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Proceedings of the Chemical Society. May 1957 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue May,
1957,
Page 129-156
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PROCEEDIN-GS OF THE CHEMICAL SOCIETY MAY 1957 CHEMICAL SOCIETY ANNIVERSARY MEETING 1957 THISyear’s Anniversary Meeting at Cambridge on April 9-12th was the most ambitious in the Society’s history four days of functions hospitality receivtd meetings and symposia. And the ambitions were realised. Whether because of the three concur- rent symposia or the other attractions offered there was an unexpectedly large number of registrations 480. Yet the variety of the programme and the skill of the arrangements prevented too great overcrowd- ing anywhere. The impossibility of attending every- thing makes the giving of a general account very difficult and this one frankly places the highlights according to the experiences of your Reporter and his wife.Brief accounts of the three symposia are given below. The full papers and the discussions will be issued by the Society later in the year as Special Publications. Attendances at each symposium were large and well-maintained there were a hundred or more at the inorganic symposium; and the large theatres were often barely adequate at the physical- chemistry and organic symposia indeed at various times those standing included democratically the President and Honorary Treasurer of the Society. As usual at the Society’s symposia very welcome con- tri butions were made by overseas visitors. The symposia sessions were interspersed with other events. The latter made a fine start on the Tuesday evening with a lecture on “Cambridge” by Alderman G.F. Hickson who traced the develop- ment of the Town University and Colleges using a large number of slides and with the art that conceals art. Dr. L. E. Sutton’s remark in the vote of thanks was no empty phrase “Alderman Hickson had a wonderful subject ‘Cambridge’ to speak on; but I have never heard a better or more enjoyable lecture on any subject.” The following morning Professor H. Brockmann of Gottingen gave the Centenary Lecture on “Photodynamically active natural pigments” in which he described how he and his school isolated from St. John’s wort and related plants a number of polycyclic polyhydroxyquinones with remarkable physiological properties how they elucidated the structures with only small quantities available and how they estimated the absolute and relative distri- butions of the closely related compounds in related species and at different times of the year.He kept his organic hearers (metaphorically) on tiptoe and his less specialist hearers in admiration at the certainty of touch involved in this intricate work. This lecture will be published in a later issue of Proceedings. The third lecture the Presidential Address on “Some aspects of the chemistry of the fructosans” was given after the formal business of the Annual General Meeting of the Society on Thursday 1lth. Immediately before the address the President pre- sented the Corday-Morgan medal and prize to Professor G. Porter and the Harrison Memorial medal and prize to Dr. L. E. Orgel.In his address Professor Hirst surveyed the occurrence and types of structure of anhydro-derivatives of fructose in a wide range of vegetable materials giving what Professor Wardlaw in his vote of thanks aptly described as “a masterly survey of a very difficult field in which Professor Hirst has worked with outstanding success”. This lecture too will be published in Proceedings later. 129 PROCEEDINGS (Parenthetically your Reporter apologises for the superlatives in accounts of all three lectures but he is a Cambridge man and an organic chemist and in his opinion the superlatives really are justified.) The Society’s Anniversary Dinner like almost everything else at this meeting was overapplied for even though it was divided between two Colleges.Toasts of the Society were proposed by Professor H. Brockmann at Trinity and Professor F. H. Westheimer at Queens’ with responses by the President and immediate Past-President respectively and toasts of the guests by Professor R. G. W. Norrish at Trinity and Sir Alexander Todd at Queens’ with responses by the Mayor of Cambridge Councillor C. E. Ridgeon and the Chancellor of the University Lord Tedder respectively. The dinners were preceded by a Reception at the invitation of the University in the ancient and beautiful University Combination Room an occasion of some very fitting dignity. There were two receptions and dances on Tuesday by invitation of the Mayor of Cambridge at the Guildhall ;and on Thursday by invitation of Fisons Limited at the Dorothy Ballroom where the fresher had opportunity to enjoy the Dashing White Sergeant with his Professor’s Lady.Both dances were well attended and to judge from the number who stayed until the end well enjoyed. Lunches to the capacity of the seating accom- modation were provided by the Directors of Aero Research Limited (a Ciba Company) and by Tube Investments Limited and were greatly appreciated. Industrial visits were to Aero Research Limited (a Ciba Company) W. G. Pye and Company Limited Unicam Limited Fisons Pest Control Limited Cambridge Instrument Company Limited Kayser Bondor Limited (Baldock) Chivers and Sons Limited and Tube Investments Limited. The non-industrial “visits” were an all-day tour of the Wool Towns of such importance in the economic history of the district and showing some of the attrac- tive country around Cambridge; and a visit to Sawston Hall a 16th century house still lived in- the beauty of the house and its furnishings coupled with the charming reception by the owners caused at least one of the visiting wives to rank this tour as outstanding from many anniversary meetings.Yet there was no need to attend symposia or to join visits or tours abroad for enjoyment. The Col- leges and Backs of Cambridge itself provide beauty that entrances on first meeting and does not fade when re-encountered; and there were conducted tours for those who wished to know more. For the scientific there were guides to the magnificent new chemical laboratories which when complete will challenge competition.And four Colleges laid their special treasures open to us. Dr. B. C. Saunders en- chanted visitors with the Pepys library at Magdalene a gentleman’s private library of 3,000 books ar- ranged by Pepys himself in his own bookcases and including the diaries and many books in demand for exhibitions on account of their subject matter or bindings. Trinity Hall and Corpus Christi placed their silver on display both collections including unusually much that escaped melting or confiscation in the Cromwellian wars. The Corpus Christi collection includes a remarkable drinking horn and the Trinity Hall collection goes back to the Founder’s Cup of 1352-5. It is pleasant that the old habit for a distinguished Fellow to present a silver piece to his college is not dead Trinity Hall showed Sir Eric Rideal’s Beaker (ca.1650) and Sir Owen Wans- borough-Jones’s Taper-stick. Yet perhaps for many the most memorable of all the occasions will have been the organ recital by Mr. Alan Hemmings in King’s College Chapel. The exquisite music ranged from the early 17th century through J. S. Bach to the contemporary as daylight faded from the great roof and the Chapel took its light from candles and the glow of the blues and reds of the West Window. Almost we forgot the cold. For in the interests of historical accuracy it must be recorded that the too early warmth of Spring gave way for this meeting to a cold though mainly dry spell; and some of us escaped gratefully from under- graduate rigours of accommodation to the Small Examination Hall that served as a conference office and a comfortable meeting place with refreshments at due times.The meeting must count as one of the most successful since the War and may well set a pattern on which future organisers will graft their local opportunities. The arrangements listed in an attrac- tive Meeting Handbook ticked over with the ease that tells of thorough preparatory work and the Society and all who took part are most grateful to the Local Organising Committee consisting of R. N. Haszeldine (the Society’s Local Representative) V. M. Clark G. W. Kenner A. G. Sharpe A. G. Maddock T. M. Sugden D. W. A. Sharp D.B. Wakefield R. F. Webb F. B. Kipping and Lady Todd to all who gave hospitality and facilities and to the many who also helped but whose names do not appear on any list. MAY 1957 131 THE ONE HUNDRED AND Sm THE Annual General Meeting was held in Lecture Room A Examination Hall the University of Cambridge at 10 a.m. on Thursday 11th April 1957. The President Professor E. L. Hirst was in the Chair. After the notice convening the Meeting had been read the Report of Council and the Accounts for the year ended December 3 1st 1956 were presented by Dr. L. E. Sutton Honorary Secretary and by Mr. M. W. Perrin Honorary Treasurer respectively. After discussion on the motion of the President seconded by Professor F. Bergel Honorary Secre- tary the Report and the Accounts were adopted by the Meeting.The President announced the results of elections to Council. On the motion of the Honorary Treasurer seconded by Dr. J. Chatt Honorary Secretary Messrs. W. B. Keen & Co. Finsbury Circus House London E.C.2 were appointed as Auditors for the year 1957. At the conclusion of the Meeting a vote of thanks to the President Officers Council and Local Repre- sentatives for their services during the past year proposed by Professor H. J. EmelCus was carried with acclamation. m ANNUAL GENERAL MEETING Vie-Presidents who have not filled the Ofice of President Professor Wilson Baker Professor R. D. Haworth Dr. L. E. Sutton Honorary Secretary Professor M.J. S. Dewar Elected Ordinary Members of Council Constituency I Professor R. S. Nyholm Dr. R. E. Richards Constituency ZI Dr. J. C. Tatlow Constituency IIZ Professor A. J. Birch Constituency I V Professor A. W. Johnson Constituency V Dr. J. D. Loudon Constituency VI Professor R. A. Raphael RECENT ASPECTS OF THE INORGANIC CHEMISTRY OF NITROGEN A SYMPOSIUM on recent advances in the chemistry of nitrogen compounds was held on April 10-12th 1957 during the Anniversary Meeting. In the first session with Professor H. J. Emelkus in the Chair a general introduction was given by C. C. Addison who indicated the scope of the papers to be presented and called attention to the several series of entities differing only in their charges which are now known to exist among nitrogen compounds.Typical examples are NO+ NO NO-; NO,+ NO, NO,-; N202+,N,O (low-temperature polymer of NO) and N,O,-. The study of the effect of the charge on the properties of these ions or molecules is an interesting branch of comparative inorganic chemistry. Investigations of the chemistry of the nitrosyl sulphuric acids (which are now recognised as hydro- gen sulphates of the NO+ or N202+ion) were described by F. Seel who told how the action of nitric oxide on nitrosonium salts leads to the forma- tion of nitric oxide nitrosonium salts containing the NzO,+ ion. Solutions of nitrosonium hydrogen sulphate NO+HS04- in sulphuric acid for example become deep violet-blue when kept under nitric oxide and the intensity of the colour increases with increase of pressure of nitric oxide; at low tempera- tures ( -90°) the colour changes to carmine-red.By spectrophotometric measurements it has been proved that the compound N20,+HS0,- is formed; this is the “blue acid” of the lead-chamber process for the manufacture of sulphuric acid. Evidence has been obtained for the formation of similar substances derived from nitrosyl fluoride in hydrogen fluoride and from a solution of dinitrogen trioxide in phos- phoric acid. At high pressures of nitric oxide and at low temperatures solid nitrosonium salts of complex chloro-acids (e.g. NOfTIC1,-) are also partially converted into nitric oxide nitrosonium salts. In the ensuing discussion attention was drawn to the blue or red colour of solid hydrogen chloride con- taining traces of oxides of nitrogen and it was suggested that here too the Nz02+ ion might be involved.G. Hetherington and P. L. Robinson described the preparation of nitryl fluoride NO,F from sodium nitrite and fluorine and discussed the physical pro- perties of this substance and the evidence leading to the assignment of a planar structure to it. Chemically the compound is extremely active. Most metals usually give nitronium salts of complex fluoro-acids and such reactions provide a general method for the preparationof e.g. NO2+SbF6- NO,+IF,- NO2+PF6-. In organic chemistry it usually acts as a nitrating agent presumably by providing NO,+ ions. Molecular complexes of dinitrogen tetroxide and their applications in preparative inorganic chemistry were discussed by B.J. Hathaway and C.C.Addison. Dinitrogen tetroxide forms addition compounds with a wide range of organic materials (e.g. ethers esters ketones carboxylic acids and nitriles); in the liquid phase partial dissociation of these adducts into [(Donor),NO]+ and NO,-ions often takes place (especially in solvents of high dielectric constant and pronounced donor properties) with consequent modification of the reactivity of the oxide. It is the ionic form which is responsible for the reactivity of liquid mixtures of dinitrogen tetroxide and organic compounds with metals. For example neither di- nitrogen tetroxide nor ethyl acetate reacts with copper but the liquid mixture reacts vigorously yielding the compound Cu(NO,),,N,O,.Thermal decomposition of this substance produces the hither- to unknown anhydrous cupric nitrate a volatile deep blue-green solid. The structure of this substance is at present being investigated and the many speculations made at the meeting show with what interest the result will be awaited. On the second day (when Professor W. Wardlaw presided) M. Becke-Goehring gave a review of the work of her school on the sulphur nitrides S4N4 S2N, and (SN) and related compounds. Although details of the structure of N4S4 are not yet agreed it is clear that the molecule consists of a non-planar eight-membered ring and chemical evidence indi- cates that all the sulphur atoms are present in the same oxidation state.Hydrogenation of tetrasulphur tetranitride leads to the formation of S4N4HQ,which may be thought of as an S unit in which half the sulphur atoms have been replaced by the >NH group. This substance forms metallic derivatives such as [Ag(NS)] and Li[Al(NS),]. The remarkable com- pound S,NH likewise contains an eight-membered ring system. When S,N4 is treated with chlorine the eight-membered ring system breaks up with the formation of “thiazyl chloride” S,N,Cl, which has a cyclic structure containing alternate >S-C1 groups and nitrogen atoms. The principles underlying the manufacture of nitric acid from ammonia were admirably discussed by D. A. Spratt who described a plant now being erected to make the 60% acid.The slowness of the decomposition of ammonia on aluminium or mag- nesium-aluminium alloy allows these substances to PROCEEDINGS be used in the construction of preheaters which operate at a much higher temperature than those made of steel. Filtered ammonia and air react on a platinum-rhodium catalyst at 800-900” according to the equation 4NH3+ 50 = 4N0 + 6H,O + 220 kcal.. .(i) This is followed by the mainly homogeneous reaction 2N0 + O2= 2N0 + 27 kcal.. . . .. . . . . . . .