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Proceedings of the Chemical Society. January 1961 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue January,
1961,
Page 1-32
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Proceedings of The Chemical Society 1961 LONDON THE CHEMICAL SOCIETY PROCEEDINGS OF THE CHEMICAL SOCIETY JANUARY 1961 CHRISTMAS COMPETITION 1960 THEChristmas Competition 1960 was for a commentary in verse or prose of not more than 60 words on the move of the Editorial Office to near Madame Tussaud’s Exhibition of wax effigies. There were thirteen entries ranging over most of the possible aspects. Unfortunately the uncomplimentary entries had not sufficient wit or rhyming invention to merit reproduction. However as the Exhibition ranges from the heroic to the rogue Riccardo’s “. ..the little less and what world’s away!” is suitably ambiguous. The same thought imbues J.C.H.3 longer (but original) contribution Forgive me Fellows if I ruminate On my future and my fate.Each day I pass the Hall of Fame; As Editor do you think I’ll rate For that Or rather for the lower Chamber where Tussaud’s Horrors stand in state? C.J.M. asked learned Fellows of the Society to draw a moral for the occasion So pass our present glory! “Telly” star Andsportsman gangster men of peace and war Are melted down to please tomorrow’s crowd. * * * Let not the gaunt ascetic beetle-browed Professor think his theories will outlast New knowledge; soon they also will be classed As “classic” (final shame!) and me1 ted down To form new models of the Great Unknown. 3 PROCEEDINGS A breath of the outside world came with a topical entry from J.d’A.J. that went to the short list poking mild fun at the Society’s forthcoming elections and neatly using two of the meanings of “model” The recent move of their Editorial Office has caused speculation in the City of a take-over bid by the Chemical Society for neighbouring Madame Tussaud’s Exhibition.Several effigies on the Council are due for replacement and this could be done with great advantage from Tussaud’s stock. Organic chemists in particular have for years advocated the wider use of models. It was disappointing nevertheless that no one really expanded on the *‘ model ” including the fashion parade. Two competitors found inspiration in the Society’s activities J.A.W. made good use of these in A New Service for Fellows The Society is now able to offer Fellows cut-rate subscription facilities for the following periodicals Hell.Chim. Acta; Rec. Trav. Chim. RBg. Infer.; Pentacle ; Current Chemical Rapers;* Bleeders’ Digest ; Progress in Sulphur Chemistry. (*Printed on one side of the asbestos only.) “Jay” scored very high marks by suggesting a more public form of commentary To celebrate the transference of the Editorial Office of the Chemical Society to premises adjacent to Madame Tus-saud’s Exhibition a lecture will be delivered in the Chamber on April lst 1961 at 12 midnight By Henry H. Crippen M.D. (Horroris Camera) Demeritus Professor of Toxicology Tusso University entitled “A Historical Survey of the Uses of Long-chain Saturated Hydrocarbons in Three-dimensional Anthropological Representation.” Long swinging lines from N.M.C.voiced the author’s viewpoint and we wish him well for his hop in the New Year They told me Cahn Cross Mitchell they told me you had gone Over by Madame Tussaud’s from the Arch of Burlington. My hope though vain I fear is that the result will be A little less blue pencil and much less referee. And may we find the nice ones though few there are to choose In effigy created enthroned among the ‘U’s,’ And the unpleasant ones until their persecutions cease Down down among the Bad Men alongside Charlie Peace. JANUARY1961 Our prize (book token 2 guineas) is awarded to J.R.D. for his most happy rhyming and ingenious idea. J.R.D. submitted two entries and asked us to choose which we preferred.We had better choose the shorter as we calculate the other to be one word over the limit of sixty; but both merit citation. Triolet Why did they move the Chem. SOC. Eds. So close to Tussaud’s show? Consider th’ light that glucose sheds On why they moved the Chem. SOC. Eds.:-The R.A. shows had lengths and bread’s But Chemistry is stereo-. . . Why! Did they move? The Chem. SOC. Eds.! So close to Tussaud’s show! Why do they think that we should laugh Because the editorial staff Have moved from exhibitions hung In two-dimensional form To where the waxes so congeal That figures which are far more real Stand there forever young Departing from the norm? Can we expect a newer age In which the Chem. Soc.’s printed page With formula= is hung In three-dimensional form ? FROM THE SOCLETY’S MAIL +Ib Editor received the following postcard from a good friend of the Society; he prefers aot to specify which items were deleted and which underlined.Dear. . . . . . . . . . . . YBamaeMbIil Tosapnm Sehr geehrter Herr Professor Doktor Distinguido Seiior Broder Thank you very much for the reprints book manuscript have read with without great interest which I{ intend to read as soon as possible next summer do not intend to read Your work will in due time bring you the reward you deserve Your work does you and your co-workers credit. You had better check your results once more before having them printed. Efforts like these may perhaps prove successful in the political field in your country some other country.Yours truly Ihr Dein ergebener Barn TBoZ~ Aprovecha esta oportunidad para reiterarle el testimonio de su consideracibn mAs distinguida su atento y seguro servidor Hej! Din tillgivne . . . .19.. . . PROCEEDINGS Semi-synthetic Penicillins By H. R. ING (PHARMACOLOGY THE UNIVERSITY DEPARTMENT OXFORD) THE astonishing success of the penicillins in the treatment of many infections has justified Ehrlich’s ideal of a chemotherapeutic agent which would be non-toxic to the host but highly toxic to the infecting micro-organism. However the routine use of the penicillins has led to the emergence of penicillin-resistant organisms ; in particular the occurrence of penicillin-resistant staphylococci in hospitals is now recognised as a major medical problem which has been only partly met by the use of alternative antibiotics S/\ R-CO-NH-YH-FH ?Me2 Penicillinase t CO-N-CH.CO,H + H,O (11 S/\R-NH-FH-YH $Me CO-N -CH *C02H (v> Variants of (V) 6-Aminopenicillanic acid R = H Penicillin G R = Ph.CH,.CO-(Na salt) Penicillin V R = PhOCH,CO-(K salt) BRL 152 or “Broxil” R = PhO-CHMeCO-(Ksalt) such as erythromycin novobiocin and vanco- mycin.Staphylococci resistant to the penicillins in common use (penicillins G and V) owe their immunity to these antibiotics to their capacity to produce an enzyme penicillinase which inacti- vates the penicillins. Penicillinase was discovered so long ago as 1940 in Escherichia coli and was subsequently found in many other bacterial species.The term penicillinase is now used to denote an enzyme whose substrate is a penicillin and whose action results in the inactivation of this class of antibiotic1 The chemical effect of penicillinase appears to be hydrolysis of the /3-lactam ring with the pro- duction of a penicilloic acid. Thus pent-2-enyl- penicillin (I; R = CH,CH,-CH CHCH2-) on inactivation by the penicillinase of Bacillus sub-tilis gave a product containing a new acidic group which was decomposed by aqueous mer- curic chloride into penicillamine (/3/3-dimethyJ- cysteine; III) pent-2-enylpenilloaldehyde(IV; R = CH,CH,CH CHCH,-) and carbon di-oxide.’ This decomposition is characteristic of penicilloic acids so that the immediate effect of penicillinase would seem to have been hydrolysis of the /3-lactam ring with production of pent-2-enylpenicilloic acid (TI).It is assumed that peni- HSCMQ~CH(NHJCO~H+ R*CO*NH*Cf-$*CHO+CO, (m> (1 v) OMe BRL1241 or “Celbenin” R = oco-OMQ (Na salt monohydrate) cillinases from other sources than B. subtilis inactivate penicillins in the same way. The penicillins are acyl derivatives of 6-amino-penicillanic acid (V; R = H) which itself possesses mild antibacterial activity. In 1959 workers2 at the Beecham Research Laboratories succeeded in isolating 6-aminopenicillanic acid from fermentation media to which no organic acid precursor had been added an achievement which lent support to the opinion of earlier workers that this amino-acid is the penultimate stage in the biosynthesis of penicillin.On acyla-tion with phenacetyl chloride 6-aminopenicil- lanic acid gave benzylpenicillin (penicillin G ;V R = PhCH,CO) so that a way was open of preparing a wide variety of new penicillins with Abraham “The Enzymes,” ed. Sumner and Myrbach Academic Press New York 1951 Vol. 1 Part 2 Ch. 37 pp. 1170-1185. a Batchelor Doyle Nayler and Rolinson Nature 1959 183 257. JANUARY 1961 different acyl groups. Many different penicillins had long been obtainable by the addition of appropriate precursors (mostly monosubstituted acetic acids) to the fermentation medium but in general none of them has shown properties which make it clinically superior to penicillins G and V.Chemical acylation of 6-aminopenicillanic acid however provides a more versatile method of making new penicillins and one which avoids the problem of devising methods of isolating new penicillins from fermentation media. The im- portance of investigating new acyl derivatives of 6-aminopenicillanic acid lies in the possibility of discovering penicillins with different antibao terial specificities and in particular of finding a penicillin more or less resistant to inactivation by penicillinase. The first new penicillin with promising clinical properties prepared by the workers at the Beecham Research Laboratories was potassium a-phenoxypropionamidopenicillanate B RL 152 or “Broil.” This side-chain homologue of peni- cillin V is less easily hydrolysed by acid than the latter and consequently better absorbed after oral administration ;thus serum concentrations after oral BRL152 were about twice those of penicillin V after equivalent oral doses.3 BRL152 is somewhat less effective than penicillin G against some species of streptococci but has a much greater activity against resistant staphy- lococci than penicillin G;4it is also more slowly inactivated by staphylococcal penicillinase in vitro than penicillin G.5Since different strains of resistant staphylococci are known to produce widely varying amounts of penicillinase BRLl52 gave some promise of overcoming a resistant staphylococcal infection provided that the amount of enzyme produced by the organism was in the lower range.The latest development by workers in the same laboratories is the preparation of sodium 6-2,6-dimethoxybenzamidopenicillanatemonohydrate BRL1241 or “Celbenin,” which is remarkably stable to staphylococcal penicillinase and is active against penicillin-resistant staphylococci.8 Knudsen and Rolinson Lancet 1959 II 1105. Garrod Brit. Med. J. 1960 I 527. The minimum inhibitory concentrations of BRL1241 in twenty-two cultures of Staphylococ-cus pyugenes varied over the narrow range 1-25-2-5 pg. per ml. regardless of the resistance of the organisms to penicillin G and other anti- biotics. This concentration range is about a hundred times that of penicillin G for sensitive staphylococci so that substantial concentrations compared with those of penicillin G have to be maintained in the blood; moreover BRL1241 is absorbed and excreted at about the same rate as penicillin G7so that relatively large doses have to be injected (for it is unstable to acid) at fre- quent intervals.Fortunately it also possesses the very low toxicity of penicillin G and is bacteri- cidal at concentrations only slightly greater than the minimum inhibitory concentrations. So far no staphylococci resistant to BRL124I have been encountered and preliminary clinical trial^^*^ indicate that it can eliminate severe in- fections of patients by staphylococci resistant to other antibiotics. Obviously more extensive clinical experience will be necessary before the potentialities and limitations of the new penicillin can be properly assessed.BRL1241 resembles penicillin V and BRLl52 in being less active than penicillin G against streptococci and particularly against Gram-negative species so that it is un- likely to replace penicillin G; at the same time it may well become the antibiotic of choice in the treatment of otherwise resistant staphylococcal infections. According to Stewart,lO BRL1241 is not en-tirely immune to staphylococcal penicillinase ; some inactivation does occur after 24-48 hours’ growth of penicillinase-forming staphylococci but this inactivation is insufficient to prevent the antibacterial effect during the first 24 hours’ in- cubation. Moreover attempts to induce two strains of Staph.aureus to become resistant to BRL 124 1 were unsuccessful. BRL 1241 could be completely inactivated by the penicillinases of B. lichenvormis and B. cerens but much more slowly than penicillin G. A point of some chemical interest arising from Gourevitch Hunt and kin Antibiot. Ann. 1959-60 1 11. Rolinson Stevens Batchelor and Wood Lancet 1960 XI 564. Knudsen and Rolinson Brit. Med. J. 1960 11 700. * Douthwaite and Traffotd Brit. Med. J. 1960 11 687. @ Stewart Nixon and Coles Brit. Med. J. 1960 XI 703. lo Stewart Brit. Med. J. 1960 11 694. PROCEEDINGS this work is that the substrate specificity of the penicillins towards the penicillinases is partly dependent on the structure of the 6-acylamino- group although the point of attack of this class of enzyme is the p-lactam ring.Similarly the antibacterial activity of the penicillins is partly determined by the nature of the acyl group al- though the p-lactam-thiazolidine unit of struc-ture is of primary importance. BRL1241 appears to be the first semi-synthetic penicillin to exhibit a nice balance between relative immunity to in-activation by staphylococcal penicillinase and a reasonably high degree of antibacterial activity. It is to be hoped that even more interesting and clinically useful penicillins may be discovered by varying the acyl or other groups attached to the amino-N-atom of 6-aminopenicillanic acid; e.g. it would be of value to discover a derivative of this amino-acid which would inhibit penicil- linase.CHEMICAL SOCIETY MEETING The following papers will be read and discussed at a Scientific Meeting of The Chemical Society to be held at Burlington House on February 9th 1961. The Crystal Structures of the Acid Salts of Some Monobasic Acidr. Part V. By H. H. SHWASTAVA and J. C. SPEAKMAN. Part VI. By J. C. SPEAKMAN and H. H. MILLS. IN “long” hydrogen bonds (O-H-O) with the 0-0 distance 2.75 A or more the proton is much nearer to one oxygen atom than to the other and the bonding is almost wholly attributable to electro- static force. As the over-all O.