X is an atom or a group (CN) linear with the carbonyl carbon have previously been studied by microwave spectrosc0py.l The barrier heights are all in the range 1000-1300 cals./mole and do not vary greatly with changes in X,which has usually been a group of high electronegativity.It seemed of interest to study a further member of this series acetylacetylene (X = CiCH) by similar methods. The geometry of this molecule closely resembles that of acetyl cyanide but it differs considerably from that substance in the group dipole of X. Details of the acetylacetylene structure are also of interest in view of the detailed study of the related substance propynal.2 Approximately 180 rotational lines of acetyl-acetylene were measured in the range 12-40 Gc./sec., and some fifty of these were assigned to transitions involving J-values less than 13. These were twelve /..t,a R-branch lines with J between 1 and 6; thirty /..t,b Q-branch lines including the series lo.^ -+ .li,u-i)y h-u -+ ]~,(J-z) and 12,~-2)-+ ]3,~-3) and the pb R-branch series -+ lo,^ 4U+~)I,(J+I)and li,~ (f+l)o,(J+i) Assignment was made possible by quantitative study of Stark effects particularly of the 6,, -6,, line.A preliminary estimate of the total dipole moment is 2.4~~ the b-component being about twice the a-component. Over 30 lines were split into A/E doublets by the restricted rotation of the methyl group the measured splittings ranging from 0.7 to 20 Mc./sec. In this case not only the A-type lines but also many E-type lines could be fitted to pseudorigid-rotor energy-level schemes the rotational constants being in Mc./sec. A-Species E-Species A = 10,257.68 f0.05 10,256'66 f0.05 B = 4,030.34 f0.1 4,029.80 & 0.1 C = 2,941.56 Ifr 0.05 2,941-56 f0.05 In order to compute a barrier height it is necessary to choose a value for the angle between the principal a-axis and the axis of the methyl group using a model which conforms to the measured constants.With such a model containing only acceptable bond- distances and angles the direction cosine ha was found to be 0.46484 corresponding to an angle of 62" 18' between the stated axes. With this as a basis the barrier height V3is calculated from the differences between the A and E rotational constants as 1073 & 60 cals./mole the error taking account of uncertainty in the constants and allowing for a possible variation of f2" in the angle between the axes discussed above. This barrier must therefore be lower than that of 1210 f30 cals./rnole found for acetyl cyanide.l Work is continuing on details of the spectra and on other isotopic forms of the molecule in order to refine the information on structure barrier height and dipole moment.We thank Dr. J. R. Majer for providing the sample of acetylacetylene. This research was sponsored by the U.S. Air Force Office of Scientific Research. (Received October 22nd 1963.) For literature see Krisher and Wilson J. Chem. Phys. 1959,31 882; 1960,33 304. * Costain and Morton J. Chem. Phys. 1959 31,389. DECEMBER 1963 369 Biosynthesis of the Indole and Ipecacuanha Alkaloids By A. R. BATTERSBY G. V. PARRY, R. BINKS W. LAWRIE and B. R. WEBSTER (THEROBERT LABORATORIES AND ROBINSON UNIVERSITY OF LIVERPOOL DEPARTMENT UNIVERSITY OF CHEMISTRY OF BRISTOL) THEorigin of the C,-Cl unit of indole and Ipeca- Several experiments with sodium [carboxy-14C]-cuanha alkaloids (thickened bonds in I and 11)has acetate were carried out on C.ipecacuanha which been considered in several biogenetic ~chemes.l-~ produces emetine 01; R = Me) and cephaeline (II; involving three units of acetic acid one of R = H); incorporations into the latter were in the malonic acid and a one carbon unit (or equivalents) range 0-02-0.04 %. Cephaeline after 0-methylation has been supported by Leete and his co-workers and rigorous purification gave results from Kuhn- whose experiments on ajmaline (I) from R. ser-Roth oxidation collected in the Table. These con- pentina plants fed with sodium [carbo~y-~~CIacetate sistent values agree with those above on ajmaline and gave results in exact agreement with theory (26% of they are not greatly affected by age of the plants or total activity at positions 3 19 and 0% at position conditions of the experiment.If the activity in 21); the labelling pattern demanded by this theory is cephaeline were randomly scattered the derived indicated on (1) and (11). When sodium [14C]formate acetic and propionic acids would carry respectively, was the precursor they reported4 12% of the total ca. 7% and ca. 10.5% of the original activity. activity at C-21 of ajmaline. All our results on Degradation5 of the cephaeline (exp. marked t) gave ajmaline differ from theirs; in addition we report 6-ethylveratric acid (38% of total activity) corre- complementary work on the Ipecacuanha alkaloids.sponding to ring F but only 4% was present in the The radioactive ajmaline (I; 0.01 % incorpn.) from carboxyl group (Schmid). Position 1’ of cephaeline R. serpentina plants fed with sodium [carbo&4~]- thus carries only the random level of activity. acetate was oxidised (Kuhn-Roth) and the acetic Ajmaline from plants fed with sodium [14C]- and propionic acids were separated chromato-formate (0.01 % incorpn.) was reduced to dihydro- graphically. They had low and different levels of ajmaline without significant change of activity. activity (Table) thus showing scatter of the label. Degradation6 of the ajmaline thus proved to be Plants Age Feeding (days) Compds. fed Total activity (%) in MeC0,H EtC0,H R.serpenrina ca. 4 yr. 26 Na [~arboxy-~~Clacetate 5.3 7.4 tC. ipecacuanha ca. 2 yr. 35 6-2 9.7 YY 1 Y9 1.5 yr. 10 6.0 9.3 9 1.5 yr. 10 Na [~arboxy-~~C]acetate + glucose 6-5 9.2 99 1.5 yr. 10 Na [carb~xy-~*C]acetate + shikimic acid 6.9 9.8 R. serpentina ca. 1.5 yr. 10 Na [14C]formate -C. ipecacuanha ca. 1.5 yr. 35 2-2 3.7 9 radiochemically pure gave decarbonoajmaline (111) which contained not less than 96% of the original activity; thus little or no activity is present at position 21 of ajmaline. In contrast the N-methyl group (an “internal standard” from the one-carbon pool) carried not less than 25% of the original activity (Hertzig-Meyer). Cephaeline from plants fed with sodium [14C]- formate (0.4 % incorpn.) had 67 % of its activity in the 0-methyl groups whereas C-12 isolated as formaldehyde dimethone by unambiguous degrada- Reviewed by Battersby The Donegani Lectures on Biosynthesis Milan September 1962 in press.a Leete Ghosal and Edwards J. Amer. Chem. Soc. 1962 84 1068; Leete and Ghosal Tetrahedrun Letters 1962, No. 25 1179. Battersby Anniversary Meeting Chem. Soc.,Sheffield April 1962 also quoted in ref. 2. * Edwards and Leete Chem. and Znd. 1961 1666. Battersby Binks and Edwards J. 1960 3474. Robinson Chem. and Znd. 1955 285. PROCEEDINGS tion carried 1.3 %. The Kuhn-Roth results (Table) counting procedures have been rigorously controlled also show low scatter of activity in the carbon on standard substances to ensure experimental skeleton.reliability. Further work is in progress. All degradations fractionation methods and (Received October 25th 1963.) Homolytic Decomposition of Diethoxydiazomethane J. CRAWFORD By ROBERT and RINTJERAAP OF CHEMISTRY OF ALBERTA ALBERTA, (DEPARTMENT UNIVERSITY EDMONTON CANADA) SALTS of toluene-p-sulphonylhydrazones can be thermally decomposed into toluene-p-sulphinate and diazo-compounds.l Under protic conditions the diazo-compound generated in this manner normally decomposes by a cationoid mechanism whereas a carbenoid mechanism prevails in aprotic so1vents.l Recently Dauben2 has shown that these decomposi- tions can be carried out photochemically at room temperature. In an attempt to prepare cyclopropanone ketals by a method analogous to that of Schollkopf,3 we have examined the decomposition of some a-alkoxy- toluene-p-sulphonylhydrazone salts.We have prepared N'-diethoxymethylenetoluene-p-sulphon-hydrazide (I; R = H),4 m.p. 85-86" in 54% yield from the reaction of diethyl imidocarbonate with toluene-p-sulphonylhydrazine hydrochloride in ethanol at room temperature. The product re-arranges slowly at room temperature to a higher- melting isomer m.p. 187-188" (decomp.) and is best stored as the sodium salt (I; R = Na). This salt is relatively stable to heat and decomposition re- quired refluxing for 3 hr. in solvent at 158". The pro- ducts of decomposition were sodium toluene-p- sulphinate (78%) N'-diethoxymethylene-N-ethyl-toluene-p-sulphonhydrazide(I; R = Et; 22 % m.p.78-79') ethyl alcohol (35-3973 and a trace of diethyl ether. The gaseous products were nitrogen carbon monoxide ethylene and ethane in relative proportions of 35:14:1.5:1 (gas chromatography). A trace of n-butane was detected but not measured. All attempts to trap a dietlioxycarbene intermediate by carrying out the thermal decomposition in dec- 1 -ene or indene4 were unsuccessful. heat (EtO),C = N.NR.SO,-C,H -+ NaSO,C,H + ('1 or hv (EtO),CN (EtO),CN -+ (EtO),C + N (EtO),C -+ EtO-+ CO + C,H,* I). . 0) . . (2) EtO-+ Solvent H 4 EtOH + Solvent-. . . (3) Et. -+ C,H + C,H ... (4) EtO. + Et. -+ Et,O ..I (5) Eta + Solvent H -f C,H + Solvent . . . (6) The products indicate that a radical decomposition has occurred which may be explained by equations (2)-(6).A mode of decomposition analogous to that suggested by Skell and Starer5 [eqn. (7)] may account for the crystalline product (I; R = Et). The large amount of ethanol formed under anhydrous condi- tions and the presence of ethane strongly suggests EtO,C:-+ Et+ + CO + EtO-. . . (7) that the homolytic pathway is important at this temperature. This type of carbene decomposition has not been observed before. When a methanolic solution of (I; R = Na) in a quartz vessel was irradiated for 12 hr. at room temperature with a 250w Hanovia ultraviolet source a 33% yield of diethoxymethoxymethane was iso- lated. 7,7-Diethoxynorcarane could not be isolated when (I; R = Na) was photochemically decomposed in 1 :1 dimethoxyethane-cyclohexene.We have also succeeded in preparing "-(a-methoxybenzy1idene)toluene-p-sulphonhydrazide;its potassium or sodium salt decomposed in 3 hr. at 115" compared with 158" for the diethoxymethylene- compound. With dec-l-ene it formed l-methoxy-2- octyl-1 -phenylcyclopropane (yield 3 %). We are grateful to the National Research Council of Canada for a grant in aid and for a Studentship (to R.R.). (Received September 8th 1963.) (a)Bamford and Stevens J. 1952 4735; (b) Powell and Whiting Tetrahedron 1959 7 305; (c) Friedman and Shechter J. Amer. Chem. SOC., 1959?81,5512; 1960,82 1002; 1961,83,3159; (d)Closs ibid. 1962,84,809; (e)Farnum, J. Org. Chem. 1963 28 870; (f)Cristol and Harrington ibid. p. 1413.Dauben and Willey J. Amer. Chem. SOC.,1962 84 1497. (a) Schollkopf and Lerch Angew. Chem. 1961 73 27; (b) Schollkopf Lerch and Pitteroff Tetrahedron Letters 1962 241. Cf. Parham Reiff and Schwartzentruber J. Amer. Chem. SOC.,1956 78 1437, Skell and Starer J. Anzer. Chem. Soc. 1959 81 41 17. DECEMBER1963 37 1 The Molecular and Crystal Structure of Caryophyllene Chlorohydrin By D. ROGERSand MAZHAR-UL-HAQUE (CHEMISTRYDEPARTMENT,IMPERIALCOLLEGE,LONDON,S.W.7) IN the unravelling of the structure of caryophyllene two derivatives played specially important parts (1) The X-ray study by Robertson and Todd1 of the halides derived from caryophyllene alcohol(1) estab- lished the mode of fusion of the cyclobutane ring and confirmed all the chemical deductions to that date.(2) An elaborate chain of experiment and deduction centring largely around Treibs’ epoxy- ketone2 indicated that it has the stereochemistry and absolute configuration of (IH).