(ii) and the absorption reaction 3N0 + H,O = 2HNO + NO + 32 kcal. ..(iii) at ordinary temperatures. The new plant utilises for the first time the heat liberated in reaction (ii). During the discussion Professor Partington gave an account of his work on the oxidation of ammonia and in connection with the kinetics of the absorption process the interesting point was made that they could be used to illustrate the general tendency of N204to react by dissociation into NO+ and NO,-ions.J. Jander gave an account of the interaction of bromine and ammonia under different conditions leading to the formation of bromamine NH,Br and the red nitrogen bromide of formula NBr3,6NH,. Nitrogen tri-iodide in liquid ammonia is decomposed by alkali-metal amides according to the scheme NI + 3NH2-+ 3NHI-+ NH 3NH1-+N + 31-+ NH In the last paper of the session B. G. Gowenlock J. Trotman and L. Bart described the interconversion of trans- and cis-dimers of nitrosomethane :vaporisa-tion of the solid trans-dimer gives the monomer which on rapid cooling forms the cis-dimer.The kinetics of the interconversion were described and an estimate of the heat of formation of gaseous nitro- somethane monomer as -4 kcal./mole was made. The complex effect of substituents on the stability of nitroso-compounds was mentioned and in the en- suing discussion the importance of the inductive effect of the CF group in stabilising the monomer of trifluoronitrosomethane was emphasised. Dr. F. Fairbrother took the chair at the third session which began with a review by R. E. Richards of the applications of nuclear resonance spectro- scopy to the study of nitrogen compounds. The width and shape of nuclear resonance spectra of solids at low temperatures depend on the configura- tion and internuclear separations of the atoms in the crystal.In simple cases the configuration of the nuclei can be identified; “nitric acid monohydrate” for example has been shown to consist in the solid state of hydroxonium H,O+ and nitrate ions. Since the location of hydrogen atoms by X-ray analysis is often impossible nuclear resonance spectra provide invaluable information in this field. Measurements of line widths and nuclear relaxation times in crystals at various temperatures provide information about molecular or ionic motion in crystals; they show for example that whereas rotation of the ammonium ion in ammonium fluoride is prevented by the strong hydrogen bonding the ammonium ions in salts of complex fluoro-acids [e.g.,NH4BF4 (NH4)2TiF6] are almost completely free to rotate.In liquids and solu- tions the lines are sharp and “chemical shifts” can be observed and used to distinguish between possible structures; applications of this process have not yet been made in the nitrogen field but should be useful in more complex nitrogen compounds. Finally applications to the investigation of chemical exchange processes were described. W. C. E. Higginson gave an account of the mechanism of the oxidation of hydrazine in aqueous solution elucidated by kinetic and tracer studies. In hot strongly acidic solution one-electron oxidising agents (typically compounds of transition-metal ions such as Co3+ Ce4+) produce nitrogen ammonium ions and hydrazoic acid ; two-electron oxidising agents (such as potassium iodate hydrogen peroxide and thallic salts) produce only nitrogen and am-monia.In dilute acid oxidising agents of the former type produce ammonia and nitrogen those of the latter type produce only nitrogen. In neutral or alkaline media all oxidation procedures produce nitrogen. The following scheme summarises the oxidation mechanisms in cold acidic solution 1-equivalent oxidation N2H4 -+ N2H3 2N& +N4H6 N4H6-+ 2NH + N2 N2H3 + N2H2 + N2 2-equivalent oxidation N2H4 + N2H2 +N2 2N2H2-+N,H4 + NH + HN The exchange of l80 between nitrous acid and water was discussed by C. A. Bunton D. R. Llewellyn and G. Stedman who showed that the exchange proceeds by the stages 2HN02 + H2N0,+ + NO2-H,N02+ + NO2-+ N,O + H20 In a sodium acetate or sodium phosphate buffer a different mechanism is operative e.g.H2N02++ OAc-$ NO-OAc + H20 These results were then discussed in relation to the interaction of nitrous acid and hydrogen peroxide or azide ion in buffered media; the rates of these reactions are independent of the concentration of peroxide or azide and therefore involve formation of the nitrosyl compound as the rate-determining step. Exchange reactions between nitrosyl chloride and chlorides of other elements with 36Cl as indicator were described by J. Lewis and D. B. Sowerby. A study of the properties of solutions of phosphorus oxychloride and arsenic trichloride in nitrosyl chloride has shown that the chlorine-donating pro- perties of these solvents is in the order NOCl > POCl > AsCl,.In arsenic trichloride nitrosyl chloride forms the complex NO+AsCI,- whereas phosphorus oxychloride has neither chlorine-donat- ing nor chlorine-accepting properties ;“C1 is rapidly exchanged between nitrosyl chloride and ferric chloride antimony pentachloride and arsenic trichloride but only very slowly between nitrosyl chloride and phosphorus oxychloride or carbon tetrachloride. The rate of the exchange with phos- phorus oxychloride suggests that the concentration of free chloride ion in nitrosyl chloride is of the order of g.-ion per litre. Finally Z. G. Szabu gave a short paper on the reducibility of the nitrate ion in which he discussed the catalytic role of the silver ion in the reduction of nitrate by ferrous hydroxide.The slow step in this reaction the formation of nitrite appears to involve the oxidation of silver to the oxide Ago; this then reacts with ferrous hydroxide regenerating metallic silver on the surface of which reduction of the nitrate is repeated. The breadth of the papers presented and the large number of participants in the discussions showed how the post-war revival of interest in inorganic chemistry in this country is beginning to bear fruit. The nature of the material discussed indicates how vital is the contribution now being made by physico- chemical and even purely physical methods to the progress of inorganic chemistry. A. G. SHARPE REACTIONS OF FREE RADICALS IN THE GAS PHASE A SYMPOSIUM on this topic formed part of the Anniversary Meetings of the Chemical Society.It was divided into four sessions (April 9-12th) each dealing with a fairly distinct aspect the first com- prising various theoretical aspects of the reactions of free radicals the second some investigations of the thermal reactions of such radicals the third photo- chemical reactions and the final one pre-flame and flame reactions. A general introduction to the whole symposium was provided by R. G. W.Nurrish who sketched the history of the concept of radicals and pointed out landmarks in the development of their chemistry. It is now possible directly to detect free radicals in many gas reactions and to elucidate their r6le in the kinetic processes concerned.In a paper on “The nature of free radicals,” H. C. Longuet-Higgins dealt with some aspects of the stability and reactivity of monoradicals. Hyperconjugation in saturated hydro- carbons and cations and the distribution of mobile electrons in aromatic substances were mentioned as affecting the behaviour of radicals. The detection of free radicals by paramagnetic electron resonance was described but little hope of its successful application in the gas phase was held out. The statistical weight factors in the combination of free radicals to give singlet and triplet states of molecules was discussed and led on to a simple account of the theory of bi- radicals. The subsequent discussion on this paper centred largely on relative levels and stabilities of the singlet and the triplet state of various molecules.The recombination of free radicals in the presence of a third body was taken up by D. E. Hoare and A. D. Walsh who discussed the overall termolecular reaction as involving three processes-the formation and dissociation of an excited compound of the two radicals and the deactivation of this excited com- pound by the intervention of a third body. This should lead to a change+from third-order to second- order kinetics of the recombination as the pressure of third bodies is increased. The factors which deter- mine the efficiency of third bodies as stabilisers were discussed for the recombination of radicals and of atoms.The reactions H- + 0 + M = HO + M CH,. + CH3-+ M =C2H6+ M CH,. +0 + M = CH,.O.O-+M and CH,*+NO+M=CH,-NO+M were considered. In the discussion following the paper the possibility of an alternative mechanism for recombination of atoms was brought up in which one atom forms a temporary complex with the third body subsequent reaction with a second atom giving the final products. This is probably less important for polyatomic radicals. The use of competitive methods in the study of free-radical reactions was dealt with by J. H. Knox and A. F. Trotman-Dickenson. The generation of free radicals in the presence of two or more reactants and the analysis of the subsequent products which has been rendered easier and more accurate by chromato- graphic methods enables the relative rates to be estimated.The relative activation energies and A factors deduced can be used to test theories of the transition state in particular with respect to the con- figuration of the intermediate complex. The second session was opened by Sir Cyril Hinshelwood who gave an introductory talk on “Thermal reactions involving free radicals.” The de- composition of certain peroxides in the gas phase PROCEEDINGS takes place at sufficiently low temperatures for the radicals which are produced to be unable to propa- gate chains in certain circumstances. Kinetic measurements can then be used to obtain informa- tion on the rates of decomposition and recombina- tion of the radicals themselves. The use of nitric oxide in the study of such reactions was described with special reference to the decomposition of tert.- butyl peroxide.This kind of work provides informa- tion a bout processes at higher temperatures such as the pyrolysis of hydrocarbons. The possibility of purely molecular mechanisms parallel with free-radical mechanisms in reactions of this type was reviewed. C. E. H. Bawn then gave a paper on “Peroxy- radicals and hydrocarbon oxidation.’’ Studies of the autoxidation of hydrocarbons and aldehydes in the liquid phase have shown the presence of a chain mechanism with a hydroperoxide (RO-OH) as pri- mary product. RO,. radicals are important inter- mediates here. The similarity of the kinetics of oxida-tion of gaseous hydrocarbons at high temperatures to these liquid-phase reactions indicates the import- ance of RO,.radicals in these processes as well. Lively discussion on the mechanism of various re- actions of hydrocarbons and related radicals followed these two papers. A paper by E. M. Bulewicz and T. M. Sugden dealt with work of a different kind-the study of the reactions of the radicals He OH. O. and 0,-in hydrogen-flame gases at temperatures in the region of 2000”~.Many reactions are in a balanced steady- state condition in these circumstances as shown by measurements of the stationary concentrations of these radicals. The recombination of atoms and radicals may also be studied in flame gases. The addi- tion of nitric oxide in small proportion produces a greenish continuum examination of which discloses the presence of a number of interesting phenomena related to the production and de-activation of excited molecules of NO,.The final paper of the session was by P.Gray and A. Williams and described the present position in the study of the alkoxy-radicals RO.. Their occurrence in a wide variety of chemical reactions was stressed. Heats of formation for a number of the lower alkoxy-radicals are now available and can be used to infer those of higher and of cycloalkoxy-radicals. These thermal data are of great value in the elucida- tion of kinetic schemes. A comparison was drawn between the behaviour of alkoxy-radicals RO-and the isoelectronic alkyl radicals RCH,.. Various re- actions of alkoxy-radicals-hydrogen abstraction addition disproportionation rearrangement and decomposition by rupture of a C-C bond-were briefly discussed.MAY 1957 The third session on “Photochemical reactions in- volving free radicals,” began with a paper by F. H. C. Edgecombe R. G. W. Norrish and B. A. Thrush on “Studies of the C10 radical by flash photolysis.” The history of the way in which this radical was intro- duced as a necessary intermediate in various reaction schemes before it was definitely detected was out- lined. After a brief account of the principles of the method of flash photolysis its application to the detection of the ClO- radicals in the photolysis of C1 + 0,,ClO, and C1,O was described. Quantita- tive measurements on the variation of the concentra- tion of radicals with time following the initial photo- lytic flash have enabled kinetic schemes for the reactions to be worked out.An interesting phenom- enon which has appeared in the course of some of this work is the production of vibrationally excited molecules of 02,whose subsequent deactivation can be followed. After a brief discussion the second paper of the session was presented by G. Porter on “Aromatic free radicals and triplet states in the gas phase.” The technique of flash photolysis has been used to produce free radicals of this type and the results in the gas phase have been related to other work in which the radicals are produced in a matrix of a suitable low-temperature glass. The dissociation of many aromatic compounds at the /?