-O distance diminishes the 0-H distance should increase the proton thus moving towards the mid-point ; the experimental evidence for a series of cases supports this expecta- tion.A truly symmetrical hydrogen bond would therefore result if the over-all shortening were sufficient. One conjecture is that O-.O NV 2-45 8 might be the upper limit of such symmetry. In these circumstances exchange forces (“resonance”) would make a substantial contribution to the bonding. Whether symmetrical bonds between oxygen atoms exist is still uncertain but examples may profitably be sought amongst those solid compounds whose structures include hydrogen bonds lying across crystallographic symmetry elements. Bonds so situated occur in a number of acid mono- carboxylates of composition RCO,H,RCO,M where M is a univalent metal. About a dozen of these acid salts have been studied by X-ray crystal-structure analysis and apparently symmetrical hydrogen bonds found in most of them.These bonds are all “short,” but hitherto the accuracy of the analyses has not been sufficient to establish the O...Odistances within f 0.05 A. X-Ray diffraction is not an efficient method for locating hydrogen atoms but Bacon and Curry have studied one of these salts potassium hydrogen bis- phenylacetate by neutron diffraction. They located the proton directly and found it at the centre of symmetry between the oxygen atoms. This is especially evident in their neutron-scattering map for 120”~: the proton peak is not appreciably elongated in the 0.-0-direction as it would be were the proton in random occupancy of alternative sites significantly displaced to either side of the centre (i.e.0-33-0 O...H-O) . The presence of (quasi-)symmetrical hydrogen bonds in a crystal appears to be associated with an anomalous infrared spectrum; Hadii and his col- laborators have discussed these spectra in some detail and have classified many hydrogen- bonded solids on this basis. Because of differences between their infrared spectra Prof. Hadii had predicted that isomeric acid potassium salts of o- andp-nitrobenzoic acid would have respectively symmetrical and un- symmetrical types of structure. His prediction has been verified by X-ray studies of rubidium hydrogen di-o-nitrobenzoate (isomorphous with the potassium compound) and potassium hydrogen di-p-nitro- benzoate. Interest attaches to sodium hydrogen diacetate NaH(C2H,0,), which is not only one of the simplest acid carboxylates but also shows the anomaly in the infrared spectra in an impressive form.The complex symmetry with which 48 acetate radicals are arranged in the (cubic) unit cell led to initial difficuIties; once these had been overcome the chemical simplicity of the repeat-unit facilitated accurate analysis which was carried out three-dimensionally. A pair of acetate groups related by a crystallographic two-fold axis have their hydroxylic oxygen atoms hydrogen- bonded across this axis. The final co-ordinates from a straight refinement of the X-ray analysis led to O.-O = 2-44 f0.01 A. Dr. Cruickshank has sub-sequently corrected these co-ordinates for the small errors due to torsional oscillation of the acetate group and thus amended O-.Ofalls to 2-43 A.This distance agrees closely with those briefly reported in acetamide hemihydrochloride and for the intramole JANUARY 1961 cular hydrogen bond (symmetrical by virtue of a crystallographic mirror-plane) in the maleate anion. These OH0 bonds are thus plausible counterparts of the FHF bond in the bifluoride ion which has long been considered symmetrical. Delocalisation and MagnetSc Properties of the Phosphonitrilic Halides. By D. P. CRAIG,M. L. HEFFERNAN, R. MASON,and N. L. PADDOCK. THEmagnetic anisotropy due to n-electron delocalisa- tion is calculated for systems of alternating pr and dn orbitals and compared with p-pn systems. Calculations on the London model show a strong dependence upon the electronegativity difference between the pn and dw orbitals and for realistic values the contribution is small compared with that in benzene.If the dn orbitals are dZa,tangentially directed the n-electron contribution is small and paramagnetic; if d, orbitals also participate their influence is opposite in sign leading to a steadily diminishing paramagnetic behaviour until with equal participation by dz2 and dyz orbitals the n-electron ring current contribution is near to zero. Measurements of diamagnetic anisotropy are reported for (PNCI,), and of average susceptibility for (PNCI,), n = 3 4 5 6 and 7. The analysis of the measured values to derive the ring-current mag- netism has many uncertainties but is compatible with a small paramagnetic or zero contribution by n-elec tr ons .Energy calculations are reported including dv orbitals as well as d,, under several sets of assump-tions as to relative electronegativities. The questions of participation of both types in cyclic delocalisation and of their relative importance are discussed. The Nuclear Magnetic Resonance Spectra of Triphosphonitrilic Fluorochlorides. By M. L. HEFFEFWAN and R. F. M. WHITE. THEmain products from the partial fluorination of triphosphonitrilic chloride with potassium fluoro- sulphite are triphosphonitrilic difluorotetrachloride PSN3F,C14 triphosphonitrilic trifluorotrichloride,. P,N,F,Cl, and triphosphonitrilic tetrafluorodi-chloride P,N,F,Cl,. The infrared and nuclear mag- netic resonance spectra of these compounds have been used to determine their structure.l In nuclear magnetic resonance spectroscopy tri- phosphonitrilic difluorotetrachloride provides an example of an AB,X system.2 In the phosphorus nuclear magnetic resonance spectrum of this com- pound the A spectrum is split into a triplet showing that the compound has the 1,l -difluorotetrachlori& structure (I).The phosphorus and fluorine spectra have been analysed by the secular-determinant method of Pople Schneider and Bernstein? the transition energies and relative intensities being ex- pressed in terms of the three different spin coupling constants Jp,p Jp,p and Jplp,together with a field- dependent phosphorus chemical shift. The fluorine spectrum was obtained at two field strengths to pro- vide a check on the assignments and to determine the relative signs of the three spin-coupling constants.It is possible to account for the fluorine spectra at the two field strengths only if the signs of Jplp and JPg are opposite and also if the sign of JpIp,is opposite to that of JPlpIt is possible to obtain the relative signs of the spin-coupling constants the values being either Jplp= 934 cycles/sec. Jpsp= -14 cycles/sec. and .Ip1,,,= -100 cycles/sec. or Jplp= -934 cycles/sec.,Jpp = 14 cycles/sec. and .Iplpt= 100 cycles/sec. Although the spectra of the trifluoro- and tetra- fluoro-compounds have not been completely analysed the broad features of the spectra show that these compounds are the 1,1,3-trifluorotetrachloride and the 1,1,3,3-tetrafluorodichloride,respectively.Chapman Paine Searle Smith and White to be published. a Pople Schneider and Bernstein “High Resolution Nuclear Magnetic Resonance,” McGraw-Hill 1959. PROCEEDINGS CHEMICAL SOCIETY SYMPOSIUM ON TERPENE CHEMISTRY AN ALL-DAY SYMPOSIUM will be held on Thursday February 23rd 1961 in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington London S.W.7 at 10 a.m. The .-following papers will beread and discussed. Professor SORM.“Terpene Compounds with Ten- membered Rings.” A systematic survey of plant material particularly the family Compositae has shown ten-membered ring compounds of the terpene series to be widely distributed in Nature.All such compounds isolated so far are oxidised terpene derivatives and all with the exception of the ketone germacrone contain a y-lactone grouping involving the oxidised isopropy 1 group. The chemistry and interrelations of the chief representatives of this group will be discussed in- cluding those of recently isolated compounds such as balchanolide isobalchanolide hydroxybalchanolide and scabiolide. A typical feature of their reactivity is the occurrence of transannular cyclisations leading as a rule stereospecifically to compounds of the santonin or elemane series. The ease with which these reactions occur suggests their relevance to the final phases in the biogenesis of some natural terpene derivatives.The peculiar steric structure of the ten- membered ring compounds also accounts for certain anomalies in their physical properties e.g. the trans- annular interaction of double bonds which has also been confirmed by quantum-chemical calculations. Professor B. C. L. WEEDON.“Carotenoids and their Natural Precursors.” The solution of structural problems in the carotenoid field is often complicated by the scarcity of the natural starting materials. This difficulty can sometimes be overcome by utilising synthesis to dis- tinguish between the various possibilities suggested by degradative studies and by invoking the aid of spectroscopic techniques. Nuclear magnetic reson- ance spectroscopy affords a valuable means of recog- nising the presence of various structural features some of which may be difficult to detect in other ways.Examples given of the use of the above methods will include bixin the carotenoid ketones echin- enone canthaxanthin astacene capsanthin and capsorubin and the bacterial pigments spiril- loxanthin (rhodoviolascin) spheroidenone (pigment R) and spheroidene (pigment Y). The application of the methods to the study of the hydrolycopenes phytoene phytofluene carotene and neurosporene which are believed to be involved in the biogenesis of carotenoids will also be described. Professor 0.JEGER. “Oxidative Degradation of Manool.” Methods will be described of degrading manool to products possessing strong ambra odour. The struc- ture and stereochemistry of these compounds will be demonstrated and oxidation experiments on these products discussed.Professor H. G. H. ERDTMAN. “Some New Sesqui- and Di-terpenes their Distribution among the Conifers and their Taxonomic Importance.” A review will be given of recent work at Stockholm on terpenes from the heartwood of various conifers. Several new compounds possessing novel structures have been isolated and structurally elucidated. The structures of some well-known substances have been revised and the distribution of these compounds in the various orders of the class Coniferae has been investigated. The chemotaxonomic importance of terpenes will be discussed. DR.G. A. SIMand Professor J. Momm ROBERT-SON. “The Structure of Clerodin and Other Terpenoid Substances by Direct X-Ray Analysis.” New methods in the X-rayanalysis of natural-product structures have recently been developed in the Glasgow laboratories and these have been applied to the elucidation of several terpenoid and bitter principle structures such as isoclovene geigerin limonin and clerodin.Structures of this degree of complexity can now be solved in a rela- tively short time if suitable derivatives can be pre- pared. An outline will be given of some of the general principles involved. The structure of clerodin was solved by an X-ray analysis of the bromo-lactone. There are four mole cules of C,,H,,O,Br in an orthorhombic unit cell (P2,2,Z1) and the positions of all the atoms (except some of the hydrogens) have now been determined with considerable accuracy.This result enables the complete structure and stereochemistry of the bitter principle clerodin to be deduced. Professor D. H. R.BARTON. “Some Recent Work on Terpenoid Bitter Principles.” In the last decade important advances have been made in our knowledge of the structures of di-and tri-terpenoid bitter principles. Some aspects of the chemistry of columbin and limonin will be used to JANUARY 1961 illustrate this theme. Recent progress in the chemistry of the interesting Indian bitter principle clerodin will be outlined. The constitution and relative stereo- chemistry of this molecule have been determined by X-ray crystallography by Professor Monteath Robertson Dr. Sim and their colleagues.The chem- ical work supports fully the X-ray structure and in addition provides a tentative assignment of absolute stereochemistry. The biogenesis of clerodin will be briefly discussed. The part played by nuclear magnetic resonance in the determination of chemical relations will be presented by Dr. L. M. Jackman. COMMUNICATIONS Electronic Excitation in Azulene By G. R. HUNTand I. G. Ross OF PHYSICAL UNIVERSITY (DEPARTMENT CHEMISTRY OF SYDNEY) THEvisible-ultraviolet spectrum of azulene shows several distinct electronic transitions. Two of these beginning near 7000 and 3500A show considerable vibrational structure and are amenable to detailed analysis. They have been investigated in detail once only by Sidman and McCIure,l who measured the polarised absorption and fluorescence of a substitu- tional solid solution of azulene in naphthalene at 20"~. Upper-state electronic symmetries were identi- fied but the data could not be fully exploited for lack of infrared assignments (since determined2) and measurements of the electronic spectrum of the vapour.We have measured the absorption of the vapour and of the pure crystal at ~OK using a Hilger E492 Littrow quartz spectrograph and quote here the more important observations and conclusions. propriately. At such intersections the vibrational levels of the lower state which in a sufficiently large polyatomic molecule are likely to be quasi-con- tinuous interact with vibrational levels of the upper state.Spectral lines recording transitions to the latter are split into irresolvably many components. The re- sultant line-broadening should measure the probabi- lity of internal conversion. In this view a level with sharp vibrational struc- ture should be radiative in the vapour state and in the absence of other mechanisms3 of line-broadening the radiative efficiency should decrease with increas- ing line-width. Among aromatic hydrocarbons this seems to be so. As far as can be judged from available data simple heterocycles also conform. (2) Pariser* has predicted bond-orders for the lower electronic states of azulene. They point to large me 7000 A transition [~B~CL~)1~~; t geometrical changes especially in the central bond (1) vapour-phase origin 14,277 cm.-l; oscillator strength f = 0409]is diffuse.At 35" the best resolved features (e.g. the arigin) appear as symmetrical bands at least 5 cm-l wide. The 3500 8 transition [lA,PL> clAl; vapour-phase origin 28,758 cm.-l; f = 0.081 is much sharper (narrowest band widths < 1 Cm.