~~~ The formation from this of a chlorohydrin was the only inexplicable reaction; both its constitution and its mode of forma- tion were obscure. An X-ray study and further chemical work reported in the next Communi~ation,~ have both led to the formulation of the chlorohydrin as (11). The crystals are trigonal prisms with three mole- cules in a cell of dimensions a = 13*14,c = 7.11 A (d&& = 1.209 g.c~.-~; dcalc = 1.21 g.~m.-~). The Laue symmetry is 3 the systematic absences are con- fined to 001for I # 3n and the molecules are optically active.The space group is therefore P3 or its en- antiomorph P3, and the former was initially chosen arbitrarily. The intensities of some 1150 Cu-Ka reflections were measured visually and the chlorine atom located from a sharpened three-dimensional Fourier. The other atoms emerged gradually from five successive Fouriers. Refinement not yet com- plete has reduced R to 0.17 for all reflections. The stereochemistry and conformational details of (11) agree very closely with those of (I) deduced by Robertson and Todd. Even the same pattern of buckling occurs in the cyclobutane ring; the dia- gonals fail to intersect by about 0.25 A the upper one being shown dotted in both (I) and (11). The preparations of these compounds from caryophyllene involve two quite different cyclisations but neither interferes with the cyclobutane ring.It is considered therefore that the close similarity of (I) and (H) and the orientation of the hydroxyl group vicinal to the chlorine atom in (11) confirm Barton’s formula (HI> and also validate all his chain of chemical argument including the deductions of relative configuration^.^ x‘-f Q Ho#Qck a* OH (0 (n) (a)” (X=OH,CI Br) Robertson and Todd J. 1955 1254. Treibs Ber. 1947 80 56. Barton and Lindsey J. 1951 2988; Barton Bruun and Lindsey J. 1952 2210; Aebi Barton and Lmdsey J., 1953 3124; Aebi Barton Burgstahler and Lindsey J.,1954,4659. * Barton and Nickon J.,1954 4665. Greenwood Qurreshi and Sutherland following Communication.Formula (I),(11) and (111) have been drawn to com- ply with Barton and Nickon's assignment of absolute configuration,4 and the Figure confirms the space group as P31. The mode of formation and other chemical implications of formula (11) are discussed by Greenwood et aL5 The Figure shows how the molecules are linked by hydrogen-bond spirals around two screws leaving a large void around the third screw. The void has an effective diameter of about 6-7 A scarcely wide PROCEEDINGS enough to admit small molecules or chains it is empty in the electron-density map and this may explain why the crystals are so difficult to grow. We are indebted to Dr. J. K. Sutherland for the specimen and for discussion to the British Council and D.S.I.R.for financial support and to Dr. 0. S. Mills and Dr. J. S. Rollett for the use of their Mercury computer programmes. (Received October 1 1 th 1963.) A ReadiIy Reversible Transannular Reaction in the Caryophyllene Series By J. M. GREENWOOD and J. K. SUTHERLAND I. H. QURRESHI DEPARTMENT COLLEGE, (CHEMISTRY IMPERIAL LONDON,S.W.7) DURING work by Barton and his collaborators1 on the structure of caryophyllene Treibs' epoxy-ketone2 (I) was converted into a chlorohydrin C14H2,C102 by hydrogen chloride. The absence of a carbonyl group (i.r. spectrum) coupled with no absorption I ascribable to Me-CCl (n.m.r.) showed that it was I not a simple addition product. On treatment with h-sodium hydroxide the chlorohydrin loses hydro- gen chloride to give the ketol (II) C14H22O2 vmax 3450 1690 cm.-l A,,, 287 mp (E 27) which con- tains a methylene group (n.m.r.and ozonolysis to formaldehyde). Similarly the chlorohydrin mono- acetate can be converted into the acetate of (11) which can be ozonised to formaldehyde and an acetoxy-dione C15H22O4 Ymax 1740 1720 1690 cm.-l. These reactions coupled with the presence in the chlorohydrin of one secondary and one tertiary hydroxyl and one tertiary chloro-group (n.m.r.) suggest the transformation It / / HO.C.CH2.C.Cl-0 == C CH2 zzz C 11 \ \ Lithium aluminium hydride reduction of the chlorohydrin gave the diol derived from (II) and another diol Cl4H2aO2 containing a -CH2.0H (n.m.r.) which must be formed by ring contraction of a 1,2-chlorohydrin3 to form an aldehyde subse- quently reduced to CH2.0H.Reduction by lithium in ammonia gave another diol C14H22O2 which can be oxidised to the ketol (IIL) C14H2202,Ymax 1710 cm.-l A,, 286 (E 23). Further oxidation of the latter gives a keto-y-lactone (IV) vmax 1770 1700 cm.-l. Part-structure (V) accounts for these reactions. Semmler and Maye@ have oxidised caryo-phyllene to a mixture of caryophyllenic (VI; n = l), norcaryophyllenic (VI; n = O) and dimethylsuccinic acids; similar oxidation of the chlorohydrin gave the same three acids identified by g.1.c. of their methyl esters. Of the two structures which are now possible for the chlorohydrin only (WI; X = C1) can be de- rived reasonably from the starting material (I).Independently Rogers and Hacque have come to the same conclusion by an X-ray structure determina- tion5 and additionally have shown the stereochem- istry to be that depicted in (VII; X = Cl). Barton and Lindsey J. 1951 2988; Barton Bruun and Lindsey J. 1952 2210; Aebi Barton and Lindsey J. 1953 3!24. a Treibs Ber. 1947 80 56. Cope Graham and Marshall J. Amer. Chem. Soc. 1954,76 6159. Semmler and Mayer Ber.,.1911,44 3657. .bi Rogers and Haque preceding Communication. DECEMBER 1963 373 ~ ~~~ ~ Insight into the mechanism of formation of the chlorohydrin comes from two observations. Firstly (I) is isomerisede to (11) with sodium iodide in acetic acid and secondly (11) is transformed into the chlorohydrin with hydrogen chloride.This ready cyclisation (a type of Prins reaction) is undoubtedly due to the proximity of the two reactive groups brought about by the geometry of the nine-membered ring and we have further shown that in aqueous acetic acid (11) is converted into (VII; X = OH) the structure of which follows from its oxidation to (LV). Satisfactory analyses and spectral data have been obtained for all compounds. We thank the D.S.I.R. (J.M.G.) and P.C.S.I.R. (I.H.Q.) for financial support and White Tomkins and Courage Ltd. for gifts of Zanzibar clove oil. (Received October 1 lth 1963.) * This is similar to the isomerisation by pyridine hydrochloride of epoxycaryophyllene to the corresponding alcohol reported by Sorm Dolejs and Pilva Call. Czech. Chem.Comm. 1950 15 186. Biogenetic Type Syntheses of the Xanthone NucIeus By J. R. LEWIS (SCHOOL OF PHARMACY TECHNICAL COLLEGE SUNDERLAND) THEbiosynthesis of the xanthone nucleus has been formulated as involving a dehydration process from the appropriate 2 :2’-dihydroxybenzophenones.lThis mode of biogenesis is supported by the isolation of griseophenone C and griseoxanthone C from P. patulum2 Experimentally the xanthone nucleus has been synthesised from 2,2’-dihydroxybenzophenonesby a variety of vigorous dehydrative procedures3 but more recently it has been sho~n~,~ that mild alkaline treatment at 1OO” of 2-hydroxy-2’-methoxybenzo-phenones also yields xanthones. It is now reported that the xanthone nucleus can be obtained by solvo- lysis at room temperature.Treatment of the ditosy- late (I; R = R = C,H,.S02) with @S~-sodium hydroxide in aqueous methanol at room temperature for 8 days gave the xanthone (111) in -1% yield together with 2,2’-dihydroxybenzophenone(I ;R = R’ = H) (98 %). It appears that the intermediate 01; R = C,H,.SO, R = H) produced during the hydrolysis had undergone an intramolecular nucleo- philic displacement (I1 3111). It is significant that these conditions are mild enough to suggest that the xanthone nucleus could occur in vivo by a similar type displacement . An alternative mode of cyclisation of dihydroxy- benzophenones to xanthones could involve oxidative coupling5 and this method is well established as a means of producing carbon-oxygen linkages in high yield if the process occurs intramolecularly.It has now been found that treatment of 2,3’,4-trihydroxy- benzophenone (IV) in alkaline solution with potas- 8 qgp q;p RO OR’ R t Fz 04 sium ferricyanide solution resulted in the formation of 2,6-dihydroxy~anthone~ (V) in 83 % yield. Paper chromatography (n-butanol-saturated ammonia solution) showed the presence of a small quantity of another material tentatively regarded as 3,5-di-hydroxyanthone (VI) thus confirming that ring closure had taken place mainly para to the activating hydroxyl group (3‘). It is interesting that a simpler pattern emerges for the biosynthesis of the known xanthones if both types of ring closure are used to predict the hydroxy- la t ed benzophen one precursor.(Received October 31st 1963.) Neelakantan and Seshadri Current Sci.. 1961 30 90. McMaster Scott and Trippett J. 1960 4628; Barnes Boothroyd McGonagle and Sommerfield Bioclwm J., 1961 81 28. Elderfield “Heterocyclic Compounds,” VoI. 2 Wiley 1951 p. 428. Barton and Scott J. 1958 1767. Lewis Chem. and Ind. 1961 159. Mittal and Seshadri J. Sci. Ind. Res. India,1955 14B 76. PROCEEDINGS Solvolysis of 2-Hydroxymethylcyclohexanol Derivatives By DON KOVACS,GWLASCHNEIDER LANG and L. KORN~LIA (INSTITUTE OF ORGANIC c3€EMISTRY J~ZSEF ATTILAUNIVERSITY SZEGED,HUNGARY) PREVIOUSLY we have reported1 that acetolysis of cis -2 -toluene -p -sulphonyloxymethylcyclohexyl acetate (I) and of trans-2-acetoxymethylcyclohexyl toluene-p-sulphonate (111) in the presence of potas-sium acetate gave a mixture of cis-and trans-2- acetoxymethylcyclohexyl acetate (VII and VIII) as main products while reaction of the trans-isomer (11) gave rise only to the trans-diacetate (VIII) under identical conditions.Similarly the ethanolysis of (I) and 011) in the presence of potassium acetate afforded the same cyclic intermediate namely 2-ethoxy-2-methyl-cis-l,3-dioxadecalinw;71% and 22.5 % respectively; synthesised from (IA) with ethyl orthoacetate]. However when the trans-isomer a)was treated under identical conditions the presence of the expected trans-isomer (VI) corres-ponding to (V) could not be detected by gas chroma- tography or infrared spectral analysis.The forma- tion of the orthoester (V)and of the mixture of the isomeric diacetates (VII and VIII) had been inter- I i t iii 11 iv preted by us and by Dolby et aZ.? by assuming a i OAc-(AcOH). ii EtOH(-H+). iii MeC(OEt)3-H+. cyclic acetoxonium ion as the intermediate (IV). In iv EtOH f H,O-H+. Acetolysis in dry acetic acid at looo. Compd. 104k1 7) Rel. (sec.-l) (min.) rate (x) 0-0506 227940 1 OII) 0.2354 490.10 4.65 (1) 23.200 4.97 458.5 our view formation of (VII) during acetolysis is due to the attack of the acetate ion at C-4 with retention of configuration while (VIII) is formed by attack on C-9 with inversion (see arrows). Our kinetic measurements showed3 that the reference compounds [cyclohexyl (IX) and cyclo- hexylmethyl toluene-p-sulphonates (X)] reacted as expected according to first-order kinetics in glacial acetic acid and according to first and second order respectively in the presence of potassium acetate.On the other hand acetolysis of (I) (11) and trans-2- acetoxycyclohexyl toluene-p-sulphonate (XI)5follow-ed first-order kinetics both in the presence and in the absence of alkali-metal acetate while acetolysis of (TI) in acetic acid is also purely of first order but in the presence of potassium acetate tends to follow second-order kinetics. Compd. 104kl 7% Rel. (sec.