PROCEEDINGS OF THE CHEMICAL SOCIETY JUNE 1962 ONE HUNDRED AND TWENTY-FIRST ANNUAL GENERAL MEETING THEOne Hundred and Twenty-first Annual General Meeting was held in the Chemistry Department of the University of Sheffield on Wednesday April 4th 1962 at 9.15 a.m. The President Lord Todd was in the Chair. After the notice convening the meeting had been read Dr. J. Chatt Honorary Secretary presented the Report of Council. He stated that the number of Fellows had again increased the growth during the year being higher than in any other year in the Society’s history except 1960. Referring to the Journal he drew attention to the increase in the number of papers submitted and observed that the proportion of papers between the various branches of chemistry had generally been maintained.With regard to Proceedings he said that despite more stringent refereeing the number of Communications had increased substantially and was giving rise to some concern. Dealing with the other activities of the Society Dr. Chatt referred to the symposia organised by the Society which had proved very popular; to the number of organisations which had joined as Library Subscribers increasing the membership of the Scheme by fifty per cent during the year; and to the interest in the Society’s activities which had been aroused through the appointment of Liaison Officers. He remarked briefly on the Research Fund pointing out that despite the limited income the Society was able to assist Fellows working at the smaller and less well-endowed establishments.He drew attention to arrangements made for Fellows to obtain Index Cheniicus at a substantial discount. Dr. Chatt then referred to the debt that the Society owed to those Fellows who gave freely of their services in arranging symposia giving lectures sitting on Committees etc. and to whom on behalf of the Council he expressed his warmest thanks. Ending on a personal note Dr. Chatt referred to his six years of office and to the changes that had taken place during that time. He stated that the Honorary Secretaries’ tasks were made much easier by the efficient work of the General Secretary and his office from which many innovations had origin- ated. On the publications side he paid tribute to the work of the Editors and their staff in dealing with the arrears of papers for publication which remained at the end of 1960 and which had now been pub- lished and expressed his regret that their removal to yet another office was imminent.The President then called upon Dr. J. W. Barrett Honorary Treasurer to present the accounts. Dr. Barrett reported that the General and Publications Fund Accounts were in sound condition and referred to the growth of Fellowship which had produced some E2000 more than the previous year. He pointed out that the Society had spent more money than in the previous year and that this was due to two main causes; the increased cost of producing a larger Journal and to the review of salaries of the permanent staff which resulted in increases of an exceptional nature.He added that the cost of capital improve- ments was lower than in the previous year and the work had now been finished in Burlington House. He stated that the Society had completed the year with a credit balance and although he expected no 197 great changes in the coming months he felt that costs must rise. However the revenue from the sale of publications to non-Fellows was also increasing. Referring to the investments he said that these were producing a larger income and that this was due to the wise policy of the Council when it decided some years ago to accept advice from the City. As a result the Society had a sound portfolio and increased income. Finally Dr.Barrett reminded Fellows that this had been his first year as Honorary Treasurer and therefore he had perforce to be especially enquiring and curious of the management side of the Society. He had found a most satisfactory situation and paid special tribute to the help he had received from Mr. H. J. Morris who on retirement left behind a great record of service and younger staff well trained in the care of the Society’s affairs. Dr. F. A. Robinson referred to the marked increased cost of the Journal and asked the Honorary Treasurer if the Society could do anything about it during the present financial year. Dr. Barrett replied that an exceptional increase was not expected in the current year and of the increased cost of some €22,000 about E16,000 included the cost of printing a very large number of pages of arrears of publica- tion which had accumulated in the previous year.He added that in any budget anticipation of costs must depend on an accurate estimate of the number of pages to be printed and if the estimate is correct the Publications Fund should be in balance at the end of the year. The President remarked that the financial results gave the Society cause for congratulation. He also drew attention to two additional funds; the Ethel Behrens Fund of the order of €2000 the income from which the Council had decided should be devoted to assisting undergraduate Fellows to attend the Anniversary Meetings of the Society; and the Robert Robinson Lectureship of the order of UOOO the income from which would be used to endow a lectureship to be given in alternate years at the Anniversary Meetings in place of the Presidential Address which in future would be given only once during the Presidential term of office.The President then moved the adoption of the Report and Accounts Professor Sykes seconded the motion and it was approved unanimously. The President then announced the names of the following new members of Council elected to fill the vacancies caused by retirement President Professor J. M. Robertson Honorary Secretary Dr. J. W. Linnett PROCEEDINGS Vice-presidents who have not $lied the ofice of President Professor D. H. R. Barton Dr. J. Chatt Professor B. Lythgoe Elected Ordinary Members 0f Council Constituency I (South-East England) Dr.G. W. A. Fowles Dr. A. R. Katritzky Dr. A. I. Vogel Constituency II (Central and South- West England and South Wales) Dr. W. J. Orville-Thomas Constituency IV (North-East England) Professor J. Baddiley Professor F. S. Dainton Dr. T. J. King The President referred to Bye-Law 57 of the Society which stated that the Council shall hold at least eight ordinary meetings during the year and added that although this number of meetings might be necessary in some years the normal business of the Society could be conducted just as efficiently with fewer meetings and he thought it unnecessary to ask members of Council to travel long distances for a purely formal meeting.He called upon Dr. Barrett to propose the following motion “That the Bye-Laws of the Society be altered by deleting from Bye-Law 57 the word ‘eight’ and substituting therefor the word ‘five’.” Dr. Chatt seconded the motion and it was carried unanimously. On the motion of Dr. J. W. Barrett seconded by Dr. J. Chatt Messrs. W. B. Keen and Company Finsbury Circus House London E.C.2 were ap- pointed as auditors of the Society’s Accounts for the year ended September 30th 1962. A vote of thanks to the President Officers Council and Local Representatives for their services during the year was proposed by Professor G. Porter. He also congratulated the President on his elevation to a Life Peerage particularly as it had happened during his term of office as President of the Society.The vote was carried with acclamation. In reply the President acknowledged the work of the Officers and Council and of the permanent officials of the Society. He added that the Society was in such good heart that he could hand over with- out any worry. He then declared the formal business of the Annual General Meeting terminated. After an interval the meeting was resumed at 10.15 a.m. in the Firth Hall. On behalf of the Society the President made a Presentation of a Silver Salver and cheque to the retiring Finance Officer and re- JUNE1962 [erred to Mr. Moms’ valuable service of more than fifty years with the Society stating that this record was unlikely to be repeated. He wished Mr. and Mrs.Morris a long and happy retirement. Mr. Morris replied briefly expressing his warmest thanks. The President then presented the Corday-Morgan Medal and Prize for 1960 to Professor R. N. Haszeldine in recognition of his outstanding contributions to the chemistry of fluorine. The President next introduced the President-elect Professor J. M.Robertson and asked him to take the Chair for the remainder of the meeting. Professor Robertson expressed his appreciation of the con- fidence shown in him by the Society and called upon Lord Todd to deliver his Preridential Address entitled “Some observations on Organic Phos- phates.” At the conclusion of the Address a vote of thanks to the President proposed by Professor E. R. H. Jones was carried with acclamation.PRESIDENTIAL ADDRESS* Some Observations on Organic Phosphates By Lord TODD IN my Address to the Society a year ago1 I discussed some of the problems then facing us in the field of polynucleotide synthesis-problems whose urgency has since been underlined by the striking develop- ments in biological and biochemical studies on the r61e of nucleic-acids in protein synthesis. In con- sidering a topic for my Address on this occasion it seemed to me that it might be of some general interest if I dealt with a broader but none the less related topic by discussing some features of the chemistry of organic phosphates The successful development of nucleotide chemistry has depended in large measure on the discovery of appropriate phosphorylation procedures and on studies of the chemical behaviour of esters of phosphoric and poly- phosphoric acids.Phosphorylation studies under- taken originally as part of nucleotide research have yielded results of importance in other fields as well by providing a rational explanation of certain bio- logical processes and by indicating possible lines of approach to the understanding of others. Before dis- cussing some of the features of our current work it may be useful as an illustration of the background to recall briefly a few of the important chemical developments in recent years where a knowledge of phosphate chemistry has proved highly relevant. Neutral triesters of phosphoric acid are readily hydrolysed by alkali to the corresponding diesters the latter being normally very resistant to alkali; presumably the formal negative charge on the anion hinders the approach of the hydroxide ion to the phosphorus atom.But there is one type of phospho- diester which does not show this resistance; the characteristic feature of this type is that one of the esterifying groups bears in the a-position a hydroxyl group. Such esters undergo hydrolysis with great ease to monoesters via a cyclic intermediate the final product being usually a mixture of two isomeric monophosphate esters; the phosphate residue always remains attached to the glycol residue. RO,B ?/P-0-0 40 ?H +ROH -O”0 P II -CH-CH-CH-CH-It was the recognition of this property of glycol phosphates that led to an understanding of the pro- perties of the ribonucleic acids and to the establish- ment of their general structure as 3’,5’-linked poly- nucIeotides.2 The effect of neighbouring hydroxyl groups on phosphate hydrolysis has also been of significance in structural studies on phospholipids and the bacterial poly-sugar phosphates.It also sug- gests a possible mechanism for the action of phos- phomonoesterases. For if a phosphomonoester became attached through the phosphate group to some point on the enzyme protein bearing a hydroxyl group in correct spatial proximity then hydrelytic removal of the phosphate group by the above mechanism could occur with great ease. Again it may be recalled that in much of the work on nucleotide synthesis benzyl groups were common- ly employed as protecting groups on phosphates and it was necessary to develop methods whereby benzyI * Delivered at the Anniversary Meeting of The Chemical Society at Sheffield on April 4th 1962.Proc. Chem. SOC.,1961 187. * Brown and Todd J. 1952 52. groups could be removed from an alkyl dibenzyl phosphate either one at a time or together under varying conditions. Notable among them were the methods of q~aternisation~ and anionic fission4 by which one benzyl residue can be removed under mild conditions from a triester. The driving force in each of these methods is the strongly electrophilic charac- ter of the methylene group of the benzyl residue which is attacked in the quaternisation method by a tertiary amine causing removal of the benzyl group by attachment to nitrogen in a quaternary ammon- ium cation or by an anion such as C1- in anionic fission when benzyl chloride is produced.In re-actions of this type the ally1 group behaves in the same way as the benzyl. y,O-CH,P h RO-P 0-Ri6.C H2P h U O.CH,Ph II RO-P< + Ph.CH,C 1 0-Li+ Although at the time these methods were dis-covered little thought was given to their possible extension to carbon-carbon bond formation by using a suitable olefin as nucleophile it is clear that such an extension should be possible. And indeed the work of Bloch Cornforth and Lynen has shown that the biosynthesis of terpenoids and steroids rests on precisely such an e~tension.~ They have demon- strated that the “active isoprene” in biosynthesis is isopentenyl pyrophosphate.The mechanism of the process in which one molecule of isopentenyl pyro- phosphate reacts with the isomeric 3,3-dimethylallyl pyrophosphate yielding geranyl pyrophosphate with liberation of a molecule of pyrophosphate is strictly analogous to the laboratory processes of quaternisa- tion and anionic fission. And indeed it can be demonstrated in the laboratory since geranyl di- phenyl phosphate passes with great ease into cyclic terpene with loss of diphenyl phosphate. Finally mention may be made of the work of Lynen6 on the fixation of carbon dioxide by biotin to produce the so-called “active CO,” which is then available for a variety of biological reactions.He has shown that a phosphorus-containing intermediate is PROCEEDINGS formed from biotin-presumably the O-pyrophos- phate or O-adenosyl pyrophosphate of the isourea form of biotin; attack by the positive carbon of the CO molecule on the doubly bound nitrogen would clearly lead to its attachment with simultaneous expulsion of the pyrophosphate group yielding the biotin carbamic acid (as its anion) which is the “active CO,” of the biochemists. This mechanism for producing the carbamate could be predicted from the known behaviour of imidoyl phosphates which act as phosphorylating agents when protonated on nitrogen. (?-POP0R f cy2 & N y -O,CN/~‘NH + RO.POP+ __c I I1 These examples illustrate the way in which it is possible to reach a better understanding of many biological processes by studying relatively simple organic phosphates and polyphosphates and in Cambridge my colleagues and I have been devoting a good deal of attention to this general approach.Some of our results and our reflections upon them may thus be of general interest. At the risk of being repetitive I would once again draw attention to the fact that there are two distinct types of phosphorylation procedure in common The first type involves a second-order dis- placement mechanism and includes in general those methods based on reagents derived from phos- phodiesters (e.g. dibenzyl phosphorochloridate tetraesters of pyrophosphoric acid) which yield as initial products phosphotriesters.Such methods are of course employed to prepare not only simple phosphates but also pyrophosphates and triphos- phates. The second type employs monoesters of phosphoric acid which are “activated” by various means (e.g. reaction with arenesulphonyl halides dicyclohexylcarbodi-imide,trichloroacetonitrile di- aryl or dialkyl phosphorochloridates) and yields phosphodiesters; again methods of this type are applicable to pyrophosphate or triphosphate syn- thesis under appropriate conditions. All available evidence seems to support the view that methods of this second type proceed by production of a meta- phosphate intermediate which probably in the hypothetical monomeric form (RO-PO,) is the true phosphorylating agent. An instructive example of a metaphosphate-type method is found in oxidative phosphorylation in which quinol phosphates are used? Quinol phos- ‘Baddiley Clark Michalski and Todd J.1949 815; Clark and Todd f.,1950 2023. Clark and Todd J. 1950 2030. For general review see Popjak and Cornforth Ah. Enzymol. 1960 22 281. Cf. e.g. Symposium on Enzyme Reaction Mechanisms f. Cell. Comp. Physiol. 1959 54 Suppl. 1 45. Todd Proc. Nat. Acad. Sci. U.S.A.,1959,45 1389. Clark Hutchinson Kirby and Todd J. 1961 715. JUNE 1962 phates are very resistant to hydrolysis and do not readily break down in the absence of oxygen. But in presence of oxidising agents (e.g. bromine ceric sulphate quinones) they act as phosphorylating agents yielding simultaneously the corresponding quinone.This reaction we formulate in the manner shown below and the postulated production of monomeric metaphosphate is supported by a sub- stantial body of evidence. Thus if quinol phosphates are oxidised in aqueous phosphoric acid pyrophos- phate is formed while if they are oxidised in di- methylformamide the main product isolated is trimetaphosphate. Moreover although both quinol phosphates and their monoesters undergo this re- action quinol phosphate diesters (which cannot yield metaphosphate without hydrolysis) do not even in the presence of reagents as powerful as ceric sulphate. 0-0 The behaviour of quinol phosphates on oxidation is of great interest in relation to the biological prob- lem of oxidative phosphorylation and it is difficult to believe that there is no connexion between these laboratory observations and the r61e of the ubi- quinones and vitamins I(in systems where oxidative phosphorylation occurs.As a laboratory demonstra- tion of the possible r61e of such compounds we have succeeded in synthesising adenosine-5’ pyrophos- phate (ADP) by oxidising a quinol phosphate in presence of muscle adenylic acidg and adenosine-5’ triphosphate (ATP) by oxidising P1-2,3-dimethyl- naphthoquinol P2-adenosine-5‘ pyrophosphate in presence of phosphate ion.1° The last-named example is of special interest since formally the reactive species produced in the oxidation is a mixed an- hydride of metaphosphoric acid and muscle adenylic acid. The production of metaphosphate as the reactive phosphorylating agent in the various methods of phosphorylation based on “activation” of a phos- phomonoester is now fairly generally accepted and is supported not only by the above observations on oxidative phosphorylation but also by the ready @ Clark Hutchinson and Todd J.1961 722. lo D. W. Hutchinson unpublished results. l1 Brown and Hamer. J.. 1960. 1155. l2 Weimann and Khorana Chem. Ind. 1962 271. l3 Stokes Amer. Chem. J. 1893 15 198. 