-1). The presence of a weak diffuse transition at lower energy than a sharper and more intense one is most uncommon (Rydberg bands excepted) in the spectra of polyatomic molecules. On energetic grounds the cause of diffuseness is unlikely to be predissociation. We suggest that spectral sharpness is here to be cor- related with the emission properties of the excited states concerned. Azulene is unique in fluorescing from the second and not the first of its excited singlet states.Degradation of excitation energy through a succession of electronic states can occur if successive potential energy surfaces intersect ap-Sidman and McClure J. Chem. Phys. 1955,24,757. Hunt and Ross,J. Mol. Spectroscopy 1959,3 604. Neporent Zhw.8~.Khim. 1956,30 1048. Pariser J. Chem. Phys. 1956 25 1112. length due to excitation. Successive electronic-state potential-energy surfaces should have their minima considerably displaced relative to the ground state- sufficiently it seems to account for the proposed pattern of intersections between them. Evidence for large changes in molecular properties on excitation can be sought in the vibrational frequencies. In naphthalene corresponding upper- and ground-state frequencies are similar.In azulene there are some large changes in the skeletal stretching region and a convincing correlation of upper- and ground-state frequencies is not yet possible. (3) Pariser fwther predicted large changes in molecular dipole moment on excitation. We see evidence for this in the pure crystal spectrum. Even at 4'~the pure crystal absorption is exceedingly diffuse (band widths -100 an.-'). Crystalline azulene is believed to be disordered in the special sense that a molecule on a given site can assume at random either of two antiparallel orientation^.^ In-termingled with the Davydov intermolecular reson- ance there is then an additional effect due to the energy of interaction between the permanent dipole moment of an excited molecule and those of its neighbours.If the dipole moment does not change appreciably on excitation the last effect is im- material; consequently the infrared spectrum of the crystal is sharp.2 If it does change the randomness in the environment of individual molecules results in line-broadening to an extent which increases though not according to any simple function with the change in dipole-moment. The observed line-widths point to a large change; appropriate calculations are in hand. (4) Comparison with the mixed-crystal spectral shows that the vibrational structure of the 7000 A transition is essentially the same in both vapour and mixed crystal. That of the 3500 8 transition is not. About 800 m.-l from its origin towards higher energies the mixed-crystal spectrum develops a com- PROCEEDINGS plicated vibrational pattern which has 111) counter-part in the vapour absorption.It is hardly possible to correlate the two spectra at all beyond this point. It is ernphasised that in this region the naphthalene host crystal does not absorb and that the vibrational frequencies appearing cannot be identified with known frequencies of either of the components. (5) Simple symmetrical molecules commonly make use of non-totally symmetric vibrations to enhance the intensity of weak transitions. Azulene behaves curiously in this regard. The weak 7000 8 absorption uses totally symmetric vibrations on1y.l The stronger 3500 A vapour-absorption system appears to use non-totally symmetric (species RJ vibrations only sparingly if at all even though the mixed-crystal spectrum (cf.4 above) has a sizeable component so polarised. On the other hand in the fluorescence of both vapouI.6 and mixed-crystal some of the strongest bands involve B vibrations. (Received November 14th 1960.) Robertson Shearer Sim,and Watson Nature 1958 182 177. Hunt and Ross 2.Naturforsch. 1956 lla 1043. An Anti-Arbuzov Rearrangement By JAMESE. GRIFFITHS and ANTON B. BURG OF CHEMISTRY OF SOUTHERN (DEPARTMENT UNIVERSITY CALIFORNIA Los ANGELES U.S.A.) 7 CALIFORNIA IN a recent communication1 we described the synthesis of the phosphinous acid (CF,),P.OH which is permanently stable and does not undergo an Arbuzov-type rearrangement to the secondary phos- phine oxide (CFa,HP:O.We now report a re-arrangement in the sense contrary to the Arbuzov reaction namely (CF,),HP 0-+ (CF,),P.OH. This seems to be the first demonstrated example of a reaction in which a proton in a secondary phosphine oxide moves from phosphorus to oxygen to form a phosphinous acid. The primary reason for it would be the lowering of the base strength of the phosphorus atom by the highly electronegative fluorocarbon groups. When a synthesis of the phosphine oxide (CF,),HP 0 was attempted by using mercuric oxide to attach an oxygen atom to the phosphine (CF,),PH the reaction proved to be spontaneous and exo- thermic giving white fumes and metallic mercury as the phosphine vapour met the solid mercuric oxide.Hence for the most useful results 0.702 mmole of (CF.J2PH vapour at 6 mm. pressure was allowed to flow over a bed of mercuric oxide (at 60-65" to minimise adsorption) and led into a series of evacu-Griffiths and Burg J. Arner. Chem. Soc. 1960,82 1507. EmelCus Haszeldine and Paul J. 1954 563. ated traps at -45" -96" and -196". Then the mercuric oxide tube was sealed to prevent further contact with the product. The -196" trap had caught 0-128 mmole of unused (or regenerated) (CF,),PH and the -96" trap held 0.03mmole of (CF,),P.OH; neither of these could have been an important com- ponent of the slightly volatile liquid in the -45" trap. However during a 14-hour storage at 25" this liquid generated 0.129 mmole of (CF,),PH and 0-128 mmole of (CF,),P.OH while forming 0.088 mmole of the slightly volatile (CF,),P( O).OH (analysed by alkaline hydrolysis to form fluoroform).2 These results could be understood only in terms of the parallel reactions (CF,),HP 0 -it (CF3)2P*OHand 2(CF,),HP :0 -f (CF,)2P( :O)-OH + (CF,),PH for (CF,),P-OH would not have disproportionated in the manner of the second equation even if much of it had been present in the -45" condensate.Also the (CF,),P-OH could not have been formed by the reverse disproportionation (CF&,P(:O)-OH + (CF,),PH -+ 2(CF3),P.0H for this reaction was shown not to occur at 60".For this experiment the (CF.J,P( O).OH was made by quantitative oxida- tion of (CF,),PH by using an excess of mercuric oxide in situ. JANUARY 1961 The analogous synthesis of (CH,),HP 0 was attempted by using 1-504mmoles of (CH,),PH with 1-062 mmoles of mercuric oxide in a water-cooled static reaction tube attached to a high-vacuum system.Within 3 min. metallic mercury began to appear along with a viscous liquid. After 20 min. at 70" the reaction had given a 98% yield of mercury (1-040 mmoles); but the amount of unrecovered (CH3),PH was only 0.778 mmole. Further heating of the viscous liquid (12 hr. at 100') yielded 0-236 mmole of (CH,),PH; and now the presence of 0.523 mmole of (CH&P(:O)*OH (m.p. 91"; known 91-92') was demonstrated by titration to pH 6.0. Thus the whole process could be summarised by the empirical equations 1.040(CHJ2PH + 1.040Hg0 -+ 1*040(CH3),HP:0+ 1.040Hg 1*040(CH3),HP:0+ 0*520(CH J,PH + 0*523(CH JPP( :O)*OH a Burg and Wagner J.Amer. Chem. Soc. 1953 75 3872. Hence it seems that (CH,),HP 0 has finite existence but can only disproportionate to (CH,),PH and (CH,),P( O)-OH and has strictly no tendency toward the anti-Arbuzov type of rearrangement. The same disproportionation was approached also through the reaction (CHa2PH + (CF,),P*OH + (CH,),P.OH + (CF,),PH whereby an apparent 0.239 mmole of (CF&P-OH (underestimated in a vapour-volume measurement) was converted into 0.257 mmole of (CF,),PH while 0.247 mmole of (CH,),PH yielded a syrup which afforded 0-126 mmole each of (CHJ,PH and (CHd,P( O)-OH. This work was supported by the United States Air Force under Contract No.AF 33(616)-6913 (Sub-contract No. l) monitored by the Materials Labora- tory Wright Air Development Center Wright- Patterson Air Force Base Ohio U.S.A. (Received November 24th 1960.) The Infrared Spectra of Monofluoro- and Monoiodo-acetylene By J. K. BROWN and J. K. TYLER (DEPARTMENT THEUNIVERSITY, OF CHEMISTRY BIRMINGHAM) As a sequel to analysis of the microwave spectra of fluoroacetylene and deuterofluoroacetylene,l the infrared spectra of these molecules and of iodo- acetylene have been investigated with prism resolu- tion in the region 4000-400 cm.-l. The preparation of the monofluoroacetylenes has been described pre- viously.'s2 Monoiodoacetylene which has not been reported as a well-characterised compound was pre- pared by bubbling acetylene through alkaline hypo- iodite.The main product was di-iodoacetylene which separated as a solid during the reaction. The mono- iodo-compound was an unstable liquid at room temperature. The spectrum of fluoroacetylene observed was in good agreement with that published by Middleton and Sharkey. Four of the five fundamentals expected for the linear molecules fluoro- and deuterofluoro- acetylene were observed in the frequency region. The fifth the doubly degenerate bending frequency v5 was located in combination with the corresponding C=C-H(D) bending mode vp in both compounds. The assignments which are listed in Table 1 were in good agreement with the product rule checks for the non-degenerate stretching and doubly degenerate bending modes.Approximate estimates of the fre- quencies of the bending modes from the I-type doubling in the microwave spectra have been rep0rted.l TABLE 1. Assignment FCrCH CH(D) Stretch v1 CC Stretch v2 C-F Stretch v3 CCH(D)bend v4 CCF bend v5 (cm. -l) 3370 2245 1064 584 (370) FCECD (cm.-l) 2640 2100* 1048 442 (370) * Approximate centre of a Fermi resonance doublet at 2070 and 2125 cm.-l between v2 and 2v3. Potential constants for the stretching modes were calculated by the F-G matrix meth~d,~ with a simple valency force field approximation containing no in- teraction terms. An off-diagonal term F' was included in the F matrix for the bending modes and was estimated by using frequencies for fluoro- and deuterofluoro-acetylene.The values calculated are given in Table 2. Tyler and Sheridan. Proc. Chern. Suc.. 1960. 119. Middleton and Sharkey J. Amer. Chem. Sob. 1959 81 803. a Wilson J. Chern. Phys. 1941 9 76. TABLE 2. FOCH FCCD (md/A) (md/& FCH 6.06 F, 6.08 F 15.80 F‘. 15-80 Fcp 8-64 Fcp 8.79 F-= 0.152rc,rcH Fccp = 0.222rcgc F’ = 0*082rcc~~c,rc The force constants calculated for the C-H and CzC stretching modes are very similar to those found for acetylene and the bond lengths found from the microwave analysis’ also approximate closely. The C-F stretching force constant is signifi- cantly higher than that appropriate to fluorine attached to a saturated carbon atom5 (6 md/& and the GF bond length is markedly shorter than that in ethyl fluoride? Although some caution is needed in drawing conclusions from force-constant analyses in the absence of interaction terms the present results PROCEEDINGS for fluoroacetylene are consistent with the conclusion from the microwave analysis1 that the C-F bond has some double-bond character.A similar situation has also been suggested for the C-X bond from infrared and microwave analyses of rnonochl~roacetylene~ and the halogen cyanides? Fundamentals at 3320 (C-H stretching) 2075 (CGCstretching) and 629 cm.-l (CrC-H bending) have been identified in the spectrum of iodoacetylene. The C-I stretching vibration frequency v3 has not been located but it is probable that it is associated with a weak absorption band which lies close to that of the C=C-H bending fundamental.The deuterium compound is being investigated to test this possibility. Since the analysis of fluoro- and deuterofluoro- acetylene was completed we have learnt that G. R. Hunt and M. K. Wilson at Tufts University Massachusetts U.S.A. have obtained results in agreement with ours. (Received Noventber 17th,1960.) Herzberg “Tnfra-red and Raman Spectra of Polyatomic Molecules,” Van Nostrand New York 1945. Crawford and Brinkley J. Chem. Phys. 1941 9 69. Kraitchman and Dailey J. Chem. Phys. 1955 23 184. ’Westenberg Goldstein and Wilson J. Chem. Phys. 1949,17,1319; Richardson and Goldstein ibid. 1950 18 1314. Penney and Sutherland Proc. Roy.SOC.,1936 A 156 654; West and Farnsworth J. Chem. Phys. 1933 1 402; Sheridan Tyler Aynsley Dodd and Little Nature 1960,185 96; Townes Holden and Merritt Phys. Rev. 1948 74, 11 13; Smith Ring Smith and Gordy ibid. p. 372; Townes and Dailey J. Chem. Phys. 1949 17 782. The Stereochemistry of the E-and F-Rings of Atisine Its ReIation to the Atisine-Isoatisine Isomerisation By A. J. SOLOand S. W. PELLETIER (THEROCKEFELLER INSTITUTE NEWYORK21 N.Y. U.S.A.) RECENTLY we presented arguments in support of the for atisine (I) namely a4. Form (Ia) in which assignment of an A-B-D trans-anti-trans-skeleton to ring E is a boat with C(22)axial is impossible since it atisine.l Complete elucidation of the stereochemistry would require a single carbon atom to bridge a 1,2-of atisine requires a consideration of the steric trans-diaxial system.Form (Ib) in which ring E is a arrangement of the E-and the F-ring. chair with C(22)axial may also be eliminated since Very great hindrance is known to exist between it would cause the rings A and F to be strongly the 17-methylene group and the c-ring of ati~ine.~,~opposed. Since the oxazolidine ring of atisine may be re-In form (Ic) which contains chair ring E with qzz). formed easily from derivatives in which C(17)is tri-equatorial opposition occurs between the free gona12(II),the 24-oxygen atom should be substituted electron pair on nitrogen and a 3-hydrogen atom. on the less hindered side of Ctl,) i.e. the side away This interaction may be relieved by converting ring A from ring c. Atisine must therefore be formulated as into a boat but such a change creates new inter- isomer (I).* actions.Form (Id) in which ring E is a boat with A priuri four E/F-arrangements must be considered Ctzz)equatorial has an interaction between the free * The absolute configuration of these compounds has not yet been settled. However recent data of Edwards6suggest that they are antipodal to the steroids (and to the above formuk). Such a relation has already been shown‘ for the related alkaloids lycoctonine and aconitine. Solo and Pelletier Chem. and Znd. 1960 1108. * Pelletier and Jacobs Chem. and Ind. 1955 1385. a Wicsner and Edwards Experienfia 1955 11 255. JANUARY 1961 electrons on nitrogen and the 10-hydrogen atom. Forms (Ic) and (Id) therefore appear to be of comparable stability.The extraordinarily high pK of atishe (12.5) and the ready isomerisation of isoatisine diacetate hydro- chloride to atisine diacetate hydrochloride have both been satisfactorily expIained as resulting from the decrease in steric strain which accompanies the trans- formation of C(17)from a tetrahedral to a trigonal f~rm.~.