-l) (min.) rate 011) 1.505 76.73 0.42 (XI) 2.030 56-89 0-31 (Ix) 6.420 17.99 1 The Table permits comparison of the half-time (7) of the first-order reactions. While the relative rate of the acetolysis of 01) is only 4.5times the value for (X),that for (I) is almost 460times higher; the value of (111) is about the same order of magnitude as (XI), for which 1,2-participation has been pr~ved.~ These data together with the isolation of (V) seem to sup- port the existence of a cyclic intermediate and con- sequently the participation of the y-acetoxy-group in the solvolyses of (I) and (111).Further investiga- tions of similar systems are in progress to elucidate the possible role of other neighbouring groups in y-position. The authors thank Professor H. Becker for the discussion of the problems. (Received October 9th 1963.) IVth Congress of the Hungarian Chemical Society Debrecen October 23rd-25th 1961; IInd International Symposium on the Chemistry of Natural Products Prague August 27th-September 2nd 1962.Dolby Lieske Rosencrantz and Schwarz J. Amer. Chem. SOC.,1963 85 47. XIXth International Congress of Pure and Applied Chemistry London July 10-17thy 1963. * Pritzkow and Schoppler Ber. 1962,95 834. Winstein and Buckles J. Amer. Chem. SOC., 1942 64 2780; Winstein Hess and BuckIes ibid. p. 2796; Winstein et a/. ibid. 1948 70 812 816 821. DECEMBER 1963 375 The Distribution of Adsorbate within Evaporated Metal Films By D. BRENNAN and J. M. JACKSON (DEPARTMENT PHYSICAL CHEMISTRY, OF INORGANIC AND INDUSTRIAL THEUNIVERSITY OF LIVERPOOL) CHEM~SORPTION on metals is frequently very rapid and the resulting surface layer is often immobile. In these circumstances a non-equilibrium distribution of adsorbate will inevitably result and where much of the available surface is to be found within the interstices of a porous medium as with evaporated metal films the relation between surface concentra- tion and extent of adsorption is likely to be complex.Evaporated films are much used for determining the variation with extent of adsorption of such para- meters as for example heat of adsorption and surface potential and a satisfactory interpretation of these variations necessitates a knowledge of the distribu- tion of the adsorbate within the film and the value of surface concentration at each stage of the adsorp- tion. We have recently carried out measurements with a view to obtaining this kind of information.The metal film was deposited onto the interior wall of a soda-glass tube (30 mm. diam.) and achieved good electrical contact with each of eight rings (0.5 mm. diam.) of platinum wire embedded in the wall of the tube and spaced at 3-cm. intervals along its length. The electrical resistance of each of the seven sections of the film between adjacent rings was determined initially and after the admission of each dose of gas; change in the electrical resistance of a film section was ascribed to the presence of adsorbate within that section. The results for two limiting cases are presented in the Figure. For the adsorption of oxygen on tung- sten it is seen that the first dose of gas is not able to penetrate down the tube further than the third film section before it is completely adsorbed; it is not until the seventh dose has been admitted that the last film section is appreciably involved in the adsorption.Later in the adsorption all the film sections tend to be similarly affected by each gas increment. The pro- file (see Figure) for each gas dose given is closely similar to the concentration gradient along the length of the adsorption vessel. In the case of the adsorption of oxygen on nickel some banding of adsorbate along the length of the tube occurs but the pre- dominant effect is one of layering in which each dose of gas has time to reach the bottom of the tube and achieve a uniform pressure along its entire length before becoming adsorbed by the film.In the Table the coverage of a tungsten film due to an increment of oxygen gas is given for each section of film at different stages of the adsorption; these coverages have been assessed from the changes in electrical resistance of the film sections. It is seen that the first dose is capable of covering an area of surface of section I some eleven times greater than its geometric area. It is concluded therefore that oxygen is able to penetrate the tungsten film faster 16-12-5 8-Q a 0 0 4-0- -4.0-30- 5 2.0-Q: a 2O 1.0-0- The distribution of oxygen on tungsten at 20°c at various stages of the adsorption as determined by changes in film resistance. Adsorption due to each dose on band* Dose No. I I1 I11 IV V VI VII 1 11.2 3.9 0.99 0.46 --2 7.6 4.6 2.3 0.61 0.18 - 3 6.6 4.8 2.7 1.06 0.45 - 7 3.8 3.5 3.0 2.0 1.34 1-04 079 17 0.45 1-OT 1.31 1.81 2.3 3.5 4.4 26 3.4 2.6 1.70 1.70 1.70 1.70 1.28 * Coverage expressed as the ratio-number of mole-cules adsorbed by a band number of molecules required to saturate the geometric area of the band.than it can flow down the tube; its ability to do this diminishes as adsorption proceeds presumably because it then has too far to travel into the film to find the clean surface. We conclude that the rate of adsorption on PROCEEDINGS evaporated-metal films is a function of the coverage as is the distribution of adsorbate and the type of behaviour (viz. banding of adsorbate versus layering) depends very much on the nature of the system CO~~erned.(Received October 26th 1963.) n-Butylmagnesium Isopropoxide :Preparation of Alkoxide Analogues of Grignard Reagents By D. BRYCE-SMITH and B. J. WAKEFIELD (THE UNIVERSITY READING) ORGANOMAGNESIUM HALIDES and dialkylmagnesium compounds are well known usually as etherates alkylmagnesium halide alkoxides have also been reported.l> No example of an alkylmagnesium alkoxide was known before Birnkraut's very recent report3 (which became available only after submis- sion of this Communication) that a by-product ob- tained by Wiberg and Bauer during the preparation of magnesium hydride by pyrolysis of a diethyl-magnesium solvate in vacao was ethylmagnesium ethoxide not ethylenemagnesium as originally claimed? The yield was small and the procedure does not seem suitable for preparative purposes.Alkyl- magnesium alkoxides have been written recently as possible intermediates in the reactions of dialkyl- magnesium compounds with ketones and alcohol^.^^^ We now report the isolation of n-butylmagnesium isopropoxide by a simple procedure and some pre- parative methods which appear likely to be general in this series." n-Butylmagnesium isopropoxide was prepared by modification of a recent method for the reduction of organic halides.' Magnesium powder (3 g.-atoms) in refluxing methylcyclohexane was caused to react with a mixture of 1-chlorobutane (1 mol.) and propan-2-01 (1 mol.) and the product was then heated with 1-chlorobutane (1 mol.) at 100" for 2 hr.The overall equation can be written as 2 BunCl + 2 Mg + Pr'OH 4BunMgOPr' + MgCl + BunH. Removal of the insoluble magnesium chloride and excess of magnesium gave a solution of n-butyl-magnesium isopropoxide in almost quantitative yield. Removal of methylcyclohexane up to 150"/1 mm. gave n-butylmagnesium isopropoxide as a colourless oil almost involatile under these condi- tions. Analysis (Mg OPri equivalent butane formed on hydrolysis) was consistent with the empirical formula BunMgOPri. The compound was freely soluble in methylcyclohexane benzene and ether. The low volatility coupled with the solubility in non- polar solvents suggests covalent association. Free magnesium di-isopropoxide and di-n-butylmag-nesium were not present since these compounds are not soluble in methylcyclohexane.Thus an equili- brium of the type 2 RMgSOR +MgR + Mg (OR') was not involved under our conditions (cf. ref. 5). n-Butylmagnesium isopropoxide gives a positive test with the Michler's ketone reagent,8 and n-valeric acid is obtained with carbon dioxide. Reaction with benzoyl chloride surprisingly gave mainly isopropyl benzoate and little valerophenone and its addition products (difference from Grignard reagents). Our method also appears to be suitable for the prepara- tion of alkylmagnesium t-butoxides and for n-alkyl derivatives other than n-butyl. Primary alcohols re- act with magnesium in the absence of added alkyl halide and in such cases the first mol.of alkyl halide can be omitted. 1-Iodobutane could not be used in place of the chloro-compound as it gave a butyl- magnesium iodide-isopropoxide complex (cf. refs. 1 and 2). Solutions of n-butylmagnesium isopropoxide have been prepared by two other methods firstly by the reaction of 1-chlorobutane (1 mol.) with magnesium (1-3 g.-atoms) and sodium isopropoxide (1 mol.) ; BunCl + Mg + NaOPri 4BunMgOPri + NaCl secondly by the reaction of unsolvated n-butyl- magnesium chloride (2 mol.) in methylcyclohexane with isopropanol (1 mol.); 2 "Bu"MgC1" + Pr'OH 4BunMgOPri + MgCl -1 BunH. We are glad to acknowledge financial support for this work from D.S.I.R. (Received October 30th 1963.) * Ethoxymagnesiomalonic ester has long been known; but it is uncertain whether it contains a carbon-magnesium bond (Lund Hansen and Voigt Kgl.danske Videnskab. Selskab Mat,-fys. Medd. 1933 12,No. 9; Chem. Abs. 1934 28 2333). Blues and Bryce-Smith Chem. and Ind. 1960 1533. Bryce-Smith Bull. SOC. chim. France 1963 1418. Birnkraut Znorg. Chem. 1963 2 No. 5 1074. Wiberg and Bauer Chem. Ber. 1952 85 593. Cowan and Mosher J. Org. Chem. 1963 28 204. House and Traficante J. Org. Chem. 1963 28 355. Bryce-Smith Wakefield and Blues Proc. Chem. Soc. 1963 219. Gilman and Schulze J. Amer. Chem. SOC. 1925,47,2002. DECEMBER 1963 377 Synthesis of 15-0x0-steroids By CARL DJERASSI VON MUTZENBECHER and GERHARD OF CHEMISTRY UNIVERSITY CALIFORNIA) (DEPARTMENT STANFORD STANFORD OF all steroid ketones those at C-15 have received the least attention1 because of their relative inac- cessibility.Apart from microbiological procedures2 and transformations of rather rare naturally-occurring steroids oxygenated at (2-14 or C-15 the only chemical method of potentially general applicability is that of Barton and Laws4 in the ergosterol series. We now report a general synthesis of 15-oxygenated steroids from the readily available androstan-17-ones. n 5a-Androst-15-en-17-0ne (11) m.p. 98-101 ',was prepared in 85% yield from 16~-bromo-l7,17-ethylenedioxy-5 a-androstane (I)5 by potassium t- butoxide dehydrobromination and deketalisation (toluene-p-sulphonic acid-acetone) and then trans- formed in 60 % yield with alkaline hydrogen peroxide into the 15/3 16/3-epoxy-l7-ketone(111) m.p.137- 138'. Rearrangement6 with hydrazine led in 30% yield to 5a-androst-16-en-15/3-01 (IV) m.p. 76-77" and thence by oxidation by Jones method' to the unstable d16-15-ketone (V) [m.p. 75-77" A,, (EtOH) 223 mp E 67801. Catalytic hydrogenation (10% palladised charcoal in ethyl acetate) of the allylic alcohol (1V) gave 5 a-androstan-15/3-01(VI) [m.p. 80.5-81.5" [a]= -34" (all rotations in chloroform)] which required heating to 70" with acetic anhydride-pyridine for complete acetylation (VII; amorphous [a], -45"). Oxidation (Jones method) of the alcohol (VI) afforded 5a-androstan- 15-one (VIII) [m.p. 92-93" [aID+ 30° positive O.R.D. Cotton effect* [a]312 (peak) 3-2236" (MeOH) [a]270 (trough) -2822'1 which upon reduction by lithium aluminium hydride gave 65% of the 15fi-alcohol (VI) and 20% of its 15a-epimer (IX) (m.p.161-163' [aID + 42") the configura- tions at C-15 being assigned on the basis of molecular-rotation difference^.^.