20 1 formation of trimetaphosphate from PIP1-diesters of pyrophosphoric acid.ll Monomeric metaphosphates are of course unknown in the free state but they seem more likely to be phosphorylating agents as such than in the trimeric form whose participation has recently been suggested12 on somewhat insecure evidence in the case of carbodi-imide reactions.It is interesting in connexion with the metaphos- phate hypothesis to speculate on the way in which ATP (adenosine-5’ triphosphate)-one of Nature’s major phosphate transfer agents-may function. It is noteworthy that ATP functions by transferring either phosphate or nucleotide but rarely by trans- ferring pyrophosphate although if the transfer pro- ceeded by a bimolecular displacement mechanism one would have thought that the central phosphorus atom would have been at least as readily attacked as either of the others. It seems possible that the central phosphate group acts as a kind of fulcrum and that blockage of the acid functions on Pl and P2 either by metal-complex formation or by the protein com- ponent of an enzyme leads to transfer of P3 as meta- phosphate (cf.analogy with PlPl-diesters of pyro- phosphoric acid). An analogous blocking of the groups on P2 and P3 would lead to transfer of nucleotide as adenoside-5’ metaphosphate but on this type of mechanism transfer of pyrophosphate would not be expected. This is of course purely speculative but it would certainly explain many of the experimental facts. Q 0 RO II R,:; P-NH -A/ P-NH; HW (11 ” 0) One important group of phosphorylating agents the monoesters of phosphoramidic acid presented an awkward problem in classification. Towards the end of last century Stokes13 reported that phosphoramidic acid gave when heated a polymeric material which has quite recently been identified as ammonium p~lymetaphosphate.~~ Clark and Todd4 in 1950 pre- pared monobenzyl hydrogen phosphoramidate (I) showed that it lost ammonia when heated and sug- gested that it could be regarded as a “base-meta- phosphate complex” of the type described by Lang- held.15 Later on the use of monoesters of phos- phoramidic acid as phosphorylating agents was described,lsJ7 and since then they have been widely used in pyro- and tri-phosphate synthesis.From l4 Becke-Goehring and Sambeth Chem. Ber. 1957 90 2075. l6 Langheld Ber. 1910,43 1857; 1911 44 2076. l6 Chambers and Khorana Chem. Ind. 1956 1022. Clark Kirby and Todd J. 1957 1497. their structure and from the work of Stokes a rather obvious explanation of their phosphorylating pro- perties would be that in the zwitterionic form (11) they lose base yielding monomeric metaphosphate which then phosphorylates.But although they are probably the best of the known reagents for pyro- phosphate preparation they are virtually useless for the phosphorylation of alcohols; this is difficult to equate with a mechanism of action involving a met aphosphate intermediate. X-Ray crystallographic studies have shown that in the solid state the monoanion of phosphoramidic acid is zwitterionic.ls Studies in Cambridge involving infrared spectroscopy,lg indicate that benzyl hydro- gen phosphoramidate is zwitterionic in the crystalline state but that when dissolved in dimethylformamide or dimethyl sulphoxide it exists as the neutral mole- cule.Benzyl hydrogen phosphoramidate crystallises as a hemihydrate and when kept at room tempera- ture in the solid state it is slowly converted after an initial lag period into the diammonium salt of PIP2-dibenzyl pyrophosphate;17 when carried out in di- methyl sulphoxide the reaction is of the second order with respect to phosphoramidate and hence no meta- phosphate intermediate is inv01ved.l~ It may be mentioned that adenosine phosphoromorpholidate is similarly converted on being kept into diadenosine pyrophosphate.20 The detailed mechanism of these reactions is unknown but a reasonable postulate would be attack on a protonated molecule of phos-phoramidate by an anion leading to expulsion of 1 mol.of base and production of the pyrophosphate linkage. The attacking anion might be that of the phosphoramidate itself (A) or there might be initial Ro,f) ?,OR'\ HO/'-'-OH hydrolysis to a phosphomonoester followed by the attack of the latter on the protonated phosphora- midate (33). There is evidence for both types of reaction. Thus adenosine phosphoromorpholidate with strong acids in non-aqueous media yields as first product the mixed anhydride of adenosine phosphate and adenosine hydrogen phosphoromor- pholidate (mechanism A).2o On the other hand PROCEEDINGS benzyl hydrogen phosphoramidate in presence of 2 mols. of water is converted without any appreciable lag period into dibenzyl pyrophosphate,19 presum- ably as a result of partial hydrolysis to benzyl di-hydrogen phosphate which then reacts accord-ing to (B).It is presumably the weakness of the phos- phoramidates themselves as nucleophiles which makes reaction according to mechanism (B) the favoured one in the reaction of phosphoramidates with nucleotide derivatives and so makes them effective reagents for the synthesis of unsymmetrical pyrophosphates of the coenzyme type (cf. for example the synthesis of coenzyme A21). 0 RO II 1 HO-L~;P-NH; -P-OH + NH H0' RO 0 \ U. P-NH,~ -H"n' ._ + NH It should be noted that if the type of mechanism indicated in (A) and (B) applies then diesters of phosphoramidic acid should also act as phos-phorylating agents; recent work in Cambridge in- dicates that although they are in certain respects weaker reagents than the monoesters the diesters can indeed function in this way.The reactivity of the phosphoramidates varies naturally enough with the nature of the amines from which they are derived. Thus monoesters derived from ammonia and non- aromatic amines such as cyclohexylamine and mor- pholine are effective reagents for pyrophosphate preparation whereas those based on say aniline are quite inactive (presumably because they are not easily protonated on nitrogen). Those based on imidazole are also active,22 while the diesters of this series behave rather like dialkyl phosphorohali- dates.23 Surprisingly however such compounds as benzyl hydrogen phosphoroguanidate (111) are stable and very ~nreactive,~~ despite the known importance of compounds of this class [e.g.phosphocreatine (IV)] in Nature as phosphate-transfer agents. The only explanation which suggests itself for this anomaly is that protonation in phosphoroguanidates does not normally occur on the nitrogen atom attached to phosphorus ;in biological systems it may be forced to do so by some form of neutralisation of the other two nitrogen atoms-possibly by complex formation. This is however a problem which requires further study. la Hobbs Corbridge and Raistrick Acta Cryst. 1953 6 621. l8 S. G. Warren unpublished results. 2o Moffatt and Khorana J. Amer. Chem. Soc. 1961 83 649. *l Moffatt and Khorana J. Amer. Chern. SOC.,1961 83 663. 22 Rathler and Rosenberg Arch.Biochem. 1956 65 319. Baddiley Buchanan and Letters J. 1956 2812. 24 G. W. Kirby and S. G. Warren unpublished results. JUNE 1962 Ph CH,O,II fNH (a) .P-NH-C’ HO/ ‘NH -U NH HO II (Ip) HO,P-NH-C // NVe CH,C02H Monoesters of phosphoramidic acids react not only with phosphoric acid derivatives to yield pyro- phosphates but also with carboxylic acids to give mixed anhydrides. Thus benzyl hydrogen phos- phoramidate when dissolved in glacial acetic acid yields acetyl benzyl hydrogen phosphate as shown by the fact that when the resulting solution is added to aqueous alkaline hydroxylamine acethydroxamic acid is formed. For this reason mixtures of benzyl hydrogen phosphoramidate with carboxylic acids can be used as acylating reagents.The behaviour of such mixtures with amino-acids is of some interest.25 A solution of benzyl hydrogen phosphoramidate in glacial acetic acid reacts at room temperature with the amino-acids glycine leucine alanine and phenyl- alanine to give the corresponding acetamido-acids ;in the absence of the phosphoramidate acylation is negligible. This reaction we interpret as probably proceeding by attack of the carboxylic group on the carbonyl group of the acetyl benzyl hydrogen phos- phate followed by a rearrangement to the acetamido- acid by intramolecular acylation. The general scheme of reaction is set out in the annexed scheme. 0 0 RO ” a P-NH +AcOH -RO HO/ HO/P-oAC +NH3 A‘ If external carboxylate anions can bring about displacement reactions with phosphoramidates lead- ing to mixed anhydrides it should be possible to bring about the same reactions intramolecularly.In particular it should be possible to develop a method of polypeptide synthesis based on this idea. In order to test this hypothesis N-(diphenyl phosphory1)- glycine benzyl ester (V; R = H R = Ph) was pre- pared and from it by catalytic hydrogenation the crystalline N-(diphenyl phosphory1)glycine (VI ;R = H R’ = Ph). In accordance with our expectation the latter compound readily yielded polyglycine under acid conditions presumably by way of an intermediate (VII; R = H R’ = Ph). Similar oligo- J. F. P. Richter and M. Michalska unpublished results. 26 J. F. P. Richter and A.R. Macrae unpublished results. peptides have been obtained by using DL-phenyl- alanine DL-leucine and m-valine.26 As far as we are aware this is a new synthesis of polypeptides but it is also of interest from another point of view. Could it be of significance in the biological synthesis of proteins ? P 1~‘d J ‘OR’ (m) Although considerable advances have recently been made in unravelling the complex course of protein biosynthesis and the part played in it by the nucleic acids we do not yet know the mechanism by which polypeptide chains are formed in the ribo- somes. We know that each amino-acid becomes attached ester-wise to the 2’ or 3’ position on the terminal nucleoside (adenosine) residue of its specific “soluble ribonucleic acid” (transfer RNA) the re- agents bringing this about being apparently nucleo- tide-amino-acid anhydrides.In this form they are transferred to the ribosomes where they are arranged in specific order by a coding procedure involving the ribosomal ribonucleic acid and then the polypeptide chain is formed. But the sequence of events in the ribosomes and the actual mechanism of polypeptide formation is still far from clear. It is possible that the transfer RNA attaches itself to the ribosomal RNA in such a way that the attached amino-acids are lined up so that direct polypeptide formation occurs. An alternative possibility that the amino-acids might be first transferred to the internucleotidic phosphate groups on ribosomal RNA has in the past been difficult to accept since the attachment of an amino- acid to a phosphodiester in the form of a mixed an- hydride gives compounds so reactive that they would not be expected to have more than a transient existence.But the observed stability of N-(diphenyl phosphoryl)glycine which can be handled and in- deed crystallised suggests that by attachment to an internucleotidic linkage through nitrogen amino- acids might be “stored” in relatively unreactive form until the appropriate sequence was built up. By acid- catalysis rearrangement to the anhydride form with immediate conversion into polypeptide could then occur without damage to the polynucleotide chain. It is not suggested that this is indeed what happens; but if it were found to fit the biological facts then it could be accepted as being at any rate chemically reasonable.It would be possible to discuss a number of other features of phosphate chemistry which may be sig- PROCEEDINGS nificant in biosynthetic processes and which may provide an approach to various aspects of enzyme action but what I have discussed will I hope suffice to indicate to you some aspects of a broad and I believe important area of research where progress demands the joint efforts of organic chemists bio- chemists and biologists. CHEMICAL SOCIETY ANNIVERSARY MEETING 1962 SYMPOSIA Held at Sheffield on April 3rd-5th Structure and Reactivity in Inorganic Chemistry THIS symposium was held in two sessions on April 4th and 5th.The size of the audiences was con- vincing if rather uncomfortable proof of keen interest in the speakers and their topics. Dr. W. C. E. Higginson took the chair for the first session and introduced Dr. J. Lewis (University College London) who gave a lecture on “Mag-netism and the Structure of Inorganic Complexes.” This was an excellent review of the magnetochem- istry of transition elements and showed how the classical approach in which the energy levels were assumed to be those of the free ion and orbital con- tributions to the magnetic moments ignored failed to account fully for the moments of many metal Complexes. Dr. Lewis had found that many octa- hedral complexes for which a crystal-field treatment predicted no spin-orbit coupling had magnetic moments that were independent of temperature and equal to the classical spin-only value.For some tetra- hedral nickel complexes in which orbital contribu- tions were expected there was poor agreement be- tween the experimental and the calculated variation of p with temperature. Dr. Lewis competently explained how this could readily be accounted for by distortion of the ligand field around the central ion. In the next lecture “The Atomic and Electronic Structures of Nickel(@ Complexes,’’ Professor F. A. Cotton (M.I.T.) opened by stating emphatically that it was now possible by application of ligand-field theory to complexes of nickel(II) to distinguish octa- hedral from tetrahedral stereochemical configura- tions. The first criteria were magnetic as previously discussed.The second were spectroscopic and were based on correlation of band positions with energy- level diagrams and on the band intensities. For square-planar compounds the position seemed less clear but Professor Cotton showed how their “anomalously” solvent- and temperaturedependent electronic structures are explained by three main mechanisms the co-ordination of solvent molecules the Boltzmann distribution of close-lying singlet and triplet states and lastly molecular association. The last point was well illustrated when Professor Cotton considered the nickel(Ir)-P-diketone complexes. In these cases apparently the degree of molecular association can change from zero when t-butyl groups are the substituents of the diketone to essentially complete trimerisation when methyl groups are used.The second session was opened by Professor A. W. Adamson who presented Professor Fred Basolo of Northwestern University. Professor Adamson also remarked in his humorous manner that all state- ments were liable to be controversial. Under the title “Kinetics and Mechanisms of some Octahedral Metal Complexes,” Professor Basolo divided the lecture into three interrelated parts. Studies on cer- tain ammine-carboxylate complexes of cobalt(III) rhodium(m) and iridium(1rr) showed that in all cases the rates of acid hydrolysis were similar thus sug- gesting that cleavage of the acyl-oxygen as against metal-oxygen bond took place. The first syntheses and kinetics of the compounds cis-and trans-[Rh(AA),Cl,]+ where AA represents ethylenediamine or a substituted ethylenediamine were reported.A most surprising feature was that trans-[Rhen 2Cl,]f was hydrolysed at the same rate at either pH 1.0 or pH 13-0,in marked contrast to the corresponding cobalt(1n) compound. New evi- dence was cited to support the theory that base hydrolysis in cobalt(rI1)-ammine complexes proceeds by an S,lcb mechanism and not by simple S,2 dis-placements. The conclusion was that the hydroxyl ion is an ineffective nucleophile for metal complexes con- taining non-bonding d-electrons. In support Profes- sor Basolo quoted the @-system [Si(acetylaceto- nate),]+ in which hydroxyl ion proved an effective reagent. The last lecture by Dr.R. G. Wilkins (Sheffield University) was entitled “The Fast Reactions of Metal Complexes.” Dr. Wilkins first surveyed the exciting techniques being used in complex-ion kinetics which enable rates of reactions to be measured which are complete in fractions of a JUNE 1962 second. This work was undertaken to illustrate the effects of ligand structure on the rates of formation and substitution of nickel@) complexes and was con- cerned particularly with nickel-amine complexes. Dr. Wilkins presented a mass of detailed kinetic data on a variety of ligands containing from 1 to 6 nitro-gen donor atoms. He considered it significant that the formation rates of complexes of nickel@) with unidentate ligands are approximately equal to the water exchange rate and so indicates strongly that an S,1 process more nearly describes the formation and that direct ligand entry is relatively unimportant.The most impressive part of the work was the resolu- tion of the stepwise cleavage of Ni-N bonds during the acid dissociation of multidentate complexes the nitrogen atoms being protonated as they were released. After a short discussion Professor Adamson called on Dr. J. Chatt (I.C.I.) to propose a vote of thanks after which the meeting closed. The symposium made it quite clear that to-day the chemistry of complexes is an intriguing and fast-moving subject. P. G. PERKINS. The Translition State* A SYMPOSIUM on this topic was held during the Anniversary Meetings in Sheffield on April 3rd to 5th.In his address of welcome Professor G. Porter remarked that although the transition-state theory had not entirely fulfilled its early promise it was nevertheless the best and most widely used theory of reaction rates which we possessed. Appropriately the first contribution was from Professor H. Eyring in which he discussed correc- tions to the idealised theory arising from departures from equilibrium kinetics. Since many activation processes in thermal reactions occur in stages the reactants will pass over a number of potential bar- riers before reaction occurs. This was shown to lead to a transmission coefficient appreciably less than unity if the free-energy difference between successive intermediate states is small compared with RT cal./mole;but as the free-energy difference increases the transmission coefficient approaches unity.In association and adsorption in which energy must be dissipated in order to stabilise the products it is the least energetic rather than the most energetic molecules which react. The first session was concluded by a discussion of two papers on unimolecular decompositions in the gaseous phase. Professor N. B. Slater suggested that Kassel’s model should be discarded as unrealistic; in his own theory it is assumed that the energy is distributed between the normal vibrations of the molecule and that dissociation can occur only when a critical co-ordinate exceeds a certain value. No energy exchange between truly harmonic vibrations can occur between collisions a restriction which leads to calculated rate constants which are often smaller than experimental values.In practice a limited flow of energy will occur because of the an- harmonicity of the molecular vibrations and Profes- sor K. J. Laidler suggested that energy could flow only between those vibrations of the same symmetry as the reaction co-ordinate. A tentative configuration of the transition state can usually be deduced if a reaction co-ordinate can be chosen which will give agreement with experiment. In discussion however several speakers stressed the importance of anhar- monic coupling between vibrations of different sym-metry in distorted molecules and