-position in the side-chain to give radicals of the benzyl type has been established in many cases and unequivocal assignment of spectra to benzyl diphenylmethyl anilino- phenoxy- and related radicals made.Another interesting phenomenon occurring is the production of molecules in the lowest triplet level as a result of intersystem crossing with an excited singlet state. The rapid deactivation of the triplet state in the gas phase was discussed. Radiochemical reactions in which radicals are produced were then considered by W.H. T. Davison in a paper on “The formation and reactions of free radicals in the high-energy irradiation of hydro- carbons in the gas phase.” The irradiation of propane and ethane with high-energy electrons and with y-radiation and the analysis of the products by gas chromatography were described.The products are generally hydrogen methane ethane higher alkanes and a little ethylene. Addition of a little iodine gives alkyl iodides instead of the higher alkanes. The latter are considered to be formed by recombination of radicals. The yields of the various products are inter- preted as related to the proportions of various radicals formed in the irradiation. The last paper of the session by R. Burgess and J. C. Rob6 was on “The mercury-photosensitised reaction between hydrogen and oxygen at room temperature.” The method of following the reaction by measurement of the heat produced as illustrated by the change in resistance of a platinunl filament was described.Analysis of the kinetics of the reaction has led to the proposal of a mechanism involving an excited form of the radical HO,.. It has been possible to derive velocity constants for various reactions of this radical in both excited and unexcited forms all of which appear to be reasonable. The last session began with a paper by W.Jost and H. G. WGgner (Gottingen) and was presented by Professor Jost. A remarkable set of photographs of spinning detonations in mixtures of carbon monoxide and oxygen with small amounts of hydrogen was shown. From these it is possible to derive the length of the reaction zone and to make conclusions about the overall rate of reaction at high temperatures and pressures.This work has been related to other studies on the rate of attainment of the water-gas equilibriumat temperatures above ~OOO”K, and on the effect of halogens on the burning rate of various combustibles. The formation of cellular and poly- hedral flames which is enhanced by halogens was also described. This was followed by a contribution from f. E. Dove R. Goss,and J. W. Linnett on “Propagation of flame in carbon monoxide-oxygen mixtures.” The burning velocities of various mixtures containing small amounts of water vapour have been deter- mined from Schlieren photographs of Bunsen flames. The results have been used to test the validity of two hypotheses concerning burning velocity-that of Tanford and Pease relating it to the equilibrium con- centration of hydrogen atoms at the calculated flame temperature and that of Semenov derived from a thermal mechanism with diffusion of the major com- ponents.The latter proved to be the more satisfac- tory particularly for the results at lower tempera- tures. A paper was then given by P. C. Ashmore on “Changes in the concentration of radicals before sensitised ignitions.” This described the conditions under which sensitised ignitions can be produced in the non-branching reactions between hydrogen and chlorine and between hydrogen and nitrogen di- oxide. Lower and upper sensitiser limits can be pro-duced in each of these systems the concentrations of chain centres being controlled by known reactions of the sensitisers.Similar considerations have been applied to the existence of sensitiser limits of ignition and of induction periods in the sensitised ignitions of branching chain reactions such as that of hydro-gen and oxygen. The mechanism of reaction in the above cases was dealt with in some detail. The final paper of the whole symposium was by F. S.Dainton K. J. Ivin and F Wilkinsonon “The reaction of methyl radicals with methane using carbon-14 as a tracer.” Dr. Ivin described a most elegant series of experiments using tracer techniques by which the energy of activation of the reaction CH,. + CH -+ CH + CH,. has been found to be 14.1 5 0.5 kcal. mole-l. This completes the series CH,. + CH, where n == 1 2 3,4 and a discussion of the heats of reaction and energies of activation was given.The zero-point effects in some of the reactions using deuterated radicals and molecules were described. It was very much regretted that Professor N. N. PHOSPHORIC ESTERS AND A SYMPOSIUM under the above general title was held during the Anniversary Meetings in four sessions on April 9-12th 1957. Four contributors came from overseas Professor B. A. Arbuzov son of the dis- coverer of the Arbuzov reaction from Kazan; Pro- fessor E. Baer from Toronto; Professor F. H. Westheimer from Cambridge Massachusetts ; and Dr. E. Y. Spencer from London Ontario. Prominent amongst those attending the meeting was Professor G. M. Kosolapoff from Alabama. At its close these visitors were thanked by Sir Alexander Todd with a special tribute in Russian to Professor Arbuzov.The first session with Sir Alexander Todd in the Chair was devoted to studies of mechanism of hydrolysis. F. N. Westheinzer described work with tetrabenzyl pyrophosphate and ethylene phosphate. The fonner ester displays an interesting variety of reactivity. Solvolysis of the benzyl-oxygen bonds can occur or particularly in the presence of certain arnines phosphorus may be the site of attack. Cal- cium ions increase the rate of the latter reaction tremendously presumably through co-ordination at the phosphoryl-oxygen atoms and it was suggested that this effect may be analogous to those in certain enzymic systems for example the magnesium-activated reactions of adenosine polyphosphates.Ethylene phosphate is remarkably reactive when compared with simple dialkyl phosphates or tri-methylene phosphate; in explanation it was sug-gested that in addition to the usual strain effects the planar ring may be strained by eclipse of the un- shared electron pairs on the cyclic oxygen atoms and the bonds between the phosphorus and the other two oxygen atoms. C. A. Vernon surveyed the general mechanisms for hydrolysis of simple phosphates. Particular stress was laid on the surprising reactivity which was first noticed by Bailly and Desjobert of the monoanion of a monoester of phosphoric acid and this theme was returned to by other speakers especially Westheimer during the discussion of several later papers. Vernon reported that phosphoric acid itself exchanges oxygen with water at about pH 4 in an analogous fashion.The acid-catalysed hydro- PROCEEDINGS Semenov (U.S.S.R. Academy of Sciences)was unable to be present and deliver a lecture. The Society was very fortunate in having for Chairman of the respec- tive sessions Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. Professor R. G. W. Norrish Sc.D. F.R.I.C. F.R.S.,Professor W. Jost and Dr. H. W. Melville D.Sc. F.R.I.C. F.R.S. whom we wish to thank for their services as well as the speakers who contributed to ma!<ing the symposium so successful. T. M. SUGDEN. RELATED COMPOUNDS lyses were also considered in detail and amongst other interesting results it was shown that fission of the bonds between oxygen and both carbon and phosphorus occurs in methyl phosphate.G. S. Hartley compared the behaviours of phosphoric esters with those of esters of other oxy-acids. It was shown how in the series of pyrophosphoric deriva- tives instability to alkali and toxicity run parallel with the prominent exception of “Schradan” ; the cause of this anomaly was the subject of the paper by Spencer at the end of the Symposium. The rela- tively high solubility in water of phosphoryl com-pounds was mentioned in relation to insecticidal action. Thionophosphates were compared with the oxygen analogues although the easy rearrangement of these substances creates difficulties in giving simple explanations of their properties. These three papers were the subject of a lively joint discussion.One point of general interest was whether cyclic esters of other oxy-acids with five-membered rings would show the same unusual reactivity as ethylene phosphate. The second session began with a paper by B. A. Arbrizov which was read by the Chairman Dr. F. G. Mann. It dealt with the reactions between sodium diethyl phosphite and various halogenated ketones. Frequently the phosphorus atom attacks the carbonyl group instead of that carbon bearing the halogen. For example bromoacetone is converted into an epoxy-phosphonic acid derivative and a tetrahydro-furan derivative is obtained from 3-chloropropyl methyl ketone. The general discussion of this paper was greatly aided by the services of G. M. Kosolapoff who acted as interpreter; some of the points raised concerned the modes of reaction with other halides and the properties of the epoxy-phosphonates.H. N. Rydun described the results of a detailed study of the triaryl phosphite dihalides. These compounds con- tain a cation of the type [PX,]+ which may be com-bined with either an anion of the type [PY,]- then resembling phosphorus pentachloride or a simple anion such as halide. As the positions of both X and Y may be occupied by either aryloxy-groups or MAY 1957 halogens this class of compounds is large and indeed evidence for the existence of many members has been obtained. The triaryl phosphite dihalides are prepara- tively important as intermediates in an ingenious method for converting alcohols into alkyl halides.F. R. Atherton showed how the neighbouring car- boxyl group profoundly affects the properties of the phosphoric ester in derivatives of salicyclic acid and how further substituents in the aromatic ring exert minor effects. The phosphoric ester of salicylamide is also unusually easily hydrolysed and this together with other evidence suggests that hydrolysis may occur through decomposition to the anion of meta- phosphoric acid and not as previously suggested through the salicyloyl phosphate. These investigations were part of a search for new methods of phos- phorylating alcohols and in the same connection the structures of several substances obtained from sali- cylic acid and phosphorus trichloride and penta- chloride were examined and clarified.The third session (Chairman Professor M. Stacey) was mainly concerned with the synthesis of natural products. A. R. Todd reviewed the methods available for the synthesis of polyphosphates. He showed how the classical route through phosphorochloridates can be modified and extended to cover a large number of cases. Nevertheless there is considerable scope for alternative methods particularly those which can be used in polar and even aqueous solutions and avoid the use of too many protecting groups. One of the most widely used reagents has been dicycbhexyl- carbodi-imide and the recent synthesis of cozymase in Cambridge was given as an example. Unpublished work showing that cyanamides can serve in place of carbodi-imides was mentioned among various related methods of synthesis.Finally attention was turned to a different kind of synthesis relying on the genera- tion from a phosphoramidate of a reactive meta- phosphate intermediate. The analogy between this reaction and the decomposition of the monoanions of monoesters of phosphoric acid was emphasised in the subsequent discussion. E. Baer described two very recent syntheses which add yet another chapter to his distinguished work in the field of glycerol phosphatides. The first example of a synthetic fully unsaturated cephalin L-a-(dioleylkephalin has been obtained after many difficulties. The ultimately successful synthesis was based on the reaction be- tween L-glycerol a-benzyl ether and the dibromide from oleyl chloride followed by successive removal of the benzyl group and the four atoms of bromine before reaction with phosphoryl chloride and then N-2-hydroxyethylphthalimide.The second synthesis was of a phosphatidyl-tripeptide in which the glycerol was linked by the phosphoryl residue to the hydroxyl group of L-serine.The plan of synthesis was generally similar to that just outlined except that stearyl residues and N-benzyloxycarbonyl-~-seryl-glycylglycine benzyl ester were used instead of oleyl residues and N-hydroxyethylph thalimide. J. Baddiley described the unexpected course of acidic hydrolysis of ribitol-1 phosphate and similar compounds. The liberation of inorganic phosphate is relatively rapid and the other product is 1:4-anhydroribitol.Similar cyclisation occurs with derivatives of other polyols to an extent dependent on their configuration and cyclisation also occurs although much more slowly with the polyols themselves. Moreover the reaction can also take place with riboflavine-5‘ phosphate and this may be the origin of the so-called “lyxoflavin”. Analysis of these reaction products affords a useful method for the characterisation of polyols and their phosphates on a micro-scale. The final session was held in two parts Professor F. Bergel being in the Chair. The first comprised two papers from Birmingham University describing the work there on the structure of nucleic acids. A. S. Jones and M. Stacey showed how deoxyribonucleic acids can be selectively degraded by a two-step pro- cess.The nucleic acid is dissolved in mercaptoacetic acid and treated with zinc chloride which causes hydrolysis of the purinedeoxyribose links and con- version of the liberated aldehyde group into a dithioacetal. The deoxyribose residues which have undergone this change now have the 4’-hydroxyl group exposed and consequently during the seccnd stage namely alkaline hydrolysis fission of the phosphate-sugar chain can occur by the familiar cyclisation mechanism. Paper chromatography and paper electrophoresis of the degradation products then affords information about the arrangement of the purine and pyrimidine residues along the nucleic acid chain. It was shown that the results with two nucleic acids differ so greatly as to exclude a merely random organisation of the residues.A. R. Peacocke surveyed the various ionising groups present in nucleic acids. He pointed out how their ionisations can be affected by their environment in a macromole- cule and that when due account is taken of these effects there is no reason to suspect any branching in the nucleic acid chains. An especially interesting phenomenon is that of irreversibility in the titration of deoxyribonucleic acids. This occurs in both acidic and alkaline regions. Its extent is very similar in the two regions and moreover the phenomenon cannot be observed in the two regions successively with the same sample. This behaviour is accounted for by hydrogen-bonding in the double helix of the macro- molecule.Consequently titrimetry is a very sensitive method for studying the denaturation of deoxyribo- nucleic acids during treatment with a variety of agents such as heat and ionising radiations. In the second part of the final session B. C. Saunders described the physiological action of phos- phorofluoridates and similar compounds on mam- mals. The most obvious effects are of a parasym- pathomimetic kind but there are also effects on the sympathetic system. This paper included an account of some ingenious experiments on the production of pyrophosphates from phosphites by means of cata- lytic amounts of iodine and peroxidase and this was coupled with some speculations about their possible biological significance.E. Y. Spencer elucidated the way in which “Schradan” (tetramethylphosphorodi-amidic anhydride) is converted by oxidation into an PROCEEDINGS unstable highly toxic derivative. This reaction occurs in plants and animals and it can also be brought about by chemical reagents such as potassium per- manganate and chlorine. The toxic product is the hydroxymethyl derivative presumably formed by re- arrangement of the hypothetical N-oxide. The cause of this considerable increase in toxicity following the comparatively small structural change was debated after the reading of the paper but no conclusion was agreed. G. W. KENNER ALCHEMY AND LITERATURE By JOHN READ F.R.S. (PROFESSOR IN THE UNIVERSITY OF CHEMISTRY OF ST.ANDREWS) THE study of alchemy has a high cultural value and offers many attractions.This study par- ticularly if integrated with that of historical chemistry could be welded into a cultural and humanistic instrument of great power in the teaching of a branch of science which is often dismissed as a medley of odours test-tubes and equations devoid of human interest. Among the manifold fields of human thought and achieve- ment upon which alchemy impinges literature and art stand out by reason of their aesthetic importance and appeal. Alchemy in Literature The association between alchemy and litera- ture is two-fold the outlook may be either from the viewpoint of literature or from that of alchemy. The first kind of view discloses that alchemy and alchemists have entered to an appreciable extent into the general literature of the nations.A few examples will serve to illustrate this statement. The two outstanding examples of the use of alchemy as the dominating theme in a literary work are to be found in two of the great masterpieces of English literature these are the “Canon’s Yeoman’s Tale” of Geoffrey Chaucer and “The Alchemist” of Ben Jonson. Both the alchemical and the human significanceof the “alchemists” of the fourteenth century and their entourage stand out in Chaucer’s masterly delineation. It would be superfluous to dwell upon the vivid impressions and picturesque language of this classical narra- tive. Let it suffice to quote the eloquent picture expressed with a master’s brevity of the ever- retreating rainbow of alchemical delusion The philosophre stoon Elixir clept we seeken it each one For had we him then were we sure y-nough; But unto God of heven I make avow For a1 oure craft when we have a1 y do And a1 oure sleight he wol not come us to.He hath i-made us spende moche good For sorrow of which almost we waxen wood But that good hope crepeth in oure herte Supposing ever though we sore smerte To be relieved by him after-ward. More than two centuries elapsed between Chaucer’s death and the appearance of Ben Jonson’s witty play “The Alchemist,’’ in which the ignis fatuus of alchemy still forms the heart of the theme. “This day I am to perfect for him,” says Subtle the “alchemist” of the play The magisterium our great work the stone And yield it made into his hands of which He has this month talked as if he were possessed.First acted in 1610 in London and published two years later “The Alchemist” constitutes a powerful attack upon the chicaneries frauds and impostures which had eaten like a canker into the life of the early Jacobeans. The credulity accorded at that time by people of high social standing to practitioners in necromancy and magic was shown up in the dazzling light of the English cause ce‘Z2bre of 1615 when the Earl and Countess of Somerset (formerly Viscount MAY 1957 Rochester and Countess of Essex) were brought to trial as accomplices in the poisoning of Sir Thomas Overbury who had opposed Rochester’s marriage.But for his timely death in 161 1 Simon Forman would undoubtedly have been arraigned and brought to the gallows for an imagined com- plicity in this crime although his contribution probably amounted to nothing worse than love- philtres waxen images and an enchanted nut- meg. Jonson clearly showed a sound judgment in making Forman (Plate 1) the prototype of his cozening alchemist Subtle. As a pillory of this familiar order of things charged moreover with telling wit and pungent satire “The Alchemist” made a great appeal to contemporary audiences. After the Restoration of King Charles I1 it aroused scarcely less en- thusiasm. Samuel Pepys who patronised it repeatedly referred to it in his diary for 1661 as “a most incomparable play.” Although in later ages its alchemical ideas imagery and vocabulary have become outmoded it may still be enjoyed by those who respond to the call of “rare Ben” Come on sir.Now you set your foot on shore In now orbe; here’s the rich Peru! And there within sir are the golden mines Great Solomon’s Ophir! Still it deserves Coleridge’s encomium as a work having one of “the three most perfect plots ever planned” ; still also it justifies Swinburne’s claim to rank as unique and to be numbered among “the greatest of comic triumphs ever accomplished.” Besides these two literary masterpieces in which alchemy provides the main theme there are many literary works containing an alchemical strand. In most of them however the professed alchemical character has rather the attributes of an astrologer or a charlatan.Cast in a truer alchemical mould is Merejkowski’s account of Galeotto alchemist at the Court of Duke Moro of Milan. Other impressive figures of the real alchemical type may be found for example in Balzac’s “La Recherche de l’absolu’’ and in Victor Hugo’s “N6tre Dame de Paris.” Balthazar Claes in the former work although placed in the post-alchemical era has the temperament of the persistent seeker after the Great Work; for in Saintsbury’s words nowhere else in literature “has the hopeless tyranny of the fixed idea the ferocious (not exactly selfish) absorption in the pursuit of a craze been portrayed with quite the same power as here.” Victor Hugo’s alchemist is of the stuff of which Khunrath and others of the mystical and vision- ary type were made to which witness is borne by his ecstatic soliloquy “The sun is born of fire the moon of the sun.Fire is the soul of the Great All; its elementary atoms are diffused and con- stantly flowing by an infinity of currents through- out the universe. At the points where these currents cross each other in the heavens they produce light; at their points of intersection in the earth they produce gold. Light-gold; it is the same thing-fire in its concrete state . . . What ! this light that bathes my hand is gold ! All that is necessary is to condense by a certain law these same atoms dilated by certain other laws! . . . Flamel considers it simpler to operate with terrestrial fire.Flamel ! there’s predestination in the name! FZamma! yes fire-that is all. The diamond exists already in the charcoal gold in fire-But how to extract it? . . .What! I hold in my hand the magic hammer!”l To which it needs but to add the words Nunc dirnittis Domine! The presentments of Victor Hugo and Balzac although possessing much psychological interest differ widely in other respects from Robert Browning’s celebrated poem “Paracelsus.” The poet’s imaginative figment of a robust and im- portant figure in the development of alchemy and medicine takes on the tenuous habit of a genius unable to resist forces which impel him to fulfil his obsession that he is destined to discover the secret of the world.Like the adepts seeking the Stone he fails in his quest; and this because with all his learning he has failed to develop sympathy and love for his fellow creatures or to com- prehend “their half-reasons faint aspirings dim struggles for truth their poorest fallacies their prejudice and fears and cares and doubts”; all of which “with a touch of nobleness,” tend upwards. The poem is not a presentment of the real Paracelsus whose historical background and Victor Hugo’s “Notre-Dame of Paris,” translated from the original French edited by E. Gosse London 1908. external circumstances are but lightly sketched in a delineation which is apt to become nebulous and diffuse. This notwithstanding the poem exercises a strong appeal by reason of its pleni- tude of noble passages and its revelation of the subtle influences that may regulate and develop conduct and character.The Literature of Alchemy The beginnings of the literature of alchemy are no less difficult to determine than the beginnings of alchemy itself. The clay tablets of Babylonia and Assyria bearing information about the working of metals and the making of glass may be said to have an alchemical interest; and so may certainly that “oldest book in the world,” the Papyrus Ebers dating back to about 1550 B.C. The oldest known treatise upon oriental alchemy is the “Ts’an T’ing Ch’i,” deal-ing with the preparation of the “pill of im- mortality” and written by Wei Po-yang in the second century A.D. Somewhat later came the Graeco-Egyptian writings including papyri of the early centuries of the Christian era; these con- tained in particular many recipes for making imitation silver and gold.2 Numerous Greek alchemical manuscripts were written in Egypt between the first and the seventh century A.D.Many transcripts of these made from about the tenth century on- wards still survive in the Bibliothkque Nationale at Paris and other libraries. Towards the end of the nineteenth century the famous French chemist Marcellin Berthelot devoted much attention to their translation and study. Some of the writers of these Greek manuscripts are known under their real names among them Zosimos whose Formula of the Crab is familiar to students of alchemy; but many of the writings were ascribed to fanciful authors such as Hermes Democritus and Moses in order to lend them authority.This cuckoo-like practice furnished Ben Jonson with one of the most barbed of his many satirical shafts I’ll show you a book where Moses and his sister And Solomon have written of the art; Aye and a treatise penned by Adam . . . 0’the philosopher’s Stone and in High Dutch .. . Which proves it was the primitive tongue. There are many surviving alchemical manu- scripts written in Arabic and Syriac from about PROCEEDINGS the eighth century onwards. Some of these were derived from Greek and Graeco-Egyptian sources and others were indigenous productions of Muslim alchemists. Beginning in the twelfth century writings from these sources gradually came to be known in Western Europe through the medium of Latin translations.In due course some of these Latin versions were rendered into German English and other languages. More- over from the thirteenth century onwards after alchemy had taken root in Europe the European alchemists and philosophers began to write tracts and treatises of their own mostly in Latin but sometimes in their vernacular languages. Although much of this has perished there is still an enormous mass of alchemical literature in the form of written manuscripts scattered through- out the world mostly in the great libraries. Many of these manuscripts have never been printed and some have not even received careful examination.Some years ago the Union Acadkmique Internationale entered upon a systematic cataloguing of such items. That there existed a demand for such manu- scripts is shown in the picturesque narrative ascribed to Salomon Trismo~in.~ Before the introduction of printing about the middle of the fifteenth century and long afterwards there was an extensive traffic in copied manuscripts; and even so the demand was only partly satisfied. A striking example is seen in Michael Scot’s “Physionomia,” which he wrote about 1228. For 250 years this medieval “best-seller” had an ex- tensive circulation in manuscript form; but the latent market was such that the first printing of 1477 was followed by a rapid succession of further editions before the fifteenth century had ended.Norton’s “Ordinall,” written in the same year 1477 was not printed until 1618 and then in Latin; but meanwhile it had circulated widely in manuscript copies some of which were of great artistic merit.4 When Elias Ashmole undertook the first printed edition in the original English (1652) he used a manuscript written on vellum. Although he considered this to be better work Fuller information on this paragraph may be found in the author’s “Prelude to Chemistry,” London 1936 and 1939 New York 1937. Ref. 2 p. 69. Ref. 2 Plate 34. MAY 1957 than a very fine copy owned by King Henry VII he collated it with fourteen other copies in pre- paring the text for the printers. Ashmole’s caution was justified because of the many mis- takes that crept into these manuscripts in the course of repeated transcriptions by one writer after another.Ashmole relates how a great number of valuable manuscripts suffered as a result of their dispersion at the dissolution of the English monasteries from 1536 onwards and describes their neglected and worm-eaten condition. A century before Ashmole in 1545 at the end of a printed collection of alchemical treatises issued in Latin at Berne the publisher inserted a note stating that “since the copies are partly injured by age and mould partly damaged by the ignorance of the copyists to such an extent that they cannot be corrected and put right save by comparison of many copies I request that if anyone has any such work either in Latin or German he will courteously allow me to have it so that by an extensive collation these writings may reach the hands of students in a more per- fect form.Those who do so may count on no small thanks from aspirants after this art and will receive several printed copies from me along with their own copy undamaged free of charge.” It is remarkable that long after the introduc- tion of printing manuscript copies of alchemical works were often made from printed originals even so late as the eighteenth century. This was sometimes because of the introduction of coloured illustrations and it may have been due in part to the cost of the printed books; but even the afffuent Sir Isaac Newton who had an absorbing interest in alchemy as also in mystical theology is said to have made alchemical tran- scriptions in his own hand amounting to the enormous total of 650,000 words (Plate 2).A page from a Latin alchemical manuscript of the fourteenth century is reproduced in Plate 3. This shows some crude drawings of common types of apparatus referred to in the text which medieval alchemists used for distillation and sublimation. The designs were fundamentally those of the Islamic alchemists and their pre- decessors of the Graeco-Alexandrian era. The apparatus consisted essentially of three parts 14 1 corresponding in modern chemistry to the still or distilling flask the condenser and the receiver. The cucurbite or gourd was embedded in sand and ashes heated in a furnace.Luted thereto was a beaked alembic helm or still-head :single and double forms of this unit are shown in the bottom row of drawings. The beak of the alembic delivered the distillate into a receiver of varied shape. In sublimation the volatile solid usually settled in the alembic but sometimes passed through into the receiver. This part of the apparatus was often luted to the beak and when a “blind” (closed) receiver was used in attempts to collect the “wild invisible spirits” now known as gases the apparatus was liable to be “struck in shivers.” Some three centuries later Clayton distilled coal from a retort and described how “a Spirit [coal gas] arose which I could noways condense but it forced my Lute or broke my Glasses.’’5 For gentler heats a water-bath was used instead of a sand-bath.Sometimes the alembic was made of tin as its beak was then less liable to be broken; but glass was preferred. Thus a later part of the description appearing at the foot of Plate 3 states that “from the first putrefaction to the end of the Work all the vessels should certainly be of glass and well luted lest the spirit should fly off in smoke and the Magisterium be lost.” The shadowy parts of the above drawings which the photographic process has accentuated show where alterations or erasures have been made. The page is reproduced from a short treatise ascribed to Albertus Magnus and con- tained in a volume consisting of twelve Latin treatises on alchemy. These manuscripts written on vellum in various hands date from the four- teenth century and belonged at one time to Dr.Cox Macro who entered the University of Leyden in 1703 and became a pupil and friend of Boerhaave. Some of the 78 leaves in particular those of the “Semita Recta,” also ascribed in the manuscript to Albertus Magnus are stained and crinkled suggesting that the treatise may have been brought near the scene of operations in the den of some scholarly “alchemister” of Chaucer’s day. The many contractions used in this and other medieval Latin manuscripts add to the difficulties of interpreting such texts. See the author’s “Humour and Humanism in Chemistry,” London 1947 p. 198. As an example of a clearly-written English alchemical manuscript of the fifteenth century a page of this same “Semita Recta” (“Straight Path”) is reproduced in Plate 4 from a copy of the treatise in the British Museum London.The extract opens by stating that “By this crafte [Alkymya] alle metailles that growen of myne and been corrupte and unparfite been brought and tourynd fro ynperfection to perfection.” Metals were pictured