~ However as both atisine and isoatisine have quaternary C(171,it is necessary to look further for the reason for the greater stability of isoatisine over atisine. Edwards4 has attempted to explain the stability difference on the basis of an interaction between the 24-oxygen atom and a 5-hydrogen atom which occurs in atisine but not in isoatisine. This interaction may be observed in models of form (Ic); but not in models of (Id).? Hence unless (Id) can be shown to be less stabile than (Ic) Edwards’ explana- tion cannot by itself account for the free energy difference between atisine and isoatisine.The driving force for the atisineisoatisine iso- merisation may now be considered. If the dihydro- atisine ring system is constructed from Dreiding-type models it is apparent that very serious crowding occurs between the 17- and the 19-hydrogen atom. Interaction dso occms between the 17- and an 18-hydrogen atom. Since the energy required to deform the bond angles of a molecule is always less than the energy gained by moving the interfering groups further aparty6 the steric compression on the 17-hydrogen must be accommodated by distortion of the ring system.The distortion undoubtedly consists mainly of bending rings c and E away from each others and rotating C(17)so as to move its sub- stituents away from ring c. However in atisine formation of a strain-free oxazolidine ring would impose a restriction on this rotation of C(l,). In iso-atisine on the other hand C(l,) is not a part of the oxazolidine system and is free to undergo essentially the same rotation as in dihydroatisine. Thus the driving force of the atisine-isoatisine isomerisation may be attributed largely to the increased hindrance resulting from the restriction which ring E imposes on the rotation of the 17-group in atisine. This investigation was supported by Grant RG 5807 (Cl) from the National Institutes of Health United States Public Health Service.(Received October 3rd 1960.) t To the extent that steric strain results from this interaction form (Id) should actually be favoured over (Jc). # If only form (Id) exists in atisine but forms corresponding to both (Ic) and (Id) exist in isoatisme then a maximum entropy difference of (RT In 2) 0.4 kcal. mole-‘ would favour isoatisine over atisine. However since atisine exists almost entirely in the open form in aqueous solution and since the open form of atisine equilibrates almost completely to isoatisine the free energy of atisine must be at Ieast 3 kcal. mole-’ greater than that of isoatisine. $ The motion bending rings c and E away from each other relieves the interaction between nitrogen and the 10-hydrogen in form (Id) but increases the hindrance encountered by nitrogen in (Ic) again suggesting that (Id) should be the favoured form.Dvornik and Edwards Proc. Chem. Soc. 1958 305. Westheimer “Steric Effects in Organic Chemistry,” ed. Newman John WiIey and Sons Inc. New York 1956, Chapter 12. Dvornik and Edwards Chem. and Znd. 1958 623. Przybylska and Marion Canad.J. 1959 37 1843. PROCEEDINGS The Electron Spin Resonance Spectrum of Triphenyhethyl By P. B. AYSCOUGH, A. P. MCCANNand R. WILSON (DEPARTMENT CHEMISTRY LEEDS, OF PHYSICAL THEUNIVERSITY 2) THE ease with which stable solutions of triphenyl- methyl may be prepared and the wealth of detail in their hyperfine spectra render them particularly suit- able as reference standards for the calibration of magnetic fields in electron spin resonance work.Most of the 196 lines are observable under proper a b basis of a simple model with absorption lines of Lorentzian shape,2 by using the values k = 45.8 k = 20.05 and k = 50.0 for the ratios of the hyper- fine splitting constants to the half-width at half- height of the individual lines agreed precisely with the observed spectrum as is shown in Fig. 1. Even FIG.1. Part of the spectrum of 5 x lO-%r-solution of triphenylmethyl in benzene at 25" (a) observed (b) computed. conditions and provide numerous reproducible reference points from which the behaviour of the field sweep units used in electron spin resonance spectrometers can be determined. For the past two years we have used the resolved hyperfine structure of solutions of triphenylmethyl in benzene as the basis of a simple and reliable method of field calibra- tion which dispenses with auxiliary proton resonance equipment.These studies also provided estimates of the iso-tropic hyperfine splitting constants for the triphenyl- methyl radical itself which are in excellent agreement with the values recently quoted by Chesnut and S1oan.l Our values for these parameters referring to interaction with the six ortho- six meta- and three para-protons are 2-55 f0.02 1.11 f0.01 and 2-78 f0.02 gauss respectively. The spectra were observed at 9-5 kMc./sec. on a Varian V-4500 EPR spectrometer with a Mullard 10-inch magnet. For convenience observations were made at 25" where the line width (0.01 gauss) is twice that reported by Chesnut and Sloan for temperatures below -20" and resolution of in-dividual lines is incomplete.Despite this a sufficient number of the major components were identifiable to estimate the splitting parameters within about 1 %. Interpretations of this kind may be confirmed and refined by computing the spectrum and making small adjustments to the splitting constants in order to obtain the best fit. A spectrum computed on the the small partially resolved lines are identical in the calculated and the observed spectra and differences of 0.2% in the relative values of the hyperfine splitting constants are detectable by this method. The computing procedure can often provide addi- tional information by indicating differences in detail which may not otherwise be seen.For instance it was apparent from the spectra of triphenylmethyl at higher microwave power that additional groups of lines were present beyond the calculated limit. These are indicated by arrows in Fig. 2a and were attributed to further splitting of some of the most intense lines A FIG.2. Spectrum of 5 x 103M-solution of triphenyl-merhyf in benzene. (a) 1 % of (C6H5)23C.(b) 10% of (C,H,),13C. Chesnut and Sloan J. Chem. Phys. 1960,33 637. Scheurs Blomgren and Fraenkel J. Chem. Phys. 1960,32 1801. JANUARY 1961 by interaction with the nuclear spin of the central 13C carbon atom appreciably reduces the total relaxation atoms present in the normal isotopic proportion of time of the spin system.Such a mechanism would 1%. This was confirmed by synthesising triphenyl- probably also result in an increase in width of the methyl with 10% of 13C in the central position and hyperfine lines from radicals containing 13C which observing the enhancement of these lines (see Fig. 2b). might explain our inability to observe individual From these spectra it is concluded that the isotropic hyperfine lines from isotopically labelled triphenyl- hyperfine splitting constant for 13C in triphenyl- methyl radicals under conditions which gave maxi- methyl is 26 f 3 gauss in good agreement with mum resolution for the unlabelled radicals. earlier value^.^ The lines arising from radicals containing 13C were We are indebted to the Department of Scientific less easily saturated by excessive microwave power and Industrial Research for a grant for purchase of than those containing only 12C.This is presumed to the spectrometer and for maintenance grants (for mean that the additional relaxation mechanism pro- A.P.M. and R.W.). vided by the presence of a nuclear spin on the central (Received November 9th 1960.) Weissman and Sowden J. Amer. Chem. SOC.,1953 75 503; Adam and Weissman ibid. 1958 80 2057. Alkaloids of Calabash Curare The Structure of Macusine-B By A. R.BATTERSBY and D. A. YEOWELL (THEUNIVERSITY, BRISTOL) A NEW quaternary alkaloid macusine-B has been C-methyl group [044 mol. of acid (Kuhn-Roth)] isolatedl from Strychnos toxifera and analysis of and a modified Kuhn-Roth oxidation3 gave only many of its derivatives now establishes the formula acetic acid.Dihydronormacusine-B however yielded C20H2,0N2+.Thermal fission of macusine-B chloride acetic and propionic acid which shows the presence at 310-320" yielded the dimorphic tertiary base of 3 CCH=CH2 or :C=CH-CH in norma-m.p. 245O (rhombic) cusine-B. The ethylidene system was established by normacusine-B C19H220N2 275O (needles) which was converted into macusine-B the nuclear magnetic resonance spectrum of nor-iodide by methyl iodide. The ultraviolet and infrared macusine-B taken at 56.4 Mc cycle/sec. in trifluoro- spectra of normacusine-B showed the presence of a acetic acid; this showed a strong doublet at 8.23 r 2,3-disubstituted indole system and hydroxyl and which was proved to be coupled with a band at 4.16 7.imino-groups. The last was shown to be the indolic Normacusine-B has no sharp bands in its infrared :NH by preparing NO-diacetylnormacusine-B spectrum between 2700 and 2800 cm.-l where trans-having the ultraviolet spectrum of an N-acylindole quinolizidines ab~orb,~ and is unaffected by pivalic and infrared bands at 1707 and 1748 cm.-l. The acid in boiling xylene,j by mercuric acetate in hot hydroxyl group is primary since reduction of 0-aqueous acetic acid,6 and by palladium in boiling toluene-p-sulphonylnormacusine-Bwith lithium alu- aqueous maleic acid.' This evidence points to a struc- minium hydride2 gave deoxynormacusine-B in which ture for normacusine-B in which it is sterically im- a new C-methyl group had been generated (1 -45 mol.possible for a 3-hydrogen atom to epimerise or of acid in a Kuhn-Roth determination; cf. norma- for ring C to be dehydrogenated [where these cusine-B below). designations refer to structures such as (I)]. Catalytic hydrogenation of normacusine-B over When the above evidence is considered in conjunc- platinum in acetic acid gave dihydronormacusine-B tion with the usual biosynthetic consideration^^^^^^ C1BH240N2,m.p. 189-190" which has unchanged for the indole alkaloids it leads to structure (I; R = ultraviolet spectrum; normacusine-B is therefore H) as the most probable for normacusine-B; the pentacyclic and the double bond is not conjugated stereochemistry is considered below. Recently the with the chromophore.Normacusine-B has one absolute stereochemistry of ajmaline has been estab- Battersbv. Binks. Hodson. and Yeowell. J.. 1960. 184 .8. Cf. Arnold von 'Philipsborn Schmid and 'Karrer Helv. Chim. Acta 1957 40 705. Garbers Schmid and Karrer Helv. Chim. Acta 1954,37 1336. Bohlmann Angew. Chem. 1957,69,641; Chem. Ber. 1958,91,2157; Wenkert and Roychaudhuri J. Amer. Chem. SOC.,1956 78 6417. Woodward Bader Bickel Frey and Kierstead Tetrahedron 1958 2 1. Weisenborn and Diassi J. Amer. Chem. SOC.,1956 78 2021. 'Wenkert and Roychaudhuri J. Amer. Chem. SOC.,1958,80 1613. a Cf. Stauffacher Hofmann and Seebeck Helv. Chim. Acta 1957 40 508; Poisson Le Men and Janot Bull. SOC. chim. France 1957 610. Cf. Mors Zaltman Beereboom Pakrashi and Djerassi Chem. and Ind.1956 173. lished by researches1* which involved among other steps the degradation of ajmaline to deoxyiso-ajmalol-B (a);the relative and absolute stereochem- istry of this product are known with certainty.'O Methylation of 0-acetyldihydronormacusine-B(III) H ,CHiOH H CH~OR' (I) 13 m.p. 192" (rhombic) 219-220" (needles) with sodamide and methyl iodide in liquid ammonia gave a mixture of N(a)-methylated products which with- out separation was hydrolysed. The resultant bases were fractionated to yield an alcohol m.p. 248-250" identical with deoxyisoajmalol-B (rr> prepared from ajmaline by the method of Bartlett ef aLIO Thus the structure (LV) is a complete expression including absolute stereochemistry for dihydronormacusine- PROCEEDINGS B.Since the structure (I; R = OH) proposedsn2for sarpagine has been and the stereochem- istry elucidated,ll a further correlation was possible. DeoxysarpagineI2 (I; R = H) was proved to be identical with normacusine-B as were the corres- ponding 0-acetyl derivatives (m.p. mixed m.p. infrared spectra optical rotation). The combined results establish the structure and stereochemistry of normacusine-B to be as in formula (I; R = H); only the configuration of the ethylidene system remains to be elucidated. Macu- sine-B chloride therefore has structure (V) and it should be noted that the absolute stereochemistry at position 15 is the same as that at the corresponding carbon of all a-and p-indole alkaloids13 with the sole exception 01 #-akuammicine.14 Grateful acknowledgement is made to Dr.W. I. Taylor and Dr. M. F. Bartlett (CIBA New Jersey) for samples of ajmaline and sarpagine derivatives and for sending us two communicationslOJ before their publication to Dr. E. Seebeck (Sandoz Basle) for a gift of sarpagine to Dr. L. M. Jackman (Imperial College) for the nuclear magnetic resonance spectrum and to the Colonial Products Council for financial support. (Received November 23rd 1960.) lo Bartlett Schlittler Sklar Taylor Amai and Wenkert J. Amer. Chem. SOC.,1960 82 3792. l1 Bartlett Sklar and Taylor J. Amer. Chem. SOC.,1960 82 3790. l2 Bartlett Sklar and Taylor unpublished work. la Bow Chatterjee and Iyer Indian J. Pharm. 1956 18 185; Wenkert Robb and Bringi J.Amer. Chem. SOC. 1957,79 6570. l4 Edwards and Smith Proc. Chem. SOC.,1960 215. Dimerisation and Disproportionation of n-Butyl Radicals By J. C. J. THYNNE* (DEPARTMENT UNIVERSITY AT Los ANGELES, OF CHEMISTRY OF CALIFORNIA Los ANGELES U.S.A.) 24 CALIFORNIA METHYL radicals can react with a higher alkyl radical or similar higher alkyl radicals with each other by (i) combination of the radicals or (ii) their dispro- portionation which leads to an alkane and an olefin. The disproportionation ratio (4) is the ratio of the rate constant for disproportionation to that for com- bination; it has been measured for several alkyl radicals1 and with one exception shown to be independent of temperature. The anomaly is for n-butyl radicals which were studied by the photolysis of valeraldehyde from 61" to 416".2 We have now studied the decomposition of butyl formate sensitised by methyl radicals which were produced by photolysis of acetone at h > 3000 8 at 70" to 195".Although formates when photolysed at short wavelengths (h < 2500 A) yield alkoxy- radicals in considerable amounts yet in the radical- sensitised decomposition of butyl formate no pro-ducts were observed that might have been produced by butoxy-radicals indicating that this reaction follows the same path as with methyl formate namely Me- + HC02R-+ CH + R02C-,followed * Permanent address Department of Chemistry The University Leeds 2. 1 Trotman-Dickenson,Ann. Reports 1959,55 36. * Kerr and Trotrnan-Dickenson J.1959 1602. 