questioned the validity of arguments based upon the symmetries of the reacting molecule and the activated complex.With Professor E. A. Guggenheim in the chair Professor K. S. Pitzer opened the second session with a paper on the calculation of transmission coefficients for reactions of the type H + H2-+H, + H. A semi-empirical equation due to Sat0 was used to describe the potential energy surface. Trans- mission coefficients were calculated for several different total energies a linear collision being assumed. At low total energies allowance for the bending of the activated complex appreciably re- duces the transmission coefficient and a correction for this is essential. The remaining papers were concerned with re- actions in solution and in the first of these Professor L.Melander discussed the transition state in electro- philic aromatic hydrogen exchange. The ratio of the rate constants for the electrophilic exchange of tritium and deuterium falls with increasing reactivity of the aromatic position. A transition state which includes both hydrogen atoms and takes their bend- ing motion into account was shown to be qualita- tively consistent with this observation. The final paper of the session was read by Pro- fessor M. Szwarc and dealt with the transition state in electrophilic radical reactions. He showed that the ratio of the rate constants of addition of CF radicals to an olefin and abstraction by CF radicals from isobutane was much greater than the corresponding ratio for reactions of CH radicals.This was inter- preted in terms of polar transition states the effect of the polarity being greater for addition than for abstraction since the polarisability of a n-bond is greater than that of a a-bond. Professor Szwarc con- sidered that the transition state probably resembles * A full report of the lectures and discussions at this symposium (but not at the other two) will be issued as Chemical Society Special Publication No. 16. This is expected to be available in October-November 1962. a a-complex rather than a n-complex since it appears to involve a particular carbon atom. Since Mr. R. P. Bell was unfortunately unable to be present Dr. J. W. Linnett took the chair for the final session. Sir Christopher Ingold began by point- ing out that whereas the idea of a transition state was extremely useful in reactions such as diene addi- tion there are many reactions in which it is ill- defined and in the benzidine rearrangement its structure “must be like nothing else in this world.” Despite much experimental work “a cloud hangs over the high central region of the mechanistic route wherein lies the transition state.” Professor H.C. Brown’s paper which may be destined to reach a wider public than most as a result of the recent burglary of the Society’s premises was concerned with strained transition states. After assuring his audience that he was not one to shirk a controversy Professor Brown discussed non-classical carbonium ions. Some of the structures suggested in the literature were likened to some of the more ex- treme forms of modern painting and Professor Brown concluded by stressing the need for a sound PROCEEDINGS experimental basis for explanations in terms of non- classical structures.Several sources of evidence for non-classical carbonium ions were discussed by Dr. A. Maccoll. Both isobutane and neopentane give the C,H,+ ion in the mass spectrometer possibly via a non-classical intermediate. It was shown that heterolytic dis- sociation energies derived from radical ionisation potentials could be correlated with the rate of heterolysis in polar solvents and of gas-phase elimination of alkyl halides suggesting a transition state of the type (R+X-). The final paper was presented by Dr. G.Kohnstam and dealt with the interpretation of entropies and heat capacities of activation in solvolytic reactions.If one assumes that the transition state is highly polar the values can be interpreted in terms of increased solvation. The interpretation of results obtained in largely aqueous solvents is highly con- troversial as ensuing discussion showed. The meeting was formally concluded by Professor K. W. Sykes who thanked the contributors and organisers of the meeting. K. R. JENNINGS. The Structure Oxidation and Biosynthesis of NaturalIy Occurring Phenols THE1962 Anniversary Meetings of the Chemical Society in Sheffield included a symposium on the above topic divided into three sessions held on April 3rd 4th and 5th which were concerned respectively with the structure the oxidation and the biosynthesis of phenols.The chairmen for the three sessions were Sir Alexander Todd Professor R. D. Haworth and Professor E. R. H. Jones respectively. The first session opened with a paper by Professor K. Freudenberg who gave a masterly exposition of the biosynthetic approach to elucidation of the struc- ture of lignin. He reviewed the degradative and synthetic evidence which suggested that lignin is bio- synthesised from phenols of C6-C3 type by initial enzymic dehydrogenation to give phenoxy-radicals the mesomeric forms of which react to form a variety of oligomers. The further combination of these oligomers either by radical coupling and sub- stitution or by addition reactions of quinone methines possibly proceeds by non-enzymic means since the lignin produced is optically inactive.He believed that lignin has an ordered structure al- though it was not possible to draw a final conclusion from the evidence now available. A discussion ensued among Sir Alexander Todd Professor D. H. R. Barton Professor K. Freudenberg and Professor C. H. Hassall on whether dienone-phenol rearrange- ments of in vivo intermediates of lignin formation were induced enzymically photochemically or by acid-ca tal ysis. The second paper given by Professor Otto Th. Schmidt was concerned with recent work on the ellagitannins the biosynthetic scheme for which was w&pHG 0 HO/ \ HO/ \ HowO 0 HO OH (1 ) (2) strengthened by the recent isolation of brevilagin I and II which contain the dehydrohexahydroxydi- phenic acid residue (1) and terchebin which con- tains the isohexahydroxydiphenic acid residue (2).After describing the degradation of these ellagitan- nins he showed how reactions of compound (2) in vitru further confirmed the biosynthetic scheme. Professor R. D. Haworth next described the application of methylation and methanolysis (de-gradation by transesterification with sodium meth- oxide) to the gallotannins. These showed that Chinese and Turkish gallotannin have structures based on penta-U-galloylglucose and a mixture of tetra-0-galloylglucoses respectively whilst tara tannin has a 3,4,5-tri-O-galloylquinicacid core. Professor D. H. R. Barton opened the second session with a lucid account of the mechanism and biogenetic role of oxidative phenolic coupling.The biosynthetic scheme for galanthamine was sub-stantiated by the recent isolation of two postulated JUNE 1962 intermediates by a biosynthetically modelled labora- tory synthesis of (-)-galanthamine and by tracer experiments in vivo with postulated precursors. An unusual resolution of nanvedine the precursor of galanthamine produced either optical isomer in yields greater than 50 %. Further verification of the biosynthetic role of oxidative phenolic coupling was provided by Dr. A. R. Battersby by reference to tracer experiments with opium and Amaryllidaceae alkaloids in vivo. Specifically labelled tyrosine and norlaudanosoline were incorporated into morphine in the predicted manner.Both (+)-and (-)-tetrahydropapaverine were incorporated into morphine but to different extents indicating enzymic control whilst other tracer experiments substantiated the postulated bio- synthetic order thebaine +codeine-+ morphine. Dr. S. Dagley was concerned with a different aspect of phenol oxidation that of microbial de- gradation by hydroxylation and oxidative fission. After a summary of existing degradation pathways new pathways motivated by recently discovered enzymes were described. Returning to oxidative coupling of phenols Dr. A. I. Scott provided in vitro analogies of suspected in vivo oxidations for example the formation of griseofulvin and the depsidones pichrolichenic acid and diploicin by oxidation of phenolic precursors (i) Anodic oxidation (ii) H+ with inorganic reagents.Enzymic oxidation of 3,4-xylenol (3) gave an optically inactive ketone (4),and griseofulvin produced enzymically in vitro was also racemic. He then suggested that coumarin biosyn- thesis might find analogy in the acid-catalysed rear- rangements of the spirodienones (6) produced by anodic oxidation of cis-4-hydroxycinnamic acid (5). Starting the ha1 session Professor A. J. Birch reviewed biosyntheses of aromatic compounds especially those not based on shikimic acid. Among examples discussed was the biosynthesis of myco- phenolic acid which incorporated mevalonate acetate and methionine. Since orsellinic acid was a precursor nuclear methylation and substitution of the side chain (which was a geranyl remnant obtained from two molecules of mevalonate) occurred after aromatisation.He also discussed the biosynthesis of novobiocin and speculated on the origin of C& compounds of the eugenol type. Dr. H. Grisebach showed that tracer experiments provided convincing evidence that flavanoids were biosynthetically derived from C,-C3 and acetate units by a scheme involving chalcone intermediates. The biosynthetic pathways to flavone and antho- cyanin probably branched before the final oxidation state of the heterocyclic ring was established and aryl (not aroyl) migration occurred in flavone bio- synthesis. Dr. Grisebach then speculated upon the intermediate in which this migration occurred.Professor C. H. Hassall gave an interesting demonstration of the application of the techniques of chemical genetics to the elucidation of biosyn- thetic problems inaccessible by the use of tracers and consideration of structural relationships. These methods revealed a common metabolic sequence for sulochrin geodin asterric acid and geodoxin which was verified by the reactions of their dechloro- analogues in vitro. A combination of these tech- niques with tracer methods revealed orcinol to be a precursor. The final paper given by Dr. J. D. Bu’Lock was concerned with a re-examination of the basic as- sumptions underlying isotope-incorporation studies with mould metabolites. This critical re-assessment was most appropriate at a time when these tech- niques are becoming more widely used.Much of the material presented by six of the contributors was published recently in a collected form (“Recent Developments in the Chemistry of Natural Phenolic Compounds,’’ Pergamon Press London 1961) but since each contributor disclosed new work this prior publication served to enhance rather than diminish the success of the symposium. The details of Professor Barton’s galanthamine syn- thesis (J. 1962 806) appeared a few days after the symposium finished. D. N. JONES. PROCEEDINGS THE ANNIVERSARY MEETING AT SHEFFIELD APRIL EARLYApril would not be the time recqmmended by Travel Agencies for a visit to the Peak District and the Fates are in no wit kinder to Fellows of the Chemical Society than they had been to the residents during the devastating previous months.Indeed it was not until the morning following the Meeting that Nature condescended to suggest that Winter might at last be satisfied; a mid-afternoon trip over Snake Pass on the previous day produced all the hazards of any mid-winter continental car-rally. Yet such was the enjoyment experienced at the Anniversary Meet- ings that these unpleasantries were not noticed. Attendance at the Meeting was one of the biggest in the Society’s history; such that the large lecture theatres were always crowded and sometimes inadequate to the extent that other accommodation had to be sought. The Society’s Annual General Meeting enabled the Honorary Officers to report on the continued success of the Stewardships of their Offices and the paucity of questions from the floor indicated clearly the satisfaction of the Fellowship with the conduct of the Society’s affairs.The Presidential address (see p. 199) which followed must have satisfied all. Although appearing to deal with a narrow specialised topic of organic chemistry it nevertheless spanned a wide range of interests drew attention to many queries in the natural and biological sciences and must have suggested several lines of thought and study to listeners. Incidentally it will probably make Chemical Society history in being the last occasion on which a President has been called on to deliver two Presidential addresses during his term of office.This easing of the Presidential burden has been made possible by the endowment of the “Robert Robinson Lectureship” (see Proceedings 1962 108). The three symposia are fully reported elsewhere in this issue and one on “The Transition State,” is to form No. 16 in the Society’s “Special Publication’’ series. Many of the papers read were stimulating and indeed challenging and discussion of them often continued long after the scheduled closing of the session. All who contributed and joined in public discussions deserve our thanks and congratulations. The programme of hospitality was much ap- preciated not least by the ladies who found much to interest them. The works visits were a balanced mix- ture of chemical and local-industry interests and the latter particularly enabled the ladies to look into the background of much that they treasure in their own homes and to enable them to appreciate that the methods of skilled craftsmen have not been entirely swept away by the need for mass-production.The display of silverware at the Ladies’ Reception given by the Mistress Cutler was spoken of most ap- preciatively. Fellows and visitors are indebted to these organisations and to others who gave hospi- tality sometimes associated with works visits United Coke and Chemicals Company Limited The Shell Chemical Company the Alkali Division the Pharmaceuticals Division and the Dyestuffs Divi- sion of Imperial Chemical Industries Limited Batchelor’s Foods Limited Newton Chambers and Company Limited and Samuel Fox and Company Limited.Situated on the fringe of some of the loveliest country in England Sheffield offers to an extent that can be rivalled by few University Cities trips to great historic houses. Three were visited-Haddon Hall Hardwick Hall and Chatsworth House-and were a source of much pleasure; some stalwart Fellows to allay the effects of generous luncheon hospitality took the unusual exercise of walking the great gardens of one of these Houses to see the axe- men tidying up the ravages of the winter’s great gale. Each day’s work was rewarded by an evening’s enjoyable relaxation-a Reception Buffet and Dance by invitation of the University the well- attended Anniversary Dinner held in the University Gymnasium and a Civic Reception in the Town Hall.Lord Hailsham as principal speaker at the Dinner told of his opinion that all science should be cul- tivated for the part it plays in promoting a higher level of culture in society at large and his belief that the corpus of human knowledge was essentially one and not two cultures-the arts and the sciences. The 1962 Anniversary Meeting had all the mark- ings of a well-conceived properly organised and efficiently run affair and all those who contributed officially (and unofficially) to making it the success it proved to be must receive our gratitude. CORDAY-MORGAN MEDAL AND PRIZE THE scheme for the administration of this Award (Proceedings 1962 135) has now been established by the Charity Commissioners and it will in future be subject to the revised rules approved by Council and given below (see also p.236). The Award consisting of a Silver Medal and a monetary Prize which for the year 1961 will amount to 400 guineas is made annually to the chemist of either sex and of British Nationality who in the judgement of the Council of the Chemical Society JUNE 1962 has published during the year in question and in the immediately preceding five years the most meri- torious contribution to experimental chemistry and who has not at the date of publication attained the age of thirty-six years. Applications or recommendations in respect of the Award for the year 1961 must be received not later than December 31st 1962 and applications for the Award for 1962 are due before the end of 1963.Rules 1. The Award shall be known as the Corday- Morgan Medal and Prize. 2. The Award shall be made annually to the chemist of either sex and of British nationality who in the judgement of the Council of the Chemical Society shall have published during the year in question and in the immediateJy preceding five years the most meritorious contribution to experimental Chemistry and who at the date of publication shall not have attained the age of thirty-six years. The date of publication of any journal shall be deemed to be the date at which the journal was first available to the public. 3. The Award shall not be made more than once to the same candidate.If in any one year two or more candidates are in the opinion of the Council of equal merit the Council may award a medal to each such candidate and divide the monetary prize equally between them. 4. The Council may at its discretion suspend the Award in any year in which no suitable candidate presents himself or is brought to the notice of the Council. In the event of such suspension a sum equal to the income otherwise available for the Award in that year shall be invested and added to the capital of the Trust Fund. 5. The Award shall consist of a silver Medal and a monetary Prize of an amount to be determined by Council having regard to the balance of the income of the Trust Fund for the year after payment of the expenses incidental to the Award.6. No restrictions shall be placed upon the branch of Chemistry for which the Award is granted or upon the place in which the work is conducted. 7. The merits of the work of any candidate for the Award may be brought to the notice of the Council either by persons who desire to recommend the candidate or by the candidate himself. 8. Details of the Award shall be published annually in the Proceedings of the Chemical Society and elsewhere. 9. Applications or recommendations for the Award shall be forwarded so that they shall reach the Society not later than the Thirty-first day of December in the year following that for which the Award is to be made. Applications or recommenda- tions should be accompanied by the birth certificate of the candidate and a list of papers published by the candidate during the years in question (see Rule 2) and nine reprints (which will be returned) of each paper or copies of any published work on which the grant of the Award is to be judged.The candidate may if he wishes submit with his application a statement on the background and main purpose of the research papers on which his application is to be judged and may refer in such a statement to his previously published work. 10. Each candidate shall give the names of two persons with a knowledge of his work to whom reference can be made by the Society. 