^ In the cholestane and ergostane series the 14a- 15-ketone is the more stable and the 14/3-isorners are as yet unknown. The opposite behaviou? has been observed in other 17-substituted 15-0x0-steroids and related perhydroindan~nes,~ and it was of obvious interest to examine the position of the equilibrium in the unsubstituted parent. Thus by heating (3 hr.) the 14a-15-ketone (WI) with 2 % methanolic sodium hydroxide solution we obtained after chromatography the pure 14P-15-ketone (X) [m.p.72-73" [a]=-37' negative O.R.D. Cotton effect [a]322 (trough) -1660° (peak) 3-2115' (MeOH)]. The actual position of the equilibrium [85-87 % of (X) and 13-15 % of (VIII)] was deter- mined by the optical rotatory dispersion techniqueY9 starting with either pure isomer. Further chemical studies with 15-0x0-androstanes (with and without substituents at C-3) notably their behaviour on bromination are under way. All substances described in this communication gave correct elemental analyses and molecular weights (determined mass spectrometrically). Financial aid from the National Institutes of Health of the U.S. Public Health Service and a travel grant (G.v.M.) from the Swiss-American Foundation for Scientific Exchange is gratefully acknowledged.(Received September 30th 1963 .) Fieser and Fieser "Steroids," Reinhold New York 1959 e.g. ch. 8. For leading references see Tam Gubler Juhasz Weiss-Berg and Ziircher Helv. Chim. Acta 1963 46 889; De Flines Van Der Waard Mijs and Szpilfogel Rec. Trav. chim. 1963 82 143. Inter al. Klass Fieser and Fieser J. Amer. Chem. Soc. 1955 77 3829; Djerassi Grossnickle and High ibid., 1956 78 3166; Lardon Sigg and Reichstein Hevl. Chim. Acta 1959 42 1457; Tschesche and Wulff Ber. 1961 94, 2019; Ragab Linde and Meyer Helv. Chim. Ada 1962 45 1794. Barton and Laws J. 1954 52. Marquet Dvolaitzky Kagan Mamlok Ouannes and Jacques Bull. SOC.chim.France 1961 1822. Wharton and Bohlen J. Org. Chem. 1961 26 3615; Wharton ibid. p. 4781; Djerassi Williams and Berkoz ibid.1962 27 2205 ;Huang-Minlon and Chung-Tungshun Tetrahedron Letters 1961 666. Bowden Heilbron Jones and Weedon J. 1946 39. * See Djerassi Riniker and Riniker J. Amer. Chem. Soc. 1956 78 6362 for optical rotatory dispersion behaviour of 14 a-and 14/3-15-oxo-steroids. Allinger Hermann and Djerassi J. Org. Chem. 1960 25 922. PROCEEDINGS Effect of Nitrogen under Pressure on the Rydberg Spectra of Polyatomic Molecules; the Nature of the Long-wavelengthOlefin Bands By I).F. EVANS DEPARTMENT COLLEGE S.W.7) (CHEMISTRY IMPERIAL LONDON FOR polyatomic molecules absorption bands belonging to a Rydberg series can often be unam-biguously assigned with the aid of the usual Rydberg equati0n.l However difficulties can arise especially with the first members whose observed positions often deviate appreciably from the calculated values.Rydberg spectra involve excitation of an electron to an orbital characterised by a higher principal quantum number and hence during excitation the effective size of the molecule will increase consider-ably. These spectra should therefore be more affected by the perturbing effect of compressed gases than intravalency-shellmolecular spectra. In the region 1909-1 837 A isopreneshows several fairly sharp absorption bands which Carr Pickett and Stiicklen2suggested were Rydberg bands. The band at 1837A was assigned as the first member of a Rydberg series by Price and Walsh? This region of the spectrum of isoprene has now been studied in the Frequency x ( "1 54 52 3 A ; I I II I I :B I I I I 1 iII ! I I II I II L 0 2ow presence of nitrogen at pressures up to 130atm.Very marked pressure broadening was observed and at the highest pressure the bands almost disappeared into the background continuum. The broadeningwas markedly asymmetric the broadened bands showing a pronounced short-wavelength tail. A similar asymmetric broadening is strikingly shown in the "B" bands of methyl iodide4 (Fig. l) which were assigned by Sutcliffe and Walsh5 as arising from excitation of one of the 5p lone-pair electrons of the iodine atom to a 6s orbital. Accord-ing to the statistical theory of the broadening of atomic lines the short-wavelength tails represent absorption by methyl iodide molecules which are comparatively close to nitrogen molecules and pre-sumably experience repulsive forces in the Rydberg excited state.In the vapour phase many alkenes give absorp-tion bands at longer wavelengths than the strong V-N transitions.' These were originally assigned by Wavelength (1) FIG. 2. Absorption spectra of (A) tetrumethyl-FIG. 1. Absorption spectra of (A) methyl iodide ethylene vapour (B) tetramethylethylene vapour 4-vapour (B) methyl iodide vapour (same concentration) 133 atrn. of nitrogen (C) cyclohexene vapour, + 128 atm. of nitrogen. (D) cyclohexene vapour + 133 atm. of nitrogen. La PagIia,J . Mol. Spectroscopy 1963 10 240 and references therein. * Carr Pickett and Stucklen Rev. Mod. Phys.1942 14 261. Price and Walsh Proc. Roy. Soc. 1940 A 174,222. Price J. Chem. Phys. 1936,4,541. Sutcliffe and Walsh Trans. Faraday SOC.,1961,57 873. Ch'en and Takeo Rev. Mod. Phys. 1957,29 20. Jones and Taylor Analyt. Chem. 1955,27 228 and references therein. DECEMBER 1963 379 Carr and Stucklens as Rydberg bands analogous to V(lB1,)-N(IAl,) bands of ethyleneg were found to be the undoubted first member of a Rydberg series in little affected by nitrogen at 130 atm. They showed ethylenes [upper state probably (nx +nx)3s 1B326]10only slight broadening and a small shift to longer whose 0,O band lies at 1744 A. Very recently Berryll wavelengths although the upper orbital of the has suggested that they involve excitation of an electron from the highest filled C-H bonding orbital to the antibonding n orbital.However the pro- nounced effect of nitrogen under pressure on these bands is tetramethylethylene and cyclohexene (Fig. 2) strongly indicates that they are in fact Rydberg bands. In agreement with this interpretation the Carr and Stucklen J. Chem. Phys. 1939 7 631. Wilkinson and Mulliken J. Chem. Phys. 1955 23 1895. lo Mulliken J. Chem. Phys. 1960,33 1596. l1 Berry J. Chem. Phys. 1963 38 1934. l2 Evans J. 1957 3885. electron being excited is the same as that suggested by Berry for the long-wavelength olefin bands. Measurements were made on a Perkin-Elmer 350 spectrophotometer (flushed with nitrogen) the high- pressure cell and techniques previously described12 being used.(Received October 16th 1963.) The Stereochemistry of Copper in 2,2'-Biphenylbis-(2-iminomethylenephenola~o)~op~r(11) By T. P. CHEESEMAN D. HALL,and T. N. WATERS (CHEMISTRY DEPARTMENT NEW ZEALAND) UNIVERSITY OF AUCKLAND Now that the normal stereochemistry adopted by copper(I1) is recognised as being the distorted (4 + 2) octahedral configuration in accord with the Jahn- Teller effect the examination of compounds in which copper has other environments is of increasing interest. This is especially true of the tetrahedral con- figuration where few examples are known and only two CS,CUC~,~ and Cs,CuBr,,2 could be thought to allow the copper atom some freedom in the choice of stereochemistry. Two further compounds CuCr,O,3 and the cupric complex of imidazole? have a tetrahedral environment forced on the copper by three-dimensional packing.Here as with the wsium salts there is the expected Jahn-Teller dis- tortion of the tetrahedron. The possibility of forcing the copper atom into a tetrahedral configuration in a finite complex by a suitable choice of ligands has been examined in 12-tungstocupric(n) acid5 and an undistorted tetrahedral environment has been claimed for the copper atom. We have undertaken a three-dimensional X-ray analysis of one of the crystalline modifications of 2,2' -biphenylbis -(2 -iminomethylenepheno1ato)-copper(n) a finite complex which also requires a tetrahedral copper environment if the ligand is to be undistorted! The crystals are monoclinic with a = 11-30,b = 10.00 c = 12.04A and @ = 118".There are 2 molecules per unit cell and the space group is Pc. The copper atoms were located and confirmed from the Patterson syntheses Puv and Pvw and a three-dimensional heavy-atom electron-density syn- thesis was computed. Although this possessed false symmetry most of the light-atom positions were eventually found the distinction between carbon nitrogen and oxygen being made on chemical grounds. Refinement proceeded smoothly to give a present reliability factor of 0.132 for the 2030 observed reflexions. An overall isotropic temperature factor has been applied to the light atoms with a separate isotropic factor for the copper. Helmholtz and Kruh J. Amer. Chem. Soc. 1952 74 1176. Morosin and Lingafelter Aeta Cryst.1960 13 807. Prince Aeta Cryst. 1957 10 554. Jarvis and Wells Acta Cryst. 1960 13 1027. Brown and Mair J. 1962 3946. Lions and Martin J. Amer. Chem. Soc. 1957 79 1273. The atomic arrangement in the molecule is shown in the Figure. Most bond lengths and angles appear to be normal but the stereochemistry about the copper is far from tetrahedral. This deviation implies some distortion in the ligand and this is found in the non-planarity of the aldimine substituents with their parent benzene rings. The copper environment is best visualised as a flattened tetrahedron although the magnitude of the flattening suggests it is more nearly a square. The distortion is reasonably regular in accord with the Jahn-Teller effect and with two PROCEEDINGS angles of approximately 153” and four of approxi- mately 92” places the compiex at the end of the series of increasingly distorted tetrahedra exhibited by CuC1,2- CUB^^^- and the cupric imidazole com- plex.’ The extent of this deviation and the accom- panying out-of-plane distortion of the ligand sup- ports the view that forces of some magnitude are involved.8 We thank Professor D.R. Llewellyn for his support and interest* (Received September 20tk 1963.) Wells “Structural Inorganic Chemistry,” 3rd edn. Clarendon 1962 Oxford p. 869. Dunitz and Orgel J. Phys. Chem. Solids 1957 3 318. The Molecular Structure of the Reaction Product from 2,3-Dimethylbuta-l,3-diene and Osmium Carbonyl By R. P. DODGE,0.S. MILLS and V. SCHOMAKER (UNION CARBIDE INSTITUTE NEW YORK U.S.A. and RESEARCH TARRYTOW DEPARTMENT 13 ENGLAND) OF CHEMISTRY UNIVERSITY OF MANCHESTER MANCHESTER THE recent preparation1 of a diene-metal complex from 2,3-dimethylbuta-l,3-dieneand osmium car-bony1 with 1igand:metal ratio of 1 :2 has further demonstrated the contrasting reactivities of the second and third row transition elements as com- pared to the corresponding elements of the first row. Significantly different structural implications from the 1 :1 butadiene-iron tricarbonyl would seem to be involved. We have therefore analysed the structure of this osmium complex. This analysis is not without practical difficulty. The preparation is very time-consuming and the yield low and we had in fact only four single crystals with which to work.The crystals are mono- clinic with a = 8.25 i 0.02 b = 18.15 f 0.05 c = 9.68 j 0.04 A and ,6 = 94.08 i 0.06”.The observed density 2.83 g.ml.-l,2 suggests 4 molecules per unit cell (D = 2.90 g.ml.-l). Systematic ab- sences are compatible with the space group P2,P. The structure was deduced by standard Fourier methods from approximately 1500 three-dimen- sional counter data. All the light atoms were unam- biguously located by difference Fourier synthesis in spite of the presence of the two heavy osmium atoms. The totally unexpected structure obtained is shown in the Figure. The structure closely resembles that of (MeC .CMe)H2Fe2(C0)2 although the preparation of the latter by reaction between an alkyne and the iron carbonyl anion HFe(CO), is very different.However similar structural features have been assumed for the complexes Fe,(CO)6(RC i CR’) formed by the direct reaction4 between alkynes and Fe,(CO), or Fe2(C0),. 