in alchemy as growing like plants and animals and this hylozoistic concep- tion has come down from the ancient civilisations to linger even yet in such expressions as “native gold,” and “living rock.” The “Semita Recta” goes on to say that “alle metaills been ingendard in therthe of sulphur and mercury,” and that although nature “intendeth alweye to make gold and silvre” this intention is often frustrated through the interveiition of corruptions (im- purities).Thus according to the last part of the extract “Whene reede sulphur and pure and not brennyng renneth in therthe with mercury thereof is ingendrid golde . . . but whene white sulphur renneth to mercury in cleene erthe thereof is ingendrid silvre and hit hath noo difference fro golde but that sulphur in gold is not corrupte but in silvre hit is corrupte.” One of the earliest alchemical works to appear in print was a collection of Latin texts entitled “Summa Perfectionis” (“Sum of Perfection”) and ascribed to Geber. The original edition of 148 1 was followed by other printed editions such as that published at Nuremberg in 1541.This was embellished with woodcuts and contained also the “Speculum Alchemiae” (“Mirror of Al-chemy”) attributed to Roger Bacon by its unknown author the “Tabula Smaragdina Hermetis” (“Emerald Table of Hermes”) and other works altogether it constitutes one of the most valuable early collections of alchemical texts. It is supposed that the “Summa” was written originally in Latin and fathered upon Geber in order to give it authority. An English translation was made in 1678 by Richard Russell who called it “The Works of Geber The Most Famous Arabian Prince and Philosopher,” The writer of the “Summa” was familiar with alchemical theory and practice and gives clear descriptions of common laboratory operations and of the properties of metals.Besides sulphur Ref. 2 p. 55. PROCEEDINGS and argent-vive he includes “arsenik” as a third natural principle of metals and regards the sulphureous principle as “a fatness of the earth.” There are some amusing comments on the quali- fications necessary in a successful alchemical adept. He should be devoid of a “Brain repleat with many Fumosities . . . should be temperate and slow to anger least he suddenly (through the force of rage) spoil and destroy his works begun. Likewise also he must keep his money least when he is come near to the end of his magistery his money being all spent he be forced to leave the end uncompleted.” Another early work on alchemy was issued from the Aldine press at Venice in 1546 under the title “Pretiosa Margarita Novella” (“The New Pearl of Alchemy”).s This is a compendium of extracts from earlier writings originally col- lected by Petrus Bonus of Pola in 1330; it in- cludes many selections from the “Summa,” and refers repeatedly to the reputed writings of Arnold of Villanova Raymond Lully Rhazes Albertus Magnus Michael Scot and other early names familiar to the alchemical fraternity.The collection now extremely rare was held in high esteem among the alchemists; so that surviving copies are often worn and stained as a result of exposures to the rigours of alchemical dens and laboratories. Credulous and uncritical this work with its metaphysical tendency stands in great contrast to such eminently practical books as Brunschwick’s “Buch zu Distillieren,” published at the opening of the sixteenth century the “De Re Metallica” of Agricola (1556) and Libavius’ “Alchymia” (1 597).The early part of the seventeenth century was marked by a great efllorescence of printed books on alchemy and it was during this century that the vast sea of alchemical literature reached its high-tide mark. Basil Valentine’s printed publica- tions began in 1599 with a work entitled “Von dem grossen Stein der Uhralten” (“Concerning the Great Stone of the Ancients”); and the first edition of the “Triumph Wagen Antimonii” (“The Triumphal Chariot of Antimony”) ap- peared in 1604. Many editions of these and other works attributed to this enigmatical figure’ were published in various languages throughout the seventeenth century.Another famous alchemical work of that time was the “Novum Lumen Ref. 2 p. 183. PLATE1 Simon Forman (1552-1611) From a print published by F Blyth London 1776 Bulfinch del Godfrey sc PLATE 2. Extract from an English alchemical MS. in Sir Isaac Newton’s handwriting From the original headed “The Hunting of ye Green Lyon.” in the St. Andrews Collection. The last line measures 17.9 cm. in the original PLATE 3. A page of a Latin alchemical MS. (14th century) From the original in the St. Andrews Collection. The bottom line measures 8.3 cm. on the original vellum page size 17.5 by 13.5 cm. PLATE4. A page of an English alchemical MS. (15th century) British Museum.Slonne MS.353. 1'. 53" ("Semita Recta," Albertus Magnus). The bottom line measures 10.3 cm. in the original PLATE5. Title-page of "Musacurn Hcrnieticuni." Frankfurt. 1625 MAY 1957 Chymicum” (“New Light of Alchemy”)* of Sendivogius first printed in 1604. In the same period the prolific Count Michael Maie~,~ whose rapid pen could scarcely keep up with his wildly fertile imagination produced more than a dozen printed works in rapid succession between the years 1614 and 1619. Maier also edited the “Tripus Aureus” (“Golden Tripod”); this was first printed by Lucas Jennis at Frankfurt in 1618 and incor- porated by the same publisher in the celebrated “Musaeum Hermeticum” (“Hermetic Museum”) of 1625. The “Golden Tripod” as the name indi- cates contains three alchemical tracts these are the “Twelve Keys” of Basilius; Norton’s “Ordi- nall,” translated from English into Latin by Maier himself‘ for this first printing; and the “Testament” of Cremer a reputed but unidenti- fiable Abbot of Westminster.The “Musaeum Hermeticum” is one of the best known and most interesting of many col- lections or “omnibus volumes,” of printed alchemical tracts. The first edition of 1625 (Plate 5) contains nine tracts amounting to 483 pages and including notably the “Golden Tripod,” the “Book of Lambspring,” and the “Gloria Mundi” (“Glory of the World”). An enlarged edition of 863 pages was issued at Frankfurt in 1678. There were many other voluminous collections of alchemical tracts most of which in com-parison with the fairly compact and beautifully illustrated items of the “Musaeum Hermeticum,” must be characterised as uninteresting prolix and often repellent; some of the writings of the mystical type are indeed unintelligible even after careful scrutiny.Zetzner’s “Theatrum Chemi- cum’ (“Chemical Theatre”) of six volumes published at Strassburg in 1659 and Manget’s “Bibliotheca Chemica Curiosa” (“The Careful Enquirer’s Chemical Library”) issued in two large folio volumes at Geneva in 1702 contain between them more than three hundred al-chemical tracts running to some seven thousand pages. These typical examples of the “omnibus volumes” to which alchemy became addicted in its later days are symptomatic of the truly colos- sal output of a specialised field of literature embracing from first to last a period of some fifteen centuries.1° Ref.5 p. 57. 5~ Ref. 2 p. 228. lo Ref. 2 is out of print but much cognate information is contained in the author’s ‘ThroughAlchemy to Chemistry” now in the press (Bell London 1957). COMMUNICATIONS Mean Vibration Frequencies in Liquids By R. M. BARRER DEPARTMENT COLLEGE AND TECHNOLOGY, (CHEMISTRY IMPERIAL OF SCIENCE S. KENSJNGTON, LONDON,S.W.7) ESTIMATES have been made of vibration frequencies of physically sorbed molecule^^-^*^ although at present there seems to be no good way of deter- mining such freauencies by a direct method. In this making use of entropies for the gaseous hydro- carbons and of entropies of vaporisation of these species.Such frequencies should be helpful in inter- preting viscous flowand self-diffusion in liquids since they may assist in evaluating pre-exponential con- stants in these rate processes e.g Do in the Arrhenius equation D = Do exp (-E/RT)for diffu- sion. Do = y;d2 where y is a coefficient 6 a mean frequency and d the mean jump distance in the activated state. $go = gssTO + &o + g&o .... . . . .. .‘ 41) where ,&,To is the translational entropy BSIo is the internal vibrati_onal and segmental rotational en-tropy while JRO denotes the rotational entropy associated with the three principal moments of Om,Trans. Faraahy Soc. 1939,35 1247. * Garden Kington,and Laing Proc. Roy.SOC.,1955 A 234 35. a Garden and Kington,Trans. Faraday SOC.,1956 52 1397. PROCEEDINGS TABLE I. Some data for hydrocarbons at 298”~ Hydrocarbon PS (cm. Hg) S/(e.u.) $3T0 (e.u.) ALP. R In (761~3(e.u.) (e.u.) up,(e.u.) n-C4H10 iso-C4H 182-4 261.1 74-1 70.4 38-1 38-1 16.9 15.3 -3.0 -3.4 0-3 0.4 n-C5H 12 51a26 83.3 38.7 21.2 +la5 0.1 ~so-C~H~2 68.77 82.0 38.7 19.7 +Is1 0.2 neo-C$3 a 128.5 73.2 38-7 17-5 -1.7 0-3 n-C6H1 4 n-C,H,,isoOctane t 15.12 4-58 4.92 92.5 101.6 102.3 39.3 39-7 40.1 25.2 29.3 28.1 +3*2 +5*6 +5.5 0.1 0.1 0.1 C6H6 9.49 66.3 39-0 27.1 +4*4 0.1 cyclopentane 31-75 70.0 38.7 23-4 +2-0 0.2 * Figures in brackets have been obtained thermochemically.6 t 2 :2 :4-Trimethylpentane. fl* (e.u.) 53.9 [55*2&0-3] 51.3 [52.09&0*01] 63.5 [62*78&0.2] 63-1 [62-24] 53.7 70.6 77.9 79.7 41-7 48.8 inertia.For the entropy Sl of the liquid under its saturated vapour pressure L7l = IS= + $1 + p!7R + J3v .. . . .... . * (2) where & is the codigurational entropy i,!?~ corres-ponds to $IO and lg~ is the rotational entropy in the liquid corresponding to the three principal moments of inertia or the vibrational entropy for rocking motions which may replace some of the rotations. 1313~is the vibrational entropy of the molecule a,s a whole in its liquid environment which replaces $3T in the gaseous state. If ps is the saturation vapour pressure and the standard state is taken as one atmosphere we may write at 298”~ Sl = sgo+Rln (76/p,) -orp -(LfH/T)2ss...(3) where AHIT = AS is the entropy of vaporisation at the chosen temperature say 298”~.ccp is a correction for non-ideality of the gas and u-.-( 27 lZ Tc) wherePC and T,are critical pressure ”32 P and temperatuie respectively.From (l) (2) and (3) we then obtain The configurational entropy for the liquid is always small. One estimate4 gives it as 4-33 e.u. a value which we shall use_ throughout. Moreover the trans- lational entropy gS3Tois given by J3T0 = 6.864 log10 M -2.313 + 11 -439 log T and so may be calculated. Similarly orp and AH/T may be obtained from published data 59G and so the left-hand side of eqn. (4) may be evaluated. In Table 1 are surnmarised the relevant data. If anything restrictions imposed by the crowded environment in the liquid_ state will tend to make (gg~o + $RO) > (lflz + IS& However if we assume that these two quantities are equal we will obtain a value for Zf3v which will at bzst be correct and at w_orst an upper limit.From ZS3v we may then find J,v and so derive a mean frequency ; from the relation hv ZSIV=R [:T-(eW-l)-l-ln(l-exp-) kT kT 1(6) In eqn. (6) we are replacing a range of frequencies by a single Einstein mean frequency. Values of z,f?lv and of V are collected in Table 2 for various hydro- carbons. All the mean frequencies are seen to be in the vicinity of 1 x 10l2sec.-l. As an approximate further check on the sequence of frequencies given in Table 2 we may set TABLE2.Calculated mean frequencies at 298”~ for some hydrocarbon liquids ISlv ;x lo12 v’ x 1w2 (298”~) (set.-') (sec.-l) Hydrocarbon (e.u.) n-C4H10 5.5 iso-C4H10 6.2 n-C 5H12 6-2 iso-C5H1 6.5 neo-C5HI2 6-3 n-C aH14 5.6 n-C,H, 5.2 isoOctane 5.7 CGHG 5-3 cycZoPentane 5-6 (eqn. 6) (eqn. 8) 1-2 0.9 0.9 0.94 0.94 1 ‘0 0.8 0-96 0.90 ~0.9~1 1.1 1.0 1-3 1.0 1.1 2 0.93 1 ‘2 1-1 1.1 1 ‘0 Slater “Introduction to Chemical Physics” McGraw-Hill Book Co. New York 1939 p. 263. Timmermans “Physico-chemical Constants of Pure Organic Compounds” Elsevier Amsterdam 1950. “Selected Values of Properties of Hydrocarbons” Nat Bur. Stand. U.S. Govt. Printing Office 1947. wherefis the mean restoring force and m the reduced This is done because of the compact structure and mass.If further we take f= kAE where k is assumed symmetry of thE molecple which makes it very to be a universal constant and AE is the energy of probable that (,$lo + gSRo) + ,s,),so that N vaporisation then Vl = 0.9 x lo12sec.-l as given in Table 2,column 3 should be the correct value for the mean frequency. 3-J””. ........................ With this figure as standard then the other fre- va AEzm1 quencies derived from eqn. (8) are given in Table 1 where m1and m2 may be taken as the molecular column 4. If allowance is made for the various masses of the species. In the use of eqn. (8) we will uncertainties there is reasonable correlation. take for the standard Vl the frequency of neopentane.(Received March 6th 1957.) Hexa(hydr0gen sulphato)plumbic Acid a Complex Acid in the Sulphuric Acid Solvent System By R. J. GILLESPIE and E. A. ROBINSON COLLEGE STREET, (UNIVERSITY GOWER LONDON,W.C.1) RECENTLY the complex acid HB(HS04)4was shown the values of the two dissociation constants of to exist in solution in sulphuric acid.l Evidence has H,Pb(HSOd, Kl = 1.1 x and K2 = 1.6 x lo3 now been obtained for the existence of another com- mole kg.-l. Thus in its first dissociation H,Pb(HSOJ plex acid in the sulphuric acid solvent system is slightly weaker than disulphuric acid H2S20 namely hexa(hydrogen su1phato)plumbic acid (K = 2 x mole kg.