11. The Award shall be presented at a meeting of the Society. 12. If any doubt shall arise as to the correct inter- pretation of these Rules the matter shall be decided by the Council of the Society.13. The Council may from time to time alter or add to the regulations for the administration of the Award provided that no regulation shall be ap- proved that is contrary to the terms of the Bequest as expressed in the Will of the late Sir Gilbert T. Morgan or to the conditions expressed by the Charity Commissioners for England and Wales. XIXth INTERNATIONAL CONGRESS OF PURE AND APPLIED CHEMISTRY LONDON, JULY10th-l7th 1963 COPIES of the first circular are now available from The Honorary Secretary XIXth International Con- gress of Pure and Applied Chemistry 14 Belgrave Square London S.W.l. The scientific programme of the Congress will consist of some 20 invited congress lectures in addi- tion to a wide range of contributed papers.The papers presented in the division of Organic Chem- istry will form the main theme; but certain aspects of Inorganic Chemistry Analytical Chemistry and Applied Chemistry will also be discussed. Each division of the Congress will comprise a number of sections and a proportion of these will meet concurrently during the period of the meeting. The specific topics to be discussed are outlined below. Details regarding the submission of papers for the Congress will appear in the second circular to be issued in October 1962. 210 PROCEEDINGS Scope of Congress A. Organic Chemistry 1. Reaction Mechanisms. 2. Physical Methods to emphasise fundamental developments in techniques and substantial applica- tions to structural problems.3. Stereochemistry and Conformational Analysis. 4. Modern Aspects of Organometallic and Related Compounds. 5. Developments in Organic Synthesis. 6. Biogenesis. 7. Biologically Important Polymers. 8. Microbiological Products and Antibiotics. 9. Steroids and Terpenoids. B. Inorganic Chemistry 1. Applications of the Newer Physical Methods (other than X-Ray Crystallography) to Structural Inorganic Chemistry to include electron-spin resonance nuclear magnetic resonance other forms of microwave spectroscopy and polarography. 2. Inorganic chemistry of the Solid State. 3. Inorganic Chemistry of the Molten State.C. Analytical Chemistry 1. Trace Analysis. 2. Separation Methods. 3. Electroanalysis. 4. Teaching of Analytical Chemistry. D.Applied Chemistry 1. Adhesion of Surface Coatings. 2. Applied Chemistry of the Solid State. 3. Food Packaging Materials; Toxicological and Analytical Problems. 4. Industrial Carbon and Graphite. 5. Utilisation and Treatment of Wastes by Biological Methods. A SYMPOSIUM ON NITROGEN HETEROCYCLIC CHEMISTRY THISmeeting arranged by the Hatfield College of Technology with the support of the Chemical Society attracted almost two hundred chemists to the College. In two days May 10th and llth this “capacity crowd,” as it would have been called in journalistic circles listened to nine papers.That number in two days is certainly not a record but is enough of a test of stamina to prove that at least two hundred people in the country take a fairly serious interest in nitrogen-heterocyclic chemistry. The smooth way in which the conference proceeded demonstrated the excellence of the arrangements made by Dr. R. F. Robbins Head of the Science Department at Hatfield. To him and to Mr. E. Roberts Registrar of the College all who attended must be grateful. Our gratitude is also due to Dr. W. A. J. Chapman Principal of the College for sanctioning the use of the College’s premises for the purpose of this meeting. Heterocyclic chemistry even when limited to the case of nitrogen compounds is a subject of endless variety and the topics discussed illustrated almost the whole range of the organic chemists’ preoccupa- tions; from the classical theme of the influence of substituents upon the behaviour of aromatic com- pounds through the stereochemical problems of saturated systems to the study of mechanism and the interpretation of physical properties.The first session under the Chairmanship of Professor W. Baker saw the Symposium off to a brilliant start with an account from Dr. J. W. Corn- forth of his experiments towards a synthesis of vitamin BIZ. An imaginary hydrolysis of the mole- cule to give a complex keto-amine led him to con- sider isoxazoles as intermediates capable of providing such a keto-amine by characteristic reductive fission.The imaginary hydrolysis led on to deeply imagina- tive sterically controlled syntheses of the fragments constituting the corners of the vitamin’s molecule. At one stage Dr. Cornforth’s scheme requires the stitching together of suitable fragments through 1,3-diketone structures and an interesting side- product of these studies is a 1,3-diketone synthesis through the acylation of a methylene group activated by adjacent carbonyl and pyridinium groups. Professor P. B. D. de la Mare followed Dr. Cornforth with a discussion of electrophilic substitu- tion in N-heterocycles. The fundamental requirement for progress here is a body of data permitting the quantitative comparison of the reactivities of fully identified substrates with the reactivity of benzene.Electrophilic attack on say quinoline almost cer- tainly occurs at nitrogen in the first instance. How- ever every electrophile is accompanied by a nucleo- phile and in some reactions the isolated product arises from a complex sequence of electrophilic attack nucleophilic addition further attack and elimination. It will clearly be some time before ex- periment indicates which of the several available theoretical treatments is relevant in the elementary sense of referring to processes which actually occur. The second session of the meeting under the Chairmanship of Professor de la Mare heard Pro- fessor w. Baker on Meso-ionic compounds Dr. J. D. Loudon on the synthesis of heterocyclic compounds by sulphur extrusion and Dr.A. R. Katritzky on N-oxides. JUNE 1962 The meso-ionic compounds contain six n-electrons associated with a five-membered ring. It is interesting to reflect amidst all the current interest in non- benzenoid aromatics that the sydnones which fall within the definition of meso-ionic are probably the only non-benzenoid compounds besides the tro-polones ferrocenes and azulenes for which aromatic character has been claimed and in which the common electrophilic substitution at carbon have been ob- served. Sulphur is a surprising element at any time but never more so than in the extrusion reactions described by Dr. Loudon. Such extrusions have been observed in passage from 7-to 6- 6-to 5- and 5-to 4-membered rings.Dr. Loudon’s studies were con- cerned originally with contraction of 7-membered thiepins thiazepines and thiadiazepines to 6-membered rings lacking sulphur. They provided an extraordinary wealth of synthetic materials and an opportunity for a classical exercise in the study of subs ti tuent influences. The recognition by Ochiai and den Hertog of the potentialities of pyridine 1-oxides was one of the most important developments in heterocyclic chem- istry in recent years. Dr. Katritzky brought out the practical importance and theoretical interest of these compounds showing how these features depend on the unusual ability of the N-oxide group both to accept and to donate electrons. The whole battery of physical methods was engaged in putting the com- parison of pyridine 1-oxides with pyridine and benzene on a quantitative basis.After the labours of the first day the members of the conference were happy to retire to the labora- tories of Messrs. Smith Kline and French Ltd. at Welwyn Garden City. There after touring the splendidly equipped laboratories they enjoyed the most profuse hospitality. The evening was enjoyable and valuable not only because we were able to enjoy the excellent food and splendid wines so generously provided by our hosts but also because of the opportunity it provided for the renewal of old acquaintances and the beginning of new ones. Whether or not such an evening helps to prepare for the next day’s work is arguable but there were no mass absences when on the following morning Professor A.Albert introduced the lecturers for the conference’s third session; Professor D. H. Hey on new cyclisation reactions and Dr. A. H. Jackson on porphyrin proton magnetic resonance spectra. Professor Hey and his colleagues had begun with the aim of extending the Pschorr phenanthrene syn- thesis to the preparation of phenanthridone. The quite inexhaustible abilities of decomposing di- azonium cations for displaying unexpected modes of reaction soon put to an end such limited ambitions. The formation of a spiro-dienone from diazotised 21 1 2-amino-N-ethyl-4’-methoxybenzanilidewas only the first fruit of a rich harvest reaped from the virtuosity of these compounds.With its large aromatic ring current the porphin nucleus is a particularly interesting source of proton magnetic resonance spectra. Dr. Jackson showed how the main features of the spectra were related to the nature of the ring substitution. It is clear that proton magnetic resonance spectra will prove in- valuable in structural studies in this field as Dr. Jackson showed in the particular instance of the copropophyrins. In addition they provide the theoretician with data of great interest. The last session under Professor Hey heard papers from the present writer on quinolizidine stereochemistry and from Dr. S. F. Mason on the electronic spectra of N-heterocycles. The bicyclic quinolizidines make interesting subjects for the application of conformational argu- ments both as regards the equilibria arising in them because of the stereochemical instability of tervalent nitrogen and because of the influence of steric factors on the kinetic process of quaternary salt formation from these bases.Nuclear magnetic resonance spectra in particular promise to make a unique con- tribution towards the solution of these stereo-chemical problems. Dr. Mason showed how the three types of electronic absorption spectra of interest in the N-heteroaromatic series due to charge transfer n+n* and T+T* excitation could be discussed in terms of a common model based on benzene orbitals. The correlations made over a large sequence of N-heteroaromatic nuclei were of appealing elegance. The introduction of strongly conjugating substituents required the use of the benzyl anion model but again the unification achieved by sur- prisingly simple means must appeal strongly to organic chemists.This Symposium is the third on heterocyclic chemistIy to be held in recent years following meet- ings at Exeter and in Canberra. In common with other branches of organic chemistry heterocyclic chemistry grows at an ever increasing rate and there can be no doubt that other meetings devoted to it will follow frequently in the coming years. It seems doubtful if any of these can be more enjoyable than this recent meeting at Hatfield. Hatfield College of Technology is indeed a particularly pleasant place for a function of this kind; its new and attractive buildings are adorned with numerous works of art including examples by Barbara Hepworth and Ben Nicholson which make it clear that the Two-Culture nonsense carries no weight here it conveys that stimulating impression of active growth and its staff is skilled in making visitors feel welcome.This was a memorable occasion. K. SCHOFIELD. PROCEEDINGS THE BELGIAN CHEMICAL SOCIETY 1887-1 962 AT the initiative of a group of chemists in the sugar industry there was founded on April 14th 1887 the Belgian Association of Chemists which since January 30th 1904 has born the name of Socibtk chimique de Belgique. Formed originally with the limited aim of solving problems in chemical analysis of sweets foodstuffs etc. this organisation has gradually enlarged its horizons and is today devoted to promoting the development of the chemical sciences.From its inception the Belgian Chemical Society has been the meeting-place of chemists who have chosen an industrial career and those who in various capacities are connected with the University. This peculiar feature is displayed in the fact that the Presidency of the Society is entrusted to a person of note alternately from the academic and the industrial world. In order to contribute to the dissemination of the work of its members the Society publishes a scientific Bulletin the pages of which are open for the results of original research. The subsidies granted for a number of years by the Ministry of National Education and by the Fondation Uni- versitaire testify to the value of this periodical.Published under the title of Bulletin des Socie‘tis chinziques belges it is edited in collaboration with the Flemish Union of Chemists. The Society also collaborates in the production of the scientific news reports of the Industrie Chimique Belge-Belgische Chemische Industrie a review published by the Federation of the Belgian Chemical Industries. The Chemical Society encourages scientific research not only by facilitating the dissemina- tion of research work but also by the annual grant of several awards. The latter are given in recognition of the best work by our young chem- ists in the light of their total research carried out during a period of ten years.Further the Central Committee of the Belgian Chemical Society in collaboration with the Com- mittees of the seven local branches (Brussels Antwerp Ghent Lihge Mons Charleroi and Louvain) organise annually some fifty lectures covering the most varied aspects of chemistry. These lectures are given in turn by Belgian and foreign scientists. Finally in common with the Flemish Union of Chemists The Belgian Chemical Society organises a “Journke des Jeunes” twice a year at which newly graduated licentiates and doctoral students report the results of their first labours and discuss them in an atmosphere of healthy rivalry. The Belgian Chemical Society has taken part in a movement developed at the initiative of the National Commission of Science presided over by H.M.Leopold 111,in favour of more effective support of scientific research by public authori- ties and of improvement in the contacts between University and Industry. With this aim an important meeting was organised by the Society in March 1958 at which several speakers stressed the urgent need to promote the teaching of science at the second- ary and higher levels to assign larger budgets to university research laboratories and to develop and stabilise the role of research in industry. A memorandum summarising the conclusions of an extensive enquiry addressed to industrial management and university teaching bodies was published in 1959 and forwarded to the National Commission of Science. The Chemical Society recorded with satisfaction that numerous recom- mendations drafted in this memorandum have been embodied in the final report of the Com- mission.From June 12th to 15th 1962 on the occasion of the seventy-fifth anniversary of the Belgian Chemical Society a Symposium devoted to the organic chemistry of natural products will be held under the auspices of the International Union of Pure and Applied Chemistry. To date we are able to give notice of the presentation of some 150 original communications by chemists of thirty-one nationalities and of seven plenary lectures by eminent scientists including Lord Todd Nobel Prize Winner. An academic session and various ceremonies will complete this inter- national gathering to which H.M.the King of Belgium has granted his distinguished patronage. A. BRUYLANTS. JUNE 1962 213 COMMUNICATIONS Signs of Nuclear Resonance Coupling Constants in Saturated Aliphatic Systems By H. FINEGOLD (NATIONAL OF STANDARDS 25 D.C.) BUREAU WASHINGTON EARLIERstudies of the significance of tenuous anomalies in the high-resolution nuclear resonance spectra of diethyl methylphosphonothionatel and di-ethyl sulphite2 have evoked much interest,,^^ and recently Kaplan and Roberts5 have successfully ap- plied an iterative computer programme to the com- plete analysis of the spectrum of diethyl sulphite in- corporating opposite signs for the vicinal and geminal coupling constants in the input data. This has suggested to us that the important general ques- tion of relative signs of coupling constants in saturated aliphatic systems requires complete re- ship to be established uniquely.Calculations were finally checked against experi,mental measurements at 5704 gauss. The results of the calculations are in the annexed Table (in c./sec.). The particular features to be noted in the above results are :(1) all three vicinal couplings must be of the same sign and the signs of the vicinal and geminal couplings must be opposite; (2) there are two long-range couplings opposite in sign to each other and having a unique relative sign relation- ship to all other coupling constants in the molecule; and (3) solvent effects are notable not only in the Compound Jab Jac Jad CHa3-CHbCI*CHCHdCl F6.56 &0-10 70.29 CHa,CHbBrCHCHdBr (20% in CCI,) 76.49 0.14 0-41 CH,CHBr.CH,Br (20% in CCI,) F6-52 k0.15 r0.31 (neat) CH,-CHBrCH,Br 76-55 f0.15 F0.30 (20% in C,H,) Jbc Jbd Jcd (THO).(THO)' (l-aab) (1-d 9-05 F4.65 511.10 147-02 34.10 FlO-82 If4.01 f 9.79 140.85 41.10 9-76 F4-20 f10-04 14140 41.25 ~10.00 If4.20 & 9.86 137.76 40.46 (THO). (l-cd) 14.48 20-32 17.49 17.65 examination. We here report on a study of asym- metric propane derivatives including detailed results for 1 ,Zdichloropropane and 1,2-dibromopropane and indicative results for several 1,l-disubstituted propanes. The 60 mc./sec. room temperature spectra of the dibromo- (see Figure) and dichloro-propane are rela- tively complex.This is attributable to the centre of asymmetry in the molecule which is necessarily attended by three distinctively valued potential- energy minima in a 360" rotation about the C1-C2 bond. The unequal shielding values of the methylene protons give rise to an A,BCD type spin system. In order to analyse this six-spin system a small number of trial Hamiltonians were constructed with approxi- mations based on low degrees of mixing. Corrections terms were then introduced to achieve precise con- vergence between computed6 and experimental in- tensities and frequencies. The sensitivity of certain of the calculated intensities and frequencies to signs of the coupling constants permitted the sign relation- 'Finegold J. Amer. Chem. Soc. 1960 82 2641.Finerrold. Proc. Chem. Suc.. 1960. 