0 i There is one major stereochemical difference the Os(CO) group co-ordinated to the heterocyclic five-membered ring is rotated through 60”relative to the iron c~mplex.~ Thus while the co-ordination polyhedron of the corresponding iron atom is a trigonal prism that of the osmium atom is an octa- hedron. The second osmium atom is surrounded by five carbon atoms in square pyramidal co-ordina- tion and a single 0s-0s bond is implied by the observed separation 2.74 A [shorter than the value 2.88 A reported5 for Os,(CO),,].Further although we cannot of course determine the presence of the hydrogen atoms we can deduce from the co-planarity of the heterocyclic five-ring and the two substituent methyls that the terminal carbon atoms of the original diolefin have each lost one proton and Fischer Bittler and Fritz 2. Nuturforsch. 1963 186 83. Fischer personal communication. Hock and Mills Acta Cryst. 1961 14 139. 4 Hiibel Braye Clauss Weiss Kriierke Brown King and Hoogzand J. Znorg. Nuclear Chem. 1959,9 204. Corey and Dahl Znorg. Chem. 1962 1 521. DECEMBER 1963 that the osmium atom involved forms essentially single bonds to these two carbons. The observed 0s-C distances are in agreement with this deduction.The molecular formula should hence be C,;H,Os,(CO),. The structure permits rationalisation of an 18-electron shell arrangement. We gratefully acknowledge the supply of crystals by Professor E. 0.Fischer and discussions with him and his co-workers. Our findings are compatible with their infrared spectral work.2 We are also indebted to the U.K.A.E.A. for computer time. (Received October 7th 1963.) Calorimetric Detection of Conformational Changes in Polypeptides By H. BLOCK OF INORGANIC AND INDUSTRIAL UNIVERSITY (DEPARTMENT PHYSICAL CHEMISTRY OF LIVERPOOL) and J. B. JACKSON (IMPERIAL INDUSTRIES AND POLYMER CHEMICAL LTD.,PETROCHEMICAL LABORATORY RUNCORN RUNCORN.) HEATH CHANCES in the conformation of polypeptides in solution have been observed mainly by optical methods by altering either the composition ratio of mixed solvents1y2 or the temperat~re.~ Theoretical treatments4 have justified consideration of the transi- tion between the a-helix and the random-coil form as a first-order effect.However the breadth of the transition is a function of molecular weight being sharper for higher polymers. Calculations of the enthalpy of the change have been made based on measurements of the temperature-induced transition. No direct evidence of a heat of transition has been reported. Herein we demonstrate the existence of observable thermal effects at the transition using a calorimetric method. The novel design of the simple calorimeter is to be described elsewhere. Measurements were carried out isothermally and temperature changes were measured by using a pair of matched thermistors in a bridge circuit the off-balance current being calibrated directly as the difference in temperature between one thermistor in the calorimeter and the other in the surrounding constant-temperature bath.Known volumes of two polymer solutions one from an r-helix solvent the second from a random-coil sol- vent were mixed in the calorimeter and the tempera- ture change noted. The polypeptides initially studied were poly-(y-benzyl-L-glutamate) and its 1 :1 copolymer with the D-enantiomorph ;molecular weights have been estimated from viscosity measurements (0.5% w/v in dichloroacetic acid) by use of the relationship of Doty et al.lb The solvents were chloroform the a-helix solvent and dichloroacetic acid the random- coil solvent.Experiments were performed at 25 rf 0.01OC. The results of several experiments are shown in the Figure. Samples 1 and 2 clearly demonstrate the Occurrence of a transition and its reversibility. The composition of the mixture at which the change Volume fraction ('A CHCG) Curves rising fiom left to right indicate addition of chloroform solution 10 dichloroacetic acid solution in the calorimeter and vice versa. Concentration of polymer solutions 5 w/v. (a) Sample 1 poly-(y-benzyl-L-glutamate) M 55,000. (b) Sample 2 poly-(y-benzyl-L-glutamate) M 160,ooO. (c) Sample 3 copolymer M 24,000. (d)Solvent mixing alone. Successive curves are displaced 0.5"~on the temperature scale.(a)Doty Holtzer Bradbury and Blout J. Amer. Chem. Sac. 1954 76 4493; (b) Doty Bradbury and Holtzer ihid. 1956 78 947. Downie Elliott Hanby and Malcolm Pruc. Roy. Suc. 1957 A 242 325. Doty and Yang J. Amer. Chem. Suc. 1956,78,498. See for example Zimm and Bragg J. Chem. Phys. 1958,28 1246; 1959,31 526. occurs corresponds with that determined by optical meth0ds.l The wider composition range for the transition exhibited by sample 1 is due to the lower molecular weight of this polymer. Unfortunately at this stage it is not possible to estimate the enthalpy of the observed effect. Calorimeter modifications are in progress to enable heat measurements to be made. Optical methods for detection of the transition obviously cannot be used for a 1:l DL-copolymer such as sample 3.However it has been inferred from experiments by optical methods on a series of 7-benzylglutamate copolymers in which the ratio of the enantiomorphs was varied that a 1 :1 copolymer contains helical segments in chloroform and is a random-coil in dichloroacetic acid.2 This view is also suggested by the kinetics of the polymerisation of a-amino-N-carb~xy-anhydrides.~ Certainly in the solid state the evidence is most compelling for the existence of an a-helix of the copolymer both from X-ray data6 and from infrared spectra.’ Further PROCEEDINGS infrared spectra of similar copolymers of leucine in solution indicate the presence of helical segments. It is unlikely therefore that no helical content is present.Consequently a transition is to be expected the calorimetric method providing a possible method for its detection. The lack of a distinct break in the curves for sample 3 may be due to one of several reasons; a “smearing” out of the transition due to molecular-weight effects as above or the transition may take place at different compositions for a-helices of various lengths connected by randomly coiled segments. Relatively few helical segments could be present so that the magnitude of the change is small and thus not easily detected. Further experiments are in hand. ‘The authors thank Professor C. H. Bamford for valuable discussion and continued interest in this work. (Received October 15th 1963.) Bamford and Block “Polyamino Acids Polypeptides and Proteins,” edited by M.A. Stahman University of Wisconsin Press Madison 1962 p. 77 and references therein. Bamford Elliott and Hanby “Synthetic Polypeptides,” Academic Press Inc. New York 1956 p. 276. Elliott Proc. Roy. Suc. 1953 A 221,104. The Crystal and Molecular Structure of [Ph*AI*N*Ph] By T. R. R. MCDONALD (NATIONAL LABORATORY MIDDLESEX) CHEMICAL TEDDINGTON and W. S. MCDONALD DEPARTMENT GLASGOW, (CHEMISTRY THE UNIVERSITY W.2) A NEW class of aluminium-nitrogen compounds of formula [Ph.Al.N.Ar] was recently rep0rted.l Alternative structures with either an eight-membered ring (I) or a cubic framework structure (TI) were suggested. Ph A< (N-At /Ph p\hA\-N ,Ar \“Ar Ar,N’+ A[’ 1 ‘A 1 I I N+AL.~~ A /A“ph Ph’ A~’*N/ Ar \ Ar ‘PL-N Ar We have carried out a three-dimensional X-ray crystal structure analysis of the octaphenyl com- pound (Ar = Ph).The crystals are tetragonal space group I&/a with 4 molecules in a unit cell of dimensions a = 20.0 A c = 10-90A. The asym- metric unit is one quarter of a molecule and each Jones and McDonald Proc. Chem. Suc. 1962,366. tetrameric molecule has crystallographic 2 sym-metry. Seven hundred and thirty-three independent structure amplitudes were measured from equi- inclination Weissenberg photographs obtained with Cu-Ka radiation. The structure was solved by Patterson and Fourier methods and refined by least squares using DEUCE computer programmes written by Dr.J. S. Rollett. At the present stage of refinement the R value is 14.7 %. Structure 11 with 12 essentially equal Al-N bonds is found. The mean Al-N bond length is 1.93 A and the A1-C and N-C bonds are 1.86 A and 1.48 A respectively. Further refinement of the structure is being carried out. We thank Miss J. M. Spink for experimental assistance Professor D. W. J. Cruickshank for dis- cussions and D.S.T.R. for a studentship (to W.S.M.). (Received October 25th 1963.) DECEMBER 1963 383 The Structure of Patchouli Alcohol By M. DOBLER and H. P. WEBER J. D. Dmz B. GUBLER (ORGANIC LABORATORY INSTITUTE ZURICH) CHEMISTRY SWISSFEDERAL OF TECHNOLOGY and G. Bucm and J. PADILLA 0. (DEPARTMENT MASSACHUSETTS OF TECHNOLOGY 39, OF CHEMISTRY INSTITUTE CAMBRIDGE MASS.) SOME of us (M.D.J.D.D. H.P.W.) have recently undertaken an X-ray analysis of the patchouli alcohol diester of chromic acid with the objective of deter- mining the Cr-0-C angles. Such a determination it was hoped might throw light on the mechanism of oxidation of primary and secondary alcohols by chromic acid. In the course of this analysis we have found that the X-ray evidence cannot be reconciled with structure (I) proposed for patchouli alcohol on the basis of degradative and synthetical studies.lS2 Our analysis leads to a carbon skeleton correspond- ing to structure (IIa) which can be written in the alternative form (IIb). Since the diester yields patchouli alcohol itself on (i) hydrolysis in ethanolic 0*2~-sodium hydroxide under reflux (69 % yield) and (ii) reduction with lithium aluminium hydride in ether at room temperature (84% yield) the possibi- lity of rearrangements in the esterification can be excluded.Hence (11) represents the structure of patchouli alcohol. un Crystals of the die~ter,~ C,,H,,O,Cr are deep orange-coloured needles. The orthorhom bic cell has a = 20-65A b = 11.45 A c = 11.92 A space group P2,2,2, and contains four formula units. The in- tensities of about 1200 reflexions were measured at room temperature with the help of the Arndt- Phillips linear diffractometer Mo-K radiation being used. The analysis followed a fairly normal course; the chromium atoms were located from the three-dimensional Patterson function and a series of electron-density syntheses phased first on the chromium atoms alone and then also on the other atoms as their positions were recognised led gradu- ally to the complete structure excluding hydrogen atoms.At the present stage of refinement after two difference syntheses the conventional R factor is 21 %. The latest difference synthesis shows no excess or deficit of electron density greater than 0.5 elec-trons/A3 except in the immediate vicinity of the chromium atom which undergoes markedly aniso- tropic thermal movement. The estimated standard deviations in the positional co-ordinates of the carbon and oxygen atoms are about 0.05 A and in view of these uncertainties there seems little point in discussing the details of the molecular geometry at present.The new structure of patchouli alcohol (11) implies that the pyrolysis of patchouli acetate to ~(111) and y-patchoulene is accompanied by an unprecedented rearrangement. A second rearrangement proceeding in precisely reverse direction occurs on oxidation of a-patchoulene (111) with peracetic acid. The product formed is not the previously claimed 1,2-diol but the rearranged 1:3-diol (IV). Since neither of these re- arrangements was recognised patchouli alcohol and a-patchoulene were assumed to have iden tical carbon skeletons. We are grateful to Professor A. Eschenmoser not only for suggesting this problem but also for valuable discussion at several stages. Part of this work was carried out with the financial support of the Schweiz.Nationalfonds zur Forderung der wissenschaftlichen Forschung. Received October 7th 1963.) Buchi Erickson and Wakabayashi J. Amer. Chem. Soc. 1961 83 927. Buchi and McLeod J. Amer. Chem. Soc. 1962,84 3205. Wienhaus Ber. 1914 47 330. Arndt and Phillips Acta Cryst. 