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Proceedings of the Chemical Society. November 1963 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue November,
1963,
Page 325-356
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PROCEEDINGS OF THE CHEMICAL SOCIETY NOVEMBER 1963 ISOTOPES-A FIFTIETH ANNIVERSARY IN the December 4th 1913 issue of Nature the following letter appeared. Intra-atomic Charge. THAT the intra-atomic charge of an element is deter- mined by its place in the periodic table rather than by its atomic weight as concluded by A. van der Broek (NATURE, November 27 p. 372) is strongly supported by the recent generalisation as to the radio-elements and the periodic law. The successive expulsion of one aand two /3 particles in three radio- active changes in any order brings the intra-atomic charge of the element back to its initial value and the element back to its original place in the table though its atomic mass is reduced by four units. We have recently obtained something like a direct proof of van der Broek’s view that the intra-atomic charge of the nucleus of an atom is not a purely positive charge as on Rutherford’s tentative theory but is the difference between a positive and a smaller negative charge.Fajans in his paper on the periodic law generalisa- tion (Physikal. Zeitsch. 1913 vol. xiv. p. 131) directed attention to the fact that the changes of chemical nature consequent upon the expulsion of a and B particles are precisely of the same kind as in ordinary electrochemical changes of valency. He drew from this the conclusion that radio-active changes must occur in the same region of atomic structure as ordinary chemical changes rather than with a distinct inner region of structure or “nucleus,” as hitherto supposed.In my paper on the same generalisation published immediately after that of Fajans (Chem. News February 28) I laid stress on the absolute identity of chemical properties of different elements occupying the same place in the periodic table. A simple deduction from this view supplied me with a means of testing the correctness of Fajans’s 325 PROCEEDINGS conclusion that radio-changes and chemical changes are concerned with the same region of atomic struc- ture. On my view his conclusion would involve nothing else than that for example uranium in its tetravalent uranous compounds must be chemically identical with and non-separable from thorium com- pounds. For uranium X formed from uranium I by expulsion of an CI particle is chemically identical with thorium as also is ionium formed in the same way from uranium II.Uranium X loses two /3 particles and passes back into uranium 11 chemically identical with uranium. Uranous salts also lose two electrons and pass into the more common hexavalent uranyl compounds. If these electrons come from the same region of the atom uranous salts should be chemically non-separable from thorium salts. But they are not. There is a strong resemblance in chemical charac- ter between uranous and thorium salts and I asked Mr. Fleck to examine whether they could be separated by chemical methods when mixed the uranium being kept unchanged throughout in the uranous or tetravalent condition.Mr. Fleck will pub- lish the experiments separately and I am indebted to him for the result that the two classes of compounds can readily be separated by fractionation methods. This I think amounts to a proof that the electrons expelled as /3 rays come from a nucleus not capable of supplying electrons to or withdrawing them from the ring though this ring is capable of gaining or losing electrons from the exterior during ordinary electro-chemical changes of valency. I regard van der Broek’s view that the number representing the net positive charge of the nucleus is the number of the place which the element occupies in the periodic table when all the possible places from hydrogen to uranium are arranged in sequence as practically proved so far as the relative value of the charge for the members of the end of the sequence from thallium to uranium is concerned.We are left uncertain as to the absolute value of the charge because of the doubt regarding the exact number of rare-earth elements that exist. If we assume that all of these are known the value for the positive charge of the nucleus of the uranium atom is about 90. ALTHOUGH this may not have been the first use of the word “isotope,” such public support by Soddy ensured its passage into the language of science. The Note also marked an important step in the development of modern chemistry and will be commemorated by an official meeting which is to be held in Glasgow on Wednesday Whereas if we make the more doubtful assumption that the periodic table runs regularly as regards numbers of places through the rare-earth group and that between barium and radium for example two complete long periods exist the number is 96.In either case it is appreciably less than 120 the number were the charge equal to one-half the atomic weight as it would be if the nucleus were made out of (x par-ticles only. Six nuclear electrons are known to exist in the uranium atom which expels in its changes six /3 rays. Were the nucleus made up of a particles there must be thirty or twenty-four respectively nuclear electrons compared with ninety-six or 102 respectively in the ring. If as has been suggested hydrogen is a second component of atomic structure there must be more than this.But there can be no doubt that there must be some and that the central charge of the atom on Rutherford’s theory cannot be a pure positive charge but must contain electrons as van der Broek concludes. So far as I personally am Concerned this has resulted in a great clarification of my ideas and it may be helpful to others though no doubt there is little originality in it. The same algebraic sum of the positive and negative charges in the nucleus when the arithmetical sum is different gives what I call “isotopes” or “isotopic elements,” because they occupy the same place in the periodic table. They are chemically identical and save only as regards the relatively few physical properties which depend upon atomic mass directly physically identical also.Unit changes of this nuclear charge so reckoned algebraic- ally give the successive places in the periodic table. For any one “place,” or any one nuclear charge more than one number of electrons in the outer-ring system may exist and in such a case the element exhibits variable valency. But such changes of number or of valency concern only the ring and its external environment. There is no in- and out-going of electrons between ring and nucleus. FREDERICK SODDY. Physical Chemistry Laboratory University of Glasgow. (Reproduced by kind permission of the Editor of Nature.) December 4th. At this meeting Dr. Andrew Kent will present an historical appreciation of Soddy Lord Fleck and Dr. John A. Cranston will deal with the contemporary scene and Professor EmCleus will show the development of the topic to the present situation.NOVEMBER 1963 327 Frederick Soddy (1877-1956) By ANDREW KENT (UNIVERSITY OF GLASGOW) “He that is used to go forward and findeth a stop falleth out of his own favour.” (Bacon.) “He was gifted in many perhaps too many ways.” (Paneth.)l THE external examiner (Sir) William Ramsay was genially impressed by the young chemist who headed the honours list at Oxford in 1898. Failures not entirely surprising to achieve im- mediate installation in the appropriate chairs at Toronto and then at Aberystwyth propelled the new graduate from a minor post at McGill into the group forming round the Research Professor of Physics Ernest Rutherford.Although East- bourne College Aberystwyth and Merton had had a steady organic bias Soddy’s flair for mathematics would surely have inclined him to physical chemistry; but these events installed him at once in the middle ground of chemistry and physics supplied the stimulus of the Cavendish group and provided the ideal arena for his talented personality. The decade between 1894 and 1904 was inevitably exciting to any imaginative scientist especially to one whose first tutorial exercise had been a painstaking historical synopsis of the history of chemistry with emphasis on the sanity of transmutation.2 Rayleigh and Ramsay discover argon :Ramsay isolates terrestial helium. Becquerel now detects the radiation from uranium J.J. Thomson defines the electron. Next Mme. Curie in-augurates radiochemistry promoting polonium to the Periodic Table without isolation of a scintilla without even a spectral line. Soon Rutherford announces the material nature of the a-particle and Crookes in 1900 separates the ephemeral uranium-X. In this context it is also relevant that in 1898 Crookes has sounded the alarm of impending famine in fossil fuels while in the following year the Queen Empress Victoria had celebrated her Diamond Jubilee. Meantime Rutherford and Soddy continued their study of the radioactive sequence from thorium explained some irregularities by postu- lating a gaseous member “emanation,” and con- sidering the equilibria of natural mixtures ad- vanced in their first joint publications (1902) the view that radioactivity involved an “atomic disintegration,” a continuous transmutation of matter.“Ever since the day of Robert Boyle,” wrote Soddy “the true chemist had perforce to be a sceptical chemist. Even to speak of trans- mutation at all was apt to be considered a breach of good taste. Now . ..it will be admitted that the instincts of chemists . . .were fully justified!”s This new style alchemist soon transferred to London where he invoked the patronage and the technical genius of Ramsay to authenticate emanation and to test his theory that it was a member of the argon family an inert gas. It was soon established that although the other inert gases evolved no radiation emanation was one of them.A windfall of radium bromide enabled them to demonstrate spectroscopically that helium was accumulating in the salt and also evolving on the decay of emanation. They estab- lished thus that a-radiation promoted the ap pearance of helium they speculated with con- fidence on their identity although it was only in 1909 that Rutherford and Royds provided final proof. Within five years of graduation Frederick Soddy had played a leading r61e in three major scientific discoveries. In the Rutherford axis he was the chemical pole :to the Ramsay researches he contributed the techniques and the outlook of the new radiochemistry. It is equally evident that in both cases and to his immediate benefit he was associated with men who had already earned a lofty academic and scientific status.So to many contemporaries he occupied a sub-sidiary rank in these first researches. Time and the l Paneth “A Tribute to Frederick Soddy,” Nature 1957 180 1087. a Howorth “Pioneer Research in the Atom,” New World Publications London 1958 p. 56. Soddy “The Interpretation of the Atom,” Murray London 1932 p. 31. charmless anemia of scientific obituaries would usually accentuate such contrasts which but for Soddy’s later achievements might have hardened into history. If this be unfair it is certainly not infrequent and in other cases is proceeding extensively now. This prospect dissolved because Glasgow University was still extending its chem- istry department under Professor John Ferguson to accommodate advanced courses in the BSc.syllabus; and also because some of its adherents notably (Sir) George Beilby (of Cassel Co. Ltd.) hoped to reinvigorate its flagging conception of research. The upshot was an offer to Dr. Soddy of a new lectureship in “Physical Chemistry (including Radio-Activity)” at a salary (E400) which em- phasised its special status. Returning from a visit to Australia where he encountered (Sir) William Bragg in Adelaide the new appointee conducted his research projects with great determination. Perhaps in this first permanent post Soddy achieved the most relatively settled phase of his career. In 1908 he married a Scotswoman (Winifred Beilby) who matched his wit and sympathised with his academic and social prob- lems.If the young English savant were ever com- fortable company it was in this Glasgow period in his new independence his scientific drive achieved results which surely justified his spon- sors and the support of his postgraduate col- leagues by the new Carnegie Trust. There evolved the Displacement Law,4 Soddy’s conception of the Isotope his view of Atomic N~rnber,~ the isolation from Ceylon thorianite of lead with an abnormal atomic weight.g The new Glasgow School was rivalling the groups under Thomson at the Cavendish Rutherford now at Man-Chester Bragg now at Leeds and others in France and Germany and the United States. Where advance on such a broad new front has been at once rapid and irregular priority issues are bound to be frequent and hard to unravel.It remains true that not since the distant day of Dr. Black (1756-66) had Glasgow chemistry sus-tained such pre-eminence; and it was in this period that Soddy earned the Nobel laureation * Cf. Fleck B.A. Report 1913 p. 447. Soddv. Nature. 1913. 92. 400. PROCE~INGS for “his investigations into the origin and nature of isotopes.” In 1914 Soddy became the successful candidate for the Chair of Chemistry at Aberdeen; and immediately his teachings and above all his researches were devastated by the outbreak of war. Apart from the completion of some in- quiries begun in Glasgow one of which led to the independent discovery of protoactini~m,~ he abandoned the prosecution of practical re-searches in radiochemistry.Unshaken by the blood-red fervours of Authority he looked with anger and dismay on the Victorian culture now being driven into bankruptcy and decay. His diagnosis was of underlying economic folly and thenceforward he wrote with skilful pungency on many topics of financial and social importance. Perhaps he was right to utilise his talents in this way but the formidable genius of radiochemistry now risked in economics the status of an amateur crank many then and since have felt that a great scientist was stranded among un- familiar shoals. He returned to Oxford in 1919 as Dr. Lee’s Professor of Chemistry. For him was the un- rewarding task of improvising a new department of chemistry from what remained after the centres of interest had moved to the new Dyson Perrins Laboratories.8 After his wife’s death he resigned his chair in 1936 at the age of 59 and turned to the completion of his other interests.Soddy had a long fruitful association with the Chemical Society. In the year following gradua- tion (1899) sponsored by his Merton tutor Dr. John Watts and by Ramsay he was elected a Fel10w.~ Throughout his active period his chief interest lay in the chemical interpretation of radioactive sequences. He was one of the earliest to use the term “radio~hemistry.”