283. shielding parameters,1,2 but also in the coupling con- stants.' The geminal coupling which would be ex- pected to show no solvent effects if its magnitude H0-t Nuclear magnetic resonance spectrum (60 mc./sec.) of 1,2-dibromopropane taken in 20 % (v/v) CCI solution (high-field band deleted). Indicated band origins correlate with labelled protons. ShafEr Davis Vogel Naga;ajan,'and Roberts Proc. Naf.Acad. Sci. USA. 1961 47 49. Waugh and Cotton J. Phys. Chem. 1961,65 562. Kaplan and Roberts J. Amer. Chem. Soc. 1961 83 4666. Computations made with IBM 7090; programme written chiefly by A. A. Bother-By C. Naar-Colin and their associates. Freeman and Pachler Mol. Phys. 1962 5 85. depended principally on the methylenic HCH angle (whose value can be assumed constant throughout widely varying rotamer populations) shows sub- stantial variation.Three 1,l-disubstituted propanes of low symmetry -chloronitropropane phenylpropanol and ethyl- propanol (pentan-3-ol)-were studied. Results of calculations on the experimental spectra indicated that the average magnitude of the vicinal coupling constants associated with the methyl group and geminal coupling constants was 7.1 and 10.6 c./sec. respectively and that the relative signs of the vicinal Karplus J Chem. Phys. 1959 30 11. PROCEEDINGS and geminal couplings were opposite in every case. It appears that the consistent relative sign relation- ship in all of the above systems may be safely generalised and opposite relative signs of the vicinal and the geminal coupling constants may be regarded as entirely typical of saturated aliphatic systems.If the valence-bond theory of coupling mechanism,* which predicts like signs for geminal and vicinal couplings is to be retained in its essential features a greater contribution of polarisation factors to the sigma network associated with the coupling may perhaps have to be postulated. (Received April 16th 1962.) The Unique Carbohydrate Portion of the Cardiac Glycoside Gomphoside By R. G. COOMBE and T. R. WATSON (PHARMACY DEPARTMENT, UNIVERSITY OF SYDNEY SYDNEY AUSTRALIA) THEcardiac glycoside gomphoside,l obtained from Asclepias fruticosa is similar to several other glyco- sides e.g.Calotropis glycosides obtained from the Asclepiadaceae,2 in that it cannot be hydrolysed by any of the usual methods without decomposition of both the carbohydrate and the aglycone. Evidence has been obtained which indicates that the carbohydrate of gomphoside has the unique structure shown in (I) i.e. is derived from a 4,6-di- deoxyhexosone. Gomphoside forms a diacetate and requires 1 mol. of periodate to produce compound (II) which forms a mono-2,4-dinitrophenylhydra-zone. Acid hydrolysis of this compound (11) and (oyo = But-I-enolide) = C0,H) steam-distillation of the products into 2’4-dinitro- phenylhydrazine reagent gave a quantitative yield of crotonaldehyde 2,4-dinitrophenylhydrazone.Hydro-lysis of compound (11) in 2~-hydrochloric acid saturated with 2,4-dinitrophenylhydrazine gave a mixture of hydrazones which were identified as the derivatives of crotonaldehyde and glyoxylic acid.Compound (11) was not saponified by potassium hydrogen carbonate. Reduction with sodium boro- hydride and subsequent hydrolysis gave (-)-butane- 1,3401 which was characterised as such and as the diphenylurethane. The presence of a CH,CH.O-group is confirmed by a doublet in the nuclear mag- netic resonance spectrum of the glycoside having T = 8.61 and J = 7 C.P.S. The atianic acid (111) obtained by the degradation of the butenolide ring by Hunger and Reichstein’s method3 shows infrared carbonyl at 1740 1725 and 1715 cm.-l (in CHCl,) which correspond to the &lactone aldehyde and carboxylic acid group res- pectively.In addition compound (11) could not be methylated with diazomethane. The aglycone which is produced on hydrolysis of compound (11) contains a vicinal glycol system as shown by periodate oxidation and is postulated as the 2 a,3/3 dihydroxy-5f-carda- 14,20(22)-dienolide. We are indebted to Dr. J. N. Shoolery for running the nuclear magnetic resonance spectrum on a Varian Associates A60 instrument with deutero- chloroform as solvent and tetramethylsilane as internal reference. (Received April 16th 1962.) Watson and Wright Austral. J. Chem. 1957 10 79. Hesse and Reicheneder Annalen 1936 526 252; cf. Hassall and Reyle J. 1959 85. Hunger and Reichstein Helv. Chim. Acta 1952 35 1073. JUNE 1962 215 ~~ Stereochemistry of Capsorubin and Synthesis of its Optically Inactive Epimers By R.D. G. COOPER and B. C. L. WEEDON L. M. JACKMAN (QUEENMARY COLLEGE E.l and IMPERIAL OF SCIENCE LONDON COLLEGE AND TECHNOLOGY S.W.7) LONDON CAPSORUBIN and capsanthin which are believed to be derived from zeaxanthin have characteristic end- groups that have been allocated a cyclopentane structure (cf. VII).1-5 Whereas we favoured a trans- configuration for the two oxygen substituents on the five-membered ring from infrared light absorption1 and nuclear magnetic resonance considerations,6 Karrer et a12 claim to have proved a cis-relationship. We have now confirmed the novel ring structures and established the trans-coniiguration of the oxygen substituents by synthesis of optically inactive forms B" Me Me I_ 5cw -yj&y Me 0 (1) (In cpr> OH i4 Me Me Mej-$Meo-"eY Me* OH CVJ OH 0 Reagents 1 (i) EtOH-p-MeC,H,.SO,H; (ii) LiAIH4 (iii) H+.2 (i) H,-Pd-C (ii) CrO,.3 0,-KOBut. 4 (i) 5% KOH (ii) H,PO,-NaBiO 5 Crocetindial-S% KOH-EtOH. R = Me). These condensed with crocetindia18 to give the "all-trans"-carotenoids (VII) presumably as mixtures of diastereoisomers of the DL-and meso-type. That from the cis-alcohol (VI; R = OH) had m.p. 203" Am,,. (in c,H,) 522 488 and 457 (in- flexion) mp Ymax. (in CHCI,) 1650 1582 1541 1006 980 and 970 crn.-l r (in CDCl,) 9.03 8.85 and 8-00 (relative intensities 2 1:2). That from the trans-alcohol (VI; R = OH) had m.p.144-146" Amax. (in C6H6) 519 486 (E 12O,OOO) and 455 (in- flexion) mp Vmax. (in CHCI,) 3623 1664 1582 of capsorubin and epicapsorubin. * The full stereo- chemistry of natural capsorubin is thus defined since the absolute configuration at C-1 and C-1' is known,4 and those of the six-membered rings in capsanthin and zeaxanthin may now be provisionally assigned on reasonable biogenetic grounds. Autoxidation of the keto-acid (111) m.p. 188" obtained from the diketo-ester' (I) via the keto- alcohol (11) m.p. 151" gave the diosphenol (IV) m.p. 137" which was converted into the keto-acid (V) m.p. 224". Borohydride reduction yielded the cis-(isolated via the lactone m.p. 181") and the trans-hydroxy-acid (VI; R = OH) m.p. ca.160" (decomp.) and 222" respectively which on treatment with methyl-lithium gave the hydroxy-ketones (VI; 1546 1006 980 and 970 crn.-l T (in CDCI,) 9.15 8-80 8.62 and 8.02 (relative intensities 1:1:1:2) ; unlike the above epimer the latter did not separate on thin-layer chromatography from natural cap- sorubin m.p. 201" Am,,. (in C6H6)' 520 486 and 455 mp Vmax. (in CHCLJ1' 3616 1664 1582 1542 1007 980 and 970 T (in CDC1,)l 9-16 8.80 8.63 and 8.03 (relative intensities 1 :1:1:2). The authors thank Roche Products Limited and Hoffmann-La Roche Limited for chemicals and financial support (to R.D.G.C.). They are indebted to Varian Associates for the nuclear magnetic resonance spectra (methyl bands only are quoted). (Received April 3rd 1962).* The isomer differing from capsorubin in the configuration at both C-4 and C-4' is termed "epicapsorubin." Barber Jackman Warren and Weedon Proc. Chem. Soc. 1960 19; J. 1961 4019. Entschel and Karrer Helv. Chim. Acta 1960,43 89. Faigle and Karrer Helv. Chim. Ada 1961 44 1257. Faigle and Karrer Helv. Chim. Actu 1961 44 1904. Cholnoky and Szabolcs Experientiu 1960 43 483. Unpublished work. 'Crossley J. 1901 138. * Isler Gutmann Lindlar Montavon Riiegg Ryser and Zeller Helv. Chirn. Acta 1956 39 463. Karrer and Jucker "Carotinoide," Birkhauser Basle 1948. lo Warren and Weedon J. 1958 3972. PROCEEDINGS Pyrazolines from Tetracyanoethylene By JUAN BAST~S and Josi CASTELLS DE QU~MICA DE BARCELONA “JUANDE LA CIERVA” (DEPARTAMENTO ORGANICA PATRONATO DE INVESTIGACI~N (C.S.I.C.) UNIVERSIDAD SPAIN) TBCNICA DE BARCELONA WHENtetracyanoethylene in dry ether* suspension1 been considered as a possible alternative for N-H is treated with one mol.of diazomethane in KOH- pyrazolines but there seems to be no theoretical dried ether under nitrogen 3,3,4,4-tetracyano-l- objection to it; the recent preparation of one of the pyrazoline (I) (termed pyrazoline-I) m.p. 133” two possible isomers of cycl~diazomethane~ (decomp.) is obtained in 72% yield the analytical (diazirine) has bearing on this point. sample being prepared by washing with benzene; The Chart summarises our views on the mechan- this product has an infrared K=N stretching band isms of the reported isomerisations an important at 1595 cm.-l (ref.2a) but no N-H stretching band. analogy for the hybrid-ion formulations of anion Pyrazoline-I evolves nitrogen even at room tempera- (IIa) and cation (IIb) [and their subsequent evolu- turet and after 16 days is completely transformed tion to structure (XI) instead of (111)] is to be found into 1,1,2,2-tetracyanocy~lopropane~ (infrared spec- tral evidence). This extreme ease of “pyrolysis” must be related to the presence of the four strong electron- (W27.-7‘CNl2 @4027-7 (CN) *HCI N HC lNle attracting cyano-substituents and to the presence of 1 “preformed” N2 in a 1-pyrazoline (contrast the ‘N’ \ r/ %N’ stability of isomeric pyrazolines reported below). (NC&5-(7!382 Pyrazoline-I (very carefully washed in the dark HC-N \ip with dry benzene to remove all traces of tetra-/ cyanoethylene) slowly dissolves when treated with -HY (W y” dry ether.After 15 minutes filtration and evapora- “&-pN)* tion afford an isomer “pyrazo1ine”-11 m.p. 120” W2?-$XCN2 HC-N (decomp.) which infrared spectrum includes an H2C N N-H band at 3295 cm.-l. “Pyrazo1ine”-11 when 0) \N& ‘N’H <m treated for about 90 minutes with a 5% solution of -Y tetracyanoethylene in dry ether yields after removal of the solvent a third isomer pyrazoline-111 m.p. 126” (decomp.) ; the analytical sample was prepared by washing with benzene; its infrared spectrum also includes an N-H band (at 3333 cm.-l),? Wet ether or dry ether containing a trace of hydrogen chloride isomerises pyrazoline-III back to “pyrazo1ine”-II.Both substances can be kept for several weeks with (NCLC-C(!)* no apparent alteration. Structures (11) and (111) respectively seem to us HC-N the best choice for the two isomeric pyrazolines with an N-H bond. We assign the conventional structure (m (NC),C ‘c * N/H (IV) of 4,4,5,5-tetracyano-2-pyrazoline (111) to pyrazoline- (CN)* fLI because in the 1700-1500 cm.? region of its in the work of Silversmith and Roberts.* The pre- spectrum there is a medium band at 161 8 cm.-l which sence of four cyano-groups explains the ease of iso- can be due to C=N st. and a weak one at 1595 cm.-l merisation of pyrazoline-I by such a weak basic agent assignable to N-H b. ;2b “pyrazo1ine”-11 which shows as ether. The catalytic action of tetracyanoethylene a weak band at 1592 crn.-l (N-H b.) is consequently in the conversion of “pyrazo1ine”-I1 into pyrazoline- given the structure 2,2,3,3-tetracyano-1,5-diazabi-111 should be probably traced to its strong rr-acid cyclo [2,1 ,O]pentane (11).To our knowledge the ~haracter,~ which could justify the formation of an diazabicyclopentane structure has not previously intermediate such as (IV). * Throughout by dry ether is meant freshly distilled sodium-dried ether. -+ Scratching of the substance may induce an explosive decomposition. 1The combined isomerisations explain why ether treatment of pyrazoline-I which has not been carefully washed leads directly to pyrazoline-111. 1 Cf. Scribner Sausen and Prichard J. Org. Chem. 1960,25 1440. Bellamy “The Infrared Spectra of Complex Molecules,” Methuen and Co.Ltd. London 2nd edn. 1958 (a)p. 271 (6) p. 256.. Schmitz and Ohme Chem. Ber. 1962,95 795. Silversmith and Roberts J. Amer. Chem. SOC.,1958 80 4083. Merriefield and Phillips J. Amer. Chenz. Soc. 1958 80 2778. JUNE 1962 During our work it was also realised that “pyra- zo1ine”-11 in dry benzene solution and under normal working conditions was completely isomerised to pyrazoline-111 but that the former could be re-covered unaltered if a benzene solution was kept (60 min.) in the dark. This result can be explained if it is assumed that for a benzene solution light induces an incipient fragmentation of “pyrazo1ine”-I1 with formation of tetracyanoethylene;6 it is tempting to accept that the n-basic properties of benzene play a role in facilitating this fragmentation (“pyrazo1ine”- I1 is stable in ether).Infrared spectra were recorded as KBr pellets. We thank Professor J. Pascual for suggesting this work and for his interest and advice Dr. F. Serratosa for helpful comments and Messrs. DuPont de Nemours and Co. for a gift of tetracyanoethylene. (Received March 12th 1962.) Cf. Rinehart and Van Auken J. Amer. Chem. Soc. 1960 82 5251. The Mechanism of Reaction of Carbonyl Chloride with Alkyl Phosphinates By M. GREENand R. F. HUDSON EUROPEAN INSTITUTE, (CYANAMID RESEARCH GENEVA) INorder to obtain direct information on the relative nucleophilic reactivity of the two kinds of oxygen atoms in esters of quinquevalent phosphorus the reaction between carbonyl chloride and a phos-phinate ester with one of the oxygen atoms labelled with l80 has been investigated.In general the annexed mechanisms are possible. * Cocr + c1-‘C 1 coz + R’Cl Mechanism l(a) can be neglected since the corresponding chloroformate which is stable under the reaction conditions is not formed In order to differentiate between the other possibi- lities benzyl [180]alcohol was preparedl and con- verted into the ester by reaction with methylphenyl- phosphinyl chloride. After reaction with a saturated solution of carbonyl chloride in carbon tetrachloride the phosphinyl chloride was isolated and converted into the corres- ponding phosphinic acid. The lack of I*O exchange in this kind of reaction is now well established and is further substantiated by the present results.Treat- ment with di-p-tolylcarbodi-imide gave the corres- ponding urea which on pyrolysis at 350” in the presence of activated bronze powder gave a quanti- tative yield of carbon dioxide. From water containing 1-70 atom % of lSO carbon dioxide containing 0.833 (=t0.02) atom % was obtained. In view of the fact that half of the l*O is lost in the reaction of the phosphinic acid with the carbodi-hide it follows that the phosphinyl chloride is produced with no change in isotope content (within the experimental error). The reaction therefore pro- ceeds by mechanism (2) with the phosphoryl-oxygen atom as the nucleophilic centre as suggested by Cad~gan.~ The results also discount the possibility of the formation of a cyclic intermediate4 which could be formed from the mixed anhydride viz.R,PO*O-COCl-+ R,P +/”\CO + C1-\/ 0 The reaction of carbonyl chloride with (+)-1- methylheptyl methylphenylphosphinate (az + 4-46’ homogeneous) prepared from (-)-1-methylheptyl alcohol (a -7.6” homogeneous) gave (+)-1- methylheptyl chloride b.p. 55-56”/10 mm. a2 + 29-3O homogeneous (yield 90 %)(Found C1 23.5. Calc. for C8H,,C1 CI 23.8 %) and methylphenyl- phosphinyl chloride. This observation shows that the alkyl chloride is produced by an S,2 displace-ment on a quasiphosphonium intermediate by chloride ions as shown in the above scheme. We thank Dr. E. R. S. Winter of John & E. Sturge Ltd. Birmingham for carrying out the ISOanalyses.(Received April 19th 1962.) Von Doering and Dorfman J. Amer. Chem. SOC.,1953 75 5595. Halmann J. 1959 305. Cadogan J. 1961 3067. Aaron Uyeda Frack and Miller J. Amer. Chem. SOC.,1962 84 617. PROCEEDINGS Tris(tri-p-fluoropheny1phosphine)pla tinum(0) By A. D. ALLENand C. D. COOK (DEPARTMENT TORONTO, OF CHEMISTRY UNIVERSITY OF TORONTO CANADA) IT has recently been reported1 that the triphenyl- phosphine complexes of platinum(0) described by Malatesta and Cariello2 contain hydrogen and should be regarded as hydrides of bivalent platinum. During an investigation into platinum complexes containing substituted triarylphosphines we have prepared an unusually stable compound of this type which appears to be tris(tri-p-fluorophenylphos-phine)platinum(O).Treatment of an ethanolic suspension of cis-di-chlorobis(tri-p -fluorophenylphosphine)platinum(n) with hydrazine hydrate produces a golden-yellow precipitate m.p. 136-139” (decomp.) (Found C 56.2; H 3.2. C,,H,,F,P,Pt requires C 56.7; H 3.2%). This compound is stable in air and can be heated to 65” under a vacuum for several hours without detectable decomposition. In a 2 % solution in benzene the molecular weight is 680 unchanged between 5 minutes and 5 hours. Nuclear magnetic resonance and infrared spectra show no sign of hydrogen bound to platinum. Treatment with iodine in benzene followed by extraction with water and titration with alkali showed Chopoorian Lewis and Nyholm Nature 1961 190 528.Malatesta and Cariello J. 1958 2323. that approximately two equivalents of acid had been produced. This we attribute to the reactions [(C6H1F)3P]3Pt+ 21 [(C6H*F),P12Pt1Z+ (C6H4F)3P1Z followed by (CGH,F),PI + 2H20 -3-(C,H,F)3P(OH)2 + 2HI since similar treatment of the free phosphine also produces two equivalents of acid. In carbon tetrachloride the compound decom- poses without producing the chloroform expected from the reaction of a hydride complex. No tetrakis-derivatives of platinum with tri-p- fluorophenylphosphine or tri-p-chlorophenylphos-phine2 have been isolated. The tendency of these substituted phosphines to accept d-electrons from the metal will be greater than that of triphenylphos- phine. It appears that this stabilises the tri-co- ordinated compound and also discourages addition of a fourth phosphine.We thank Dr. S. S. Danyluk for examination of the nuclear magnetic resonance spectrum. (Received ApriZ 4th 1962.) Xenon Hexafluoroplatinate(v) Xe+[PtF,]- By NEIL BARTLETT (DEPARTMENT THE UNIVERSITY OF CHEMISTRY OF BRITISHCOLUMBIA VANCOUVER 8 B.C. CANADA) A RECENT Communication1 described the compound dioxygenyl hexafluoroplatinate(v) 02+PtF,- which is formed when molecular oxygen is oxidised by platinum hexafluoride vapour. Since the first ionisa-tion potential of molecular oxygen,2 12.2 ev is com- parable with that of xenm,2 12.13 ev it appeared that xenon might also be oxidised by the hexa- fluoride. Tensimetric titration of xenon (AIRCO “Reagent Grade”) with platinum hexafluoride has proved the existence of a 1:1 compound XePtF,.This is an orange-yellow solid which is insoluble in carbon tetrachloride and has a negligible vapour pressure at room temperature. It sublimes in a vacuum when heated and the sublimate when treated with water vapour rapidly hydrolyses xenon and oxygen being evolved and hydrated platinum dioxide deposited 2XePtF6+ 6H20-f 2Xe + 0,+ 2Pt0 + 12HF The composition of the evolved gas was established by mass-spectrometric analysis. Although inert-gas clathrates have been described this compound is believed to be the first xenon charge-transfer compound which is stable at room temperatures. Lattice-energy calculations for the xenon compound by means of Kapustinskii’s equa- tion give a value -110 kcal.mole-l which is only 10 kcal. mole-l smaller than that calculated for the dioxygenyl compound. These values indicate that if the compounds are ionic the electron affinity of the platinum hexafluoride must have a minimum value of 170 kcal. mole-l. The author thanks Dr. David Frost for mass spectrometric analyses and the National Research Council Ottawa and the Research Corporation for financial support (Received May 4th1962.) Bartlett and Lohmann Prac. Gem. Soc. 1962 115. Field and Franklin “Electron Impact Phenomena,” Academic Press Tnc. New York 1957 pp. 114-1 16. Kapustinskii Quart. Rev.,1956 10 284. JUNE 1962 219 ~~~~~ ~~ Fourteen-membered Hydrogen-bonded Dimers of Some meta-Substituted Phenols By F.A. L. ATand J. M. MUCHOWSKI (DEPARTMENTOF CHEMISTRY,UNIVERSITYOF OTTAWA,OTTAWA2 CANADA) ALTHOUGH phenols are known to associate in non- polar media by hydrogen-bonding the aggregates so formed have no great stabi1ity.l We have now found that phenols with meta-substituents such as methoxy- carbonyl or nitro-groups form unexpectedly stable dimers in non-polar solvents. Infrared and nuclear magnetic resonance studies indicate that the dimers contain two hydrogen bonds in a geometrically favourable fourteen-membered ring (e.g.,I). The effect was discovered during analysis of the nuclear magnetic resonance spectrum (60 Mc./sec.) of methyl 3-hydroxy-4-isopropylbenzoate(11) in carbon tetrachloride solution (0.27~).The bands of the aromatic protons were assigned (see Figure) on the basis of the expected coupling constants (J = 6-8 J = 1.5-2 J, < 1 c./sec.) and analysis of the spectrum as an ABX system.However the rela- tive chemical shifts thus found for the aromatic pro- tons were unexpected. From the effects of substitu- ents,2 it was expected that H-2 and H-6 would have very similar chemical shifts with H-2 at perhaps very slightly higher field than H-6 whereas the assign- ments made on the basis of coupling constants placed H-2 at much lower field than H-6. This anomaly was resolved when it was found that the chemical shift of H-2 was concentration-dependent although only at such extremely low con- centrations that the limit of the dilution shift could not be observed.A more satisfactory way of break- ing the self-association was by addition of acetone or methanol. The addition of about one molar propor- tion of methanol (concn. ca. 1% v/v) resulted (see Figure) in a large upfield shift in the position of H-2 with little shift in H-6 and practically no shift in H-5. The phenolic hydroxyl proton became broad because of exchange with the methanol-hydroxyl proton and was shifted to low field because of the basicity of methanol. With the addition of a little more methanol H-2 became practically coincident with H-6. These effects are most simply explained if two molecules of the monomer are involved in a hydrogen-bonded dimer of structure (I). In this each H-2 experiences the ring-current3 effect of two benzene rings whereas in the monomer (or approxi- mately so in a non-cyclic dimer) H-2 is affected by only one benzene ring.Whether structure (I) is H2 I n I I I I II I 2.x) 2.62 2.88 2-52 Nuclear magnetic resonance spectra of methyl 3-hydroxy-4-isopropylbenzoate.Top in carbon tetra- chloride. Bottom in carbon tetrachloride containing 1% by volume of methanol. The chemical shifts in both cases are in p.p.m. with internal tetramethylsilane at 10.00. The OH bands were located by O-deutera- tion. The high-field regions of the spectra are not shown. ,OMe planar or not the ring-current effect is of the required magnitude and direction. The infrared spectrum of the ester was studied in carefully dried carbon tetrachloride solution at a path length of 5 cm.Except at concentrations below 104~,two bands (3455 and 3613 cm.-l) were ob-served. By application of the treatment4 of Liddel and Becker the equilibrium constant (K = [dimerll Pimentel and McClellan “The Hydrogen Bond,” Freeman and Co.,London 1960 p. 377. Garnett Henderson Sollich and Tiers Tetrahedron Letters 1961 516. Pople Schneider and Bernstein “High-resolution Nuclear Magnetic Resonance,” McGraw-Hill New York 1959 p. 180. Liddel and Becker Spectrochim. Acta 1958. 10,70. 220 PROCEEDINGS [m~nomer]~) was calculated to be 463 & 10 mole/l. netic resonance spectra of these compounds were too and was constant over a ten-fold concentration complicated for simple analysis although marked range.By comparison,l K for phenol in carbon changes were observed on addition of small amounts tetrachloride has the value of about 1 mole/l. of methanol. For methyl rn-hydroxybenzoate K was equal to 544 f 10 mole/l. In the case of m-nitrophenol This work was supported by the National Research hydrogen bonding also persisted to low concentra- Council of Canada. tions but K was not calculated. The nuclear mag-(Received April 5th 1962.) Ion-pair Formation in Aqueous Solutions of Organic Electrolytes By A. PACKTER and M. DONBROW OF PHARMACY COLLEGE AND TECHNOLOGY, (SCHOOL CHELSEA OF SCIENCE LONDON) SEVERAL workers1 have reported marked interaction equation.2 However the (l-c plots for the salts of between long-chain aliphatic ammonium cations and naphthalene-1-,anthraquinone-1- and azobenzene-4- arenesulphonate anions but the phenomenon has not sulphonic acid deviated significantly from the been systematically studied.theoretical curves. (The salts of anthracene-l-sul- The alkyltrimethylammonium salts of some simple phonic acid did not give a suitable range of con-arenesalphonic acids were prepared in aqueous solu- centrations.) Pronounced ion-pair formation was tion by neutralisation of the acid by the appropriate indicated. base and the conductivities were measured by the The degree of dissociation (a)at various salt usual techniques over the concentration range 1 0-4~ concentrations was obtained from the Onsager- up to the solubility limit at 25" (10-200 x lo-%).Falkenhagen equation :3 The results are presented in the Figures. In the A = (1 -(B2 + B1(l~)(~c)o*s/(l + KCZ) benzenesulphonic acid series only the decyltri-methylammonium salt gave a (l-c plot which devi- (In these preliminary calculations dimmisation ated from the theoretical Onsager-Falkenhagen effects have been neglected.) Curves Ar.SO,.NMe,R I K -AG"R/T R (.$I (g.-ions (kcal. per per 1.) g. ion.) Bun 4.2 >0.3 <1 4.2 >0.3 <1 c6H13 C8H17 4-2 >0-3 <1 C10H21 4-2 0.140 1.8 Bun 5-2 >0.3 (1 C&,3 6.6 >0.3 <I C8H17 7.2 0.140 1.8 ClOH21 7.2 0.049 2.7 Bun 5-2 >0.3 <1 C6H13 6.6 0.103 2.3 8-0 0.040 3-2 C8H17 C10H21 9.4 0.0038 5-7 Bun 5.2 0.182 1.7 GH13 6.6 0.051 2.9 8.0 0*0098 4-6 C8H17 ClOH21 9-4 0.00024 8-4 Anthraquinone-1-sulphonate.t Azobenzene-4-sulphonate. Colichman J. Amer. Chern. Soc. 1950 72 1834; Mukherjee and Mysels ibid. 1955 77 2937. JUNE 1962 I I I I 4d 20 40 60 80 10~~ (9 -ions per I) I 45p( I I I 40 20 40 60 80 104c (9.-ions per 1) Plots of conductivity against concentration. Full lines are experimental broken lines are calculated. Numerals key the substances listed in the Table. 221 I I l 1 I 20 40 60 80 104c (9.-ions per 1) Dissociation constants (K)for the equilibria RMe3N+.-O3S*Ar+ RMe,N+ + Ar-SO3-were then calculated. Average K and -AGO values are summarised in the Table together with values of I the length of “overlapping” organic sections3 common to the two ions of each salt (as measured from Courtauld models).Generally 1 is determined by the long axis of the organic section of the smaller ion. The -AGO values increase with the length of “overlapping” organic portions common to the cation and anion of the salt and with the degree of “c~acervation”~ of the whole salt from the aqueous phase. The association is evidently caused predominately bY interaction between the organic Portions of the ions. (Received March 29th 1962.) * Robinson and Stokes “Electrolyte Solutions,” Butterworths 1959 Chapter 7 p. 144. Coates and Rigg Trans. Faraday SOC.,1961 57 1637. Higuchi J. Amer. Pharm. Assoc. 1957 46,21. Intermolecular Charge-transfer Bonds in rn-Bromonitrobenzene By T. L.CHARLTON and J. TROTTER OF CHEMISTRY OF BRITISH VANCOWER8, (DEPARTMENT UNIVERSITY COLUMBIA B.C. CANADA) MUCH attention has been devoted to complexes between halogen molecules with a halogen atom act- ing as an electron acceptor and donor molecules possessing lone pairs or n-electrons; in these there are short intermolecular distances indicative of charge-transfer b0nds.l We have now found a Hassel and Ramming Quart. Rev. 1962 16 1. similar close approach in an aromatic halogen deriva- tive rn-bromonitrobenzene. Crystals of rn-bromonitrobenzene are ortho-rhombic with four molecules in a unit cell of dimen- sions a = 5-92 b = 21.52 c = 5-34 A space group Pbn2,; the structure has been determined by two- dimensional X-ray methods.The molecule is planar within the limits of experimental error. There is an unusually short intermolecular contact involving a bromine atom and an aromatic ring; the bromine atom of each molecule is situated exactly above the midpoint of and at a distance of 3-30 A from the C1-C6 bond of a molecule related to the first by the C I glide plane operation n the C-Brq-C angle being 169". The Br-C1 and Br-C contacts are 3-38 .$,in comparison with a van der Waals separation of 3.65 A and are thus indicative of charge-transfer bonds which join the molecules together in chains along [loll. All the other intermolecular contacts are equal to or greater than the normal van der Waals Smith and Rundle J. Amer. Chem. SOC.,1958 80 5075. PROCEEDINGS separations; the perpendicular distance between the planes of molecules related by translation c is 3-40A close to the spacing in graphite.The bromine-ring separation is very similar to the distance in the Br,-benzene complex (3-36A) but in the latter each bromine atom is symmetrically situ- ated with respect to all the C-C bonds of a particular aromatic ring.l The situation in m-bromonitro-benzene is quite different and more closely related to that in the benzene-AgC10 complex where there is interaction between silver ions and particular C-C bonds. The authors thank the National Research Council of Canada and the President's Research Fund Uni- versity of British Columbia for financial support. (Received April 24th 1962.) The Structure of Gedunin By Miss S.A. SUTHERLAND ROBERTSON G. A. SIM,and J. MONTEATH DEPARTMENT GLASGOW, (CHEMISTRY THEUNIVERSITY W.2) HALSALLand his co-workers1 isolated from the heartwood of the West African timber Entandro-phragma angolense a crystalline lactone C28H340, which they named gedunin; analogies with the chem- istry of lirnonin led them to propose3 (I) as the likely structure. We have carried out an X-ray analysis of dihydrogedun-3P-yl iodoacetate kindly supplied by Drs. T. J. King and F. E. King who isolated dihydro- gedunin from the heartwood of Guarea thompsonii and our X-ray results establish conclusively the con- stitution and relative stereochemistry shown in (10. Since gedunin is an a$-unsaturated ketone3 our results also establish that gedunin is correctly formu- lated as (I).Gedunin is clearly a triterpenoid of the euphol* type intermediate in oxidation pattern between lim~nin~~~ (HI) and cedrelone6 (IV). Dihydrogedun-3/3-yl iodoacetate crystallises in the orthorhombic system space group P2,212, with four molecules of C,,H3,108 in a unit cell of dimen- sions a =21-52,b = 10.57 c = 12.96hA. In all 1201 independent structure amplitudes were measured. The crystal and hence molecular structure was elucidated by Fourier methods. The value of R is now 22 % and refinement is continuing. O ICH,CO Ow OAc CW 0 OH (IV) We are indebted to Miss J. A. Spittal for assistance in the early stages of the analysis. (Received April 1 1 th 1962.) Akisanya Bevan Hirst Halsall and Taylor J.1960 3827. Barton Pradhan Sternhell and Templeton J. 1961,255; Arigoni Barton Corey and Jeger in collaboration with Cagliotti Dev Ferini Glazier Melera Pradhan Schaffner Sternhell Templeton and Tobinaga Experientia 1960, 16 41. Akisanya Bevan Halsall Powell and Taylor J. 1961 3705. Barton McGhie Pradhan and Knight Chem. and Ind. 1954 1325; J. 1955 876. Amott Davie Robertson Sim and Watson Experientia 1960 16 49; J. 1961 4183. Grant Hamilton Hamor Hodges McGeachin Raphael Robertson and Sim Proc. Chem. Soc. 1961,444. JUNE 1962 223 ~~ ~~~~ ~ ~ ~~~ The Rates of Some Reactions of Hydrogen Atoms in Water at 25"c By F. S. DAINTON and S. A. SILLS (DEPARTMENT CHEMISTRY LEEDS OF PHYSICAL THE UNIVERSITY 2) WHENan aqueous solution of potassium iodide for which 3.5 < pH < 11 and containing nitrous oxide is irradiated by light of wavelength 2537 A the following reactions occur (* and $ denote photo- excited ions) I-aq + hv + * -+ * t 01 1 $ TI-+ H + OH-+ 1,-2 H + N,O 4 N,+ OH Slow 3 HO + I-+ HO-+ I Fast 4 I + I-+ I,-Fast 5 21 -+ I + 21-or I,-+ I-6 H + I,-+ H+ + 21-Consequently $(N2) = $(I2) increases with concen- tration of nitrous oxide and potassium iodide to a limiting value of 0.165 which is the maximum attain- able yield of hydrogen atoms as a result of the fist two processes and k,/k can be evaluated from the experimental results.At low [N20] the rate of re-action tends to become proportional to (&[N20])213 and the rotating-sector technique can be used to obtain the values of k2,k, and k4shown in the Table.Change of pH below 3.5 and above 11 has the dramatic effects shown in the Figure. The sharp decline in +(I2) the constancy of 4(N2) and the appearance of oxygen in yields such that +(N2)= $(I2) + 2$(02) = 0.16 when the pH is increased above pH 11 are caused by a simple competition between reaction 3 and reaction 7 the 0-emerging from the latter reaction destroying the intermediate 7 HO + OH-+ 0-aq 12-in a reaction the stoicheiometry of which is given by expression 8. The dependence of $(I2) and $(O,) 8 0-aq + I,-4 40 + 21-on pH leads to the value of k,lk7 shown in the Table. The striking decrease of $(N2) the increase of 4(H2) from zero and the minimum in $(I2) which occur when the pH is decreased below 3.5 are due to two causes.First Hf competes with N20 for H forming H2+ in reaction 9 which always oxidises Data concerning rate processes in the photolysis of KI solutions Limiting & at high [KI] k2(H + N2O +N2 + OH) kQ(H+ H+ -+ H2+) k,(H + 12-+H+ + 213 k,(212-+ I2 + 21- or I,-+ I-) k,(OH + I--f OH-+ I)/R7(OH + OH-+ 0-aq) 0.16 (1.25 i0.5) x lo4 1. mole-l sec.-l (2.6 & 1.1) x lo3I. mole-l sec.-l (1.8 f0.8) x lo7 1. mole-l sec.-l (2-2 f0.8) x lo61. mole-l sec.-l (4.5 & 0-3) PW The variation of #(N2) = 0;+(I2) = a 4(H2) = and #(02)= () with pH at 25"~.KI 0.276~; L= PNlo= 310 mm. Hg. 9 H + H++ H$ iodide according to expression 10.Consequently 10 Ha++ I--+ H + I Fast over this pH range #(I2) = +(H,) + &NZ and #(H&b(Na = k [H+]/k,[N,O]. Secondly small concentrations of H+ interfere with reaction (l) so that & decreases as the pH changes from 3.0 to 1-2 but larger concentrations of H+ facilitate the forma- tion of H presumably involving a reaction which PROCEEDINGS may be written according to equation 11 so that & increases as the pH is further reduced. 11 *+H++H+I The numerical values given in the Table permit prediction of values of +(I2) for certain deaerated N,O-free solutions which are in agreement with values which we have measured. We are greatly indebted to the Distillers Company Ltd. for generous financial help in this work.(Received March 8th 1962.) Perfluoroalkyl-bismuthand -thallium Compounds By T. N. BELL B. J. PULLMAN, and B. 0.WEST (UNIVERSITY ADELAIDE, OF ADELAIDE SOUTHAUSTRALIA) REACTION of trifluoroiodomethane with alkyl deriva- tives of phosphorus,l arsenic antimony,l tin,2p3 and leads at moderate temperatures yields mixed alkyl- perfluoroalkyl compounds of these elements. In the reactions with trialkyl-phosphorus -arsenic and -antimony the appropriate tetra-alkyl-'onium iodide is also formed. It has now been found that trimethyl- bismuth reacts completely in the presence of an ex- cess of trifluoroiodomethane at 100"to give dimethyl- trifluoromethylbismuth (82 % conversion) methyl- bistrifluoromethylbismuth (1 8 % conversion) and methyl iodide.The products were separated by vapour-phase chromatography (di-isodecyl phthalate as column packing; and nitrogen as carrier gas at 70"). No evidence for the production of tristrifluoro-methylbismuth was obtained. Methylbistrifluoro-methylbismuth is formed readily when dimethyltri- fluoromethylbismuth is heated with an excess of trifluoroiodomethane at 100" but does not react with further trifluoroiodomethane in a further 48 hours at this temperature. The two alkylperfluoroalkylbismuth compounds are oxidised readily on exposure to air and ignite spontaneously under certain conditions. Their vapours are lachrymatory. Both compounds are rapidly hydrolysed by S~-sodium hydroxide at room temperature fluoroform being produced quantitatively.Dilute acid also hydrolyses the com- pounds but slowly liberating fluoroform. The boil- ing points are BiMe,-CF 121"/760 mm.; BiMe(CF,) 132"/760 mm. (determined by the iso- teniscopic method). There is thus a rise in boiling point accompanying substitution of CF for CH in Haszeldine and West. J.. 1956. 3631. Clark and Willis J. kmer. Chem. Soc. 1960 82 1888. BiMe (b.p. 110"/760mm.) which is contrary to the cases of the corresponding phosphorus arsenic and antimony compounds4 where the boiling points rise with the replacement of one CH group in (CHa,M and then fall through CH,(CF3)2M to (CF,),M. The observed decrease in decomposition temperature of (CF,),M compounds from phosphorus to anti-mony5y6 may suggest a high degree of thermal instability for tristrifluoromethylbismuth.Iodine reacts violently with each of the perfluoro- alkylbismuth compounds at room temperature but smoothly at -26". Methyl iodide and trifluoroiodo- methane are liberated and a mixture of methyltri- fluoromethylbismuth iodides remains. This observa- tion is to be compared with that reported by earlier worker^^?^ who find that alkyl groups are split preferentially from the alkylperfluoroalkyl-tin and -lead compounds by halogens. Attempts to prepare thallium derivatives by the reaction of trimethylthallium and trifluoroiodo-methane or heptafluoroiodopropane or by the reaction of methyl-lithium with thallous iodide in the presence of heptafluoroiodopropane (cf. Gilman') failed.In the former case dimethylthallium fluoride is produced even at -78"; in the latter apart from a 10% conversion of thallous iodide into trirnethyl- thallium the reactants can be recovered unchanged. We are grateful to the C.S.I.R.O. for a Post-Graduate Studentship to B.J.P. (Received April 2nd 1962.) Kaesz Phillips and Stone J. Amer. Chem. Soc. 1960 82 6228. * Haszeldine and West J. 1956 3880. Bennett Emeleus and Haszeldine J. 1953 1565. Dale Emelkus Haszeldine and Moss J. 1957 3708. ' Gilman and Jones J. Amer. Chem. SOC., 1946 68 517. JUNE 1962 225 The Light-induced Addition of Formamide to Esters of Maleic Fumaric and Acetylenedicarboxylic Acid By D. ELAD SIEFF INSTITUTE,THEWEIZMANN OF SCIENCE, (DANIEL RESEARCH INSTITUTE REHOVOTH, ISRAEL) THE light-induced addition of formamides to ester (I) (25 %) which on alkaline hydrolysis yielded terminal olefins has been reported by US.