8 Ausloos Canad. J Chem. 1958 36 383. Kutschke personal communication 1958. JANUARY 1961 immediately by R02C 3 C02 + R..In this way the particular alkyl radical R-produced is thermally equilibrated. The ease and simplicity with which the R02C. radical breaks down is analogous to the breakdown of the acyloxy-radical RCO-0. pro- duced by the thermal decomposition of the diacyl peroxides e.g. Ac202-+ 2Ac0. -+ 2Me. + C02. For butyl formate the following reactions are important within this temperature range kl Me-+ H-CO,Bun -+ CHI + CO + Bun. k, Bun. + H*CO,Bun -+ C4H10 + CO + Bun. k, 2Me. -+ C,H6 k4 Me* + Bun. 3 CH4+ C4Hs k -+ C& k6 2Bun* -t C*H + C4H1 k -+ CsH, The products were analysed by gas chromato- graphy and mass spectrometry and all the above products were observed the olefin being but-1-ene and the alkanes all normal alkanes.The results obtained lead to the following values for A (i) Me. + Bun. k,/k = 0.15 and showed no temperature-dependence. This value may be com- pared with those for methyl-ethyle (0.06) and methyl- n-propy17 (0.14). (ii) Bun. + Bun. k,/k = 0.94 f0.05 and showed no temperature-dependence. This value corresponds well with that (0.92) predicted by Kraus and Calvert8 on the basis of the number of hydrogen atoms available for abstraction. Kerr and Trotman-Dickenson2 reported temperature- dependent values which ranged from 0369 at 61" to 1-04 at 204". From our work it appears that the anomaly in the case of butyl formate is not real but that such varia- tions in d might be due to the production of "hot" radicals by direct photolysis so that wherever pos- sible thermally equilibrated radicals should be used in such studies.I thank Professor F. E. Blacet for many helpful discussions. (Received November 23rd 1960.) Rembaum and Szwarc J. Amer. Chem. SOC.,1954 76 5975. Heller J. Chem. Phys. 1958 28 1255. Thynne unpublished work 1960. Kraus and Calvert J. Amer. Chem. SOC.,1957 79 5921. Rotenoid Reactions Prefaced by Alkaline Attack By L. CROMBIE and D. A. WHITING P.J. GODIN K. S SIDDALINGAIAH OF CHEMISTRY COLLEGE W.C.2 and (DEPARTMENTS KING'S STRAND IMPERIALCOLLEGE AND TECHNOLOBY S.W.7) OF SCIENCE SOUTHKENSINGTON ROTENONE (Ia)l* and its relatives are racemised at both positions 6a and 12a by acetate ion or stronger bases.Cahn and his colleagues2 considered inter- mediate (11) to be implicated but Jennen3 (cf. Butenandt4) preferred the ion from (III) formed as in (IV). By modifying Jennen's techniques3 we have been able to isolate the pure phenol (111) m.p. 96" vmax. 1646 cm.-' A,,,. 305 (4.31) and 315i (4.29) mp,t and it reverts rapidly to mutarotenone2t when treated with sodium acetate in ethanol. Its acetyl derivative is identical with a specimen made rational- ly by dehydrogenating the acetyl derivative of rotenol (V)with active manganese dioxide in acetone (this reagent converts rotenoids into 6a 12a-dehydro- rotenoids and isoflavanones into isoflavones in good yield).By treatment of rotenone with 2~-aqueous potassium hydroxide however the two diastereo- isomers (5.p) of Cahn's hypothetical intermediate [ketonised form (Vla)] can be isolated; they have m.p. 150-151" [a] + 203" Amm. 244 (4.14) and 296 (4-36) mp and m.p. 122-123" [a] -235". These compounds are too resistant to isomerisation by acetate ion to be the direct intermediate and are formo,d from the intermediate (111) by prototropic shift. When treated with the stronger base potassium carbonate in wet acetone the racemate (Vr) derived * Formula (a) denotes ring E of the rotenone series formula (b) that of the isorotenone series. f Log c in parenthesis. $ Mixture of 6afi,12aP,5'8 and 6a ar,l2a a,5'&disstereoisomers.Buchi Kaltenbronn Crombie Godin and Whiting Proc. Chem. Soc. 1960 274. Cab Phipers and Boam J. 1938 51 3. Jennen Bull. SOC.chem. beiges. 1952 61 536. (a) Butenandt and McCartney Annufen 1932,494 17; (6) Butenandt and Hilgetag ibid. 1933,506 158. 20 PROCEEDINGS from (f)-isorotenone (Ib) is reconverted into the latter. of iso-oxime~,~~~~ the a+/%toxicarol change,2 the formation of rotenol and derritol,loa,ll and the for- (f)-Isorotenolone C m.p. 212" vmax. 1706 cm.-l [cf. (f)-isorotenone Ymax. 1680 cm.-l] Amax. 241 (4.76) 247i (4.69) 2643. (4.07) 281 (4-1 l) 292i (3-98) and 335 (3.74) mp obtained when isorotenone is mation of rotenolones and isoroten~lones~ can be unified mechanistically by invoking initial formation of the ion (IV) and then the ion from (HI).The di-chotomous alkaline methylation of rotenone and /t\ VJ 0 (I V. treated with alkaline hydrogen peroxide5 and hitherto unformulated is now found to have structure (VIIb; R = OH) and is considered to be formed by alkaline epoxidation of the a-unsaturated ketonic ion corre- sponding to (III) followed by intramolecular epoxide opening.6 It is thus skeletally different from iso- rotenolones A and B;' we have been unable to isolate isorotenolone D5though a polymorph of C has been found having the m.p. assigned to this compound D. Spectral data suggest that iso-rotenolone C is structurally related to compounds obtained by treating rotenol (Va)8§ or isorotenol with manganese dioxide or alkaline ferricyanide. The product from the latter reaction has m.p.126" Vmax. 1709 cm.-l Amax. 240 (4.72) 246i (4*65) 264i (4.02) 281 (4.06) 290 (4.02) and 335 (3-74) mp and degradation shows it to be the spiro-compound (VLIb; R = H) formed by oneelectron transfer via a mono-or bi-radical (VIII). Many facets of rotenoid chemistry such as the isolation of dehydronetoric a~id,~~~~ the formation (V) (v I) toxicaro112 also receives explanation. Rotenone (Ia) yields an enol ether derived from (IV without arrows) but a-toxicarol (X; R = R = H) gives the diphenolic ether (IX). In sodium hydroxide solution or potassium carbonate in wet acetone,l2 ionisation of the 1 1-phenol occurs [ionisation not enolisation,2 is indicated by the instantaneous rotational and spectroscopic change when alkali is added to toxi- carol thus the phenolic ketone (X; R = OH R = H) shows an immediate shift of maximum but the cx 0 (x I I> acetate (X; R = H R' = OAc) does not] and enolisation ensues on this ion.The resultant di-ion (XT)is severely destabilised relative to the form (Xn) by adjacent-charge repulsion and attack to give the ether (IX) occurs on the stable and predominant species (XU). (Received November 21~1 1960.) Q Rotenol m.p. 120" has always passed in the literature as an individual. It should be and is a mixture of two 5',!?-diastereoisomers separable by crystallisation m.p. 141-143" [a]il-245" and m.p. go" [ + 33". They equilibrate readily at 12a in the presence of base. LaForge and Haller J. Amer. Chern. SOC., 1934 56 1620.Vander Werf Heisler and McEwen J. Amer. Chem. SOC.,1954 76 1231. Crombie and Godin Proc. Chem. SOC.,1960 276. * Haller and LaForge J. Amer. Chem. SOC.,193 1,53,2271; Haller ibid. 1932,54,2126. Butenandt and Hilgetag Annalen 1932,495 176; Clark J. Amer. Chem. SOC.,1932,54 2537. lo (a)Butenandt Annalen 1928,454 253; (b) LaForge and Haller J. Amer. Chem. SOC.,1932,54 810. l1 LaForge and Smith J. Amer. Chem. SOC.,1929 51 2574. le Cahn Phipers and Boam J. 1938 734. JANUARY 1961 NEWS AND ANNOUNCEMENTS Joint Library Committee.-The Council has ap- pointed Dr. W. Gerrard and Professor B. C. L. Weedon as representatives of the Society on the Joint Library Committee in succession to Mr. D. J. Halliday and Mr. H. M. Powell who retired at the end of 1960.Appointmentof Senior Assistant Librarian.-Mr. J. Kennedy has been appointed Senior Assistant Librarian to the Society and commenced his duties on January lst 1961. Research Fund.-The Council has awarded research grants totalling S951 7s. 6d. to 28 Fellows. The Harrison Memorial Prize 1959.-At the meeting of the Harrison Memorial Prize Selection Committee held on December 7th 1960 it was decided that the Harrison Memorial Prize for 1959 should be awarded to Dr. Amyand David Bucking- ham in consideration of his research work in the field of physical chemistry and especially on account of his theoretical contributions to the understanding of solvent effects upon molecular spectra and to the theory of pressure-induced spectra.Dr. Buckingham is a graduate of the University of Sydney Australia. After a period of post-graduate research at Cam- bridge he took up an appointment at Oxford where he is now a Demonstrator and Lecturer in inorganic chemistry and a Student of Christ Church. This Prize may be awarded for outstanding merit in any branch of Pure or Applied Chemistry. It was created in 1922 to commemorate the services of the late Colonel Edward Frank Harrison formerly Deputy Controller of the Chemical Warfare Depart- ment for the protection of the British Forces from poison gas in the 1914-1918 war. It is awarded to the British chemist under 30 years of age who in the opinion of the Selection Committee has during the previous five years conducted the most meritorious and promising original investigations in Chemistry and published the results.The Royal Society.-The President of the Royal Society Sir Howard Florey has appointed the following Vice-presidents for the year ending November 30th 1961 Sir Alexander Fleck K.B.E. Treasurer of the Royal Society; formerly Chairman of Imperial Chemical Industries Limited. Sir Lindor Brown C.B.E. Biological Secretary of the Royal Society; Waynflete Professor of Physiology at Oxford University. Sir William Hodge Physical Secretary of the Royal Society; Lowndean Professor of Geometry and Astronomy in the University of Cambridge. Sir Patrick Linstead Foreign Secretary of the Royal Society; Rector of the Imperial College of Science and Technology.Professor T.M. Harris Professor of Botany in the University of Reading. Dame Kathleen Lonsdale D.B.E. Professor of Chemistry at University College London. Royal Society’s New Gold Medal.-The Council of the Royal Society has much pleasure in announc- ing its acceptance of an offer by the Trustees of the Leverhulme Trust Fund to mark the occasion of the Royal Society’s Tercentenary by the award of a gold medal. Under the terms of the offer the medal is “for award by the Society every three years to the individual who in the opinion of its Council shall have made the most significant contribution in the field of pure or applied chemistry or engineering in- cluding chemical engineering. The medal which will be in gold will be accompanied by a monetary award of five hundred pounds.’’ The Council has made the first award of the medal to Sir Cyril Hinshelwood O.M.F.R.S. who retired as President of the Royal Society on November 30th last for his outstanding contributions to physical chemistry. The Royal Institute of Chemistry.-The Teaching of Inorganic Chemistry A one-day symposium on the teaching of inorganic chemistry at pre-university level will be held in the Donnan Laboratories Uni- versity of Liverpool on Saturday April 15th 1961. The symposium which has been arranged to follow the Annual Meeting of the Chemical Society in Liverpool on April ll-l4th is being organised by the Liverpool and North Western Section of the Royal Institute of Chemistry.Among the speakers will be Professor C. C. Addison (University of Nottingham) Dr. H. M. Irving (University of Oxford) Professor R. S. Nyholm F.R.S. (University College London) and Dr. A. G. Sharpe (University of Cambridge). Dis-cussion sessions will be introduced by senior members of the S.M.A. Further details and application forms are avail- able from The Education Officer Royal Institute of Chemistry 30 Russell Square London W.C.1. The registration fee is 10s. Od. including morning coffee and afternoon tea. International Congresses etc.-7th Common-wealth Mining and Metallurgical Congress will be held in Johannesburg and Ndola and Salisbury Rhodesia on April 10th-May 21st 1961. Enquiries should be addressed to H. McL. Husted Congress Manager P.O.Box 809 Johannesburg South Africa. Fourteenth International Institute of Welding Assembly held in conjunction with the American Welding Society will be held in New York on April ll-l3th 1961. Enquiries should be addressed to G. Parsloe Secretary General 54 Princes Gate London S.W.7 or Fred L. Plummer Secretary American Council c/o American Welding Society 33 W. 39th Street New York 18 N.Y. U.S.A. An International Congress on Analytical Chem- istry will be held in Budapest on April 24-29th 1961. Enquiries should be addressed to Magyar Kemikusok Egyesiilete Szabadsag-ter 17 Budapest V Hungary. An International Meeting on High-powered Radiotherapy part of the 4th International Medical- Surgical Meetings June 3-15th will be held in Turin on June 10-llth 1961.Enquiries should be addressed to Minerva Media Corso Bramante 83-85 Turin Italy. An International Congress on Vacuum Tech- niques will be held in Paris on June 20-24th 1961. Enquiries should be addressed to Professor P. Fleury Secretary-General International Union of Pure and Applied Physics c/o Institut d’Optique 3 boul. Pasteur Paris 15e France. Fourth International Light Metals Congress will be held in Leoben on June 21-24th 1961. Enquiries should be addressed to Montanistische Hochschule Leoben Styria Austria. Fifth International Symposium on Free Radicals will be held in Uppsala Sweden on July 6-7th 1961. Enquiries should be addressed to Symposium Secretariat c/o Institute of Physical Chemistry Uppsala Sweden.First International Congress of Biophysics will be held in Stockholm on July 3lst-August 4th 1961. Enquiries should be addressed to Dr. Bo. Lindstrom Dept. of Medical Physics Karolinska Institutet Stockholm 60 Sweden. An International Congress on Pharmacology will be held in Stockholm on August 3rd-l0th 1961. Enquiries should be addressed to Professor Borje Uvnas Pharmacology Institute Karolinska Mediko- Kirurgiska Institutet Solnavagen 1 Stockholm Sweden. An International Symposium on Microchemical Techniques will be held in Princeton N.J. on August 13-18th 1961. Enquiries should be ad-dressed to H. J. Francis Jr. c/o Pennsalt Chemical Corp. P.O. Box 4388 Chestnut Hill P.O. Phila- delphia 18 Pa.USA. First International Pharmacological Meeting will be held in Stockholm on August 22nd-25th 1961. Enquiries should be addressed to Dr. kid Wretlind Secretary General Karolinska Institutet Stockholm 60,Sweden. Fifth International Conference on Ionization Phenomena in Gases will be held in Munich on September 4-9th 1961. Enquiries should be ad-dressed to Dr. Paul Schulz Lichttechn. Institutes PROCEEDINGS der Tech. Hochschule Hertzstr. 16 Karlsruhe Germany. Fourth International Seaweed Symposium will be held in Biarritz on September 18-25th 1961. Enquiries should be addressed to M. Barriety Directeur Centre Scientifique B.P. 28 Biarritz France. Second International Congress on Vacuum Science and Technology will be held in Washington D.C.on October 15th 1961 in connexion with the International Organisation for Vacuum Science and Technology and the American Vacuum Society. Enquiries should be addressed to W. M. Welch International Organisation for Vacuum Science and Technology 1515 Sedgwick Street Chicago 10 Illinois U.S.A. An International Congress for Microbiology will be held in Montreal on August 19-25th 1962. Further details may be obtained from Dr. N. E. Gibbons Secretary-General National Research Council Ottawa 2 Canada. Mass Spectrometry Conference.The Mass Spectro- metry Panel of the Institute of Petroleum in con- junction with A.S.T.M. Committee E-14 are organis- ing a conference of Mass Spectrometry which is to be held at Oxford University on September 12-14th and the morning of the 15th 1961.Papers dealing with any aspect of Mass Spectro- metry will be welcome but special sessions will be held which will deal with high-resolution mass spectrometry the mass spectrometry of organic compounds and the mass spectrometry of inorganic solids. Authors who wish to present papers at the Con- ference are asked to send full abstracts by February 28th 1961 to Dr. R. R. Gordon chairman Mass Spectrometry Panel National Coal Board Coal Research Establishment Stoke Orchard Chelten- ham Gloucestershire. Details regarding Conference membership and all other arrangements can be obtained from the Organising Secretary W. J. Brown Instrumentation Division A.E.I. (Man-Chester) Ltd. Trafford Park Manchester 17.High Polymer Research Group.