-1).4 H2Pb(HS04),. It is interesting that plumbic sulphate is only Cryoscopic and conductimetric measurements TABLE1.Results of cryoscopic and conductimetric were made on solutions of lead tetra-acetate in measurements of solutions of lead tetra-acetate sulphuric acid. From the results of the conductivity in sulphuric acid measurements the number of hydrogen sulphate V* Y* ions (y)produced by the ionisation of one molecule 102m 0.5 8.20 3.41 of lead tetra-acetate was found.2 This varied with 1.0 7-82 3-23 concentration as shown in Table 1. From the results 1.5 7-71 3.00 of the cryoscopic measurements the total number of 2.0 7.62 2.82 particles (v) produced in solution by one molecule 2- 5 7-58 2.71 of lead tetra-acetate was found.3 This also varied 3.0 7.55 2.65 with concentration (see Table 1). A number of pos- 3-5 7-54 2- 59 sible reactions of lead tetra-acetate are shown in 4.0 7-53 2.56 Table 2 together with the corresponding values of 4.5 7.52 2.52 v and y.The results in Table 1 are consistent only 5.0 7.50 2.50 with the formation of H2Pb(HS04) and its anions 5.5 7.48 2.48 (reactions 2 3 and 4 of Table 2). The degree of ionisation of the acid increases with increasing con- *Theoretically on the basis of equations 2 3 and 4 in Table 2 v = y + 5 for all concentrations of added centration because of simultaneous increase in the solute. This is true within the limits of experimental concentration of hydrogen sulphate ion. accuracy especially if due allowance is made for the effect of the non-ideality of the solutions on the freezing From the values of v or y it is possible to calculate point.TABLE 2. Possible ionisations of lead tetra-acetate in sulphuric acid YV (1) P~(OAC)~ + 8H2S0 = Pb4+ + 4AcOH,+ + 8HS04-8 13 (2) Pb(OAc) + 10H2S04= H,Pb(HSO,) + 4AcOH2++ 4HS04-4 9 (3) P~(OAC)~ + 9H2S04= HPb(HSO,),-+ 4AcOH2++ 3HS04-3 8 (4) Pb(OAc) + 8H2S04= Pb(HS0q);-+ 4AcOH2++ 2HS04-2 7 (5) Pb(OAc) + 8H2S04= Pb(HSOJ2-+ 4AcOH2+ 0 5 Flowers Gillespie and Oubridge J. 1956 1925. Gillespie and Wasif J. 1953 221. Gillespie Hughes and Ingold J. 1950 2473. PROCEEDINGS \ / 4\Pb/ 4\Pb/ 4\pb/ / / \ I /Pb\ SO,/ I \ so4 I \ SO I Pb(I-ISO4)2- exists only in dilute solution and at higher concentrations it presumably polymerises with elimination of sulphuric acid to give complex polymeric anions containing sulphate bridges such as (I) and (11).A similar phenomenon has been observedl in the case of HB(HSO& whose salts which are soluble with difficulty in sulphuric acid always appear to contain complex polymeric anions so so \ I / so4\Pb/I sod /pb\ / \ I so I so SO4 SO so so4 I /SO\ I / nM+ /p\ /Pb\ I so I SO SO A New Route to Trifluoroacetic Acid By R. N. HASZELDINE and F. NYMAN (CHEMICAL CAMBRIDGE) LABORATORY AN improved method for the preparation of trifluoroacetic acid has been found by extension of earlier work1 on photochemical oxidation. The com- pounds CF3CH,Cl (I) and CF3*CHC1 (11) are readily synthesised by reaction of trichloroethylene with hydrogen fluoride and chlorination of the monochloro-compound(I) respectively.Photochem- ical oxidation of chloro-1:1 :1-trifluoroethane (I) gives 50-60 % yields of trifluoroacetic acid; when chlorine is added as sensitiser the oxidation is rapid and a mixture of trifluoroacetyl chloride (60%) and trifluoroacetic acid (1 5-20 %) results. Dichloro-1 :1 :1-trifluoroethane (11) is oxidised even more readily and gives a 90% yield of trifluoroacetyl chloride within a few minutes; loss of chlorine from an intermediate perhalogenoalkoxy-radical is prob- able? CF3CHC12+ Cl. + HC1 + CF3CC12* + CF3CC12*02* + CF3CC12*O- + CF,-COCl + C1- -+ etc. These photochemical oxidation chain reactions can be carried out on a half-molar scale in the apparatus described earlier, thus providing a convenient laboratory method for the preparation of trifluoro- acetic acid.Even 1:1 :1-trichlorotrifluoroethane CF,CC13 which is extremely inert to normal chemical reagents and is converted by fuming sulphuric acid into tri- fluoroacetic acid in only 10% yield can be oxidised photochemically in presence of water to give tri- fluoroacetic acid in 60-65 % yield; the rate-deter- mining step here is the homolytic fission of the C-Cl bond to give the CF,-CCl,* radical so that irradiation times of 2-4 days are necessary. Finally it should be noted that heat and oxygen can be used instead of light and oxygen for these oxidations. At 200° with small amounts of chlorine as sensitiser the compounds (I) and (11) are oxidised to trifluoroacetic acid in 75 % and 92 % yield respec- tively and these relatively simple autoclave reactions clearly provide the most convenient and probably the least expensive route to the acid yet described.(Received March 19th 1957.) 1 Francis and Haszeldine J. 1955 2151 ; Barr,Francis and Haszeldine Nature 1956 177,785. Barr and Haszeldine J. 1955 1881. MAY 1957 147 The Photochemistry of Prednisone Acetate By D. H. R. BARTON and W. C. TAYLOR (THEUNIVERSITY W.2) GLASGOW [It is regretted that errors occurred in reproduction of the formulre in the Communication under the above title $HiOAc printed in Proceedings for March 1957 p. 96. These rendered the Communication misleading and it is there- fore reprinted below with correct formula.-ED.] IT has been shown1 that irradiation of santonin (I) in aqueous acetic acid with ultraviolet light gives the guaianolide derivative (11). Under the same condi- tions prednisone acetate (IIQ2 gives the photo-analogue (IV) m.p. (from methanol) 240-243" [a] + 134" (c 0.51 in CHCl& Amax. 233 mp (E 15,500 in EtOH) infrared bands (in CHCl solu- tion) at 1740 (acetate) 1723 (20-ketone) 1685 (H-U bonded 1 1-ketone and cycfopentenone) and m.p. (from chloroform-methanol) 270-275" Amax. 1609 cm.-l (conjugated ethylenic linkage) (Found 391 mp (E 29,500 in CHCI,)]. The constitution (IV) C 66.0; H 7.4; Ac 10.7. C23H3@ requires C 66.0; assigned is based on analogy the data cited the fact H 7.25 ; 1 Ac 10-4 %) [2 :4-dinitrophenylhydrazone that dihydroallocortisone acetate was recovered un- changed after irradiation for three times as long under the same conditions and the following critical experiment (cf.ref. 1). Ozonolysis of the product (IV) in chloroform at -50" gave the y-lactone (V) m.p. 143-145" [a] + 128" (c 0-66 in CHCI,) O%*O% 0 infrared bands (in CHCZ solution) at 1768 (y-lactone) 1740 (acetate) and 1712 cm.-l (1 1-ketone 20-ketone and cycfoheptanone) (Found :C 62-6;H 6-6. C22H2808 requires C 62.8; H 6.7%). Both products (IV) and (V) gave positive Dische colour tests3 for the corticosteroid side chain. We thank Messrs. Glaxo Laboratories Ltd. for Fellowship support (W.C.T.). (Received February 20fh 1957.) Barton de Mayo and Shafiq J.1957,929. Herzog Payne Jevnik Gould Shapiro Oliveto and Hershberg J. Amer. Chem. Soc. 1955 77 4781 ; Nobile, Charney Perlman Herzog Payne Tully Jevnik and Hershberg ibid.,p. 4184. 'Clark Nature 1955 175 123. Synthesis of "Active Sulphate" By J. BADDILEY and R. LETTERS J. G. BUCHANAN (KING'SCOLLEGE OF DURHAM UPON TYNE) UNIVERSITY NEWCASTLE THE sequence of enzymic reactions1 which brings pyridine-sulphur trioxide complex on adenosine-5 about the synthesis of sulphuric esters has been phosphate in dilute sodium hydrogen carbonate shown to include the formation of adenosine-5' solution.2 sulphatophosphate (I ;R = H) from inorganic The necessary intermediate for the chemical syn- sulphate and adenosine triphosphate (ATP). A thesis of active sulphate itself would be adenosine- further reaction between the sulphatophosphate and 3' :5' diphosphate (11).This is known as a degradation the triphosphate yields adenosine 3'-phosphate product of coenzyme A but is not readily available. 5'-sulphatophosphate (I ;R = P03H2) sometimes We are grateful to Dr. J. D. Gregory for providing known as "active sulphate". We have synthesised us with a few milligrams of this diphosphate isolated adenosine-5' sulphatophosphate by the action of the from natural sources. The diphosphate was treated Robbins and Lipmann J. Amer. Chern. Soc. 1956 78 2652 6409; Bandurski Wilson and Squires ibid. p. 6408. * Baddiley Buchanan and Letters J. 1957 1067. with the pyridinesulphur trioxide reagent in dilute sodium hydrogen carbonate solution at 40° and the products were separated by adsorption on charcoal elution with dilute aqueous ammonia and paper chromatography.In addition to unchanged diphos- phate two main ultraviolet-absorbing products were observed in n-propyl alcohol-ammonia (d 0.88)-water (6:3:1). One of these was identified as adeno- sine 2’ :3’-phosphate S’-phosphate (111) from its behaviour on paper chromatography and on electro- phoresis. It showed the migration rates at pH 4 and 7 expected for a diphosphate of adenosine containing two primary and one secondary phosphoric acidic group. On acid or alkaline hydrolysis it yielded an inseparable mixture of adenosine-3’ :5’ and -2’ :5’ diphosphate. d 0 PROCEEDINGS The second major product of the sulphation reaction was indistinguishable from natural active sulphate both by paper chromatography and by electrophoresis at various pH values.It was readily hydrolysed in acid to inorganic sulphate and a mix- ture (presumably) of diphosphates of adenosine with the same properties on paper chromatograms as adenosine-3’:5’ diphosphate. The product showed marked but somewhat variable activity in the enzyme system for the synthesis of organic sulphates (experiments by Dr. F. Lipmann). We ascribe the variation in activity of different samples to the natural hazards expected during preparation and transit of a very sensitive substance between this country and America. l/”\I The cyclic phosphate (111) would be expected to arise by spontaneous decomposition of an inter-mediate 3’-sulphatophosphate.In this connexion it was shown that a mixture of adenosine2’ and -3’ phosphate was partly converted into the correspond- ing cyclic phosphate when treated with the pyridine- sulphur trioxide reagent. (Received March 20th 1957.) Synthesis of the N-Glycyl-D-Ribofuranosylamines By J. BADDILEY R. HODGES, J. G. BUCHANAN and J. F. PRESCO~T (KING’S COLLEGE UNIVERSITY OF DURHAM UPON TYNE) NEWCASTLE THE5-phosphate of N-glycyl-D-ribofuranosylamine is a natural precursor of the purine nuc1eotides.l Methods for the synthesis of N-glycyl-P-D-glucosyl- amine were recently2 developed in connection with a projected synthesis of the ribofuranosyl compound. We have now extended the methods to the D-ribo- furanose series.2 :3 :5-Tri-0-benzoyl-P-D-ribofuran-osyl azide (I; R = Bz) was prepared in 76% yield from the corresponding ribosyl chloride3 by reaction with sodium azide in methyl cyanide. Its structure was proved by debenzoylation to the syrupy azide (I; R = H) which consumed 1 mol. of periodate to give the same dialdehyde as was derived from p-D-glucopyranosyl a~ide.~ Catalytic reduction of the benzoyloxy-azide (I; R = Bz) yielded the unstable ribosylamine (U) which was immediately treated with benzyloxycarbonylglycyl ethyl carbonate. The product was purified on neutral alumina to give a syrupy mixture of anomers (I11 and IV; R = Bz R0.H ROH HCOCH~NHR‘ (I) RO OR RO OR (rn) Goldthwait Peabody and Greenberg J.Biol. Chem. 1956 221,555; Peabody Goldthwait and Greerkerg ibid. p. 1071; Hartman Levenberg and Buchanan ibid. p. 1057. Baddiley Buchanan Handschumacher and Prescott J. 1956 2818. a Kissman Pidacks and Baker J. Amer. Chem. SOC.,1955 77 18. * Bertho Ber. 1930 63 836. MAY 1957 R' = CH,Ph-OCO). Debenzoylation afforded first the a-anomer (111; R = H R' = CH,Ph.O-CO) m.p. 169-170" [aID+ 63.3" (in pyridine) and from the mother-liquors was isolated the monohydrate of the /3-anomer (IV; R = H R' = CH,Ph-OCO) m.p. 98-101" [a] -31.9" (in pyridine). Each isomer reacted with only 1 mol. of periodate the /%isomer giving the same dialdehyde as that from a similar oxidation of N-(benzyloxycarbonylglycy1)-@-D-glucopyranosylamine.2 The N-glycylribofuranosylamines (111 and IV ; R = R' = H) were prepared by hydrogenolysis of the corresponding benzyloxycarbonyl compounds.The a-compound had [a],+ 88.9" (in H20) and the @-compound had [a],-49.7" (in H,O). Oxidation of the @-compound with periodate gave the same dialdehyde as was obtained from N-glycyl-P-D-glucopyranosylarnine. The isomeric N-glycylribo- furanosylamines had the same RF value on paper chromatography and gave an initial yellow colour with the ninhydrin spray and the usual slowly form- ing blue-purple colour of a glycoside with the periodate-Schiff spray.2 We are indebted to the Royal Commissioners of the 1851 Exhibition for an Overseas Studentship (to R.H.) and the Council of King's College for a Johnston Studentship (to J.F.P.).(Received April 8th 1957.) Synthesis of 5-Amino-l-(~-~-ribofuranosyl)glyoxaline-4-carboxy~de By J. BADDILEY and J. STEWART J. G. BUCHANAN (KING'S COLLEGE ~NIVERSITYOF DURHAM UPON TYNE) NEWCASTLE GREENBERG reported the isolation of and SPILMAN~~~ 5-amino-1-(#3-~-ribofuranosyl)glyoxaline-4-carboxy-amide (I)from the culture medium of sulphonamide- inhibited E. coli. They regarded it as having been formed from its 5'-phosphate the true purine nucleotide precursor by enzymic dephosphorylation. The riboside (I) has now been synthesised by a method based on an unsuccessful attempt to prepare 9-glycosylxan thine~.~ The silver or mercury salt of methyl 5-nitroglyoxaline-4-carboxylate (11) was treated with 2:3:5-tri-O-benzoyl-@-~-ribofuranosyl n chloride4 in boiling xylene.Chromatography on neutral alumina gave a fraction which was essentially a mixture of (111) and (IV) (R = tri-O-benzoyl-/b-ribofuranosyl). Treatment of this mixture with methanolic ammonia gave a mixture of nitro-amides (V) and (VI) (R= /h-ribofuranosyl). Chromato-graphically pure amide (V) was obtained by counter- current distribution and catalytic reduction of this isomer gave the amino-amide (I) which was isolated as its crystalline picrate. Identity was confirmed by elementary analysis chromatographic comparison with an authentic sample and conversion into inosine by way of the formyl derivative.2 The amino- amide (I) could be detected on chromatograms by modified Bratton-Marshall reagents,2 by the period- ate-Schiff spray,5 or by examination under ultra- violet light.We are indebted to Dr. G. R. Greenberg for a generous sample of the riboside (I) isolated from natural sources and to the Nuffield Foundation for financial assistance. (Received April 8th 1957.) 'Greenberg J. Amer. Chem. SOC., 1952,74 6307. 'Greenberg and Spilman J. Biol. Chem. 1956 219,411. 'Allsebrook Gulland and Story J. 1942 232. * Kissman Pidacks and Baker J. Amer. Chem. SOC.,1955 77 18. Baddiley Buchanan Handschumacher and Prescott J. 1956 2818. 150 PROCEEDINGS FORTHCOMING SCIENTIFIC MEETINGS London Thursday June 6th 1957 at 7.30 p.m. Meeting for the Reading of Original Papers. “The Vapour Pressure of Anhydrous Copper Nitrate and its Molecular Weight in the Vapour State,” by C.C. Addison and B. J. Hathaway. “Aromatic Reactivity. Part 11. The Cleavage of Aryltrimethylsilanes by Bromine in Acetic Acid,” by C. Eaborn and D. E. Webster. “The Kinetics of the Oxidation of Ethane by Nitrous Oxide,” by R. Kenwright A. B. Trenwith and P. L. Robinson. To be held in the Rooms of the Society Burlington House W. 1. Monday and Tuesday July 8th and 9th 1957. Symposium “Solvent Effects and Reaction Mechan- ism.” To be held at Queen Mary College (cf. Proc. Chem. SOC.,1957 62). Closing date for applications June 20th. Glasgow Thursday and Friday July 11 th and 12th 1957. Official Meeting and Symposium “Recent Advances in the Chemistry of Terenoid Compounds.” To be held in the Chemistry Department The University (cf.Proc. Chem. SOC.,1957 4). Closing date for applications June 10th. NEWS AND ANNOUNCEMENTS Congresses.-The XXXth International Congress of Industrial Chemistry will be held in Athens on September 17-24th 1957. Further details forms of application and copies of the provisional programme of the Conference which is divided into 20 Sections may be obtained from the Organising Committee 10 Rue Kaningos Athens Greece. The third circular for the XVIth International Congress of I.U.P.A.C. which is to be held in Paris on July 18-24th 1957 may now be obtained from Secrktariat General du XVIe Congres de Chimie 28 Rue Saint-Dominique Paris 7e. The circular in- cludes an application form and details of the lectures tours etc.(cf. Proc. Chem. SOC.,1957 3). This Con- gress will be preceded by the Centenary Celebration of the “Societe Chimique de France” on July 16-18th 1957. An International Congress and Exhibition of Measuring Instrumentation and Automation will be held in Diisseldorf on November 2-10th 1957. Further information and copies of a circular relating to the Congress may be obtained from Nordwest- deutsche Ausstellungs-Gesellschaftm.b.H. Ehrenhof 4 Diisseldorf Germany. The Royal Institute of Chemistry.-At the Annual General Meeting of the Royal Institute of Chem- istry held on Friday April 5th 1957 Professor William Wardlaw C.B.E. was elected President of the Institute in succession to Dr. D. W. Kent-Jones who has completed his two-year period of office and now becomes a Vice-president ex oficio.Professor Wardlaw who is a Professor of Chemistry in the University of London at Birkbeck College is the immediate past-President of The Chemical Society. His election as President of the Institute follows a long period of distinguished service as a Member of Council an Examiner and a Censor of the Institute. Chemical Society Library.-The Library will be closed for the Whitsun holiday on June 10th and 11th 1957. Wellcome Trust Benefactions.