^ We have the known tricarboxylic acid.now found a similar addition to ap-conjugated Similarly irradiation of a solution of dimethyl ethylenic and acetylenic bonds. Two mol. of acetylenedicarboxylate (5.5 g.) in formamide (1 35 8.) formamide add to the acetylenic bond.2 gave the diamide (11) (25 %); use of diethyl acetylene- dicarboxylate gave the analogue (111) (30 %). Both EtO,C.CH:CH.CO,Et + H-CO-NH,-+ Et02C-CH2.CH(C0,Et).C0.NH2 (I) products on hydrolysis yielded ethane-1 ,1,2,2-tetra-R0,C.C i C*CO,R + 2H.C0.NH24 carboxylic acid. NH,*CO-CH(C02R)CH (CO,R)*CO*NH (11; R = Me) (111; R = Et) We are indebted to Professor F.Sondheimer for Irradiation3 of a solution of diethyl maleate or his interest and to Dr. S. Pinchas for the infrared fumarate (8.5 g.) in formamide (135 g.) with the spectral measurements. exclusion of oxygen at room temperature gave the (Received May lsf 1962.) Elad Chem. and Ind. 1962 362. Cf. Schlubach Franzen and Dahl Annalen 1954 587 124; Wiley and Harrell J. Org. Chem. 1960 25 903. Hanau immersion quartz lamps Q 81. Photochemistry of Hecogenin Derivatives :A Novel Cyclisation Reaction of c-Seco-steroids By PETER W. MCMEEKIN A. WILLIAMS BLADON and IVOR DEPARTMENT OF SCIENCE GLASGOW, (CHEMISTRY ROYALCOLLEGE AND TECHNOLOGY C. 1) THE initial product of ultraviolet irradiation of hecogenin acetate by standard methods4 into 3p- hecogenin acetate (I; X = p-OAc,a-H R = H) in acetoxy- 14 a-hydroxy-5 a-pregn-16-ene-12,20- dione dioxan solution was 3~-acetoxy-12-oxo-12,13-seco-(111) Am,, 228.5 mp (E 7320) [cf.3/3-acetoxy-5a- 13-ene (lumihecogenin acetate) (I1; ~regn-l6-ene-12,20-dione,~ 227-230 mp (E 5 a,25~-spirost-A,,, A,,,. 204 mp (E 4800) vmax. SSlO)] and by formation of the spirolactone (IV) on R = Ac R’= CHO) (in KCl) 2740 (CHO) 1739 (OAc) 1709 (CHO), 1240 cm.-l (OAc). The presence of the aldehyde group was confirmed by the barely resolved triplet in the nuclear magnetic resonance spectrum at T 0.85. By reduction with lithium aluminium hydride lumi- hecogenin acetate was converted into the known1s2 anhydrohecolyl alcohol (11; R = H R’= CH,.OH). RO Oxidation of lumihecogenin acetate with chrom- ium trioxide in aqueous sulphuric acid acetone3 gave 14a-hydroxyhecogenin acetate (I; X = p-OAc a-H R = OH) vmax.(in CCl,) 3550 (OH) 1739 (OAC) 1706 (12-C=0) 1250 cm.-l (OAc). This is a general reaction oxidation of anhydrohecolyl alcohol giving the corresponding 14 a-hydroxyhecogenone (I; X = 0,R =OH). In these compounds the hydroxyl groups cannot be acetylated and are therefore tertiary. The ultraviolet irradiation. The spiran (IV) had no ultra- presence of‘a hydroxyl group at position 14 (and not violet absorption in the 205 mp region and no 17)was indicated by the conversion of 14a-hydroxy-hydroxyl absorption in the infrared spectrum. On Rothman Wall and Eddy J. Amer. Chem. SOC.,1954 76 527. Bladon and McMeekin J.1961 3504. Bladon Fabian Henbest Koch and Wood J. 1951 2402. Cameron Evans Hamlet Hunt Jones and Long J. 1955 2807. Wagner Moore and Forker J. Amer. Chem. SOC. 1950,72 1856. PROCEEDINGS reduction with lithium aluminium hydride and treat- ment of the product with perchloric acid in methanol it yielded anhydrohecolyl alcohol (11; R = H R’ = CH,*OH). &\ -LO HO-f=&+ Ht OH 0 f-p 1 HO-7-OH OH I t (I ; R-W) These reactions show that in anhydrohecolyi alcohol and related compounds,l the double bond the position of which has hitherto been uncertain,* is in the 13(14)- and not the 13(17)-position. The novel oxidation process is envisaged as proceeding by the mechanism shown (cf.Waters6). The photochem- ical transformations are in line with currently held theories (cf. Mayo’). The authors thank Dr. A. Melera (Varian A.G. Zurich) for the nuclear magnetic resonance spectrum and Dr. C. L. Hewett Organon Laboratories Ltd. Newhouse for a gift a hecogenin acetate and loan of photochemical apparatus. ~ (Received April 25th 1962.) (I Waters Quart. Rev. 1958 12,277. ‘.Mayo “Advances in Organic Chemistry,” Interscience Publ. Inc. New York 1960 Vol. 11 p. 367; Mayo and Reid Quart. Rev. 1961 15 393. * In our earlier paper (ref. 2) we anticipated the presently disclosed findings on the position of the double bond. The Catalytic Action of Anionic Catalysts By ALWYNG.EVANS E. D. OWEN,and B. J. TABNER J. C. EVANS DEPARTMENT COLLEGE, (CHEMISTRY UNIVERSITY CARDIFF) and J.E. BEWIT LTD. THORNTON CHESTER) (“SHELL”RESEARCH RESEARCHCENTRE BUTYL-LITHIUM adds to 1 1 -diphenylethyIene form- ing the ion pair Bu-CH,.CPh,-Lif in benzene but does not add to 1,1,3,3-tetraphenylbut-l-eneor tetraphenylethylene owing we believe to the steric hindrance of the phenyl gr0ups.l On mixing the tetraphenylbutene with sodium naphthalene in tetrahydrofuran the green colour of the sodium naphthalene was immediately replaced by a red colour showing that the electron had been trans- ferred from the naphthalene to the olefh2 We now find the same behaviour for tetraphenylethylene. We have also brought tetrahydrofuran solutions of these two olehs into brief contact with a sodium film and then filtered the mixtures.Electron-spin resonance spectra (some of which are given in the Figure) and visible spectra of both types of solution have been measured. The electron-spin resonance spectra show that radicals are present in these solutions and that their concentration increases with decrease in temperature. At room temperature the concentration of radicals is greater when tetraphenylethylene is used than when the tetraphenylbutene is used. The visible spectra at room temperature show a peak at 479 mp and a shoulder at 432 mp when the latter olefin is used and a peak at 466 mp and a shoulder at 700 mp when the Evans and George J. 1961,4753. Evans Evans and Owen PPOC.Chem. SOC.,1961 339. former is used; with decrease in temperature the heights of the peaks at 479 and 466 mp decrease and the heights of the shoulders 432 and 700rnp increase.[The spectrum of an unstable solution from the tetraphenylbutene (see ref. 2) has a peak at 432 and a shoulder at 479 mp.] Thus although the Bu- ion cannot add to either of these olefins an electron can. The radical ion formed by addition of an electron to the olefin can- not dimerise because of steric hindrance (even a Bu- ion cannot add on to these oleks) and to explain the change of radical concentration with temperature we postulate the disproportionation reaction From our results we conclude that equilibrium (1) lies further to the right for the butene than for the 99 99 (8) (A) CH;CPhiCH-CPh Ph,C-CFh JUNE1962 ethylene and that reaction (1 a) is endothermic.Since the absorptions at 479 and 466 mp decrease with I I I I I I I I 170 60 50 40 70 60 50 40 30 (A) Electron-spin resonance spectrum of a solution at room temperature obtained by allowing 1.92 ml. of a tetrahydrofuran solution of Ph,C:CPh (2.05 x 1W2 mole to come into brief contact with a sodium film,filtering and then adding 5.92 ml. of a tetrahydrofuran solution of Ph,C :CPh (8-6 x mole I.-l). (B) Same as A at -100”. decrease in temperature and those at 432 and 700 mp increase with decrease in temperature and with increase in radical concentration we attribute these peaks to the species (A-D) as shown respect- ively. If to obtain an estimate of the extinction coefficient we assume that equilibrium (1) lies com-pletely to the right we obtain E = 1.5 x loP for (A) and 1-8 x loP for (B) [compare E = 1.6 x 104 for the monoion (E) absorption peak 428 mpl].When solutions formed by mixing sodium naphthalene with olefm in 1:l molar ratio were treated with distilled water practically all the olefin was recovered unchanged. The predominant effect of the water is thus to remove the electron from the olefin. The probable reason for this is steric opposi- tion to attachment of groups to these olefins as shown by the inability of the Bu-ion to add to either of them. We thank D.S.I.R. for a Research Studentship (to J.C.E.) University of Wales for a Research Student- ship (to B.J.T.) and “Shell” Research Ltd.for the use of the electron-spin resonance machine. (Received April 18th 1962.) The Dissociation Energy of the NH Radial By M. A. A. CLYNEand B. A. THRU~ OF PHYSICAL UNIVERSITY (DEPARTMENT CHEMISTRY OF CAMBRIDGE) THERE appears to be very little direct thermochemical evidence on the dissociation energy of the NH radical and Gaydon’sl recommended value of 85f 10 kcal./mole is based on a linear Birge-Sponer extra- polation of the ground state of NH to a limit at 92 kcal./mole.2 We have recently shown that the bond-dissociation energy of nitroxyl D(H-NO) = 48.6 k~al./mole,~ giving dHfo(HNO)g = 23.8 kcal./mole at 298”~. HNO is isoelectronic with 0 and with di-imide for which Foner and Hudson4 have determined dHf0(N2H2) = 48.7 f5 kcal./mole at 298”~.If using Gaydon’s value of D(N-H) as a reference point we put D(N-H) = (85 -x) kcal./mole we obtain D(HN=O) = (114 + x) kcal./mole and D(HN=NH) = (109 + 2x & 5) kcal./mole which may be compared with D(O=O) = 118 kcal./mole. These bond energies should be fairly similar since the species concerned are isoelectronic and all have the same nuclear charge on each side of the bond concerned. For the related group of compounds with two fewer or with two more electrons one obtains D(NrN) = 225 D(H,N-NHJ = 60 f3 kcal./mole D(HC=N) = 223.5 D(H2N-OH) = 48 & 2 kcal./mole D(HC_CH) = 228 D(H0-OH) = 5 1 kcal./mole. The experimental results for the heats of formation therefore support a value of D(N-H) = 81 f 3 kcal./mole in excellent agreement with the value of 83 kcal./mole recently calculated by Companion and Ellison5 using a semi-empirical valence-bond treat- ment.Our value for D(N-H) together with D(NH,-H) = 104 & 2 kcal./mole6 gives D(NH-H) = 95 4 kcal./mole. (Received May 3rd 1962.) Gaydon “Dissociation Energies,” Chapman and Hall London 1953. Pannetier and Gaydon J. Chim. phys. 1951 48 221. Clyne and Thrush Trans. I3arada.y SOC.,1961 57 1305. Discuss. Faraday Soc. 1952 in the Press. Foner and Hudson J. Chein. Phys. 1958 28 719. Companion and Ellison J. Chem. Phys. 1960 32 1132. Szwarc Proc. Roy. SOC., 1949 A 198 267. PROCEEDINGS Substituent Effects of the -NH3+and the -Me,+ Group in Nitration BRICKMAN JOHNSON, By MADELINE SHEENA and J.H. RIDD (WILLIAM RAMSAY AND RALPH FORSTER LABORATORIES UNIVERSITY LONDON, COLLEGE W.C. 1) THEdirect comparison of the substituent effects of x 1013 mole-l sec.-l 1.) considerably exceeds that the -NH$ and the -NMe$ group in nitration is calculated from the encounter rate of the reactants complicated by preliminary proton loss from the (-lo9 mole-l sec.-l 1.). Thus from the tabulated -NH3+ group leading to substitution in the neutral rate coefficients the reactivity of the para-position in amino-compound. The contribution of this reaction the anilinium ion appears to exceed slightly that of path can be determined from a kinetic study of the one of the meta-positions. nitration as a function of acidity. Such results for the Nitration of the trimethylphenylammonium ion is nitration of aniline in concentrated sulphuric acid at usually considered to give only meta-substitution,2 25" are tabulated below in terms of the stoicheio- but from the infrared spectrum of the product and Ph*NH,+ Ph.NMe,+ A r -%SO* (%I 89.4 92.4 94.8 96.4 98.0 98.0 k (mole-l sec.-l 1.) 1-36 0.945 0.590 0.454 0.259 0.0013 k (mole-l sec-l l.)* 0-62 0.532 0.390 0.313 0.210 0.0055 * Calc.for a single meta-position. metric second-order rate coefficients k and k for from the ultraviolet spectrum of the product after substitution at the para-position and at one of the demethylation we estimate that about 11 % of para- meta-positions. In concentrations of sulphuric acid substitution occurs The rate coefficients tabulated above 93 % the amount of ortho-substitution is very for this substrate are calculated from this product small (< 3%).meta-Substitution should be limited analysis and from the kinetic study of Gillespie and to reaction through the anilinium ion and as might N0rton.l It appears that the replacement of the be expected the decrease in its rate from 90 % to 98 % -NMe,+ group by the -NH,+ group increases the sulphuric acid is very similar to that reported1 for rate of meta-substitution by a factor of 38 and the the nitration of the trimethylphenylammonium ion rate of para-substitution by a factor of about 200. and attributed to a medium effect. However the rate The reason for this difference in the electron- profile for the para-substitution has a similar form; donating effects of these groups is not yet clear.the ratio k,/k changes by less than a factor of two Possible interpretations include the effects of N-H over this range of acidity. Since the corresponding hyperc~njugation~ and of hydrogen bonding with change in h is by a factor of 14 it is improbable that the medium;4 it may also be useful to consider the reaction through the free amine contributes signi- mobility of the N-H protons in the transition state. ficantly to the nitration in 98% sulphuric acid. This We hope that a current study of related compounds conclusion is supported by the overall rate of para-and of medium effects will help to distinguish substitution at this acidity; if a bimolecular rate between these possibilities.coefficient is calculated by using the expected con- One of us (M.B.) thanks the D.S.I.R. for a main- centration of the free arnine the value obtained (2.5 tenance award. (Received May lst 1962.) Gillespie and Norton J. 1953 971. a Vorlander and Siebert Ber. 1919,52 294. de la Mare Tetrahedron 1959 5 107. Willi 2.phys. Chem. (Frankfurt) 1961,27 233. Biosynthesis of Berberine By IAND. SPENSER and J. R. GEAR (DEPARTMENT UNIVERSITY HAMILTON, OF CHEMISTRY MCMASTER ONTARIO CANADA) RECENTLYwe reported the isolation of labelled dopamine2 had been administered. Stepwise degrada- hydrastine and berberine from plants of Hydrastis tion of the radio-hydrastine demonstrated that canadensis L. to which [14C]tyr~~ine1~2 and [14C]- tyrosine1s2 and dopamine2 both served as specific Gear and Spenser Nature 1961 191,1393.Spenser and Gear J. Amer. Chem. SOC.,1962,84 1059. JUNE 1962 precursors of this phthalide-isoquinoline alkaloid. We have now completed the systematic degrada- tion of radio-berberine (specific activity* 10.5 x 104 counts min.-l mole-l) obtained from plants which had grown for 17 days in the presence of DL-[2J4C]-tyrosine (I) (total activity 8-68 x lo7 counts min.-l specific activity 5.15 x lo8 counts min.-l mmole-l). As predicted by biogenetic hypothesis,3 radioactivity was confined to carbon atoms 1 and 3 of the berberine nucleus.7 Berberine (11) isolated from the plants as the BH hyde (VI) and hydrastinine (V) which retained all the activity of the original berberine.Hydrastinine degraded as previously described,l gave the bromide (VII) (carbon atoms 3-1 1 of berberine) and carbon dioxide (carbon atom J) which was assayed after conversion into benzoic acid. Oxidation of the bromide (VII) gave 6-bromopiperonaldehyde (VIII) (carbon atoms 4-11) which was isolated as the acetone derivative. The relative specific activities of berberine and its degradation products are summarised in the Chart. CH=CHPh H2c\o \ Br :B‘ P~CH?H H2c (Vlllj (2) {Vll) (49 (5 4 (v) (97) OH ivt) (1) * Denotes radiocarbon. Relative specific activities (berberine = 100) are given in parentheses. hydrochloride was converted into hydrastinine (V) by a modification of the method originated by Freund and Fleischer? A Grignard reaction with benzyl chloride gave benzyldihydroberberine which was reduced with sodium borohydride to benzyl-tetrahydroberberine (111).Conversion into the methiodide and Hofmann degradation gave de-N- methyltetrahydrostyrylberberine (IV). Oxidation of this led to inactive 3,4-dimethoxy-2-styrylbenzalde-The degradation sequence shows that tyrosine serves as a specific precursor of berberine and that two tyrosine units participate in the biosynthesis of the alkaloid. Financial assistance by the National Research Council of Canada and by the Ontario Research Foundation is gratefully acknowledged. (Received April 6th 1962.) * The specific activity of the sample originally reported’ as 12.4 x lo*counts fin.-’ mmole-l dropped to a constant value of 10.5 x lo4 after further recrystallisation.7 It had been shown4 that in Coptis japonica Makino ~~-[2-~~C]tyrosine gave rise to berberine containing radio- activity of unknown distribution in the nucleus of the alkaloid. Robinson “The Structural Relations of Natural Products,” Clarendon Press Oxford 1955. Imaseki Oneyama and Tajima J. Pharrn. SOC.Japan 1960 80 1802. Freund and Fleischer AnnaZen 1913 397 30. Electron-spin Resonance Spectra of Ketyls of Benzophenone By P. B. AYSCOUGH and R. WILSON (DEPARTMENT OF PHYSICAL CHEMISTRY THEUNIVERSITY LEEDS,2) AROMATIC ketyls formed by the reaction of alkali metals with aromatic ketones are believed to exist as contact ion-pairs in ethers. The valency-electron of the alkali metal is transferred to the lowest un-occupied 2pr-orbital of the ketone where it can inter- act with the nuclear spins of the ring protons to produce hyperfine structure in the electron-spin resonance spectra.In previous work only the mag- nitude of the interaction with the sodium atom in the sodium ketyl has been established with any certainty because of the complexity of the spectra.l No inter- action with potassium was observed in an examina- tion of the potassium ketyl.2 The anion of benzophenone can be prepared by Adam and Weissman J. Arner. Chern. Soc. 1958 80 1518. Kojakova and Syrkin Doklady Akad. Nauk S.S.S.R. 1958 131 346. 230 PROCEEDINGS electrolytic reduction of the ket~ne.~ Using the tech- Hyperfine splitting constants (Mc./sec.) for the nique described by Geske and Maki? we have ob-ortho- meta- and para-protons and the cation in served the simple spectrum shown in Fig.a from a benzophenone ketyls. a0 am a am Ph,CO-6.96 2.32 9.28 -Ph,CO-Na+ 7-23 2.41 9-63 3.15 Ph,CO-K+ 7.08 2-35 9-66 0.64 These much more complex spectra are derived from the basic pattern observed in the anion with an addi- tional splitting caused by interaction with the sodium or potassium nucleus (I = 3/2). These inter- 10Mc./sec. actions are approximately four-thirds and one-third respectively of that of the mefa-protons so that the Electron-spin resonance spectra of (a) the anion and total number of observable lines is considerably re- (b) the sodium ketyl of benzophenone at 25' duced by superposition.Exact values were obtained by computing theoretical spectra as described 2 x 10-3~-solution of benzophenone in methyl earlier.5 If the species observed during electrolysis is cyanide containing 0-1 M-tetraethylammonium per- the free anion it appears that the cation has a chlorate as electrolyte. At least twenty-three equally negligible effect on the distribution of the unpaired spaced lines each about 0.04Mc./sec. wide may be electron in the aromatic system. This is not sur-seen under high power. Such a small number of prising since the hyperfine interactions with the alkali narrow lines can be observed only if the hyperfine metal corresponds to an unpaired spin density on the splitting constants of the four ortho- four mefa- and metal of < 1% as in the case of the sodium two para-protons are in a simple integral ratio.This naphthalenide ion-pair.6 The sodium and potassium has been shown to be 3 :1:4,from which twenty-five hyperfine splittings also vary in a manner similar to lines are predicted with relative intensities 1 :4 :6 :8 that observed for the sodium naphthalenide ion-pair 19:32:34:44:71:80:72:88:106:88:72:80:71:44:34:in various solvents. However in contrast to these 32 :19:8 :6 :4 :1. The outermost lines are not seen but systems variation of the concentration of the sodium the remainder have the correct relative intensities. ketyl from about ~O-*M to 10-2~ affects only the line Absolute values of the hyperfine interaction con-width from which it is concluded that under our stants (& 273 measured by comparison with the experimental conditions dissociation of the ion-pair standard spectrum of triphenylmethy1,j are given in is negligible.the Table together with those obtained for the sodium and potassium ketyls. We are indebted to D.S.I.R. for purchasing the Spectra were also observed from solutions (-5 x spectrometer and providing a research grant (for 10"~) containing the sodium and potassium ketyls R.W.). of benzophenone in 1,Zdimethoxyethane (Fig. b). (Received April 9th 1962.) Austen Given Ingram and Peover Nature 1958 182 1784. Geske and Maki J. Amer. Chem. SOC.,1960 82 2671. Ayscough McCann and Wilson Proc. Chem. SOC.,1961 16. Atherton and Weissrnan J. Amer. Chem. SOC.,1961 83 1330. Total Synthesis of (&)-Gibberic Acid By H.J. E. LOEWENTHAL (CHEMISTRY DEPARTMENT, MASSACHUSETTS INSTITUTE OF TECHNOLOGY CAMBRIDGE, MASS. U.S.A.) and S. K. MALHOTRA LABORATORIES UNIVERSITY, (CHANDLER COLUMBIA NEWYORK,U.S.A.) THEnovel type of ring closure to the bicyclo[3,2,1]- a stereospecific synthesis of (-J-)-gibberic acid (I) the octane system previously utilised in a synthesis of racemate of a key intermediate2p3 in the degradation (+)-gibberonel has now been successfully applied to of gibberellic acid. Loewenthal Proc. Chem. SOC.,1960 355. Cross J. 1954 4670. Stork and Newman J. Amer. Chem. SOC.,1959 81 3168. JUNE 1962 Dime t h yl (2-me t hox ycarbon yl-6-met hylpheny1)- succinate? on cyclisation with sodium hydride in benzene-dimethylformarnide gave dimethyl 7-methyl-3-oxoindane- 1,2-dicarboxylate whose alkyl- ation with ethyl bromoacetate and sodium hydride in benzene-dimethylformamide followed by acid hydrolysis led to 3-carboxy-4-methyl-1-oxoindan-2-ylacetic acid.The dimethyl ester of this product on reaction with isopropenyl methyl ketone in methano- lic sodium methoxide afforded in SO% yield the CJIqq; (!V) Me0,C .3 expected1 half-ester (11) m.p. 200-201 (decomp.), O Amax. 231 (E 9100) 235 (E 9100) and 296 mp (E 31,400) (in MeOH). Cyclisation of this with the boron trifluoride-ether complex in acetic acid-acetic anhydride gave in nearly 80% yield the diketo-ester (111) m.p. 148.5-149° A,,, 236.5 (E 8400) 298 (E 20,600) and 324 mp (E 14,100) (in MeOH). This was converted into the ketal with ethylene glycol and toluene-p-sulphonic acid in benzene the product was * Malhotra Ph.D.Thesis Columbia University 1961. 