~~ The opening paper with Rutherford preceding the theory of “atomic disintegration,” was the first one read before the Society in 1902. The first issue (1904) of Annual Reports carried almost as an afterthought a section by Soddy on “the new subject of Radio-activity” this was a brilliant historical rksumk giving “prominence ,..mainly Soddyand Hymans,’Trans.Chem. SOC.,1914,105 1402. Soddy and Cranston Pvoc. Rov. SOC.,A 1918,94 384. Hartley J. ROV.Inst. Chem. 1955 79 11%. Cf. Proc. Chem. SOC.,1899 15 vi 42 46; 1902,18 2. lo Broda “Advances in Radiochemistry,” Cambridge University Press Cambridge 1950. NOVEMBER 1963 to the chemical evidence and. ..the spontaneous transmutation of the radioactive matter.” (Else- where the same Reports deal gravely with the element “coronium,” with a material “ether,” with the “radioactive” mercury of some cin- nabars.) Till 1920 Soddy continued with regular reviews:except for 1908 the year of his marriage these appeared annually throughout his Glasgow period :they provide a continuous contemporary discourse of great historical value and their writer drew extensively upon them in his Nobel prize address.It is obvious that he hoped and failed to establish this new form of chemistry in Britain when he gave up the Society turned to F. W. Aston-who was not then a Fellow.ll One factor restrictive of success was the con- temporary appeal of Physical Chemistry where such as Nernst and Ramsay were building en- viable reputations. Another was certainly ex- pense both Rutherford and Soddy were at times dependent on private benefactors for materia1s.l2 Soddy’s brilliance of exposition was in some degree negatived by the monolithic solidarity of the Cavendish group the atomic physicists.Only following the discovery of the neutron did radio- chemistry achieve the extension which Soddy had struggled to promote. There were 1,200 papers in 1936 alone on radioactivity.13 Although he later wrote lectured and travelled on other concerns-he was an untiring traveller-he never overlooked or abandoned his first interest. To his early best-sellers on radio- chemistry “Radio-activity” (1 904) and “Chem- istry of the Radio-elements” (1910) he added “Collected Papers,” followed by the “Interpreta- tion of the Atom” (1932) and “The Story of Atomic Energy” (1947). In every recension he emphasised the r6le of chemistry with charac- teristic witty references to economic or social analogies.“The Interpretation of Radium” (1909) based on “popular lectures” in Glasgow was a long-sighted analysis by one who was already conscious of his social responsibilities. Meantime after Oxford he preached with new emphasis on social subjects. His earlier “strange system of economics ...based on the laws of thermodynamic^"^^ shared his en-thusiasm now with the potential for good or evil of nuclear energy. He was one of the earliest conscious citizens of the Atomic Age (he pre- ferred “Tomic”) :he furthered the ecological in- terests of the Le Play Society he became President of the Institute of Atomic Energy for the Layman (1952) with other Nobel laureates he signed the Mainau Statement (1955).Wher-ever man sought measures against atomic idiocy he was present eager and active. The propa- gandist mellowed into the seer and like some Indian guru he collected a company of admirers followers and disciple^.'^ Criticism of such a figure comes easily to some. He moved with dangerous ease from the objectivity of scientific discussion to the coarser dialectic of the platform. He wrote carelessly in mischief what others might read as malice. Kind and thoughtful to his juniors as Fleck and A. S. Russell emphasise,ls he was forcibly critical of all authority. “The bauble reputation” lives harshly in such breaches. One must note also that his formal teaching made little impress that few of the fledgling Glasgow scientists enrolled beneath his banner and that the research team so rudely dispersed in 1914 was never revived.There remains a scientific writer and pro- tagonist of immense power and persistence an ingenious contriver of apparatus and calculating machinery a mathematician whose ingenuity as in “the Kiss Precise” still excites admiration and comment,17 a commanding director of research the first radio-chemist of his day in technique speculation and exposition. The characters drawn by Fleck J. A. Cranston Paneth A. S. Russell Hevesy and R. A. Houston all indicate exceptional powers and personality. If his “day” were shorter than in other scientific lives it was astoundingly effective if it had little afternoon it had no twilight. He moved at length like his own shadow into a pre- dicted future Hiroshima and Calder Hall.His scientific apogee was realised in his letter to l1 Aston Annual Reports 1922. 19. 267 l2 Soddy “The Interpretation of Radium,” Murray London 1909 p. ix; Evans “Man of Power,” Paul London 1939 n.d. p. 53. l3 Hevesy and Paneth “Radio-Activity,” trans. Lawson 2nd edn, Oxford University Press 1938 vi. Soddy “The Accursed Element,” Youth Cambridge Feb. 1922 p. 156. l5 A Soddy Memorial Trust was founded in 1957. Ref. 2 p. 330. l6 Fleck “Frederick Soddy,” Biog. Memoirs of Fellows of the Roy. Soc. 1957 3 212. l7 The Scientific American 1961 April p. 168. Nature of December 4th 1913 where he came down boldly for the theory of isotopes and gave a confident early appraisal of Atomic Number.Here is one whose name for these and other reasons will not be writ in water. Early Work in the Radioactive Elements. By LORDFLECK. SODDYcame to Glasgow in 1904 and I was attached to him towards the end of that year. Practical chemical work on radioactive materials was already very much to the forefront particu- larly on the purification of relatively large quantities of uranium salts by means of organic solvents. T. D. MacKenzie was the research student who was the most important worker in these earlier years. Miss Ruth Pirrret was also a contributor but on a less prominent scale. Thus in the Physical Chemistry Department a tradition of practical chemical work on the radio- elements had been established before I began to play any substantial part in the work of the laboratory.This development started in about 1909. In this field my early efforts were directed to thorium derivatives and we worked on largely empirical methods on the waste products of the gas mantle industry in order to attempt to obtain products which would be alternatives to radium salts. These efforts were financed by the company of which Sir George Beilby F.R.S. was an in- fluential member namely the Cassel Gold Extracting Co. Ltd. However they did not develop in any substantial way. It was in 1910 that Soddy initiated systematic chemical work on the shorter lived radioele- ments. At that time we had of course definite knowledge of the chemical properties of the longer lived radioelements like radiothorium but very little knowledge of the shorter lived ele- ments like thorium B.I have a distinct recollec- tion of Soddy saying that I should look very closely to analogies of the chemical behaviour of such elements with the chemistry of gold and other “noble” elements. Other chemists were working on those prob- lems at the same time and perhaps one of the most penetrating of such workers was Otto PROCEEDINGS Hahn. In a volume published by the Metall- gesellschaft in 1956 entitled “Science and the Economic Order” he has contributed a paper on uranium which recounts some of his failures to achieve isolation of various radioelements ; for example in attempting to isolate mesothorium from radium and in the separation of radium D from lead.It was with such work in mind his own for example and that of others such as Hahn that Soddy put forward the idea that these types of elements had properties that were very much closer together than anything that had been so far scientifically acknowledged. As Hahn says on p. 97 “. . . . I should never have had the courage to declare that these were chemically identical ele- ments. But Frederick Soddy possessed that courage.” As Soddy put it “these elements were chemically non separable.” This led us back to the age-old problem of whether it is possible to prove a negative and I have always understood that a lively correspondence between Soddy and the then editor of the Journal ensued.A similar correspondence found expression in Nature1 All this discussion was of course put on an entirely different footing with the evolution of the Group Displacement Law to be discussed by Dr. Cranston presently which in turn led to the generalised conception of isotopes. Finally I would mention the introduction of the word “Isotopes” by Soddy in his letter to Nature. We owe the word “Isotopes” to Dr. Margaret Todd a medically qualified Glasgow friend of Mr. and Mrs. Soddy who made her name as a writer using the pen name of Graham Travers. This word was coined at a dinner party -I have always understood a normal informal Sunday evening meal in the home of Sir George Beilby. It has been a happy inspiration and “Isotopes” has found its place in all languages where modern science has a place.Schuster Nature 1913,91 30. The Group Displacement Law. By J. A. CRANSTON. A GREAT step forward in the elucidation of the three natural radioactive series of elements was made in 1913 when as a result of Fleck‘s work on the chemical nature of the beta-emitters it became possible to place all the radioelements in the Periodic Table. The consequent formulation NOVEMBER 1963 of the Group Displacement Law enabled a close examination of the Series to be made to see (1) if the accepted parent daughter relationship be- tween successive radioelements had always been supported by experimental evidence (2) if branches occurred in the main Series through the dual disintegration of any of the radioelements (3) if any light could be thrown on the origin of actinium whose comparatively short life of 19 years precluded it from being the first member of any naturally occurring series.Cranston worked on these problems and was able to show that radiothorium was produced directly by the disintegration of mesothorium 2; that no branching occurred in the early elements of the thorium series (that the heavy halogen obtainable from thorium ores is pure iodine and not mixed with a halogen which would have the atomic number 85); and that by passing carbon 331 tetrachloride over heated uranium ore the vola- tile chloride of a new element could be obtained which would disintegrate to produce actinium. New Elements.By H. J. EMELEUS. A BRIEF review will be given of the main events following Rutherford’s first experiments which led to the discovery of nuclear fission. An outline will be given of the discovery and isolation of the transuranic elements and on the way in which they fit into the classical radioactive decay series and extend the Periodic Table. Mention will also be made of the filling of gaps in the latter by the discovery of technetium astatine and francium. Finally a general review will be made of some of the major uses of enriched natural isotopes and of radioactive isotopes in current science and technology. CHEMICAL SOCIETY MEETING THEfollowing papers were read and discussed at a Scientific Meeting held in the Society’s rooms at Burlington House on Thursday June 6th 1963 at 6 p.m.Some Observations on the “Rare-gas Rule.” By D. P. CRAIGand G. DOGGETT. THE “rare-gas rule” expresses a feature of the electronic structures of many complexes of transi- tion metals especially in low valence states. The em- pirical fact is that with certain classes of ligands such as carbon monoxide and nitric oxide the most stable complexes have rare-gas configurations of the transi- tion metals. In other cases such as the hexammine- cobaltic ion a rare-gas configuration seems to be merely incidental to stability. The rule is discussed in relation to changes in the electrostatic potential field of the metal caused by ligands. Support is found for the view that in those cases in which the a-bonds are formed by ligand lone-pair donation the rare-gas rule will apply only if there is electron transfer out of metal d-orbitals in n-bonding.Expansion of d-orbitals under the in- fluence of ligand lone-pairs is probably important in facilitating electron withdrawal. Molecular Orbital Theory of Organometallic Com- pounds. Part 4. Substitution Reactions of Tricar-bonylbenzene-chromium.By DAVID A. BROWN. SIMPLEmolecular orbital theory of organometallic systems of the type applied previously by the author is used to discuss substitution reactions of tricar- bonylarenechromiums. It is assumed that the transi- tion state for substitution of the complex is of the Wheland type with the carbon atom undergoing substitution effectively removed from interaction with both the ring and the Cr(CO)3 moiety.The total n-electron energy of the transition state is cal-culated by standard methods assuming that the resonance integrals are proportional to the group overlap integrals and that the Coulomb terms may be obtained from the relevant ionisation potentials and spectral data. The proportionality constant k between resonance integral and overlap integral was varied over a wide range to allow for varying degrees of interaction in the transition state. The welectron energy of the complex was calculated in exactly the same way. The difference in the values gives the v-electron activation energy dEi (complex) the value of which varies from electrophilic radical and nucleophilic substitution by the quantity H(4u14al) the Coulomb term of the highest filled orbital in the transition state.The n-electron energy for benzene itself is given by the expression AE‘ (benzene) = -[(2-n)HC,3-2.536/3,,] where H, is the Coulomb term of the isolated 2p carbon orbital and n is 2 1 0 for nucleophilic, radical and electrophilic substitution respectively. The difference in the two df?;values gives the rela- tive activation energies of the complex and benzene for the different types of substitution; we consider this to be a direct measure of the difference in activa-tion energies neglecting entropy differences etc. It is found that for nucleophilic substitution for all reasonable values of pCcand k the activation energy is lower for the complex and so substitution should be easier.However for both electrophilic and radical substitution it is necessary to assess the value of H, which introduces some ambiguity; it does appear nevertheless that even in these cases the rate differences should be small. The theoretical predic- tions are compared with the available evidence. In discussion Dr. Waters asked whether calcula- tions of this type could be extended to consideration of the reactivity of aromatic hydrocarbons in com- plexes such as their picrates for this might have some bearing on the degree of reactivity of the carcino- genic polycyclic hydrocarbons in vivo. Dr. Brown replied that in principle this is the case although such complexes are normally con- sidered in terms of change-transfer theory.It would however be useful to have some structural evidence for these compounds; estimation of some of the required Coulomb terms might also be difficult. Structure and Reactivity of the Oxyanions of the Transition Metals. Part XV. Mechanism of Oxidation by Chromate and Related Ions. By M. C. R. SYMONS. DIFFERENCES in the mode of oxidation of chromate and periodate are discussed in terms of the structures of these ions and their reduced forms. In particular the contrast in their behaviour towards aliphatic alcohols and glycols cited by Rocek and West- heimerl is explained in terms of structural require- ments. Both chromate and periodate form esters with alcohols and probably cyclic esters with glycols; but in doing so chromate retains its local tetrahedral symmetry whereas periodate is thought to expand its co-ordina tion shell to give octahedrally co-ordinated heptivalent iodine.Removal of an a-proton from chromate esters by solvent results in an ester which may be described either as derivatives of sexivalent chromium or of quadrivalent chromium but most satisfactorily in terms of a simple molecular orbital model. Hydro- lysis to the corresponding ketone should be energetically favoured. No such easy route to the corresponding ketone is available for periodate esters which are therefore relatively stable. However cyclic periodate esters of glycols can by simple flow of electrons become transformed into the oxidation products without solvent participation.Whilst this mechanism is equally available for chromate derivatives it must compete with the energetically more favourable loss of a-hydrogen if one is present in the ester. PROCEEDINGS In the ensuing discussion Dr. J. S. Littler enquired whether the decrease of co-ordination numbers of the oxidant concurrent with its reduction which Professor Symons had suggested might favour glycol fission by periodate might not be the most important effect. Thallium(m) and mercury(@ which are good oxidisers of monohydric alcohols by 2-electron transfer are not effective glycol splitting agents; this can obviously be explained stereo- chemically. The relative rates of reaction of various glycols are similar when oxidised by vanadium(v) manganese- (III) and cerium(rv) and