-Amongst other benefactions the Trustees have agreed to buy two items of special equipment for indefinite loan to research centres. They will be a nuclear magnetic resonance spectrometer (costing approximately €17,000) for the Department of Chemistry Univer- sity College London and a photo-electric spectro- polarimeter (costing approximately f.3,600) for the Department of Biochemistry Postgraduate Medical School of London.Awards.-The University of Cambridge is to confer the Honorary Degree of Doctor of Science on Professor Otto Hahn President of the Max Planck Society for the Advancement of Science Gottingen (Honorary Fellow). The University of Durham is to confer the Honorary Degree of Doctor of Science on Professor H. C. Urey Professor of Chemistry in Chicago University. Dr. H.W.Melville has been awarded the Gunning Victoria Jubilee Prize of the Royal Society of Edinburgh for the period 1952-56. Mr. W. Gordon Carey has been elected President of the Society for Water Treatment and Examination.The Meldola Medal for 1956 has been awarded to Dr. T. S. West Lecturer in Professor M. Stacey’s department at the University of Birmingham. This Medal which is the gift of the Society of Macca- baeans is awarded each year to the chemist who being a British subject and under 30 years of age at December 31st in that year is considered to have shown the greatest promise as indicated by his or her MAY 1957 published work. Awards are made by the Council of the Royal Institute of Chemistry with the concur- rence of the Society of Maccabaeans on the recom- mendation of a specially appointed advisory commit tee. The Royal Australian Chemical Institute has awarded the Rennie Memorial Medal for 1956 to Dr.P.R. Jeferies Senior Lecturer in Chemistry at the University of Western Australia. The Council of the Faraday Society recently announced the institution of an award to be known as The Marlow Medal accompanied by a grant of not more than fifty pounds. The award is made annually and is based on publications (not neces- sarily in the Transactions) over the preceding three years on any subject normally published in the Transactions. It is restricted to members of the Faraday Society of not less than three years standing and not exceeding 33 years of age. The first award has been made to Dr. J. S. Rowlinson of the Chem- istry Department Manchester University for his researches on the thermodynamics and statistical mechanics of gases liquids and mixtures.The pre- sentation will be made at the Annual General Meeting of the Faraday Society to be held at Oxford Univer- sity in September 1957. Personal.-The Council of the University of Southampton has approved the appointment of Dr. R. C. Cookson Lecturer in Chemistry at Birk- beck College London to be Professor of Chemistry with effect from October 1st. The title and status of Reader has been conferred on Dr. R. S. Bradley Senior Lecturer in the Depart- ment of Inorganic and Structural Chemistry at the University of Leeds. The title and status of Reader in Mathematical Chemistry has been conferred on Dr. D. W.J. Cruickshank Lecturer in Mathematical Chemistry in the same Department. Dr.M. Gordon Courtauld Fellow in the Man- Chester College of Science and Technology has taken up his appointment as Assistant Director of the new Arthur D. Little Research Institute at Inveresk Gate Musselburgh Midlothian. Dr. R. J. Wicker has been appointed Research Manager Howards of Ilford Limited. Mr. N. Kirby Government Chemist Jamaica has been transferred to Nairobi as Government Chemist Kenya. A Postdoctorate Fellowship at the State Univer- sity of New York Syracuse N.Y. has been awarded to Dr. D. H. Richards previously of the British Thomson-Houston Co. Ltd. Mr. F. Courtney Harwood after 21 years in the position has retired as Director of the British Launderers’ Research Association. Fellows in the Union of South Africa Professor W.F. Barker Rhodes University who has been on leave working at the National Chemical Laboratories Teddington is now continuing his studies at the Case Institute of Technology Cleve- land Ohio. Dr. L. J. Dry has resigned his lectureship at the University of Natal to take up the post of Senior Organic Chemist at Sasol Factory. Dr. J. R. Nunn originally in the Cape Town unit of the National Chemical Research Laboratory has been appointed officer-in-charge of the Organic Div- ision in Pretoria. Dr. J. R. Parrish formerly Lecturer at Rhodes University has joined the Staff of the National Chemical Research Laboratory C.S.I.R. Pretoria. Mr. H. A. Candy has been promoted to Senior Lecturer hChemistry at the University of Natal. Deaths.-We regret to announce the deaths of Mr.E. W. Hood (21.2.57) of Shell Central Labora- tories and Mr. W. B. Walker (18.3.57) Chief Chemist of J. S. Fry & Sons Ltd. OBITUARY NOTICES FRANK SHERWOOD TAYLOR 1897-1956 THEname of Frank Shenvood Taylor who died on January 5th 1956 near London is well known to chemists through his text-books of chemistry and his books on the history of science. He was a most unusuaI person with a widely ranging mind. To his interest in scientific ideas and their evolution and his skill in presenting them he added a social historian’s sense of their importance in human life; he had more- over a humanist’s appreciation of poetry and the plastic arts and a deep love of the classic spiritual authors both of East and West.It was characteristic of him that he moved easily from one plane to another declining to restrict himself to a single mode of thought; this ideal was the theme of a small book he wrote in 1945 “The Fourfold Vision.” Sherwood Taylor was born in 1897 and was educated at Sherborne School. He won a classical scholarship at Lincoln College Oxford but war ser- vice prevented him from taking it up at once; after the war he asked and was allowed to read science instead. The combination of a classical with a scientific training reflected the bent of his mind and made possible the studies on the alchemists which he pursued at intervals throughout his academic life. The first of these studies was his Ph.D. thesis on the Greek alchemists written under the supervision of Dr.Charles Singer as a student of the Department of the History and Philosophy of Science University College London. Meanwhile he was teaching chem- istry at various schools including Gresham’s and Repton and in 1933 was appointed assistant lecturer in inorganic chemistry at Queen Mary College London where he taught for five years. It was during these years from 1921 to 1938 that he wrote his text- books on inorganic and organic chemistry. In 1936 he published “The World of Science” which was an attempt to bring a scientist’s knowledge of the world to the general intelligent public. It was a maxim with him that any topic could with sufficient care be presented to the general reader and his books were always readable as well as scholarly.His historical books which he now began to write were models of their kind keeping close to the primary sources but never pedantic; one thinks especially of “Galileo and the Freedom of Thought” (1939) “The Century of Science” (1940) and “Science Past and Present” (1945). Sherwood Taylor was interested from its beginning in the British Society for the History of Science of which he was president for a time. He was also a founder member of the Society for the Study of Alchemy and Early Chemistry and editor of its journal Arnbix in which he published translations and papers on the history of alchemy. In 1940 he went to Oxford as Curator of the Museum of the History of Science and began to PROCEEDINGS lecture there while continuing to write on the history of science.He became a Roman Catholic in 1941 and soon afterwards published translations of two works by medieval spiritual writers Ruysbroek’s “Seven Lamps of Spiritual Love” and Hugh of St. Victor’s “Betrothal of the Soul.” In 1950 he was appointed Director of the Science Museum at South Kensington. Here his initiative was felt particularly in the development of the teaching side of the museum and in the expansion of the library’s collec-tion of early scientific books. His “Illustrated History of Science” and “History of Industrial Chemistry” date from this period. He retained his interest in the teaching of science in schools and wrote some new text-books for this purpose.He wrote and lectured a good deal on the place of science in Christian life and as an ex-materialist sought to expose the fallacies of materialism. The longest meditated and probably the most enduring of his books was “The Alchemists” (1949). Here the theme engaged his chemical interests his historical and literary techniques his sympathy with mysticism both of east and west and his understand- ing of symbolism and poetic language (William Blake was one of his favourite poets). Few other men could have written such a book distinguishing the practical advances of the alchemists from the interpretations they put upon their work and relating those inter- pretations to the great themes of human thought. Sherwood Taylor was a delightful companion witty well-informed courteous and kindly.He was much in demand as a lecturer and always prepared his talks with the greatest care. He would take great pains in reading and commenting on manuscripts designed for publication. He was generous in his recognition and encouragement of young writers. With his concern for science religion and the arts his was a singularly complete personality. E. F. CALDIN. FRANCIS HEREWARD BURSTALL 1903-1955 FRANCIS HEREWARDBURSTALLwas born in Birmingham on November 29th 1903 and died after two long and painful illnesses on December 2nd 1955 at his home in Hampton Hill. He was the younger son of Professor F. W. Burstall who for many years was Professor of Mechanical Engineering and later Vice-principal of Birmingham University.Burstall received his early education at Brighton College and then entered the University of Birming- ham where he graduated with first-class honours in chemistry in 1925. In October of that year the Chemical Research Laboratory was opened with Professor (later Sir) Gilbert Morgan as its first Super- intendent. Morgan brought Burstall with him from Birmingham and there then began a long and valu- able collaboration in the field of co-ordination chemistry a field in which Burstall with his penetrat- ing mind and experimental skill was soon at home and to which like his senior colleague he was greatly attracted. Moreover Burstall soon saw that co-ordination covered vast areas of pure and applied chemistry and the words with which he opened the section on “Co-ordination Compounds” in the Annual Report of the MAY 1957 Society for 1938 are more than ever true today “It will cause no surprise that the study of co- ordination compounds continues to be prosecuted with unabated vigour when it is realised how far the co-ordination theory in its modern form has become interwoven into the fabric of chemistry.” The early work at Teddington was largely concerned with the stabilisation of normally unstable salts of the currency metals through co-ordination with ethylenediamine ethylenethiocarbamide and other ligands.One practical object of this work was the search for relatively simple and stable water- soluble aurous compounds which might be useful in chemotherapy and a patent was taken out on the therapeutic complexes obtained with ethylthio-carbamide.In the early days chemotherapy was attracting considerable interest at the Chemical Research Laboratory and it led Burstall to forsake co-ordination chemistry for a couple of years in order to take up work on tellura- and selena-cycloalkanes. Morgan and his collaborators at Birmingham had prepared many telluracyclopentane-3 :5-diones some of which had considerable germicidal power and the work was continued at Teddington with Dr. H. Burgess who prepared the parent telluracyclopentane and some of its derivatives. When Burgess left the Laboratory in 1928 Burstall took on the work and quickly there came a stream of communications to the Society on tellura- and selena-cycloalkanes and their derivatives as well as one in collaboration with Professor Sugden on the parachor of tellurium as obtained from some of these organic compounds.Unfortunately none of the compounds had much chemotherapeutic interest. In 1930 a return was made to co-ordination chemistry and there commenced the study of the polypyridyls which was to occupy much of the next eight years. Commencing with 2:2‘-dipyridyl it was shown that this addendum was able to stabilise silver in its bivalent state. The trisdipyridyl nickelous chloride (Ni 3dipy)Cl, first made by Blau was then prepared and resolved into optically active forms by means of ammonium (+)-and (-)-tartrate thus demonstrating the octahedral distribution of the co- ordinated groups around the nickel atom.This was the first authentic occasion of the separation into optically active forms of a co-ordination compound of nickel. Concurrently with these researches there was commenced an extensive programme on the synthesis of the polypyridyls. The Laboratory had recently acquired a 10-litre autoclave and using this Burstall studied the dehydrogenation of pyridine by an-hydrous ferric chloride; the Laboratory either reeked of pyridine or had the sweetish smell of polypyridyls. Some 20 products were isolated from the reaction including 5 of the 6 possible dipyridyls as well as the hitherto unknown 2:2’:2”-terpyridyl which has since proved such a useful chelating and analytical reagent.The high-temperature bromina- tion of these products was also studied and from the mono- and di-bromoderivatives there were synthesised the tetrakis- pentakis- and hexakis-pyridyls. Tetrakispyridyls were also produced by dehydrogen- ating 2:2’-dipyridyl with iodine ferric chloride or ruthenium chloride. Most of these polypyridyls served as chelating agents although compounds sub- stituted in the 6-position showed a considerable decline in co-ordinating power. At this time considerable interest was being displayed in the quadricovalent derivatives of bi-valent platinum palladium and nickel and in the question whether the valency bonds had a planar or a tetrahedral distribution. Resolutions of such com- pounds containing unsymmetrical chelate groups had been claimed suggesting configurations other than the planar ones which Pauling had predicted for these elements.Using the new 2 :2’:2”-terpyridyl Morgan and Burstall were able to isolate a red crystalline salt [Pt (tripy) Cl]C1,2(or 3)H,O which must have a planar configuration and they were thus able to add to the growing volume of evidence for a square arrangement. Although bivalent platinum forms square com- plexes yet with bivalent ruthenium only 6-co-ordinated compounds are formed. A series of such compounds with dipyridyl was next prepared by Burstall. They were extremely stable red salts of the general formula [Ru 3dipy]X2,yH20 and like the corresponding nickel derivative they could be re- solved into optically active forms.It was during the preparation of the chloride by heating RuCI and dipyridyl that 2 :2‘ :2”:2“’-tetrakispyridyl was first obtained as a by-product. At the same time the opportunity was also taken of re-examining “ruthenium red.” The formula assigned to this curious inorganic dye by Joly its discoverer was Ru,C~,(OH)~,~NH~,~H~O and as this was obviously at variance with modern ideas the compound and a number of derivatives were examined again. Morgan and Burstall were able to prove that the dye was [Ru(OH)C1(NH,),]C1,H20 and that there was a con- siderable