231 hydrolysed with alkali and the resulting mixture of acids was separated by chromatography of their methyl esters giving as chief product the monoketal- ester (IV). Wolff-Kischner reduction of this followed by ketal cleavage and esterification gave methyl (f)-dehydrogibberate (V; R = Me). The derived acid (V; R = H) m.p. 220-222" (decornp.) Amax. 259 (E 15,500) 269 (E 13,50) 288 (E 3400) and 299 m,x (E 3000) (in MeOH) on catalytic hydrogena- tion gave ( f)-gibberic acid (I) m.p. 175-177'. The (V) k0,R -" infrared spectrum of the latter in CHClS solution was identical with that of (+)-gibberic acid m.p.155-1 55-5' obtained by degradation of gibberellic acid.2 We are greatly indebted to Professor G. Stork (Columbia University) for valuable assistance and to Professor G. Buchi (M.I.T.) for the hospitality of his laboratory. (Received March 23rd 1962.) NEWS AND ANNOUNCEMENTS Programme of Meetings 1962-63.-The Council has agreed that as an experiment scientific meetings held during the first part of the session 1962-63 should start at 6 p.m. instead of at 7.30 p.m. This decision is subject to review in the late autumn of 1962. The Harrison Memorial Prize.-The Selection Committee consisting of the Presidents of The Chemical Society The Royal Institute of Chemistry The Society of Chemical Industry and The Pharma- ceutical Society will in 1963 consider making an award of the Harrison Memorial Prize.The Prize which consists of a bronze plaque and a monetary payment of 100 guineas will be awarded to the chemist of either sex who being a natural-born British subject and not at the time over thirty years of age shall in the opinion of the Selection Com- mittee during the five years ending December lst 1962 have conducted the most meritorious and pro- mising original investigations in Chemistry and pub- lished the results of those investigations in a scientific periodical or periodicals. Applications five copies of which must be sub-mitted should include the full names of the applicant; age (birth certificate to be enclosed); degrees (with name of University); any other qualifications and experience; titles and reprints if available of pub-lished papers (with co-authors' names) ; where re- search was carried out ; testimonials and references and any other relevant particulars.The Selection Committee is prepared to consider applications nominations or information as to candidates who have not attained the age of thirty years at December lst 1962 and are otherwise eligible for the Prize. Any such communications must be received by the President of the Chemical Society Burlington House London W.l not later than December 31st 1962. Ethel Behrens Fund.-This is a new fund the purpose of which is to provide grants towards the travelling expenses including maintenance of Fellows of the Society studying at a University or Technical College in the British Isles for the first University degree or other equivalent qualification to enable them to attend the Anniversary Meetings of the Society and any Scientific Symposia or Dis- cussions in conjunction therewith.The first awards are to be made in connection with the Anniversary Meetings to be held in Cardiff in March 1963. Forms of application together with regulations governing the award of travel grants may be ob- tained from the General Secretary and must be returned by February 15th 1963. Research Fund.-The Research Fund of the Chemical Society provides grants for the assistance of research in all branches of Chemistry. Applica- tions for grants will be considered in December 1962 and should be submitted on the appropriate form not later than November 15th 1962.The total amount available for distribution is approximately El ,000 and applications from Fellows will receive prior consideration. Forms of application together with the regulations governing the award of grants may be obtained from the General Secretary. Local Representatives.-Dr. C. C. Barker has been appointed as the Local Representative for Hull in succession to Dr. G. C. Bond who has resigned. Liaison Officers.-The following Fellows have agreed to act as Chemical Society Liaison Officers Brighton Technical College .. Mr. J. D. Donald Royal Naval College Greenwich Dr. J. H. Pryor University of Glasgow . . Dr. S. J. Thomson Organon Laboratories Ltd.Newhouse-by-Motherwell . . Dr. C. L. Hewett Election of New Fellows.-258 Candidates whose names were published in Proceedings for April have been elected to the Fellowship. Deaths.-We regret to announce the deaths of the following Dr. A. G. Foster (25.5.62) of Royal Holloway College; Mr. V. C. HewZett (12.4.62) formerly Chairman C. J. Hewlett and Sons Ltd.; Mr. S. J. Pentecost (3.5.62) Director Hicking Pentecost and Co. Ltd. and a Fellow for over 75 years; Dr. E. A. H. Roberts (13.3.62) Research Manager Indian Tea Association (London) ; and Dr. S. Smith (23.5.62) formerly Director Wellcome Chemical Research Laboratories. Royal Society Visiting Professorship.-The Council of the Royal Society has appointed Professor M.Szwarc Research Professor at the State University PROCEEDINGS College of Forestry at Syracuse University New York U.S.A. to be the Royal Society Visiting Pro- fessor for the academic year 1962-63. He is expected to take appointment on August lst 1963 and to work at the University of Liverpool on ionic and anionic and stereospecific polymerisation. The Bragg Lectures.-At intervals of three years or so a lecture will be given to commemorate the work of Sir William Bragg and his son Sir Lawrence Bragg. It will be given in one or other of the centres in which the Braggs’ work has been done-Cam- bridge Leeds London and Manchester-and if possible repeated in more than one of them. The first Bragg lecture will be given in June 1962 the centenary of W.H. Bragg’s birth by Professor P. P. Ewald F.R.S Emeritus Professor of Physics at the Polytechnic Institute of Brooklyn U.S.A. on “William Henry Bragg and the New Crystallo-graphy.” It will be given twice in Leeds on Thursday June 7th at 5.15 p.m. in the Arts Lecture Theatre of the University (admission free no tickets) and in London on Wednesday June 13th at 5.15 p.m. in the Royal Institution 21 Albemarle Street London W.l (admission free by ticket obtainable from the Secretary of the Royal Institution). Symposia etc.-The 2nd International Symposium on Passivity sponsored jointly by the Electrochem- ical Society the German Bunsen Society for Physical Chemistry and the Faraday Society will be held in Toronto Canada on September 3rd-7th 1962.Further enquiries should be addressed to Mr. Cohen National Research Council of Canada Ottawa Ontario Canada. An International Metal Congress will be held in Vienna on September 23rd-27th 1962. Further enquiries should be addressed to Metall-u. Farben A.G. Karntnerstrasse 7 Vienna I Austria. The 14th International Plastics Congress will be held in Turin on October lst-3rd 1962 in con- nection with the 12th International Technical Exhibi- tion. Further enquiries should be addressed to Segretaria Congress0 Internazionale delle Materie Plastiche Corso Galileo Ferraris 60 Turin Italy. The First Australian Conference on Electro-chemistry under the joint sponsorship of the Royal Australian Chemical Institute the University of Tasmania and the University of New South Wales will be held in Sydney on February 13-15th and in Hobart on February 18-20th 1963.Further en- quiries should be addressed to the Honorary Secre- tary Sydney Committee Dr. F. Gutmann Depart- ment of Physical Chemistry University of New South Wales P.O. Box 1 Kensington New South Wales. The 2nd International Congress on Metallic Cor- rosion will be held in New York on March 11-15th 1963. Further enquiries should be addressed to the JUNE 1962 National Association of Corrosion Engineers 1061 M & M Building Houston 2 Texas U.S.A. Persona1.-Honorary Membership of the City and Guilds of London Institute has been conferred upon Mr. A. Baker in recognition of distinguished services to that Institute.Professor D. H. R. Barton is to give the Minnesota Mining and Manufacturing Company (Canada) Special Lecture Series in Chemistry at the University of Western Ontario in July 1962. Mr. R. P. Bell has been elected a Foreign Member of the Royal Danish Academy of Science and Letters. Professor Endre Berner has retired from the Chair of Chemistry at the University of Oslo. Dr. J. Biggs Assistant Lecturer in Chemistry at Hull University has been appointed Lecturer with effect from October lst 1962. MY.B. K. Blenkinship has resigned from the posi- tion of Chief Chemist of the South African Breweries Ltd. to take up a new appointment as Assistant to the General Manager (Production) of Dominion Breweries Ltd. Auckland C.I.New Zealand. Miss Caynor Cor-eld of the Chemistry Depart- ment of the University College of Wales Aberyst- wyth has been elected to the Gritton Postgraduate Research Award at Sydney University New South Wales where she will pursue further research studies under the direction of Professor R. J. W. Le Fkvre. Dr. J. S. G. Cox has been appointed Development Director of Genatosan Ltd. Dr. D. W. Davies Research Fellow University of Keele has been appointed Lecturer in Theoretical Chemistry at the University of Groningen from June lst 1962. Dr. B. K. Davison has joined the International Nickel Company (Mond) Limited as a Development Chemist. Dr. H. C. Dunn U.K.A.E.A. Risley has now returned from Japan. Mr. C. Fox formerly Lecturer in Chemistry Rotherhain College of Technology has taken up an appointment as a Technical Officer Research Department Imperial Chemical Industries Limited Heavy Organic Chemicals Division Billingharn.Dr. T. R. Grifiths of the North-East Essex Tech- nical College and School of Art has been granted one year’s leave of absence and will take up an appointment in August as Visiting Scientist at Oak Ridge National Laboratories Oak Ridge Tennessee U.S.A. Dr. R. D. Guthrie and Dr. S. Trippett have been appointed to Senior Lectureships at the University of Leicester from October next. Professor S. H. Harper Department of Chemistry University College of Rhodesia and Nyasaland is visiting England until the beginning of August. Professor T.P. HiEditch of Liverpool has been awarded the Lampitt Medal by the Council of the Society of Chemical Industry. Sir Christopher Ingold Emeritus Professor of Chemistry in the University of London is spending some weeks in Ireland as Visiting Professor of Chemistry in University College Dublin. Mr. G. C. Israel has resigned his position as Professor of Chemistry at the University of Ghana and has taken up an appointment as Principal Lecturer in Chemistry at the Welsh College of Advanced Technology Cardiff. Dr. A. R. Katritzky of Cambridge University has been appointed Professor of Chemistry at the Uni- versity of East Anglia. He is at present lecturing in Poland by invitation of the Polish Academy of Sciences. Dr. D. F. C. Morris has been appointed Reader in the Department of Chemistry Brunel College.London. Dr. J. A. K. Quarfey,Lecturer in Chemistry at the University of Ghana has been elected to a Fellow- ship for 1962-5 at Churchill College Cambridge. Dr. R. J. W. Reynolds has been appointed to the staff of the new Imperial Chemical Industries Petro- chemicals and Polymers Laboratory to assist the Head of the Laboratory Dr. D. S. Davies in drawing up the preliminary programme and to manage a part of the research team when it is set up later in the year. Professor J. B. Speakman Professor of Textile Industries University of Leeds has been elected President of the Textile Institute. Dr. F. S. Spring Research Director of Laporte Industries Ltd. has been appointed Chairman of Howards & Sons Ltd.Professor Burje Steenberg of the Royal Institute of Technology Sweden was presented with the “Stora Ekmansmedaljen” award at the annual meet- ing of the Swedish Association of Pulp and Paper Engineers. Dr. D. E. Wheeler Managing Director of The Wellcome Foundation Ltd. has been appointed President of the Association of the British Pharma- ceutical Industry. PROCEEDINGS APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings. Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Ahsan Ahmad Mubashshar Ph.D.C.S.I.R. Central Laboratories 35 P.N.H. Lines Karachi-4 Pakistan. Andrus Milton Henry Jr. B.S. Bagley Hall University of Washington Seattle 5 Washington U.S.A. Annan William Douglas B.A. 61 Fountainhall Road Edinburgh 9. Avchen Bgrney B.A. 636 Brooklyn Avenue Brooklyn 3 N.Y. USA. Bailin Gary B.S. 385 Grand Street New York City 2, N.Y. U.S.A. Bardsley William Gregory MSc. 16 Baron Road Gee Cross Hyde Cheshire. Behrens Helmut Dr.Ing. 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Pp.352.Pergamon Press. Oxford. 1962. Recent advances in processing cereals papers read at a symposium organised by the Food Group held at the Royal Society of Medicine London 1961. (S.C.I. Mono-graph No. 16). Pp. 199. Society of Chemical Industry. London. 1962. (Presented by the publisher.) Snow Michael Robert B.Sc. School of Chemistry, University of Sydney Sydney Australia. Stanway David Neil B.Sc. Department of Organic Chemistry University of Liverpool Liverpool 3. Stoddart Robert William. Heathfield Albion Street Wall Heath Brierley Hill Staffordshire. Sullivan. Michael Anthony. 464 Green Lane Seven Kings. -_ Ilford; Essex. TalaDatra. Sunil Kumar. M.Sc.. D.Phi1. Deuartment of Chemistry Ohio State'University Columbus 10 Ohio, USA.Ternay Andrew Louis Jr. M.Sc. 1049 Huntington Avenue New York City 65 N.Y. USA. Thornton Kenneth Kedley. 13 Monomeath Avenue Canterbury Melbourne Australia. Towner Robert Leslie. Rutland Hall Ashby Road Loughborough. Urenovitch Joseph Victor B.A. Harrison Lab. Chem- istry University of Pennsylvania Philadelphia 4 Pa., U.S.A. Vala Martin Thorvald B.A. Institute for Study of Metals The University of Chicago 5640 Ellis Avenue Chicago Illinois U.S.A. Vandendriessche Laurent G. G. Dr. Florastraat 18 De Pinte Belgium. Wall Harvey Michael B.Sc. 334 Great West Road Hounslow Middlesex. Wansey Margaret Mary. Lady Margaret Hall Oxford. Waring Juliet Mary B.Sc. 68 Cowper Crescent Bengeo Hert ford. Wiley Michael David B.S. Department of Chemistry University of Washington Seattle 5 Washington, USA.Williams Lyall Richard BSc. Organic Chemistry Department The University of Adelaide South Australia. Wiseall Barrie B.Sc. Department of Physical Chemistry The University Leeds 2. Wright Christopher Robin. 184 High Road Broxbourne Herts. Wyllie Stuart GIant M.Sc. Chemistry Department Uni- versity of Otago Dunedin New Zealand. Wystrach Vernon Paul Ph.D. University Chemical Laboratory Lensfield Road Cambridge. Zander Maximilian Dr.rer.nat. Castrop-Rauxel 2, Juliusstrasse 3 West Germany. THE LIBRARY New approaches to the study of catalysis. P. H. Emmett. (36th Annuals Priestley Lecture.) Pp. 157. Pennsylvania State University. Pennsylvania. 1962. (Presented by the publisher.) Organic chemistry of bivalent sulfur.E. E. Reid. Vol. 4. Pp.437. Chemical Publishing Co. New York. 1962. Methods in carbohydrate chemistry. Edited by R. L. Whistler and M. L. Wolfrom. Vol. 1. Pp.589. Academic Prens. New York. 1962, The chemistry of flavonoid compounds. Edited by T. A. Geissman. Pp. 666. Pergamon Press. Oxford. 1962. (Presented by the publisher.) Natural organic macromolecules. B. Jirgensons. Pp. 464. Pergamon Press. Oxford. 1962. (Presented by the publisher.) Comparative biochemistry a comprehensive treatise. Edited by M. Florkin and H. S. Mason. Vol. 3. Pp.959. Academic Press. New York. 1962. Les mbthodes de la chimie analytique analyse quanti- tative minerale. G. Charlot. 4th edn. Pp. 1024.Masson. Paris. 1961. Toxicity of arsenic compounds. W. D. Buchanan. Pp. 151 Elsevier. Amsterdam. 1962. The production of chemicals from reactors. Part 6. Anhydrous hydrazine from the pile and fission fragment irradiation of liquid ammonia. D. A. Landsman and C. M. Noble. Pp. 18. A.E.R.E. Harwell Berks. 1961. Eighth symposium (International) on Combustion, held at the California Institute of Technology Pasadena, California 1960 and published for the Combustion Institute. Pp. 1164. Williams and Wilkins Co. Baltimore. 1962. NEW JOURNALS Journal of Catalysis from 1962 1. Photochemistry and Photobiology from 1962,l. CORDAY-MORGAN MEDAL AND PRIZE ADDENDUM The scheme for the administration of this Award (Froceedings,1962,135,208)has now been established by the Charity Commissioners who have requested that the following be published CHARITY COMMISSION The Corday-Morgan Medal and Prize Fund admin-istered by the Chemical Society.Scheme for the amendment of the terms of the Will. The Charity Commissioners have made an order establishing a scheme for this and other purposes. Copies can be obtained by written request to the Charity Commission 14 Ryder Street London S.W.1 (quoting ref. No. JEH-129779-A). and may also be seen at that address. It will in future be subject to the revised rules approved by Council and given on pp. 208-209.