also chromium(w) but are different with lead(1v) and iodine(w1).This suggests that the mechanism of oxidation by chromium(v1) is not closely similar to that by iodine&@ and lead(1v). A common feature of the first group of oxidants is that a change of multiplicity is necessary during the reaction. Dr. W. A. Waters said that any help from theorists as to how transition elements rearrange their electrons when they act as oxidants would be of great help to organic chemists. It is striking that the ions XO, of manganese chromium and vanad- ium do not resemble each other in their reactions; with chromic acid the favoured change is undoubted- ly chromium(w) -chromium(Iv) but vanadium(v) oxidises only as a cation and then changes from vanadium(v) to vanadium(rv) resembling mangan- ese(II1) and cobalt(m) in its reactivity.In mono-hydric alcohol oxidation with chromium(v1) experi- mental evidence in the main is agginst base-catalysed decomposition of the ester to R,C-0-Cr0,H and in favour of a cyclic concerted process. With regard to glycol fission by chromium(v1) it must be remem- bered that C-C fission occurs with many other molecules e.g. pinacol monoethyl ether and Ph-CH(OH)CMe, which can be oxidised in an exactly similar way by vanadium(v) cerium(1v). and cobalt(II1). These too are very effective oxidants for di-tertiary glycols so that chromium(w) does exhibit to some degree features typical of 1-electron oxidants and Symons’ key point is that with chromium(vI) unlike iodine(wr) oxidations involve the transfer of electrons to d orbitals.We should like theorists to tell us whether each transition element in a high valence state should tend to gain d electrons singly or in spin-balanced pairs and to what extent the energy levels determining these changes depend on the co-ordination struc- tures of the ions concerned. Professor Symons replied that with respect to the problem of gain of d electrons singly or in pairs it is probably impossible to generalise. In the specific case of the intermediate postulated in my paper the NOVEMBER 1963 333 ~-~ structure presupposes that the d-orbital degeneracy rather the electrons to be transferred are (paired) in is lifted in such a way that a singlet lies lowest.It is a delocalised n-orbital. They will remain concen- this orbital which combines with the carbon and trated on the metal when hydrolysis occurs and it is oxygen p-orbitals and the four electrons are thought at this stage (probably not rate determining) that to be paired in the two lowest molecular orbitals. At they will unpair to give the normal triplet state of this stage there is no complete electron transfer chromium(1v). COMMUNICATIONS The Isomerisation of the n-Octenes in Acidic and Basic Media By M. D. CARR,J. R. P. CLARKE, and M. C. WHITING (THE DYSON mRRINS LABORATORY, OXFORD UNIVERSITY) THEseven n-octenes have been equilibrated in homo- the AG andAAH values to calculate four sets of semi- genous solutions (i) of boron trifluoride and hydrogen experimental gas-phase values of AH; the two fully fluoride (0.2~ each) in a mixture (2 1 v/v) of tetra- experimental sets of AH values were also corrected hydrothiophen-1 ,l -dioxide (su1pholane)l and methyl for AAH of solution.The results so obtained are bromide and (ii) of lithium 2-aminoethylamide in given in Table 1; the good agreement between the ethylenediamine.2 In each case two different tempera- four sets of semi-experirnental values confirmed by tures were used and at each the equilibrium was agreement within wider limits for the fully experi- approached both from oct-l-ene and from (cis + mental values justifies our methods and assumptions. trans)-oct-4-ene; mixtures were analysed completely Details and comparison with existing thermochemical TABLE1.Estimated values for isomerisation to trans-oct-4-ene in gaseous state. (a) from sulpholane-methyl bromide data Octene trans-3-ene AAH (273-304.5")-140 f 41 semiexp. AH (275.5")244 f 43 semiexp. AH (313")244 JZ 47 exp. AH (corr.)249 f 218 trans-2-ene -220 f 66 264 f 67 310 f 68 -70 f 168 cis-4-ene cis-3-ene -23 j 36 -104 f 34 913 f 45 1290 f 39 945 f 45 1317 & 42 680 f 296 1091 f 237 cis-2-ene -245 f 80 1055 f 83 1121 f 84 568 f 260 1 -ene 14 f 14 2726 rfr 77 2654 & 67 3252 f 790 (b) from ethylenediamine-lithium 2-aminoethylamide data Octene AAH (273-304.5") semiexp. AH (331") semiexp. AH (373") trans-3-ene -50 j 50 261 i. 53 212 f 61 trans-2-ene -115 & 42 242 f 46 258 i45 exp.AH (corr.) 645 f 253 119 f 212 cis-4-ene -50 f 50 1042 & 61 1004 rf 62 1337 j 425 cis-3-ene -50 & 50 1314 f 59 1321 f 57 1262 f 356 cis-2-ene -115 f 42 1040 f 53 968 f 48 1613 f 401 1 -ene -50 & 50 2810 f 136 2811 f 66 2800 f 1174 by gas-liquid chromatography 7-16 analyses on data must await our main paper but the main con- each mixture allowing calculation of 95 % confidence clusions e.g. that trans-oct-4-ene is ca. 0-25 kcal. limits. Free-energy changes for the conversion of more stable than the other two trans-isomers where- each of the six other isomers into trans-oct-4-ene as cis-oct-3-ene is ca. 0-25 kcal. less stable than the were calculated along with derived values for en- other two cis-isomers are probably secure although thalpies and entropies of isomerisation.Estimates for not easily rationalised. AAH of solution were obtained3 by comparing reten- Reactions were also followed to the extent of tion times on non-volatile models of the equilibra- 2-25% at lower temperatures in more dilute solu- tion solvents [(i) sulpholane-l,2,3-tribromopro-tions of the same reagents and in (iii)-p-nitrobenzene- pane ; (ii) tetraethylenepentamine]. Statistical con- sulphonic acid in sulpholane-methyl bromide. All tributions to AS were estimated as Rln 2 (oct-Zene minor products were expressed as percentages of the and oct-3-ene) and Rln 3 (oct-1-ene) and used with principal product. When these were plotted against Powell and Whiting Proc. Chem. Soc. 1960 412. Reggel Friedel and Wender J.Org. Chem. 1958 23 1136. Littlewood Phillips and Price J. 1955 1488. PROCEEDINGS the extent of reaction and extrapolated (linear least- probability patterns for proton loss in varying ways squares) to zero reaction the intercept should give which differ significantly and intelligibly. This im- the composition of the initial product mixture. Rates plies that even in this very weakly nucleophilic of reaction (f 30% or 10 % relatively between runs solvent the lifetime of a secondary carbonium ion is with the same catalyst) and initial product mixtures comparable with that for rotation about C-C bonds. are shown in Table 2. Variation of counter-ion has a detectable but small In the base-catalysed process our results agree effect on product ratios.essentially with those of Nicholls Herb and Riemen- Rates of isomerisation are approximately propor- schneidefl on unconjugated diene-acids in diethylene tional to the square of "tetrafluoroboric acid" con- glycol-sodium hydroxide at 200"c and with those of centration i.e. to [HF][BF3] it being assumed that TABLE 2. Rates and initial products of isomerisation Product Starting material 1 -ene cis-4-ene cis-4-ene trans-4-ene (i) Sulpholane-methyl bromideHBF (0.067~ at 273 ") 1 -ene -0 f 0.5 0 60.5 0 f 0.5 trans-2-ene 100 22 f 4 26 f 6 20 f 4 cis-2-ene 66 f 2 14 f 2 13 i. 1 16 & 2 trans-3-ene 16 f 1 100 100 100 cis- 3-ene <5 16 f 6 5&7 35 f4 trans-4-ene 4f2 52 f 4 57 f 2 -cis-4-ene 0 f 0.5 -27 f 1 k x 103 1.5 2.0 -0.9 (ii) Sulpholane-methyl bromide-p-nitrobenzenesulphonicacid (0.5~at 276") 1 -ene -0 f 0.5 0 f 0.5 trans-2-ene 100 19 f 4 28 f 7 cis-2-ene 80 f 3 11 f2 20 f 3 trans-3-ene 20 f 2 100 100 cis-3-ene <5 20 rt 7 41 f 5 trans-4ene 112 57 f 3 -cis-4-ene 0 f 0.5 -22 f 6 k x lo7 1.1 1.3 0-55 (iii) Ethylenediamine-lithium 2-aminoethylamide (0.55~at 298 ") 1 -ene -0 10.5 0 f 0-5 trans-2-ene 15 & 1 0 & 0.5 0 f 0.5 cis-2-ene 100 1&1 1f1 trans-3-ene 0 j 0.5 100 31 & 2 cis-3-ene 0 f 0.5 0 j 0.5 100 -trans-4-ene 0 & 0.5 0 f 0.5 cis-4-ene 0 & 0.5 -0 f 0.5 k x lo5 150 6.0 1 *7 All energies are in cal.mole-l and temperatures in degrees K. Schriesheim Hofmann and Rowe5 (olefins in di- there is little association of these compounds; in- methyl sulphoxide-potassium t-butoxide at 55 "); dicator ratios follow a similar law.The ratio of rates that is migration is stepwise the terminal olefin for the two acids studied also approximates to pro- reacts most rapidly terminal and trans-olefins give portionality to the h ratio as determined via several mainly cis-isomers and cis-olefins give almost en- Hammett-type indicators.6 tirely trans-isomers. In acidic solutions isomerisation involves simultaneously with the obvious protona- We thank the Department of Scientific and In- tion-deprotonation sequence a route which includes dustrial Research and the British Petroleum Com- presumably an intramolecular proton transfer. The pany for a Studentship (to J.R.P.C.) and a Research data reveal a preference for the maintenance of con- Fellowship (to M.D.C.).formation a cis-bent and a trans-bent ion-pair having (Received September 16th 1963.) Nicholls Herb and Riemenschneider J. Amer. Chem. SOC.,1951 73 247. Schriesheim Hofmann and Rowe J. Amer. Chem. Soc. 1961,83 3731 et seq. Alder Chalkley and Whiting unpublished. NOVEMBER 1963 335 A Novel Synthesis of Lactones By D. H. R. BARTON and A. J. L. BECKWITH (IMPERIAL LONDON, COLLEGE S.W.7) THEreaction of iodine-lead tetra-acetate under ultraviolet irradiation with alcohols1 and with carboxylic acids2 yields primarily alkyl and acyl hypoiodites respectively. We have now investigated the analogous reaction with amides and have found that it affords initially N-iodo-amides photolysis of which in suitable cases provides a novel method for the preparation of lactones.When iodine (0.5 mole) was added without illumination to a cold stirred suspension of benz- amide (1 mole) and lead tetra-acetate (03 mole) in chloroform under nitrogen until the iodine colour persisted a precipitate of N-iodobenzamide was formed. On rapid crystallisation from acetone-light petroleum this formed pale yellow needles m.p. 123-124" (decomp.) Ymax (in Nujol) 1575 1605 and 3230 cm.-l. VCO*NHR -= Ac The reaction of 3p-acetoxy-1 l-0x04 a-pregnane- 20-carboxamide((I; R = H) (1 rnol.) m.p. 292-295" (evac. tube) [a19 + 30-5" (in CHCl,)) with lead tetra-acetate (3 rnol.) and iodine (4 mol.) in chloro- form for 5 hr.at 15" under irradiation with ultra- violet light through Pyrex afforded after alkaline hydrolysis and acetylation of the crude product 3/3- acetoxy- 1 6/3- hydroxy- 11-0x0 -5 a-pregnane- 20- carboxylic lactone (11) (0.55 mol.) m.p. 265-267" (lit.3 m.p. 266-268") [a]? -23" (in CHCl,) Vmax. (in CHCl,) 17 10-1 720 (broad) and 1765 cm.-l. The use of higher reaction temperatures a smaller excess of lead tetra-acetate a shorter reaction period and benzene or carbon tetrachloride as solvent resulted in lower yields of the lactone. The anilide (I;R = Ph) m.p. 246-247" [a] -39" was also converted into the lactone (11) in 14% yield. Phthalide (25 %) was similarly prepared from o-toluamide. When stearamide was treated with lead tetra- acetate-iodine in benzene under ultraviolet irradia- tion the major product (60%) after alkaline hydro- lysis of the mixture was y-stearolactone m.p.49-50" (lit? m.p. 50"),vmax (in CHC13) 1765 cm.-l which was characterised by conversion into 4-hydroxystearic acid m.p. 86-87" (lit.5 m.p. 87") and N -benzyl- 4 -hydroxystearamide m.p. 96-97". Chromatography of the crude product on silica gel also gave &stearolactone m.p. 38-39' Vmax 1720 crn.-l (in CHCl,) which was readily hydrolysed to 5-hydroxystearic acid m.p. 81" (lit.5 m.p. 82") and on treatment with benzylamine afforded N-benzyl-5-hydroxystearamide, m.p. 90-92". The mechanism of the formation of y-lactones from amides undoubtedly involves photolysis of an N-iodo-amide (111) followed by intramolecular hydrogen-atom transfer (IV -V) and coupling of the resultant radical with iodine according to the general scheme previously postulated.6 Hydrolysis of the 7-iodo-amide (W) so produced would then give a y-lactone via an intermediate y-iminolactone.Satis- factory analytical data have been obtained for all new compounds. One of us (A.L.J.B.) gratefully acknowledges a travel grant from the British Council under the Commonwealth Universities Interchange Scheme. We thank Messrs. B.P. Ltd. and R.I.M.A.C. (Cambridge Mass.) for financial assistance. (Received September 1lth 1963.) Meystre Heusler Kalvoda Wieland Anner and Wettstein Experientia 1961 17,475; Helv. Chim. Acta 1962 45 1317; Heusler Kalvoda Meystre Anner and Wettstein ibid.1962 45 2161;Heusler Kalvoda Wieland Anner and Wettstein ibid. 1962 45 2575. Barton and Serebryakov Proc. Chem Soc. 1962 309. Cameron Evans Hamlet Hunt Jones and Long J. 1955 2807. Fosbinder and Rideal Proc. Roy. SOC.,1933 A 143 61. Bergstrom Aulin-Erdtman Rolander Stenhagen and ostling Acta Chem. Scand. 1952 6 1157. Barton Beaton Celler and Pechet J. Amer. Chem. Suc. 1960 82 2640. PROCEEDINGS Electric-field Induced Overtones in Nuclear Magnetic Resonance By A. D. BUCKINGHAM (INORGANIC LABORATORY OF OXFORD) CHEMISTRY UNIVERSITY EXPECTED effects on high resolution nuclear magnetic resonance spectra arising from the partial orientation of polar molecules by a strong electric field are (i) shifts proportional to anisotropies in the chemical shift tensors,l (ii) nuclear dipole-dipole couplings proportional to the inverse cube of the distance between the nuclei,ls2 and (iii) splittings due to nuclear quadrupole coupling to the induced field gradient.3 Effect (ii) has recently been observed and has yielded the sign of the spin coupling constant J of the ortho and meta protons in p-nitrotoluene? Another effect is now predicted; it is dependent on a radiofrequency oscillation of the electric field.In the conventional n.m.r. experiment trans-itions between the eigenvalues of the hamjltonian are induced by a weak radiofrequency magnetic field Hi cos ot,which yields a time-dependent perturbation The linearity of A?