loss of tinctorial power when the ammonia molecules were replaced by ethylenediamine ethyl- amine or pyridine; it was suggested that this curious phenomenon might indicate that ammonia molecules induced a different distribution of the hydroxy- and chloro-groups from that with the other bases.This work with ruthenium was rounded off by a study of the polypyridyl derivatives corresponding to the nitrosoruthenium ammines which had been prepared by Joly and were later studied by Werner. Burstall also examined the use of ter- and tetrakis- pyridyls as chelating agents with a number of bi- and ter-valent metals. Tt had been the intention to examine the co-ordina ting properties of the pentakis- and hexakis-pyridyls as well but the retirement of Sir Gilbert Morgan in 1938 and the mounting inter- national tension early in 1939 caused the work to be put on one side. Nevertheless the decade between 1928 and 1938 had been one of great effort and grand achievement.Over 20 original communications were published in this Society’s Journal. In addition time was found to produce with Sir Gilbert Morgan an excellent text-book on modern developments in inorganic chemistry in which as it is only natural to expect special emphasis was given to the theory of co-ordination. In 1939 Burstall along with several other members of the Laboratory had to take on more pressing problems provided by other Ministries including the newly formed Ministry of Home Security. Among the tasks assigned to him were the control of insect pests in stored products and the study of methods of producing carbon black two topics rather far re- moved from the realm of co-ordination chemistry.Nevertheless he tackled these with his customary quiet enthusiasm and efficiency and secured some valuable results. With the return of peace the in- organic work of the Laboratory was taken up once more and was soon expanded to meet the needs of a growing atomic energy programme. Soon a Radio- chemical Group was set up with Burstall in charge and he quickly gathered around him a large staff which he inspired with his own enthusiasm and to whom he imparted his skill in research. Much of the early work of the group had perforce to be concerned with analytical problems and here his long experience with so many elements and his profound knowledge of their properties proved of immense value. Also Burstall and his Group joined in the early stages of the work on the application of paper chromato- graphy to the separation of inorganic compounds.PROCEEDINGS Later a section was set up in the Radiochemical Group to study chromatographic methods of analysis and a number of papers and reports has been published on this topic. In spite of his increased responsibilities and the greater demand on his time Burstall found opportunities to go back to his first love and to collaborate with F. P. Dwyer and E. C. Gyarfas in studying some dipyridyl derivatives of osmium. The bivalent trisdipyridylosmium iodide (0s 3dipy)12,3H,0 like its ruthenium analogue was resolved into optically active forms through the optically active antimony1 tartrate. He also published with Professor Nyholm a paper on the magnetic moments of octahedral complexes of chromium manganese nickel cobalt and iron with the chelat- ing agents dipyridyl and o-phenylenebisdimethyl-arsine.In this paper is reported the first instance of a co-ordination compound of tervalent chromium with a tertiary arsine. Burstall gained his M.Sc. in 1926 and received his D.Sc. in 1952. In him the Chemical Research Laboratory has lost a very fine chemist but worse than that the staff has lost a grand colleague quiet and unassuming yet one who was always approach- able and to whom one could always turn for help in the sure knowledge that it would be generously given. He was an excellent example as a workman an enthusiastic chemist who was ready to tackle any problem however uninviting it might appear with the same thoroughness and painstaking efficiency.Apart from an occasional game of bowls he did not play outdoor games himself; nevertheless he would often turn out to watch matches in which the C.R.L. was engaged and was generally interested in the social and sporting activities of the Laboratory. In 1929 Burstall married Jean Lyle who had been a fellow student at Birmingham and survives him with the two sons born to them. Both the sons are following scientific careers the elder as a chemist and the younger as a physicist. G. R. DAVIES. LEO WALLERSTEIN 1882-1956 THEdeath occurred on November 6th 1956 of Dr. Leo Wallerstein in his 75th year. Born in Fuerth Germany Wallerstein after his University training in Brussels joined his brother the late Dr.Max Wallerstein in New York to found the Wallerstein Laboratories. This firm provided a consultant service to the Brewing Industry but soon pioneered the use of specific enzymic preparations in many manufacturing industries. The organisation has several plants for these and allied purposes including one in Great Britain. On the death of his brother in 1937 Leo Waller-stein became President of his Company but he had wide additional interests both industrial and cultural. It has for instance gradually become known that with typical lack of ostentation he made many MAY 1957 generous contributions to leading charities and presented a number of works of art to important museums in the U.S.A.It was characteristic of him to assist many young scientists and to lend a particu- larly active hand to numerous refugees from the Hitler regime. Probably all who knew Wallerstein will remember him best for his restless energy both in scientific endeavour and human relations over an immense field. I am much indebted to Mr. Philip Gray for help in preparing this Notice. A. H. COOK 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.) Aoyama Shinjiro D.Pharm.18 Nikawa-Gokayama Nishinomiya Hyogo-Ken Japan. Ashton Kenneth Sydney Richard B.Sc. 53 Quorn Gardens Leigh-on-Sea Essex. Barber Michael Stuart. 54 Strathmore Gardens Horn- church Essex. Bly Robert Stewart jun. M.S. Department of Chem- istry University of Colorado Boulder Colorado U.S.A. Borrell Peter B.Sc. Emmanuel College Cambridge. Brooker Peter John B.Sc. 49 Ashdon Road Saffron Walden Essex. Bufford Michael John B.Sc. 13 Ramsden Road Orpington Kent. Bunbury David Leslie B.A. Ph.D. 1040 11th Boulder Colorado U.S.A. Cusmano Sigismondo. Istituto Chimica Organica, Universita Bari Italy. Ebsworth Evelyn Algernon Valentine B.A. 69 Storey’s Way Cambridge. England Derek Herbert B.Sc.39 Elton Avenue Green- ford Middlesex. Field Leonard Frederick B.Sc. 24 Ty-Gwyn Road Llandudno Caerns. Gallagher Michael John. 65 Davies Road Ashgrove Brisbane Queensland Australia. Grove John Richard B.A. B.Sc. Ph.D. 1132 New Chester Road Eastham Wirral Cheshire. Hanley James Richard jun. B.S. Department of Chem-istry University of Illinois Urbana Illinois U.S.A. Hassner Alfred M.Sc. Ph.D. Converse Memorial Laboratory Harvard University Cambridge 38, Massachusetts U.S.A. Hay Robert Walker B.Sc. 15 Allan Park Stirling. Hey Arthur Wilson. 61 Boxhill Road Abingdon Berks. Hignett Richard Charles B.Sc. 3 Woodside Drive Hyde Cheshire. Holler Howard Van Alstine B.S. Chemistry Department University of Colorado Boulder Colorado U.S.A.Hughes David William B.Sc. Chemistry Department The University Nottingham. Hurlock Ronald James B.Sc. A.R.I.C. 81 Mimms Hall Road Potters Bar Middlesex. Jambor Bela D.Tech. Institute of Plant Physiology The University Muzeum krt. 4/a Budapest Hungary. Jampolsky Lester Mischa D.Sc.tech. B.A. 14 Winder- mere Road Upper Montclair New Jersey U.S.A. Johnson Brian Lloyd B.Sc. 27 Cooloongatta Road Camberwell Victoria Australia. Jordan Henry Francis. Raemoir Hotel Banchory, Kincardineshire. Kon Tsurujiro D.Pharm. c/o Sanzen Seiyaku K.K. Omiya Lab. No. 300 Amanuma-cho 2-chome, Omiya-shi Saitana-ken Japan. Lieber Eugene Ph.D. Department of Chemistry De Paul University 1036 Belden Avenue Chicago 14, Illinois U.S.A. Liler Milica D.Sc.tech.13 West Avenue Gosforth Newcastle-upon-Tyne. Lord Peter Anthony B.Sc. 31 Dale Street Bacup Lancs. Madle David Victor B.Sc. Flying Fox Harwich Road Colchester Essex. Michel Georges Lic. es Sc. Laboratoire de Chimie Biologique Faculte Catholique des Sciences 25 Rue du Plat Lyon France. Miller John Joseph B.S. Ph.D. Rohm & Haas Co. Redstone Arsenal Research Division Huntsville Alabama U.S.A. Mondon Albert Dr.Rer.nat. Institut fur organische Chemie Ohlshausenstr. 40-60 Kiel Germany. Moore Barry M.Sc. 84 Chapel Road Bankstown N.S.W. Australia. Morgan Keith B.Sc. Ph.D. 8 Newton Lane Hoole Cheshire. Nunn Ernest Keith B.Sc. 17 Glebe Street Hobart Tasmania Australia. Pauncz Rezso D.Ph. Israel Institute of Technology, Department of Chemistry Haifa Israel.Pavlow George B.S. c/o Chemistry Department, University of Colorado Boulder Colorado U.S.A. Pledger Huey jun. M.S. Ph.D. 3816 Moorland Drive Midland Michigan U.S.A. Reid James F. 13 Dunn Street Paisley Renfrewshire. Rogers Francis E. B.S. M.A. Ph.D. Chemistry Depart- ment University of Colorado Boulder Colorado U.S.A. Sanderson Arnold Raymond B.Sc. 7 Bowsden Terrace Gosforth Newcastle upon Tyne 3. Sandri Joseph Mario B.S. Ph.D. 7219 S. Phillips Avenue Chicago 49 Illinois U.S.A. Sim George Andrew B.Sc. Ph.D. 2 Marchmont Terrace Glasgow W.2. Smith Peter Sidney. 5 Rosebery Avenue Melton Mowbray Leics. Smith Peter Warnock B.Sc. c/o Chemistry Department University College Gower Street London W.C.l.Soady Richard John Charles B.Sc. 415 Pacific Highway Artarmon Sydney New South Wales Australia. Sugden Theodore Morris M.A. Ph.D. Department of Physical Chemistry Free School Lane Cambridge. Sutor Dorothy June M.A. M.Sc. Ph.D. Girton College Cambridge. Tharby Ronald Desmond B.Sc. Officers’ Mess Royal Air Force. Cosford nr. Wolverhampton Staffs. Wolff Robert Etienne. 6 Avenue Boffrand Nancy (Meurthe et Moselle) France. ADDITIONS TO THE LIBRARY The chemical catechism with notes illustrations and experiments. S. Parkes. 9th edn. Pp. 576. Baldwin, Cradock and Joy. London. 1819. (Presented by F. A. Jones.) Biographisch-literarischesHandworterbuch der exakten Naturwissenschaften. Vol. VII a Part 2 F-K Nos. 1 & 2. Pp. 256.Akademie-Verlag. Berlin. 1957. Quantum chemistry an introduction. W. Kauzmann. Pp. 744. Academic Press Inc. New York. 1957. Solvents. T. H. Durrans. 7th edn. Pp. 244. Chapman & Hall Ltd. London. 1957. (Presented by the Author.) Textbook of polymer chemistry. F. W. Billmeyer. Pp. 518. Interscience Publ. Inc. New York. 1957. Encyclopedia of chemical reactions. Vol. VI. Compiled by C. A. Jacobson. Edited by C. A. Hampel. Pp. 438. Reinhold Publ. Corp. New York. 1956. The chemistry of petrochemicals. M. J. Astle. Pp. 267. Reinhold Publ. Corp. New York. 1956. Heterocyclic compounds. Vol. V. Five-membered heterocycles containing two hetero atoms and their benzo derivatives. Edited by R. C. Elderfield. 8 Collaborators. Pp. 741. John Wiley & Sons Inc.New York. 1957. CIBA Foundation Symposium on the chemistry and biology of purines. Edited by G. E. W. Wolstenholme and C. M. O’Connor. Pp. 327. J. &A. Churchill Ltd. London. 1957. Festschrift Prof. Dr. Arthur Stoll zum siebzigsten Geburtstag 8. Januar 1957. Arbeiten aus dem Gebiet der Naturstoffchemie. Pp. 91 1. Birkhauser. Basle. 1957. (Presented by Prof. Dr. A. Stoll.) Technique of organic chemistry. Vol. 111. Part 11. Laboratory engineering. Edited by A. Weissberger. 8 Collaborators. 2nd edn. Pp. 391. Interscience Publ. Inc. New York. 1957. Kinetics and thermodynamics in biochemistry. H. G. Bray and K. White. Pp. 343. J. & A. Churchill Ltd. London. 1957. Amino acid handbook methods and results of protein analysis.R. J. Block and K. W. Weiss. Pp. 386. Charles C. Thomas. Springfield Illinois. 1956. Methods in enzymology. Vol. 111. Edited by S. P. Colowick and N. 0. Kaplan. Numerous Collaborators. Pp. 1154. Academic Press Inc. New York. 1957. Principles of biological assay. C. W. Emmens. Pp. 206. Chapman & Hall Ltd. London. 1948. Probit analysis a statistical treatment of the sigmoid response curve. D. J. Finney. 2nd edn. Pp. 3 18. Cambridge University Press. 1952. The volumetric analysis of thorium-tungsten solutions. G. W. C. Milner and G. A. Barnett. (Atomic Energy Research Establishment C/R 1865.) Pp. 8. A.E.R.E., Harwell. 1956. Semimicro qualitative organic analysis :the systematic identification of organic compounds. N. D. Cheronis and J.B. Entrikin. 2nd edn. Pp. 774. Interscience Publ. Inc. New York. 1957. Vapour phase chromatography proceedings of the symposium sponsored by the Hydrocarbon Research Group of the Institute of Petroleum held at London 1956. Edited by D. H. Desty and C. L. A. Harbourn. Pp. 436. Butterworths. London. 1957. Colorimetric analysis. Vol. I. Determinations of clinical and biochemical significance. N. L. Allport and J. W. Keyser. 2nd edn. Pp. 424. Chapman & Hall Ltd. London. 1957. The principles and applications of polarography and other electroanalytical processes. G. W. C. Milner. Pp. 729. Longmans Green & Co. London 1957. Modern instruments in chemical analysis. F. M. Biffen and W. Seaman. Pp. 333. McGraw-Hill Book Company Inc.New York. 1956. Ullmann’s Encyklopadie der technischen Chemie. Edited by Wilhelm Foerst. Vol. VIII. Gefrierschutzmittel bis Iridium. 3rd edn. Pp. 860. Urban & Schwarzenberg. Munich. 1957 Chemical engineering operations an introduction to the study of chemical plant. F. Rumford. 2nd edn. Pp. 387. Constable & Co. Ltd. London. 1957. An introduction to electrostatic precipitation in theory and practice. H. E. Rose and A. J. Wood. Pp. 166. Constable & Co. Ltd. London. 1956. Instrument technology. Vol. 111. Telemetering and automatic control. E. B. Jones. Pp. 198. Butterworths. London. 1957. Chemie und Technologie der Kunststoffe. Vol. 11. Herstellungsmethoden und Eigenschaften. Edited by R. Hoowink. 19 Collaborators. 3rd edn. Pp.700. Akademische Verlagsgesel. Geest & Portig K.-G. Leipzig. 1956. The chemistry and technology of leather. Vol. I. Preparation for tannage. Edited by F. O’Flaherty W. T. Roddy and R. M. Lollar. 15 Collaborators. (Amer. Chem. SOC. Monograph Series No. 134.) Pp. 495. Reinhold Publ. Corp. New York. 1956. Proceedings of the International Wool Textile Research Conference Australia 1955. Volumes A B and C. Pp. 838. C.S.I.R.O. Australia. Melbourne. 1956. The halogenated aliphatic olefinic cyclic aromatic and aliphatic-aromatic hydrocarbons including the halogen- ated insecticides their toxicity and potential dangers. W. F. von Oettingen. (Public Health Service Publication No. 414.) Pp. 430. U.S. Public Health Service. Washing- ton. 1955.Specifications for pesticides insecticides rodenticides molluscicides and spraying and dusting apparatus. Pp. 400. World Health Organization. Geneva. 1956. Bell’s Sale of food and drugs. Edited by J. A. O’Keefe. Pp. 931. 13th edn. Butterworths. London. 1956. 1956 Supplement to book of ASTM standards including tentatives. Part 1. Ferrous metals Pp. 446. Part 3. Cement concrete ceramics thermal insulation road materials waterproofing soils. Pp. 332. Part 4. Paint, naval stores cellulose wax polishes wood acoustical materials sandwich and building constructions fire tests. Pp. 222. American Society for Testing Materials. Philadelphia. 1956 (Parts 1 & 3) 1957 (Part 4). British Standards Institution yearbook 1957. Pp. 484. British Standards Institution. London. 1957. (Presented by the Publishers.)
ISSN:0369-8718
DOI:10.1039/PS9570000129
出版商:RSC
年代:1957
数据来源: RSC
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