-The High Poly- mer Research Group has been founded under the Chairmanship of Sir Harry Melville K.C.B. D.Sc. F.R.I.C. F.R.S. for the purpose of organising study conferences. The first conference which will be held from April 17-20th 1961 will consider the relationship between chemical structure and physical properties of elastomers. The policy of the Group is to encourage the free exchange of ideas between active workers from all countries in the chosen field and for that reason participation will be by invitation only. JANUARY1961 The proceedings of the Group will not be recorded nor will papers which are read before the Group be available for publication. The offices of the Group are at 14 Belgrave Square London S.W.1. Explosion at Kingsport U.S.A.-Tennessee East-man Company has announced that it is believed that the explosion which occurred at its Kingsport plant on October 4th 1960 was the detonation of a mix- ture of nitrobenzene nitric acid and water. It has been concluded that a substantial concentration of water was present at the time of the explosion. The violence of the explosion indicated that the mixture was detonated with a speed and power comparable to TNT. This experience warns of the great potential dangers associated with a mixture of nitrobenzene and nitric acid even with substantial quantities of water present. Election of New FeIlows.-llO Candidates whose names were published in Proceedings for November have been elected to the Fellowship.Deaths.-We regret to announce the deaths of the following Mr. C. S. Garland (6.12.60) Chairman and Managing Director Caston Barber Ltd. and other companies; Mr. A. H. Moore (16.11.60) of Pepsi-Cola Ltd. Feltham; Mr. F. J. Phillips (19.11.60) of Edinburgh University; Mr. W. H. Simmons (2.12.60) Analytical and Consulting Chemist; and Mr. F. Wade,T.D. (1 8.10.60) a Fellow since 1901. Personal.-University College of Wales. The fol-lowing appointments became effective in The Edward Davies Chemical Laboratories Aberyst- wyth on October lst 1960; Dr. W. J. Orvilfe-Thomas Senior Lecturer; Dr. J. A. Kerr Lecturer; Drs. A. H. Price and C. J. Young Assistant Lecturers. Dr. Myron L. Bender formerly of the Illinois Institute of Technology has been appointed Associate Professor of Chemistry at Northwestern University Evanston Illinois U.S.A.Dr. J. C. Craig formerly of the University of Sydney was appointed to the Chair of Pharma- ceutical Chemistry University of California San Francisco and took up his duties on October lst 1960. Professor F. S. Dainton of Leeds University has been elected to an honorary fellowship at St. Catharine’s College University of Cambridge. Dr. R. M. Huines took up an appointment as senior Lecturer at the Institute of Technology Bradford on January lst 1961. Professor S. H. Harper has been re-elected Dean of the Faculty of Science for 1961 at the University College of Rhodesia and Nyasaland.He has held this position since 1956. Dr. H. M. N. H. Irving has been appointed to the Chair of Inorganic and Structural Chemistry University of Leeds. Mr. F. A. Jones has been elected a Vice-president of the Institution of the Rubber Industry. Dr. R. H. Marriott has been elected President of the International Federation of Societies of Cos- metic Chemists. Dr. R. F. Naylor has been appointed to the Chair of Chemistry at the new University College in Nairobi. Dr. J. 0. V. Oubridge has been appointed senior lecturer in inorganic chemistry at the College of Technology Liverpool. Dr. G. D. Parkes has been elected to the office of Sub-warden of Keble College Oxford. Dr. P. A. Robins lecturer in organic chemistry at the University College of Rhodesia and Nyasaland will be visiting the United Kingdom during December 15th-February 5th.Dr. R. F. Robbins has been appointed Head of the Department of Science Hatfield Technical College with effect from January lst 1961. Dr. F. S. Stone has been appointed to an eight- month visiting lectureship as from January 1961 under the sponsorship of the Petroleum Research Fund of the American Chemical Society. He will lecture on catalysis and the solid state at John Hopkins and Northwestern Universities. Mr. D. J. O’Sullivan has taken up an appointment as works chemist Irish Ropes Ltd. Newbridge Co. Kildare. Dr. Mary R. Truter lecturer in the Department of Inorganic and Structural Chemistry in the University of Leeds has been given the title of Reader in Structural Crystallography.Dr. C. F. Wells has been appointed lecturer in the Department of Chemistry University of Birming- ham. Dr. T. White F.R.Z. C. Hon. Editor of the Journal of the Society of Leather Trades’ Chemists and presently Director of Research of the Forestal Land Timber and Railways Co. Ltd. will set up an inde-pendent consultant practice as from January lst 1961 at Highlands Wood End Road Harpenden Hem. Professor Heinrich Zollinger D.Sc. has been awarded the Ruzicka Prize for Chemistry for 1960. PROCEEDINGS FORTHCOMING SCIENTIFIC MEETINGS London Thursday February 9th 1961 at 7.30 p.m. The following papers will be presented “The Crystal Structures of the Acid Salts of Some Monobasic Acids Part V,” by H.H. Shrivastava and J. C. Speakman. “Part VI” by J. C. Speakman and H. H. Mills. “Delocalisation and Magnetic Properties of the Phosphonitrilic Halides,” by D. P. Craig M. L. Heffernan R. Mason and N. L. Paddock. “The N.M.R. Spectra of Triphosphonitrilic Fluoro- chlorides,” by M. L. Heffernan and R. F. M. White. To be held in the Rooms of the Society Burlington House W. 1. (Abstracts of the papers can be obtained from the General Secretary.) Thursday February 23rd at 10 a.m. All-day Symposium on Terpene Chemistry arranged by Professor A. W. Johnson Ph.D. Sc.D. A.R.C.S. To be held in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington S.W.7.The meeting will be followed by a dinner at Imperial College.Full particulars will be circulated to Fellows. Aberdeen Monday February 20th 1961 at 8 p.m. Pedler Lecture “Some Problems in the Chemistry of the Gallotannins,” by Professor R. D. Haworth D.Sc. Ph.D. F.R.S. to be given in the University Chemistry Department Old Aberdeen. Aberystwyth (Joint Meetings with the University College of Wales Chemical Society to be held in the Edward Davies Chemical Laboratories University College.) Thursday February 9th 1961 at 5 p.m. Lecture “Biosynthesis of Terpenoids with Special Reference to Carotenoids,” by Professor T. W. Goodwin M.Sc. A.R.I.C. Thursday March 2nd at 5 p.m. Lecture “Polymer Kinetics,” by Dr. T. T. Jones. Thursday March 9th at 5 p.m.Lecture “Chemical Processing of Power Reactor Fuels,” by Dr. F. F. Kemp. Birmingham (Joint Meetings with the Birmingham University Chemical Society to be held in the Chemistry Department The University.) Friday February 3rd 1961 at 4.30 p.m. Lecture “Physical Adsorption,” by Professor D. H. Everett M.B.E. D.Phi1. Friday February 24th at 4.30 p.m. Lecture “The Structure of Bacteria,” by Professor J. Baddiley D.k. Ph.D. Friday March loth at 4.30 p.m. Lecture “Very Fast Chemical Reactions,” by Professor G. Porter M.A. Ph.D. Bristol (Meetings will be held in the Department of Chem- istry The University unless otherwise stated.) Thursday February 2nd 1961 at 6.30 p.m. Lecture “The Discovery and Development of Terylene,” by Mr.J. R. Whinfield C.B.E. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Thursday February 9th at 5.15 p.m. Lecture “The Infrared Spectra of Some Inorganic Complexes,” by Dr. D. W. A. Sharp. Joint Meeting with the Student Chemical Society. Thursday February 16th at 5.15 p.m. Lecture “Death by Poisoning,” by Dr. A. Hunt. Joint Meeting with the Student Chemical Society. Thursday February 23rd at 6.30 p.m. Lecture “The Simplest Type of Chemical Reaction,” by Professor T. L. Cottrell. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Thursday March 2nd at 5.15 p.m. Lecture “Oxidation in Aqueous Solution,” by Pro- fessor F. s. Dainton M.A. Ph.D. F.R.S. Joint Meeting with the Student Chemical Society.Thursday March 2nd at 6.30 p.m. Lecture “Titrations in Non-aqueous Solvents,” by Mr. E. Minshall M.Sc. F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Technical College Brunswick Road Gloucester. Thursday March 9th at 6.30 p.m. Society of Chemical Industry Annual General Meeting and Film “Water Treatment.” Joint Meet- ing with the Royal Institute of Chemistry and the Society of Chemical Industry. Cambridge (Meetings will be held in the University Chemical Laboratory Lensfield Road.) Friday February loth 1961 at 8.30 p.m. Lecture “The Mobile Stereochemistry of Nitrogen,” by Dr. K. Schofield. Joint Meeting with the Univer- sity Chemical Society.Monday February 13th at 5 p.m. Lecture “Some Aspects of Aromatic Reactivity,” by Dr. C. Eaborn A.R.I.C. Friday February 24th at 8.30 p.m. Lecture “Recent Advances in the Chemistry of D Vitamins,” by Professor B. Lythgoe Ph.D. F.R.I.C. F.R.S. JANUARY 1961 Monday March 6th at 5 p.m. Lecture “Some Molecular Structure Studies by Microwave Spectroscopy,” by Dr. J. Sheridan M.A. Friday March loth at 8.30 p.m. Lecture “Some Aspects of the Radiation Chemistry of Aqueous Systems,” by Professor J. Weiss Ph.D. Joint Meeting with the University Chemical Society. Durham (Joint Meetings with the Durham Colleges Chemical Society to be held in the Science Laboratories The University.) Monday February 13th 1961 at 5 p.m.Lecture “Very Fast Chemical Reactions,” by Professor G. Porter M.A. Ph.D. Tuesday February 28th at 5 p.m. Lecture “The Stereochemistry of Metal Ions,” by Professor L. E. Orgel M.A. D.Phi1. Edinburgh Thursday February 16th 1961 at 7.30 p.m. Lecture “Some Aspects of the Chemistry of Iso-quinoline Alkaloids,” by Dr. K. W. Bentley M.A. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the North British Station Hotel. Tuesday February 21st at 4.30 p.m. Pedler Lecture “Some Problems in the Chemistry of the Gallotannins,” by Professor R. D. Haworth D.Sc. F.R.I.C. F.R.S. Joint Meeting with the Uni- versity Chemical Society to be held in the Chemistry Lecture Theatre The University West Mains Road.Exeter {Meetings will be held in the Washington Singer Laboratories The University .) Friday February loth 1961 at 5 p.m. Lecture “Aspects of Phenol Biogenesis,” by Pro-fessor C. H. Hassall M.Sc. Friday March 1&h at 5 p.m. Lecture “Spectra of Gases and Vapours under High- frequency Excitation,” by Professor C. L. Wilson Ph.D. D.Sc. F.R.I.C. Glasgow Thursday February 16th 1961 at 4 p.m. Lecture “Physical Adsorption,” by Professor D. 1-3. Everett M.B.E. D.Phil. F.R.I.C. Joint Meeting with the Alchemists Club to be held in the Chem- istry Department The University. Hull {Meetings will be held in the Department of Chem-istry The University.) Thursday February 16th 1961 at 5 p.m. Lecture “The Mechanism of Some Organometal Substitutions,” by Sir Christopher Ingold D.Sc.F.R.I.C. F.R.S. Joint Meeting with the University Students Chemical Society. Thursday March 9th at 7.30 p.m. Lecture “Infrared Spectra,” by Dr. L. J. Bellamy. Joint Meeting with the Royal Institute of chemistry. Irish Republic (Meetings will be held in the Chemistry Department Trinity College Dublin unless otherwise stated.) Wednesday March lst 1961. The Official Meeting and Tilden Lecture arranged for this date has been postponed until April 26th 1961. Friday March 3rd at 7.45 p.m Lecture “The Kinetics of Some Halogenation Re actions,” by Mr. R. P. Bell M.A. F.R.S. Joint Meeting with the Werner Society. LeedS Thursday March 9th 1961 at 6.30 p.m.Lecture “Phytol,” by Professor B. C. L. Weedon D.Sc. A.R.C.S. F.R.I.C. Joint Meeting with the Leeds University Union Chemical Society to be held in the Chemistry Department The University. Leicester Monday February 6th 1961 at 4.30 p.m. Lecture “The Mechanism of Some Organometal Substitutions,” by Sir Christopher Ingold D.Sc. F.R.I.C. F.R.S.Joint Meeting with the University Chemical Society to be held in the University. Liverpool Thursday February 23rd 1961 at 5 p.m. Lecture “Chemical Control of Plant Growth,” by Professor R. L. Wain Ph.D. F.R.I.C. F.R.S. Joint Meeting with the University Student Chemical Society to be held in the Department of Inorganic and Physical Chemistry The University. Manchester Thursday March 9th 1961 at 4.30 p.m.Lecture “Some Problems in the Chemistry of Phos- phorus,” by Dr. S. H. Pollard. Joint Meeting with the University Faculty of Technology Chemical Society to be held in Room F1 The College of Science and Technology. Newcastle upon Tyne (Meetings will be held in the Chemistry Department Kings College.) Friday February 17th 1961 at 5.30 p.m. Bedson Club Lecture “Synthetic Fused Silica,” by Dr. K. H. Jack F.R.I.C. Friday March loth at 5.30 p.m. Bedson Club Lecture “Some Reflections on the Detergent Industry,” by Dr. A. Koebner. North Wales Thursday February 2nd 1961 at 5.45 p.m. Lecture “Very Fast Chemical Reactions,” by Pro- fessor G. Porter M.A. Ph.D. Joint Meeting with the University College Chemical Society to be held in the Chemistry Department University College Bangor.Northern Ireland (Joint Meetings with the Royal Institute of Chem- istry and the Society of Chemical Industry to be held in the chemistry Department Queens Univer- sity Belfast.) Tuesday February 14th 1961 at 7.45 p.m. Lecture “Recent Advances in Infrared Spectro-scopy,” by Dr. L. J. Bellamy. Thursday February 23rd at 7.45 p.m. Lecture “The Principles of Radiation Chemistry and the Possibilities of its Industrial Application,” by Professor F. S. Dainton M.A. Ph.D. F.R.S. Reading Thursday February 23rd 1961 at 6 p.m. Lecture “Saturated Electrophilic Substitutions,” by Sir Christopher Ingold D.Sc. F.R.I.C. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the University Chemical Society to be held in the University.St Andrews and Dundee Friday February loth 1961 at 5.1 5 p.m. Lecture “Hydrogen Bonding and Some Crystal Structures,” by Dr. J. C. Speakman. Joint Meeting with the University of St. Andrews Chemical Society and the Royal Institute of Chemistry to be held in the Chemistry Department St. Salvators College St. Andrews. Tuesday February 14th at 5 p.m. Lecture “Transi tion-metal Complexes Derived from Cycloheptatriene,” by Professor P. L. Pauson Ph.D. To be given in the Chemistry Department Queen’s College Dundee. Friday February 24th at 5.15 p.m. Lecture “Some Problems in the Structural Chem- istry of Polysaccharides,” by Professor E. L. Hirst C.B.E. D.Sc. F.R.S.Joint Meeting with the Uni- versity of St. Andrews Chemical Society to be held in the Chemistry Department St. Salvators College St. Andrews. Sheffield (Joint Meetings with the Royal Institute of Chemistry and the University Chemical Society to be held in the Chemistry Department The University.) PROCEEDINGS Thursday February 16th 1961 at 4.30 p.m. Lecture “Aspects of the Chemistry of Transitional Metal Complex Hydrides,” by Professor G. Wilkin-son Ph.D. A.R.C.S. F.R.I.C. Thursday March 9th at 4.30 p.m. Lecture “The Electronic Orbitals Shapes and Spectra of Simple Molecules,” by Professor A. D. Walsh M.A. Ph.D. Southampton Wednesday February 8th 1961 at 7 p.m. Lecture “Silicones Their Properties and Industrial Applications,” by Mr.A. N. Tizard F.R.J.C. Joint Meeting with the Portsmouth and District Chemical Society to be held in the College of Technology Portsmouth. Friday February loth at 5 p.m. Lecture “The Porphyrin Group of Natural Pig-ments,” by Professor A. W. Johnson Sc.D. Ph.D. A.R.C.S. Joint Meeting with the University Chem- ical Society to be held in the Chemistry Department The University Southampton. Friday February 24th at 5 p.m. Lecture “The Spectroscopy of Benzene,” by Dr. D. H. Whiffen M.A. Joint Meeting with the Univer- sity Chemical Society to be held in the Chemistry Department The University Southampton. Swansea Monday February 27th 1961 at 5 p.m. Lecture “Recent Work on the Gallotannins,” by Professor R. D. Haworth D.Sc. Ph.D.F.R.S. Joint Meeting with the University College Chemical Society to be held in the Department of Chemistry University College. Tees-side Friday February 3rd 1961 at 8 p.m. Tilden Lecture “Recent Studies on Many-membered Rings,” by Professor R. A. Raphael Ph.D. A.R.C.S. A.R.J.C. To be given in the Constantine Technical College Middles brough. Wednesday February 15th at 8 p.m. Lecture “Some Developments in Analytical Chem- istry,” by Professor R. Belcher F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Stockton and Billingham Technical College Billing- ham. Tuesday February 28th at 8 p.m. Lecture “Progress and its Effects on our Food Supplies,” by Mr. T. McLachlan D.C.M.F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the William Newton School Norton-on-Tees. J ANUARY 1961 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.) Anderson John Edgar. 12A Arnothill Gardens Falkirk Stirlingshire. Arrayed Jalil B.A. University Department of Education 152 Upper New Walk Leicester. Ashworth Victor. 28 Treve Avenue Harrow Middlesex. Atkins Peter William.Alma Villas Sycamore Road Chalfont St. Giles Bucks. Bamkole Titus Olubode B.Sc. Tedder Hall University College Jbadan Nigeria. Boothroyd John Arthur B.Sc. 11 Wormald Street, Almondbury Huddersfield. Bride Michael Henry Ph.D. 122 Liswerry Drive Llanyravon Cwmbran Mon. Broughton James Hartley. 110 Bladindon Drive Bexley Kent. Chakravarti Debi M.Sc. D.Phi1. Chemistry Depart- ment Bethune College Calcutta 6 India. Chan Tin Lok B.Sc. National Court. Flat A-1 12th Floor Nathan Road Kowloon Hong Kong. Clarke Donald. 34 Princes Avenue Hedon nr. Hull, Yorks. Cocker David John Be%.22 Torkington Road Gatley Cheadle Cheshire. Cohen Harvey M. A.B. 82-3 Middlesex Road Waltham Mass. U.S.A. Cook Edward Werner Jr.. A.B. Chemistry Department University of Colorado Boulder Colorado U.S.A.Cooper Peter Michael B.Sc. c/o L. Light and Co. Ltd., Poyle Estate Colnbrook Bucks. Corfield Margaret Gaynor B.Sc. Glenhaven Abermulle Montgomeryshire. Cowell Geoffrey B.Sc. 257 Victoria Road London N.22. Craig Alan Daniel Ph.D. Chemistry Dzpartment Uni- versity of Pennsylvania. Philadelphia 4 Penn. U.S.A. Cule Geoffrey B.Sc. Edward Davies Chemical Labora- tories Aberystwyth. Davidson George. Jesus College Oxford. Davis Gerald Gordon B.Sc. Chemistry Department Queens University Kingston Ontario Canada. Deverell Christopher. 9 Southdown Avenue Lewes Sussex. Dichlian Michael George. 8 Copthall Drive London N.W.7. Dixon John Richard B.Sc. Edward Davies Chemical Laboratories Aberystwyth.Dodd James William B.Sc. Department of Physical and Inorganic Chemistry The University Bristol 8. Dolphin Roger Jean Julien D.Sc. 82 Ebury Street London S.W.l. Donnelly Rrendan James B.Sc. 27 Copeland Avenue Clontarf Dublin. Downing Douglas Crawford Ph.D. Shawinigan Chem- icals Ltd. Box 330 Shawinigan P.Q. Canada. Downing Roland Granville A.B. 4408 Lone Oak Road Nashville 12 Tenn. U.S.A. Duggleby Peter McCowan M.Sc.Tech. 12 Circular Road Withington Manchester 20. Dunnett James Sangster. Corpus Christi College, Oxford. Edwards David Nun B.Sc. 2 Creighton Road London w.5. Ege Sehyan Nurettin M.A. Ph.D. Chemistry Depart- ment Boston University Boston 15 Mass. U.S.A. Evans Hugh Einydd B.Sc. Chemistry Department The University Leeds.Fedrick James Love M.S. Ph.D. Lederle Laboratories Building 65-A Room 209 Pearl River New York U.S.A. Feld Raoul Ph.D. 17 Eastwood Avenue Grimsby Lincs. Fendler JAnos Hugo B.Sc. 143 King Richards Road Leicester. Fisher Derek. 12 Cumberland Walk Sutton Coldfield Warw icks. Fox Winston Michael. Barlborough Close Boughton Lane Clowne Chesterfield. Freed Seymour. 14 Athlone House Sidney Estate London E.1. Freedman Jules M.S. College of Pharmacy University of Michigan Ann Arbor Michigan U.S.A. Frost David James. 42 High Street Poole Dorset. Gabb Edward George B.Sc. 60 Otterfield Road, Yiewsley Middlesex. Ganti Venkatrao M.Sc. Ph.D. Chemistry Department University of British Columbia Vancouver 8 B.C., Canada.Ghosez Leon Ph.D. Chemistry Department 12 Oxford Street Cambridge Mass. U.S.A. Gil-av Emanuel Ph.D. Wehann Institute Rehovoth Israel. Gladstone William Anthony Francis. 38 Woodthorne Road Tettenhall Staffs. Goldstein Michael B.Sc. 24 Binyon House MiIton Grove London N. 16. Goodall Seonaid Roberta B.S. 22 Florence Road London W.5. Gough Terence Edward. 28 Campbell Road Southsea Hants. Grant Henry Claud B.Sc. 23 Wrexham Road Romford Essex. Green Michael John. 124 The Drive Bexley Kent. Guy George Bruce. 87 Greenleach Lane Roe Green Worsley nr. Manchester Lancs. Hansen Richard Laverne Ph.D. 2219 West 61st Street Minneapolis 19 Minnesota U.S.A. Hill Robert Charles. 1 Carlyle Road Greenbank, Bristol 5. Hinde Peter Terence B.Sc.Bryn Rheidol Penparcau Road Aberystwyth. Hocking Martin Blake B.Sc. Chemistry Department The University Southampton Holbrook Kenneth Arthur P1i.D. 41 Sherbrook Street Downfield Dundee. Horvath Bert M.S. 9073 E. 6th Street Tucson Arizona U.S.A. Hughes David B.Sc. A.R.C.S. Thunderley Parsonage Cole End Saffron Walden Essex. Hunt Kenneth B.A. M.Sc. Ph.D. Chemistry Depart- ment West Mains Road Edinburgh 9. Irons George Michael. 31 Wellington Road Hatch End Pinner Middlesex. Jefcoate Colin Robert. Hill Top Ashley Green Road Chesham Bucks. Johnston Peter. B.Sc. 4 Strathmore Road Newsham Park Liverpool 6. Jones Evan Wyn B.Sc. Edward Davies Chemical Laboratories Aberystwyth. Jones Peter Trefor B.Sc. 29 Sandhill Oval beds 17.Jmgensen Christian Klixbiill Ph.D. 5 Rue des Cordiers Geneva Switzerland. Kerr James Alistair Ph.D. Chemistry Department University College of Wales Aberystwyth. Kirk Peter Geoffrey. 9 Richmond Park Crescent, Sheffield 13. Kirkham William Jeffrey Ph.D. 4A Briardale Gardens London N.W.3. Koleoso Olajide Adedokun. Tedder Hall University College Ibadan Nigeria. Kuszewski James Robert B.S. Noyes Laboratory 156 University of Illinois Urbana Illinois U.S.A. Kybett Brian David B.Sc. Barons Cross Inn Leo-minster Herefordshire. Larnbert Richard Michael. 273 Abingdon Road, Oxford. hrdy Ivor Adair B.Sc.18 Greenwood Road Clarkston Glasgow. Lederer Florence. Institut de Chimie 2 rue Goethe, Strasbourg France. Le ROW Norman William B.Sc.1 Hereford Road London W.2. Lewis Dennis Osborne B.Sc. Edward Davies Chemical Laboratories Aberystwyth. Liebesny Felix B.Sc. 179 Chevening Road London N.W.6. List Colin Frederick B.%. Birshaw Watford Road Northwood Middlesex. Lloyd Bernard. 175 Cumberland Road London E.13. Locke John Michael. 1420 25th Avenue South Nash- ville Tenn. U.S.A. hckley John Campbell. “The Grange,” Rawnsley, Cannock Staffs. koev Bernard M.A. Ph.D. 321 Robinson Drive, Broomall Penna. U.S.A. Lupin Michael Sidney. Hillel House 2 Springfield Mount Leeds 2. McDowell Berma L. B.A. Department of Chemistry University of California Berkeley California U.S.A. Madden Ian Oscar B.Sc. 50 Shandon Park Belfast 5. Margolis Phyllis M.S. 2918 Ellsworth Berkeley 5, California U.S.A.Mathews Carl Fraser B.Sc. West Winds Warren Vale Rawmarsh Rotherham Yorks. Mobbs Richard Henry B.Sc. Chemistry Department Science Laboratories South Road Durham. Narula Jagdish LA M.Sc. 50 Palace Road London s.w.2. ‘Oakes Vincent M.Sc. Ph.D. A.R.I.C. Pure Chemicals Ltd. Kirkby Industrial Estate Liverpool. .Ojechi Patrick. Tedder Hall University College Ibadan Nigeria. Okafor Charles Okolo. Tedder Hall University College Ibadan Nigeria. Oldfield William. 45 Belfield Road West. Ewell Surrey. Peacock George Brandwood. 75 Downs Hill Beckenham Kent. Pei Chuan Lee Margaret Ph.D. Chemistry Department Stanford University Stanford California U.S.A. Perrv. Clark William. B.S. 110 Graduate House. M.I.T.. Cimbridge 39 Mass.U.S.A. Pitt. Michael Charles. 27 Moorfield Road. West Dids- bury Manchester 20. PROCEEDINGS Poole Donald B.Sc. South View Sowood Green, Stainland nr. Halifax. Rafos Robert Roland B.A. 1631-GSpartan Village East Lansing Michigan U.S.A. Ross Peter Angus. Yoxall Lodge Worsley Road Southsea Hants. Robinson James Henry B.Sc. Oriel College Oxford. Rogers Geoffrey Trevor M.A. Ph.D. 24 Castle Grove Newbury Berb. Roobol Norman R. B.S. 110-A University Village East Lansing Michigan U.S.A. Rothenbury Raymand Albert B.Sc. A.R.I.C. 14 Outram Road London E.6. Rowarth Brian B.Sc. Embley Park School Embley Park Romsey Hants. Sadler Ian Howard. 14 Hadley Road New Barnet Herts. Shaub Harold M.S. 2135 Wightman Street Pittsburgh 17 Penna.U.S.A. Siddiqui Mohammad Nasim Uddin M.Sc. Chemistry Department Kings College London W.C.2. Sorensen Theodore Strang Ph.D. Chemistry Depart- ment The University Leicester. Spencer Ronald Howard B.Sc. 248 Burnt Oak Lane Sidcup Kent. Still Richard Heywood. 14 Poplar Walk Herne Hill London S.E.24. Storey Edward Anthony. Queens Elms,University Road Belfast 7. Subba Rao Ganugapaty Sree Rama M.Sc. Chemistry Department Andhra University Waltair South India. Sutcliffe Martin Barry B.A. New College Oxford. Syme Robert John B.Sc. 28 Mardale Crescent Edin- burgh 10. Tipper Donald John Ph.D. Chemists Laboratory, Arthur Guinness Son and Co. Ltd. St. James’s Gate Dublin. Todd George Ph.D. A.R.I.C. Little Birchetts Wester- ham Road Keston Mark Bromley Kent.Trahe Robert M. B.S. Chemistry Department Univer- sity of California Los Angeles 24 California U.S.A. Van Maarseveen Gerard B.Sc. 23 Buckingham Hall P.O. Northrand Transvaal South Africa. Van Meter James Philip B.Sc. 51E 16th Avenue Columbus 1 Ohio U.S.A. Walker Cyril B.Sc. F.R.I.C. 69 Bolsover Road, Sheffield 5. Wallis Stanley Richard Chemistry Department The University Southampton. Whipps Peter William. 13 Lynmouth Avenue Bush Hill Park Enfield Middlesex. White Hugh Briggs. Gladshot Haddington East Lo thian. White Sydney Henry B.Sc. 3 Berkeley Place London S.W.19. Wilkes Robert Arthur. 66 Palmerston Road Buckhurst Hill Essex. Witheridge Paul Raymond. 598 Ashley Road Parkstone Poole Dorset.JANUARY 1961 OBITUARY NOTICES OSWALD JOHN SILBERRAD 1 878- 1960 DR.0. J. SXLBERRAD who died on June 17th at his home Dryads Hall Loughton Essex would have completed sixty years as a Fellow of the Society on June 21st of this year. Silberrad was born in 1878 at Buckhurst Hill Essex and educated at Dean Close Memorial School Cheltenham the City 8z Guilds Technical College Finsbury and the University of Wurzburg in Germany where he obtained his Ph.D. At Wiirzburg he studied under Professor Hantzsch who to quote his own words “learnt to respect and know Doctor Silberrad as a scientific practical and excellent chemist and I can say absolutely without exaggera- tion that in all my wide experience of practical scientists scarcely ever has there been anyone who could compare with him in exactness cleverness in experimentation and independence and clear-sightedness of judgment.” In 1901 at the age of 23 he became the first super- intendent of the research department which he planned designed and equipped at the Royal Arsenal Woolwich.During his tenure of office he discovered tetryl of which Sir William Crookes Past President of the Royal Society wrote “using tetryl as his exploder Dr. Silberrad succeeded in detonating shell of all calibre filled with lyddite and subsequently with T.N.T. thus introducing T N.T. which prior to that date (1902) had never been used as a high explosive into the British Service.” In 1908 at the request of the Director of Naval Construction Silberrad investigated the cause of a form of erosion in ships’ propellers so severe that it looked as if the application of the steam turbine to shipbuilding was doomed and that a speed exceeding about 20-22 knots was impracticable for surface craft.Dr. Silberrad discovered the cause of and a remedy for this erosion with the result that the entire Royal Navy was later fitted with propellers made of his bronze as also were other high-speed ships including the world’s great liners. Working in conjunction with the Hotchkiss Co. he contributed much towards the development of the erosion-resisting gun steel which rendered the 75 mm. gun a practical proposition in the war of 1914-1918. In that war he was honorary consultant to the Director-General of Explosives Supply in which capacity he solved many problems and indicated how many others could be solved.Earlier in 1902 he had discovered the cause of the flash from a gun and applying this discovery in 1915-1916 to cordite he developed at his own expense a fiashless powder for use in the big howitzers. He also discovered a means of manufacturing Iyddite in bulk. In 1915 the scientific committees attached to the Ministry of Munitions insisted that lyddite could be made only in earthenware; hence its manufacture from chlorodinitrobenzene via dinitro-phenol which needs a high temperature was im- practicable Silberrad showed how this could be done in immense charges in iron vessels in perfect safety in a manner so unexpected that Lord Moulton went straight down to North Wales where Silberrad was working to see for himself; many thousands of tons were later made by this method.Silberrad however did not confine his work to armament research in 1907 he started practice as a research consultant in his own laboratories at Buckhurst Hill. Typical of the problems with which he dealt were an artificial method of retting flax a new means of blasting petroleum wells the manufacture of dye- stuffs from carbon and also from T.N.T. residues and drugs. He worked on photographic developers special paints for the motor industry refrigerators washing machines and ships’ condensors the production of insulating slewing for radio-equipment special cables for high-frequency currents and PVC fuel pipes for aircraft.His more purely scientific researches