&?) in Ii restricts transitions to dFz = f1 (except for high radiofrequency powers when two-quantum transitions dF = f 2 can occur at approximately the same resonant frequency) where F = CIiz.i In a strong radiofrequency electric field Ez whereLrj= (hyiyj/4n2Rbi3) (3 cos2& -l) Pijbeing the angle between the internuclear vector Rij and the molecular dipole moment of magnitude p; -eqi is the field gradient at the ith nucleus in the direction of the dipole moment. The coupling constant L represents the direct dipole coupling of nuclei and may be -lo4c.P.s. and e2qQ is the nuclear quadru- pole coupling constant and may be -lo6C.P.S. for nuclei with acceptable relaxation times Tl. The quadratic terms in the nuclear spin Iiz in the hamiltonian (3) can induce transitions in which dF = rf 2 or 0 giving signals at the sum and diference frequencies of the resonances of nuclei i andj and at twice the usual frequency for quadrupolar nuclei.Electric-field induced transitions should occur in polar molecules of types A, AB and AX at the frequencies [yi(l -ai) + yj(l -af)]H0/2nand [yA(l -0,) -yx(l -ox)]Ho/2.rr.In A2X there should be doublets at yA(l-o,)Ho/n with a spacing . . . (1) of WAXand at [yA(l -0,) 4 yx(l -aX)]Ho/2n with spacings of J-. For A,X there is a doublet at yA(l-aA)Ho/n with a spacing of WAXand triplets with spacings of JAxat [yA(l-a,) fyx(l -ax)] H0/27r. In the quadrupofar case*the the n.m.r. signal into 24 lines if dFz = f 1 and (212-1) lines if dF = f2; the splittings would give e2qiQr for the molecule in the fluid.Typical high-resolution n.m.r. transitions are in- duced by oscillating magnetic fields Hi -lo4 gauss but with quadrupolar nuclei with shorter relaxation times TI somewhat stronger fields are possible. The transition probability is proportional to I<Fz I#(?) IF + dF,> l2 and for Ii == * Buckingham and Lovering Trans. Faraday SOC.,1962,58,2077. a Strandberg Phys. Rev.,1962 127 1162. a Vasil'ev J. Exp. Theor.Phys. 1962 43 1526. Buckingham and McLauchlan Proc. Chern. Soc. 1963 144. NOVEMBER 1963 337 ~__~ ~ The factor (p2EZ2/15k2T2) is the mean value of P,(cos 8) = *(3 cos2 8 -1) in the field E, where 8 is the angle between @e molecular dipole and E, and for strong fields P may be -lo4.A typical value for the quotient (4) would be Q if Eg were a static field of about 100 e.s.u.; however it may not be practicable to apply a radiofrequency high- voltage and the most convenient arrangement may be one in which E = Eg + E where EZ is a large static field and Ei oscillates at the overtone frequency. Because e2qQ may be much larger than I, the electric-field induced overtones might be easier to detect in the quadrupolar case. The prize for finding the overtones would com- prise some of the advantages that would be associated with a doubling of the magnetic field strength and in addition all AB and Ax molecules would yield single sharp lines and more complicated spectra would be simplified. (Received September 9th 1963.) The Stereochemistry of 1-Oxoquinofizidine By S.F. MASON,K. SCHOFIELD, and R. J. WELLS (CHEMISTRY UNIVERSITY DEPARTMENT OF EXETER) IN continuation of work on the stereochemistry of quinolizidinesl we have extended our experiments to the oxoquinolizidines and record here a preliminary description of a study of the circular dichroism of 1-oxoquinolizidine. The ketone [one enantiomorph of which is represented by (I)] was resolved by means of (+)-a-bromocamphor-n-sulphonic acid giving (-)-1-oxoquinolizidine [a]? = -32.9" (c = 1.5) in iso-octane. The circular dichroism of this substance and its ultraviolet absorption spectrum measured in iso-octane are illustrated in the Figure. Application of the Octant Rule to the three most important conformations (11 111 and IV) of the enantiomorph (I) suggests that (11) would give a markedly negative (axial lone-pair) (111) a negative and (IV) a positive Cotton effect.The curves in the Figure are thus each the resultant of three curves and the major negative Cotton effect is due to (I1 + HI) whilst the minor positive Cotton effect is due to (IV). It follows that (I) represents (-)-1-0x0- quinolizidine absolutely and that conformations (I1 + 111) greatly predominate over (IV). Examination of the temperature dependence of the positive part of the circular dichroism curve at 342 mp permits calculation of the enthalpy difference between the mixture (I1 + 111) and (IV). This proves to be -1-9 kcal./mole and thus (IV) represents about 3 % of the mixture at 20".Whilst models show that conformation (111) is more stable than (IV) a preliminary analysis2 of the variation of the negative circular dichroism with temperature suggests that 40-2.0 1.8 30-I *6 1.4 I -2 20- 1.0-w a 0.8 10-36 ~ U.V.34 3.2 c.d. 0 240 280 320 360 Wavelength (my) UItravioIet absorption (upper curve) and circular dichroism of (-)-1-oxoquinolizidine in iso-octane. (11) and (111) differ in energy by 13-2 kcal./mole. Thus the trans-fused conformation (11) represents about 90% of the equilibrium mixture at room temperature and is represented absolutely by the expression (V). (Received September 30th 1963.) Moynehan Schofield Jones and Katritzky J. 1962 2637; Schofield and Wells Chern.and Ind. 1963 572. Ballard Mason and Vane Discuss. Furuday SOC.,1963 35 43. PROCEEDINGS A Novel Synthesis of the B12H122-Anion By N. N. GREENWOOD and J. H. MORRIS @EPARTMENT OF INORGANIC CHEMISTRY NEWCASTLE THE UNIVERSITY UPON TYNE) THEimportance and potential chemical applications of the icosahedral ion B12H1$- and its derivatives have recently been described,l but a study of these systems has been hampered by lack of a convenient method of preparation. The only reported synthesis2 is in 34% yield from 24ododecaborane which is itself only prepared with difficulty and in small yield. Metal borohydrides are known to react with decaborane3 to give M+BloH13- or under more drastic conditions M+B11H14- but further reaction to give B12H122- does not occur.To overcome this difficulty triethylamine-borane* was used instead of a borohydride and this gave a one-step synthesis of the desired anion in high yield BloHl + 2EtSNBHS = (Et3NH+)2B12H1,2-+ 3H2. Decaborane (1.727 g.) and an excess of triethyl- amine-borane (5.688 g.) were heated under reflux in an evacuated vessel; 888 ml. of hydrogen were col- lected (theory 951 ml.). Unchanged triethylamine- borane (2.440 g.) was recovered indicating that 3.248 g. (theory 3.255 g.) had reacted. Volatile pro- ducts included 28 ml. of diborane and -0.5 ml. of an unidentified air-reactive liquid. The main pro- duct was (Et3NH),B12H12 (4.60 g. 76%) which was analysed after recrystallisation from acetonitrile (Found C 41-6; H 12.8; B 37-5; N 8.1.Calc. for C12H,4B,2N2:C 41.6; H 12-4; B 36.5; N 8.1 %). The Bl2H1Z- anion was confirmed by its infrared spectrum5 and by boron-1 1 nuclear magnetic reson- ance in acetonitrile solution at 20 Mc/sec. which showed only a doublet at -I-34.3 p.p.m. (methyl borate as internal standard) with J(B-H) 124 C.P.S. (Et,NH)2B12H12 dissolved readily in aqueous potassium hydroxide to liberate triethylamine quantitatively and form K2B12H12 in solution; the n.m.r. doublet in aqueous solution occurred at + 32.1 p.p.m. (potassium borate as internal standard) with J(B-H) 115 C.P.S. The sparingly soluble salts Cs2B12H12 (Me4N),B12H12 and [(l,lO-phenanthr~line)~Ni]B, 2H12 were prepared by precipitation from aqueous solution.Passage of the alkaline solution through a cation exchange resin yielded the strong acid (H30)2B12H12 from which the salt Ag2B12H12 was precipitated with silver nitrate. When the preparation was carried out in light petroleum (b.p. 100-120") the yield of (Et,NH)2Bl,Hl was reduced and side reactions occurred BloH14+ 2Et3NBH3= (Et3NH+)(Et3NB,,Hl,-) + 4H2 BloHi4 + 2Et3NBHS = (E~~N),B~,H~o + 5Hp These in turn yielded new derivatives; for example when the reaction mixture was kept in air for several weeks crystallisation from methylene chloride yielded the hydroxy-derivative (Et3NH)2B12Hll~OH (Et,N H+)(Et3N B12H11-) + H20=(Et3N H+)2(B12Hll*OH2-) (Found B 35.8; N 7.7. C12H4,Bl,0N requires B 34.0; N 7.8%) from which the caesium salt Cs2Bl,Hll~OH was obtained (Found B 30.6; H 2.8; Cs 62.7.B12H120Cs requires B 30.3; H 3.2; cs 59.9%). In an attempt to prepare disubstituted derivatives of B12H1$- adducts of the type L2BloH12 were treated with triethylamine-borane. With weak ad- ducts (e.g. L = dimethyl sulphide or tetrahydro- thiophen) the ligand and hydrogen were liberated and the main product was again (Et3NH),B1,Hl2. With strong adducts (e.g. L = triphenylphosphine) no reaction occurred. The bisacetonitrile adduct (MeCN),BloHl, when treated with two moles of triethylarnine-borane in benzene yielded (Et3NH),BlOHl,. These reactions suggest that con- version of decaborane into Bl2H1,2- may proceed by dissociation of triethylamine-borane the slow formation of the triethylamine adduct of decaborane and the rapid electrophilic attack of this by the two BH groups Et3NBH f" Et,N + [BH,] B10H14 + 2Et3N -'(Et3N)2B10H12+ HZ (Et3N),B,oH1 + 2[BH3I -+(Et3NH)2B12H123-2H2 With weak adducts the ligand is readily displaced by triethylamine and the course of the reaction is un- altered; with strong adducts displacement is not possible and the reaction does not proceed; with the bisacetonitrile adduct electrophilic attack of the borane radicals on the liberated acetonitrile leaves an excess of the adduct (Et3N)2B,oH12 in solution and this then rearranges by proton transfer to the observed product (Et3NH)2BloHlo.* The award of a Frank Schon Fellowship to J.H.M.is gratefully acknowledged. (Received September 26th 1963.) Knoth Miller England Parshall and Muetterties J.Amer. Chern. SOC.,1962 84 1056. Hawthorne and Pitochelli J. Amer. Chem. Soc. 1960 82 3228. Aftandilian Miller Parshall and Muetterties Inorg. Chem. 1962 1 734. Greenwood and Morris J. 1960,2922. Muetterties Merrifield Miller Knoth and Downing J. Amer. Chern. SOC.,1962 84 2506. 6 Hawthorne and Pitochelh J. Amer. Chem. SOC.,1959 81 5519. NOVEMBER: 1963 339 Proton Resonance Spectra of Cobaltaminines By P. CLIFTON and L. PRA~ (IMPERIAL COLLEGE LONDON,S.W.7) THEproton resonance spectra of cobaltic complexes show differences between the cis-and trans-ammine groups. This is seen clearly in acido-penta-ammine complexes such as the fumarato-derivative MO2C.CH :CHCO2.Co(NH&J2+ whose spectrum in a freshly prepared solution in deuterium oxide (PD x 1) is shown in Figure A.The olefinic protons A t I I I I I I I I -300 -200 -100 C.P.S. give the sharp AB pattern and we assign the large and the small broad lines of relative intensities 12 and 3 to the protons in the ammine groups which are respectively cis and trans to the oxygen atom. Similarly the cis-dichlorobis(ethy1enediamine)Co-@I)+ ion (Figure B; pD “N 3) shows two lines for the amine groups the one at higher field being assigned to those which are trans to the chlorine atoms by comparison with the trans-isomer. Some data for other complexes are given in the Table. Separations smaller than about 20 C.P.S. are difficult to measure since the NH lines are broad a result of quadrupole relaxation of the nitrogen-14 nuc1eus.l The cis-protons may be shifted to the lower field by intramolecular hydrogen bonding between the cis-ammine groups and the ligand which is expected in acido-complexes and by the effects of magnetic anisotropy2 in the ligand.Also there seems to be an upfield shift of the trans-protons suggesting a reduced polarity of the trans-ammine group due to polarisation of the metal ion by the negative ligand.3 In solution in deuterium oxide the broad lines gradually become weaker as the ammine hydrogen atoms are replaced by deuterium. The intensity of the trans-line decreases faster than the cis showing that the trans-protons are more labile. This agrees with deductions drawn from studies of the overall rates of hydrogen exchange in ammine c~mplexes.~~~ The separate rates can now be estimated by measuring at intervals the intensities of the NH lines relative to that of a standard line.For the fumarato- complex the second-order rate constants for the exchange catalysed by hydroxide ion were found to be about 2.0 x lo7and 3-5x lo51. mole-l sec.-l for the trans- and cis-protons respectively at 21 O. The absence of appreciable hydrolysis was shown by observing the gradual reappearance of the trans- proton line when a partially deuterated complex was isolated and redissolved in ordinary water. In cis-[Co(NH2CH %*CH ,C12]+ the trans- 2*NH2) protons are again the most labile but measurements of the rate for the cis-ones were complicated by the aquation and subsequent isomerisation of the com- trans-NH CH protons 134 Cobaltic complex Hexa-ammine Fumaratopenta-ammine (pD x 1) Maleatopenta-ammine (PD x 1) Fluoropenta-ammine Chloropenta-ammine Bromopenta-ammine Carbonatopenta-ammine Carbonatotetra-ammine cis- [Co(en) 2C1 J+ trans- [Co(en) 2C1 2]+ (cis) [cO(en)2c204~ cis-NH 152 1485 151 162 143 144 138 250 232 230 Jfi 2.0 94.5 rt 2.0 94-7 78 300.3 and 313.1 (JH-H= 15.9) 275.3 and 291.3 (JH-B = 12.1) 109 108 91 112 178 ca.84 and 96 - 100 183 86 (Line positions in c./sec. to low field side of t-butyl alcohol in deuterium oxide solutions at 56.45 mc,/sec.) Pople Mol. Phys.1958 1 168. Spiesecke and Schneider J. Chem. Phys. 1961,35,722. Basolo and Pearson “Progress in Inorganic Chemistry,” Interscience New York 1962,4 381. Basolo Palmer and Pearson J. Amer. Chem. Soc. 1960 82 1073. Palmer and Basolo,J. Phys. Chem. 1960,64,778. plex.6 Since the amine protons are not displaced during aquation and isomerisation the formation of the chloroaquo-isomers results in changes in the line shapes of the cis-amino- and the methylene groups. Such changes can be used to follow the replacement Baldwin Chan and Tobe J. 1961 4637. PROCEEDINGS of one ligand by another in acid solutions where the proton exchanges are very slow. We thank the D.S.I.R. for a maintenance grant (to P.C.). (Received August 8th 1963.) The Coupling of Allenic Halides with Ethynyl Compounds By C.S. L. BAKER D. LANDOR PHYLLIS and S. R. LANDOR (THECHEMISTRY DEPARTMENT, WOOLWICH POLYTECHNIC) THE allenyne system >C=C=C.C=C. has been found in a number of mould metabo1ites.l We now report a general method for the synthesis of allenynes in which an allenic bromide or iodide2 is condensed with a terminal acetylenic compound in the presence of cuprous ions and a suitable base (tributylamine for tertiary allenic halides ethylamine or t-butyl- amine for secondary allenic halides) in NN-dimethyl- formamide. The products (see Table) after being tion at 0.019 mm. and identified by infrared and ultraviolet spectra and analyses. The reaction is analogous to the coupling of a bromoacetylene and a terminal acetylenic com-to give unsymmetrically substituted di- acetylenes.Naturally occurring allenyne compounds such as marasin and mycomycin show activity against Mycobacteriurn tuberculosis which is lost when the RR1C-C=CH*C~C.[CH2];R2 R R1 R2 n X Yield (%)* (mp) Eb Me H OH 1 I 40 Pri H OH 1 I 49 Pr' H OH 2 I 36 Pri H Me 3 I 62 But H OH 1 I 54 Me H HC=C 0 I 15 Pri Pri OH 1 Br 62 But Me OH 1 Br 62 Et Me OH 1 Br 51 Me Me OH 1 Br 33 Prn 11 OH 1 Br 51 Et H OH 1 Br 31 But Me Me 3 Br 82 Et Me HC-C 0 Br 25 a Crude yield after being washed with AgNO (70-90% purity). b Determined immediately on distilled or chromatographed sample. c Contains 10%dienyne. d Also Amax 237.5 249 263 278.5; E 11,800 13,200 14,600 11,200.e Also Amax. 237.5 249.5 263 278.5; E 12,300 13,400 13,700 11,600. 219.5 11,800 220 13,700 220 16,000 221 10,500" 221 10,100 210d 60,600 222 18,300 221 16,800 220 14,400 221 16,300 220 15,800 220 12,800 222 15,100 210e 38,800 washed with ammoniacal silver nitrate (to remove terminal acetylenic compounds produced by some coupling occurring at position 3 of the allenic halides) were purified by chromatography or distilla- Cu+ RR'C=C=CHX + CH=C*[CHJ,*R2 base RR1C=C=CH.C=C.[CH2],,.R2 R and R1= Alkyl or H R2 = Alkyl ethynyl or hydroxyl X = Br or I allenic group is destroyed by alkaline isomerisation. Our synthetic allenynes were tested for antibiotic activity as part of a programme relating structure to biological activity; most show a high level of activity in vitro against Mycobacterium tuberc~losis.~ We thank D.S.I.R.for a special research grant and Drs. E. P. Abraham R. J. W. Rees and D. W. F. Wheater for microbiological testing. (Received October 1 1 th 1963.) Celmer and Solomons J. Amer. Chem. Soc. 1952,74 1870; Bu'Lock Jones and Leeming J. 1955,4270; 1957 1097; 1960,2257; Bendg Arkiv Kemi 1959,14 305. Black Landor Patel and Whiter Tetrahedron Letters 1963,483 and unpublished work from these laboratories. * Chodkiewicz Ann. Chim.(France),1957,2 819. U.K. Patent Appln. 