1961 14 807. PROCEEDINGS VACANCIES ON COUNCIL 1964 NOTICE is hereby given that in accordance with the Bye-Laws the following vacant places in the Council fall due to be filled at the Annual General Meeting to be held in Birmingham on Wednesday April 8th 1964. Ofice No. of Names of Members who are vacancies to retire President .. .. .. .. .. .. .. .. . . ONE Professor J. M. Robertson Vice-presidents who have filled the Office of President .... ONE Sir Cyril Hinshelwood Vice-presidents who have not filled the Office of President .. ONE Dr. E. J. Bowen Elected Ordinary Members of Council Constituency I .. .. *. .. .. .. ,. FIVE Dr. L. J. Bellamy (South-East England) Professor D. P. Craig Professor L. Crombie (retires January lst 1964 under Bye-Law 56) Dr. W. Gerrard Mr. H. M. Powell Constituency I1 .. .. .. *. .. .. .. ONE Professor D. H. Everett (Central and South-West England and South Wales) Constituency I11 .. .. .. *. .. 0. . . TWO Dr. A. K. Holliday (North-West England North Wales and Isle of Man) Dr. J. Honeyman Constituency V . . .. *. .. .. *. . . ONE Dr. G. 0. Aspinall (Scotland) Constituency VI .. .. .. *. .. .. .. ONE Professor W.Cocker (Ireland) No vacancies arise in Constituency IV. Members who are to retire are not eligible for re-election to the same office until a lapse of one year. In accordance with Bye-Law 24 the Council has nominated Sir Ewart Jones to the Office of President. In accordance with Bye-Law 46,Professor J. M. Robertson becomes a Vice-president who has filled the Office of President. Nominations by Fellows for the Offices of President and Vice-president who has not filled the Office of President should be made in writing and must be signed by at least twenty Fellows. Fellows resident in a constituency may nominate any Fellow resident in that constituency for election to the Council to fill a vacancy among Elected Ordinary Members of Council allotted to that constituency.Every such nomination must be in writing signed by at least fifteen Fellows (resident in that constituency). Fellows may obtain forms of nomination from the General Secretary and should state the vacancy for which they are requested. Every nomination must relate to one vacant place only and must be accompanied by a signed declaration by the nominee that he is willing to accept office if elected. Nominations must be received by the Society not later than Friday February 14th 1964. A. W. JOHNSON K. W. SYKES J. W. LINNETT Honorary Secretaries. December lst 1963. DECEMBER 1963 385 NEWS AND ANNOUNCEMENTS Election of New Fellows.-143 Candidates were elected to the Fellowship in November 1963. Deaths.-We regret to announce the deaths of the following Dr.D. J. Coyle (14.7.63) of the Aerospace Corporation Los Angeles ; Mr. G. Dodd (24.10.63) of Monsanto Chemicals Ltd. London; Dr. S. A. Fuqua jun. (2.9.63) of Stanford Research Institute California. The Davy Medal.-The Royal Society has awarded the Davy Medal to Dr. E. J. Bowen for his dis- tinguished work on the elucidation of photochemical reactions and for his study of fluorescence and phosphorescence in relation to the molecular processes concerned. International Council of Scientific Unions.-Dr. H. W. Thompson C.B.E. F.R.S. was elected President for the next two years of the International Council of Scientific Unions at the Tenth General Assembly of the Council held recently in Vienna. Professor D.Blaskovic Czechoslovakia was elected Secretary General and Ing. GCn. G. Laclavkre France was re- elected Treasurer. Symposia etc.-A one-day meeting on Polysac- charides organised by the Plant Phenolic Group will be held in London on January 7th 1964. Professor H. K. Porter and Drs. G. 0.Aspinall E. E. Percival and W. J. Whelan will be among the speakers; topics will include starch gums and pectic sub- stances and seaweed polysaccharides. Further details can be obtained from A. H. Williams Research Station Long Ashton Bristol. A one-day Symposium on Process Optimisation organised by the East Midlands Centre of the Graduates and Students Section of the Institution of Chemical Engineers will be held in Loughborough on February 24th 1964.Further enquiries should be addressed to the Centre Secretary Mr. K. A. Pike Department of Chemical Engineering Lough-borough College of Technology Loughborough Leicestershire. The Third Festival of Technical-Scientific Films will be held in Budapest on April 15-25th 1964. Further enquiries should be addressed to Filmklub- Fesztivaliroda Szabadsig ter 17 Budapest V/Magyarorszag. A Conference on Fundamental Problems of Low Pressure Measurements organised jointly by the National Physical Laboratory and The Institute of Physics and The Physical Society will be held in Teddington on September 23rd-25thY 1964. Further enquiries should be addressed to Mr. R. S. Dadson Standards Division National Physical Laboratory Teddington Middlesex.Personal.-Dr. E. R. Buckle has been appointed Visiting Associate Professor of Engineering and Applied Science at Yale University for the Spring Term 1964. Dr. P. Coackley has been appointed Senior Lecturer in Public Health Engineering within the Civil Engineering Department at the Royal College of Science and Technology Glasgow. Dr. B. E. Dawson has been appointed Lecturer in Education at King’s College London. He was formerly Head of the Science Department at Coopers’ Company’s School London. Dr. A. F. Ferris has been appointed Senior Advisor for Chemistry at the Midwest Research Institute Kansas City Missouri. Dr. A. R. Forrester has been appointed Assistant Lecturer in the Chemistry Department of the University of Aberdeen.The title of Emeritus Professor has been conferred on Professor R. D. Haworth at the University of Sheffield. Mr. A. J. Jones formerly of the University of Keele has been appointed to a Senior Teaching Fellowship in Chemistry at Monash University Melbourne Australia. Dr. S. S. M. A. Khorasani has been awarded a Swiss Federal Government scholarship for work under Professor G. Schwarzenbach at the Eidg. Technische Hochschule Zurich. He is on study leave from the University of Dacca. Dr. G. L. Kington formerly a Director of Morgan- ite Research and Development Limited has been appointed Director of Research of the British Aluminium Company Limited. The University of Leeds has conferred the honorary degree of D.Sc. upon Sir Hans Krebs and upon Sir Hurry Melville.Dr. J. S. Littler has been appointed Lecturer in Organic Chemistry at the University of Bristol. Dr. D. H. Lohmann has been appointed Senior Research Chemist at the Tin Research Institute Greenford Middlesex. Dr. P. Molyneux formerly I.C.I. Research Fellow at the University of Keele has been appointed Lecturer in Pharmaceutical Chemistry (Physical Aspects) in the School of Pharmacy of Chelsea College of Science and Technology London. Professor R. A. Morton has been appointed Chairman of the Food Additives and Contaminants Sub-committee of the Food Standards Committee. Dr. A. Packter formerly Lecturer in Physical Chemistry (applied to Pharmacy) at Chelsea College of Technology has been appointed Senior Lecturer in Physical Chemistry at West Ham College of Technology London.Dr. N. Sheppard formerly of the University of Cambridge has been appointed Professor of Chem- istry in the School of Chemical Sciences at the University of East Anglia. Dr. G. Sosnovsky formerly Senior Scientist at I.I.T.R.I. (formerly Armour Research Foundation) has been appointed Associate Professor in the PROCEEDINGS Department of Chemistry Illinois Institute of Technology Chicago. Dr. H. M. Stanley has been appointed a Director of the Distillers Company Limited. Dr. T. D. Whittet of University College Hospital London has been elected a Member of the New York Academy of Sciences. PROGRAMME OF MEETINGS JANUARY TO JUNE 1964” Anniversary Meetings 1964 THE Anniversary Meetings of the Society will be held in Birmingham on April 7th to 9th.A programme of the meetings will be sent separately to all Fellows. London Thursday January 23rd 1964 at 6 p.m. Tilden Lecture “Activated Molecules,” by Professor A. F. Trotman-Dickenson Ph.D. To be given in the Lecture Theatre School of Pharmacy Brunswick Square W.C.l. Thursday February 13th at 6 p.m. Simonsen Lecture “Molecular Rearrangements of Terpenes,” by Professor G. Ourisson Ph.D. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology Imperial Institute Road S.W.7. Thursday February 27th at 6 p.m. Tilden Lecture “A Glow in the Dark-The Rationale of Phosphorylation,” by Dr. V. M.Clark M.A. To be given in the Lecture Theatre School of Pharmacy Brunswick Square W.C. 1. Thursday March 19th at 2 p.m. Symposium on “Aspects of Molecular Dissym- metry.” To be held at the Battersea College of Technology S.W. 1 1. Details have been issued separately. This meeting is held in association with the unveiling of the memorial plaque to the late Dr. J. Kenyon F.R.S. Thursday May 7th at 6 p.m. Meeting for the Reading of Original Papers. To be held in the Rooms of the Society Burlington House w.l. Thursday June llth at 6 p.m. Centenary Lecture “Applications of Optical Rota- tory Dispersion and Circular Dichroism in Stereo- chemistry,” by Professor C. Djerassi Ph.D. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology Imperial Institute Road S.W.7.