covered many subjects incIuding work on fluoresceins the rhodamines of mellitic and pyromellitic acid and catalytic acceleration of chlorination with sulphuryl chloride-he prepared pentachlorotoluene from toluene in twenty minutes before the Society of Chemical Industry. L. G. SILBERRAD. STANLEY ROBSON 1888-1960 STANLEYROSSONwas born on March 28th 1858 at Sunderland. He was educated at Bede School and then studied chemistry at Armstrong College (now King’s College) Newcastle. In 1913 he obtained an Exhibition Scholarship to Imperial College where he intended to specialise in geology which was one of his early interests. He did not continue long as a geologist however but under the influence of Pro- fessor Bone began to work on industrial catalysis.He also took the first course in chemical engineering PROCEEDINGS instituted in the country under Professor Hinchley with whom he formed a lifelong friendship. These were the determining influences in his later career and it followed naturally that in 1917 he joined the staff of the Admiralty plant at Holton Heath where he was largely responsible for the construction and operation of a Tentelev contact plant for the manu- facture of sulphuric acid. He subsequently became an expert of world-wide renown in this technology. In 1920 he joined the British Dyestuffs Corporation where again he was mainly concerned with the pro- duction of sulphuric acid.In 1923 The National Smelting Company Limited was formed to develop the zinc smelting industry in the country. The Swansea Vale Spelter Company was taken over and the derelict Ministry of Munitions plant at Avonmouth which had consisted of a number ofcontact sulphuric acid units operated from sulphur burners and the shells of eight horizontal retort zinc furnaces which had never been completed. The proposal which was discredited by most ex- perts was to operate the contact acid units with gas from the Delplace zinc roasting furnaces. Stanley Robson was asked to take charge of the operation and he accepted the challenge. He realised that success would depend upon the development of an adequate purification system to treat the fume-laden gases from the roasting furnaces and by the applica- tion of exceptional persistence and skill he solved the problem.The next step was to replace the Delplace hearth furnaces which gave a fine powdered product with Dwight Lloyd-type sintering grates. This in- volved the development of a new technique of return- ing a large proportion of the output to dilute the raw zinc sulphide forming the feed to the machines to avoid excessive heat generation. This was carried out successfully and the method is still known as the Robson process in many parts of the world. The problem of purifying the SO,-bearing gases from the machines which carried even more fume than from the old hearth furnaces was also solved and the con- tact plants made to operate successfully and sulphuric acid produced at high efficiency.In 1933 he was largely responsible for introducing at Avonmouth the continuous vertical retort process for zinc production developed by the New Jersey Company. He supported and largely inspired the early work on the blast furnace production of zinc which has been brought to full commercial operation at Avonmouth. He therefore laid the foundation for the present zinc industry in this country. In 1947 he moved to London and became a con- sultant to the Zinc Corporation and was responsible for the construction of sulphuric acid plants in a number of places in the world. He was elected to the Board of Huntington Heberlein and Company Limited in 1954 and served on it until his retirement in 1959.He was honoured by a number of societies. He was President of the Society of Chemical Industry from 1949-1951 of the Institution of Chemical Engineers from 1952-1953 and of the Institution of Mining and Metallurgy from 1955-1956. He was Honorary Foreign Secretary of the Society of Chemical In- dustry from 1941-1948 and Honorary Secretary of the Royal Institution from 1953 until he retired due to ill-health in 1957. In 1917 he married Elsie Foster who with their two sons survives him. Throughout his life he was strongly attached to his family and to the church. A man of great humanity and a most attractive personality he was a constant inspiration particu- larly to those of us who were privileged to serve under him.S. W.K. MORGAN. ALFRED EGERTON 1886-1959 SIR ALFREDEGERTON, M.A. F.R.S. born on November 11 th 1886,died suddenly on September 7th 1959 as a result of a heart attack. He main- tained an active personal interest in research throughout a life which was also marked by many public services. His main researches extended over combustion in various aspects; the richness and diversity of the phenomena had an unexhausted fascination for him. A somewhat secondary research interest for him lay in the determination of important thermodynamic properties of substances with high accuracy. For example investigations alone and with various collaborators on the vapour pressures of metals’ and on the saturation pressures of steam2 provided results of high quality and enduring value Egerton also showed a perennial zest in the devising of instruments and research gadgets; eleven devices are described in separate papers and many others are described in conjunction with other researches.In the main field of research on combustion the first investigations which made a major contribution to knowledge originated in studies of engine “knock” action in relation to mechanisms of ignition. With S. F. Gates as collaborator he published a Summary Phil. Mag. 1917 33 33; 1920 39 1; 1924 48 1048; Proc. Roy. SOC.,1923 A 103 471 499; A 113 520 533; Phil. Trans.,1935 A 234 177; Trans. Chem. SOC.,1923 123 3024. Phil. Trans.,1932 A 231 147. JANUARY 1961 Report of these researches in 1926 (H.M.Stationery Office) and more extensive papers in 1927.3 The effects on the ignition of combustible mixtures of the addition of a wide variety of substances in small quantities were studied. By using fairly simple apparatus marked inhibiting effects were demon- strated and roughly calibrated particularly in the case of certain metal aerosols which greatly raised “ignition temperatures.” The nature of these in- hibitors suggested that they acted by “decomposing fuel peroxides” though at that time no very precise chemical formulation of these could be given. The next major step was to isolate and analyse samples of the combustible mixture at various phases of a compression-expansion cycle in an internal combus- tion engine.Results of these pioneering researches in collaboration with F. Ll. Smith A. R. Ubbelohde J. W. Drinkwater and T. K. Hanson4 focused the need to characterise much more accurately the chem- ical nature and modes of “decomposition” of the various “pro-knocks” that appeared to be formed from the fuel in small quantities inside the engine cylinder. Various studies on the decomposition of organic peroxides5 and on the formation of hydrogen per- oxide in combustion6 illustrate ways in which Egerton and his colleagues developed these aspects of pro- cesses of slow combustion that take place at fairly low temperatures. Studies of ultraviolet absorption spectra during combustion may also be mentioned in this connection,’ as well as studies of various methods for the analysis of peroxides and other com- bustion products.8 Investigations of the physical pro- perties of peroxides were also carried out in relation to their importance for processes of slow combustion at fairly low temperature^.^ In addition to these investigations Egerton carried out numerous researches in combustion under much more intensive conditions in flame and detonation.Early work on detonationlo and on explosionll was followed considerably later by various studies of flame propagation under more nearly stationary con- ditions.12 In these studies his work on the “flat flame” seems particularly fascinating. Though this enumeration of some of the leading contributions to knowledge resulting from Egerton’s researches is not exhaustive it aims to show how in the tapestry of an active research life different strands recurred as the pattern developed.All this was woven into a life that was also very active in other ways. Brief mention has already been made to his many public services which have been described more fully in other obituary notices of a more general character. Egerton was also a productive and gifted painter in water colour and more recently in oils. His former pupils and colleagues greatly miss him. A. R. UBBELOHDE. J. Inst. Pet. Tech. 1927 13 244 256 273 281. Phil. Trans.,1935 234 433; Proc. Roy. SOC.,1935 A 153 103; 1937 A 163 90. Egerton and Harris Proc. Roy. SOC. 1938 A 168 1. Egerton and Minkoff Proc. Roy.SOC. 1947 A 191 145; Egerton and Jain Fuel 1952 31 62; Egerton and Rudrakanchana ibid. 1954 33 274; Egerton Minkoff and Salooja Proc. Roy. SOC. 1956 A 235 158; Egerton, Minkoff and Salooja Combustion and Flume 1957 1 25. Egerton and Pidgeon Proc. Roy. SOC. 1933 A 142 26; Egerton Harris and Young Trans. Furuduy SOC.,1948, 44,745-764. Egerton Everett Minkoff Rudrakanchana and Salooja Anal. Chim. Acta 1954 10 422; Egerton Minkoff and Salooja ibid. 523. Egerton Erste and Minkoff Disc. Furuday SOC. 1951 10 278. lo Egerton and Gates Proc. Roy. SOC. 1927 A 114 137 152. l1 Egerton and Gates Proc. Roy. SOC.,1927 A 116 516. la Egerton and Pauling Proc. Roy. SOC. 1948 A 193,172,190; Egerton and Thabet ibid. 1952 A 211,445; Egerton and Lefebvre ibid. 1954 A 222 206; Egerton and Badami Fuel 1954 33 406.ADDITIONS TO THE LIBRARY Chemistry in the service of man. A. Findlay. (In Sloveniun.) Pp. 380. Ljubljana. 1954. (Presented by Professor A. Findlay.) Henry Cavendish his life and scientific work. A. J. Berry. Pp. 208. Hutchinson. London. 1960. A bibliography of Dr. Robert Hooke. Sir Geoffrey Keynes. Pp. 115. Clarendon Press. Oxford. 1960. Biographisch-Literarisches Handworterbuch der exac- ten Naturwissenschaften by J. C. Poggendorff. Vol. 7a; Part 4 S-Z. Pp. 336. Akademie-Verlag. Berlin. 1960. Chemical periodicity. R. T. Sanderson. Reinhold. New York. Encyclopedia of chemical technology. Edited by R. E. Kirk and D. F. Othmer. Second Supplement Volume-edited by Anthony Standen. Pp. 970. Inter-science Publishers Inc.New York. 1960. Tables for identification of organic compounds. Edited by C. D. Hodgman et uf. Issued by the Chemical Rubber Publishing Co. (Supplement to Hand- book of Chemistry and Physics.) Pp. 239. Chemical Rubber Publishing Co. Cleveland Ohio. 1960. Alphabetical index to tables of chemical kinetics. Homogeneous reactions. Sponsored by the United States Department of Commerce National Bureau of Standards. (National Bureau of Standards Circular 510-Supple- ment 2.) Pp. 37. United States Government Printing Office.Washington. 1960. The Merck index of chemicals and drugs :an encyclo- pedia for chemists pharmacists physicians and members of allied professions. Edited by P. G. Stecher et al. 7th edn. Pp. 1641. Merck and Co.Inc. Rahway N.J. 1960. Addendum 1960 to the British Pharmacopoeia 1958. Pp. 83. Pharmaceutical Press. London. 1960. Infrared methods principles and applications. G. K. T. Conn and D. G. Avery. Pp. 203. Academic Press. New York. 1960. Photographic chemistry. P. Glafkides. Translated from the French 2nd edn. K. M. Hornsby. Vol. 2. Pp. 996. Fountain Press. London. 1960. (Presented by the publisher.) Flame photometry. J. A. Dean. Pp.354. McGraw-Hill. New York. 1960. Molecular distillation. G. Burrows. Pp. 214. Clarendon Press. Oxford. 1960. (Presented by the publisher.) Fine particle measurement size surface and pore volume. Clyde Orr jun. and J. M. Dallavalle. Pp. 353. Macmillan. New York. 1959. Crystal structures. R. W.G. Wyckoff. Supplement 5. Interscience. New York. 1960. Physical chemistry of surfaces. A. W. Adamson. Pp. 629. Interscience. New York. 1960. Isotope effects on reaction rates. L. Melander. Pp. 181. Ronald Press Co. New York. 1960. Transport phenomena. R. Byron Bird W. E. Stewart, and E. N. Lightfoot. Pp.780. John Wiley and Sons. New York. 1960. (Presented by the publisher.) Hand buch der praparativen anorganischen Chemie. Edited by G. Brauer. Vol. 1.2nd edn. Pp.884. Ferdinand Enke. Stuttgart. 1960. Arbeitsgemeinschaft fur Forschung des bandes Nordrhein-Westfalen. Heft 75. Neue Wertigkeitsstufen bei den Ubergangselementen. W. Klemm; Die Woll- forschung in Chemie und Physik von Heute. H. Zahn. Pp. 87. Westdeutscher Verlag. Cologne. 1960.(Presented by the publisher.) The radiochemistry of barium calcium and strontium D. N. Sunderman and C. W. Townley. Sponsored by the United States Atomic Energy Commission. (Nuclear Science Series NAS-NS 3010.) Pp. 118. Subcommittee on Radiochemistry. Washington. 1960. (Presented by the publisher.) The radiochemistry of indium. D. N. Sunderman and C. W. Townley. Sponsored by the United States Atomic Energy Commission. (Nuclear Science Series NAS-NS 3014). Pp. 46. Subcommittee on Radiochemistry. Washington. 1960. (Presented by the publisher.) The radiochemistry of zirconium and hafnium. E. P. Steinberg. Sponsored by the United States Atomic Energy Commission. (Nuclear Science Series NAS-NS 3011.) Pp. 52. Subcommittee on Radiochemistry. Washington.1960. (Presented by the publisher.) Hydrogen peroxide data manual. Pp. 80. Laporte Chemicals Ltd. Luton. 1960. (Presented by the publisher.) Gas purification. A. L. Kohl and F. C. Riesenfeld. Pp. 556. McGraw-Hill. New York. 1960. Pulp and paper; chemistry and chemical technology. J. P. Casey. Vol. 1. 2nd edn. Pp. 580. Interscience. New York. 1960. The natural pigments. K. W.Bentley. (The chemistry of natural products. Edited by K. W. Bentley. Vol. 4.) Pp. 306. Interscience. New York. 1960. Mass spectrometry and its applications to organic chemistry. J. H. Beynon. Pp. 640.Elsevier. Amsterdam. 1960. The carbohydrates. S. F.Dyke. (The chemistry of the natural products. Edited by K. W. Bentley. Vol. 5.) Pp. 232. Interscience. New York.1960. Chemie der organischen Fluorverbindungen. M. Hudlicky. Pp.416. Veb Deutscher Verlag der Wissen- schaften. Berlin. 1960. (Presented by the publisher.) Properties and structure of polymers. A. V. Tobolsky. Pp.331. John Wiley and Sons Inc. New York. 1960. Classifications of high polymers a review prepared for the Plastics and High Polymers Division R. Houwink and H. Bouman. Pp. 54. Buttenvorths. London. 1960. Nitroglycerine and dynamite a contribution to the history of manufacture. S.Nauckhoff and 0.Bergstrom. (In Swedish with an English translation.) Pp. 304. Nitro-glycerin Aktiebolaget. Gyttorp Sweden. 1959. Theoretische Grundlagen der Gaschromatographie. G. Schay. (Physikalisch-chemische Trenn-und Mess-methoden. Edited by E. 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ISSN:0369-8718
DOI:10.1039/PS9610000001
出版商:RSC
年代:1961
数据来源: RSC
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