47567/62. NOVEMBER 34 1 1963 Nuclear Magnetic Resonance Spectra of Iodine Heptafluoride and Iodine Oxide Pentafluoride By LOUISG. ALEXAKOS and STEPHEN C.D. CORNWELL B. PIERCE (DEPARTMENT UNIVERSITY MADISON, OF CHEMISTRY OF WISCONSIN WISCONSIN) WHILEstudying the fluorine n.m.r. spectrum of iodine heptafluoride in Pyrex sample tubes we ob- served slow changs in the spectrum. New lines which we were unable to ascribe to any known substance were visible after a few minutes at room temperature in gaseous samples and after an hour or so at room temperature in the case of liquid samples. Resonances due to silicon tetrafluoride also appeared and increased with time and a weak quadruplet due to boron trifluoride was detected in the spectrum of the liquid. The spectra of partially reacted gaseous and liquid samples are shown in the Figure. Gaseous IF7shows a single line shifted 336 -& 2 parts per million to lower field from gaseous SiF,.The spectrum of IF as liquid at 27” consists of a broad doublet with field-independent separation (measured at 40.00and at 56.44 Mc/sec.) of 4000 & 200 c.P.s. at a mean position corresponding to a chemical shift of 336 f 4 p.p.m. to lower field froin the resonance of dis- solved SiF,. The latter observation is consistent with those of Gutowsky and Hoffman,l who reported for liquid IF7 a broad multiplet centred at 337 rt 11 p.p.m. down in field from liquid SiF,. The new substance was tentatively identified as IOF on the basis of the following evidence (1) The n.m.r. lines of the gas Fig. (a) consist of a doublet and a quintet corresponding to the pattern for an AB spectrum,2 indicating the presence of one unique and four equivalent fluorine atoms.The new lines in the liquid Fig. (b) are obviously due to the same substance though here the J-splitting was not resolved. The spin-spin coupling and shielding constants are given in the Table rela- tive to SiF as internal reference. The AB spectrum is definitely not that of IF5.1 (2) A plausible reaction scheme can be constructed in which IOF5 SiF, and BF3 result from the reaction of IF with water adsorbed on Pyrex IF7 + H20 -IOF5 + 2HF 2HF -t $30 -+iSiF + H20 2HF + 4B203-+$BF3+ H,O Only a trace of water is required as it is regenerated in the reaction. This reaction cycle could also be initiated by a small amount of hydrogen fluoride. (3) The substance which gives the AB spectrum Spin-Spin Coupling and Shielding Constants* for IOF,.J a~-Uref. UB-oref C.P.S. (P.P.rn.1 (p.p.m.1 IOF (g) 250 & 10 -271.6 f0.2 -235.1 0.2 IOF (1) -272 f1 -236 f 1 * J is the spin-spin coupling constant UA and C~Bare shielding constants for the unique fluorine and equivalent set of four respectively. The reference substance is SiF4(g) and SiF4 (dissolved) for the gaseous and liquid spectra respectively. Measurements were made at 27”, with a spectrometer frequency of 56-44 Mclsec. ’ 25 20 15 10 5 + V -V (kchec.) Fluorine n.rn.r. spectra of partially reacted samples of IF in Pyrex sample tubes (a) gaseous sample (b) liquid sample. Spectrometer frequency 56-44 Mclsec. Gutowsky and Hoffman J. Chem. Phys.1951 19 1259. 2 Pople Schneider and Bernstein “High-resolution Nuclear Magnetic Resonance,” McGraw-Hill Book Company Inc. New York N.Y. 1959 p. 152. PROCEEDINGS was isolated (m.p. 4*1-4-8”)by vacuum distillation geometry though one can not on this evidence alone from a sample which had apparently reacted to rule out structures of lower symmetry in which some completion. Several determinations of vapour rapid internal motion effectively raises the symmetry density at pressures ranging from 30 mm. to 450 mm. to c4,. gave M 236 & 4 (IOF requires 238). We have recently learned of the synthesis and We thank Professor Bartlett for his courtesy in identification of IOF by Bartlett and Le~chuk.~ exchanging information with us in advance of Comparison of physical data and infrared spectra publication of his results on IOF and IF,.This leaves no doubt that the substance reported by them research was supported by grants from the National is the same as that described here and thus provides Science Foundation and from the Graduate School final confirmation of our assignment of the AB of the University of Wisconsin from funds provided spectrum to IOF,. by the Wisconsin Alumni Research Foundation. The n.m.r. spectrum suggests a C, molecular (Received September 4th 1963.) Bartlett and Levchuk following communication. Iodine Oxide Pentafluoride and Iodine Heptafluoride By NEIL BARTLETT and L. E. LEVCHUK (DEPARTMENT THE UNIVERSITY OF CHEMISTRY OF BRITISHCOLUMBIA VANCOUVER 8 B.C. CANADA) WITH the discovery of osmium oxide pentafluoridel amount of the oxyfluoride 1ogePcm.= 17-38 -and the demonstration that it possesses a near-3781/T. Ruff and Keim,3 who probably worked with octahedral molecular structure,2 we have sought to a mixture of the two compounds give logepcm. = prepare and similarly characterise other EOF 17-64 -3690-81Tand m.p. 5-6” for their iodine compounds. heptafluoride. Since the heptafluoride is difficult to The preparation of iodine oxide pentafluoride by free from oxyfluoride it is best to prepare it by the interaction of iodine heptafluoride with water fluorination of a metal iodide which can be rigorous- (IF + H,O IOF + 2HF) with iodine pentoxide ly dried (e.g. PdI,) since iodine is not easily dried. (21F + I,O -+ 210F5 + 2IOF,) or with glass It is probable that in all previous work on iodine @IF7+ SiO -+ 2IOF + SiF4) was readily achieved heptafluoride the oxyfluoride was present as im- at room temperature.The progress of the reactions purity. Lynch’s material,* as investigated by Lord was followed by infrared spectroscopy. Vapour- and his co-workers,j was certainly badly con-density measurements at pressures of -300 mm. of taminated by the oxyfluoride as their infrared spectra material m.p. 4.4-4-5” shown by infrared spectral show. All the structural investigations except the analysis to be free from heptafluoride indicated a X-ray crystallographic work used Lynch’s material molecular weight of 243 .i. 7. (IOF requires M which must be regarded as suspect. The material 238).The heptafluoride m.p. 6.3-6-5” which was used for the X-ray investigation may also have been prepared in a prefluorinated “Monel” vessel and impure; the melting point and vapour-pressure data handled in “Monel” and “Kel F” apparatus and which Burbank gives6 are those of Ruff and Keim. which contained traces of the oxyfluoride was used Clearly there is a need for a re-investigation of the for vapour-density measurements at -300 mm. molecular structure of iodine heptafluoride which pressure and gave M = 259 f-7 (calc. for IF 260). has been the subject of much controversy (see ref. 6). The infrared spectra showed peaks IOF, 2375 X-Ray crystallographic n.m.r. and detailed infrared 1850 1350 925 850 705; IF (containing some studies are in progress here. IOF,) 1400,1290,1250,1160,1100 (925) 745,670 The infrared spectrum of the oxyfluoride closely 425 cm.-l.The vapour pressure-temperature rela- resembles the spectra of rhenium oxide pentafluoride tionship for the oxyfluoride is logepcm. = 18.31 -and osmium oxide pentafluoride (which we are now 360517‘and for the heptafluoride containing a small studying) and of some hexafluorides. Clearly the l Bartlett. Jha. and Trotter Proc. Chem. Soc.. 1962. 277. Bartlettand Trotter to bk published. Ruff and Keirn 2.anorg. Chem. 1930,193 176. * Schurnb and Lynch Znd. Eng. Chem. 1950,42 1383. Lord Lynch Schumb and Slowinski J. Amer. Chem. Soc. 1950 72 522. Burbank Acta Cryst. 1962 15 1207. NOVEMBER 1963 molecular symmetry expected to be C,, is close to Oh; a consequence of near equality in size and mass of the oxygen and fluorine ligands.The findings of Alexakos Cornwell and Pierce' and of Gillespie and Quaila confirm the C, symmetry. The authors thank Professor C. D. Cornwell for the communication of his findings before publication and Professor R. J. Gillespie for the prompt notice of his communication. Grateful acknowledgment is made to the National Research Council Ottawa and the Research Corporation for financial support. (Received August 29th 1963.) * Alexakos Cornwell and Pierce preceding communication. Gillespie and Quail Proc. Chem. SOC.,1963 278. Unambiguous Synthesis of a 2-Amino-4-hydroxy-6-polyhydroxyalkyIpteridine By J. M. LAGOWSKI and H. S FORREST (GENETICS OF TEXAS AUSTIN TEXAS FOUNDATION UNIVERSITY U.S.A.) and H.C. S. WOOD (THE ROYAL COLLEGE AND TECHNOLOGY, OF SCIENCE GLASGOW) WE have succeeded in preparing 2-amino-3,4-di hydro -4-0x0- 6 -( 1,2,3-L-erythro-tri hydroxypropy1)- pteridine (I)* from the 1 -pyrimidinylamino- 1 -deoxy- 0 0 HO-TH CH,OH L-erythro-pentulose (IT). It has previously been reported2 that cyclisation of the enantiomorph of the pyrimidine (11) followed by aerial oxidation in alkaline solution of the resulting dihydropteridine gave only xanthopterin. We now find that loss of the side chain can be avoided by manganese dioxide oxidation of a dilute acetic acid solution3 of the di- hydropteridine (L-configuration) which gave the aromatic derivative (I).Usually xanthopterin could not be detected among the reaction products by paper chromatography.The acetic acid solution of the aromatised com- pound (20 % yield estimated spectrophotometrically based on 1 -amino- 1 -deoxy-L-erythro-pentulose oxal-ate) was freed from manganese dioxide adjusted to pH2 with hydrochloric acid and fractionated on charcoal4; the desired compound was eluted with water-ethanol-concentrated ammonia (1 3 :5 :5). The fractions with a ratio of ultraviolet absorption in solutions of pH 13 at 255 mp to that at 363 mp of 3.25 were concentrated in vacuo and the residue was crystallised froni 20% acetic acid giving the pale yellow trihydroxypropyl mmpound [a]? -29.1 (c 026 in 0.lrv-sodium hydroxide); Amax. (log E) 363 (3.87) 255 (4.38) in O-lN-sodium hydroxide and 321 (3-90) 248 (4.05) in 0.h-hydrochloric acid; infrared spectrum (potassium bromide pellet) identical with that from the material synthesised by Patterson et aZ.;6 and uptake of sodium meta- periodate (spectroph~tometric~) 2 moles/mole (1 hr).The following R values were obtained (Whatman's No. 1 paper ascending values for isoxanthopterin in brackets) 5% boric acid 0.69 (0.41); BunOH-AcOH-H,O (4:1:1) 0-14 (0.18); 5% NH4CI 0.63 (0-28); 4% sodium citrate 0.60 (0.30); PrnOH-1 % aq. NH (2 l) 0.31 (0.21). This represents the first unambiguous synthesis of a compound of this type all earlier syntheses* being based on methods which yield mixtures of 6- and 7-hydroxyalkyl isomers; these are then separated chromatographically and identified by degradative procedures.The synthesis also confirms the chemical * A compound of this structure but with the D-configuration in the side chain has been isolated from honey-bee pupae and named ne0pterin.l Rembold and Buschmann Annulen 1963,662 72; Chem. Ber. 1963 96 1406. Stuart and Wood J. 1963,4186. Hatfield Van Baalen and Forrest Plant Physiol. 1961 36 240. * Stambaugh and Wilson J. Chromatog. 1960,3 221. Petering and Schmidt J. Amer. Chem. Soc. 1949,71 3977. Patterson Milstrey and Stokstad J. Amer. Chem. Soc. 1958 80 2018. Dixon and Lipkin Amlyt. Chem. 1954 26 1092. See e.g. Patterson Milstrey and Stokstad ref. 6; Rembold and Metzger 2.physiol. Chem. 1962,329 291. PROCEEDINGS validity of the biogenetic schemes suggested for This work was supported by a research grant from pteridines of this types and perhaps all pteridines.Its the National Institutes of Health Public Health application to the synthesis of neopterin biopterin Service by the Robert A. Welch Foundation and the glycerol phosphate derivative isolated from Houston Texas and by the British Empire Cancer E. colilo is being studied. Campaign. (Received September 4th 1963.) sWeygand Simon Dahms Waldschmidt Schliep and Wacker Angew. Chem. 1961,73 402; Forrest Proc. Seven-teenth Intern. Congr. Pure and App. Chem. Munich 1959. 1960,2,40. lo Goto and Forrest Biochem. Biophys. Res. Comm.,1961 6 180. A New Indole Rearrangement By R. M. ACHESON and R. W. SNAITH (DEPARTMENT UNIVERSITY OF BIOCHEMISTRY OF OXFORD) TRIMETHYL l-rnethylindole-2,3,4-tricarboxylate(I) coal hydrogen iodide in acetic acid and distillation with bromine1 in anhydrous acetic acid yields only with zinc gave successively compounds (11) (IV) and the 6-bromo-derivative whereas a second cornpound 1-methyloxindole itself.The ultraviolet infrared and nuclear magnetic resonance spectra of these com- pounds are consistent with the structures suggested. The formation of the oxindole-3,3-dicarboxylicester (111) requires the movement of the ester group from the 2-position of the original indole (I). This is accommodated in the scheme outlined which in its first stages resembles Taylor's general reaction.2 Only two other 1 ,2-shifts of ester groups have previously been describedl~~ and in contrast these proceed through nucleophilic attack on the migrating ester group.R =C02Me We thank Dr. P. W. Sadler for a gift of l-methyl- (111) is also formed if water is present. This second oxindole. compound with hydrogen over palladium on char- (Received September 30th 1963.) Acheson and Vernon J. 1963 1907. Taylor Proc. Chem. SOC.,1962 247. Acheson and Vernon Proc. Chem. SOC.,1962,277; Fahr and Scheckenbach Annalen 1962,655,86. An Acetylenic Diazonium Salt By E. ROBSON and J. M. TEDDER OF CHEMISTRY SHEFFIELD (DEPARTMENT THE UNIVERSITY 10) N~IC OXIDE was bubbled through a solution of spectra (infrared and ultraviolet) of the products 1-nitrosohex-1-ynel in methylene dichloride at -78". present in this golden-yellow solution were frustrated The green colour of the solution slowly changed to a by the rapid evolution of nitrogen at > -2O"c.deep golden-yellow. Attempts to investigate the However the solution proved very reactive even at BUCE C-N= 0 12NO / B~C=C-&I=N NO^ \ B-C,0H,*OH/ YzNPh J BUCEC-N= N-C,oH,*OH-2 BuC= C-N= N-C,H,.NMe,-p I I HX 4-+ '1, BuCECH + N=N=ClOH,=O-2 BuCzCH + N=N-CsH,.NMe,-p Robson and Tedder Proc. Chem. Soc. 1963 13. NOVEMBER 1963 -78". The cold solution was thoroughly swept through with dry nitrogen and then treated with /%naphthol in ether. An immediate red colour developed which slowly changed to yellowish brown. The mixture was allowed to warm to room tempera- ture and naphthalene 1 -diazo-2-oxide (m.p.and mixed m.p. 89-91"; Vmax 2100 cm.-l) was then isolated together with regenerated hex-1 -yne. In another experiment a solution of dimethylaniline in methylene dichloride was added to the cold golden- yellow solution. An orange-red colour developed immediately and the spectrum of the crude product had a strong band at 2260 cm.-l. However this band was slowly replaced by absorption at 2140 cm.-l (characteristic of a diazonium salt). The final pro- ducts were NN-dimethyl-p-nitroaniline(m.p. 162" and correct analysis) and regenerated hex-1-yne and p-dimethylaminobenzenediazoniumsalt (character- ised by coupling with 19-naphthol to give 1-p-di- meth ylaminophen y lazo-2-napht hol ,m.p. and mixed m.p. 182"; correct analysis). We interpret these observations as evidence that the golden-yellow solution contains hex-1 -ynedi- azonium nitrate which couples with ,&naphthol and dimethylaniline.The coupling products are unstable and rearrange to the aromatic diazo-compound and the regenerated acetylene. The isolation of dimethyl- p-nitroaniline is also in accord with this view. The golden-yellow solution undergoes other coupling reactions but in every case so far investigated the arylazoacetylene formed initially has dissociated into an aryldiazonium salt and the acetylene. (Received September loth 1963.) An Aliphatic '*Diazocyanide" By JOHN HARLEY-MASON C. W. TIMS and JOHN (UNIVERSITY LABORATORY, CHEMICAL CAMBRIDGE) INthe preparation of anthracene9,lO-bi-iminelby the alkaline hydrolysis of the Diels-Alder adduct (I) of anthracene and diethyl azodicarboxylate the q).z 0) NC-N=N*C02Et (U monodecarboxylated compound 01; R = H) was obtained as a by-product in substantial amount.