[British Railways are offering concessionary fares (single fare plus one half for the return journey) for London meetings; a travel voucher for any meeting will be sent by the General Secretary on receipt of a stamped and addressed envelope.] Aberdeen (Joint Meetings with the Royal Institute of Chem- istry and the Society of Chemical Industry to be held in the Medical Physics Lecture Theatre Marischal College unless otherwise stated.) Wednesday January 22nd 1964 at 8 p.m. Lecture “Microbial Synthesis in Industry Progress and Possibilities,” by Dr. S. J. Pirt. Thursday February 13th at 8 p.m. Liversidge Lecture “Some Contemporary Problems in Solid-state Chemistry,” by Professor J.S. Ander-son Ph.D. F.R.S. To be given in the Chemistry Department The University. Thursday February 27th at 8 p.m. Lecture “Some Aspects of the Chemistry of Flames,” by Dr. T. M. Sugden M.A. F.R.S. Tuesday March 17th at 8 p.m. Lecture “Aspects of Enzymes,” by Dr. D. J. Manners M.A. F.R.I.C. Wednesday March 18th at 8 p.m. Lecture “Aspects of Enzymes,” by Dr. D. J. Manners M.A. F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held at The Technical College Thurso. Aberystnyth (Joint Meetings with the University College of Wales Chemical Society to be held in the Edward Davies Chemical Laboratory.) * Offprints of this programme can be obtained from the General Secretary The Chemical Society Burlington House London W.l.DECEMBER 1963 Thursday January 23rd 1964 at 5 p.m. Lecture “Experiments in Strong Electric Fields,” by Dr. A. D. Buckingham M.A. Wednesday February 5th at 5 p.m. Lecture “Flames Cool and Hot,” by Dr. C. F. H. Tipper. Thursday February 20th at 5 p.m. Lecture “Tetraterpenes,” by Professor B. C. L. Weedon Ph.D. F.R.I.C. Thursday March 5th at 5 p.m. Lecture “The Stability of Lanthanide Chelates,” by Dr. F. J. C. Rossotti M.A. Birmingham (Joint Meetings with the University Chemical Society to be held in the Chemistry Department The University unless otherwise stated.) Friday January 24th 1964 at 4.30 p.m. Lecture “Some Aspects of the Chemistry of Flames,” by Dr.T. M. Sugden M.A. F.R.S. Friday February 14th at 4.30 p.m. Lecture “Naturally Occurring Acetylenic Com- pounds,” by Sir Ewart Jones D.Sc. F.R.S. Friday February 28th at 5.30 p.m. Lecture “Some Applications of n.m.r. Spectro-scopy in Organic Chemistry,” by Professor A. R. Katritzky D.Phil. Sc.D. Joint Meeting with the Chemical Society of the College of Technology to be held in the College of Advanced Technology. Friday May 8th at 4.30 p.m. Lecture “The Scientific Examination of Questioned Documents,” by Professor C. L. Wilson Ph.D. D.Sc. F.R.I.C. Bristol (Joint Meetings with the Royal Institute of Chem- istry and the Society of Chemical Industry to be held in the Department of Chemistry The University unless otherwise stated.) Thursday January 9th 1964 at 6.30 p.m.Lecture “Recent Development in Collagen Re- search,” by Professor A. G. Ward O.B.E. M.A. Thursday January 30th at 6.30 p.m. Lecture “Recent Developments in Tyre Tech-nology,” by Mr. G. F. Morton B.Sc. A.1nst.P. Thursday February 13th at 6.30 p.m. Lecture “The Catalytic Activation of Hydrogen,” by Professor D. D. Eley O.B.E. Ph.D. Sc.D. Tuesday February 18th at 7.30 p.m. Lecture “Polymerisation Mechanisms with Ionic Catalysts,” by Professor A. G. Evans D.Sc. F.R.I.C. To be given at the Technical College Gloucester. Thursday February 27th at 5.15 p.m. Lecture “Tarnishing Reactions,” by Dr. S. J. Gregg F.R.I.C. Joint Meeting with the University Student Chemical Society. Thursday March Sth at 6.30 p.m.Lecture “Freeze Drying of Pharmaceuticals and Food,” by Mr. T. W. G. Rowe. Also joint with the Institute of Fuel. Thursday March 12th at 7 p.m. Lecture “A Chemist at Sea,” by Dr. L. H. N. Cooper F.R.I.C. To be given at Bridgwater. Cambridge (Joint Meetings with the University Chemical Society to be held in the University Chemical Laboratory Lensfield Road unless otherwise stated.) Friday January 17th 1964 at 8.30 p.m. Lecture “New Results in Reaction Kinetics ob- tained by Photochemical Methods,” by Professor R. G. W. Norrish Sc.D. F.R.S. Friday January 31st at 8.30 p.m. Lecture “The Chemistry of the Vitamin B, Coenzyme,” by Professor A. W. Johnson Sc.D. F.R.I.C. Friday February 28th at 8.30 p.m. Lecture “Liquid Sodium,” by Professor C.C. Addison D.Sc. F.R.I.C. Wednesday March llth at 6.15 p.m. Lecture “Applications of Electron Spin Resonance Spectroscopy in the Elucidation of Reaction Mechanisms,” by Dr. R. 0. C. Norman M.A. To be given at Mander College Bedford. Monday June 8th at 5.30 p.m. Centenary Lecture “Applications of Optical Rota- tory Dispersion and Circular Dichroism in Stereo- chemistry,” by Professor C. Djerassi Ph.D. Cardif€ (Meetings to be held in the Department of Chem- istry University College Cathays Park Cardiff.) Monday February 3rd 1964 at 5 p.m. Lecture “The Infrared Spectra of Surface adsorbed Molecules,” by Dr. N. Sheppard M.A. Monday March 9th at 5 p.m. Lecture “Sugars and Antibiotics,” by Dr. A. B. Foster.Monday April 27th at 5 p.m. Tilden Lecture “A Glow in the Dark-The Rationale of Phosphorylation?” by Dr. V. M. Clark M.A. Dublin Friday February 7th 1964 at 7.45 p.m. Lecture ‘‘The Chemistry of the Pneumococcus Imuno-polysaccharides,” by Professor M. Stacey D.Sc. F.R.S. Joint Meeting with the Werner Society to be held in the Department of Chemistry Trinity College. Friday February 14th It is regretted that the Simonson Lecture by Professor G. Ourisson arranged for this date has been cancelled. Monday February 24th at 7.45 p.m. Lecture “Protonation of Some Transitional-metal Complexes,” by Professor G. Wilkinson Ph.D. F.R.I.C. Joint Meeting with the Werner Society to be held in the Department of Chemistry Trinity College.Wednesday April 22nd at 5.30 p.m. Lecture “Polycomponent Liquid Crystals and Their Place in Living Matter,” by Dr. A. S. C. Lawrence F.R.I.C. To be given in the Department of Chemistry University College. DtEham (Joint Meetings with the University Chemical Society to be held in the Science Laboratories South Road unless otherwise stated.) Monday February 3rd 1964 at 5 p.m. Lecture “Organometallic Chemistry-Some Recent Studies,” by Professor F. G. A. Stone M.A. Ph.D. Wednesday February 12th at 3 p.m. Meeting for the Reading of Original Papers in Inorganic Chemistry. Joint Meeting with the Chemical Societies of Newcastle and the Tees-side to be held in the Chemistry Department The University Newcastle-upon-Tyne. Monday February 24th at 5 p.m.Lecture “Modern Developments in Free-radical Chemistry,” by Dr. W. A. Waters F.R.S. Monday March 16th at 5 p.m. Lecture “Big Rings,” by Professor R. A. Raphael Ph.D. F.R.S. Dundee (Meetings to be held in the Chemistry Department Queen’s College.) Tuesday January 28th 1964 at 5 p.m. Lecture “Quantum Mechanical Tunnelling in Proton Transfer Reactions,” by Dr. E. F. Caldin M.A. Tuesday February 18th at 5 p.m. Lecture “The Stereochemical and Spectroscopic Aspects of Optical Rotatory Power,” by Dr. S. F. Mason M.A. Tuesday February 25th at 5 p.m. Lecture “Excitons and the Spectra of Molecular Crystals,” by Professor D. P. Craig D.Sc. F.R.I.C. PROCEEDINGS Edinburgh Tuesday January 14th 1964 at 4.30 p.m.Lecture “Carbonium ions carbanions and olefin rearrangement,” by Dr. M. C. Whiting. Joint Meet- ing with the University Chemical Society to be held in the Department of Chemistry The University. Thursday January 16th at 7.30 p.m. Lecture “Hemicelluloses Gums and Pectic Sub- stances,” by Dr. G. 0. Aspinall F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Thursday February 20th at 7.30 p.m. Lecture “How Poppies Make Opium,” by Professor A. R. Battersby D.Sc. Ph.D. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Tuesday March 3rd at 4.30 p.m. Lecture “Simple and Complex Metal Nitrates and Nitrites,” by Professor C.C. Addison D.Sc. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University. Thursday March 12th at 7.30 p.m. Symposium of three short papers “Radioactivity.“ Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Exeter (Meetings to be held in the Department of Chem- istry The University unless otherwise stated.) Friday January 24th 1964 at 5.15 p.m. Tilden Lecture “A Glow in the Dark-The Rationale of Phosphorylation,” by Dr. V. M. Clark M.A. To be given in the Washington Singer Labora- tories. Friday February 28th at 5.15 p.m. Lecture “Biogenesis of Some Alkaloids,’’ by Professor D.H. R. Barton DSc. F.R.S. Thursday March 12th at 5.15 p.m. Lecture “The Duplex Origin of Petroleum,’’ by Sir Robert Robinson O.M. D.Sc. F.R.S. Friday April 24th at 4.15 p.m. Lecture “Chemical Control Mechanisms of Meta- bolism,” by Sir Hans Krebs F.R.S. M.D. Glasgow Thursday January 30th 1964 at 4 p.m. Lecture “Electron Spin Resonance,” by Professor M. C. R. Symons D.Sc. F.R.I.C. Joint Meeting with The Andersonian Chemical Society to be held in the Chemistry Department The Royal College of Science and Technology. DECEMBER 1963 Thursday February 13th at 4 p.m. Lecture “Modern Chemical Applications of Infrared Spectroscopy,” by Dr. N. Sheppard M.A. Joint Meeting with the Alchemists’ Club to be held in the Chemistry Department The University.Wednesday February 19th at 4 p.m. Simonsen Lecture “Molecular Rearrangements of Terpenes,” by Professor G. Ourisson Ph.D. To be given in the Chemistry Department The University. Friday March 13th at 4 p.m. Annual General Meeting of Local Fellows to be followed by Meeting for Reading of Original Papers. To be held in the Chemistry Department The Royal College of Science and Technology. Tuesday March 24th at 5 p.m. Lecture “The Interaction of Slow Electrons with Molecules,” by Professor T. L. Cottrell D.Sc. F.R.I.C. To be held during Scottish Research Students Colloquium at Chester’s House Bearsden. Tuesday May 26th at 4 p.m. Centenary Lecture “Applications of Optical Rota- tory Dispersion and Circular Dichroism in Stereo-chemistry,” by Professor Carl Djerassi Ph.D.To be given in the Chemistry Department The University. Hull (Joint Meetings with the University Students Chemical Society to be held in the Department of Chemistry The University.) Thursday January 16th 1964 at 4 p.m. Lecture “Magnetism and Stereochemistry of Transition-metal Complexes,” by Professor J. Lewis D.Sc. Ph.D. Thursday February 13th at 4 p.m. Lecture “A New Family of Antibiotics,” by Professor W. D. Ollis Ph.D. Thursday February 27th at 4 p.m. Lecture “Infrared Spectra of Molecules Adsorbed on Surfaces,” by Dr. N. Sheppard M.A. Leeds Thursday March 5th 1964 at 6 p.m. Lecture “Electron transfers in Aprotic Solvents and some Chain-transfer Complexes,” by Professor M.Szwarc Ph.D. D.Sc. Joint Meeting with the University Union Chemical Society to be held in the Chemistry Department The University. Leicester (Joint Meetings with the University Chemical Society to be held in the Department of Chemistry The University unless otherwise stated.) Monday January 13th 1964 at 4.30 p.m. Lecture “Some New Natural Products-Structural and Biosynthetical Studies,” by Professor W. D. Ollis Ph.D. Monday February loth at 4.30 p.m. Lecture “Co-ordination Complexes and Organic Chelating Agents in Modern Analytical Chemistry,” by Dr. T. S. West F.R.I.C. Monday March 9th at 4.30 p.m. Lecture “Determination of the Stereochemistry of Cobalt(I1) Complexes,” by Professor J.Lewis Ph.D. D.Sc. Thursday March 12th at 4.30 p.m. Lecture “The Forces Between Atoms,” by Professor C. A. Coulson D.Sc. F.R.S. Joint Meeting with the Loughborough Colleges Chemical Society to be held in the Lecture Theatre The Union Building College of Technology Loughborough. Liverpool (Joint Meetings with the University Chemical Society to be held in the Donnan Laboratories The University.) Thursday January 30th 1964 at 5 p.m. Lecture “Some Applications of Reaction Kinetics to Analytical Problems,” by Professor H. Irving M.A. D.Sc. F.R.I.C. Monday February 17th at 5 p.m. Simonsen Lecture “Molecular Rearrangements of Terpenes,” by Professor G. Ourisson Ph.D. Manchester (Meetings to be held in the Lecture Theatre R/G7 Renold Building (Lecture Room Block) Manchester College of Science and Technology unless otherwise stated.) Thursday January 16th 1964 at 6.30 p.m.Lecture “Stereochemistry of Squalene Biosyn- thesis,” by Dr. G.J. PopjBk F.R.S. Thursday January 30th at 5 p.m. Lecture “Alkaloid Biosynthesis,” by Professor A. R. Battersby D.Sc. Ph.D. Joint Meeting with the Royal College of Advanced Technology Chemical Society to be held in the Royal College of Advanced Technology Salford. Thursday February 20th at 6.30 p.m. Lecture “Catalytic Reactions of Aromatic Mole- cules on Metals,” by Professor C. Kemball M.A. Sc.D. F.R.I.C. Thursday February 27th at 6.30 p.m. Lecture “Recent Developments in Anionic Poly- merisation,” by Professor M.Szwarc Ph.D. D.Sc. Thursday March 19th at 6.30 p.m. Lecture “Stereochemical Correlations,” by Profes- sor W. Klyne M.A. D.Sc. Ph.D. Tuesday April 7th at 10 a.m. Symposium “Chemicals in the Service of Petrol-eum.” Joint Meeting with the Institute of Petroleum the Society of Chemical Industry and the Royal Institute of Chemistry. To be held in the R/C2 Renold Building Manchester College of Science and