* Treatment of this with cyanogen bromide gave the N-cyano-compound 01; R = CN).At 150-170"/ 0.3 mm. smooth decomposition occurred to give ethyl 2-cyanodi-imide carboxylate (III) an orange- red liquid of irritant odour b.p. 58-59"/21 mm. and anthracene. This is the first aliphatic "diazo- cyanide" to be prepared through aromatic examples e.g. p-ClC,H,.N :NCN have long been known.2 The cyano-ester (111) is a very reactive dienophile adding readily to anthracene to regenerate (11; R = CN) and reacting exothermically with 1,4-diphenyl- butadiene.The cyano-ester is sparingly soluble in water giving a yellow solution which on addition of silver nitrate at O" gives a precipitate of silver cyanide with gas evolution indicating heterolysis of the N-CN bond. (Received September 2 1st 1963.) * In a private communication Professor Corey has informed us that he also encountered this compound. Corey and Mock J. Amer. Chem. Sac. 1962 84 685. Hantzsch and Schulze Ber. 1895 28 666; Hantzsch and Danziger Ibid. 1897 30 2529. A Novel Pyrazole Synthesis By M. S. GIBSON and A. W. MURRAY (CHEMISTRY FACULTY UNIVERSITY DEPARTMENT OF TECHNOLOGY OF MANCHESTER) REACTION of cinnamaldehyde phenylhydrazone with PhCHBrCHBr*CBr=N.NHCsH,Br,. an excess of bromine has been shown to give 1,2,3- The stereochemistry of the product was not indicated tribromo-3-phenylpropaldehyde2,4-dibromophenyl-but the trans-disposition of groups in cinnamalde- hydrazone:l hyde itself and the known mode of addition of Chattaway and Irving J.1935 90. PROCEEDINGS bromine to carbon-carbon double bonds2 suggests give compound (11). The threo-configuration of this the 2,3-erythro-configuration.The conjugate base is favourable for E2 elimination of hydrogen bro- (I) in the configuration shown should be capable mide to give the pyrazole (111). of undergoing concerted displacement of the 3-bro- Accordingly 1,2,3 -tribromo -3 -phenylprop-mine as bromide ion with inversion at position 3 to aldehyde 2,4-dibromophenylhydrazone was refluxed for 2 hours in acetic acid containing anhydrous sodium acetate (34 equiv.) this yielded the pyrazole (111 Ar = C6H3Bra (26% pure) m.p.162-163" (Found C 39.7; H 2.2; Br 52.7; N 6-0. C,,H,Br,N requires C 39-4; H 1.9; Br 52.5; N 6.1 %). The corresponding 2-bromo-4-nitro- phenylhydrazonel yielded the pyrazole (111; Ar = C,H,Br-NO,) (21 % pure). Spectroscopic data are in accord with these structural assignments. The above yields are not considered optimal and the reaction is being further investigated to deter- mine whether competing4 acetolysis occurs. (Received September 5th 1963.) Gould "Mechanism and Structure in Organic Chemistry," Holt Rinehart and Winston New York 1959 Chapter 13. Cf. O'Connor J. Org. Chem. 1961 26,4375. Chattaway and Walker J.1925 127 975. Replacement of Methanesritphonyloxy-groups:the Conversion of the D-ghco-into the D-galacto-Configuration* By J. HILL,L. HOUGH, and A. C. RICHARDSON OF ORGANIC BRISTOL) (DEPARTMENT C%IEMISTRY THEUNIVERSITY DISPLACEMENTS of sulphonyloxy-groups at secondary was unlikely5 to be facilitated by participation of the carbon atoms of carbohydrates by nucleophilic vicinal trans-acyloxy-group via a cyclic cation an reagents such as sodium benzoate in NN-dimethyl-analogous reaction of methyl 3-acetamido-2-0-formarnide have been achieved in circumstances acetyl-3-deoxy-4,6-di-0-methanesulphonyl-a-D-glu-favourable to either an SN2 reaction or neighbouring- copyranoside with iodide led to a 4,6-di-iodo-group participation .l Direct replacements of sulpho- derivative probably as a result of acetamido-group nates attached to a pyranose ring are rare.Reist ef al. participation. However reaction of the glucoside have prepared 4-azid0-4-deoxy-~ and 4-0-benzoyl-~- (I; R = Bz) with sodium benzoate in dimethyl- glucopyran~sides~ from methyl 2,3,6-tri-O-benzoyI- formamide at 140" for 20 hr. gave methyl 2 3 4 4 -0-methanesulphonyl-a -D -galactopyranoside by 6- tetra- 0-benzoyl -a-D-galactopyranoside (11; R treatment with sodium azide and sodium benzoate = Bz R = OBz) as the only product thus respectively in dimethylformamide an approach excluding neighbouring acyloxy-group participation. that led to the synthesis of amosamine (4,6-dideoxy- Thus the equatorial 4-sulphonyIoxy-group of the 4-dimethylarnino-~-glucose).* We have prepared glucoside is replaced by an SN2 process as readily as the 2,3-diacetate and the 2,3-dibenzoate of methyl the axial 4-sulphonyloxy-group of the galactoside 4,6-di-0-m e t h a ne su 1p h on y I-a-D-glucopyranoside contrary to a previous view.' (1; R = Ac and Bz respectively) with a view to Replacement with sodium azide in dimethylform- examining the nucleophilic displacements of the amide very rapidly (3 hr.at 150-155") gave in 70% primary and secondary sulphonates. Whilst the yield the 4,6 -diazido-4,6 -dideoxy-D-galactoside departure of the 4-methanesulphonyloxy-substituent (11; R = Bz and Ac R' = NJ as revealed by Baker and Haines J. Org. Chem. 1963 28,438. Reist Spencer Baker and Goodman Chem. and Ind. 1962 1794. Reist Spencer and Baker J.Org. Chem. 1959 24 1618. Stevens Blumbergs and Daniher J. Amer. Chern. SOC.,1963 85 1552. Richardson Proc. Chem. SOC.,1963 131. Jeanloz and Jeanloz J. Amer. Chem. SOC.,1958 80 5692. Reist Goodman Spencer and Gueffry 19th I.U.P.A.C. Congress London 1963 Abstract A3-45. NOVEMBER 1963 proton magnetic resonance (p.m.r.) spectroscopy and this derivative was converted into syrupy methyl 4,6 -diamino-4,6- dideoxy-cc-D-g a 1a c t op y r a n osi d e (11; R = H R’ = NH,) chardcterised as the crystalline di-N-acetyl (11; R = H R’ = NHAc) tetra-acetyl (11; R = Ac R’ = NHAc) and tetrabenzoyl (TI; R = Bz R’ = NHBz) derivatives. H OR (1) (w) (a) “The 4,6-dideoxy-4,6-di t hiocyana to-deriva t ive (I1; R = Bz R’ = SCN) was similarly prepared in 40% yield by the use of potassium thiocyanate in dimethylformamide (130” for 48 hr.) the ~-galacto- configuration being assigned by p.m.r.spectra. Treatment of the dithiocyanate with either sodium ethoxide8 or ethanolic sodium sulphide9 led with simultaneous de-0-benzoykdtion to the dithiolate (11; R = H R’ = S-) which on de-ionisation underwent rapid atmospheric oxidation to the crystalline 4,6-disulphide (111) (Found M 226 225 C,H,,O,S requires M 224). This is the first example of an intramolecular disulphide in the carbohydrate field. Desulphurisation of the disulphide (III) or dithiocyanate (11; R = Bz R’ = SCN) by Raney nickel afforded methyl 4,6-dideoxy-ot-~-xyfo-hexopyranoside (IV) and its di-@benzoate respec- tively.Mild acid hydrolysis of the pyranoside (IV) gave 4,6-dideoxy-ot-~-xyfo-hexose (m.p. 137-1 38” ; [aID + 103” 4+ 33”) a new dideoxy-sugar. Kochetkov and Usovl0 haw synthesised chalcose (4,6-dideoxy-3-O-methyl-~-xyZo-hexose) use of by triphenyl phosphite methiodide for removal of the 4,6-hydroxyl groups of a suitably protected glucoside. Overendll has briefly mentioned the preparation of compound (IV) from methyl 4-deoxy- a-D-xylo-hexopyranoside by standard procedures. We thank Drs. D. H. Ball J. G. Buchanan and L. D. Hall and Mr. A. MI. Lewis for physical measurements. (Received August 17th 1963.) Miiller and Wilhelms Ber. 1941 74 698. @ Panchenko and Smirnov. J. Gen. Chem. (U.S.S.R.),1932,2 193; Takiura and Takino J. Pharrn.SOC.Japan 1954 74 839. lo Kochetkov and Usov Tetrahedron Letters 1963 519. l1 Overend Chem. and hd. 1963. 352. *The above communication originally appeared on p. 314 of October Proceedings and the formulae were then omitted. NEWS AND ANNOUNCEMENTS Library.-The Library will be closed for the Christmas Holiday from 6 p.m. on Monday Dec- ember 23rd to 9.30 a.m. on Monday December 30th 1963. Aspects of Molecular Dissymmetry.-A Chemical Society Symposium on this subject will bz held from 2 p.m. to 5.45 p.m. on Thursday March 19th 1964 at Battersea College of Technology London S.W.ll. As the topic is close to the life-long inter- ests of the late Dr. J. Kenyon for many years Head of the Chemistry Department in the College this meeting has been chosen as the occasion for the unveiling by Sir Christopher Ingold of a memorial plaque as part of the tribute of his many friends to his work and inspiration.The following speakers will take part:-Dr. C. L. Arcus (Battersea College sf Technology) Dr. M. Green (Manchester College of Science and Technology) Dr. D. M. Hall (Bedford College London) Professor W. Klyne (Westfield College London) Dr. D. G. Neilson (Queens College Dundee) Dr. C. F. Wells (Uni-versity of Birmingham). Full details will be circulated. Visit to Rhodesia and Nyasa1and.-Profissor G. W. Perold Head of the Department of Chemistry of the University of South Africa Pretoria visited the University College of Rhodesia and Nyasaland in early October under the auspices of the Chemical Society.He gave two lectures in the Department of Chemistry on “The Chemistry of Leaf Constituents of Proteaceae” and “Microchemistry as a Practical Art.” Whilst in Salisbury he visited the Elia Salzman Rhodesia Tobacco Science Institute the Kutsaga Laboratory of the Tobacco Research Board and the Mazoe Citrus Estate of the British South Africa Company. Deaths.-We regret to announce the deaths of the following Mr. T. B. Mann (5.9.63) Andover a Bio- logical Research Chemist; Mr. R. W. Scott (18.9.63) a former Science Master at Rugby School; and Professor W. E. S. Turner (27.10.63) Emeritus Pro-fessor of Glass Technology University of Sheffield. Election of New Fellows.-39 Candidates were elected to the Fellowship in October 1963.The Perkin Centenary Trust.-The Trust was established to commemorate the centenary of the discovery by William Henry Perkin in 1856 of Mauveine the first important synthetic dye. Its pur- pose is to promote technical education in all aspects of the manufacture and the application of colouring matters. The Trustees invite applications for the following awards for the Academic Year 1964-65 to be sub- mitted on forms available from the Secretary. The Perkin Centenary Scholarship. These awards are offered each for one or two years renewable at the discretion of the Trustees for one further year to enable candidates employed in an industrial firm or other institution concerned with the manufacture or the application of colouring matters to study at a university or technical college.Two types of awards are available some to the value of €100 to be used in conjunction with an L.E.A. grant and others to a value of €350 (this may be increased to a00 for a student living away from home). The $300 scholar- ships are intended for students who would normally receive a fairly substantial grant from the Local Education Authority. The higher value scholarships cancel out any L.E.A. award and so they are in- tended for students whose normal grant inclusive of fees would be less than about €250-€300. There will be no formal means test but the Trustees are prepared to discuss with the individual student which type of award would be most suitable. Appli- cations must be received not later than May lst 1964.Perkin Travel Grants. These are available to teachers concerned with the study of any aspect of the manufacture or the application of colouring matters at a university technical college or other institution. Awards will be made primarily to assist those for whom grants are not readily available from other sources and the Trustees expect that preference will be given to applications from lecturers senior lecturers and readers or the equivalent grades in other institutions wishing to gain experience at a similar institution or in industry on the Continent of Europe. The object of the intended visit must be clearly stated (e.g.,study of special techniques apparatus or industrial processes; to assist some stated research PROCEEDINGS project; or to study some specific educationar method) and the applicant will be expected to devote sufficient of his time to that object so that effective study is possible.Each application will be considered on its merits but in general the Trustees favour an extended stay at one or two institutions rather than brief visits to a larger number of establishments. Applications for which the sole or primary purpose is to participate in a conference overseas will not normally be entertained. Grants for the year commencing April 6th 1964 will be available towards the cost of travel and maintenance at rates of up to €5 per day for periods of from one to four months. Applications accom- panied by a recommendation from the Head of the Department in which the candidate is working must be received not later than December 31st 1963.The Perkin Centenary Fellowship. This will not be awarded in the year 1964-65. Enquiries relating to Scholarships or Travel Grants should be addressed to The Secretary The Perkin Centenary Trust c/o The Chemical Society Burlington House London W. 1. International Symposia.-A Symposium OD Nucleic Acids (Structure Biosynthesis and Func- tion) will be held at Hyderabad on January 16th- 23rd 1964. Further enquiries should be addressed to Dr. P. M. Bhargava Regional Research Laboratory Hyderabad-9 India. The Sixth International Metal Finishing Con- ference will be held in London on May 25-29th 1964. Further enquiries should be addressed to Dr.S. Wernick Honorary Secretary Institute of MetaP Finishing 32 Great Ormond Street London W.C. 1-The Fourth International Congress of Photo-biology organised by the British Photobiology Group will be held in Oxford on July 26-30th 1964. Further enquiries should be addressed to the Fourth International Photobiology Congress Con- gress Office Blandford Site Whiteknight Park Reading. Personal.-Dr. B. BeagZey is spending the second year of his D.S.I.R./N.A.T.O. Research Fellowship at the Department of Chemistry University of Oslo Norway. Dr. B. C. Bishop formerly Research Chemist at Hynes Chern-Research Corporation Durham Caro- lina U.S.A. has been appointed to the Chemistry Research Division War Department C.D.E.E.Porton Down Wilts. Dr. P. Clarke has been appointed Head of the Department of Chemistry and Biology in the Nottingham and District Technical College. NOVEMBER 1963 Mr. M. A. Crook has resigned from British Insulated Callenders’ Cables Limited to become Lecturer in Physical Chemistry at the Borough Polytechnic London. Dr. B. E. Cross has resigned from Akers Research Laboratories Imperial Chemical Industries Limited to take up an appointment in the Organic Chemistry Department at the University of Leeds. Mr. J. R. Dixon of the University of Newcastle has been appointed Senior Demonstrator in the School of Chemistry. Dr. M. Donbrow is Visiting Professor and Head of the Pharmacy Department of the Hebrew University of Jerusalem for the current academic year.Dr. C. P. Falshaw has been appointed Assistant Lecturer in Chemistry at the University of Sheffield. Dr. P. I. A. Finan formerly of the University of Sheffield has been appointed Lecturer in Chemistry at University College Galway. Lord Halsbury has relinquished his Directorship of Head Wrightson Processes Limited and has joined the Board of Head Wrightson and Company Limited. Dr. D. G. Hardy has been appointed a Senior Research Chemist with Reckitt and Sons Hull. Dr. H. M. R. Hoffmann has been appointed Lecturer in Organic Chemistry at University College London. Mr. J. R. Hughes has been appointed a Research Fellow in the Department of Chemistry at the University of Birmingham.Dr. R. H. Kerlogue has been appointed Managing Director of Stillite Products Limited. He was former- ly on the Boards of the Washington Chemical Com- pany Limited and Newalls Insulation Company Limited. Dr. D. N. Kevill formerly of the University o Nebraska has been appointed Assistant Professor of Chemistry at the Northern Illinois University. Dr. S. R. Landor of the Woolwich Polytechnic has been appointed to the Chair in Chemistry at Fourah Bay College the University College of Sierra Leone as from January 1964. Dr. N. J. I;. Megson has retired as Director of Materials and Structures Research and Develop- ment in the Ministry of Aviation. Dr. M. Moyle has left the University of California Medical Research Centre to take up a position as Research and Development Chemist with Nipa Laboratories Limited Pontypridd.Mr. Y. 0. Nwoko has been awarded the David B. Goodstein Foundation Fellowship at the Massachu- setts Institute of Technology through the English Speaking Union of the Commonwealth. Dr. T‘. C. Owen has been appointed Associate Professor of Organic Chemistry in The University of South Florida from January lst 1964 when he will relinquish his post as Senior Lecturer Liverpool College of Technology. Dr. D. Y. W. Parke Senior Lecturer in Biochem- istry at St. Mary’s Hospital Medical School has been appointed Reader. Dr. J. Pomeraniec has been appointed Managing Director of Commercial Plastics Industries Limited a newly formed holding Company and Chairman of Commercial Plastics Limited Dr.I/. G. Shapiro has been appointed to the Board of Commercial Plastics Limited. Mr. H. M. PowelZ Reader in Chemical Crystallo- graphy at Hertford College Oxford has been elected to a Professorial Fellowship in the College. Dr. J. R. Quayle has been appointed Senior Lecturer in Biochemistry at the University of Sheffield. Dr. C. W. Rees Lecturer at King’s College has been appointed to the Readership in Organic Chemistry tenable at that College. Dr. R. G. SutherZand formerly of Columbia University has taken up a Research Fellowship in the Chemistry Department of the California Institute of Technology Pasadena. Mu. R. C. Thompson a Second Year Honours Chemistry student in the University of Exeter has been placed first in the English region of the 1962- 63 Chemistry Achievement Award Programme spon- sored by the Chemical Rubber Company of Cleveland Ohio.This is the second consecutive year in which the award has been won by a student from the University of Exeter. Lord Todd Professor of Organic Chemistry at the University of Cambridge is to be the first Chancellor of Scotland’s new university-The University of Strathclyde (the present Royal College of Science and Technology Glasgow). Dr. D. J. Walton has been appointed Lecturer in Organic Chemistry at the College of Technology Swansea. Dr. I. Wellings has been appointed Research Chemist in the Medicinal Chemistry Section of the Du Pont Company in Wilmington Delaware U.S.A.from December 30th 1963. Dr. F. P. Woodford has been appointed Executive Editor of the Journal of Lipid Research and Guest Investigator at the Rockefeller Institute New York. Dr. R. J. Woods formerly Senior Research Fellow Physics Department Royal Military College of Science Shrivenham Wilts is now with the Chemistry Department University of Saskatchewan Saskatoon Canada. PROCEEDINGS Anniversary Meetings 1964 THEprogramme of the Meetings to be held in Birmingham on April 7-9th will be circulated to all Fellows with Proceedings for January 1964 and will include details of scientific contributions as follows ROBERT ROBINSON LECTURE R. B. Woodward (Harvard University U.S.A.) SYMPOSIA Synthetic and Stereochemical Aspects of Organic Chemistry J.A. Berson (University of Wisconsin U.S.A.) R. C. Cookson (University of Southampton) E. J. Corey (Harvard University U.S.A.) A. S. Dreiding (The University Zurich Switzerland) E. L. Eliel (Notre Dame University U.S.A.) H. B. Henbest (Queen’s University of Belfast) J. Sicher (Czechoslovak Academy of Science Prague) J. C. Tatlow (University of Birmingham) G. Wittig (The University Heidelberg Germany) Inorganic Halogen Chemistry E. H. Appelman (Argonne National Laboratory U.S.A.) G. L. Goodman (Argonne National Laboratory U.S.A.) V. Gutmann (University of Technology Vienna Austria) R. D. Peacock (University of Birmingham) H. Schafer (The University Munster Germany) V. A. Stenger (Dow Chemicals U.S.A.) M. C. R. Symons (University of Leicester) A.F. Wells (Imperial Chemical Industries Ltd. Dyestuffs Division) New Methods of Organic Analysis F. Feigl (Ministry of Agriculture Brazil) R. Belcher (University of Birmingham) F. Critchfield (Union Carbide Chemical Co. U.S.A.) E. A. M. F. Dahmen (Shell Laboratories Amsterdam The Netherlands) J. R. Majer (University of Birmingham) P. Zuman (Polarographic Institute Prague Czechoslovakia) Molecular Structure and Arrangement D. W. J. Cruickshank (University of Glasgow) M. J. S. Dewar (University of Texas U.S.A.) 0. Hassell (University of Oslo Norway) J. Sheridan (University of Birmingham) A. R. Ubbelohde (Imperial College London) Some additional speakers are expected to take part. The papers will not be published in full but abstracts will be available to those who register for the Meetings.Full details of the Meetings will also be available to non-Fellows in January 1964 on application to the General Secretary. NOVEMBER 1963 351 FORTHCOMING SCIENTIFIC MEETINGS ISOTOPES. A FIFTIETH ANNIVERSARY AN official meeting of the Chemical Society to commemorate the fiftieth anniversary of the first published use of the term “Isotopes,” will be held in the Chemistry Department University of Glasgow on Wednesday December 4th 1963. The programme will be as follows 3.00 p.m. Opening by the President 3.15 p.m. Dr. Andrew Kent M.A. “Frederick Soddy. A Historical Note.” 3.30 p.m. Lord Fleck K.B.E. F.R.S. “Early Work in the Radioactive Elements.” 4.20 p.m.Dr. John A. Cranston LL.D. F.R.I.C. “The Group Displacement Law.” 4.30 p.m. Tea Interval 4.45 p.m. Professor H. J. Emelbus C.B.E. F.R.S. “New Elements.” London Thursday December 12th 1963 at 6 p.m. Liversidge Lecture “Some Contemporary Problems of Solid-state Chemistry,” by Professor J. S. Anderson Ph.D. F.R.S. To be given in the Lecture Theatre The Royal Institution 2 Albemarle Street w.l. Aberdeen Thursday December 5th 1963 at 8 p.m. Lecture “Some New Natural Products Structural and Biosynthetic Studies,” by Professor W. D. Ollis Ph.D. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Medical Physics Lecture Theatre Marischal College. Aberystwyth Thursday December 5th 1963.(It is regretted that the meeting has been cancelled.) Bristol Thursday December 5th 1963 at 6.30 p.m. Lecture “Development of Severnside,” by Mr. J. Davidson B.Sc. Joint Meeting with the Society of Chemical Industry and the Royal Institute of Chem- istry to be held in the Department of Chemistry The University. Durham Tuesday December loth 1963 at 5 p.m. Lecture “The ‘Rare-gas Rule’ in Transition-metal Complexes,” by Professor D. P. Craig D.Sc. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Science Laboratories South Road. ]Edinburgh Thursday December 12th 1963 at 7.30 p.m. Lecture “The Chemical Activation of Cheap Organic Molecules,” by Dr. I). S. Davies M.A.Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt College. Glasgow Wednesday December 4th 1963 at 3.30 p.m. Official Meeting and Symposium (for further details see above). Hull Thursday December 5th 1963 at 4 p.m. Lecture “Seeing Molecules with Microwaves,” by Dr. J. Sheridan M.A. Joint Meeting with the Uni- versity Students Chemical Society to be held in the Department of Chemistry The University. Manchester Thursday December 12th 1963 at 6.30 p.m. Lecture “Some Applications of Electron Spin Resonance to Chemistry,” by Professor H. C. Longuet-Higgins M.A. D.Phil. F.R.S. To be given at the Manchester College of Science and Technology. Newcastle-upon-T yne Friday December 13th 1963 at 5.30 p.m.Bedson Club Lecture “Natural Polyacetylenes,” by Sir Ewart Jones D.Sc. F.R.S. To be given at the Chemistry Department The University. Nottingham Thursday December 5th 1963 at 5 p.m. Lecture “Diffusion Incorporation and Trans-formation Processes during Chemisorption of Gases on Metals,” by Professor F. C. Tompkins Ph.D. F.R.S. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University. Southampton Friday December 6th 1963 at 5 p.m. Lecture “Co-ordination Complexes,” by Professor J. Lewis D.Sc. F.R.I.C. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University. Swansea Monday December 2nd 1963 at 4.30 p.m.Lecture “Some Problems of Photochemistry and Reaction Kinetics Exposed by Kinetic Spectro- scopy,” by Professor R. G. W. Norrish Sc.D. F.R.S. Joint Meeting with the Student Chemical PROCEEDINGS Society to be held in the Department of Chemistry University College. Tees-side Thursday December 12th 1963 at 8 p.m. Lecture “Gibberellins and Plant Growth,” by Professor P. W. Brian D.Sc. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the William Newton School Norton. OBITUARY NOTICES ALEC DUNCAN MITCHELL 1888-1963 A. D. MITCHELL knew and was known to a very large number of British chemists through his work for the examinations of London University and the Royal Institute of Chemistry and as Assistant Editor to the Chemical Society; many were grateful to him but few were in a position to realise the scientific knowledge and technical skill that lay behind his modest manner and likeable personality.Mitchell was born on October 22nd 1888. He was educated at Cooper’s Company’s School and at East London (now Queen Mary) College. On entering college he started an hQnours course in mathematics. Later he was attracted to chemistry by the personality of the late J. T. Hewitt; in 1908 he obtained the B.Sc. degree with First Class Honours in Chemistry and spent the next year as student demonstrator (1 908-1 909). In these years writes Professor E. E Turner he established an almost legendary reputation as mathematician goalkeeper and cricketer-he was almost of county class playing for Essex Club and Ground and until his death retained his interest watching Essex games as often as he had time and being a life member of the Marylebone Cricket Club.In 1909-1910 he was research assistant to J. F. (later Sir Jocelyn) Thorpe as Sorby Research Fellow at Sheffield University. In 1910 he left Thorpe on being appointed Scientific Assistant in Chemistry at London University and there began his main spheres of activity. Until 1958 he dealt with practical examinations for several thousand London Univer- sity candidates yearly; from 1926 to 1961 he was Examiner’s Assistant for A.R.I.C. and F.R.I.C. practical examinations; and from 1926 to 1962 he was Assistant Editor to the Chemical Society.He became a Freeman of the City of London “by servitude” in 1910. In the early years of his London University appointment he continued research at East London College and published papers with Clarence Smith on hydroxy-azo-compounds on the association of optically active compounds and racemates in the liquid state and on the volumetric determination of sulphates; with G. M. Bennett on total molecular surface energy; and independently on hypo-phosphorous acid. It was during this period too that Mitchell developed great skill in and acquired a wide knowledge of analytical chemistry. He obtained a D.Sc. in 1925. He had been elected a Fellow of the Chemical Society on December lst 1910 and was elected an Associate of the Royal Institute of Chem-istry in 1919 and a Fellow in 1927.In that period also fell his service during the first German war; he joined the London Scottish Regiment as private in 1914 was gazetted 1st Lieut. in the Essex Regiment in 1915 and served from then until 1918 in Gallipoli Egypt Palestine and Syria from 1917 as Divisional Gas Officer with the rank of Captain. During the whole of the 1939-1945 war he was engaged on confidential work for the Post Office. Mitchell’s practical and theoretical knowledge of analytical techniques was invaluable to the London University and R.I.C. Examiners who regarded him as a colleague; equally invaluable was his organising ability in handling the very large numbers of candidates-though he himself was wont to give the credit for this to his assistants E.H. Mould and A. Hebdon. And many of the less gifted in the examinations owed so far as conditions allowed more than they perhaps realised to Mitchell. A sound and detailed knowledge of English and an ability to write simple clear prose found outlet in his scientific writings. With G. T. (later Sir Gilbert) Morgan he edited chemical articles in the 14th edition of the Encyclopaedia Britannicu; with NOVEMBER 1963 A. M. Ward he wrote “Modern Methods in Quanti- tative Chemical Analysis” (1932); he produced the 12th edition (1935) of “Sutton’s Volumetric Analysis”; and in 1948 be published “British Chemical Nomenclature” in which were assembled for the first time the principles practices and difficulties of the nomenclature used in the pub- lications of the Chemical Society.It was from the knowledgeable strict fastidious Clarence Smith that Mitchell learnt his craft as Assis- tant Editor to the Chemical Society; to that he allied his own chemical and literary knowledge ;and all these he passed on to successive editors-C. S. Gibson J. E. Driver the writer and L. C. Cross-so that the high traditions remained unbroken. Each editor in turn acknowledged his debt. Technically Mitchell’s skill was uncanny; he would detect a misprint by a glance at a page an analytical miscalculation by inspection a mistaken reference by means of a retentive and photographic memory ; suspected errors had to be investigated at no matter what labour; false grammar or syntax was not tolerated; clumsy prose had to be recast and many a foreign or young British author was indebted to Mitchell for substantial rewriting into intelligible English.Mitchell was a member of the I.U.P.A.C. Com-mission on the nomenclature of organic chemistry from 1947 and saw to it that British experience of nomenclature was not overlooked in the large international fief d. Although Mitchell listed his interests as cricket football chess and walking his professional devotion to London University and the Chemical Society was unlimited. Behind a personal reserve lay unshakable rectitude a devotion to the ideals of the scientist a life-time of hard work and an inde-fatigable willingness to help those who lacked his particular gifts.All who knew him held him in esteem and affection. He married Marjorie Gwendolen Fyson B.A. in 1918 and had one daughter (who died in 1939) and two sons. His devoted wife shared his rectitude and fortitude; to her he owed much his relaxed mind and his ability to meet each strain unrumed. Their many friends offer Mrs. Mitchell and her sons their deep sympathy. Mitchell died on March 26th 1963 two days before he was to have received a retirement pres- entation from the Chemical Society at its Anniversary Meeting in Cardiff. In compiling this appreciation I have been greatly helped by information from Mr. A. Hebdon Professor E. E. Turner Mrs. F. A. Robinson (nee Beth Clarence Smith) and Professor D.H. Hey and by the curriculum vitae which with characteristic consideration for others Mitchell had deposited with the Chemical Society. R. S. CAHN. PROFESSOR JOHN READ 1 884-1 THEdeath on January 21st 1963 of John Read Professor of Chemistry in the University of St. Andrews removed from us a personality unique in the field of modern science and letters. A West- countryman born at Maiden Newton in Dorset in 1884 he was proud of his Somerset ancestry up- bringing and education. His first schooling was at Queen Camel then at Sparkford village school and later at Sexey’s School at Bruton in Somersetshire. He retained throughout his life an interest in the West of England which even his later deep affection for the more northern clime of St.Andrews did nothing to diminish. From Bruton he went to study at Finsbury Technical College (1 901-1 905) and then to Zurich (1905-1907) where he gained his doctorate for research in chemistry under Alfred Werner. Following this he worked for nine months at the School of Technology in Manchester in Pope’s laboratory. In 1908 Pope was appointed to the Chair of Chemistry in Cambridge and Read joined him there spending eight fruitful years (1 908-191 6) at Cambridge continuing his investigations into various 963 aspects of stereochemistry. In 1916 Read was ap- pointed to the Chair of Pure and Applied Organic Chemistry in the University of Sydney in succession to Robert Robinson (later Sir Robert Robinson O.M.F.R.S.) and he worked for the next seven years in Australia where he found in materials from the almost unexamined flora of that continent a wealth of chemical problems which his previous experience had specially fitted him to tackle. In 1916 shortly after his arrival in Sydney Professor Read married Ida Suddards who survives him with one of their two sons the other having lost his life tragically in a mountaineering accident in December 1961. In 1923 he returned to this country to the Purdie Chair of Chemistry in St. Andrews where once again he succeeded Robinson who had moved to Manchester. He soon settled happily in this very different environment and during a period of very nearly forty years his tall spare figure cycling to and from the Chemical Laboratory was well known to all St.Andreans. He continued his work on natural products with special reference to the chemistry of the terpenes and essential oils and in addition he was actively engaged in problems of stereochemistry particularly with the study of simple asymmetric molecules and with methods of optical resolution. Amongst many noteworthy achievements of Read and his collaborators the following may be men-tioned in this brief summary. He was interested in the preparation and resolution of the simplest optically active substances such as CHCII*SO,H. With Pope he participated in the optical resolution of the first known compound containing no formally asymmetric atom (methylcyclohexylideneaceticacid) -now a classic in the history of stereochemistry.Another