Technology. Thursday May 14th at 6.30 p.m. Official Meeting and Niels Bohr Memorial Lecture given by Sir George Thomson F.R.S. To be held at the University of Manchester. Thursday May 28th at 6.30 p.m. Centenary Lecture “Applications of Optical Rota- tory Dispersion and Circular Dichroism in Stereo- chemistry,” by Professor C.Djerassi Ph.D. Newcastle upon Tyne (Meetings to be held in the Chemistry Department The University.) Friday January 24th 1964 at 5.30 p.m. Bedson Club Lecture. “Diffusion Incorporation and Transformation and Transformation Processes during Chemisorption of Gases on Metals,” by Professor F. C. Tompkins DSc. F.R.S. Wednesday February 12th at 3 p.m. Meeting for the Reading of Original Papers in Inorganic Chemistry. Tuesday March 3rd at 5.30 p.m. Lecture “Chemical and Biochemical Studies on the Cephalosporins,” by Dr. E. P. Abraham M.A. F.R.S. Northern Ireland (Joint Meetings with the Royal Institute of Chem- istry the Society of Chemical Industry and the Andrews Club to be held in the Department of Chemistry David Keir Building Queen’s University Belfast.) Thursday February 6th 1964 at 7.45 p.m.Lecture to be given by Professor M. Stacey D.Sc. F.R.S. Tuesday March 3rd at 7.45 p.m. Lecture “The Synthesis of Polypeptides,” by Professor H. N. Rydon D.Sc. F.R.I.C. North Wales (Meetings to be held in the Chemistry Department University College of North Wales Bangor.) Thursday January 30th 1964 at 5.45 p.m. Liversidge Lecture “Some Contemporary Problems in Solid-state Chemistry,” by Professor J. S. Anderson Ph.D. F.R.S. Joint Meeting with the University College of North Wales Chemical Society. Thursday February 13th at 5.45 p.m. Lecture “Some Unusual Electrophilic Aromatic Substitutions,” by Professor C. Eaborn D.Sc. F.R.I.C. Joint Meeting with the University College of North Wales Chemical Society.Thursday March 12th at 5.45 p.m. Lecture “The Chemist’s Role in the Brewing PROCEEDINGS Industry,” by Dr. J. Todd A.R.I.C. Joint Meeting with the Society of Chemical Industry. Norwich (Meetings to be held in Lecture Room 2 The University of East Anglia Wilberforce Road.) Thursday January 30th 1964 at 5.30 p.m. Lecture “Development and Mechanisms of Ziegler Mixed Organometallic Catalytic Systems,” by Dr. E. W. Duck F.R.I.C. Thursday February 6th at 5.30 p.m. Lecture “The Kinetics of Nitration of Heterocyclic Compounds,” by Dr. K. Schofield F.R.I.C. Thursday February 13th at 5.30 p.m. Lecture “Recent Developments in Petroleum Pro- duct Technology,” by Mr. J. B. Berkeley M.A. A.F.Inst.Pet.Thursday February 20th at 5.30 p.m. Lecture “Reactions of Carbon-Silicon Bonds,” by Professor C. Eaborn D.Sc. F.R.I.C. Thursday March 5th at 5.30 p.m. Lecture “Sufphoxide Oxidations,” by Dr. D. N. Jones. Thursday March 12th at 5.30 p.m. Lecture “Nuclear Magnetic Resonance and Self- diffusion in Aqueous Solutions,” by Dr. B. A. Pethica D.I.C. Thursday March 19th at 5.30 p.m. Lecture “Synthetic Glues,” by Dr. W. Wilson A.R.C.S. F.R.I.C. Thursday April 30th at 5.30 p.m. Lecture “Claudogenic Steroids,” by Dr. V. Petrow F.R.I.C. Thursday May 14th at 5.30 p.m. Lecture “Solvolysis and Olefin Rearrangement,” by Dr. M. C.Whiting M.A. A.R.C.S. Nottingham (Joint Meetings with the University Chemical Society to be held in the Chemistry Department The University unless otherwise stated.) Tuesday January 28th 1964 at 5 p.m.Lecture “Stereochemistry of Squalene Biosyn- thesis,” by Dr. J. W. Cornforth. Tuesday February 11 th at 5 p.m. Lecture “The Structure of Some Simple Inorganic Radicals,” by Professor M. C. R. Symons D.Sc. Ph.D. F.R.I.C. Tuesday February 25th at 5 p.m. Lecture “Kinetic Theory of Gases Old and New,” by Professor P. Gray M.A. Ph.D. Wednesday June 3rd at 5 p.m. Lecture “Applications of Optical Rotatory Disper- sion and Circular Dichroism in Stereochemistry,” by DECEMBER 1963 Professor C. Djerassi Ph.D. To be given in the Chemistry Department The University. Tuesday March loth at 5 p.m. Presidential address to Nottingham University Chemical Society by Professor D.D. Eley O.B.E. Ph.D. Sc.D. Oxford (Joint Meetings with the Alembic Club to be held in the Inorganic Chemistry Laboratory.) Monday January 27th 1964 at 3.30 p.m. Lecture “Six-co-ordinate Silicon(rv),” by Professor S. Kirschner Ph.D. Friday February 14th at 3.30 p.m. Simonsen Lecture “Molecular Rearrangements of Terpenes,” by Professor G. Ourisson Ph.D. (Please note the amended date of this meeting.) Monday March 2nd at 3.30 p.m. Tilden Lecture “Activated Molecules,” by Professor A. F Trotman-Dickenson Ph.D. Friday June 5th at 3.30 p.m. Centenary Lecture “Applications of Optical Rota- tory Dispersion and Circular Dichroism in Stereo- chemistry,” by Professor C. Djerassi Ph.D.Reading (Joint Meetings with the Royal Institute of Chem- istry and the University Chemical Society to be held in the Large Chemistry Theatre The University.) Monday February loth 1964 at 5.30 p.m. Lecture “Liquids and Solids,” by Professor D. H. Everett M.B.E. M.A. D.Sc. Tuesday March 3rd at 5.30 p.m. Lecture “Chemistry of the Excited State,” by Profes- sor G. Porter Sc.D. F.R.I.C. F.R.S. St. Andrews (Joint Meetings with the University Chemical Society to be held in the Chemistry Department St. Salvator’s College.) Thursday January 16th 1964 at 5.15 p.m. Lecture “Some Halogen Compounds of Group V Elements,” by Dr. G. S. Harris. 7hursday January 23rd at 5.1 5 p.m. Lecture “Symmetry Structure and Spectroscopy,” by Professor A.D. Walsh M.A. Ph.D. F.R.I.C. Thursday January 30th at 5.15 p.m. Lecture “A Natural Product Problem in Terpene Chemistry,” by Dr. J. McLean. Thursday April 23rd at 5.15 p.m. Lecture to be given by Professor B. Lythgoe M.A. Ph.D. F.R.S. Sheffield (Joint Meetings with Royal Institute of Chemistry and the University Student Chemical Society to be held in the Department of Chemistry The University unless otherwise slated.) Thursday January lGth 1964 at 4.30 p.m. Lecture “Transient Chemical Species formed in Irradiated Liquids,” by Dr. J. W. Boag. Thursday January 23rd at 4.30 p.m. Lecture “Some Recent Work on Hydrogen Isotope Effects,” by Dr. V. Gold. Thursday January 30th at 4.30 p.m. Lecture “Claudogenic Steroids,” by Dr. V.Petrow F.R.I.C. Monday June lst at 4.30 p.m. Centenary Lecture “Applications of Optical Rota- tory Dispersion and Circular Dichroism in Stereo- chemistry,” by Professor C. Djerassi Ph.D. (Not a joint meeting.) Southampton (Joint Meetings with the University Chemical Society to be held in the Chemistry Department The University unless otherwise stated.) Wednesday January 22nd 1964 at 7 p.m. Lecture “A Chemist at Sea,” by Dr. L. H. N. Cooper F.R.I.C. Joint Meeting with the Portsmouth and District Chemical Society to be held in the Department of Chemistry College of Technology Portsmouth. Friday February 7th at 5 p.m. Lecture “Aliphatic Electrop hilic Substitution,” by Sir Christopher Ingold D.Sc. F.R.S. Friday February 14th at 7 p.m.Lecture “Fuel Cells,” by Dr. A. B. Hart. Joint Meeting with the Portsmouth and District Chemical Society to be held in the Department of Chemistry College of Technology Portsmouth. Friday March 13th at 5 p.m. Lecture “Natural Polyacetylenes,” by Sir Ewart Jones D.Sc. F.R.S. Friday March 13th at 7 p.m. Lecture “Physiological Effect of Alcohol on the Human Body,” by Dr. D. W. Kent-Jones F.R.I.C. Joint Meeting with the Portsmouth and District Chemical Society to be held in the Department of Chemistry College of Technology Portsmouth. Swansea (Joint Meetings with the Student Chemical Society to be held in the Department of Chemistry Univer- sity College.) Monday January 27th 1964 at 4.30 p.m. Lecture “The Principles and Chemistry of Colour Photography,” by Dr.R. A. Jeffreys F.R.I.C. Wednesday February 12th at 4.30 p.m. Lecture “Organic Semi-conductors,” by Professor D. D. Eley O.B.E. Sc.D. Ph.D. PROCEEDINGS -Monday March 2nd at 4.30 p.m. Lecture to be given by Professor B. Lythgoe M.A. Ph.D. F.R.S. Monday March 16th at 4.30p.m. Lecture “The Chemistry and Technology of Urethane Polymers,” by Dr. H. T. Howard. Tees-side (Joint Meetings with the Royal Institute of Ghem- istry and the Society of Chemical Industry.) Thursday January 9th 1964 at 8 p.m. Lecture “Catalysis from the Standpoint of Solid- state Chemistry,” by Dr. F. s. Stone. To be given in the William Newton School Norton. ~ ~~ Wednesday February 19th at 8 p.m. Tilden Lecture “A Glow in the Dark-The Rationale of Phosphorylation,” by Dr.V. M. Clark M.A. To be given at the Constantine College of Technology Middlesbrough. Tuesday March 17th at 8 p.m. Lecture “Chemistry in the Future of Power Genera- tion,” by Mr. J. M. Ward F.R.I.C. To be given at the Constantine College of Technology Middles- brough. Wednesday April lst at 8 p.m. Lecture “The Scientific Examination of Anti-quities,” by Dr. A. E. Werner. To be given at the Vane Arms Hotel High Street Stockton-on-Tees. OBITUARY NOTICE JAMES BELL WHITWORTH 1895-1963 DR. JAMESBELLWHITWORTH died in Cambridge on February llth 1963; it was a sad disappointment to his friends as he was apparently convalescing from an illness contracted a month or so before.He is survived by his wife. Whitworth was born on November 6th 1895 at Carmarthen and educated at the Lampeter College School and Aberystwyth taking his B.Sc. at the latter in Chemistry. He stayed at Aberystwyth as Assistant Lecturer and De-monstrator until the beginning of the war and then served in the forces from 1914-1918. He came to Cambridge in October 1920 and spent the rest of his life there. It was during the time when the author was a research student (1922-25) that he worked on the next bench to Whitworth and came to know him extremely well. Whitworth took his Ph.D. in 1925 working partly under Sir William Pope and partly under W. H. Mills. After this he was appointed a research assistant by the Chemical Defence Research Department but quite shortly he relin- quished this post to become a private assistant to Sir William Pope.During this time he started doing supervision for his college and gradually built up a very big practice he showed an infinite capacity for taking pains especially with the weaker students and any medicals who could not get through their examinations were advised to go to Dr. Whitworth for supervision or coaching they almost always got through in the end! His capacity as a teacher and advisor to students was recognised by Fitzwilliam House at which he held the position of Director of Studies for a number of years. Final recognition was accorded by his election to a Fellowship but his death prevented him enjoying this honour. Whit- worth also demonstrated in the practical organic chemistry classes where again lame dogs received support and kindly help.His lectures on elementary organic chemistry in the long vacation were always delivered with very great care and attention to detail. Those of us who knew him well at Cambridge feel a very great sense of personal loss of a valued colleague who was always ready to help and take on any task required. Whitworth’s first published papers dealt with the condensation of o-aminothio- phenol and a$-unsaturated acids (with W. H. Mills) and tri-o-phenyfenediarsine (with N. P. McCleland) but his more important work was done with Sir William Pope this concerned the optical resolution of spirodihydantoin which remains to the present day the simplest spirocyclic compound shown to exhibit optical activity.F. B. KIPPING.
ISSN:0369-8718
DOI:10.1039/PS9630000357
出版商:RSC
年代:1963
数据来源: RSC
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