series of investigations was concerned with stereochemical relationships in the hydrobenzoin series. Studies were made also of the formation of halogenohydrins from unsaturated compounds but in his main field of work at St. Andrews he main- tained the traditional interest of the Purdie Labora- tories in the structural chemistry of natural organic products. In Read’s case this involved systematic studies in the difficult field of terpene chemistry. Many of the problems required the resolution of peculiarly intractable racemic mixtures and success depended upon skill in choosing appropriate optical- ly active reagents such as D-and L-hydroxyhydrind- amine and D-and L-menthoxyacetic acid and both skill and patience in carrying out the long series of fractional crystallisations.In this way with piperi- tone playing a central part in the scheme he under- took a systematic chemical and stereochemical study of menthols menthones piperitones phellandrenes carvone and related substances derived directly or indirectly from the essential oils of plants. In the background there was always the idea that by these investigations some insight might be gained of the biochemical origin and ancestry of these substances thereby linking up the chemical work with that of Baker and Smith on the chemistry of eucalyptus oils. Highlights of these researches include the isolation and characterisation of pure D-menthol and D-neo- menthol the full elucidation of the chemistry and stereochemistry of the menthones the menthols and the menthylamines similar investigations with piperitone the piperitols the piperitylamines the a-phellandrenes and other related materials e.g.the carvone series and the thujone series of sub- stances. The value and importance of Read’s con- tributions to organic chemistry were recognised in 1935 by his election to the Fellowship of the Royal Society and the award of the Sc.D. degree by the University of Cambridge. In 1948 he was President of the Chemistry Section of the British Association for their meeting at Brighton where he delivered a notable Presidential address on the subject of “Specialisation and Culture in Chemistry.” His scientific work important as it was neverthe- PROCEEDINGS less represented only a part of Professor Read’s activities.As the years went by he became intensely interested in the history and chemistry of alchemy and in the contributions made by chemistry to humanism and to cultural activities in general. His skill in languages-he was amongst other things an expert in the Somerset dialect which he spoke fluently-and his delightful easy style of writing coupled with his scientific and philosophic outlook fitted him admirably for these studies and the results of his work are recorded in a series of well known books amongst which may be mentioned “Prelude to Chemistry’’ (1936); “The Alchemist in Life and Literature and Art” (1 947) ;“Humour and Human- ism in Chemistry” (1947 translated into Spanish in 1953); “Through Alchemy to Chemistry” (1957 with a French edition two years later and Spanish and Italian editions in 1960).His skill as teacher and expositor is shown also in his textbooks of organic chemistry which have served as an inspiring intro- duction to organic chemistry for many generations of students. His “Textbook of Organic Chemistry,” first published in 1926 has passed through several editions and is in great demand in its latest form (1958) revised in collaboration with Dr. F. D. Gunstone. The smaller “Introduction to Organic Chemistry” (1931 onwards) has been equally popular and has already run to sixteen editions. Read was specially interested in student activities.At St. Andrews he took part in the work of the Men’s Union of which he became Honorary Life Member and in the affairs of the Mermaid Dramatic Society. He organised visits of parties of overseas students to St. Andrews acting as guide to the historic buildings of the city and University. These talks led to the publication of his book “Historic St. Andrews and its University.” On occasions he accompanied these parties on extended tours of Britain and the Continent and a highlight of these activities was the very successful visit he arranged for a group of St. Andrews students to the cities and Universities of Canada claimed to be the first official visit of a party of British undergraduates to a Dominion. Special mention must be made however of two of Professor Read’s achievements in the way of exposi- tion.During the war he published in the Pelican Series an account of the chemistry of explosives which was given a whole page review in “Punch” and of which more than 100,OOO copies were sold. In 1948 came his popular account of the field of organic chemistry entitled “A Direct Entry to Organic Chem- istry.” The clarity of this and the easy style ensured for it a truly phenomenal success both in this country and abroad. It gained for Professor Read the Premio Europeo Cortina Prize in 1949 and very NOVEMBER 1963 shortly afterwards Italian German and American editions of it were published whilst its author was invited to lecture in Italy Switzerland Germany and Austria-in each country in the appropriate language.Nevertheless it is probably true to say that the work Professor Read most enjoyed writing was not to be found amongst his scientific or historical con- tributions but was instead his altogether delightful study of a bygone age in Dorset and Somerset which he depicted in “Farmer’s Joy,” published in 1949. His insight into human character his versatility and his highly characteristic sense of humour are further shown in the series of plays he wrote in the Somerset dialect. So authentic is the language in these that scenes from them have been recorded for various Dialect Surveys. Many of us whether chemists or not will recall his discovery of a group of epigrams written in Latin elegiac couplets embodying al- chemical doctrines and set to music by Count Michael Maier Alchemist to Rudolf 11.These set in modem musical notation by F. W. Sawyer were sung by a choir from St. Andrews University at the Royal Institution by invitation of Sir William Bragg. Recorded versions of the music have since been heard on many occasions. It is not altogether surprising therefore to learn that the first British recipient of the American Chemical Society’s Dexter Award for distinguished contributions to the history of Chemistry was John Read who received it in 1959. The citation for the award aptly sums up much of Professor Read’s achievement in that it commemorates “the meri- torious services over a long period of time” of “one of the most versatile of Scientists as well known for his literary accomplishments as for his researches in organic chemistry.” E.L. HIRST. DENIS CHESELDEN QUIN 191 1-1963 DENIS QUM was born in Hampstead on CHESELDEN November 9th 1911 the only child of the late Henry Osborne Quin and Mildred Quin. He became totally deaf at the age of four as a result of concussion following a fall. Despite this great handicap he successfully followed a normal educational and professional career. He was educated at The Dragon School Oxford Bradfield College near Reading and later at Corpus Christi College Oxford. He gained his B.A. in 1933 and his R.Sc. in 1934. For the next three years he was a research assistant to Professor (now Sir) Robert Robinson his D.Phi1.Thesis (1937) being a disserta- tion upon “The Influence of Molecular Structure on Antimalarial Activity of Compounds of the Plasmo- quin Series” (see Quin and Robinson J. 1943 555). He became a Fellow of the Chemical Society in 1933 and an Associate of the Institute of Chemistry in 1934. From 1937 to 1945 he was a research chemist with A. Boake Roberts and Co. Ltd. and in 1945 he moved to the Research Department of the Distillers Co. Ltd. at Epsom. Here he became an authority on all aspects of the liquid phase autoxidation of hydro- carbons. His original suggestions led Distillers Co. Ltd. to investigate the oxidation of cumene on which subject he is co-author of a paper (J. 1950 666) and co-inventor of a number of patents.This work cul- minated in Distillers Co. Ltd’s phenol from cumene process which is now used to produce a substantial part of the world’s synthetic phenol. He also investigated the autuxidation of the di- isopropylbenzenes and isopropylnaphthalenes meth ylcyclopen tane and met hylcyclohexane (J. 1950 2798) and a variety of olefins (J. Appl. Chem. 1956 6 1) and paraffins. In other fields he did valuable work on liquid-phase hydrogenation and on the purification of phenol derived from cumene. His experimental work was at all times charac- terised by extreme elegance and attention to detail. He had a flair for devising and erecting his own experimental apparatus. He made light of his handicap of deafness with a courage which his colleagues and friends greatly admired.It is said that he learned much of his chem- istry from the borrowed lecture notes of fellow students at Oxford. He taught himself scientific Russian to pass the time on bus journeys to work and subsequently he was relied on by many of his colleagues for translations of Russian papers. In 1942 he married Dora Blanche daughter of the late Stanley Ernest Bisley and of Mrs. Bisley. His wife survives him; he and his wife were most delightful and hospitable hosts at their riverside bungalow. He was greatly respected and much liked by all his col- leagues and to younger chemists he was a source of advice encouragement and inspiration. He led a full life and was particularly fond of sporting activities.When at Oxford he swam and rowed for his college and was selected for the Uni- versity Trial Eights. Later he played badminton and hockey. Surprisingly he was a good ballroom dancer and refused to be led by his partner. In recent years he took up dinghy sailing with characteristic en- thusiasm and no small success and it was while taking part in a race on the River Thames near his home at Teddington on April 21st 1963 that he had a fatal heart attack. A. R. GRAHAM. ADDITIONS TO THE LIBRARY Chemical applications of group theory. F. A. Cotton. Pp. 295. Interscience Publishers Inc. New York. 1963. Shock tube in high-temperature chemical physics. A. G. Gaydon and I. R. Hurle. Pp. 307. Chapman and Hall. London. 1963. Molecular vib-rotors :the theory and interpretation of high resolution infrared spectra.H. C. Allen Jr. and P. C. Cross. Pp. 324. J. Wiley and Sons. New York. 1963. Magnetism and the chemical bond. J. B. Goodenough. Pp. 293. Interscience Publishers Inc. New York. 1963. Catalysis and inhibition of chemical reactions. P. G. Ashmore. Pp. 375. Butterworths Scientific Publications. London. 1963. Polyanions et polycations. M. P. Souchay. (Mono- graphies de Chimie MinCrale.) Pp. 247. Gauthier-Villars. Paris. 1963. (Presented by the publisher.) Infrared spectra of inorganic and co-ordination com- pounds. K. Nakamoto. Pp. 328. J. Wiley and Sons. New York. 1963. Modern polarographic methods. H. Schmidt and M. von Stackelberg. Pp. 99. Academic Press. New York.1963. (Presented by Dr. R. E. W. Maddison.) Line interference in emission spectrographic analysis a general emission spectrographic method including sensi- tivities of analytical lines and interfering lines. J. Kroonen and D. Vader. Pp. 213. Elsevier. Amsterdam. 1963. Radioactivation analysis. H. J. M. Bowen and D. Gibbons. Pp. 295. Oxford University Press. Oxford. 1963. Chemical analysis by flame photometry. R. Herrmann and C. T. J. Alkemade. (Chemical Analysis-Vol. 14). 2nd edn. Pp. 644.Interscience Publ. Inc. New York. 1963. Colorimetric analysis. Vol. 2. 2nd edn. N. L. Allport and J. E. Brocksopp. Pp. 368. Chapman and Hall. London. 1963. Inorganic thermogravimetric analysis. C. Duval. 2nd edn. Pp. 722. Elsevier. Amsterdam. 1963.Organic functional group analysis. F. E. Critchfield. Pp. 187. Pergamon Press. Oxford. 1963 Quantitative organic analysis via functional groups. S. Siggia. 3rd edn. Pp. 697. J. Wiley and Sons. New York. 1963. Spectrometric identification of organic compounds. R. M. Silverstein and G. C. Bassler. Pp. 117. J. Wiley and Sons. New York. 1963. Analytical microbiology. Edited by F. Kavanagh. Pp. 707. Academic Press. New York. 1963. Methods of enzymatic analysis. Edited by H. U. Berg-meyer. Pp. 1064. Verlag Chemie. Weinheim. 1963. Zone electrophoresis in blocks and columns. H. Bloemendal. Pp. 21 9. Elsevier. Amsterdam. 1963. Zone melting of organic compounds. E. F. G. Hering- ton. Pp. 162. Blackwell ScientificPublications. Oxford. 1963. Nucleophilic substitution at a saturated carbon atom.C. A. Bunton. (Reactions in Organic Chemistry. Edited by E. D. Hughes.Vol.1.) Pp. I 72. Elsevier.Amsterdam. 1963 -Newer methods of preparative organic chemistry- Edited by W. Foerst. Vol. 2. Pp. 417. Academic Press.. New York. 1963. Friedel-Crafts and related reactions. Edited by G. A. Olah. Vol. 1. General aspects. Pp. 1031. interscience Publishers Inc. New York. 1963. Organic reactions in liquid ammonia. H. Smith. (Chemistry of Nonaqueous Ionizing Solvents. Edited by G. Jander H. Spandau and C. C. Addison. Vol. 1 Part 2). Pp. 363. Interscience Publishers Inc. New York 1963. Polyhydric alcohols. I. hifellan. Pp. 208. Spartan Books. Washington. 1962. Essays on nucleic acids. E. Chargaff.Pp. 21 1. Elsevier.. Amsterdam. 1963. Chemistry and function of proteins. F. Haurowitz. 2na edn. Pp. 455. Academic Press. New York. 1963. Fuel cells. Edited by W. Mitchell Jr. Pp. 442. Academic Press. New York. 1963. The design of research laboratories the report of a study carried out by the Division for Architectural Studies of the Nuffield Foundation. Pp. 211. Oxford University Press. London. 1961. New approaches to pest control and eradication a symposium sponsored by the Pesticides Subdivision of the Division of Agricultural and Food Chemistry at the 142nd Meeting of the American Chemical Society, Atlantic City 1962. (Advances in Chemistry Series No.. 41.)Pp. 74. American Chemical Society. Washington. 1963. Enzyme chemistry of phenolic compounds :proceedings.of the Plant Phenolics Group Symposium Liverpool 1962. Edited by J. B. Pridham. Pp. 142. Pergamon Press. Oxford. 1963. (Presented by the Editor.) Determination of trace elements with special reference to fertilisers and feeding stuffs prepared by the Trace Elements in Fertilisers and Feeding Stuffs Sub-Com- mittee of the Analytical Methods Committee of the Society for Analytical Chemistry. Pp. 39. Society for Analytical Chemistry. London. 1963. Analytical chemistry 1962 proceedings of the Inter- national Symposium held at Birmingham University 1962 in honour of Fritz Feigl to commemorate his 70th Birthday. Organised by the Society for Analytical Chem- istry Midlands Section under the patronage of the International Union of Pure and Applied Chemistry.Edited by P. W. West A. M. G. Macdonald and T. S. West. Pp. 41 1. Elsevier. Amsterdam. 1963. Batteries research and development in non-mech- anical electrical power sources proceedings of the 3rdi International Symposium held at Bournemouth 1962.. Sponsored by the Inter-Departmental Committee OD Batteries. Edited by D. H. Collins. Pp. 464. Pergarnont Press. Oxford. 1963. CHRISTMAS COMPETITION MOSTreaders will recollect the exploits of LittIe Tommy the schoolboy who always managed to get his answers wrong by false association of ideas and syllables. A prize (book token for two guineas) is offered for the best set of four of Little Tommy’s answers to the following What are (a) Birch reduction (e) Conformational analysis (b) Bitter principles (f)Luciferin (c) Catalysis (g) Optical activity (d) Chemical shifts (h) Royal jelly Entries must reach the Editor (The Chemical Society 20-21 Cornwall Terrace Regent’s Park London N.W.l) not later than December 31st 1963 and may be accompanied by a pseudonym for publication.It is hoped to issue a report in the January 1964 issue of Proceedings. The Editor’s decision will be final.
ISSN:0369-8718
DOI:10.1039/PS9630000325
出版商:RSC
年代:1963
数据来源: RSC
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